CN101643527A - Amphoteric or cationic polymeric flocculating agent - Google Patents
Amphoteric or cationic polymeric flocculating agent Download PDFInfo
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- CN101643527A CN101643527A CN200810117712A CN200810117712A CN101643527A CN 101643527 A CN101643527 A CN 101643527A CN 200810117712 A CN200810117712 A CN 200810117712A CN 200810117712 A CN200810117712 A CN 200810117712A CN 101643527 A CN101643527 A CN 101643527A
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Abstract
The invention belongs to the field of environment-friendly materials, relates to an amphoteric or cationic polymeric flocculating agent having efficient phase variation capacity, in particular to a polymeric flocculating agent containing acrylic morpholine alkyl esters or methacrylic morpholine alkyl esters. The flocculating agent is prepared by adopting aqueous solution polymerization, and comprises the following steps: preparing solution by using a certain amount of neutral monomer, cationic monomer (acrylic morpholine alkyl ester monomer or methacrylic morpholine alkyl ester monomer) and anionic monomer, adjusting the pH value of the solution, introducing inert gases into the solution to remove oxygen, then adding other agents such as initiating agent and the like into the solution, stopping introducing the inert gases into the solution and keeping a reaction closed, and adjusting the reaction temperature at the temperature of between 0 and 60 DEG C to carry out polymerization so asto obtain the amphoteric or cationic polymeric flocculating agent.
Description
Technical field
The invention belongs to the environment-friendly materials field, relate to a class and have amphoteric or the cationic high-molecular flocculant that efficiently changes ability mutually, be specifically related to contain the polymeric flocculant of vinylformic acid morpholine alkyl esters or methacrylic acid morpholine alkyl esters.
Background technology
Amphoteric and cationic high-molecular flocculant are family macromolecule polyelectrolyte, and it can play neutralization and bridging action with electronegative colloidal particle in the water, makes the particulate in the system take off surely, flocculate, thereby helps particulate sedimentation and filter dehydration.It is widely used in paper industry and helps filter, retention, enhancing, the sludge dewatering in the urban sewage treatment process, field waste water flocculatings such as textile printing and dyeing, leather processing, processing of aquatic products, food-processing.20th century six the seventies, Merck company and Halliborton company take the lead in succeeding in developing cationic polyacrylamide---dimethyl diallyl ammonium chloride homopolymer (PDMDAAC) and dimethyl diallyl ammonium chloride and acrylamide copolymer [P (DMDAAC/AM)], and very fast input suitability for industrialized production and obtain U.S. FDA authentication and be used for water treatment.The nineties is comparatively active to research, the exploitation of amphiprotic polyacrylamide abroad, and existing procucts come out.In American-European countries, the development of amphoteric and cationic-type polyacrylamide is more and more faster, has accounted for 60% of flocculation agent total amount, and with annual about 6% speed increment.But the output at present amphoteric of China and cationic-type polyacrylamide flocculation agent only accounts for about 10% of synthetic flocculant total amount, and exists the monomer kind few, and cationic degree is not high, the price height, relative molecular mass is lower, and efficient is the deficiency of high aspect inadequately, with the big gap of external existence.And the Application and Development gap of amphoteric and cationic-type polyacrylamide is bigger.
The cationic monomer of widespread use at present mainly contains methylacryoyloxyethyl trimethyl ammonium chloride (being called for short DMC), dimethylaminoethyl methacrylate (being called for short DMAEMA), dimethyl diallyl ammonium chloride (being called for short DADAAC), acrylyl oxy-ethyl-trimethyl salmiac (being called for short DAC), dimethylaminoethyl acrylate (being called for short DMAEA) etc.Use these cationic monomer institute synthetic flocculation agents to have better effects, but effect is relatively poor when flocculation is dissolved in organic waste such as dyestuff in the water at the suspended particulates of flocculation in the sewage.In order to overcome these shortcomings, usually adding hydrophobic monomer when preparing polymeric flocculant with these monomers with acrylamide makes polymkeric substance have the ability that changes mutually, hydrophobic grouping can combine with organism in the water body simultaneously, and this has all improved the bridge formation adsorptive power of flocculation agent, strengthens throwing out.The adding of hydrophobic monomer also helps improving the forms consumption of flocculation agent.General hydrophobic monomer is poorly soluble in the aqueous solution, need use surface active agent solubilization during interpolation, and it is dispersed in the solution.Tensio-active agent may contain impurity, letting nitrogen in and deoxidizing can produce a large amount of foams during polymerization, the hydrophobic monomer reactive behavior also with system in other monomer have than big difference, this all can cause institute's synthetic polymeric flocculant molecular weight low, poorly soluble, directly influence flocculating effect.Also make simultaneously polymerizing condition relatively harsher, polymerization is difficult to control.Seek new itself having suitable hydrophobic cationic monomer and be used for synthetic both sexes and the cationic high-molecular flocculant tool bright prospects that efficiently change ability mutually that have.Vinylformic acid morpholine alkyl esters monomer or methacrylic acid morpholine alkyl esters monomer are a kind of potential cationic monomers, once have bibliographical information to cross its synthetic method and polyreaction [C.E.Rehberg, W. A.Faucette; J.Am.Chem.Soc.; 1949; 71 (9); 3164～3165.], but use it for preparation amphoteric and cationic high-molecular flocculant clearly and yet there are no report.
Summary of the invention
One of purpose of the present invention provides has amphoteric or the cationic high-molecular flocculant that efficiently changes ability mutually, particularly contains the polymeric flocculant of vinylformic acid morpholine alkyl esters or methacrylic acid morpholine alkyl esters.
Two of purpose of the present invention provides to have efficiently and changes the amphoteric of ability or the preparation method of cationic high-molecular flocculant mutually, particularly contains the preparation method of the polymeric flocculant of vinylformic acid morpholine alkyl esters or methacrylic acid morpholine alkyl esters.
Institute of the present invention synthetic amphoteric or the required monomer of cationic high-molecular flocculant comprise neutral monomer, cationic monomer, anionic monomer.It is to adopt the aqueous solution polymerization preparation: with certain amount of neutral monomer, cationic monomer, anionic monomer wiring solution-forming, regulate the pH value, logical rare gas element is to remove oxygen, add other reagent such as initiator etc. again, stop logical rare gas element and keep reactor airtight, regulate temperature of reaction down at 0 ℃～60 ℃ polymerization is carried out, just can make amphoteric or cationic high-molecular flocculant.
Of the present invention have the amphoteric or the cationic high-molecular flocculant that efficiently change ability mutually and prepare by the following method:
In closed reactor, adding neutral monomer, cationic monomer in proportion---vinylformic acid morpholine alkyl esters monomer or methacrylic acid morpholine alkyl esters monomer, anionic monomer, deionized water are mixed with the polymerization reaction system aqueous solution; Telo merization system pH value of aqueous solution is 2～9, the ice-water bath cooling; Logical rare gas element (being generally 15～40 minutes) is to remove oxygen in reactor, add initiator, stop logical rare gas element, under 0 ℃～60 ℃, carry out polyreaction (being generally 2～24 hours), translucent colloid, be and have amphoteric or the cationic high-molecular flocculant that efficiently changes ability mutually; Obtain having amphoteric or the cationic high-molecular flocculant powder that efficiently changes ability mutually with this colloid granulation, oven dry, after pulverizing, sieving.
Wherein: neutral monomer, cationic monomer, the total concn of anionic monomer in the polymerization reaction system aqueous solution are 5wt%～40wt%; Described neutral monomer accounts for the 20wt%～95wt% of above-mentioned total monomer; Cationic monomer---vinylformic acid morpholine alkyl esters monomer or methacrylic acid morpholine alkyl esters monomer account for the 5wt%～80wt% of above-mentioned total monomer; Anionic monomer accounts for the 0wt%～75wt% of above-mentioned total monomer.
The synthetic product is a cationic high-molecular flocculant when no anionic monomer polymerization time institute; As cationic monomer and anionic monomer polymerization time institute synthetic product is the amphoteric polymeric flocculant.
The concentration of described initiator in the polymerization reaction system aqueous solution is 0.005wt%～1wt%, and used initiator is selected from azo-initiator, organic peroxy class initiator, inorganic peroxy class initiator, more than one in the oxidation-reduction class initiator etc.
Described azo-initiator is (being called for short ABVN) or their mixtures such as Diisopropyl azodicarboxylate (being called for short AIBN), 2,2'-Azobis(2,4-dimethylvaleronitrile); Described organic peroxy class initiator is selected from more than one in dibenzoyl peroxide (being called for short BPO), peroxy dicarbonate ethylhexyl (being called for short EHP), dicumyl peroxide, dilauroyl peroxide, the special butyl ester of peroxidation phenylformic acid etc.; Described inorganic peroxy class initiator is selected from more than one in Potassium Persulphate, ammonium persulphate, the hydrogen peroxide etc.; Oxygenant in the described oxidation-reduction class initiator (mol ratio of oxygenant and reductive agent is 1: 5 to 5: 1) is Potassium Persulphate, ammonium persulphate, hydrogen peroxide or potassium permanganate etc., and reductive agent is S-WAT, sodium bisulfite, ferrous sulfate, amine or oxalic acid etc.
Described neutral monomer is selected from more than one in acrylamide, Methacrylamide, the N,N-DMAA (being called for short DMAA) etc.
Described cationic monomer is vinylformic acid morpholine alkyl esters monomer or methacrylic acid morpholine alkyl esters monomer, has following structure:
R
1For-H or-CH
3R
2For containing the alkyl of 1 to 6 carbon; R
3For-H ,-CH
3,-CH
2-CH
3Or-CH
2-C
6H
5Deng; X is negatively charged ion such as halogen (fluorine, chlorine, bromine or iodine) ion or sulfate ion.
But the vinylformic acid morpholine ethyl ester hydrochloride reference literature [Chem.Abstr. of one of above-mentioned cationic monomer wherein; 77; 88822t; 1972.] method synthesize and obtain:
3.67ml morpholine ethanol and 20ml acetone are added 50ml single port flask, abundant cooling and stirring under the ice-water bath condition.Slowly in morpholine ethanol solution, splash into the 2.44ml acrylate chloride with constant pressure funnel, after acrylate chloride dropwises, remove ice-water bath, be warming up to room temperature naturally and continued stirring reaction 4 hours, stopped reaction.Filter to isolate vinylformic acid morpholine ethyl ester hydrochloride solid, normal temperature vacuum-drying gets vinylformic acid morpholine ethyl ester hydrochloride 5.0g.Meet other cationic monomer of said structure, all can synthesize with reference to aforesaid method.
Described anionic monomer is selected from more than one in vinylformic acid, acrylate, methacrylic acid, methacrylate, 2-acrylamido-2-methyl propane sulfonic acid (being called for short AMPS), 2-acrylamido-2-phenyl ethyl sulfonic acid (being called for short AMSS), the 2-acrylamido dodecyl sodium sulfonate (being called for short ADS) etc.
Described rare gas element comprises nitrogen or argon gas etc.
Described telo merization system pH value of aqueous solution is to regulate with sodium hydroxide, potassium hydroxide, hydrochloric acid or sulfuric acid etc.
Employed cationic monomer reactive behavior height was easy to polymerization and obtains high-molecular weight amphoteric or cationic high-molecular flocculant when the present invention prepared amphoteric or cationic high-molecular flocculant; Gained amphoteric or cationic high-molecular flocculant have surfactivity, can in the aqueous solution, form micella, when polyreaction, the free radical that initiator was decomposed to form enters in the micella that cationic monomer forms and makes cationic monomer homopolymerization in the micella microcell, free radical entered other monomer reaction in the aqueous phase continuation and the aqueous solution after cationic monomer in the micella exhausted, and multipolymer just has micro-block structure like this.Simultaneously this type of cationic monomer has hydrophobicity, and hydrophobic grouping can combine with organism in the water body, and these characteristics make prepared polymeric flocculant bridge formation high adsorption capacity, it is high and have efficient flocculating ability and a wide application field to change ability mutually.
The present invention compared with prior art has following characteristics:
The present invention has introduced cationic monomer---synthetic amphoteric of vinylformic acid morpholine alkyl esters monomer or methacrylic acid morpholine alkyl esters monomer or cationic high-molecular flocculant.Because the cationic monomer that adopts has the effect of tensio-active agent, can in the aqueous solution, form micella and make multipolymer have micro-block structure; Have hydrophobicity, make the polymeric flocculant of preparation have hydrophobicity, make polymkeric substance have the ability that changes mutually, hydrophobic grouping can combine with organism in the water body simultaneously.These characteristics make prepared polymeric flocculant bridge formation high adsorption capacity, change the ability height mutually.Prepared amphoteric polymkeric substance has the zwitterion synergy when being used as flocculation agent, the floc sedimentation of generation is big and tight, and dehydrating effect is good.
Embodiment
Embodiment 1
At capacity is to add 23.75g deionized water, 1.1875g acrylamide, 0.0375g vinylformic acid morpholine ethyl ester hydrochloride and 0.025g vinylformic acid in the tool plug scale test tube of 25ml, and dissolving mixes.Using the NaOH solution of 1mol/L, the hydrochloric acid telo merization system pH value of aqueous solution of 1mol/L is 2, the ice-water bath cooling, and logical nitrogen 15 minutes is to remove oxygen.Add 1.875 * 10
-4The Potassium Persulphate of g and 0.855 * 10
-4The oxidation-reduction initiator system that the S-WAT of g is formed stops logical nitrogen and stoppered test tube plug preventing air admission, 20 ℃ of polyreactions 6 hours, translucent colloid, be and have the colloid that efficiently changes the amphoteric polymeric flocculant of ability mutually; Obtain the powder of amphoteric polymeric flocculant with this colloid granulation, oven dry, after pulverizing, sieving, it have change mutually ability height, bridge formation high adsorption capacity, molecular weight height (can reach more than 1,500 ten thousand), solvability good, to organism adsorb, dehydrating effect is good, is particularly suitable for the processing of sewage such as oily(waste)water, sanitary sewage, papermaking sewage, dyeing and printing sewage such as oil field.
Embodiment 2
At capacity is to add 22.5g deionized water, 2.125g acrylamide, 0.225g vinylformic acid morpholine ethyl ester methyl quaternary ammonium and 0.025g vinylformic acid in the tool plug scale test tube of 25ml, and dissolving mixes.Using the NaOH solution of 1mol/L, the hydrochloric acid telo merization system pH value of aqueous solution of 1mol/L is 7.4, the ice-water bath cooling, and logical nitrogen 20 minutes is to remove oxygen.Add 0.208 * 10
-4The ammonium persulphate of g and 0.095 * 10
-4The oxidation-reduction initiator system that the S-WAT of g is formed stops logical nitrogen and stoppered test tube plug to prevent air admission, and 25 ℃ were reacted 6 hours, got translucent colloid, were to have the colloid that efficiently changes the amphoteric polymeric flocculant of ability mutually; Obtain the powder of amphoteric polymeric flocculant with this colloid granulation, oven dry, after pulverizing, sieving, it have change mutually ability height, bridge formation high adsorption capacity, molecular weight height (can reach more than 1,500 ten thousand), solvability good, to organism adsorb, dehydrating effect is good, is particularly suitable for the processing of sewage such as oily(waste)water, sanitary sewage, papermaking sewage, dyeing and printing sewage such as oil field.
Embodiment 3
At capacity is to add 20g deionized water, 2.5g Methacrylamide, 2.25g vinylformic acid morpholine ethyl ester hydrochloride and 0.25g 2-acrylamido-2-methyl propane sulfonic acid in the tool plug scale test tube of 25ml, and dissolving mixes.Using the NaOH solution of 1mol/L, the hydrochloric acid telo merization system pH value of aqueous solution of 1mol/L is 7.0, the ice-water bath cooling, and logical nitrogen 25 minutes is to remove oxygen.Add 0.832 * 10
-4G Potassium Persulphate and 0.18 * 10
-4The oxidation-reduction initiator system that the g S-WAT is formed stops logical nitrogen and stoppered test tube plug to prevent air admission, and 5 ℃ were reacted 12 hours, got translucent colloid, were to have the colloid that efficiently changes the amphoteric polymeric flocculant of ability mutually; Obtain the powder of amphoteric polymeric flocculant with this colloid granulation, oven dry, after pulverizing, sieving, it have change mutually ability height, bridge formation high adsorption capacity, molecular weight height (can reach more than 1,500 ten thousand), solvability good, to organism adsorb, dehydrating effect is good, is particularly suitable for the processing of sewage such as oily(waste)water, sanitary sewage, papermaking sewage, dyeing and printing sewage such as oil field.
Embodiment 4
At capacity is to add 20g deionized water, 3g N,N-DMAA, 1g vinylformic acid morpholine propyl ester ethyl quaternary ammonium salt and 1g vinylformic acid in the tool plug scale test tube of 25ml, and dissolving mixes.Using the NaOH solution of 1mol/L, the hydrochloric acid telo merization system pH value of aqueous solution of 1mol/L is 9, the ice-water bath cooling, and logical nitrogen 15 minutes is to remove oxygen.Add 1 * 10
-2G 2,2'-Azobis(2,4-dimethylvaleronitrile) initiator stops logical nitrogen and stoppered test tube plug to prevent air admission, and 15 ℃ were reacted 8 hours, got translucent colloid, were to have the colloid that efficiently changes the amphoteric polymeric flocculant of ability mutually; Obtain the powder of amphoteric polymeric flocculant with this colloid granulation, oven dry, after pulverizing, sieving, it have change mutually ability height, bridge formation high adsorption capacity, molecular weight height (can reach more than 1,500 ten thousand), solvability good, to organism adsorb, dehydrating effect is good, is particularly suitable for the processing of sewage such as oily(waste)water, sanitary sewage, papermaking sewage, dyeing and printing sewage such as oil field.
Embodiment 5
At capacity is to add 22.5g deionized water, 2g acrylamide, 0.5g methacrylic acid morpholine ethyl ester benzyl quaternary ammonium salt in the tool plug scale test tube of 25ml, and dissolving mixes.Using the NaOH solution of 1mol/L, the hydrochloric acid telo merization system pH value of aqueous solution of 1mol/L is 6.2, the ice-water bath cooling, and logical nitrogen 20 minutes is to remove oxygen.Add 5 * 10
-3G dibenzoyl peroxide initiator stops logical nitrogen and stoppered test tube plug to prevent air admission, and 45 ℃ were reacted 8 hours, got translucent colloid, were to have the colloid that efficiently changes the cationic high-molecular flocculant of ability mutually; Obtain the powder of cationic high-molecular flocculant with this colloid granulation, oven dry, after pulverizing, sieving, it have change mutually ability height, bridge formation high adsorption capacity, molecular weight height (can reach more than 1,500 ten thousand), solvability good, to organism adsorb, dehydrating effect is good, is particularly suitable for the processing of sewage such as oily(waste)water, sanitary sewage, papermaking sewage, dyeing and printing sewage such as oil field.
Embodiment 6
At capacity is to add 20g deionized water, 2g acrylamide, 3g methacrylic acid morpholine ethyl ester ethyl quaternary ammonium salt in the tool plug scale test tube of 25ml, and dissolving mixes.Using the NaOH solution of 1mol/L, the hydrochloric acid telo merization system pH value of aqueous solution of 1mol/L is 5.4, the ice-water bath cooling, and logical nitrogen 30 minutes is to remove oxygen.Add 0.625 * 10
-4G ammonium persulphate and 0.285 * 10
-4The oxidation-reduction initiator system that the g S-WAT is formed stops logical nitrogen and stoppered test tube plug to prevent air admission, and 25 ℃ were reacted 4 hours, got translucent colloid, were to have the colloid that efficiently changes the cationic high-molecular flocculant of ability mutually; Obtain the powder of cationic high-molecular flocculant with this colloid granulation, oven dry, after pulverizing, sieving, it have change mutually ability height, bridge formation high adsorption capacity, molecular weight height (can reach more than 1,500 ten thousand), solvability good, to organism adsorb, dehydrating effect is good, is particularly suitable for the processing of sewage such as oily(waste)water, sanitary sewage, papermaking sewage, dyeing and printing sewage such as oil field.
Embodiment 7
At capacity is to add 15g deionized water, 2g acrylamide, 8g vinylformic acid morpholine ethyl ester methyl quaternary ammonium in the tool plug scale test tube of 25ml, and dissolving mixes.Using the NaOH solution of 1mol/L, the hydrochloric acid telo merization system pH value of aqueous solution of 1mol/L is 6.4, the ice-water bath cooling, and logical nitrogen 40 minutes is to remove oxygen.Add 0.625 * 10
-4G ammonium persulphate and 0.285 * 10
-4The oxidation-reduction initiator system that the g S-WAT is formed stops logical nitrogen and stoppered test tube plug to prevent air admission, and 0 ℃ was reacted 24 hours, got translucent colloid, was to have the colloid that efficiently changes the cationic high-molecular flocculant of ability mutually; Obtain the powder of cationic high-molecular flocculant with this colloid granulation, oven dry, after pulverizing, sieving, it have change mutually ability height, bridge formation high adsorption capacity, molecular weight height (can reach more than 1,500 ten thousand), solvability good, to organism adsorb, dehydrating effect is good, is particularly suitable for the processing of sewage such as oily(waste)water, sanitary sewage, papermaking sewage, dyeing and printing sewage such as oil field.
Embodiment 8
At capacity is to add 22.5g deionized water, 0.5g acrylamide, 0.125g vinylformic acid morpholine ethyl ester hydrochloride and 1.875g 2-acrylamido dodecyl sodium sulfonate in the tool plug scale test tube of 25ml, and dissolving mixes.Using the NaOH solution of 1mol/L, the hydrochloric acid telo merization system pH value of aqueous solution of 1mol/L is 8.0, the ice-water bath cooling, and logical nitrogen 15 minutes is to remove oxygen.Add 2.5 * 10
-2G Diisopropyl azodicarboxylate initiator stops logical nitrogen and stoppered test tube plug to prevent air admission, and 60 ℃ were reacted 2 hours, got translucent colloid, were to have the colloid that efficiently changes the amphoteric polymeric flocculant of ability mutually; Obtain the powder of amphoteric polymeric flocculant with this colloid granulation, oven dry, after pulverizing, sieving, it have change mutually ability height, bridge formation high adsorption capacity, molecular weight height (can reach more than 1,500 ten thousand), solvability good, to organism adsorb, dehydrating effect is good, is particularly suitable for the processing of sewage such as oily(waste)water, sanitary sewage, papermaking sewage, dyeing and printing sewage such as oil field.
Embodiment 9
At capacity is to add 20g deionized water, 4.75g acrylamide, 0.25g vinylformic acid morpholine ethyl ester hydrochloride in the tool plug scale test tube of 25ml, and dissolving mixes.Using the NaOH solution of 1mol/L, the hydrochloric acid telo merization system pH value of aqueous solution of 1mol/L is 4.0, the ice-water bath cooling, and logical nitrogen 35 minutes is to remove oxygen.Add 2.5 * 10
-2G dilauroyl peroxide initiator stops logical nitrogen and stoppered test tube plug to prevent air admission, and 5 ℃ were reacted 8 hours, got translucent colloid, were to have the colloid that efficiently changes the cationic high-molecular flocculant of ability mutually; Obtain the powder of cationic high-molecular flocculant with this colloid granulation, oven dry, after pulverizing, sieving, it have change mutually ability height (can reach more than 1,500 ten thousand), bridge formation high adsorption capacity, molecular weight height, solvability good, to organism adsorb, dehydrating effect is good, is particularly suitable for the processing of sewage such as oily(waste)water, sanitary sewage, papermaking sewage, dyeing and printing sewage such as oil field.
Embodiment 10
At capacity is to add 20g deionized water, 1g acrylamide, 0.25g methacrylic acid morpholine butyl ester methyl quaternary ammonium in the tool plug scale test tube of 25ml, the 3.75g methacrylic acid, and dissolving mixes.Using the NaOH solution of 1mol/L, the hydrochloric acid telo merization system pH value of aqueous solution of 1mol/L is 6.0, the ice-water bath cooling, and logical nitrogen 25 minutes is to remove oxygen.Add 2.5 * 10
-4G potassium permanganate and 1.425 * 10
-4The initiator system that g oxalic acid is formed stops logical nitrogen and stoppered test tube plug to prevent air admission, and 0 ℃ was reacted 24 hours, got translucent colloid, was to have the colloid that efficiently changes the amphoteric polymeric flocculant of ability mutually; Obtain the powder of amphoteric polymeric flocculant with this colloid granulation, oven dry, after pulverizing, sieving, it have change mutually ability height, bridge formation high adsorption capacity, molecular weight height (can reach more than 1,500 ten thousand), solvability good, to organism adsorb, dehydrating effect is good, is particularly suitable for the processing of sewage such as oily(waste)water, sanitary sewage, papermaking sewage, dyeing and printing sewage such as oil field.
Embodiment 11
At capacity is to add 23.75g deionized water, 1.1875g acrylamide, 0.0375g vinylformic acid morpholine ethyl ester hydrochloride and 0.025g vinylformic acid in the tool plug scale test tube of 25ml, and dissolving mixes.Using the NaOH solution of 1mol/L, the hydrochloric acid telo merization system pH value of aqueous solution of 1mol/L is 6.2, the ice-water bath cooling, and logical nitrogen 15 minutes is to remove oxygen.Add 0.375 * 10
-4G ammonium persulphate and 0.875 * 10
-4The oxidation-reduction initiator system that the g S-WAT is formed stops logical nitrogen and stoppered test tube plug preventing air admission, 20 ℃ of polyreactions 6 hours, translucent colloid, be and have the colloid that efficiently changes the amphoteric polymeric flocculant of ability mutually; Obtain the powder of amphoteric polymeric flocculant with this colloid granulation, oven dry, after pulverizing, sieving, it have change mutually ability height, bridge formation high adsorption capacity, molecular weight height (can reach more than 1,500 ten thousand), solvability good, to organism adsorb, dehydrating effect is good, is particularly suitable for the processing of sewage such as oily(waste)water, sanitary sewage, papermaking sewage, dyeing and printing sewage such as oil field.
Embodiment 12
At capacity is to add 23.75g deionized water, 1.1875g acrylamide, 0.0375g vinylformic acid morpholine ethyl ester hydrochloride and 0.025g vinylformic acid in the tool plug scale test tube of 25ml, and dissolving mixes.Using the NaOH solution of 1mol/L, the hydrochloric acid telo merization system pH value of aqueous solution of 1mol/L is 6.2, the ice-water bath cooling, and logical nitrogen 15 minutes is to remove oxygen.Add 1.875 * 10
-4G ammonium persulphate and 4.375 * 10
-4The oxidation-reduction initiator system that the g S-WAT is formed stops logical nitrogen and stoppered test tube plug preventing air admission, 20 ℃ of polyreactions 6 hours, translucent colloid, be and have the colloid that efficiently changes the amphoteric polymeric flocculant of ability mutually; Obtain the powder of amphoteric polymeric flocculant with this colloid granulation, oven dry, after pulverizing, sieving, it have change mutually ability height, bridge formation high adsorption capacity, molecular weight height (can reach more than 1,500 ten thousand), solvability good, to organism adsorb, dehydrating effect is good, is particularly suitable for the processing of sewage such as oily(waste)water, sanitary sewage, papermaking sewage, dyeing and printing sewage such as oil field.
Embodiment 13
At capacity is to add 20g deionized water, 4.75g acrylamide, 0.25g vinylformic acid morpholine ethyl ester hydrochloride in the tool plug scale test tube of 25ml, and dissolving mixes.Using the NaOH solution of 1mol/L, the hydrochloric acid telo merization system pH value of aqueous solution of 1mol/L is 4.0, the ice-water bath cooling, and logical nitrogen 35 minutes is to remove oxygen.Add 2.5 * 10
-4The g ammonium persulfate initiator stops logical nitrogen and stoppered test tube plug to prevent air admission, and 5 ℃ were reacted 8 hours, got translucent colloid, were to have the colloid that efficiently changes the cationic high-molecular flocculant of ability mutually; Obtain the powder of cationic high-molecular flocculant with this colloid granulation, oven dry, after pulverizing, sieving, it have change mutually ability height, bridge formation high adsorption capacity, molecular weight height (can reach more than 1,500 ten thousand), solvability good, to organism adsorb, dehydrating effect is good, is particularly suitable for the processing of sewage such as oily(waste)water, sanitary sewage, papermaking sewage, dyeing and printing sewage such as oil field.
Claims (6)
1. amphoteric or cationic high-molecular flocculant is characterized in that this amphoteric or cationic high-molecular flocculant prepare by the following method:
In closed reactor, add neutral monomer, cationic monomer, anionic monomer, deionized water and be mixed with the polymerization reaction system aqueous solution; Telo merization system pH value of aqueous solution is 2～9, the ice-water bath cooling; Logical rare gas element adds initiator to remove oxygen in reactor, stops logical rare gas element, carries out polyreaction under 0 ℃～60 ℃, gets translucent colloid, is amphoteric or cationic high-molecular flocculant;
Wherein: neutral monomer, cationic monomer, the total concn of anionic monomer in the polymerization reaction system aqueous solution are 5wt%～40wt%; Described neutral monomer accounts for the 20wt%～95wt% of above-mentioned total monomer; Cationic monomer accounts for the 5wt%～80wt% of above-mentioned total monomer; Anionic monomer accounts for the 0wt%～75wt% of above-mentioned total monomer;
Described neutral monomer is selected from more than one in acrylamide, Methacrylamide, the N,N-DMAA;
Described cationic monomer is vinylformic acid morpholine alkyl esters monomer or methacrylic acid morpholine alkyl esters monomer;
Described anionic monomer is selected from more than one in vinylformic acid, acrylate, methacrylic acid, methacrylate, 2-acrylamido-2-methyl propane sulfonic acid, 2-acrylamido-2-phenyl ethyl sulfonic acid, the 2-acrylamido dodecyl sodium sulfonate.
2. amphoteric according to claim 1 or cationic high-molecular flocculant is characterized in that: the synthetic product is a cationic high-molecular flocculant when no anionic monomer polymerization time institute; As cationic monomer and anionic monomer polymerization time institute synthetic product is the amphoteric polymeric flocculant.
3. amphoteric according to claim 1 or cationic high-molecular flocculant is characterized in that: the concentration of described initiator in the polymerization reaction system aqueous solution is 0.005wt%～1wt%.
4. according to claim 1 or 3 described amphoteric or cationic high-molecular flocculants, it is characterized in that: described initiator is selected from azo-initiator, organic peroxy class initiator, inorganic peroxy class initiator, more than one in the oxidation-reduction class initiator.
5. amphoteric according to claim 4 or cationic high-molecular flocculant is characterized in that: described azo-initiator is Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile) or their mixture; Described organic peroxy class initiator is selected from more than one in dibenzoyl peroxide, peroxy dicarbonate ethylhexyl, dicumyl peroxide, dilauroyl peroxide, the special butyl ester of peroxidation phenylformic acid; Described inorganic peroxy class initiator is selected from more than one in Potassium Persulphate, ammonium persulphate, the hydrogen peroxide; Oxygenant in the described oxidation-reduction class initiator is Potassium Persulphate, ammonium persulphate, hydrogen peroxide or potassium permanganate, and reductive agent is S-WAT, sodium bisulfite, ferrous sulfate, amine or oxalic acid; Wherein: the mol ratio of oxygenant and reductive agent is 1: 5 to 5: 1.
6. amphoteric according to claim 1 and 2 or cationic high-molecular flocculant is characterized in that: described cationic monomer is vinylformic acid morpholine alkyl esters monomer or methacrylic acid morpholine alkyl esters monomer, has following structure:
R
1For-H or-CH
3R
2For containing the alkyl of 1 to 6 carbon; R
3For-H ,-CH
3,-CH
2-CH
3Or-CH
2-C
6H
5Deng; X is halide-ions or sulfate ion.
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