CN115624867B - Preparation method of filter membrane - Google Patents
Preparation method of filter membrane Download PDFInfo
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- CN115624867B CN115624867B CN202211644772.XA CN202211644772A CN115624867B CN 115624867 B CN115624867 B CN 115624867B CN 202211644772 A CN202211644772 A CN 202211644772A CN 115624867 B CN115624867 B CN 115624867B
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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
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
- B01D46/54—Particle separators, e.g. dust precipitators, using ultra-fine filter sheets or diaphragms
- B01D46/543—Particle separators, e.g. dust precipitators, using ultra-fine filter sheets or diaphragms using membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
- B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
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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
- B01D2323/00—Details relating to membrane preparation
- B01D2323/39—Electrospinning
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Abstract
The invention discloses a preparation method of a high-performance filter membrane, belonging to the field of environmental materials. The preparation method comprises the steps of taking dicyclopentadiene and monomers as raw materials, preparing an intermediate polymer through catalytic polymerization reaction under the action of a catalyst and an initiator, dispersing the intermediate polymer and a nano material into a solvent to prepare a spinning solution, and preparing the filter membrane through an electrostatic spinning method. The filter membrane prepared by the method has a large number of fluorene units and uniformly dispersed nano materials, so that the filter membrane has super strong capacity of capturing dioxin and ultrafine particles, the adsorption rate of the filter membrane on the dioxin is up to more than 87%, the capture rate of the filter membrane on 0.3 micron particles is up to more than 98%, and the filter membrane has a wide industrial application prospect.
Description
Technical Field
The invention relates to the field of environmental materials, in particular to a preparation method of a filter membrane.
Background
Dioxin is a common name of polychlorinated triepoxide heteroaromatic toxic chemicals, is not a single substance, is a mixture consisting of more than 200 isomers, homologues and the like, and actually comprises two most dangerous environmental pollutants in the world: polychlorinated dibenzo-dioxins are abbreviated as (PCDD) and polychlorinated dibenzo-furans (PCDF), which are collectively called dioxins in the national environmental standards. It has great toxicity 130 times that of sodium cyanide and 900 times that of arsenic, and is classified as the first-class carcinogen in human by the international center for cancer research, known as "toxicity in the century". Conventionally, there are adsorbing materials and filter membranes developed for removing dioxins, but the adsorbing materials are generally activated carbons, and dioxins in exhaust gas from a waste incineration site are often contained in tar components of the exhaust gas, but particularly in the case of exhaust gas containing a large amount of tar components, not only is the removal of tar components itself not necessarily sufficient, but also pores are clogged due to adhesion of tar components to the surface of activated carbon, and as a result, the ability to remove dioxins is lowered. In addition, the membrane separation technology is one of the modern high and new technologies developed in recent years by using a filtration separation technology, and the membrane separation technology utilizes a functional separation membrane as a filter medium to realize high separation and purification of liquid or gas. However, the filter membrane in the prior art still has the problems that the capture rate of dioxin in waste gas is low, the filter membrane is difficult to use under the high-temperature condition, and the requirement for capturing and collecting the dioxin is further met. Therefore, it is of great significance to develop a filter membrane with high efficiency of filtering and adsorbing dioxin.
Disclosure of Invention
Based on this, in order to solve the problems that the filter membrane in the prior art still has low capture rate of dioxin in waste gas, is difficult to use at high temperature, and further meets the requirements for capturing and collecting the dioxin, the invention provides a preparation method of the filter membrane, which has the following specific technical scheme:
a method of making a filtration membrane, the method comprising the steps of:
dispersing dicyclopentadiene in a first solvent, and uniformly stirring to obtain a mixture A;
introducing nitrogen into the mixture A, then adding a monomer and a catalyst, and uniformly stirring to obtain a mixture B;
adding an initiator into the mixture B under the condition of continuous stirring to obtain an intermediate polymer;
adding the intermediate polymer and the nano material into a second solvent, uniformly mixing to prepare a spinning solution, and obtaining a filter membrane by an electrostatic spinning method;
wherein the monomer is one or a mixture of more than one of 2, 7-dibromo-9, 9-dimethylfluorene, 2, 7-dibromo-9, 9-didecylfluorene, 2, 7-dibromo-9, 9-didodecylfluorene, 2, 7-dibromo-9, 9-spirobifluorene, 2, 7-dibromofluorene, 9-dihexyl-2, 7-dibromofluorene, 9-dioctyl-2, 7-dibromofluorene, 2, 7-diiodofluorene and 2, 7-dichlorofluorene;
the nanomaterial comprises Bi 2 Te 3 、SnSe、Sb 2 Te 3 、PbTe、SnTe、GeTe、MnTe、Ag 2 Te、Cu 2 One or more of Te and AgCuTe.
Preferably, the first solvent is one or a mixture of several of dichloromethane, trichloromethane, carbon tetrachloride, N-methyl pyrrolidone, toluene, 1, 4-dioxane and tetrahydrofuran.
Preferably, the mass ratio of the dicyclopentadiene to the first solvent is 1.5 to 1.
Preferably, the molar ratio of said dicyclopentadiene to said monomer is 2:1.
preferably, the catalyst comprises a compound i and a compound Π, and the compound i comprises one or a mixture of more of bis (triphenylphosphine) carbonyl rhodium chloride, tris (triphenylphosphine) ruthenium (II) chloride acetate, tetrakis (triphenylphosphine) platinum, triphenylphosphine, dichloro (p-methyl isopropylphenyl) triphenylphosphine ruthenium dichloride, tetrakis (triphenylphosphine) palladium, pentamethylcyclopentadienylbis (triphenylphosphine) ruthenium chloride, palladium acetate, palladium (II) acetate (trimer), and triphenylphosphine palladium acetate;
the compound II comprises one or a mixture of more of potassium carbonate, sodium carbonate, bismuth iodide and iodoalkane.
Preferably, the mass ratio of the dicyclopentadiene to the catalyst is 60 to 120.
Preferably, the initiator is one or a mixture of several of azobisisobutyronitrile, azobisisoheptonitrile and benzoyl peroxide.
Preferably, the mass ratio of the catalyst to the initiator is 5 to 1.
Preferably, the nanomaterial comprises 1 to 10wt% of the mass of the intermediate polymer.
Preferably, the second solvent is one or a mixture of several of dichloromethane, trichloromethane, tetrahydrofuran, N-dimethylformamide and 1, 4-dioxane.
In the scheme, dicyclopentadiene and monomers are used as raw materials, an intermediate polymer is prepared through catalytic polymerization reaction under the action of a catalyst and an initiator, then the intermediate polymer and a nano material are dispersed in a solvent to prepare a spinning solution, and the filter membrane is prepared through an electrostatic spinning method. The filter membrane prepared by the method has a large amount of fluorene units and uniformly dispersed nano materials, so that the filter membrane has super strong capacity of capturing dioxin and ultrafine particles, the adsorption rate of the filter membrane on the dioxin is up to more than 87%, the capture rate of the filter membrane on 0.3 micron particles is also up to more than 98%, and the filter membrane has a wide industrial application prospect.
Drawings
FIG. 1 is a flow chart of the present invention for preparing a filter membrane;
FIG. 2 is a graph showing the adsorption rate of dioxin on the filter membrane prepared in example 1;
FIG. 3 is a graph showing the adsorption rate of dioxin on the filter membrane prepared in example 2;
FIG. 4 is a graph showing the adsorption rate of dioxin on the filter membrane prepared in comparative example 1;
fig. 5 is a graph showing the adsorption rate of dioxin on the filter membrane prepared in comparative example 2.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to embodiments thereof. It should be understood that the detailed description and specific examples, while indicating the scope of the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The preparation method of the filter membrane in one embodiment of the invention comprises the following steps:
dispersing dicyclopentadiene in a first solvent, and uniformly stirring to obtain a mixture A;
introducing nitrogen into the mixture A, then adding a monomer and a catalyst, and uniformly stirring to obtain a mixture B;
adding an initiator into the mixture B under the condition of continuous stirring to obtain an intermediate polymer;
adding the intermediate polymer and the nano material into a second solvent, uniformly mixing to prepare a spinning solution, and obtaining a filter membrane by an electrostatic spinning method;
wherein the monomer is one or a mixture of more than one of 2, 7-dibromo-9, 9-dimethylfluorene, 2, 7-dibromo-9, 9-didecylfluorene, 2, 7-dibromo-9, 9-didodecylfluorene, 2, 7-dibromo-9, 9-spirobifluorene, 2, 7-dibromofluorene, 9-dihexyl-2, 7-dibromofluorene, 9-dioctyl-2, 7-dibromofluorene, 2, 7-diiodofluorene and 2, 7-dichlorofluorene;
the nanomaterial comprises Bi 2 Te 3 、SnSe、Sb 2 Te 3 、PbTe、SnTe、GeTe、MnTe、Ag 2 Te、Cu 2 One or more of Te and AgCuTe.
In one embodiment, the first solvent is one or a mixture of several of dichloromethane, trichloromethane, carbon tetrachloride, N-methylpyrrolidone, toluene, 1, 4-dioxane and tetrahydrofuran.
In one embodiment, the mass ratio of the dicyclopentadiene to the first solvent is 1.5 to 1.
In one embodiment, the molar ratio of the dicyclopentadiene to the monomer is 2:1.
in one embodiment, the catalyst comprises a compound i and a compound Π, and the compound i comprises one or a mixture of several of bis (triphenylphosphine) carbonyl rhodium chloride, tris (triphenylphosphine) ruthenium (II) chloride acetate, tetrakis (triphenylphosphine) platinum, triphenylphosphine, dichloro (p-methyl isopropylphenyl) triphenylphosphine ruthenium dichloride, tetrakis (triphenylphosphine) palladium, pentamethylcyclopentadienylbis (triphenylphosphine) ruthenium chloride, palladium acetate, palladium (II) acetate (trimer), and triphenylphosphine palladium acetate;
the compound II comprises one or a mixture of more of potassium carbonate, sodium carbonate, bismuth iodide and iodoalkane.
In one embodiment, the molar ratio of compound i to compound Π is 1:3-3:1.
in one embodiment, the mass ratio of the dicyclopentadiene to the catalyst is 60 to 120.
In one embodiment, the initiator is one or a mixture of azodiisobutyronitrile, azodiisoheptonitrile and benzoyl peroxide.
In one embodiment, the mass ratio of the catalyst to the initiator is 5 to 1.
In one embodiment, the nanomaterial comprises 1 to 10wt% of the intermediate polymer mass.
In one embodiment, the size of the nanomaterial is 100nm to 800nm.
In one embodiment, the nanomaterial is one or both of a nanoparticle, a nanosheet, or both.
In one embodiment, the second solvent is one or a mixture of dichloromethane, chloroform, tetrahydrofuran, N-dimethylformamide and 1, 4-dioxane.
In one embodiment, the spinning dope has a solid content of 8 to 20wt%.
In one embodiment, the filter membrane has a thickness greater than 5mm.
In the scheme, dicyclopentadiene and monomers are used as raw materials, an intermediate polymer is prepared through catalytic polymerization reaction under the action of a catalyst and an initiator, then the intermediate polymer and a nano material are dispersed in a solvent to prepare a spinning solution, and the filter membrane is prepared through an electrostatic spinning method. The filter membrane prepared by the method has a large amount of fluorene units and uniformly dispersed nano materials, so that the filter membrane has super strong capacity of capturing dioxin and ultrafine particles, the adsorption rate of the filter membrane on the dioxin is up to more than 87%, the capture rate of the filter membrane on 0.3 micron particles is also up to more than 98%, and the filter membrane has a wide industrial application prospect.
Embodiments of the present invention will be described in detail below with reference to specific examples.
Example 1:
a preparation method of a filter membrane comprises the following steps:
s1: 2644g of dicyclopentadiene is added into 6610g of dichloromethane solution, then nitrogen is introduced, and stirring is carried out for 10min to obtain a mixture A;
s2: 3520g of 2, 7-dibromo-9, 9-dimethylfluorene are added to the mixture A and stirring is continued for 20min, followed by 26.26g of tetrakis (triphenylphosphine) palladium and 3.14 potassium carbonate, followed by stirring for 30min to obtain a mixture B;
s3: 2.9g of azobisisobutyronitrile are added to the mixture B and reacted for 60 h with stirring, followed by collection of the intermediate polymer obtained;
s4: taking 24g of the intermediate polymer synthesized above and 1.2g of Bi with a particle size of 400nm-600nm 2 Te 3 Dispersing the nano material in 176g of N, N-dimethylformamide solution, stirring for 12h to prepare spinning solution, and preparing a filter membrane with the thickness of 8mm by an electrostatic spinning method under the conditions that the voltage is 17.8KV, the sample injection speed is 1.2 mL/min and the humidity is below 18%.
When the filter membrane prepared in this example 1 was subjected to a dioxin adsorption test, the adsorption rate for dioxin was 92% or more, and the collection rate for 0.3 μm particulate matter was as high as 99.7% or more.
Example 2:
a preparation method of a filter membrane comprises the following steps:
s1: 2644g of dicyclopentadiene is added into 9254g of trichloromethane solution, then nitrogen is introduced, and the mixture is stirred for 10min to obtain a mixture A;
s2: 6045g of 2, 7-dibromo-9, 9-didecylfluorene was added to the mixture A and stirring was continued for 20min, followed by addition of 33.05g of a catalyst of 19.32g of tetrakis (triphenylphosphine) platinum and 13.73 g of potassium carbonate, followed by further stirring for 30min to obtain a mixture B;
s3: 2.2g of benzoyl peroxide are added to said mixture B and reacted for 72h with stirring, and the intermediate polymer obtained is subsequently collected;
s4: and (2) dispersing 20g of the synthesized intermediate polymer and 1.6g of SnTe nano material with the particle size of 500nm-700nm in 180g of N, N-dimethylformamide solution, stirring for 12h to prepare spinning solution, and then preparing a filter membrane with the thickness of 10mm by an electrostatic spinning method under the conditions that the voltage is 18KV, the sample injection speed is 1.5 mL/min, and the humidity is below 18%.
When the filter membrane prepared in example 2 was subjected to a dioxin adsorption test, the adsorption rate for dioxin was 90% or more, and the collection rate for 0.3 μm particulate matter was as high as 99.1% or more.
Example 3:
a preparation method of a filter membrane comprises the following steps:
s1: 2644g of dicyclopentadiene is added into 7932g of dichloromethane solution, then nitrogen is introduced, and the mixture is stirred for 10min to obtain a mixture A;
s2: 4742g of 2, 7-dibromo-9, 9-spirobifluorene was added to the mixture A and stirring was continued for 20min, followed by addition of 19.13g of triphenylphosphine and 3.86 g of sodium carbonate, followed by stirring for 30min to give a mixture B;
s3: 2.87g of azobisisobutyronitrile (catalyst to initiator ratio 8: 1) are added to the mixture B and reacted for 72h with stirring, followed by collection of the obtained intermediate polymer;
s4: taking 28g of the synthesized intermediate polymer and 1.68g of SnSe nano material with the particle size of 400nm-600nm, dispersing the intermediate polymer and the SnSe nano material into 172g of N, N-dimethylformamide solution, stirring for 12 hours to prepare spinning solution, and then preparing a filter membrane with the thickness of 6mm by an electrostatic spinning method under the conditions that the voltage is 18KV, the sample injection speed is 1.0 mL/min and the humidity is below 18%;
when the filter membrane prepared in this example 3 was subjected to an adsorption test of dioxin, the adsorption rate of dioxin was 87% or more and the collection rate of 0.3 μm particulate matter was as high as 98.6% or more.
Comparative example 1:
a preparation method of a filter membrane comprises the following steps:
comparative example 1 differs from example 1 in that no Bi is added to comparative example 1 2 Te 3 Nanomaterial, other processes are the same as example 1.
The filter membrane prepared in comparative example 1 was subjected to a dioxin adsorption test, and the filter membrane prepared in comparative example 1 had an adsorption rate of dioxin of 72% and a trapping efficiency of 83.1% for 0.3 μm particulate matter.
Comparative example 2:
a preparation method of a filter membrane comprises the following steps:
comparative example 2 is different from example 1 in that polyacrylonitrile is used instead of the intermediate polymer prepared in example 1 and the other processes are the same as example 1. The method comprises the following specific steps:
taking 24g of polyacrylonitrile and 1.2g of Bi 2 Te 3 Dispersing the nano material in 176g of N, N-dimethylformamide solution, stirring for 12h to prepare composite spinning solution, and preparing a filter membrane with the thickness of 10mm by an electrostatic spinning method under the conditions that the voltage is 17.8KV, the sample injection speed is 1.2 mL/min and the humidity is below 18%.
The filter membrane prepared in comparative example 2 was subjected to an adsorption test of dioxin, and the adsorption rate of the filter membrane prepared in comparative example 2 to dioxin was 61%, and the trapping efficiency to 0.3 μm particulate matter was 74.6%.
Comparative example 3:
a preparation method of a filter membrane comprises the following steps:
comparative example 3 differs from example 1 in that polyacrylonitrile was used instead of the intermediate polymer prepared in example 1, and Bi was not added 2 Te 3 Nanomaterial, other processes are the same as example 1. The method comprises the following specific steps:
24g of polyacrylonitrile is dispersed in 176g of N, N-dimethylformamide solution, stirring is carried out for 12h, composite spinning solution is prepared, and then a filter membrane with the thickness of 10mm is prepared by an electrostatic spinning method under the conditions that the voltage is 17.8KV, the sample injection speed is 1.2 mL/min, and the humidity is below 18%.
The filter membrane prepared in comparative example 3 was subjected to an adsorption test of dioxin, and the filter membrane prepared in comparative example 3 had an adsorption rate of dioxin of 47% and a trapping efficiency of 62.1% for 0.3 μm particulates.
As can be seen from fig. 2 to 4, the present application has an excellent dioxin adsorption effect.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is specific and detailed, but not to be understood as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (9)
1. A preparation method of a filter membrane is characterized by comprising the following steps:
dispersing dicyclopentadiene in a first solvent, and uniformly stirring to obtain a mixture A;
introducing nitrogen into the mixture A, then adding a monomer and a catalyst, and uniformly stirring to obtain a mixture B;
adding an initiator into the mixture B under the condition of continuous stirring to obtain an intermediate polymer;
adding the intermediate polymer and the nano material into a second solvent, uniformly mixing to prepare a spinning solution, and obtaining a filter membrane by an electrostatic spinning method;
wherein the monomer is one or a mixture of more of 2, 7-dibromo-9, 9-dimethylfluorene, 2, 7-dibromo-9, 9-didecylfluorene, 2, 7-dibromo-9, 9-didodecylfluorene, 2, 7-dibromo-9, 9-spirobifluorene, 2, 7-dibromofluorene, 9-dihexyl-2, 7-dibromofluorene, 9-dioctyl-2, 7-dibromofluorene, 2, 7-diiodofluorene and 2, 7-dichlorofluorene;
the nano material comprises Bi 2 Te 3 、SnSe、Sb 2 Te 3 、PbTe、SnTe、GeTe、MnTe、Ag 2 Te、Cu 2 One or more of Te and AgCuTe;
the catalyst comprises a compound I and a compound II, wherein the compound I comprises one or a mixture of more of bis (triphenylphosphine) carbonyl chloride rhodium, tris (triphenylphosphine) ruthenium chloride (II) acetate, tetrakis (triphenylphosphine) platinum, triphenylphosphine, dichloro (p-methyl isopropylphenyl) triphenylphosphine ruthenium dichloride, tetrakis (triphenylphosphine) palladium, pentamethylcyclopentadienyl bis (triphenylphosphine) ruthenium chloride, palladium acetate, palladium (II) acetate (trimer) and triphenylphosphine palladium acetate;
the compound II comprises one or a mixture of more of potassium carbonate, sodium carbonate, bismuth iodide and iodoalkane.
2. The method according to claim 1, wherein the first solvent is one or more selected from dichloromethane, chloroform, carbon tetrachloride, N-methylpyrrolidone, toluene, 1, 4-dioxane, and tetrahydrofuran.
3. The production method according to claim 1, wherein the mass ratio of the dicyclopentadiene to the first solvent is 1.5 to 1.
4. The method according to claim 1, wherein the molar ratio of dicyclopentadiene to monomer is 2:1.
5. the preparation method according to claim 4, wherein the mass ratio of the dicyclopentadiene to the catalyst is 60 to 120.
6. The preparation method of claim 1, wherein the initiator is one or more of azobisisobutyronitrile, azobisisoheptonitrile and benzoyl peroxide.
7. The preparation method according to claim 6, wherein the mass ratio of the catalyst to the initiator is 5 to 18.
8. The method of claim 1, wherein the nanomaterial comprises 1 to 10wt% of the intermediate polymer.
9. The preparation method according to claim 1, wherein the second solvent is one or more of dichloromethane, chloroform, tetrahydrofuran, N-dimethylformamide and 1, 4-dioxane.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2001009239A (en) * | 1999-06-30 | 2001-01-16 | Hiroshi Kokuta | Waste gas treating device and waste gas purifying method |
| JP2004148304A (en) * | 2002-10-11 | 2004-05-27 | Osaka Gas Co Ltd | Dioxins removing filter, and method of removing dioxins and device for treating exhaust gas using the filter |
| US8007573B2 (en) * | 2007-09-28 | 2011-08-30 | General Electric Company | Filter and associated method |
| CN101306280A (en) * | 2008-06-26 | 2008-11-19 | 南京际华三五二一特种装备有限公司 | Dual-effect filter material for removing dust and decomposing dioxin and preparation method thereof |
| CN101708424B (en) * | 2009-12-11 | 2011-11-02 | 天津泰达环保有限公司 | Method for removing dioxin in waste incineration flue gas and equipment thereof |
| CN103804658A (en) * | 2014-01-20 | 2014-05-21 | 浙江大学 | Polymerizable polyfluorene macromonomer and synthesis method thereof |
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