CN102675534A - Cationic fluorocarbon modified polyacrylamide prepared by ultrasonic auxiliary method - Google Patents
Cationic fluorocarbon modified polyacrylamide prepared by ultrasonic auxiliary method Download PDFInfo
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- CN102675534A CN102675534A CN2012101541602A CN201210154160A CN102675534A CN 102675534 A CN102675534 A CN 102675534A CN 2012101541602 A CN2012101541602 A CN 2012101541602A CN 201210154160 A CN201210154160 A CN 201210154160A CN 102675534 A CN102675534 A CN 102675534A
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Abstract
The invention discloses a cationic fluorocarbon modified polyacrylamide prepared by an ultrasonic auxiliary method; the method comprises the steps of: firstly, evenly mixing fluorine-containing monomer, cation monomer, acrylamide and water, filling nitrogen for expelling oxygen, adding initiator, carrying out free radical polymerization under the ultrasonic-assistant condition to obtain the cationic fluorocarbon modified polyacrylamide. Due to the efficient dispersive action of ultrasonic wave, hydrophobic monomer can be well dispersed into water solution without adding emulsifying agent or surface active monomer, and copolymerization can be carried out between the hydrophobic monomer and hydrophilic monomer. According to the preparation method, the emulsifying agent or surface active monomer can be avoided being used, so that the aftertreatment of HAPAM is completely omitted, the preparation technology is simplified, and the production efficiency is improved.
Description
Technical field
The invention belongs to chemical field, particularly a kind of ultrasonic auxiliary law prepares cation fluorine carbon modified polyacrylamide.
Background technology
SEPIGEL 305 and verivate thereof are important polymkeric substance, and Application Areas is extensive.In the type of numerous SEPIGEL 305s, the hydrophobic association type SEPIGEL 305 is an important branch.The hydrophobic association type SEPIGEL 305 is introduced a small amount of hydrophobic grouping and is processed on the polyacrylamide main chain; Bunch collection takes place owing to the hydrophobic interaction between the hydrophobic grouping makes the SEPIGEL 305 molecular chain; Thereby significantly change the rheological property of solution, improve effect, broadened application field.At present, the hydrophobic grouping of introducing on the hydrophobic association type SEPIGEL 305 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 acrylic amide copolymerization.
For the uncompatibility that overcomes hydrophobic monomer and hydrophilic monomer, realize both copolymerization, the surface active monomer method had appearred again more in the micelle assay that adopt in recent years during preparation hydrophobic association type SEPIGEL 305.Micelle assay is in polymerization system, to add a large amount of emulsifying agents; With after the hydrophobic monomer emulsification again with copolymerization such as hydrophilic monomer such as acrylic amide, cationic monomer, but the raising that adds affiliation impact polymer molecular weight of emulsifying agent, increase the problems such as complexity of multipolymer aftertreatment.Surface active monomer is claimed polymerisable surfactant again, is one type of tensio-active agent that contains polymerizable groups, has both had surfactivity, can under certain initiation conditions, can produce all (being total to) polyreactions again, can eliminate the aftertreatment of HAPAM fully.At present, be applicable to that the surface active monomer preparation of HAPAM is complicated, with high costs, so the research work of surface active monomer method is carried out seldom.
Summary of the invention
The objective of the invention is to overcome the shortcoming of above-mentioned prior art, provide a kind of ultrasonic auxiliary law of emulsifying agent and surface active monomer that do not use to prepare cation fluorine carbon modified polyacrylamide.
For achieving the above object, the technical scheme that the present invention adopts is:
1) at first, with fluorochemical monomer, cationic monomer, acrylic amide and water by 1: (1-30): (10-200): mass ratio (10-10000) mixes and makes mixing solutions;
2) secondly, in mixing solutions, led to nitrogen 10-60 minute with the speed of 20mL/min-200mL/min;
3) then, the initiator of adding monomer total mass 0.1%-1.0% stirs;
4) last, transfer at 20 ℃-90 ℃ and to place ultrasonic generator to carry out ultrasonic polymerization, ultrasonic power 80W-200W reacts and obtains cation fluorine carbon modified polyacrylamide after 0.5-5 hour.
Said fluorochemical monomer is vinylformic acid trifluoro ethyl ester, trifluoroethyl methacrylate, vinylformic acid hexafluoro butyl ester, methylacrylic acid hexafluoro butyl ester, dodecafluorhe-ptylacrylate or methylacrylic acid ten difluoro heptyl esters.
Said cationic monomer is methylacryoyloxyethyl trimethyl ammonium chloride, dimethylaminoethyl methacrylate or dimethyl diallyl ammonium chloride.
Said nitrogen is liquid nitrogen or gasiform nitrogen.
Said initiator is ammonium persulphate, Potassium Persulphate, azo diisobutyl amidine hydrochloride, ammonium persulphate-S-WAT, Potassium Persulphate-S-WAT, ammonium persulfate-sodium bisulfite, Potassium Persulphate-sodium sulfite anhy 96, ammonium persulphate-Sulfothiorine or Potassium Persulphate-Sulfothiorine, and wherein the mass ratio of oxygenant and reductive agent is 2: 1 in the oxidation-reduction trigger system.
Because the dissemination of ultrasonic high-efficiency need not to add emulsifying agent or surface active monomer and just can make hydrophobic monomer be dispersed in well in the aqueous solution, carries out copolymerization with hydrophilic monomer.Adopt preparation method of the present invention can avoid the use of emulsifying agent or surface active monomer,, simplify preparation technology, enhance productivity to eliminate the aftertreatment of HAPAM fully.
Embodiment
Embodiment 1,1) at first, with fluorochemical monomer vinylformic acid trifluoro ethyl ester, cationic monomer methylacryoyloxyethyl trimethyl ammonium chloride, acrylic amide and water by 1: 1: 10: 10 mass ratio mixes and makes mixing solutions;
2) secondly, in mixing solutions, led to nitrogen 60 minutes with the speed of 20mL/min;
3) then, the initiator ammonium persulfate of adding monomer total mass 1.0% stirs;
4) last, transfer at 20 ℃ and to place ultrasonic generator to carry out ultrasonic polymerization, ultrasonic power 80W reacts and obtains cation fluorine carbon modified polyacrylamide after 5 hours.
Embodiment 2,1) at first, with fluorochemical monomer methylacrylic acid ten difluoro heptyl esters, cationic monomer diallyldimethylammonChloride Chloride, acrylic amide and water by 1: 30: 200: 10000 mass ratio mixes and makes mixing solutions;
2) secondly, in mixing solutions, led to nitrogen 10 minutes with the speed of 200mL/min;
3) then, the initiator azo diisobutyl amidine hydrochloride of adding monomer total mass 0.1% stirs;
4) last, transfer at 90 ℃ and to place ultrasonic generator to carry out ultrasonic polymerization, ultrasonic power 200W reacts and obtains cation fluorine carbon modified polyacrylamide after 0.5 hour.
Embodiment 3,1) at first, with fluorochemical monomer trifluoroethyl methacrylate, cationic monomer dimethylaminoethyl methacrylate, acrylic amide and water by 1: 10: 50: 100 mass ratio mixes and makes mixing solutions;
2) secondly, in mixing solutions, led to nitrogen 30 minutes with the speed of 50mL/min;
3) then, the initiator ammonium persulfate-Sulfothiorine of adding monomer total mass 0.3% stirs;
4) last, transfer at 50 ℃ and to place ultrasonic generator to carry out ultrasonic polymerization, ultrasonic power 100W reacts and obtains cation fluorine carbon modified polyacrylamide after 2 hours.
Embodiment 4,1) at first, with fluorochemical monomer dodecafluorhe-ptylacrylate, cationic monomer methylacryoyloxyethyl trimethyl ammonium chloride, acrylic amide and water by 1: 20: 100: 1000 mass ratio mixes and makes mixing solutions;
2) secondly, in mixing solutions, led to nitrogen 30 minutes with the speed of 100mL/min;
3) then, the initiator azo diisobutyl amidine hydrochloride of adding monomer total mass 0.5% stirs;
4) last, transfer at 60 ℃ and to place ultrasonic generator to carry out ultrasonic polymerization, ultrasonic power 140W reacts and obtains cation fluorine carbon modified polyacrylamide after 3 hours.
Embodiment 5,1) at first, with fluorochemical monomer methylacrylic acid hexafluoro butyl ester, cationic monomer methylacryoyloxyethyl trimethyl ammonium chloride, acrylic amide and water by 1: 15: 150: 5000 mass ratio mixes and makes mixing solutions;
2) secondly, in mixing solutions, led to nitrogen 30 minutes with the speed of 100mL/min;
3) then, the initiator azo diisobutyl amidine hydrochloride of adding monomer total mass 0.4% stirs;
4) last, transfer at 50 ℃ and to place ultrasonic generator to carry out ultrasonic polymerization, ultrasonic power 160W reacts and obtains cation fluorine carbon modified polyacrylamide after 3 hours.
Claims (5)
1. ultrasonic auxiliary law prepares cation fluorine carbon modified polyacrylamide, it is characterized in that:
1) at first, with fluorochemical monomer, cationic monomer, acrylic amide and water by 1: (1-30): (10-200): mass ratio (10-10000) mixes and makes mixing solutions;
2) secondly, in mixing solutions, led to nitrogen 10-60 minute with the speed of 20mL/min-200mL/min;
3) then, the initiator of adding monomer total mass 0.1%-1.0% stirs;
4) last, transfer at 20 ℃-90 ℃ and to place ultrasonic generator to carry out ultrasonic polymerization, ultrasonic power 80W-200W reacts and obtains cation fluorine carbon modified polyacrylamide after 0.5-5 hour.
2. ultrasonic auxiliary law according to claim 1 prepares cation fluorine carbon modified polyacrylamide, it is characterized in that: said fluorochemical monomer is vinylformic acid trifluoro ethyl ester, trifluoroethyl methacrylate, vinylformic acid hexafluoro butyl ester, methylacrylic acid hexafluoro butyl ester, dodecafluorhe-ptylacrylate or methylacrylic acid ten difluoro heptyl esters.
3. ultrasonic auxiliary law according to claim 1 prepares cation fluorine carbon modified polyacrylamide, it is characterized in that: said cationic monomer is methylacryoyloxyethyl trimethyl ammonium chloride, dimethylaminoethyl methacrylate or dimethyl diallyl ammonium chloride.
4. ultrasonic auxiliary law according to claim 1 prepares cation fluorine carbon modified polyacrylamide, it is characterized in that: said nitrogen is liquid nitrogen or gasiform nitrogen.
5. ultrasonic auxiliary law according to claim 1 prepares cation fluorine carbon modified polyacrylamide; It is characterized in that: said initiator is ammonium persulphate, Potassium Persulphate, azo diisobutyl amidine hydrochloride, ammonium persulphate-S-WAT, Potassium Persulphate-S-WAT, ammonium persulfate-sodium bisulfite, Potassium Persulphate-sodium sulfite anhy 96, ammonium persulphate-Sulfothiorine or Potassium Persulphate-Sulfothiorine, and wherein the mass ratio of oxygenant and reductive agent is 2: 1 in the oxidation-reduction trigger system.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106467601A (en) * | 2016-09-29 | 2017-03-01 | 陕西科技大学 | A kind of hydrophobic association type PAMC and its preparation method and application |
| CN107936173A (en) * | 2017-11-29 | 2018-04-20 | 陕西科技大学 | A kind of hydrophobic association type cationic polyacrylamide and its preparation method and application |
| CN108654401A (en) * | 2018-05-29 | 2018-10-16 | 安徽工业大学 | The surface supersonic modifying processing method of coal-based carbon film |
| CN111925477A (en) * | 2019-05-13 | 2020-11-13 | 中国石油化工股份有限公司 | Preparation method of fluorine-containing thickening agent capable of thickening hydrochloric acid solution |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4997873A (en) * | 1988-06-08 | 1991-03-05 | Bayer Aktiengesellschaft | Copolymers containing perfluoroalkyl groups |
| CN1613883A (en) * | 2004-09-17 | 2005-05-11 | 浙江大学 | Preparation of water dispersed fine emulsion of fluorine acrelate copolymer for anti-oil and anti-water agent |
| CN100999565A (en) * | 2006-12-29 | 2007-07-18 | 陕西科技大学 | Process of preparing fluorine-containing soapless emulsion using amphiphilic polymer |
| CN100999562A (en) * | 2006-12-29 | 2007-07-18 | 陕西科技大学 | Preparation process of non organic solvent type fluorine-containing soapless emulsion |
| CN100999563A (en) * | 2006-12-29 | 2007-07-18 | 陕西科技大学 | Preparation process of containing emulsion with surfactant low transportting performance |
-
2012
- 2012-05-17 CN CN2012101541602A patent/CN102675534A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4997873A (en) * | 1988-06-08 | 1991-03-05 | Bayer Aktiengesellschaft | Copolymers containing perfluoroalkyl groups |
| CN1613883A (en) * | 2004-09-17 | 2005-05-11 | 浙江大学 | Preparation of water dispersed fine emulsion of fluorine acrelate copolymer for anti-oil and anti-water agent |
| CN100999565A (en) * | 2006-12-29 | 2007-07-18 | 陕西科技大学 | Process of preparing fluorine-containing soapless emulsion using amphiphilic polymer |
| CN100999562A (en) * | 2006-12-29 | 2007-07-18 | 陕西科技大学 | Preparation process of non organic solvent type fluorine-containing soapless emulsion |
| CN100999563A (en) * | 2006-12-29 | 2007-07-18 | 陕西科技大学 | Preparation process of containing emulsion with surfactant low transportting performance |
Non-Patent Citations (1)
| Title |
|---|
| 李刚辉等: "表面活性含氟单体-丙烯酰胺共聚物溶液性质研究", 《高分子学报》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106467601A (en) * | 2016-09-29 | 2017-03-01 | 陕西科技大学 | A kind of hydrophobic association type PAMC and its preparation method and application |
| CN107936173A (en) * | 2017-11-29 | 2018-04-20 | 陕西科技大学 | A kind of hydrophobic association type cationic polyacrylamide and its preparation method and application |
| CN107936173B (en) * | 2017-11-29 | 2020-10-23 | 陕西科技大学 | Hydrophobic association type cationic polyacrylamide and preparation method and application thereof |
| CN108654401A (en) * | 2018-05-29 | 2018-10-16 | 安徽工业大学 | The surface supersonic modifying processing method of coal-based carbon film |
| CN111925477A (en) * | 2019-05-13 | 2020-11-13 | 中国石油化工股份有限公司 | Preparation method of fluorine-containing thickening agent capable of thickening hydrochloric acid solution |
| CN111925477B (en) * | 2019-05-13 | 2022-05-03 | 中国石油化工股份有限公司 | Preparation method of fluorine-containing thickening agent capable of thickening hydrochloric acid solution |
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Application publication date: 20120919 |