CN101016182A - Preparing method for fluorine containing copolymer flocculating agent - Google Patents
Preparing method for fluorine containing copolymer flocculating agent Download PDFInfo
- Publication number
- CN101016182A CN101016182A CN 200610105351 CN200610105351A CN101016182A CN 101016182 A CN101016182 A CN 101016182A CN 200610105351 CN200610105351 CN 200610105351 CN 200610105351 A CN200610105351 A CN 200610105351A CN 101016182 A CN101016182 A CN 101016182A
- Authority
- CN
- China
- Prior art keywords
- solution
- fluorinated copolymer
- flocculation agent
- mass ratio
- ammonium chloride
- 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.)
- Granted
Links
Abstract
The invention discloses a making method of fluorine copolymer flocculant, which comprises the following steps: blending fluorine monomer, emulsifier and water evenly to make solution A; blending cation monomer, acrylamide, solution A and water evenly to make solution B; adding initiator into solution B; polymerizing; obtaining the product. The invention improves effluent disposing effect greatly, which is benefit to protect environment and natural resource.
Description
Technical field
The invention belongs to chemical field, particularly a kind of preparation method of fluorinated copolymer flocculation agent.
Background technology
The principal item of polymeric flocculant is polyacrylamide and derivative thereof, and hydrophobic association type polyacrylamide flocculant wherein then is the kind that occurs in the recent period.The hydrophobic association type polyacrylamide is introduced a small amount of hydrophobic grouping and is made on the polyacrylamide main chain, owing to the hydrophobic interaction between the hydrophobic grouping makes the polyacrylamide molecular chain bunch collection taking place, thereby can obviously improve the bridging action and the effect of flocculation agent.At present, the hydrophobic grouping of introducing on the hydrophobic association type polyacrylamide flocculant molecular backbone chain mainly is hydrocarbon hydrophobic monomer.Fluorochemical monomer is a kind of strong-hydrophobicity monomer, and its hydrophobic association effect is stronger than hydrocarbon hydrophobic monomer, so have the better application effect by the cationic fluorochemical polyacrylamide copolymer of fluorochemical monomer, cationic monomer and acrylamide copolymerization.
Summary of the invention
The objective of the invention is to improve the effect of conventional polymeric flocculant, a kind of preparation method of fluorinated copolymer flocculation agent of flocculating property excellence is provided.
For achieving the above object, the technical solution used in the present invention is: at first with fluorochemical monomer, emulsifying agent and water by 1: the mass ratio of 0.01-40: 10-10000 mixes and makes solution A; Then with cationic monomer, acrylamide, solution A and water by 1: the mass ratio of 0.01-100: 1-500: 5-1000 mixes and makes solution B; Under 20 ℃-90 ℃ initiator is added in the solution B at last, wherein, the mass ratio of solution B and initiator is 100: 0.01-5 obtains the fluorinated copolymer flocculant solution after polymerase 10 .5-48 hour then.
Another technical scheme that the present invention adopts is: at first with fluorochemical monomer, emulsifying agent and water by 1: the mass ratio of 0.01-40: 10-10000 mixes and makes solution A; Then with cationic monomer, acrylamide, solution A and water by 1: the mass ratio of 0.01-100: 1-500: 5-1000 mixes and makes solution B; Under 20 ℃-90 ℃ initiator is added in the solution B at last, wherein, the mass ratio of solution B and initiator is 100: 0.01-5 obtains fluorinated copolymer flocculant solution C then after polymerase 10 .5-48 hour; Solution C is dry down at 30 ℃-100 ℃, drying pressure is 100mmHg-760mmHg, obtain unpurified fluorinated copolymer flocculation agent, can obtain unpurified fluorinated copolymer flocculation agent in extracting 1-48 hour the fluorinated copolymer flocculation agent of purifying then in organic solvent, the mass ratio of wherein unpurified fluorinated copolymer flocculation agent and organic solvent is 1: 1-1000.
Fluorochemical monomer of the present invention is the vinylformic acid trifluoro ethyl ester, trifluoroethyl methacrylate, vinylformic acid hexafluoro butyl ester, methacrylic acid hexafluoro butyl ester, dodecafluorhe-ptylacrylate, methacrylic acid ten difluoro heptyl esters, vinylformic acid 19 fluorine esters, methacrylic acid 19 fluorine esters, perfluoro capryl (N-methyl-N-ethyl propenoate base) sulphonamide, perfluoro capryl (N-methyl-N-Jia Jibingxisuanyizhi base) sulphonamide, perfluoro capryl (N-ethyl-N-ethyl propenoate base) sulphonamide or perfluoro capryl (N-ethyl-N-Jia Jibingxisuanyizhi base) sulphonamide; Emulsifying agent is dodecylbenzyl alkyl dimethyl ammonium chloride, dodecyl benzyl dimethyl ammonium bromide, Dodecyl trimethyl ammonium chloride, Trimethyllaurylammonium bromide, palmityl trimethyl ammonium chloride, cetyl trimethylammonium bromide, octadecyl trimethyl ammonium chloride, octadecyl trimethylammonium bromide, octadecyl benzyl dimethyl ammonium chloride or octadecyl benzyl dimethyl brometo de amonio; Cationic monomer is methylacryoyloxyethyl trimethyl ammonium chloride, dimethylaminoethyl methacrylate or dimethyl diallyl ammonium chloride; Initiator is ammonium persulphate, Potassium Persulphate, ammonium persulfate-sodium bisulfite, Potassium Persulphate-sodium bisulfite, ammonium persulphate-S-WAT, Potassium Persulphate-S-WAT, ammonium persulphate-Sulfothiorine or Potassium Persulphate-Sulfothiorine; Organic solvent is acetone, methyl alcohol, ethanol, methylethylketone, tetrahydrofuran (THF), methyl acetate, ethyl acetate, butylacetate, N, dinethylformamide or N,N-dimethylacetamide.
Because the special performance of fluorine-containing groups, the fluorinated copolymer flocculation agent that adopts preparation method of the present invention to make can improve wastewater treatment efficiency greatly, improves the reusing sewage rate, is beneficial to the protection of environment and natural resources.
Embodiment
Embodiment 1, at first vinylformic acid trifluoro ethyl ester, dodecylbenzyl alkyl dimethyl ammonium chloride and water mixed by 1: 0.01: 10 mass ratio and makes solution A; Then with methylacryoyloxyethyl trimethyl ammonium chloride, acrylamide, solution A and water by 1: 0.01: 1: 5 mass ratio mixes and makes solution B; Under 90 ℃, initiator ammonium persulfate is added in the solution B at last, wherein, the mass ratio of solution B and initiator is 100: 0.01, obtains fluorinated copolymer flocculant solution C then after polymerase 10 .5 hour, solution C is unpurified fluorinated copolymer flocculant solution, can directly use; The present invention can also be dry down at 100 ℃ with solution C, drying pressure is 760mmHg, obtain unpurified fluorinated copolymer flocculation agent, can obtain the extracting in organic solvent-acetone of unpurified fluorinated copolymer flocculation agent in 1 hour the fluorinated copolymer flocculation agent of purifying then, the mass ratio of wherein unpurified fluorinated copolymer flocculation agent and organic solvent is 1: 1000.
Embodiment 2, at first methacrylic acid hexafluoro butyl ester, Trimethyllaurylammonium bromide and water mixed by 1: 1: 100 mass ratio and make solution A; Then with dimethylaminoethyl methacrylate, acrylamide, solution A and water by 1: 1: 50: 100 mass ratio mixes and makes solution B; Under 80 ℃, initiator potassium persulfate is added in the solution B at last, wherein, the mass ratio of solution B and initiator is 100: 0.05, and polymerization obtains fluorinated copolymer flocculant solution C after 5 hours then, solution C is unpurified fluorinated copolymer flocculant solution, can directly use; The present invention can also be dry down at 90 ℃ with solution C, drying pressure is 700mmHg, obtain unpurified fluorinated copolymer flocculation agent, can obtain the extracting in organic solvent ethanol of unpurified fluorinated copolymer flocculation agent in 10 hours the fluorinated copolymer flocculation agent of purifying then, the mass ratio of wherein unpurified fluorinated copolymer flocculation agent and organic solvent is 1: 500.
Embodiment 3, at first methacrylic acid ten difluoro heptyl esters, palmityl trimethyl ammonium chloride and water mixed by 1: 10: 1000 mass ratio and make solution A; Then with methylacryoyloxyethyl trimethyl ammonium chloride, acrylamide, solution A and water by 1: 10: 200: 300 mass ratio mixes and makes solution B; Under 60 ℃, initiator ammonium persulfate-sodium bisulfite is added in the solution B at last, wherein, the mass ratio of solution B and initiator is 100: (0.06: 0.04), polymerization obtains fluorinated copolymer flocculant solution C after 15 hours then, solution C is unpurified fluorinated copolymer flocculant solution, can directly use; The present invention can also be dry down at 80 ℃ with solution C, drying pressure is 660mmHg, obtain unpurified fluorinated copolymer flocculation agent, can obtain the extracting in the organic solvent ethyl acetate of unpurified fluorinated copolymer flocculation agent in 20 hours the fluorinated copolymer flocculation agent of purifying then, the mass ratio of wherein unpurified fluorinated copolymer flocculation agent and organic solvent is 1: 100.
Embodiment 4, at first perfluoro capryl (N-methyl-N-ethyl propenoate base) sulphonamide, octadecyl trimethyl ammonium chloride and water mixed by 1: 20: 5000 mass ratio and make solution A; Then with dimethyl diallyl ammonium chloride, acrylamide, solution A and water by 1: 50: 400: mass ratio 600, mixes and makes solution B; Under 50 ℃, initiator ammonium persulfate-S-WAT is added in the solution B at last, wherein, the mass ratio of solution B and initiator is 100: (0.8: 0.4), polymerization obtains fluorinated copolymer flocculant solution C after 24 hours then, solution C is unpurified fluorinated copolymer flocculant solution, can directly use; The present invention can also be dry down at 50 ℃ with solution C, drying pressure is 400mmHg, obtain unpurified fluorinated copolymer flocculation agent, can obtain the extracting in the organic solvent methylethylketone of unpurified fluorinated copolymer flocculation agent in 30 hours the fluorinated copolymer flocculation agent of purifying then, the mass ratio of wherein unpurified fluorinated copolymer flocculation agent and organic solvent is 1: 50.
Embodiment 5, at first perfluoro capryl (N-ethyl-N-Jia Jibingxisuanyizhi base) sulphonamide, octadecyl benzyl dimethyl brometo de amonio and water mixed by 1: 40: 10000 mass ratio and make solution A; Then with dimethylaminoethyl methacrylate, acrylamide, solution A and water by 1: 100: 500: 1000 mass ratio mixes and makes solution B; Under 20 ℃, initiator potassium persulfate-Sulfothiorine is added in the solution B at last, wherein, the mass ratio of solution B and initiator is 100: (3: 2), polymerization obtains fluorinated copolymer flocculant solution C after 48 hours then, solution C is unpurified fluorinated copolymer flocculant solution, can directly use; The present invention can also be dry down at 30 ℃ with solution C, drying pressure is 100mmHg, obtain unpurified fluorinated copolymer flocculation agent, can obtain the extracting in organic solvent tetrahydrofuran of unpurified fluorinated copolymer flocculation agent in 48 hours the fluorinated copolymer flocculation agent of purifying then, the mass ratio of wherein unpurified fluorinated copolymer flocculation agent and organic solvent is 1: 1.
The present invention is suitable for the processing of multiple sewage, as oil recovery and oil refining sewerage, oil scum silica frost waste water, slime water, river, water of coal ash, activity charcoal powder water, bulking sludge, paper pulp wastewater, building materials waste water, black liquid, dyeing waste water etc.
Claims (7)
1, the preparation method of fluorinated copolymer flocculation agent is characterized in that:
1) at first with fluorochemical monomer, emulsifying agent and water by 1: the mass ratio of 0.01-40: 10-10000 mixes and makes solution A;
2) then with cationic monomer, acrylamide, solution A and water by 1: the mass ratio of 0.01-100: 1-500: 5-1000 mixes and makes solution B;
3) under 20 ℃-90 ℃ initiator is added in the solution B at last, wherein, the mass ratio of solution B and initiator is 100: 0.01-5 obtains the fluorinated copolymer flocculant solution after polymerase 10 .5-48 hour then.
2, the preparation method of fluorinated copolymer flocculation agent is characterized in that:
1) at first with fluorochemical monomer, emulsifying agent and water by 1: the mass ratio of 0.01-40: 10-10000 mixes and makes solution A;
2) then with cationic monomer, acrylamide, solution A and water by 1: the mass ratio of 0.01-100: 1-500: 5-1000 mixes and makes solution B;
3) under 20 ℃-90 ℃ initiator is added in the solution B at last, wherein, the mass ratio of solution B and initiator is 100: 0.01-5 obtains fluorinated copolymer flocculant solution C then after polymerase 10 .5-48 hour;
4) solution C is dry down at 30 ℃-100 ℃, drying pressure is 100mmHg-760mmHg, obtain unpurified fluorinated copolymer flocculation agent, can obtain unpurified fluorinated copolymer flocculation agent in extracting 1-48 hour the fluorinated copolymer flocculation agent of purifying then in organic solvent, the mass ratio of wherein unpurified fluorinated copolymer flocculation agent and organic solvent is 1: 1-1000.
3, the preparation method of fluorinated copolymer flocculation agent according to claim 1 and 2 is characterized in that: said fluorochemical monomer is the vinylformic acid trifluoro ethyl ester, trifluoroethyl methacrylate, vinylformic acid hexafluoro butyl ester, methacrylic acid hexafluoro butyl ester, dodecafluorhe-ptylacrylate, methacrylic acid ten difluoro heptyl esters, vinylformic acid 19 fluorine esters, methacrylic acid 19 fluorine esters, perfluoro capryl (N-methyl-N-ethyl propenoate base) sulphonamide, perfluoro capryl (N-methyl-N-Jia Jibingxisuanyizhi base) sulphonamide, perfluoro capryl (N-ethyl-N-ethyl propenoate base) sulphonamide or perfluoro capryl (N-ethyl-N-Jia Jibingxisuanyizhi base) sulphonamide.
4, the preparation method of fluorinated copolymer flocculation agent according to claim 1 and 2 is characterized in that: said emulsifying agent is dodecylbenzyl alkyl dimethyl ammonium chloride, dodecyl benzyl dimethyl ammonium bromide, Dodecyl trimethyl ammonium chloride, Trimethyllaurylammonium bromide, palmityl trimethyl ammonium chloride, cetyl trimethylammonium bromide, octadecyl trimethyl ammonium chloride, octadecyl trimethylammonium bromide, octadecyl benzyl dimethyl ammonium chloride or octadecyl benzyl dimethyl brometo de amonio.
5, the preparation method of fluorinated copolymer flocculation agent according to claim 1 and 2 is characterized in that: said cationic monomer is methylacryoyloxyethyl trimethyl ammonium chloride, dimethylaminoethyl methacrylate or dimethyl diallyl ammonium chloride.
6, the preparation method of fluorinated copolymer flocculation agent according to claim 1 and 2 is characterized in that: said initiator is ammonium persulphate, Potassium Persulphate, ammonium persulfate-sodium bisulfite, Potassium Persulphate-sodium bisulfite, ammonium persulphate-S-WAT, Potassium Persulphate-S-WAT, ammonium persulphate-Sulfothiorine or Potassium Persulphate-Sulfothiorine.
7, the preparation method of fluorinated copolymer flocculation agent according to claim 2, it is characterized in that: said organic solvent is acetone, methyl alcohol, ethanol, methylethylketone, tetrahydrofuran (THF), methyl acetate, ethyl acetate, butylacetate, N, dinethylformamide or N,N-dimethylacetamide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006101053514A CN100488997C (en) | 2006-12-29 | 2006-12-29 | Preparing method for fluorine containing copolymer flocculating agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006101053514A CN100488997C (en) | 2006-12-29 | 2006-12-29 | Preparing method for fluorine containing copolymer flocculating agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101016182A true CN101016182A (en) | 2007-08-15 |
| CN100488997C CN100488997C (en) | 2009-05-20 |
Family
ID=38725435
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006101053514A Expired - Fee Related CN100488997C (en) | 2006-12-29 | 2006-12-29 | Preparing method for fluorine containing copolymer flocculating agent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100488997C (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104085973A (en) * | 2014-07-10 | 2014-10-08 | 秦皇岛首秦金属材料有限公司 | Preparation method of industrial water fluorine removal agent |
| CN104194747A (en) * | 2014-08-11 | 2014-12-10 | 东北石油大学 | 200-DEG C temperature-resistant oil-in-water drilling fluid |
| CN110342624A (en) * | 2019-07-27 | 2019-10-18 | 重庆工商大学 | A kind of preparation method of oxidisability organic polymer coargulator |
| CN111793166A (en) * | 2020-07-22 | 2020-10-20 | 重庆工商大学 | Preparation method of hydrophobic flocculant |
| CN117164752A (en) * | 2023-11-03 | 2023-12-05 | 中石化西南石油工程有限公司 | Flocculant for oil-based drilling fluid and preparation method thereof |
-
2006
- 2006-12-29 CN CNB2006101053514A patent/CN100488997C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104085973A (en) * | 2014-07-10 | 2014-10-08 | 秦皇岛首秦金属材料有限公司 | Preparation method of industrial water fluorine removal agent |
| CN104194747A (en) * | 2014-08-11 | 2014-12-10 | 东北石油大学 | 200-DEG C temperature-resistant oil-in-water drilling fluid |
| CN110342624A (en) * | 2019-07-27 | 2019-10-18 | 重庆工商大学 | A kind of preparation method of oxidisability organic polymer coargulator |
| CN111793166A (en) * | 2020-07-22 | 2020-10-20 | 重庆工商大学 | Preparation method of hydrophobic flocculant |
| CN117164752A (en) * | 2023-11-03 | 2023-12-05 | 中石化西南石油工程有限公司 | Flocculant for oil-based drilling fluid and preparation method thereof |
| CN117164752B (en) * | 2023-11-03 | 2024-02-27 | 中石化西南石油工程有限公司 | Flocculant for oil-based drilling fluid and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100488997C (en) | 2009-05-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100488997C (en) | Preparing method for fluorine containing copolymer flocculating agent | |
| Zheng et al. | UV-initiated polymerization of hydrophobically associating cationic flocculants: Synthesis, characterization, and dewatering properties | |
| CN102719234B (en) | Thickened oil viscosity depressant as well as preparation method and application thereof | |
| CN104085971B (en) | Compound cationic flocculant and preparation method thereof | |
| CN104341546B (en) | A kind of preparation method of shelly oil absorbing polymer microsphere | |
| CN107915802B (en) | Hydrophobic association type amphoteric polyacrylamide and preparation method and application thereof | |
| CN107556435B (en) | Preparation method and application of cationic polyacrylamide grafted carboxymethyl cellulose | |
| CN108299592B (en) | 3-methacrylamide dopamine and acrylamide mixed polymer and preparation method and application thereof | |
| CN103435750B (en) | Hydrophobic associated polymer containing capsaicine activity monomer and preparation method thereof | |
| CN110982009B (en) | Fluoropolymer microemulsion wetting reversal agent and preparation method and application thereof | |
| CN106467601A (en) | A kind of hydrophobic association type PAMC and its preparation method and application | |
| CN101613435A (en) | A kind of cationic terpolymer that contains hydrophobic grouping and preparation method thereof and application | |
| CN1955125A (en) | Cationic dehydrating agent and its preparation method | |
| CN110938013A (en) | Three-dimensional cage-shaped hyperbranched monomer and preparation method and application thereof | |
| CN1982232A (en) | Method for producing organic cation flocculating agent containing hydrophobic based group | |
| CN108794688A (en) | A kind of synthetic method of modified starch environment-friendly materials | |
| CN100515968C (en) | Method for synthesizing positive ions sludge dewatering agent | |
| CN1884322A (en) | Preparation method of repeatedly usable high oil-absorbent material | |
| CN103204975A (en) | Preparation method of modified natural high-molecular polymer plain boiled water flocculating agent | |
| CN103524672A (en) | Method for preparing cationic flocculant | |
| CN114426654B (en) | Acrylic ester copolymer containing lignin structure and polyether structure, preparation method thereof and treatment method of crude oil water-in-oil emulsion | |
| CN114436500A (en) | Functional composite flocculant for sludge and preparation method thereof | |
| CN100404612C (en) | Preparation method of swelled vermiculite/ polyacrylic acid potassium- acrylamide high water absorption composite material | |
| CN105504161A (en) | Anionic high-polymer flocculant and preparation method thereof | |
| CN101618937A (en) | Hydrophobic cation polymeric flocculant and preparation method and application 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 | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20090520 Termination date: 20111229 |