CN104163887A - Hydrophobically associating dimethyl diallyl ammonium chloride cation flocculating agent and preparation method thereof - Google Patents
Hydrophobically associating dimethyl diallyl ammonium chloride cation flocculating agent and preparation method thereof Download PDFInfo
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- CN104163887A CN104163887A CN201410325971.3A CN201410325971A CN104163887A CN 104163887 A CN104163887 A CN 104163887A CN 201410325971 A CN201410325971 A CN 201410325971A CN 104163887 A CN104163887 A CN 104163887A
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Abstract
The invention relates to a hydrophobically associating dimethyl diallyl ammonium chloride cation flocculating agent and a preparation method thereof, which concretely relates to a copolymer by taking dimethyl diallyl ammonium chloride as a main body. According to the invention, a hydrophobic group is introduced in a main chain of poly-dimethyl diallyl ammonium chloride, interacting effect of an organic matter in the flocculating agent and sewage can be increased, performance of the flocculating agent is increased, by adding an auxiliary agent, the fluidity and stability of the product can be increased. The prepared cation flocculating agent is in a liquid state, and has the advantages of low production cost, fast dissolving speed, friendly environment, energy saving and consumption reduction, convenient use and stable performance.
Description
Technical field
The present invention relates to hydrophobic association cationic flocculant and preparation thereof.What be specifically related to is that dimethyl diallyl ammonium chloride and hydrophobic monomer carry out copolyreaction, and prepared multipolymer is mainly used in the field such as water treatment, oil recovery, belongs to chemical technology field.
Background technology
Diallyl QAS polymer, mainly the homopolymer of dimethyl diallyl ammonium chloride (DMDAAC) and the multipolymer with acrylamide (AM), vinylformic acid etc. thereof, because positive charge density is high, good water solubility, high effect nontoxic, the advantages such as price is lower, obtain widespread use in water treatment, oil production, daily-use chemical industry, sterilization algae removal and the field such as anticorrosion.According to incompletely statistics, 4.7 ten thousand tons of global Poly Dimethyl Diallyl Ammonium Chloride (PDMDAAC) sales volumes in 2006.The U.S. in 2007 is at the consumption aspect water treatment: in industrial water supply is processed, be 1.15 ten thousand tons, it in sewage disposal, is 0.43 ten thousand ton, and in the former water treatment in city, be 1.66 ten thousand tons, in municipal sewage treatment, be 0.28 ten thousand ton, wherein the consumption in the former water treatment in city far exceedes 0.75 ten thousand ton of polyacrylamide.This base polymer is being obtained many successful Application aspect urban domestic wastewater and Industrial Wastewater Treatment, particularly colloidalmaterial and soluble organic matter are had to strong charge neutrality and adsorption bridging effect, and removal effect is good.In addition, affected by pH value little for flocculating effect.
PDMDAAC is as strong cation ionogen, and usually the size of molecular weight is closely related corresponding thereto for its application performance.Scientific worker, in order to improve the performance of PDMDAAC, adopts the whole bag of tricks to improve its relative molecular weight conventionally both at home and abroad.For example, patent JP 05601861121, by the 70% DMDAAC aqueous solution, adopts water-soluble azo diisobutyl amidine hydrochloride (V-50) to cause 48 h at 40 DEG C, and obtaining intrinsic viscosity maximum value is the wax-like product of 4.07 dL/g.But this processing condition can improve production cost on the one hand, because the specification of industrialization DMDAAC is mostly 60% and 65%, and use expensive azo-initiator, industrialization degree is poor on the other hand.United States Patent (USP) U.S.P 4742134 adopts in the radical polymerization system of DMDAAC and adds appropriate F-, improves the molecular weight of polymkeric substance, and rate of polymerization has been accelerated in adding of F-.Patent U.S.P 5422408 by adding inorganic salt to improve the molecular weight of PDMDAAC in the DMDAAC aqueous solution, and result shows that the halide anion of inorganic salt does not form chain-transfer agent or chain terminator with monomer.Be 67% at monomer concentration, sodium-chlor add-on is that 20%, V-50 accounts under the condition of monomer concentration 0.99%, at 52 DEG C, causes for some time, can obtain the polymkeric substance of limiting viscosity up to 2.07 dL/g.The PDMDAAC of the high relative molecular weight more than obtaining adopts expensive azo-initiator, while using over cure acids oxygenant to carry out free radical initiation, generate Cl free radical and termination reaction because over cure acids initiator can make Cl-1, and can not obtain the PDMDAAC of high molecular.The monomer DMDAAC aqueous solution carries out radical polymerization, and the relative molecular weight of its product is not only subject to the impact of monomer concentration, initiator amount, auxiliary agent, kick off temperature, but also is subject to the impact of monomer purity.U.S.P 4151202 and JP 44819 have studied propenyl chloride and the impact of dimethylamine purity on synthetic DMDAAC and PDMDAAC.It is that 70% ~ 80%DMDAAC solution has been prepared the PDMDAAC of limiting viscosity up to 3.99 dL/g that Chinese patent CN 101081883A adopts massfraction, but require the amount of impurity propenyl chloride, dimethylamine, vinyl carbinol and allyl aldehyde in monomer to be all less than 1 mg/kg, the amount of allyl dimethyl base amine is less than 1 mg/kg, the amount of allyl dimethyl base amine hydrochlorate is less than 500 mg/kg, the amount of dimethylamine hydrochloride is less than 1000 mg/kg, the amount of sodium-chlor is less than 2000 mg/kg, and Cu, Fe ionic weight are all less than 1 mg/kg.
In order to improve the performance of PDMDAAC, conventionally adopt DMDAAC and other monomer to carry out copolymerization, normal and AM carries out copolymerization.U.S.P 4713431 discloses DMDAAC and a small amount of AM carries out letex polymerization and obtains the multipolymer of the dimethyl diallyl ammonium chloride of high molecular, because the reactive behavior of AM is far above DMDAAC, is conducive to obtain the polymkeric substance of high molecular.In multipolymer, AM mass content is 0.44% ~ 13%, and the limiting viscosity of corresponding polymkeric substance changes between 1.7 dL/g and 4.6 dL/g.When the mass content of AM is less than 1%, the limiting viscosity of resulting polymers is less than 2.0 dL/g, and emulsion contains the DMDAAC monomer remnants up to 7%.
Because development and the growth in the living standard of modernization industry cause the organic content in draining greatly to improve, existing flocculation agent can not meet the requirement of sewage disposal well.As everyone knows, five-membered ring structure in DMDAAC molecule is given the rigidity of main polymer chain excellence, cation group gives polymkeric substance good water-soluble, if introduce appropriate hydrophobic grouping in PDMDAAC main chain, can not only improve widely flocculation efficiency, and utilize the lipophilicity of hydrophobic grouping, can easily make oily(waste)water breaking milk and removing oil, the waste water larger to oleaginousness will have good adsorption-flocculation effect, hydrophobic grouping also will improve the water separation capability of floc sedimentation simultaneously, make filter cake strength increase, be easy to flocculating settling.In addition, with respect to other water-soluble cationic, DMDAAC is cheap, nontoxic, can not cause secondary pollution to environment.
Summary of the invention
The object of the invention is to provide a kind of cheap, environmental friendliness, easy to use, stable performance also can the organic flocculation agents of efficient flocculating, such flocculation agent is mainly taking dimethyl diallyl ammonium chloride as molecular skeleton, in molecular backbone chain, contain suitable hydrophobic grouping, adopt DMDAAC to carry out copolyreaction preparation from different hydrophobic monomers.
To achieve these goals, the present invention adopts following scheme:
(1) the dimethyl diallyl ammonium chloride aqueous solution (mass percent 60% or 65%), comonomer, complexing agent etc. join in four-hole boiling flask by certain mass ratio, regulator solution is to certain temperature, after inflated with nitrogen deoxygenation certain hour, add initiator, initiated polymerization at a certain temperature, finally can be according to actual needs, add appropriate auxiliary agent, be made into the flocculant solution of respective quality ratio;
(2), before polymerization, in polymerization process or after polymerization completes, added appropriate viscosity-depression agent, be conducive to the stable and easy to use of product;
The present invention adopts dimethyl diallyl ammonium chloride and other hydrophobic monomer to carry out aqueous solution polymerization, can prepare hydrophobic type dimethyl diallyl ammonium chloride cationic polymers.The mass concentration of monomer whose is 50 ~ 70%, and preferred concentration is 60 ~ 65%.With the monomer of dimethyl diallyl ammonium chloride copolymerization can be the monomers such as VINYL ISOBUTYL ETHER, Diethylene Glycol divinyl ether, triethylene glycol divinyl ether, vinyl-acetic ester, methacrylic Soxylat A 25-7, allyl polyglycol, thiazolinyl ethers polycarboxylic acid water reducing agent.
The composite initiator system that initiator of the present invention can be made up of oxidation-reduction agent and water-soluble azo class initiator or oxidation initiator, water-soluble azo class initiator uses separately or be oxidized initiator and water-soluble azo class initiator forms composite initiation system, wherein oxygenant is persulphate, as Potassium Persulphate, ammonium persulphate or Sodium Persulfate, be preferably ammonium persulphate, add-on is monomer mass 0.50 ~ 3.00%; Reductive agent is sulphite, as S-WAT, ammonium sulphite, potassium sulfite, sodium bisulfite, Potassium hydrogen sulfite, Sodium Metabisulfite, potassium metabisulfite etc., and preferably sodium bisulfite, add-on is monomer mass 0.25 ~ 0.50%.Water-soluble azo class initiator is two (two the narrow base propane) dihydrochlorides (V-44), 4 of azo diisobutyl amidine hydrochloride (V50), azo, 4'-azo two (4-cyanopentanoic acid) (V-501), azo two isopropylformic acid two formicesters (V-601) etc., preferably azo diisobutyl amidine hydrochloride, add-on is 0.01 ~ 1.50% of monomer mass, and preferred version is 0.10 ~ 1.00%.Complexing agent is disodium ethylene diamine tetraacetate, and add-on is monomer mass 0.01 ~ 0.15%, and preferred version is 0.05 ~ 0.08%.Auxiliary agent is halogen inorganic salt or vitriol, Sodium Fluoride, Neutral ammonium fluoride, Potassium monofluoride, sodium-chlor, ammonium chloride, ammonium sulfate, potassium sulfate etc., preferably sodium-chlor, and add-on is 0 ~ 20.0%.
Reaction involved in the present invention all need to be carried out under inert atmosphere, and preferred rare gas element is high pure nitrogen.Polymerization temperature of the present invention can specifically be set according to polymerization kind.It is at 30 DEG C that the intrinsic viscosity of product is measured, and 1mol/L NaCl solution records.According to formula [η]=
calculate M.
Tool of the present invention has the following advantages:
1, adopted dimethyl diallyl ammonium chloride to carry out copolyreaction from different hydrophobic monomers, in main polymer chain, introduced hydrophobic grouping, can increase with sewage in organic interaction, be conducive to flocculating settling.
2, by adding auxiliary agent, be not only conducive to reduce the viscosity of reaction system, and be conducive to remaining oxygenant in reduzate, be conducive to improve the security that product is deposited.
3, the hydrophobic type cationic flocculant of preparation is liquid, has advantages of that production cost is low, dissolution rate is fast, environmental friendliness, energy-saving and cost-reducing, easy to use and stable performance.
Therefore, adopt the present invention prepared cationic flocculant, its performance is better than the homopolymer of dimethyl diallyl ammonium chloride, and such flocculation agent is applicable to being applied to the fields such as sewage disposal that oleaginousness is large, papermaking, tertiary oil recovery very much.
Brief description of the drawings
The product infrared spectrum of Fig. 1 embodiment bis-;
The product infrared spectrum of Fig. 2 embodiment tri-;
The product infrared spectrum of Fig. 3 embodiment tetra-;
The product infrared spectrum of Fig. 4 embodiment five.
concrete embodiment
The impact of the interpolation of table 1 inorganic salt on synthetic polymer performance
The different flocculation agent Performance Ratios of table 2
embodiment mono-
Take 65% DMDAAC solution 270 g, 1% disodium ethylene diamine tetraacetate 13.00 g, ammonium persulphate 1.68 g and 7.82 g deionized waters are furnished with in the four-hole boiling flask of mechanical stirring, thermometer, prolong and nitrogen inlet in 1000 ml, stir lower logical nitrogen deoxygenation 30 min, each reaction 3 h at 45 DEG C, 55 DEG C respectively, then at 70 DEG C, reacted 24 h, appropriate amount of deionized water is added in discharging.Solid content is 39.97%, not [η]=0.98 dL/g of refining sample, M=15.12 × 10
4, [η]=1.02 dL/g of refining sample, M=16.12 × 10
4.
embodiment bis-
65% DMDAAC solution 270.00 g, VINYL ISOBUTYL ETHER 15.50 g, 1% disodium ethylene diamine tetraacetate 13.00 g are furnished with in the four-hole boiling flask of mechanical stirring, thermometer, prolong and nitrogen inlet in 1000 ml, stir after lower logical nitrogen deoxygenation 30 min, add 1% V-50 solution 15.00 g and be heated to 50 DEG C, at this temperature, react 6 h, then at 75 DEG C, react 20 h, add during this time appropriate water adjustment and control system viscosity, the solid content of final product is 40.0%.Kinematic viscosity > 60000 mpas 25 DEG C time, the limiting viscosity [η] of product is 1.01 dL/g, M=15.83 × 10
4, [η]=1.06 dL/g of refining rear sample, M=17.05 × 10
4.
embodiment tri-
65% DMDAAC solution 90.00 g, Diethylene Glycol divinyl ether 2.86 g, 1% disodium ethylene diamine tetraacetate 3.60 g, ammonium persulphate 0.18 g are furnished with in the four-hole boiling flask of mechanical stirring, thermometer, prolong and nitrogen inlet in 250 ml, stir after lower logical nitrogen deoxygenation 30 min, add 1% sodium sulfite solution 5.80 g and be heated to 45 DEG C, at this temperature, react 6 h, then at 75 DEG C, react 20 h, add during this time appropriate water adjustment and control system viscosity, the solid content of final product is 33.5%.The limiting viscosity [η] of product is 0.77 dL/g, M=10.57 × 10
4, [η] of refining sample is 0.79 dL/g, M=10.98 × 10
4.
embodiment tetra-
Take 60% DMDAAC solution 30.0 g, triethylene glycol divinyl ether, 1.50 g, 1% disodium ethylene diamine tetraacetate 1.20 g and ammonium persulphate 0.18 g in being furnished with mechanical stirring, temperature is taken into account in 100 ml four-hole boiling flasks of nitrogen inlet, stir after lower logical nitrogen deoxygenation 30 min, at 45 DEG C and 55 DEG C, cause respectively 4 h, 20 h at 70 DEG C, finally add the 30 min dischargings of appropriate deionized water and stirring.Solid content is 34.94%, not [η]=0.80 dL/g of refining sample, M=11.16 × 10
4, [η]=0.80 dL/g of refining sample, M=11.12 × 10
4.
embodiment five
Take 60%DMDAAC solution 60.00 g, allyl polyethenoxy ether 2.00 g, ammonium persulphate 0.31 g, 1% disodium ethylene diamine tetraacetate 2.40 g, 11.30 g deionized waters are furnished with in the four-hole boiling flask of mechanical stirring, thermometer, prolong and nitrogen inlet in 150 ml, stir after lower logical nitrogen deoxygenation 30 min, at 45 DEG C, 60 DEG C each reaction 3 h, then at 80 DEG C, react 20 h respectively, obtain the opaque liquid of oyster white.Solid content is 38.99%, not [η]=0.79 dL/g of refining sample, M=10.93 × 10
4.[η]=0.87 dL/g of refining sample, M=12.59 × 10
4.
embodiment six
Take 60% DMDAAC solution 30.0 g, VINYL ISOBUTYL ETHER 0.78 g, 1% disodium ethylene diamine tetraacetate 1.30 g, ammonium persulphate 0.18g, 3.60 g NaCl in being furnished with mechanical stirring, temperature is taken into account in 250 ml four-hole boiling flasks of nitrogen inlet, stir lower logical nitrogen deoxygenation 30 min, at 45 DEG C and 55 DEG C, react respectively 4 h, at 70 DEG C, react 20 h, cooling has been added 30 ml deionized waters and has stirred 30 min, obtains transparent emulsion.Solid content is that at 41.69%, 25 DEG C, kinematic viscosity is 48000 mpas, not [η]=0.70 dL/g of refining sample, M=9.21 × 10
4, [η]=0.83 dL/g of refining sample, Mw=11.74 × 10
4.Add 1.00 g sodium-chlor to the product of 10 g gained, surveying kinematic viscosity at its 25 DEG C is 32160 mpas.
embodiment seven
Adopt identical proportioning raw materials and polymerizing condition, just by the ammonium sulfate of the quality such as sodium-chlor changes into (or ammonium chloride), the results are shown in Table 1.Result shows, inorganic salt can reduce the kinematic viscosity of system, but also can make the molecular weight and molecular weight of synthetic product.
In view of adding the viscosity that inorganic salt can product system, in order not reduce the molecular weight of polymkeric substance, adopt polymerization to complete, then add inorganic salt to reduce the viscosity of product, easy to use.Get sample in appropriate embodiment bis-, adding content is 10% sodium-chlor, and after mixing, surveying its kinematic viscosity at 25 DEG C is 37530 mpas.Adding of sodium-chlor also helps oxygenant excessive in reduction system, is beneficial to product stability and safety and deposits.
Products obtained therefrom, for flocculating experiment, be the results are shown in Table to 2.The flocculating experiment of multipolymer is obviously better than equal PDMDAAC.
Claims (8)
1. hydrophobic association dimethyl diallyl ammonium chloride cationoid flocculation agent is characterized in that:
The dimethyl diallyl ammonium chloride aqueous solution (mass ratio 60% or 65%), hydrophobic monomer, complexing agent etc. join in four-hole boiling flask by certain mass ratio, regulator solution is to certain temperature, after inflated with nitrogen deoxygenation certain hour, add initiator, initiated polymerization at a certain temperature, finally can be according to actual needs, add appropriate auxiliary agent, be made into the flocculant product of respective quality ratio.
2. according to claim 1, with the monomer of dimethyl diallyl ammonium chloride (DMDAAC) copolymerization can be VINYL ISOBUTYL ETHER, Diethylene Glycol divinyl ether, triethylene glycol divinyl ether, vinyl-acetic ester, methacrylic Soxylat A 25-7, allyl polyglycol, thiazolinyl ethers polycarboxylic acid water reducing agent etc., other molecule that contains two keys and hydrophobic grouping is all applicable to the present invention, in actual production, can, according to concrete Application Areas, select suitable flocculation agent.
3. according to claim 1, the composite initiator system that described initiator can be made up of oxidation-reduction agent and water-soluble azo class initiator or oxidation initiator, water-soluble azo class initiator uses separately or be oxidized initiator and water-soluble azo class initiator forms composite initiation system, wherein oxygenant is persulphate, as Potassium Persulphate, ammonium persulphate or Sodium Persulfate, be preferably ammonium persulphate, add-on is monomer mass 0.50 ~ 3.00%, reductive agent is sulphite, as S-WAT, ammonium sulphite, potassium sulfite, sodium bisulfite, Potassium hydrogen sulfite, Sodium Metabisulfite, potassium metabisulfite etc., preferably sodium bisulfite, add-on is 0.25 ~ 1.50% of monomer mass, water-soluble azo class initiator is azo diisobutyl amidine hydrochloride (V50), two (two the narrow base propane) dihydrochlorides (V-44) of azo, 4, 4'-azo two (4-cyanopentanoic acid) (V-501), azo two isopropylformic acid two formicesters (V-601) etc., preferably azo diisobutyl amidine hydrochloride, add-on is 0.01 ~ 1.50% of monomer mass.
4. according to claim 1, described complexing agent is disodium ethylene diamine tetraacetate, and add-on is monomer mass 0.01 ~ 0.15%.
5. according to claim 1, polymeric reaction temperature regulates and controls according to variant production performance requriements between 10 ~ 130 DEG C, reaction times 5 ~ 80 h.
6. according to claim 1, auxiliary agent is halogen inorganic salt or vitriol, Sodium Fluoride, Neutral ammonium fluoride, Potassium monofluoride, sodium-chlor, ammonium chloride, ammonium sulfate, potassium sulfate etc., preferably sodium-chlor, add-on is 0 ~ 20.0%, the other material that can reduce polymer viscosity is all suitable for the present invention.
7. according to claim 1, auxiliary agent add can be before polymerization, polymerization process and polymerization add after completing.
8. according to claim 1, described polyreaction is to carry out under protection of inert gas, and rare gas element can be high pure nitrogen, argon gas, carbon dioxide etc., preferably high pure nitrogen.
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Cited By (5)
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| CN107804884A (en) * | 2017-12-01 | 2018-03-16 | 北京恒聚化工集团有限责任公司 | A kind of oilfield sewage treatment agent and preparation method thereof |
| CN108191027A (en) * | 2017-12-27 | 2018-06-22 | 南昌水业集团有限责任公司 | The preparation method of cation-modified polyacrylamide, sewage water treatment method |
| CN109679036A (en) * | 2018-12-28 | 2019-04-26 | 厦门大学 | The preparation method and cationic high-molecular flocculant of a kind of cationic high-molecular polymer and its application |
| CN111621269A (en) * | 2020-06-12 | 2020-09-04 | 保定市三拓化工产品有限公司 | Large cation coated flocculant and preparation method thereof |
| CN112724317A (en) * | 2020-12-29 | 2021-04-30 | 科之杰新材料集团有限公司 | Preparation method of modified chitosan, flocculant, preparation method of flocculant and testing method of flocculant |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112724317A (en) * | 2020-12-29 | 2021-04-30 | 科之杰新材料集团有限公司 | Preparation method of modified chitosan, flocculant, preparation method of flocculant and testing method of flocculant |
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