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CN102689969A - Water-solubility organic copolymerization amphoteric macromolecular flocculant and preparation method - Google Patents

Water-solubility organic copolymerization amphoteric macromolecular flocculant and preparation method Download PDF

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CN102689969A
CN102689969A CN2012101942379A CN201210194237A CN102689969A CN 102689969 A CN102689969 A CN 102689969A CN 2012101942379 A CN2012101942379 A CN 2012101942379A CN 201210194237 A CN201210194237 A CN 201210194237A CN 102689969 A CN102689969 A CN 102689969A
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朱明�
张静
丁瑶
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Sichuan Normal University
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Abstract

本发明公开了一种水溶性有机共聚两性高分子絮凝剂及制备方法,该两性高分子絮凝剂是由丙烯酰氧乙基三甲基卤化铵、丙烯酸-N,N-二甲胺基乙酯和衣康酸(盐)三种单体及双官能团单体二丙烯酸酯共聚合形成的共聚物。制备过程中同时使用氧化还原引发剂、无机过氧化物引发剂及聚合助剂,提高了单体的转化率,减少了残留单体;絮凝剂制备操作简单,可直接使用;所制备的絮凝剂具有用量小,絮体直径大和沉降快等优点。

Figure 201210194237

The invention discloses a water-soluble organic copolymerized amphoteric polymer flocculant and a preparation method thereof. The amphoteric polymer flocculant is composed of acryloyloxyethyltrimethylammonium halide, acrylic acid-N,N-dimethylaminoethyl It is a copolymer formed by copolymerizing three monomers of itaconic acid (salt) and diacrylate, a bifunctional monomer. Redox initiators, inorganic peroxide initiators and polymerization aids are used simultaneously in the preparation process, which improves the conversion rate of monomers and reduces residual monomers; the preparation of flocculants is simple and can be used directly; the prepared flocculants It has the advantages of small dosage, large floc diameter and fast settlement.

Figure 201210194237

Description

A kind of water-soluble organic copolymerization Amphiphatic high polymer coagulant and preparation method
Technical field
The present invention relates to water-soluble organic copolymerization Amphiphatic high polymer coagulant 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 (Mannich) reaction, 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 the organic copolymerization Amphiphatic high polymer coagulant of malicious, practical, the effective and economic new type water-solubility 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, copolymerization 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, copolymerization is selected redox initiator for use at low temperature, and high temperature is selected the inorganic peroxide initiator for use, is equipped with acidity regulator and reagent and additive in polymerization simultaneously, makes the molecular weight of product satisfy request for utilization, also reduces residual monomer.
Summary of the invention
Through new technology, provide a kind of stable performance, use range wider and organic copolymerization Amphiphatic high polymer coagulant of flocculating effect better water-solubility and preparation method simple to operate.
This water-soluble organic copolymerization Amphiphatic high polymer coagulant is by acrylyl oxy-ethyl-trimethyl ammonium halide, vinylformic acid-N, and the multipolymer that TMSDMA N dimethylamine base ethyl ester and methylene-succinic acid (salt) and the copolymerization of bifunctional monomer's diacrylate form is characterized in that,
Monomer 1 is the acrylyl oxy-ethyl-trimethyl ammonium halide, and structural formula does
Figure 617219DEST_PATH_IMAGE001
X is Cl, Br in the formula;
Monomer 2 is vinylformic acid-N, TMSDMA N dimethylamine base ethyl ester, and structural formula does
Figure 892343DEST_PATH_IMAGE002
?;
Monomer 3 is methylene-succinic acid (salt), and structural formula does
Figure 590608DEST_PATH_IMAGE003
Y is H, Na or K in the formula;
Bifunctional monomer's diacrylate, structural formula does
Figure 145348DEST_PATH_IMAGE004
1 ≦ i in the formula ≦ 23 (i is a positive integer),
Figure 874270DEST_PATH_IMAGE005
Figure 186040DEST_PATH_IMAGE006
Three kinds of monomers and bifunctional monomer's diacrylate according to the structural formula of the multipolymer that certain amount forms than copolymerization do
Figure 598187DEST_PATH_IMAGE007
1 ≦ n in the formula ≦ 41305; 1 ≦ m ≦ 55859; 1 ≦ p ≦ 61487; 1 ≦ q ≦ 47004; 1 ≦ i ≦ 23, n, m, 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=CHCOO (CH 2) 2N +(CH 3) 3X -The acrylyl oxy-ethyl-trimethyl 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 2=C (COOY) CH 2The methylene-succinic acid of COOY (salt), general formula can be expressed as CH 2=CHCOO (R) iOOCCH=CH 2Bifunctional monomer's diacrylate.Test-results shows; For use properties and the economy that makes the prepared water-soluble organic copolymerization Amphiphatic high polymer coagulant 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 water-soluble organic copolymerization Amphiphatic high polymer coagulant of macromolecule 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 methylene-succinic acid (salt), 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, in the acrylyl oxy-ethyl-trimethyl ammonium halide, add vinylformic acid-N, TMSDMA N dimethylamine base ethyl ester mixes the tap funnel of packing into (a) with distilled water diluting, with the distilled water diluting bifunctional monomer diacrylate tap funnel (b) of packing into;
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, and tap funnel (a) drips acrylyl oxy-ethyl-trimethyl ammonium halide and vinylformic acid-N, and the aqueous solution that the mixed solution of TMSDMA N dimethylamine base ethyl ester, tap funnel (b) drip bifunctional monomer's diacrylate 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 10 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 20 minutes, keeping pH is 2~9; 1~3.5 hour reaction times; Cooling, discharging obtains water-soluble organic copolymerization Amphiphatic high polymer coagulant product;
The inventive method is to carry out the alternating temperature copolymerization by three kinds of monomers and bifunctional monomer's diacrylate, 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 2g methylene-succinic acid (salt), 0.006g reagent and additive in polymerization sodium ethylene diamine tetracetate and 15g zero(ppm) water stirring and dissolving; Vacuumize twice; Each 5 minutes time, the centre leads to nitrogen once, 5 minutes time;
Step 2, in 16g acrylyl oxy-ethyl-trimethyl ammonium halide, add 3g vinylformic acid-N; TMSDMA N dimethylamine base ethyl ester mixes the tap funnel of packing into (a) with the 4g distilled water diluting, with the 12g distilled water diluting 1g bifunctional monomer diacrylate tap funnel (b) of packing into;
Step 3, under continuously stirring and logical nitrogen condition, the mixture of disposable adding 0.17g redox initiator Potassium Persulphate and Potassium hydrogen sulfite, oxygenant is 1:0.7 with the ratio of the amount of substance of reductive agent; Be warming up to 35 ℃, adjustment aqueous solution pH is 5, and tap funnel (a) drips acrylyl oxy-ethyl-trimethyl ammonium halide and vinylformic acid-N; The aqueous solution that the mixed solution of TMSDMA N dimethylamine base ethyl ester, tap funnel (b) drip bifunctional monomer's diacrylate is in four neck reaction flasks; Two tap funnels drip simultaneously, the control rate of addition, and the dropping time is 1 hour; Dripped back constant temperature 3.5 hours; In dropping and the thermostatic process, the pH value of reaction liquid in one time four neck reaction flask of inspection in per 10 minutes, keeping pH is 5;
Step 4, be warming up to 80 ℃, add 0.05g inorganic peroxide initiator potassium persulfate and continue reaction, the pH value of reaction liquid in one time four neck reaction flask of inspection in per 20 minutes; Keeping pH is 5; 2.5 hours reaction times, cooling, discharging; Obtain water-soluble organic copolymerization Amphiphatic high polymer coagulant product, molecular weight is 7.4 * 10 6, transformation efficiency is 98.1%.
Embodiment 2
Step 1, in the four neck reaction flasks of the 250mL that TM, logical nitrogen device and whisking appliance are housed, add 4g methylene-succinic acid (salt), 0.045g reagent and additive in polymerization sodium ethylene diamine tetracetate and 30g zero(ppm) water stirring and dissolving; Vacuumize twice; Each 5 minutes time, the centre leads to nitrogen once, 5 minutes time;
Step 2, in 30g acrylyl oxy-ethyl-trimethyl ammonium halide, add 6.8g vinylformic acid-N; TMSDMA N dimethylamine base ethyl ester mixes the tap funnel of packing into (a) with the 8g distilled water diluting, with the 25g distilled water diluting 2g bifunctional monomer diacrylate tap funnel (b) of packing into;
Step 3, under continuously stirring and logical nitrogen condition, the mixture of disposable adding 0.35g redox initiator Potassium Persulphate and Potassium hydrogen sulfite, 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 5, and tap funnel (a) drips acrylyl oxy-ethyl-trimethyl ammonium halide and vinylformic acid-N; The aqueous solution that the mixed solution of TMSDMA N dimethylamine base ethyl ester, tap funnel (b) drip bifunctional monomer's diacrylate 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 10 minutes, keeping pH is 5;
Step 4, be warming up to 75 ℃, add 0.15g inorganic peroxide initiator potassium persulfate and continue reaction, the pH value of reaction liquid in one time four neck reaction flask of inspection in per 20 minutes; Keeping pH is 5; 2 hours reaction times, cooling, discharging; Obtain water-soluble organic copolymerization Amphiphatic high polymer coagulant product, molecular weight is 7.8 * 10 6, transformation efficiency is 98.5%.
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)

1.一种水溶性有机共聚两性高分子絮凝剂,其特征在于分子量为9×104~8×106,它是由三种单体及双官能团单体二丙烯酸酯共聚合而成, 1. A water-soluble organic copolymerized amphoteric polymer flocculant, characterized in that the molecular weight is 9×10 4 to 8×10 6 , and it is formed by copolymerization of three monomers and bifunctional monomer diacrylate, 单体1是丙烯酰氧乙基三甲基卤化铵,结构式为 Monomer 1 is acryloyloxyethyltrimethylammonium halide with the structural formula
Figure 31303DEST_PATH_IMAGE001
Figure 31303DEST_PATH_IMAGE001
式中X是Cl、Br; In the formula, X is Cl, Br; 单体2是丙烯酸-N,N-二甲胺基乙酯,结构式为 Monomer 2 is N,N-dimethylaminoethyl acrylate, the structural formula is
Figure 913808DEST_PATH_IMAGE002
 ;
Figure 913808DEST_PATH_IMAGE002
;
单体3是衣康酸(盐),结构式为 Monomer 3 is itaconic acid (salt), the structural formula is  
Figure 180462DEST_PATH_IMAGE003
 
Figure 180462DEST_PATH_IMAGE003
式中Y是H、Na或K; In the formula, Y is H, Na or K; 双官能团单体二丙烯酸酯,结构式为 Difunctional monomer diacrylate, the structural formula is
Figure 77005DEST_PATH_IMAGE004
Figure 77005DEST_PATH_IMAGE004
式中1≦i≦23(i为正整数), Where 1≦i≦23 (i is a positive integer),
Figure 13474DEST_PATH_IMAGE005
Figure 13474DEST_PATH_IMAGE005
Figure 198206DEST_PATH_IMAGE006
    
Figure 198206DEST_PATH_IMAGE006
    
三种单体及双官能团单体二丙烯酸酯按照一定的量比共聚合形成的共聚物的结构式为 The structural formula of the copolymer formed by copolymerization of three kinds of monomers and bifunctional monomer diacrylate according to a certain amount ratio is
Figure 670775DEST_PATH_IMAGE007
Figure 670775DEST_PATH_IMAGE007
式中1≦n≦41305;1≦m≦55859;1≦p≦61487;1≦q≦47004;1≦i≦23,n、m、p、q、i为正整数。 In the formula, 1≦n≦41305; 1≦m≦55859; 1≦p≦61487; 1≦q≦47004; 1≦i≦23, n, m, p, q, i are positive integers.
2.一种如权利要求1所述的水溶性有机共聚两性高分子絮凝剂的制备方法,其特征在于,该方法包括的步骤及工艺条件是 2. a kind of preparation method of water-soluble organic copolymerization amphoteric macromolecule flocculant as claimed in claim 1, is characterized in that, the step that this method comprises and processing condition are     步骤1、在四颈反应瓶中加入衣康酸(盐)、聚合助剂和蒸馏水搅拌溶解,抽真空两次,每次时间5分钟,中间通氮一次,时间5分钟;   Step 1. Add itaconic acid (salt), polymerization aids and distilled water to the four-neck reaction flask, stir to dissolve, vacuumize twice, each time is 5 minutes, and pass nitrogen once in the middle, time is 5 minutes; 步骤2、在丙烯酰氧乙基三甲基卤化铵中加入丙烯酸-N,N-二甲胺基乙酯用蒸馏水稀释,用蒸馏水稀释双官能团单体二丙烯酸酯; Step 2. Add N,N-dimethylaminoethyl acrylate to acryloyloxyethyltrimethylammonium halide and dilute with distilled water, and dilute the bifunctional monomer diacrylate with distilled water; 步骤3、在连续搅拌和通氮条件下,一次性加入氧化还原引发剂,升温至35℃~45℃,调整水溶液pH为2~9,一支滴液漏斗滴加丙烯酰氧乙基三甲基卤化铵与丙烯酸-N,N-二甲胺基乙酯的混合液、一支滴液漏斗滴加双官能团单体二丙烯酸酯的水溶液到四颈反应瓶中,二支滴液漏斗同时滴加,控制滴加速度,滴加时间是0.5~3小时,滴加完后恒温0.5~4小时,滴加和恒温过程中,每10分钟检查一次四颈反应瓶中反应液体的pH值,保持pH为2~9; Step 3. Under the conditions of continuous stirring and nitrogen flow, add the redox initiator at one time, raise the temperature to 35 ° C ~ 45 ° C, adjust the pH of the aqueous solution to 2 ~ 9, add acryloyloxyethyl trimethyl ammonium halide and acrylate-N,N-dimethylaminoethyl ester mixture, a dropping funnel to drop the aqueous solution of bifunctional monomer diacrylate into the four-necked reaction flask, two dropping funnels drop Add, control the dropping speed, the dropping time is 0.5 to 3 hours, keep the temperature for 0.5 to 4 hours after the dropping, during the dropping and constant temperature process, check the pH value of the reaction liquid in the four-necked reaction flask every 10 minutes, and keep the pH 2 to 9; 步骤4、升温至75℃~85℃,加入无机过氧化物引发剂继续反应,每20分钟检查一次四颈反应瓶中反应液体的pH值,保持pH为2~9,反应时间1~3.5小时,冷却,出料,得到水溶性有机共聚两性高分子絮凝剂产品; Step 4. Heat up to 75°C-85°C, add inorganic peroxide initiator to continue the reaction, check the pH value of the reaction liquid in the four-neck reaction bottle every 20 minutes, keep the pH at 2-9, and the reaction time is 1-3.5 hours , cooling, and discharging to obtain a water-soluble organic copolymerized amphoteric polymer flocculant product; 所用原料为丙烯酰氧乙基三甲基卤化铵、丙烯酸-N,N-二甲胺基乙酯、衣康酸(盐)、双官能团单体二丙烯酸酯、氧化还原引发剂、无机过氧化物引发剂、聚合助剂和酸度调节剂, The raw materials used are acryloyloxyethyltrimethylammonium halide, N,N-dimethylaminoethyl acrylate, itaconic acid (salt), bifunctional monomer diacrylate, redox initiator, inorganic peroxide Initiators, polymerization aids and acidity regulators, 其中丙烯酰氧乙基三甲基卤化铵、丙烯酸-N,N-二甲胺基乙酯、衣康酸(盐)三种单体的物质的量之比为(15~80):(10~70):(5~60)(mol%), Among them, the ratio of the amount of the three monomers of acryloyloxyethyltrimethylammonium halide, acrylate-N,N-dimethylaminoethyl ester, and itaconic acid (salt) is (15-80): (10 ~70): (5 ~ 60) (mol%), 双官能团单体二丙烯酸酯的质量为其它三种单体质量之和的0.8%~10%, The mass of the bifunctional monomer diacrylate is 0.8% to 10% of the sum of the mass of the other three monomers, 三种单体与双官能团单体二丙烯酸酯的质量总和占反应体系总质量的质量分数为10%~60%; The mass fraction of the mass sum of the three monomers and the bifunctional monomer diacrylate in the total mass of the reaction system is 10% to 60%; 氧化还原引发剂的质量为单体质量总和的0.1%~2%,其中氧化剂与还原剂的物质的量之比为1:(1~0.2); The mass of the redox initiator is 0.1% to 2% of the total mass of the monomers, and the ratio of the amount of the oxidizing agent to the reducing agent is 1: (1 to 0.2); 无机过氧化物引发剂的质量为单体质量总和的0.02%~2.0%; The mass of the inorganic peroxide initiator is 0.02% to 2.0% of the total mass of the monomers; 聚合助剂的质量为单体质量总和的0.01%~1.5%。 The mass of the polymerization aid is 0.01% to 1.5% of the total mass of the monomers. 3.如权利要求2所述的水溶性有机共聚两性高分子絮凝剂的制备方法,其特征在于权利要求2中的氧化还原引发剂是氧化剂为过氧化氢、过硫酸铵、过硫酸钠、过硫酸钾中的任一种,还原剂为亚硫酸氢钠、亚硫酸氢钾、亚硫酸钠、硫代硫酸钠中的任一种。 3. the preparation method of water-soluble organic copolymerized amphoteric macromolecule flocculant as claimed in claim 2 is characterized in that the redox initiator among the claim 2 is that oxidant is hydrogen peroxide, ammonium persulfate, sodium persulfate, persulfate Any one of potassium sulfate, and the reducing agent is any one of sodium bisulfite, potassium bisulfite, sodium sulfite, and sodium thiosulfate. 4.如权利要求2所述的水溶性有机共聚两性高分子絮凝剂的制备方法,其特征在于权利要求2中的无机过氧化物引发剂是过氧化氢、过硫酸铵、过硫酸钠、过硫酸钾中的任一种。 4. the preparation method of water-soluble organic copolymerization amphoteric polymer flocculant as claimed in claim 2 is characterized in that the inorganic peroxide initiator among the claim 2 is hydrogen peroxide, ammonium persulfate, sodium persulfate, persulfate Any of potassium sulfate. 5.如权利要求2所述的水溶性有机共聚两性高分子絮凝剂的制备方法,其特征在于权利要求2中的酸度调节剂是氢氧化钠、氢氧化钾、氢氧化钙、碳酸钠、碳酸氢钠、盐酸中的任一种。 5. the preparation method of water-soluble organic copolymerized amphoteric polymer flocculant as claimed in claim 2 is characterized in that the acidity regulator in claim 2 is sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, carbonic acid Any of sodium hydrogen, hydrochloric acid. 6.如权利要求2所述的水溶性有机共聚两性高分子絮凝剂的制备方法,其特征在于权利要求2中的聚合助剂是二乙醇胺、三乙醇胺、乙二胺四乙酸及其盐、水溶性含氟化合物如氟硅酸、氟硅酸钙、氟化钾、氟化钠中的任一种或二种以上的混合物。 6. the preparation method of water-soluble organic copolymerized amphoteric macromolecule flocculant as claimed in claim 2 is characterized in that the polymerization assistant in claim 2 is diethanolamine, triethanolamine, ethylenediaminetetraacetic acid and its salt, water-soluble Fluorine-containing compounds such as any one or a mixture of two or more of fluorosilicic acid, calcium fluorosilicate, potassium fluoride, and sodium fluoride.
CN2012101942379A 2012-06-14 2012-06-14 Water-solubility organic copolymerization amphoteric macromolecular flocculant and preparation method Pending CN102689969A (en)

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