CN102701372A - Water-soluble organic amphiprotic polymer flocculating agent and preparation method - Google Patents
Water-soluble organic amphiprotic polymer flocculating agent and preparation method Download PDFInfo
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Abstract
The invention discloses water-soluble organic amphiprotic polymer flocculating agent and a preparation method. The amphiprotic polymer flocculating agent is a kind of polymers which are formed by three kinds of monomers, i.e. dimethyl diallyl ammonium chloride, dimethylaminoethyl acrylate and crotonic acid (crotonate), and a kind of difunctional monomers, i.e. diacrylate in a polymerizing way. In the preparation process, oxidation reduction initiators, inorganic peroxide initiators and additives for polymerization are used at the same time, the conversion rate of monomers is improved and the residual monomers are reduced; the operation for the preparation of the flocculating agent is simple and the flocculating agent can be directly used; and the prepared flocculating agent has the advantages of small dosage, large floc diameter, rapid sedimentation and the like.
Description
Technical field
The present invention relates to water-soluble organic amphiprotic polymeric flocculant and preparation method.
Background technology
Water is the base substance of human survival and social development.The interior water surrounding of world wide is faced with the problem of water scarcity, transition consumption and severe contamination at present.The World Health Organization's investigation shows: human 80% disease is dangerous relevant with water quality.China is a water resources big country, and the while is again a serious water shortage, water utilization rate is extremely low and the with serious pollution country of water, and three big factors have seriously restricted normal life of people and economic Sustainable development.Therefore, useless (dirt) water is effectively handled and reuse be solve certainty that limited water resource satisfies the growing production of people and life requirement by way of.In useless (dirt) processing and sludge dewatering process; Flocculence is a kind of important, effective and economic, easy method; Trade effluent both domestic and external, sewage use flocculation technique to handle ratio 55%～85%, and tap water industry and sludge dewatering 100% use flocculence to handle; The effect of useless (dirt) water flocculation and sludge dewatering is to the operation of subsequent handling, the qualified discharge and the processing costs close association of water outlet; And flocculation agent is one of key factor of useless (dirt) water treatment, solid-liquid separation, and the research and development of therefore carrying out novel, nontoxic and efficient flocculant are the emphasis and the direction of water treatment work.
Flocculation agent can be divided into several big type of microbial flocculant, inorganic flocculating agent and organic polymer coargulator etc.Microbial flocculant has higher security to environment with the mankind, and microbial flocculant also is in the screening stage of bacterial classification mostly at present, and exists cost higher, can't adapt to the requirement of suitability for industrialized production and application.Inorganic flocculating agent is because consumption is big, generation mud is many, corrodibility strong, produce secondary pollution and (dirt) water water quality impact that is subject to give up, and is undesirable at some occasion purifying water effect, uses and receives great limitation, just progressively replaced by organic floculant.Organic polymer coargulator has that consumption is few, flocculation rate is fast, generate that mud is few, decolourising property good and given up advantages such as (dirt) water water quality impact is little and come into one's own day by day; Different according to the source, the organic polymer coagulating agent can be divided into natural organic high-molecular flocculant and synthetic organic polymer flocculation agent; The natural organic high-molecular flocculant advantage is that raw material sources are abundant, low price, nontoxic basically, be prone to biochemical degradation and do not cause secondary pollution basically; Shortcoming is complicated component, it is unstable to form, performance inconsistency is big, possibly exist rotten in the storage process and production process is used a large amount of problems such as organic solvent, and its practical application is restricted; The stable performance of synthetic organic polymer flocculation agent can be controlled the advantage such as molecular weight and structure of synthetic product as required, can be divided into nonionic, negatively charged ion, positively charged ion and amphoteric.Along with society and expanding economy, the quantity discharged of modern industry and sewage and COD (Chemical Oxygen Demand, COD
Cr) constantly increase; It is complicated day by day that useless (dirt) water is formed and character becomes; Flocculation agent with conventional is difficult to meet the demands; And the microparticle surfaces in (dirt) water that gives up has negative charge usually, contains a certain amount of toxic metal ion in the water body simultaneously, and the use of nonionic, negatively charged ion and cationic high-molecular flocculant is restricted; Comprise the positive and negative charge group on the polymer molecular chain of both sexes organic polymer coargulator simultaneously; Be called Amphiphatic high polymer (amphoteric polymer) or polyamphoteric electrolyte (amphoteric polyelectrolyte); Because of the special construction of its molecule has some characteristics; Like charge neutrality, adsorption bridging and intermolecular " winding " package action; Be applicable to useless (dirt) water of yin, yang ion coexist; For by AS stable dispersion liquid, emulsion and all kinds of mud or by positively charged ion stable various colloidal dispersions, good flocculation and sludge dewatering effect are all arranged, can be used as water treatment flocculant, sludge dehydrating agent, sorbent material and metal ion chelation agent etc.; Owing to have preferably advantages such as dehydration property, metals ion are removed property, wide and salt resistance is good to pH value claimed range, make the both sexes organic polymer coargulator that very broad field of application arranged, become the focus of domestic and international research.
Synthetic type of both sexes organic polymer coargulator of research and development both at home and abroad at present mainly contains the modification through SEPIGEL 305 (pAM); I.e. chemical reaction through carboxamido-group; Like (Mannich) reaction of Manny phase, hydrolysis or graft reaction modification; Reaching with polyacrylonitrile (pAN) is macromolecular chain, with both sexes polyacrylonitrile-dicyandiamide (pAN-DCD) two big classes of dicyandiamide modification; " Organic Chemicals " [M], January in 1999 the 3rd edition, Chemical Industry Press, the boat chief editor of department has introduced acrylic amide (AM), vinyl cyanide (AN) belongs to hypertoxic chemical; " acrylamide polymer " [M], April in 2006 the 1st edition, Chemical Industry Press, chief editors such as Fang Daobin have introduced the harm of acrylic amide to human body and environment, and " the contact acrylic amide has three kinds of forms, and per os, respiratory tract suck and skin exposure.After being inhaled into, acrylic amide is distributed in the body fluid.Water is most important contaminated thing.Non-professional property contact acrylic amide is mainly from the tap water and the food that are polluted by acrylic amide.The toxicity of acrylic amide mainly shows as skin lesion and nervous system damage.USEPA (EPA) to acrylic amide to the regulation of people's toxic reaction is: short-term is with long-term per os or contact the neural injury that acryloyl can cause the people, and thinks that the lower concentration acrylic amide also is a kind of to the prejudicial material of neural system.The acute poisoning reaction is that skin and respiratory tract are had pungency, the contact site fash.Chronic poisoning causes the neurotoxicity reaction, influences nervus centralis and peripheral nerve "." l994 international cancer research institution (IARC) investigates animal gene toxicity, classifies acrylic amide as 2B group (might be carcinogenic) by original 1987 and has risen to 2A group (carcinogenic probably) "." in view of acrylic amide to human and environment and health affected, WHO, IARC, U.S. food in drug administration (FDA), EPA, European Union (EU) and Chinese Government etc. to environment in limiting the quantity of of acrylic amide all made strict regulation "." various countries allow the maximum of residual monomer acrylic amide in dosage and the polyacrylamide amine product to allow content that strict qualification is arranged to the maximum of SEPIGEL 305 in the water treatment.For example, WHO be defined in water purify in the dosage of SEPIGEL 305 must not surpass 1mg/L.The residual quantity of acrylic amide must not surpass 0.05% in the product, i.e. residual quantity 0.0005 mg/L of acrylic amide maximum in drinking-water ".Along with the severe situation of the enhancing of environmental protection consciousness and useless (dirt) water pollution control, the requirement of water treatment is more and more high.The object of the invention and meaning are intended to the monomeric toxicity that has the preparation flocculation agent both at home and abroad now; Selecting does not have (low) toxic monomer; Adopt suitable polymerization method and processing condition; Prepare malicious, practical, the effective and economic new type water-solubility organic amphiprotic polymeric flocculant of a kind of nothing (low), to satisfy the demand of useless (dirt) water treatment.
There is following defective in a synthetic at present type Amphiphatic high polymer coagulant:
1, synthetic Amphiphatic high polymer coagulant has been selected the monomer of acrylic amide, vinyl cyanide hypertoxicity for use, the polymerization residual monomer with decompose after small molecules all can produce secondary pollution;
2, Mannich (Mannich) reaction needs is used a large amount of organic solvents, does not meet the principle of Green Chemistry;
3, through the polyacrylamide Amphiphatic high polymer coagulant of Mannich reaction modification, be not suitable for and handle the high waste water of pH, package stability is not high;
The present invention is under the precondition that the flocculation efficiency that keeps flocculation agent does not reduce, and attainability can better situation:
1, selects for use monomer not have (low) poison, do not cause secondary pollution, more meet the Green Chemistry requirement;
2, polymerization is solvent with water, meets the principle that cleans production;
3, overcome because the shortcoming of polyacrylamide flocculation agent costs and poor dehydration results, unstable properties;
4, be aggregated in low temperature and select redox initiator for use, high temperature is selected the inorganic peroxide initiator for use, is equipped with acidity regulator and polymeric additive simultaneously, makes the molecular weight of product satisfy request for utilization, also reduces residual monomer.
Summary of the invention
Summary of the invention provides a kind of stable performance, use range wider and flocculating effect better water-solubility organic amphiprotic polymeric flocculant and preparation method simple to operate through new technology.
This water-soluble organic amphiprotic polymeric flocculant is by dimethyl diallyl ammonium halide, vinylformic acid-N, and the multipolymer that TMSDMA N dimethylamine base ethyl ester and Ba Dousuan (salt) and bifunctional monomer's diacrylate are polymerized is characterized in that,
Monomer 1 is the dimethyl diallyl ammonium halide, and structural formula does
X is Cl, Br in the formula;
Monomer 3 is Ba Dousuan (salt), and structural formula does
Y is H, Na or K in the formula;
Bifunctional monomer's diacrylate, structural formula does
1 ≦ i in the formula ≦ 23 (i is a positive integer),
Three kinds of monomers and bifunctional monomer's diacrylate according to the structural formula of the polymkeric substance that certain amount forms than copolymerization do
1 ≦ n in the formula ≦ 49481; 1 ≦ m ≦ 55859; 1 ≦ p ≦ 92920; 1 ≦ q ≦ 47004; 1 ≦ i ≦ 23, n, m, n, p, q, i are positive integer.
Preparing method of the present invention is to above-mentioned comonomer, bifunctional monomer's diacrylate, redox initiator, inorganic peroxide initiator, acidity regulator and reagent and additive in polymerization etc. and have no special requirements.Copolymerization monomer for example, general formula can be expressed as (CH
2=CHCH
2)
2N
+(CH
3)
2X
-The dimethyl diallyl ammonium halide, chemical molecular formula is expressed as CH
2=CHCOO (CH
2)
2N (CH
3)
2Vinylformic acid-N, TMSDMA N dimethylamine base ethyl ester, general formula can be expressed as CH
3The Ba Dousuan of CH=CHCOOY (salt), general formula can be expressed as CH
2=CHCOO (R)
iOOCCH=CH
2Bifunctional monomer's diacrylate.Test-results shows that for use properties and the economy that makes the prepared water-soluble organic amphiprotic polymeric flocculant of the present invention reaches best effect, the ratio of three kinds of monomeric amount of substances is controlled at (15～80): (10～70): (5～60) (mol%); The quality of bifunctional monomer's diacrylate is 0.8%～10% of other three kinds of monomer mass sums; The monomer total mass account for reaction system massfraction 10%～60%.
As aforementioned, the present invention adds redox initiator when copolymerization lesser temps in early stage, its objective is to obtaining the multipolymer of macromolecule.The oxygenant of for example selecting for use can be any in hydrogen peroxide, ammonium persulphate, Sodium Persulfate, the Potassium Persulphate, and reductive agent is any in sodium sulfite anhy 96, Potassium hydrogen sulfite, S-WAT, the Sulfothiorine.Test-results shows that oxygenant is 1 with the ratio of the amount of substance of reductive agent: (1～0.2), consumption can reach the ideal effect in 0.1%～2% scope of monomer total mass.
As aforementioned, the present invention adds the inorganic peroxide initiator during comparatively high temps in the polymerization later stage, its objective is to reducing monomeric residually, improves monomer conversion.For example select hydrogen peroxide, ammonium persulphate, Sodium Persulfate, Potassium Persulphate for use.Test-results shows that its consumption is that monomer conversion can reach the ideal effect in 0.02%～2.0% scope of monomer total mass.
As aforementioned, the present invention adds acidity regulator in copolymerization, and pH=2～9 of adjustment polymerization system its objective is to guaranteeing that used initiator can reach optimal efficiency of initiation.The material of used adjustment pH is any aqueous solution in sodium hydroxide, Pottasium Hydroxide, calcium hydroxide, yellow soda ash, sodium hydrogencarbonate, the hydrochloric acid.
As aforementioned, the present invention adds reagent and additive in polymerization in copolymerization, its objective is that elementary radical and monomer radical that redox initiator cause to be formed do not crossed early stopping.For example select any or the mixture more than two kinds of diethylolamine, trolamine, YD 30 and salt thereof, water-soluble fluorochemicals such as silicofluoric acid, calcium silicofluoride, Potassium monofluoride, Sodium Fluoride for use.Test-results shows that its consumption is in 0.01%～1.5% scope of monomer total mass, and the copolymerization that redox initiator is caused obtains the macromolecule water-soluble organic amphiprotic polymeric flocculant and makes rate of polymerization be able to control.
Method of the present invention may further comprise the steps and processing condition:
Step 1, in four neck reaction flasks, add dimethyl diallyl ammonium halide, reagent and additive in polymerization and zero(ppm) water stirring and dissolving, vacuumize twice, each 5 minutes time, middle logical nitrogen once, 5 minutes time;
Step 3, under continuously stirring and logical nitrogen condition, disposable adding redox initiator is warming up to 35 ℃～45 ℃; Adjustment aqueous solution pH is 2～9, tap funnel (a) dropwise addition of acrylic acid-N, and the aqueous solution that the mixed solution of TMSDMA N dimethylamine base ethyl ester and bifunctional monomer's diacrylate, tap funnel drip (b) Ba Dousuan (salt) is in four neck reaction flasks; Two tap funnels drip simultaneously, the control rate of addition, and the dropping time is 0.5～3 hour; Dripped back constant temperature 0.5～4 hour; In dropping and the thermostatic process, the pH value of reaction liquid in one time four neck reaction flask of inspection in per 15 minutes, keeping pH is 2～9;
Step 4, be warming up to 75 ℃～85 ℃, add the inorganic peroxide initiator and continue reaction, the pH value of reaction liquid in one time four neck reaction flask of inspection in per 15 minutes; Keeping pH is 2～9,1～3.5 hour reaction times, cooling; Discharging obtains the water-soluble organic amphiprotic polymeric flocculant product.
The inventive method is to carry out the alternating temperature copolymerization by three kinds of monomers and bifunctional diacrylate monomer, and there is the living radical of capacity in reaction system, and copolymerization is carried out continuously; Adopt the water soluble oxidized reductive agent as low temperature initiators, guaranteed that flocculation agent has sufficiently high molecular weight; The pH of adjustment reaction system makes efficiency of initiation even more ideal; Be aided with a certain amount of reagent and additive in polymerization, reduced the impurity in the reaction system, prevent that living radical from crossing early stopping; Add the inorganic peroxide initiator in polymerization reaction late stage, reduced monomeric residually, improved transformation efficiency.
The present invention compares with the existing amphoteric polyacrylamide flocculation agent that is used for water treatment, has the following advantages:
1, compare with organic copolymerization Amphiphatic high polymer coagulant that prior art is produced, used monomer does not have (low) poison, and environment is not almost had influence;
2, adopt the water soluble oxidized reductive agent as low temperature initiators, add the water-soluble peroxide initiator in the later stage, guaranteed that flocculation agent has sufficiently high molecular weight, and transformation efficiency is higher, residual monomer content is lower;
3, the preparation method is simple, and reaction conditions is gentle, is suitable for and applies;
4, stable performance is applicable to the pH value scope of broad, and it is many to handle kind of waste water, and input amount is little (to be merely 1～200mg/L), to have tangible economic benefit.
Appended drawings be monomer 1, monomer 2, monomer 3 and bifunctional monomer's diacrylate according to a certain amount of ratio, under initiator and reagent and additive in polymerization effect, carry out the chemical formula of copolymerization.
Case study on implementation combines embodiment that the present invention is further specified as follows:
Embodiment 1
Step 1, in the four neck reaction flasks of the 250mL that TM, logical nitrogen device and whisking appliance are housed, add the mixture and the 3g zero(ppm) water stirring and dissolving of 16g dimethyl diallyl ammonium halide, 0.009g reagent and additive in polymerization sodium ethylene diamine tetracetate and Sodium Fluoride; Vacuumize twice; Each 5 minutes time; The centre leads to nitrogen once, 5 minutes time;
Step 3, under continuously stirring and logical nitrogen condition, the mixture of disposable adding 0.18g redox initiator Potassium Persulphate and sodium sulfite anhy 96, oxygenant is 1:0.8 with the ratio of the amount of substance of reductive agent; Be warming up to 35 ℃, adjustment aqueous solution pH is 3, tap funnel (a) dropwise addition of acrylic acid-N; The aqueous solution that the mixed solution of TMSDMA N dimethylamine base ethyl ester and bifunctional monomer's diacrylate, tap funnel drip (b) Ba Dousuan (salt) is in four neck reaction flasks; Two tap funnels drip simultaneously, the control rate of addition, and the dropping time is 2 hours; Dripped back constant temperature 2.5 hours; In dropping and the thermostatic process, the pH value of reaction liquid in one time four neck reaction flask of inspection in per 15 minutes, keeping pH is 3;
Step 4, be warming up to 85 ℃, add 0.06g inorganic peroxide initiator and continue the reaction Potassium Persulphate, the pH value of reaction liquid in one time four neck reaction flask of inspection in per 15 minutes; Keeping pH is 3; 2.5 hours reaction times, cooling, discharging; Obtain the water-soluble organic amphiprotic polymeric flocculant product, molecular weight is 7.1 * 10
6, transformation efficiency is 97.8%.
Step 1, in the four neck reaction flasks of the 250mL that TM, logical nitrogen device and whisking appliance are housed, add the mixture and the 10g zero(ppm) water stirring and dissolving of 30g dimethyl diallyl ammonium halide, 0.048g reagent and additive in polymerization sodium ethylene diamine tetracetate and Sodium Fluoride; Vacuumize twice; Each 5 minutes time; The centre leads to nitrogen once, 5 minutes time;
Step 3, under continuously stirring and logical nitrogen condition, the mixture of disposable adding 0.38g redox initiator Potassium Persulphate and sodium sulfite anhy 96, oxygenant is 1:0.4 with the ratio of the amount of substance of reductive agent; Be warming up to 45 ℃, adjustment aqueous solution pH is 4, tap funnel (a) dropwise addition of acrylic acid-N; The aqueous solution that the mixed solution of TMSDMA N dimethylamine base ethyl ester and bifunctional monomer's diacrylate, tap funnel drip (b) Ba Dousuan (salt) is in four neck reaction flasks; Two tap funnels drip simultaneously, the control rate of addition, and the dropping time is 1.5 hours; Dripped back constant temperature 3 hours; In dropping and the thermostatic process, the pH value of reaction liquid in one time four neck reaction flask of inspection in per 15 minutes, keeping pH is 4;
Step 4, be warming up to 75 ℃, add 0.15g inorganic peroxide initiator and continue the reaction Potassium Persulphate, the pH value of reaction liquid in one time four neck reaction flask of inspection in per 15 minutes; Keeping pH is 4; 3.5 hours reaction times, cooling, discharging; Obtain the water-soluble organic amphiprotic polymeric flocculant product, molecular weight is 7.7 * 10
6, transformation efficiency is 98.2%.
The application implementation example
The flocculation treatment (seeing table 1, table 2) that the water-soluble organic copolymerization Amphiphatic high polymer coagulant of NO.1, NO.2 of above embodiment 1,2 preparations is used for dyeing waste water.
Claims (6)
1. a water-soluble organic amphiprotic polymeric flocculant is characterized in that molecular weight is 9 * 10
4～8 * 10
6, it is to be polymerized by three kinds of monomers and bifunctional monomer's diacrylate,
Monomer 1 is the dimethyl diallyl ammonium halide, and structural formula does
X is Cl, Br in the formula;
Monomer 2 is vinylformic acid-N, TMSDMA N dimethylamine base ethyl ester, and structural formula does
?；
Monomer 3 is Ba Dousuan (salt), and structural formula does
Y is H, Na or K in the formula;
Bifunctional monomer's diacrylate, structural formula does
1 ≦ i in the formula ≦ 23 (i is a positive integer),
Three kinds of monomers and bifunctional monomer's diacrylate according to the structural formula of the polymkeric substance that certain amount forms than copolymerization do
1 ≦ n in the formula ≦ 49481; 1 ≦ m ≦ 55859; 1 ≦ p ≦ 92920; 1 ≦ q ≦ 47004; 1 ≦ i ≦ 23, n, m, p, q, i are positive integer.
2. the preparation method of a water-soluble organic amphiprotic polymeric flocculant as claimed in claim 1 is characterized in that, step and processing condition that this method comprises are
Step 1, in four neck reaction flasks, add dimethyl diallyl ammonium halide, reagent and additive in polymerization and zero(ppm) water stirring and dissolving, vacuumize twice, each 5 minutes time, middle logical nitrogen once, 5 minutes time;
Step 2, at vinylformic acid-N, add bifunctional monomer's diacrylate in the TMSDMA N dimethylamine base ethyl ester and use distilled water diluting, with dissolved in distilled water Ba Dousuan (salt);
Step 3, under continuously stirring and logical nitrogen condition, disposable adding redox initiator is warming up to 35 ℃～45 ℃; Adjustment aqueous solution pH is 2～9, tap funnel dropwise addition of acrylic acid-N, and the aqueous solution of the mixed solution of TMSDMA N dimethylamine base ethyl ester and bifunctional monomer's diacrylate, a tap funnel dropping Ba Dousuan (salt) is in four neck reaction flasks; Two tap funnels drip simultaneously, the control rate of addition, and the dropping time is 0.5～3 hour; Dripped back constant temperature 0.5～4 hour; In dropping and the thermostatic process, the pH value of reaction liquid in one time four neck reaction flask of inspection in per 15 minutes, keeping pH is 2～9;
Step 4, be warming up to 75 ℃～85 ℃, add the inorganic peroxide initiator and continue reaction, the pH value of reaction liquid in one time four neck reaction flask of inspection in per 15 minutes; Keeping pH is 2～9,1～3.5 hour reaction times, cooling; Discharging obtains the water-soluble organic amphiprotic polymeric flocculant product;
Raw materials used is dimethyl diallyl ammonium halide, vinylformic acid-N, TMSDMA N dimethylamine base ethyl ester, Ba Dousuan (salt), bifunctional monomer's diacrylate, redox initiator, inorganic peroxide initiator, reagent and additive in polymerization and acidity regulator,
Wherein dimethyl diallyl ammonium halide, vinylformic acid-N, the ratio of TMSDMA N dimethylamine base ethyl ester, three kinds of monomeric amount of substances of Ba Dousuan (salt) is (15～80): (10～70): (5～60) (mol%),
The quality of bifunctional monomer's diacrylate is 0.8%～10% of other three kinds of monomer mass sums,
The massfraction that the quality summation of three kinds of monomers and bifunctional monomer's diacrylate accounts for the reaction system total mass is 10%～60%;
The quality of redox initiator is 0.1%～2% of a monomer mass summation, and wherein oxygenant is 1 with the ratio of the amount of substance of reductive agent: (1～0.2);
The quality of inorganic peroxide initiator is 0.02%～2.0% of a monomer mass summation;
The quality of reagent and additive in polymerization is 0.01%～1.5% of a monomer mass summation.
3. the preparation method of water-soluble organic amphiprotic polymeric flocculant as claimed in claim 2; It is characterized in that the redox initiator in the claim 2 is that oxygenant is any in hydrogen peroxide, ammonium persulphate, Sodium Persulfate, the Potassium Persulphate, reductive agent is any in sodium sulfite anhy 96, Potassium hydrogen sulfite, S-WAT, the Sulfothiorine.
4. the preparation method of water-soluble organic amphiprotic polymeric flocculant as claimed in claim 2 is characterized in that inorganic peroxide initiator in the claim 2 is any in hydrogen peroxide, ammonium persulphate, Sodium Persulfate, the Potassium Persulphate.
5. the preparation method of water-soluble organic amphiprotic polymeric flocculant as claimed in claim 2 is characterized in that acidity regulator in the claim 2 is any in sodium hydroxide, Pottasium Hydroxide, calcium hydroxide, yellow soda ash, sodium hydrogencarbonate, the hydrochloric acid.
6. the preparation method of water-soluble organic amphiprotic polymeric flocculant as claimed in claim 2 is characterized in that reagent and additive in polymerization in the claim 2 is any or the mixture more than two kinds in diethylolamine, trolamine, YD 30 and salt thereof, water-soluble fluorochemicals such as silicofluoric acid, calcium silicofluoride, Potassium monofluoride, the Sodium Fluoride.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104163887A (en) * | 2014-07-10 | 2014-11-26 | 中昊(大连)化工研究设计院有限公司 | Hydrophobically associating dimethyl diallyl ammonium chloride cation flocculating agent and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1426429A (en) * | 2000-06-29 | 2003-06-25 | 翁德奥纳尔科公司 | Structurally-modified polymer flocculants |
| CN101249996A (en) * | 2007-12-11 | 2008-08-27 | 四川师范大学 | Organic high polymer coagulant and preparation method thereof |
-
2012
- 2012-06-13 CN CN2012101924084A patent/CN102701372A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1426429A (en) * | 2000-06-29 | 2003-06-25 | 翁德奥纳尔科公司 | Structurally-modified polymer flocculants |
| CN101249996A (en) * | 2007-12-11 | 2008-08-27 | 四川师范大学 | Organic high polymer coagulant and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104163887A (en) * | 2014-07-10 | 2014-11-26 | 中昊(大连)化工研究设计院有限公司 | Hydrophobically associating dimethyl diallyl ammonium chloride cation flocculating agent and preparation method thereof |
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Application publication date: 20121003 |