CN1982232A - Method for producing organic cation flocculating agent containing hydrophobic based group - Google Patents
Method for producing organic cation flocculating agent containing hydrophobic based group Download PDFInfo
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- CN1982232A CN1982232A CNA2005101342308A CN200510134230A CN1982232A CN 1982232 A CN1982232 A CN 1982232A CN A2005101342308 A CNA2005101342308 A CN A2005101342308A CN 200510134230 A CN200510134230 A CN 200510134230A CN 1982232 A CN1982232 A CN 1982232A
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- flocculating agent
- cationic
- monomer
- quaternary ammonium
- organic cation
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Abstract
Production of organic cationic polymer flocculating agent containing hydrophobic group is carried out by inducing into tertiary amine with different chain-length and hydrophobic group by active chlorine, synthesizing quaternary ammonium salt, grafting acrylamide to obtain quaternary ammonium salt monomer by epoxy chloropropane ring-opening activity, controlling quaternary ammonium salt monomer and acrylamide monomer proportion to regulate flocculating agent cationic degree, and obtaining cationic organic flocculating agent with different hydrophobic group, cationic degree and specific viscosity. It's efficient, has excellent hydrophobic performance and molecular formation.
Description
Technical field
The present invention relates to contain the preparation method of the cationic organic polymer coargulator of hydrophobic grouping, the copolymerization derivative of acrylamide copolymer is added the product that an amount of hydrophobic grouping obtains, be applicable to the water treatment flocculation of industrial and domestic waste water, help flco dehydration and solid-liquid separation.Belong to the water treatment agent field.
Background technology
Because content organic in the modern industry sanitary wastewater improves greatly, particulate in these waste water is electronegative mostly, and is littler than the specific inductivity of water, electronegative as containing oil particles in the refinery, in water, be combined into stable O/w emulsion with some surfactants, be not easy to oily water separation; And for example the thin high negative electricity of mud pellet band in coal separating plant's black water repels mutually, tends towards stability, and stops flocculation.Use cationic flocculant to handle to this class waste water, can play charge neutrality and adsorption bridging effect with the particulate in the water, thereby the particulate in the water is taken off surely, help sedimentation and filter dehydration.
Organic cation flocculating agent develops into has had suitable scale now, product innovation, new kind continue to bring out, and mainly comprise reactant of quaternary ammonium salt, epoxy chloropropane and amine such as Polyacrylamide Grafted and copolymerization derivative, alkyl allyl group halogenation ammonium or the like.These flocculation agents all play an important role in our productive life process.External researchdevelopment aspect cationic flocculant is very fast, just carries out towards expanding Application Areas and research mechanism direction at present.Though China's research has in this respect also obtained some progress, also can not satisfy actual needs far away, the water-soluble polymer flocculation agent that needs the real industrialization of development energy and have industrial potential.
Along with organic cation flocculating agent has occupied more and more important position in water treatment, its synthetic method is also more and more, how to select the easiest method to synthesize the highest flocculation agent of usefulness, when reducing cost, obtaining better wastewater treatment efficiency, is investigators' questions of common concern.The cationic flocculant that develops at present water-soluble all fine, the particulate effect that this helps in it and the water reaches the flocculation purpose.But first and last, problem of flocculation agent ubiquity, that is exactly that dehydration rate is not high, causes the water ratio of flco too high, brings difficulty to subsequent disposal.Therefore, the dehydration problem that further improves flocculation agent also is the focus of current foreign study.
As far back as the seventies, Japan is with regard to the useful example that adds cationic flocculant with raising flco intensity and dewatering performance of sludge, as cationic modified compound (high molecular) and the usefulness of people such as Yamamoto with the cationic modified polymkeric substance (lower molecular weight) and the polyacrylic ester of aromatic hydrocarbons, discovery is compared with independent use inorganic flocculating agent or high molecular weight cationic modified flocculant, filtration velocity significantly improves (water drain Xie Hui Chi, 1971,91).In recent years, the research to this aspect increased gradually in the world, and the report of relevant various cationic high-molecular flocculants also increases gradually.Investigators find the dewatering efficiency of flocculation agent and molecular structure composition (the Colloid andPolymer Science of flocculation agent, 281,5,423-430), molecular weight (Colloids and Surfaces A, 218,1-3,47-57), molecular chain length (Starch/Staerke, 54,3-4,132-139) etc. factor is relevant.
The present invention is not influencing under the water miscible prerequisite of flocculation agent for solving this type of problem, adds different hydrophobic groupings, thereby influences its extension degree in water body, and then have influence on the water treatment effect.In addition, the hydrophobicity of flocculation agent strengthens, and also can have influence on the problem of the water ratio of flocculation mud.This all is directly connected to the economic benefit in the sewage treatment process.
Summary of the invention
Purpose of the present invention mainly is to provide a kind of long-chain of hydrophobic grouping, preparation method of Organic Polymer Flocculant with High Cation of containing.
Major technique content of the present invention is: adopted a comparatively novel synthetic route, utilize active chlorine on the epoxy chloropropane to introduce the tertiary amine of different chain length, introduce new hydrophobic grouping, synthetic quaternary ammonium salt, utilize the open loop activity of epoxy chloropropane to obtain quaternary ammonium monomer again with acrylamide graft, regulate the cationic degree of flocculation agent by the proportioning of controlling this quaternary ammonium monomer and acrylamide monomer, thus the organic cation flocculating agent that obtains having different hydrophobic groupings, different cationic degree and limiting viscosity.
Principal reaction principle of the present invention is:
All reaction process of the present invention are all carried out under normal pressure, and reaction raw materials is easy to get, synthesis step is simple, by product is few, productive rate is high.
The present invention has changed the order that classical inverse is answered, and utilizes the as easy as rolling off a log character of reacting with amine of active chlorine on the epoxy chloropropane molecule earlier, has both removed other side reaction products, has solved the interference problem of epoxy chloropropane in polyreaction again.
Adopt three kinds of new hydrophobic groupings to be incorporated in the quaternary amine structure among the present invention, generate new cationic structural.Because the repulsive interaction of hydrophobic grouping is fully stretched flocculation agent in water, reach good net and catch effect, R=-C
8H
17The time, whole molecule is reticulated structure.
The temperature of reaction (1) is chosen in about 50 ℃ among the present invention, and the time separates out with layer oily matter and is as the criterion.
The temperature of reaction (2) is controlled between 60～70 ℃ among the present invention, and the time is 10～12 hours, can reach optimum yield.
The present invention's reaction (3) is with inorganic peroxide K
2S
2O
8As initiator, and use NaHSO
3As auxiliary redox initiator, the consumption of initiator is 0.05%K
2S
2O
8And 0.1%NaHSO
3The time, product reaches high viscosity.
The pH value of the present invention's reaction (3) is between 6.5～7.5, and temperature is between 60～70 ℃, and the time of polyreaction obtains maximum output when being 24 hours, and it is best that polymer properties reaches.
Embodiment
Example 1:
Take by weighing 46.27g epoxy chloropropane and 52.00g triethylamine, 10mL acetone reacts under 50 ℃ of conditions to lower floor and a large amount of oily matter occur, separates out white granular crystal 4 6.93g after placing for some time.Getting this crystal 2 .00g and acrylamide 0.80g, is to react 12 hours under 60～70 ℃ of conditions of reaction medium with water, obtains the aqueous solution of cationic monomer.Obtained aqueous solution and acrylamide 1.42g, magnetic agitation refluxes, logical N
2, under 60～70 ℃ the condition, add the K of 0.002g
2S
2O
8NaHSO with 0.004g
3Initiator carries out polyreaction, and 12 hours postcooling are carried out in reaction.Cooled solution is slowly poured in a certain amount of beaker that fills methyl alcohol, and the limit bevelling stirs, and after product is poured into fully, gets supernatant liquid and splashes in the methyl alcohol, does not have white floss to be and extracts fully.The white jelly that extraction is obtained places 60 ℃ of vacuum drying ovens in culture dish, oven dry in 3 hours promptly gets product behind the porphyrize, and the product cationic degree is 19.82%, and productive rate is 26.42%.
Example 2:
Take by weighing 18.40g epoxy chloropropane and tri-n-butylamine 37.00g, 15mL acetone reacts under 50 ℃ of conditions to lower floor and a large amount of oily matter occur, separates out colourless tabular crystal 36.73g after placing for some time.Getting this crystal 2 .78g and acrylamide 0.80g, is to react 12 hours under 60～70 ℃ of conditions of reaction medium with water, obtains the aqueous solution of cationic monomer.Obtained aqueous solution and acrylamide 2.84g, magnetic agitation refluxes, logical N
2, under 60～70 ℃ the condition, add the K of 0.003g
2S
2O
8NaHSO with 0.006g
3Initiator carries out polyreaction, and 16 hours postcooling are carried out in reaction.Cooled solution is slowly poured in a certain amount of beaker that fills methyl alcohol, and the limit bevelling stirs, and after product is poured into fully, gets supernatant liquid and splashes in the methyl alcohol, does not have white floss to be and extracts fully.The white jelly that extraction is obtained places 60 ℃ of vacuum drying ovens in culture dish, oven dry in 3 hours promptly gets product behind the porphyrize, and the product cationic degree is 11.59%, and productive rate is 32.92%.
Example 3:
Take by weighing 6.50g epoxy chloropropane and 24.70g tri-n-octyl amine, 15mL acetone reacts under 50 ℃ of conditions to lower floor and a large amount of oily matter occur, separates out colourless acicular crystal 17.27g after placing for some time.Getting this crystal 2 .30g and acrylamide 0.40g, is to react 12 hours under 60～70 ℃ of conditions of reaction medium with water, obtains the aqueous solution of cationic monomer.Obtained aqueous solution and acrylamide 1.42g, magnetic agitation refluxes, logical N
2, under 60～70 ℃ the condition, add the K of 0.002g
2S
2O
8NaHSO with 0.004g
3Initiator carries out polyreaction, and 16 hours postcooling are carried out in reaction.Cooled solution is slowly poured in a certain amount of beaker that fills methyl alcohol, and the limit bevelling stirs, and after product is poured into fully, gets supernatant liquid and splashes in the methyl alcohol, does not have white floss to be and extracts fully.The white jelly that extraction is obtained places 60 ℃ of vacuum drying ovens in culture dish, oven dry in 3 hours promptly gets product behind the porphyrize, and the product cationic degree is 27.15%, and productive rate is 34.56%.
Claims (5)
1, the synthetic route of a comparatively novel organic cation flocculating agent, it is characterized in that: utilize active chlorine on the epoxy chloropropane to introduce the tertiary amine of different chain length, thereby synthetic quaternary ammonium salt structure with new hydrophobic grouping utilizes the open loop activity of epoxy chloropropane to obtain cationic monomer with acrylamide graft again.Regulate the cationic degree of polymeric flocculant by the proportioning of controlling this quaternary ammonium monomer and acrylamide monomer, thus the organic cation flocculating agent that obtains having different hydrophobic groupings, different cationic degree and limiting viscosity.
2, quaternary amine according to claim 1 is characterized in that: hydrophobic grouping is respectively different structures such as ethyl, normal-butyl, n-octyl, and increases with hydrophobicity, and the molecular structure of synthetic product stretches more, gradually reticulates structure.
3, the synthetic method of cationic monomer according to claim 1 is characterized in that: the time is 10～12 hours, and temperature is controlled between 60～70 ℃.
4, synthesis method for high molecular polymer according to claim 1 is characterized in that: the pH value of reaction medium is between 6.5～7.5, and temperature is between 60～70 ℃, and the time of polyreaction is 24 hours.
5, the polymerization starter in the macromolecular polymerization reaction according to claim 1 is characterized in that: with inorganic peroxide K
2S
2O
8As initiator, and use NaHSO
3As auxiliary redox initiator, the consumption of initiator is respectively 0.05% (K of reaction monomers total mass
2S
2O
8) and 0.1% (NaHSO
3).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2005101342308A CN1982232A (en) | 2005-12-14 | 2005-12-14 | Method for producing organic cation flocculating agent containing hydrophobic based group |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2005101342308A CN1982232A (en) | 2005-12-14 | 2005-12-14 | Method for producing organic cation flocculating agent containing hydrophobic based group |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101225160B (en) * | 2008-02-21 | 2011-03-23 | 河南科技大学 | Method for preparing epoxy propyl ionic liquid and polyether-type macroion liquid |
| CN101225163B (en) * | 2008-02-21 | 2011-05-11 | 河南科技大学 | Method for preparing polyether-type macroion liquid by polyepichlorohydrin |
| CN102492071A (en) * | 2011-12-09 | 2012-06-13 | 湖南科技大学 | Macromolecule chelating agent and preparation method thereof |
| CN102674520A (en) * | 2011-03-10 | 2012-09-19 | 中国石油天然气股份有限公司 | Oil field water-based fracturing wastewater decolorizing flocculant and preparation method thereof |
| CN106243276A (en) * | 2016-07-03 | 2016-12-21 | 青岛大学 | A kind of method improving oil recovery factor polymer for raw material preparation with aphthenic acids |
| CN106430502A (en) * | 2016-10-26 | 2017-02-22 | 中国石油大学(华东) | Hydrophobically associative type polymer flocculant and preparation method and application thereof |
| CN107487831A (en) * | 2017-09-29 | 2017-12-19 | 太仓市金锚化工有限公司 | A kind of compound plant source high polymer coagulant |
| CN113773441A (en) * | 2021-08-09 | 2021-12-10 | 佳化化学科技发展（上海）有限公司 | Anti-flocculant and preparation method and application thereof |
| CN115559116A (en) * | 2022-10-08 | 2023-01-03 | 滨州亚光家纺有限公司 | Single-component washing-resistant antibacterial finishing agent and preparation method and application thereof |
| CN117463305A (en) * | 2023-12-27 | 2024-01-30 | 西安益维普泰环保股份有限公司 | Deep defluorinating agent and preparation method thereof |
-
2005
- 2005-12-14 CN CNA2005101342308A patent/CN1982232A/en active Pending
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101225163B (en) * | 2008-02-21 | 2011-05-11 | 河南科技大学 | Method for preparing polyether-type macroion liquid by polyepichlorohydrin |
| CN101225160B (en) * | 2008-02-21 | 2011-03-23 | 河南科技大学 | Method for preparing epoxy propyl ionic liquid and polyether-type macroion liquid |
| CN102674520A (en) * | 2011-03-10 | 2012-09-19 | 中国石油天然气股份有限公司 | Oil field water-based fracturing wastewater decolorizing flocculant and preparation method thereof |
| CN102674520B (en) * | 2011-03-10 | 2014-04-02 | 中国石油天然气股份有限公司 | Oil field water-based fracturing wastewater decolorizing flocculant and preparation method thereof |
| CN102492071A (en) * | 2011-12-09 | 2012-06-13 | 湖南科技大学 | Macromolecule chelating agent and preparation method thereof |
| CN102492071B (en) * | 2011-12-09 | 2014-04-16 | 湖南科技大学 | Macromolecule chelating agent and preparation method thereof |
| CN106243276A (en) * | 2016-07-03 | 2016-12-21 | 青岛大学 | A kind of method improving oil recovery factor polymer for raw material preparation with aphthenic acids |
| CN106243276B (en) * | 2016-07-03 | 2018-07-31 | 青岛大学 | A method of it is prepared as raw material using aphthenic acids and improves oil recovery factor polymer |
| CN106430502B (en) * | 2016-10-26 | 2019-08-30 | 中国石油大学(华东) | A kind of hydrophobic associated polymer flocculant and its preparation method and application |
| CN106430502A (en) * | 2016-10-26 | 2017-02-22 | 中国石油大学(华东) | Hydrophobically associative type polymer flocculant and preparation method and application thereof |
| CN107487831A (en) * | 2017-09-29 | 2017-12-19 | 太仓市金锚化工有限公司 | A kind of compound plant source high polymer coagulant |
| CN113773441A (en) * | 2021-08-09 | 2021-12-10 | 佳化化学科技发展（上海）有限公司 | Anti-flocculant and preparation method and application thereof |
| CN115559116A (en) * | 2022-10-08 | 2023-01-03 | 滨州亚光家纺有限公司 | Single-component washing-resistant antibacterial finishing agent and preparation method and application thereof |
| CN115559116B (en) * | 2022-10-08 | 2024-09-27 | 滨州亚光家纺有限公司 | Single-component water-resistant antibacterial finishing agent and preparation method and application thereof |
| CN117463305A (en) * | 2023-12-27 | 2024-01-30 | 西安益维普泰环保股份有限公司 | Deep defluorinating agent and preparation method thereof |
| CN117463305B (en) * | 2023-12-27 | 2024-04-02 | 西安益维普泰环保股份有限公司 | Deep defluorinating agent and preparation method thereof |
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