CN105366789A - Multifunctional amphoteric polymer flocculant and preparation method thereof - Google Patents

Multifunctional amphoteric polymer flocculant and preparation method thereof Download PDF

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CN105366789A
CN105366789A CN201510764513.4A CN201510764513A CN105366789A CN 105366789 A CN105366789 A CN 105366789A CN 201510764513 A CN201510764513 A CN 201510764513A CN 105366789 A CN105366789 A CN 105366789A
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acid
acrylamide
mannich base
mixture
preparation
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CN105366789B (en
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郭睿
甄建斌
李晓芳
王超
刘爱玉
李欢乐
杨江月
程敏
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Changzhou Zhenbang Chemical Manufacturing Co ltd
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Shaanxi University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
    • C02F1/56—Macromolecular compounds

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  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Separation Of Suspended Particles By Flocculating Agents (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The invention discloses a multifunctional amphoteric polymer flocculant and a preparation method thereof. The preparation method comprises that deionized water, a chelating agent, an initiator, a chain transferring agent and p-acrylamide-benzenesulfonic acid are added into a reactor, pH of the mixture is adjusted to 7-9, Mannich base is added into the mixture, N2 is fed into the reactor to remove oxygen in the reactor, the mixture undergoes a polymerization reaction at a temperature of 20-60 DEG C for 3-6h to produce a transparent copolymer, and the transparent copolymer is cooled to a room temperature, is washed and is dried to form the multifunctional amphoteric polymer flocculant. The multifunctional amphoteric polymer flocculant has flocculation-corrosion inhibition dual functions and contains positively and negatively charged groups on the molecular chain element so that the multifunctional amphoteric polymer flocculant has good water solubility. The multifunctional amphoteric polymer flocculant is suitable for an anion-cation coexistence pollution system, is suitable for a wide pH range and has the advantages of short water treatment flow, less equipment and high effects.

Description

A kind of multi-functional amphoteric polymeric flocculant and preparation method thereof
Technical field
The invention belongs to field of fine chemical, relate to a kind of sewage treatment flocculating agent, be specifically related to a kind of multi-functional amphoteric polymeric flocculant and preparation method thereof.
Background technology
Along with the raising of industrial expansion and living standards of the people, the specification of quality of people to water is also more and more higher; The quantity discharged of trade effluent and municipal effluent also gets more and more, and especially industrial wastewater pollution not only destroys ecotope, is even detrimental to health; Therefore industrial wastewater pollution is prevented and treated extremely urgent.
During Industrial Wastewater Treatment Process not only relates to purification of water quality, also has the maintenance problem of equipment pipe, and traditional method uses multiple water treatment agent respectively, and this makes aftertreatment very loaded down with trivial details.In addition, along with water-quality constituents becomes increasingly complex, also more and more higher to the requirement of flocculation agent, unicity flocculation agent can not meet water treatment requirement.
At present, some experts have carried out the research of multifunctional water treating agent gradually.The external existing water conditioner having the several functions such as flocculation, inhibition, scale inhibition, sterilization concurrently, but range of application is narrow, and be suitable for pH value range little, water treatment process is loaded down with trivial details, does not realize large-scale promotion.Because China lacks the production of cationic monomer, the development of Amphiphatic high polymer organic floculant is hindered.Therefore, develop multi-functional both sexes organic polymer coargulator, the flocculation agent developed is made to have purification concurrently, inhibition, scale inhibition, the several functions such as sterilization are also main trend of Syn-Organic flocculants, simultaneously amphoteric polymeric flocculant has and well water-solublely has the moon concurrently, the feature of cation group, be applicable to various wastewater treatment of different nature, especially to sludge dewatering, not only there is electrical counteract, adsorption bridging effect and have intermolecular " winding " package action, make the mud granule of process thick, dehydration property is good, even to the mud of different degree of spoilage of different nature, also the filtrating aid function that dewaters preferably can be played, therefore the research of multifunctional type flocculation agent is extremely urgent, significant.
Summary of the invention
The advantages such as the object of the invention is a kind of method preparing multi-functional amphoteric polymeric flocculant, have productive rate high, consumption is few, and flocculation is fast, and corrosion mitigating effect is strong, and the wide and salt resistance of the pH value range be suitable for is good.
To achieve these goals, the present invention is realized by following technical proposals:
A kind of multi-functional amphoteric polymeric flocculant, this flocculation agent structure is as follows:
Wherein, x=1 ~ 30; Y=1 ~ 50.
A preparation method for multi-functional amphoteric polymeric flocculant, by deionized water, sequestrant, initiator, chain-transfer agent with join in reactor acrylamide Phenylsulfonic acid, and adjust ph is add Mannich base, logical N after 7 ~ 9 2after removing the oxygen in reactor, at 20 ~ 60 DEG C, initiated polymerization 3 ~ 6h, obtains transparent copolymer, is cooled to room temperature, by transparent copolymer washing, drying, obtains multi-functional amphoteric polymeric flocculant; Wherein, deionized water account for ionized water, to acrylamide Phenylsulfonic acid and Mannich base total mass 15% ~ 40%, to acrylamide Phenylsulfonic acid account for ionized water, to acrylamide Phenylsulfonic acid and Mannich base total mass 20% ~ 50%, Mannich base account for ionized water, to acrylamide Phenylsulfonic acid and Mannich base total mass 20% ~ 50%, sequestrant is 0.1% ~ 0.2% of deionized water quality, initiator is 0.1% ~ 1.0% of deionized water quality, and chain-transfer agent is 0.1% ~ 2% of deionized water quality.
Described acrylamide Phenylsulfonic acid to be obtained by the following method:
Being joined by Sulphanilic Acid in olefin(e) acid and to add catalyzer, being warmed up to 30 ~ 60 DEG C under stirring, condensing reflux reaction 2 ~ 6h, obtains alkene acid amides Phenylsulfonic acid after purifying; Wherein, Sulphanilic Acid and the amount of substance of olefin(e) acid are than being 1:(1 ~ 3); Catalyzer is 0.1 ~ 2% of Sulphanilic Acid amount of substance.
In described step (1), olefin(e) acid is vinylformic acid or α-methacrylic acid; Catalyzer in step (1) is DMAP or DCC.
Described Mannich base obtains by the following method:
(1) by unsaturated hydroxy ester and acid binding agent by amount of substance than 1:(0.5 ~ 1.5) mix after, be placed in ice-water bath, stir and lead to N 2to drive away water vapour, then drip Acetyl Chloride 98Min., dropping temperature is-5 ~ 10 DEG C, dropwises, condensing reflux reaction 0.5 ~ 2h at 0 ~ 30 DEG C, obtained methyl acrylate second diester and triethylamine hydrochloride mixture; Wherein, unsaturated hydroxy ester and the amount of substance of Acetyl Chloride 98Min. are than 1:(1 ~ 2);
(2) by after methyl acrylate second diester and triethylamine hydrochloride mixture washed with diethylether, suction filtration removing triethylamine hydrochloride, obtain the mixture of unsaturated ester and ether, then distillation removes ether and unnecessary Acetyl Chloride 98Min. at 30 DEG C ~ 60 DEG C, obtained unsaturated ester;
(3) join after formaldehyde solution being mixed with amine in solvent, then adjust ph is 2 ~ 5,50 ~ 80 DEG C are warming up under stirring, reaction 0.5h ~ 1h, continue to be warmed up to 60 ~ 90 DEG C, drip unsaturated ester, after dropwising, at temperature 70 ~ 100 DEG C, react 5 ~ 8h, after purifying, obtain Mannich base; Wherein, in formaldehyde solution, the amount of substance ratio of formaldehyde, amine, unsaturated ester is (1 ~ 3): (1 ~ 1.5): 1; Amine is ammonia, diethylamine or diethanolamine; Solvent is ethanol or deionized water.
In described step (1), unsaturated hydroxy ester is Hydroxyethyl acrylate or α-methacrylic acid hydroxyl ethyl ester.
In described step (1), acid binding agent is triethylamine, pyridine, sodium hydroxide or potassium hydroxide.
In described step (3), the massfraction of formaldehyde solution is 20% ~ 50%.
Described sequestrant is ethylenediamine tetraacetic acid (EDTA), methyl ethyl diketone or trisodium phosphate.
Described chain-transfer agent is Virahol or sodium formiate; Initiator is one or more or Diisopropyl azodicarboxylate in potassium bromate, potassium sulfite, Potassium Persulphate, Sodium Persulfate; Washing specifically adopts volume ratio to be (2 ~ 4): the ethanol of 1, the mixture washing of acetone 2 ~ 3 times.
Compared with prior art, beneficial effect of the present invention is: the present invention obtains multi-functional amphoteric flocculation agent by Mannich reaction, amidate action, copolyreaction, such flocculation agent is by Mannich base and gathers acrylamide Phenylsulfonic acid and form, the inhibitor molecular that Mannich base is is active centre with N and O atom, can be combined with atoms metal, cover equipment surface with the form of adsorption film and belong to again a cationoid unsaturated ester simultaneously it contains polar group ester group and has throwing out.To the suspended substance generation adsorption bridging effect had in acrylamide Phenylsulfonic acid in amide group energy and sewage, increase the size of flco alumen ustum, be conducive to its rapid subsidence and reach throwing out, sulfonic acid group hydrophilic radical adds water-soluble, sulfonic acid group is with negative electricity simultaneously, by charge neutrality, macromolecular chain and multiple colloidal solid are combined with chemical bond and be conducive to the stretching, extension of flocculating agent molecule chain, improve its net and catch ability, so belong to anionic flocculant to acrylamide Phenylsulfonic acid, contain the large π key of phenyl ring and H in molecule simultaneously, O atom also makes it have certain rust inhibition, therefore Mannich base not only has rust inhibition but also have certain flocculence, to acrylamide Phenylsulfonic acid, not only there is flocculence and also there is certain rust inhibition, it is poly-and rear to have consumption compared with general unicity flocculation agent few, flocculation is fast, corrosion mitigating effect is strong, the advantages such as the wide and salt resistance of pH value range be suitable for is good.Flocculating property experimental result shows: oil field waste is after homemade Amphiphatic high polymer coagulant process, and transmittance reaches 87.4%, COD clearance 84.8%, and turbidity removal rate is 88.5%, and flocculating effect reaches standard in the industry; Rust inhibition experimental result shows: the corrosion inhibition rate of A3 steel disc reaches 96.2%, is better than the corrosion inhibition of general inhibiter.
Accompanying drawing explanation
Fig. 1 is synthetic route chart of the present invention;
Fig. 2 is Mannich base preparation technology schema;
Fig. 3 is to acrylamide Phenylsulfonic acid preparation technology schema;
Fig. 4 is multifunctional flocculants process flow diagram of the present invention.
Fig. 5 is Hydroxyethyl acrylate, the infrared spectra of methyl acrylate diethyl ester and Mannich base is shown in figure.
Fig. 6 is vinylformic acid and the infrared spectrogram to acrylamide Phenylsulfonic acid.
Embodiment
Further illustrate embodiment of the present invention below by specific embodiment, but be not limited to practical range of the present invention.
The structural formula of the present invention's multi-functional amphoteric polymeric flocculant is as follows:
Wherein, x=1 ~ 30; Y=1 ~ 50.
Above-mentioned multi-functional amphoteric polymeric flocculant preparation method carries out according to the following steps:
Synthetic method comprises Mannich reaction, amidate action and copolyreaction.
1. prepare Mannich base, comprise the following steps, its flow process as shown in Figure 2:
(1) by unsaturated hydroxy ester (one in Hydroxyethyl acrylate, α-methacrylic acid hydroxyl ethyl ester) and acid binding agent (one in triethylamine, pyridine, sodium hydroxide or potassium hydroxide) by amount of substance than 1:(0.5 ~ 1.5) mix and be placed in ice-water bath, stir and pass into N 220 ~ 30min is to drive away water vapour, then by the amount of substance of unsaturated hydroxy ester and Acetyl Chloride 98Min. than 1:(1 ~ 2) Acetyl Chloride 98Min. is slowly dripped, dropping temperature is-5 ~ 10 DEG C, dropwise in 10 ~ 30min, then condensing reflux reaction 0.5 ~ 2h at 0-30 DEG C, obtained methyl acrylate second diester and triethylamine hydrochloride mixture.
(2) by methyl acrylate second diester obtained for step (1) and triethylamine hydrochloride mixture washed with diethylether 2 ~ 3 times, methyl acrylate second diester and triethylamine hydrochloride mixture and ether volume ratio are 1:(3 ~ 1), suction filtration removing triethylamine hydrochloride, obtain the mixture of unsaturated ester and ether, distillation removing ether and unnecessary Acetyl Chloride 98Min. at 30 DEG C ~ 60 DEG C, obtained unsaturated ester.
(3) be mixed to join in solvent (one in ethanol, deionized water) by formaldehyde (formaldehyde solution of massfraction 20% ~ 50%) and amine (one of ammonia, diethanolamine, diethylamine), pH=2 ~ 5 are regulated with concentrated hydrochloric acid, 50 ~ 80 DEG C are warming up under stirring, reaction 0.5h ~ 1h, continue to be warmed up to 60 ~ 90 DEG C, drip the unsaturated ester that step (2) obtains, dropwise in 10 ~ 30min; The amount of substance of aldehyde, amine and unsaturated ester is than being (3 ~ 1): (1.5 ~ 1): 1; 5 ~ 8h is reacted, the obtained thick product of Mannich base at temperature 70 ~ 100 DEG C; Wherein, the amount of solvent is the 30-60% of the volume of formaldehyde solution and amine.
(4) the Mannich base crude product that step (3) obtains is forwarded in Rotary Evaporators carry out decompression and heat up in a steamer distillation, distillation temperature is 30 ~ 60 DEG C, vacuum tightness is-0.07 ~-0.09MPa, till bubble-free produces, the weak yellow liquid finally obtained is the mixture of Mannich base and diethanolamine;
(5) mixture of Mannich base and ether is obtained after step (4) being obtained the mixture anhydrous diethyl ether extraction 2 ~ 3 times of Mannich base and diethanolamine;
(6) Mannich base step (5) obtained and the mixture of ether distill at 35 DEG C, and removing ether obtains Mannich base.
2. preparation to acrylamide Phenylsulfonic acid, specifically comprise the following steps, its flow process as shown in Figure 3:
(1) Sulphanilic Acid is added olefin(e) acid (one in vinylformic acid, α-methacrylic acid), and add catalyzer (one in DMAP, DCC), 30 ~ 60 DEG C are warmed up under stirring, condensing reflux reaction 2 ~ 6h, obtained to alkene acid amides Phenylsulfonic acid and ethylenic unsaturation acid mixture.Wherein, Sulphanilic Acid is 1:(1 ~ 3 with the amount of substance ratio of olefin(e) acid), the add-on of catalyzer is 0.1 ~ 2% of Sulphanilic Acid amount of substance.
(2) with extracted with diethyl ether step (1) obtain to alkene acid amides Phenylsulfonic acid and ethylenic unsaturation acid mixture 2 ~ 3 times, obtain alkene acid amides Phenylsulfonic acid crude product.
(3) with ethanol to step (2) obtain to alkene acid amides Phenylsulfonic acid crude product recrystallization, obtained to alkene acid amides Phenylsulfonic acid.
3. prepare multi-functional amphoteric flocculation agent, specifically comprise the following steps, its flow process as shown in Figure 4:
By deionized water, sequestrant (one in ethylenediamine tetraacetic acid (EDTA), methyl ethyl diketone or trisodium phosphate), chain-transfer agent (one in Virahol, sodium formiate) with obtained join in 1L reactor to alkene acid amides Phenylsulfonic acid, and with sodium hydroxide solution (massfraction 30% ~ 60%), system pH is adjusted to 7 ~ 9, add obtained Mannich base solution again, logical N 220 ~ 30min is with after driving oxygen, (initiator is the mixture of potassium bromate and potassium sulfite to add initiator, Potassium Persulphate, one or more or Diisopropyl azodicarboxylate in Sodium Persulfate), initiated polymerization 3 ~ 6h at 20 ~ 60 DEG C, obtain the larger transparent products of viscosity and be the thick product of multipolymer, be cooled to room temperature, by multipolymer crude product ethanol/acetone (volume ratio (4 ~ 2): 1) repetitive scrubbing, until elutant is transparent, product after purifying is left standstill 12 ~ 36h, at 30 ~ 60 DEG C, vacuum-drying is to constant weight, pulverizing obtains Mannich base-to alkene acid amides Phenylsulfonic acid multipolymer, i.e. multi-functional amphoteric polymeric flocculant.Wherein, compare for (2 ~ 5) to the amount of substance of alkene acid amides Phenylsulfonic acid and Mannich base: 1.
Embodiment of the present invention is further illustrated below by specific embodiment.
Embodiment 1
See Fig. 1, Hydroxyethyl acrylate and triethylamine to mix than 1:0.5 by amount of substance and are placed in ice-water bath by (1), logical N 220min drives away water vapour, and presses Hydroxyethyl acrylate with Acetyl Chloride 98Min. amount of substance than 1:1, slowly drips Acetyl Chloride 98Min., dropping temperature is-5 DEG C, dropwise in 15min, then condensing reflux reaction 0.5h at 10 DEG C, obtained methyl acrylate second diester and triethylamine hydrochloride mixture.
(2) by methyl acrylate second diester obtained for step (1) and triethylamine hydrochloride mixture washed with diethylether 2 times, methyl acrylate second diester and triethylamine hydrochloride and ether volume ratio are 1:1; Suction filtration removing triethylamine hydrochloride, obtains the mixture of methyl acrylate second diester and ether; Distillation removing ether at 52 DEG C, obtained methyl acrylate second diester.
(3) join in 20mL dehydrated alcohol after formaldehyde solution being mixed with diethanolamine, pH=5 is regulated with the hydrochloric acid of massfraction 15%, be warming up to 50 DEG C and stirring reaction 0.5h, then at 60 DEG C, drip the methyl acrylate second diester that step (2) obtains, drip Bi Shengwen and react 5h at 70 DEG C, the obtained thick product of Mannich base.Wherein, in formaldehyde solution, the amount of substance ratio of formaldehyde, amine, unsaturated ester is 1:1:1.
(4) the thick product of Mannich base step (3) obtained is at temperature 45 C, and vacuum tightness is emerged for being distilled to bubble-free under-0.08MPa; Collect final weak yellow liquid, by extracted with diethyl ether 3 times, obtain the mixture of Mannich base and ether.
(5) Mannich base step (4) obtained and the mixture of ether distill at 35 DEG C, and removing ether obtains Mannich base.
(6) Sulphanilic Acid is joined in vinylformic acid, Sulphanilic Acid and acrylic acid amount of substance are than being 1:1, and add catalyzer DMAP, its consumption accounts for 0.1% of Sulphanilic Acid mole number, 40 DEG C are warmed up under stirring, condensing reflux reaction 2h, obtained to acrylamide Phenylsulfonic acid and acrylic acid mixture.
(7) what obtain step (6) with ether extracts 3 times to acrylamide Phenylsulfonic acid and acrylic acid mixture, obtained to acrylamide Phenylsulfonic acid crude product.
(8) with ethanol to step (7) obtain to acrylamide Phenylsulfonic acid crude product recrystallization, obtain acrylamide Phenylsulfonic acid.
(9) 45.4g that 60mL deionized water, 0.1g ethylenediamine tetraacetic acid (EDTA) (EDTA), 0.15g Virahol and step (8) are obtained is joined in reactor to acrylamide Phenylsulfonic acid, and with the sodium hydroxide solution of massfraction 30%, system pH is adjusted to 7, add the 27.5g Mannich base that step (5) is obtained again, logical N 2after 20min drives oxygen, add 0.16g Potassium Persulphate, initiated polymerization 3h in 35 DEG C, obtain the transparent products that viscosity is larger, be cooled to room temperature, transparent products ethanol/acetone (volume ratio 2:1) larger for viscosity is washed 3 times and leave standstill 18h afterwards, at 40 DEG C, vacuum-drying is to constant weight, pulverizing obtains Mannich base-to acrylamide Phenylsulfonic acid multipolymer, i.e. multi-functional amphoteric polymeric flocculant.
Embodiment 2
(1) Hydroxyethyl acrylate and triethylamine to be mixed than 1:0.8 by amount of substance be placed in ice-water bath, logical N 220min drives away water vapour, and Acetyl Chloride 98Min. is slowly added drop-wise in Hydroxyethyl acrylate than 1:1.5 by Hydroxyethyl acrylate and Acetyl Chloride 98Min. amount of substance, dropping temperature is 0 DEG C, dropwise in 15min, then condensing reflux reaction 1h at 15 DEG C, obtained methyl acrylate second diester and triethylamine hydrochloride mixture.
(2) mixture washed with diethylether step (1) obtained 2 times, methyl acrylate second two ester mixture and ether volume ratio are 1:2; Suction filtration removing triethylamine hydrochloride, obtains the mixture of methyl acrylate second diester and ether; Distillation removing ether and unnecessary Acetyl Chloride 98Min. at 55 DEG C, obtained methyl acrylate second diester.
(3) formaldehyde solution and diethanolamine are mixed to join in 25mL anhydrous ethanol solvent, pH=3 is regulated with the hydrochloric acid of massfraction 15%, be warming up to 55 DEG C and stirring reaction 0.5h, be warming up to the methyl acrylate second diester dripping step (2) at 60 DEG C and obtain, continue to heat up and at 80 DEG C, react 6h obtain the thick product of Mannich base.Wherein, in formaldehyde solution, the amount of substance ratio of formaldehyde, amine, unsaturated ester is 1.2:1:1.
(4) the thick product of Mannich base step (3) obtained is at temperature 45 C, and vacuum tightness is emerged for being distilled to bubble-free under-0.08MPa; Collect final liquid, obtain the mixture of Mannich base and ether by extracted with diethyl ether for 3 times.
(5) Mannich base step (4) obtained and the mixture of ether distill at 35 DEG C, and removing ether obtains Mannich base.
(6) join in vinylformic acid by Sulphanilic Acid, amount of substance ratio is 1:1.5, and adds catalyzer DMAP, its consumption accounts for 0.7% of Sulphanilic Acid mole number, be warmed up to 45 DEG C of stirrings, condensing reflux reaction 3h, obtained to acrylamide Phenylsulfonic acid and acrylic acid mixture.
(7) what obtain step (6) with ether extracts 3 times to acrylamide Phenylsulfonic acid and acrylic acid mixture, obtained to acrylamide Phenylsulfonic acid crude product.
(8) with ethanol to step (7) obtain to acrylamide Phenylsulfonic acid crude product recrystallization, obtain acrylamide Phenylsulfonic acid.
(9) 56.75g that 80mL deionized water, 0.15g ethylenediamine tetraacetic acid (EDTA) (EDTA), 0.2g Virahol and step (8) are obtained is joined in 1L reactor to acrylamide Phenylsulfonic acid, and with the sodium hydroxide solution of massfraction 35%, system pH is adjusted to 7, add the 27.5g Mannich base that step (5) is obtained again, logical N 2after driving oxygen 20min, add 0.22g Potassium Persulphate, initiated polymerization 3.5h in 45 DEG C, obtain the transparent products that viscosity is larger, be cooled to room temperature, wash 3 times by ethanol/acetone (volume ratio 2:1) and leave standstill 12h afterwards, at 40 DEG C, vacuum-drying is to constant weight, the pale yellow powder Mannich base that pulverizing obtains-to acrylamide Phenylsulfonic acid multipolymer, i.e. multi-functional amphoteric polymeric flocculant.
Embodiment 3
(1) Hydroxyethyl acrylate and triethylamine to be mixed than 1:1 by amount of substance be placed in ice-water bath, logical N 225min drives away water vapour, and Acetyl Chloride 98Min. is slowly added drop-wise in Hydroxyethyl acrylate than 1:1.2 by Hydroxyethyl acrylate and Acetyl Chloride 98Min. amount of substance, dropping temperature is 5 DEG C, dropwise in 20min, then condensing reflux reaction 1h at 20 DEG C, obtained methyl acrylate second diester and triethylamine hydrochloride mixture.
(2) mixture washed with diethylether step (1) obtained 2 times, methyl acrylate second two ester mixture and ether volume ratio are 1:2; Suction filtration removing triethylamine hydrochloride, obtains the mixture of methyl acrylate second diester and ether; Distillation removing ether and unnecessary Acetyl Chloride 98Min. at 58 DEG C, obtained methyl acrylate second diester.
(3) formaldehyde solution and diethanolamine are mixed to join in 30mL anhydrous ethanol solvent, pH=3 is regulated with the hydrochloric acid of massfraction 15%, be warming up to 60 DEG C and stirring reaction 0.5h, drip the methyl acrylate second diester that step (2) obtains at this temperature, heat up and at 80 DEG C, react 7h obtain the thick product of Mannich base.Wherein, in formaldehyde solution, the amount of substance ratio of formaldehyde, amine, unsaturated ester is 1.5:1:1.
(4) the thick product of Mannich base step (3) obtained is at temperature 45 C, and vacuum tightness is emerged for being distilled to bubble-free under-0.08MPa; Collect final liquid, obtain the mixture of Mannich base and ether by extracted with diethyl ether for 3 times.
(5) Mannich base step (4) obtained and the mixture of ether distill at 35 DEG C, and removing ether obtains Mannich base.
(6) join in vinylformic acid by Sulphanilic Acid, amount of substance ratio is 1:2, and adds catalyzer DMAP, its consumption accounts for 1.5% of Sulphanilic Acid mole number, be warmed up to 50 DEG C of stirrings, condensing reflux reaction 4h, obtained to acrylamide Phenylsulfonic acid and acrylic acid mixture.
(7) what obtain step (6) with ether extracts 3 times to acrylamide Phenylsulfonic acid and acrylic acid mixture, obtained to acrylamide Phenylsulfonic acid crude product.
(8) with ethanol to step (7) obtain to acrylamide Phenylsulfonic acid crude product recrystallization, obtain acrylamide Phenylsulfonic acid.
(9) 68.1g that 100mL deionized water, 0.19g ethylenediamine tetraacetic acid (EDTA) (EDTA), 0.25g Virahol and step (8) are obtained is joined in 1L reactor to acrylamide Phenylsulfonic acid, and with the sodium hydroxide solution of massfraction 40%, system pH is adjusted to 7, add the 27.5g Mannich base that step (5) is obtained again, logical N 2after driving oxygen 30min, add the mixture of 0.28g Potassium Persulphate and sodium bisulfite, initiated polymerization 4h in 50 DEG C, obtain the transparent products that viscosity is larger, be cooled to room temperature, wash 3 times by ethanol/acetone (volume ratio 3:1) and leave standstill 18h afterwards, at 50 DEG C, vacuum-drying is to constant weight, pulverizing obtains Mannich base-to acrylamide Phenylsulfonic acid multipolymer pale yellow powder, i.e. multi-functional amphoteric polymeric flocculant.
Embodiment 4
(1) Hydroxyethyl acrylate and triethylamine to be mixed than 1:1.2 by amount of substance be placed in ice-water bath, logical N 230min drives away water vapour, and Acetyl Chloride 98Min. is slowly added drop-wise in Hydroxyethyl acrylate than 1:1.5 by Hydroxyethyl acrylate and Acetyl Chloride 98Min. amount of substance, dropping temperature is 0 DEG C, dropwise in 25min, then condensing reflux reaction 1.5h at 25 DEG C, obtained methyl acrylate second diester and triethylamine hydrochloride mixture.
(2) mixture washed with diethylether step (1) obtained 3 times, methyl acrylate second two ester mixture and ether volume ratio are 1:2.5; Suction filtration removing triethylamine hydrochloride, obtains the mixture of methyl acrylate second diester and ether; Distillation removing ether and unnecessary Acetyl Chloride 98Min. at 60 DEG C, obtained methyl acrylate second diester.
(3) formaldehyde solution and diethanolamine are mixed to join in 35mL anhydrous ethanol solvent, pH=4 is regulated with the hydrochloric acid of massfraction 15%, be warming up to 65 DEG C and stirring reaction 1h, be warming up to the methyl acrylate second diester dripping step (2) at 70 DEG C and obtain, continue to heat up and at 90 DEG C, react 8h obtain the thick product of Mannich base.Wherein, in formaldehyde solution, the amount of substance ratio of formaldehyde, amine, unsaturated ester is 1.8:1:1.
(4) the thick product of Mannich base step (3) obtained is at temperature 45 C, and vacuum tightness is emerged for being distilled to bubble-free under-0.08MPa; Collect final liquid, obtain the mixture of Mannich base and ether by extracted with diethyl ether for 3 times.
(5) Mannich base step (4) obtained and the mixture of ether distill at 35 DEG C, and removing ether obtains Mannich base.
(6) join in vinylformic acid by Sulphanilic Acid, amount of substance ratio is 1:2, and adds catalyzer DMAP, its consumption accounts for 2% of Sulphanilic Acid mole number, be warmed up to 55 DEG C of stirrings, condensing reflux reaction 5h, obtained to acrylamide Phenylsulfonic acid and acrylic acid mixture.
(7) what obtain step (6) with ether extracts 3 times to acrylamide Phenylsulfonic acid and acrylic acid mixture, obtained to acrylamide Phenylsulfonic acid crude product.
(8) with ethanol to step (7) obtain to acrylamide Phenylsulfonic acid crude product recrystallization, obtain acrylamide Phenylsulfonic acid.
(9) 79.45g that 150mL deionized water, 0.2g trisodium phosphate, 0.25g sodium formiate and step (8) are obtained is joined in 1L reactor to acrylamide Phenylsulfonic acid, and with the sodium hydroxide solution of massfraction 45%, system pH is adjusted to 7, add the 27.5g Mannich base that step (5) is obtained again, logical N 2after driving oxygen 30min, add 0.3g Diisopropyl azodicarboxylate (AIBN), initiated polymerization 4.5h in 55 DEG C, obtain the transparent products that viscosity is larger, be cooled to room temperature, wash 3 times by ethanol/acetone (volume ratio 3:1) and leave standstill 10h afterwards, at 50 DEG C, vacuum-drying is to constant weight, pulverizing obtains Mannich base-to acrylamide Phenylsulfonic acid multipolymer pale yellow powder, i.e. multi-functional amphoteric polymeric flocculant.
Embodiment 5
(1) Hydroxyethyl acrylate and triethylamine to be mixed than 1:1.5 by amount of substance be placed in ice-water bath, logical N 230min drives away water vapour, and Acetyl Chloride 98Min. is slowly added drop-wise in Hydroxyethyl acrylate than 1:1.5 by Hydroxyethyl acrylate and Acetyl Chloride 98Min. amount of substance, dropping temperature is 0 DEG C, dropwise in 30min, then condensing reflux reaction 1.5h at 30 DEG C, obtained methyl acrylate second diester and triethylamine hydrochloride mixture.
(2) mixture washed with diethylether step (1) obtained 3 times, methyl acrylate second two ester mixture and ether volume ratio are 1:3; Suction filtration removing triethylamine hydrochloride, obtains the mixture of methyl acrylate second diester and ether; Distillation removing ether and unnecessary Acetyl Chloride 98Min. at 65 DEG C, obtained methyl acrylate second diester.
(3) formaldehyde solution and diethanolamine are mixed to join in 40mL anhydrous ethanol solvent, pH=4 is regulated with the hydrochloric acid of massfraction 15%, be warming up to 70 DEG C and stirring reaction 1h, be warming up to the methyl acrylate second diester dripping step (2) at 80 DEG C and obtain, heat up and at 90 DEG C, react 8h obtain the thick product of Mannich base.Wherein, in formaldehyde solution, the amount of substance ratio of formaldehyde, amine, unsaturated ester is 2:1:1.
(4) the thick product of Mannich base step (3) obtained is at temperature 45 C, and vacuum tightness is emerged for being distilled to bubble-free under-0.08MPa; Collect final liquid, obtain the mixture of Mannich base and ether by extracted with diethyl ether for 3 times.
(5) Mannich base step (4) obtained and the mixture of ether distill at 35 DEG C, and removing ether obtains Mannich base.
(6) join in vinylformic acid by Sulphanilic Acid, amount of substance ratio is 1:2.5, and adds catalyzer DMAP, its consumption accounts for 2% of Sulphanilic Acid mole number, be warmed up to 60 DEG C of stirrings, condensing reflux reaction 5h, obtained to acrylamide Phenylsulfonic acid and acrylic acid mixture.
(7) what obtain step (6) with ether extracts 3 times to acrylamide Phenylsulfonic acid and acrylic acid mixture, obtained to acrylamide Phenylsulfonic acid crude product.
(8) with ethanol to step (7) obtain to acrylamide Phenylsulfonic acid crude product recrystallization, obtain acrylamide Phenylsulfonic acid.
(9) 90.8g that 200mL deionized water, 0.25g trisodium phosphate, 0.3g sodium formiate and step (8) are obtained is joined in 1L reactor to acrylamide Phenylsulfonic acid, and with the sodium hydroxide solution of massfraction 55%, system pH is adjusted to 7, add the 27.5g Mannich base that step (5) is obtained again, logical N 2after driving oxygen 30min, add 0.32g Potassium Persulphate, initiated polymerization 5h in 60 DEG C, obtain the transparent products that viscosity is larger, be cooled to room temperature, wash 3 times by ethanol/acetone (volume ratio 3:1) and leave standstill 24h afterwards, at 60 DEG C, vacuum-drying is to constant weight, pulverizing obtains Mannich base-to acrylamide Phenylsulfonic acid multipolymer pale yellow powder, i.e. multi-functional amphoteric polymeric flocculant.
Embodiment 6
A preparation method for multi-functional amphoteric polymeric flocculant, comprises the following steps:
(1), after unsaturated hydroxy ester being mixed than 1:1 by amount of substance with acid binding agent, be placed in ice-water bath, stir and lead to N 2to drive away water vapour, then drip Acetyl Chloride 98Min., dropping temperature is-2 DEG C, dropwises, condensing reflux reaction 2h at 0 DEG C, obtained methyl acrylate second diester and triethylamine hydrochloride mixture; Wherein, unsaturated hydroxy ester compares 1:2 with the amount of substance of Acetyl Chloride 98Min.; Unsaturated hydroxy ester is α-methacrylic acid hydroxyl ethyl ester; Acid binding agent is pyridine;
(2) by after methyl acrylate second diester and triethylamine hydrochloride mixture washed with diethylether, suction filtration removing triethylamine hydrochloride, obtain the mixture of unsaturated ester and ether, then distillation removes ether and unnecessary Acetyl Chloride 98Min. at 30 DEG C, obtained unsaturated ester;
(3) by massfraction be 30% formaldehyde solution mix with amine after join in solvent, then adjust ph is 2, is warming up to 80 DEG C under stirring, reaction 0.6h, continues to be warmed up to 90 DEG C, drips unsaturated ester, after dropwising, at temperature 100 DEG C, react 5h, after purifying, obtain Mannich base; Wherein, in formaldehyde solution, the amount of substance ratio of formaldehyde, amine, unsaturated ester is 1:1.5:1; Amine is ammonia; Solvent is deionized water;
(4) being joined by Sulphanilic Acid in olefin(e) acid and to add catalyzer, being warmed up to 30 DEG C under stirring, condensing reflux reaction 2h, obtains alkene acid amides Phenylsulfonic acid after purifying; Wherein, Sulphanilic Acid and the amount of substance of olefin(e) acid are than being 1:3.Catalyzer is 0.5% of Sulphanilic Acid amount of substance; Olefin(e) acid is α-methacrylic acid; Catalyzer is DCC.
(5) by deionized water, sequestrant, initiator, chain-transfer agent with join in reactor acrylamide Phenylsulfonic acid, and adjust ph is add Mannich base, logical N after 8 2after removing the oxygen in reactor, at 20 DEG C, initiated polymerization 6h, obtains transparent copolymer, is cooled to room temperature, adopted by transparent copolymer volume ratio to be the mixture washing 2 ~ 3 times, dry of the ethanol of 4:1, acetone, obtain multi-functional amphoteric polymeric flocculant; Wherein, deionized water account for ionized water, to acrylamide Phenylsulfonic acid and Mannich base total mass 15%, to acrylamide Phenylsulfonic acid account for ionized water, to acrylamide Phenylsulfonic acid and Mannich base total mass 50%, Mannich base account for ionized water, to acrylamide Phenylsulfonic acid and Mannich base total mass 20%, sequestrant is 0.1% of deionized water quality, initiator is 1.0% of deionized water quality, and chain-transfer agent is 2% of deionized water quality.Sequestrant is methyl ethyl diketone; Chain-transfer agent is sodium formiate; Initiator is potassium bromate.
Embodiment 7
A preparation method for multi-functional amphoteric polymeric flocculant, comprises the following steps:
(1), after unsaturated hydroxy ester being mixed than 1:0.6 by amount of substance with acid binding agent, be placed in ice-water bath, stir and lead to N 2to drive away water vapour, then drip Acetyl Chloride 98Min., dropping temperature is 8 DEG C, dropwises, condensing reflux reaction 1h at 15 DEG C, obtained methyl acrylate second diester and triethylamine hydrochloride mixture; Wherein, unsaturated hydroxy ester compares 1:1.2 with the amount of substance of Acetyl Chloride 98Min.; Unsaturated hydroxy ester is α-methacrylic acid hydroxyl ethyl ester; Acid binding agent is sodium hydroxide;
(2) by after methyl acrylate second diester and triethylamine hydrochloride mixture washed with diethylether, suction filtration removing triethylamine hydrochloride, obtain the mixture of unsaturated ester and ether, then distillation removes ether and unnecessary Acetyl Chloride 98Min. at 60 DEG C, obtained unsaturated ester;
(3) by massfraction be 40% formaldehyde solution mix with amine after join in solvent, then adjust ph is 3.5,50 DEG C are warming up under stirring, reaction 0.7h, continue to be warmed up to 70 DEG C, drip unsaturated ester, after dropwising, under temperature 70 C, react 6h, after purifying, obtain Mannich base; Wherein, in formaldehyde solution, the amount of substance ratio of formaldehyde, amine, unsaturated ester is 3:1.2:1; Amine is diethylamine; Solvent is ethanol;
(4) being joined by Sulphanilic Acid in olefin(e) acid and to add catalyzer, being warmed up to 40 DEG C under stirring, condensing reflux reaction 6h, obtains alkene acid amides Phenylsulfonic acid after purifying; Wherein, Sulphanilic Acid and the amount of substance of olefin(e) acid are than being 1:2.Catalyzer is 1.2% of Sulphanilic Acid amount of substance; Olefin(e) acid is α-methacrylic acid; Catalyzer is DCC.
(5) by deionized water, sequestrant, initiator, chain-transfer agent with join in reactor acrylamide Phenylsulfonic acid, and adjust ph is add Mannich base, logical N after 9 2after removing the oxygen in reactor, at 30 DEG C, initiated polymerization 5h, obtains transparent copolymer, is cooled to room temperature, adopted by transparent copolymer volume ratio to be the mixture washing 2 ~ 3 times, dry of the ethanol of 2:1, acetone, obtain multi-functional amphoteric polymeric flocculant; Wherein, deionized water account for ionized water, to acrylamide Phenylsulfonic acid and Mannich base total mass 25%, to acrylamide Phenylsulfonic acid account for ionized water, to acrylamide Phenylsulfonic acid and Mannich base total mass 20%, Mannich base account for ionized water, to acrylamide Phenylsulfonic acid and Mannich base total mass 30%, sequestrant is 0.2% of deionized water quality, initiator is 0.1% of deionized water quality, and chain-transfer agent is 0.1% of deionized water quality.Sequestrant is methyl ethyl diketone; Chain-transfer agent is Virahol; Initiator is the mixture of Potassium Persulphate, Sodium Persulfate.
Embodiment 8
A preparation method for multi-functional amphoteric polymeric flocculant, comprises the following steps:
(1), after unsaturated hydroxy ester being mixed than 1:1.4 by amount of substance with acid binding agent, be placed in ice-water bath, stir and lead to N 2to drive away water vapour, then drip Acetyl Chloride 98Min., dropping temperature is 10 DEG C, dropwises, condensing reflux reaction 1.5h at 20 DEG C, obtained methyl acrylate second diester and triethylamine hydrochloride mixture; Wherein, unsaturated hydroxy ester compares 1:1.6 with the amount of substance of Acetyl Chloride 98Min.; Unsaturated hydroxy ester is α-methacrylic acid hydroxyl ethyl ester; Acid binding agent is potassium hydroxide;
(2) by after methyl acrylate second diester and triethylamine hydrochloride mixture washed with diethylether, suction filtration removing triethylamine hydrochloride, obtain the mixture of unsaturated ester and ether, then distillation removes ether and unnecessary Acetyl Chloride 98Min. at 40 DEG C, obtained unsaturated ester;
(3) by massfraction be 50% formaldehyde solution mix with amine after join in solvent, then adjust ph is 4.5, is warming up to 60 DEG C under stirring, reaction 0.8h, continues at 60 DEG C, drips unsaturated ester, after dropwising, at temperature 80 DEG C, react 7h, after purifying, obtain Mannich base; Wherein, in formaldehyde solution, the amount of substance ratio of formaldehyde, amine, unsaturated ester is 2:1:1; Amine is ammonia; Solvent is deionized water;
(4) being joined by Sulphanilic Acid in olefin(e) acid and to add catalyzer, being warmed up to 60 DEG C under stirring, condensing reflux reaction 4.5h, obtains alkene acid amides Phenylsulfonic acid after purifying; Wherein, Sulphanilic Acid and the amount of substance of olefin(e) acid are than being 1:1.Catalyzer is 1.7% of Sulphanilic Acid amount of substance; Olefin(e) acid is α-methacrylic acid; Catalyzer is DMAP.
(5) by deionized water, sequestrant, initiator, chain-transfer agent with join in reactor acrylamide Phenylsulfonic acid, and adjust ph is add Mannich base, logical N after 7 2after removing the oxygen in reactor, at 40 DEG C, initiated polymerization 3h, obtains transparent copolymer, is cooled to room temperature, adopted by transparent copolymer volume ratio to be the mixture washing 2 ~ 3 times, dry of the ethanol of 3:1, acetone, obtain multi-functional amphoteric polymeric flocculant; Wherein, deionized water account for ionized water, to acrylamide Phenylsulfonic acid and Mannich base total mass 40%, to acrylamide Phenylsulfonic acid account for ionized water, to acrylamide Phenylsulfonic acid and Mannich base total mass 35%, Mannich base account for ionized water, to acrylamide Phenylsulfonic acid and Mannich base total mass 50%, sequestrant is 0.15% of deionized water quality, initiator is 0.5% of deionized water quality, and chain-transfer agent is 1% of deionized water quality.Sequestrant is trisodium phosphate; Chain-transfer agent is sodium formiate; Initiator is the mixture of potassium bromate, potassium sulfite, Potassium Persulphate, Sodium Persulfate.
The multi-functional amphoteric flocculation agent that the present invention obtains is characterized, see Fig. 5, as can be seen from C with figure in Fig. 5, B peak shape is compared, Hydroxyethyl acrylate C through with Acetyl Chloride 98Min. generation alcoholysis reaction after its infrared absorption peak there occurs considerable change, be embodied in Hydroxyethyl acrylate C at 3515cm -1place-OH stretching vibration absorption peak through reaction after completely dissolve, show that the alcoholysis reaction of acyl chlorides generates product B completely, namely in infrared figure C at 3515cm -1there is absorption peak, and at 3500cm in B -1left and right does not have absorption peak.Mannich base A is generated, again at 3458cm in the infrared spectra of Mannich base A after B and diethanolamine and formaldehyde generation Mannich reaction -1occur that absorption peak is the stretching vibration absorption peak of-OH, illustrated that diethanolamine success there occurs Mannich reaction with formaldehyde and methyl acrylate diethyl ester B, in the Mannich base A due to generation, have two adjacent-OH, so-OH stretching vibration the absorption peak of A is more fat; At 2982cm -1the peak at place is=C-H stretching vibration absorption peak in monomer A, B and C, 1732cm -1the peak at place is the stretching vibration absorption peak of C=O, 1638cm -1the peak at place is the stretching vibration absorption peak of C=C.
Fig. 6 is vinylformic acid and the infrared spectrum to acrylamide Phenylsulfonic acid, in figure, A is vinylformic acid, B is to acrylamide Phenylsulfonic acid, from Fig. 6, the waveform of A with B is compared and can be found out, vinylformic acid (A) through with Sulphanilic Acid generation amidate action after its infrared absorption peak there occurs considerable change, to be embodied in figure B at 1599cm -1, 1569cm -1, 1511cm -1and 1409cm -1the charateristic avsorption band at place is the charateristic avsorption band of phenyl ring; In figure, the infrared absorption peak of B is at 3306cm -1~ 3000cm -1there is absorption band in place, and due to association peak shape wide and loose, be the charateristic avsorption band of amide group; In sum, show that vinylformic acid and Sulphanilic Acid there occurs amidate action, generate acrylamide Phenylsulfonic acid, namely in figure, B is the infrared spectrum absorpting peak to acrylamide Phenylsulfonic acid.
Flocculating property is evaluated: by the multi-functional Amphiphatic high polymer coagulant of synthesis at room temperature, pH=6, and consumption is under the condition of 190mg/L, carries out flocculating experiment to oil field waste, the results are shown in following table 1:
Table 1 flocculating experiment data
Test item Transmittance, % COD/(mg·L -1) Turbidity (NTU)
Before process 24.6 344.5 164.0
After process 87.4 52.3 18.8
As seen from the above table, oil field waste is after homemade Amphiphatic high polymer coagulant process, and transmittance reaches 87.4%, COD clearance 84.8%, and turbidity removal rate is 88.5%, and flocculating effect reaches standard in the industry.The multi-functional amphoteric flocculating agent that as can be seen here prepared by the present invention has good flocculating property.
Slow-releasing: with reference to Chinese name republic oil and gas industry standard SY5405-1996 " acidifying inhibiter method for testing performance and evaluation index ", static steel weight-loss method is adopted to measure, normal pressure, corrosion temperature 30 DEG C, the add-on massfraction of inhibiter is 1.0%, leave standstill corrosion 8h in the hydrochloric acid soln of massfraction 20%, the corrosion inhibition rate recording A3 steel disc reaches 96.2%, is better than the corrosion inhibition of general inhibiter.
Flocculation agent provided by the invention has flocculation-inhibition dual-use function concurrently, and the group simultaneously containing positive and negative electric charge on molecule joint makes it have well water-soluble.This type of flocculation agent is applicable to the Pollution System that anions and canons coexists, and be suitable for pH value wide ranges, water treatment process is short, equipment is few, improves the advantages such as effect.
The invention solves unicity flocculation agent and be subject to solution ph and the problems such as salt impact that coexist, adopt the synthetic method of copolymerization to obtain multi-functional amphoteric polymeric flocculant; At oilfield sewage, there is good flocculation-inhibition dual-use function in the process such as dyeing waste water and paper-making effluent, prove that this type of flocculation agent has wider temperature and potential of hydrogen subject range through a large amount of experiments.
Above content is the further description made the present invention in conjunction with concrete preferred implementation, can not assert it is unique embodiment, the conversion of those of ordinary skill in the art by reading specification sheets of the present invention to any equivalence that technical solution of the present invention is taked, all should be considered as claims of the present invention and contained.

Claims (10)

1. a multi-functional amphoteric polymeric flocculant, is characterized in that, this flocculation agent structure is as follows:
Wherein, x=1 ~ 30; Y=1 ~ 50.
2. the preparation method of a multi-functional amphoteric polymeric flocculant as claimed in claim 1, it is characterized in that, by deionized water, sequestrant, initiator, chain-transfer agent with join in reactor acrylamide Phenylsulfonic acid, and adjust ph is add Mannich base, logical N after 7 ~ 9 2after removing the oxygen in reactor, at 20 ~ 60 DEG C, initiated polymerization 3 ~ 6h, obtains transparent copolymer, is cooled to room temperature, by transparent copolymer washing, drying, obtains multi-functional amphoteric polymeric flocculant; Wherein, deionized water account for ionized water, to acrylamide Phenylsulfonic acid and Mannich base total mass 15% ~ 40%, to acrylamide Phenylsulfonic acid account for ionized water, to acrylamide Phenylsulfonic acid and Mannich base total mass 20% ~ 50%, Mannich base account for ionized water, to acrylamide Phenylsulfonic acid and Mannich base total mass 20% ~ 50%, sequestrant is 0.1% ~ 0.2% of deionized water quality, initiator is 0.1% ~ 1.0% of deionized water quality, and chain-transfer agent is 0.1% ~ 2% of deionized water quality.
3. the preparation method of a kind of multi-functional amphoteric polymeric flocculant according to claim 2, is characterized in that, describedly obtains by the following method acrylamide Phenylsulfonic acid:
Being joined by Sulphanilic Acid in olefin(e) acid and to add catalyzer, being warmed up to 30 ~ 60 DEG C under stirring, condensing reflux reaction 2 ~ 6h, obtains alkene acid amides Phenylsulfonic acid after purifying; Wherein, Sulphanilic Acid and the amount of substance of olefin(e) acid are than being 1:(1 ~ 3); Catalyzer is 0.1 ~ 2% of Sulphanilic Acid amount of substance.
4. the preparation method of a kind of multi-functional amphoteric polymeric flocculant according to claim 3, is characterized in that, in described step (1), olefin(e) acid is vinylformic acid or α-methacrylic acid; Catalyzer in step (1) is DMAP or DCC.
5. the preparation method of a kind of multi-functional amphoteric polymeric flocculant according to claim 2, it is characterized in that, described Mannich base obtains by the following method:
(1) by unsaturated hydroxy ester and acid binding agent by amount of substance than 1:(0.5 ~ 1.5) mix after, be placed in ice-water bath, stir and lead to N 2to drive away water vapour, then drip Acetyl Chloride 98Min., dropping temperature is-5 ~ 10 DEG C, dropwises, condensing reflux reaction 0.5 ~ 2h at 0 ~ 30 DEG C, obtained methyl acrylate second diester and triethylamine hydrochloride mixture; Wherein, unsaturated hydroxy ester and the amount of substance of Acetyl Chloride 98Min. are than 1:(1 ~ 2);
(2) by after methyl acrylate second diester and triethylamine hydrochloride mixture washed with diethylether, suction filtration removing triethylamine hydrochloride, obtain the mixture of unsaturated ester and ether, then distillation removes ether and unnecessary Acetyl Chloride 98Min. at 30 DEG C ~ 60 DEG C, obtained unsaturated ester;
(3) join after formaldehyde solution being mixed with amine in solvent, then adjust ph is 2 ~ 5,50 ~ 80 DEG C are warming up under stirring, reaction 0.5h ~ 1h, continue to be warmed up to 60 ~ 90 DEG C, drip unsaturated ester, after dropwising, at temperature 70 ~ 100 DEG C, react 5 ~ 8h, after purifying, obtain Mannich base; Wherein, in formaldehyde solution, the amount of substance ratio of formaldehyde, amine, unsaturated ester is (1 ~ 3): (1 ~ 1.5): 1; Amine is ammonia, diethylamine or diethanolamine; Solvent is ethanol or deionized water.
6. the preparation method of a kind of multi-functional amphoteric polymeric flocculant according to claim 5, is characterized in that, in described step (1), unsaturated hydroxy ester is Hydroxyethyl acrylate or α-methacrylic acid hydroxyl ethyl ester.
7. the preparation method of a kind of multi-functional amphoteric polymeric flocculant according to claim 5, is characterized in that, in described step (1), acid binding agent is triethylamine, pyridine, sodium hydroxide or potassium hydroxide.
8. the preparation method of a kind of multi-functional amphoteric polymeric flocculant according to claim 5, is characterized in that, in described step (3), the massfraction of formaldehyde solution is 20% ~ 50%.
9. the preparation method of a kind of multi-functional amphoteric polymeric flocculant according to claim 2, it is characterized in that, described sequestrant is ethylenediamine tetraacetic acid (EDTA), methyl ethyl diketone or trisodium phosphate.
10. the preparation method of a kind of multi-functional amphoteric polymeric flocculant according to claim 2, it is characterized in that, described chain-transfer agent is Virahol or sodium formiate; Initiator is one or more or Diisopropyl azodicarboxylate in potassium bromate, potassium sulfite, Potassium Persulphate, Sodium Persulfate; Washing specifically adopts volume ratio to be (2 ~ 4): the ethanol of 1, the mixture washing of acetone 2 ~ 3 times.
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Publication number Priority date Publication date Assignee Title
CN106220522A (en) * 2016-08-09 2016-12-14 陕西科技大学 A kind of Mannich base quarternary ammonium salt compound and preparation method thereof
CN106277264A (en) * 2016-08-25 2017-01-04 陕西科技大学 A kind of both sexes organic high molecular compound and preparation method thereof
CN106380538A (en) * 2016-08-25 2017-02-08 陕西科技大学 Double-effect organic macromolecular compound and preparation method thereof
CN106565508A (en) * 2016-11-14 2017-04-19 烟台智本知识产权运营管理有限公司 Mannich base quaternary ammonium salt oil removing agent for binary compound flooding sewage and preparation method thereof
CN107629164A (en) * 2017-09-18 2018-01-26 广州振清环保技术有限公司 A kind of preparation method of cation type water-soluble polymer polymer
CN107793525A (en) * 2017-09-18 2018-03-13 广州振清环保技术有限公司 A kind of cation type water-soluble polymer polymer
CN107793525B (en) * 2017-09-18 2019-11-08 广州振清环保技术有限公司 A kind of cation type water-soluble polymer polymer
CN107629164B (en) * 2017-09-18 2019-11-12 广州振清环保技术有限公司 A kind of preparation method of cation type water-soluble polymer polymer

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