CN107892372A - Water-soluble quadripolymer molecular brush dyestuff catches sedimentation agent and preparation method thereof and its application - Google Patents

Water-soluble quadripolymer molecular brush dyestuff catches sedimentation agent and preparation method thereof and its application Download PDF

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CN107892372A
CN107892372A CN201711127104.9A CN201711127104A CN107892372A CN 107892372 A CN107892372 A CN 107892372A CN 201711127104 A CN201711127104 A CN 201711127104A CN 107892372 A CN107892372 A CN 107892372A
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side chain
water
polymer
cooh
parts
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CN107892372B (en
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刘锋
陈燕舞
霍应鹏
洪丹
张浥琨
郭志杰
刘祥军
唐秋实
彭琦
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Hefei Jiuzhou Longteng Scientific And Technological Achievement Transformation Co ltd
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Shunde Vocational and Technical College
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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
    • 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
    • C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
    • 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
    • C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
    • C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C08G81/021—Block or graft polymers containing only sequences of polymers of C08C or C08F
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/308—Dyes; Colorants; Fluorescent agents

Abstract

The present invention relates to a kind of water-soluble quadripolymer molecular brush dyestuff to catch sedimentation agent and preparation method thereof and its application, and feature is by main polymer chain poly-hydroxyethyl acrylamide, the carboxylic polymethyl acyloxyethyl trimethyl ammonium chloride of cationic high-molecular side chain terminal, the carboxylic polymethyl tert-butyl acrylate in anionic polymer side chain precursor polymer end, the carboxylic poly- N vinyl formamides in functional polymer side chain precursor polymer end, dimethylformamide（DMF）Solvent, catalyst, (3 dimethylamino-propyl) the carbodiimide iodomethane salt of 1 ethyl 3, potassium hydroxide, 1,2 1,2-diaminocyclohexane tetraacetic acid dianhydrides and carbon disulfide prepare water-soluble quadripolymer molecular brush dyestuff and catch sedimentation agent, and water-soluble quadripolymer molecular brush dyestuff is caught into sedimentation agent and is used to handle the waste water from dyestuff given off in Dyestuff synthesis or dyeing and finishing process and art coatings waste water.With easy to operate, processing cost is low, strong adaptability, and trapping ability is good, and sinking speed is fast, can handle complexation heavy metal ion, the advantages that dye of positive ion, anionic dye and solvay-type heavy metal ion can be captured within the several seconds.

Description

Water-soluble quadripolymer molecular brush dyestuff catch sedimentation agent and preparation method thereof and its Using
Technical field
The invention belongs to water technology and polymer-function material field, and in particular to a kind of quadripolymer molecular brush Dyestuff catches sedimentation agent and preparation method thereof and its application.Its dyestuff mainly given off in Dyestuff synthesis or dyeing and finishing process gives up Applied in water and art coatings waste water, can realize while remove the dye of positive ion, anionic dye and solvay-type of waste water from dyestuff Heavy metal ion.
Background technology
In the last few years, the annual quantity of wastewater effluent in China is up to more than 390 hundred million tons, and wherein trade effluent accounts for 51%, and waste water from dyestuff The 35% of total discharged volume of industrial waste water is accounted for again, but also is being increased year by year with 1% speed.Waste water from dyestuff mostlys come from dyestuff conjunction Into and dyestuff use enterprise, be made up of the dyestuff, the auxiliary agent etc. that are given off in synthesis or dyeing and finishing process.It is at full speed with printing and dyeing industry Development, China are textile production and processing big country, and row occupy first place in the world textile exports volume for many years, the life of annual dyestuff Yield is up to 1.5 × 105Ton, wherein about 10%~15% dyestuff directly can be discharged into water body with waste water, waste water from dyestuff has turned into One of important pollution sources of water body.To strengthen the control of textile dyeing and finishing industrial water pollution, 2012, Environmental Protection Department and national quality were supervised The joint revision of inspection and quarantine general bureau is superintended and directed to issue《Textile dyeing and finishing industrial water pollution thing discharge standard》(GB 4287-2012).According to New discharge standard, using traditional treatment technology, many printing and dyeing enterprises are unable to reach new discharging standards, occur a lot Phenomenon is discharged steathily, and there occurs serious water body environment pollution event.On the whole, current dye wastewater treatment technology can not also Reach discharging standards, the research and development for being badly in need of new material and new technology solve current enterprise's emission problem.Waste water from dyestuff has pole Strong pollution sense, and colored water knows from experience influence solar radiation, is unfavorable for the growth of aquatile, in general biochemical process is difficult to it Handled.The discharge capacity of waste water from dyestuff is also very big, and discharges with intermittence, and water quality is also unstable, and it is useless to belong to refractory reason Water.
Traditional method of wastewater treatment has physico-chemical process, chemical coagulation process, physisorphtion, biochemical process, electrochemical process etc..Change It is that coagulant is added in waste water from dyestuff to learn Coagulation Method, pollutant is formed micelle, by coagulating sedimentation or air supporting, so as to remove Pollutant in waste water.Coagulant sedimentation is widest in practical application.Coagulation Method can remove dyestuff contaminant and its simultaneously His macromolecular suspended contaminant.The structural property of coagulant is depended primarily on to the treatment effect of waste water.What is used at present is mixed Solidifying agent mainly has inorganic coagulant and organic polymer coagulant.Inorganic coagulant is mainly based on aluminium salt and molysite, to glue The dyestuff that body or suspended state are present in waste water has preferable coagulation effect, but smaller for water-soluble dye middle-molecular-weihydroxyethyl , coagulation effect is then poor.Organic polymer coagulant molecular weight is big, and huge number of linear point is separated into after dissolving in water Son is strong to the adsorption bridging ability of the colloidal suspension particle in water.Organic polymer coagulant property is stable, and residue is few, to pH Value requires wider, wherein most representative is exactly polyacrylamide.But polyacrylamide chemical constitution is more single, there is Poor to dye molecule capturing ability, sinking speed is slower, the problems such as can not handling solvay-type heavy metal ion.
The content of the invention
The purpose of the present invention is overcome the deficiencies in the prior art and provides a kind of water-soluble quadripolymer molecular brush dyestuff Sedimentation agent and preparation method thereof and its application are caught, easy to operate, processing cost is low, strong adaptability, and trapping ability is good, sedimentation speed Degree is fast, can handle complexation heavy metal ion, can be captured within the several seconds dye of positive ion, anionic dye and solvay-type heavy metal from Son, the big aggregate particle of fast-growth, realizes quick separating dyestuff and solvay-type heavy metal ion.
In order to achieve the above object, water-soluble quadripolymer molecular brush dyestuff of the invention catches the technical side of sedimentation agent Case, which is achieved in that, is characterized in that the main polymer chain poly-hydroxyethyl acrylamide for including 1~10 part（PHEMAA）, 20~ 50 parts of the carboxylic polymethyl acyloxyethyl trimethyl ammonium chloride of cationic high-molecular side chain terminal（PDMC- COOH）, 20~50 parts of the carboxylic polymethyl tert-butyl acrylate in anionic polymer side chain precursor polymer end (PtBMA-COOH), 5~15 parts of the carboxylic polyvinylformamide in functional polymer side chain precursor polymer end （PNVF-COOH）, 100~500 parts of dimethylformamide（DMF）Solvent, 1~5 part of catalyst are N- hydroxysuccinimidyls acyl Asia Amine (NHS), 1~5 part of 1- ethyls -3- (3- dimethylamino-propyls) carbodiimide iodomethane salt (EDCCH3I), 1~10 part Potassium hydroxide, 1~20 part of 1,2- 1,2-diaminocyclohexane tetraacetic acids dianhydride (CDTAD) and 1~10 part of carbon disulfide；It is above Mass fraction.
In the technical program, the main polymer chain poly-hydroxyethyl acrylamide（PHEMAA）Gathered by general radical Close or controllable living polymerization synthesizes PHEMAA main polymer chains；
It is common free that the cationic high-molecular side chain PDMC-COOH mainly uses azo dicyano valeric acid to pass through for initiator Base polymerization synthesizes the carboxylic polymethyl acyloxyethyl trimethyl ammonium chloride in end（PDMC-COOH）Polymer；
The anionic macromolecule precursor polymer PtBMA-COOH mainly uses azo dicyano valeric acid to lead to for initiator Cross the general radical polymerization synthesis carboxylic polymethyl tert-butyl acrylate in end（PtBMA-COOH）Polymer；
The functional polymer side chain precursor polymer PNVF-COOH mainly uses azo dicyano valeric acid to pass through for initiator The general radical polymerization synthesis carboxylic polyvinylformamide in end（PNVF-COOH）Polymer；
The synthetic method of the 1,2- 1,2-diaminocyclohexane tetraacetic acids dianhydride (CDTAD) is：By 5~20 parts of 1,2- cyclohexanediamine four Acetic acid and 5~20 parts of acetic anhydride are dissolved in 10~30 parts of pyridine, are controlled in 50~70 DEG C, are reacted 20~40 hours, are obtained Obtain 1,2- 1,2-diaminocyclohexane tetraacetic acid dianhydrides.
In order to achieve the above object, water-soluble quadripolymer molecular brush dyestuff of the invention catches the preparation side of sedimentation agent The technical scheme of method, which is achieved in that, is characterized in that 1~10 part of main polymer chain poly-hydroxyethyl acrylamide （PHEMAA）, 20~50 parts of the carboxylic polymethyl acyloxyethyl trimethyl ammonia chloride of cationic high-molecular side chain terminal Ammonium（PDMC-COOH）, 20~50 parts of the carboxylic polymethyl in anionic polymer side chain precursor polymer end Tert-butyl acrylate (PtBMA-COOH) and 5~15 parts of the carboxylic poly N-ethylene in functional polymer side chain precursor polymer end Base formamide（PNVF-COOH）Mixing is dissolved in 100~500 parts of dimethylformamide（DMF）In solvent, 1~5 part of addition is urged Agent is 1- ethyls -3- (3- dimethylamino-propyls) carbodiimide iodomethane of n-hydroxysuccinimide (NHS) and 1~5 part Salt (EDCCH3I), temperature control carries out esterification 10~70 hours in 50~80 DEG C, acquisition poly-hydroxyethyl acrylamide-connect Branch-（Polymethyl acyloxyethyl trimethyl ammonium chloride-random-polymethyl tert-butyl acrylate-is random-poly N-vinyl first Acid amides）(PHEMAA-g-(PDMC-r-PtBMA-r-PNVF))；Add 1~10 part of potassium hydroxide, temperature control in 50~80 DEG C, Reaction is hydrolyzed 12~48 hours, obtains poly-hydroxyethyl acrylamide-grafting-（Polymethyl acyloxyethyl trimethyl chlorine Change ammonium-random-sodium polymethacrylate-it is random-polyvinylamine）（PHEMAA-g-(PDMC-r-PMAANa-r-PVA）)；Again plus Enter 1~20 part of CDTA dianhydride (CDTAD), carry out acylation reaction 5~24 hours, acylation degree scope control 60~99% are made as, obtains poly-hydroxyethyl acrylamide-grafting-（Polymethyl acyloxyethyl trimethyl ammonium chloride-random-poly- Sodium methacrylate-random-polyvinylamine basic ring hexamethylene tetraacetic acid sodium-is random-polyvinylamine）(PHEMAA-g-(PDMC-r- PMAANa-r-PVACDTANa-r-PVA))；1~10 part of carbon disulfide is added, it is anti-to carry out addition in 20~40 DEG C for temperature control Answer 1~3 hour, it is final to obtain poly-hydroxyethyl acrylamide-grafting-（Polymethyl acyloxyethyl trimethyl ammonium chloride-nothing Rule-sodium polymethacrylate-random-polyvinylamine basic ring hexamethylene tetraacetic acid sodium-is random-polyethylene amido dithiocarbamates first Sour sodium）(PHEMAA-g-(PDMC-r-PMAANa-r-PVACDTANa-r-PVACS2Na)) it is water-soluble quadripolymer molecule Brush dyestuff catches sedimentation agent, is mass fraction above.
In the technical program, the poly-hydroxyethyl acrylamide（PHEMAA）The degree of polymerization be 10~500, it is described sun from Subtype polymer side chain PDMC-COOH, anionic polymer side chain precursor polymer PtBMA-COOH and functional polymer The side chain precursor polymer PNVF-COOH degree of polymerization is 10~500, and cationic high-molecular side chain PDMC grafting rates are 1 ~40%, cationic high-molecular side chain PMAANa grafting rates be 1~40%, chelating type side chain PVACDTANa grafting rates be 1~ 15% and help sedimentation type side chain PVACS2Na grafting rate is 1~5%.
In order to achieve the above object, water-soluble quadripolymer molecular brush dyestuff of the invention catches the application of sedimentation agent Technical scheme, which is achieved in that, is characterized in that 0.1~1 part of water-soluble quadripolymer molecular brush dyestuff seizure sedimentation Agent is added in 100~1000 parts of waste water, is stirred 1~5 minute under normal temperature, adjust pH to 2~9, Wastewater Dyes molecule with Water-soluble quadripolymer molecular brush dyestuff catches cationic side chain PDMC and anionic side chain the PMAANa hair of sedimentation agent Raw Electrostatic Absorption, heavy metal ions in wastewater catch the chelating type side chain of sedimentation agent with water-soluble quadripolymer molecular brush dyestuff Chelating absorption occurs for PVACDTANa, adds 0.01~0.1 part of the sedimentation agent that helps, is stirred 1 minute under normal temperature, help sedimentation agent Metal ion settles side chain PVACS by quick with helping for water-soluble quadripolymer molecular brush dyestuff seizure sedimentation agent2Na occurs Chemical precipitation is reacted, and flco of the particle diameter more than 100 μm is generated in 10 seconds and is precipitated, and can quickly realize the cation dye removed in waste water Material, anionic dye and solvay-type heavy metal ion, go out water colorless, reach discharging standards, be mass fraction above.
It is described to help sedimentation agent as calcium chloride, magnesium sulfate, frerrous chloride, ferric trichloride, alchlor in the technical program One or more kinds of any combination.
The present invention compared with prior art, has the following advantages and effect：
1st, the present invention solves the defects of single conventional synthesis family macromolecule dyestuff flocculant structure and seizure poor performance, the present invention There is good electrostatic to inhale to anionic dyes for polymer side chain containing four kinds of difference in functionalitys, cationic high-molecular side chain Attached ability, anionic polymer side chain PMAANa have good Electrostatic Absorption ability to cationic dyes, chelate side chain Chelating absorption occurs for PVACDTANa heavy metals ion, is helping sedimentation side chain PVACS2Under Na synergy, PVACS2Na is high Molecular side chain reaches efficiently seizure and rapid subsidence function, gone out with helping sedimentation agent metal ion that chemical precipitation reaction quickly occurs Water is substantially colorless, reaches discharging standards；
2nd, the present invention has the technical advantage of sinking speed, chelating precipitation reaction can occur, in the several seconds in the case where helping sedimentation agent on a small quantity Big aggregation is quickly generated, caused sludge quantity is few；
3rd, the present invention's has dual-use function, can catch dyestuff and heavy metal ion simultaneously, solving traditional flocculant can not locate Manage solvay-type Heavy metal ions in waste water from dyestuff.
Embodiment
With reference to embodiment, the present invention is described in further detail, but the implementation of the present invention is not limited to this. Involved number is mass fraction in following examples.
Embodiment one
It is that a kind of water-soluble quadripolymer molecular brush dyestuff catches sedimentation agent, is prepared by following steps：
Step 1 synthesizes PHEMAA main polymer chains
Take 1 part azodiisobutyronitrile initiator, 100 parts of hydroxyethyl acrylamide（HEMAA）, 400 part methanol, in nitrogen Protect lower 80 DEG C to carry out polymerisation 1 hour, obtain the degree of polymerization（DP）For 30 poly-hydroxyethyl acrylamide（PHEMAA）；
Step 2 synthesizing cationic type polymer side chain PDMC-COOH, anionic polymer side chain precursor polymer PtBMA-COOH and functional polymer side chain precursor polymer PNVF-COOH
Cationic high-molecular side chain PDMC-COOH synthesis：Take 1 part azo dicyano valeric acid initiator, 100 parts of methyl Acrylyl oxy-ethyl-trimethyl salmiac（DMC）With 300 parts of water, 60 DEG C carry out Raolical polymerizable 2 under nitrogen protection Hour, obtain the degree of polymerization（DP）For 30 PDMC-COOH；
Anionic polymer side chain precursor polymer PtBMA-COOH synthesis：1 part of azo dicyano valeric acid is taken to trigger Agent, 100 parts of Tert-butyl Methacrylate（tBMA）, 300 parts of toluene, under nitrogen protection 60 DEG C to carry out radical polymerizations anti- Answer 1 hour, obtain the degree of polymerization（DP）For 30 PtBMA-COOH；
Functional polymer side chain precursor polymer PNVF-COOH synthesis：Take 1 part azo dicyano valeric acid initiator, 100 The N- vinyl formamides of part（NVF）With 600 parts of water, 50 DEG C carry out Raolical polymerizable 1 hour under nitrogen protection, obtain To the degree of polymerization（DP）For 20 PNVF-COOH；
Step 3 synthesis 1,2- 1,2-diaminocyclohexane tetraacetic acids dianhydride (CDTAD)
5 parts of CDTA and 5 parts of acetic anhydride are dissolved in 10 parts of pyridine, are controlled in 50 DEG C, reaction 20 hours, obtain CDTA dianhydride；
Step 4 synthesis PHEMAA-g- (PDMC-r-PMAANa-r-PVACDTANa-r-PVACS2Na)
By 1 part of poly-hydroxyethyl acrylamide resulting in step 1（PHEMAA）With 20 parts of sun resulting in step 2 Ionic polymer side chain PDMC-COOH, 20 parts of anionic polymer side chain precursor polymer PtBMA-COOH and 5 parts Functional polymer side chain precursor polymer PNVF-COOH mixing be dissolved in 100 parts of dimethylformamide（DMF）In solvent, The catalyst for adding 1 part is that n-hydroxysuccinimide (NHS) and 1 part 1- ethyls -3- (3- dimethylamino-propyls) carbon two are sub- Amine iodomethane salt (EDCCH3I), temperature control carries out esterification 70 hours in 50 DEG C, makes each unit of main polymer chain Hydroxyl functional groups and the carboxylic cationic high-molecular side chain PDMC-COOH in end, the carboxylic anionic in end are high Molecular side chain precursor polymer PtBMA and the carboxylic functional polymer side chain precursor polymer PNVF in end are randomly sent out Raw esterification, obtains poly-hydroxyethyl acrylamide-grafting-（Polymethyl acyloxyethyl trimethyl ammonium chloride-random-poly- Tert-butyl Methacrylate-random-polyvinylformamide）(PHEMAA-g-(PDMC-r-PtBMA-r-PNVF))；Again plus 1 The potassium hydroxide of part, temperature control is in 80 DEG C, to grafting on main polymer chain anionic polymer side chain precursor polymer PtBMA And reaction 48 hours is hydrolyzed in functional polymer side chain precursor polymer PNVF, poly-hydroxyethyl acrylamide-grafting-is obtained （Polymethyl acyloxyethyl trimethyl ammonium chloride-random-sodium polymethacrylate-is random-polyvinylamine）（PHEMAA-g- (PDMC-r-PMAANa-r-PVA）)；Add 5 parts synthesized in step 3 of 1,2- 1,2-diaminocyclohexane tetraacetic acid dianhydrides (CDTAD), acylation reaction 24 hours, acylation degree 80%, poly-hydroxyethyl acrylamide-grafting-is obtained（Polymethyl acyl Random-polyvinylamine basic ring hexamethylene tetraacetic acid the sodium-of oxy-ethyl-trimethyl salmiac-random-sodium polymethacrylate-is random- Polyvinylamine）(PHEMAA-g-(PDMC-r-PMAANa-r-PVACDTANa-r-PVA))；Add 1 part of carbon disulfide, temperature control In 40 DEG C, addition reaction 1 hour is carried out, it is final to obtain water-soluble poly hydroxyethyl acrylamide-grafting-（Polymethyl acyl-oxygen Ethyl-trimethyl salmiac-random-polyvinylamine basic ring hexamethylene tetraacetic acid sodium-of random-sodium polymethacrylate-is random-poly- Ethene amido nabam）(PHEMAA-g-(PDMC-r-PMAANa-r-PVACDTANa-r-PVACS2Na)) i.e. Water-soluble quadripolymer molecular brush dyestuff catches sedimentation agent.Using nmr determination PDMC, PMAANa, PVACDTANa And PVACS2The grafting rate of Na side chains is respectively 17%, 18%, 4% and 1%.
In the present embodiment, water-soluble quadripolymer molecular brush dyestuff catches the application of sedimentation agent
Take the water-soluble quadripolymer molecular brush dyestuff of the present embodiment to catch sedimentation agent and do waste water from dyestuff test, take 100 parts to contain The mg/L of methylene blue 50 and the mg/L of methyl red 20 waste water, it is added to 0.1 part of water-soluble quadripolymer molecular brush dyestuff Sedimentation agent is caught, is stirred 1 minute under normal temperature, pH value of waste water is adjusted to 2.0 using 0.1 mol/L hydrochloric acid, adds 0.01 part Sedimentation agent calcium chloride is helped, is stirred under normal temperature and flco precipitation filtering of the particle diameter more than 110 μm is generated in 1 minute, 10 seconds, using purple Outer absorption spectrophotometer measure filtrate Methylene Blue concentration is 0.04 mg/L and methyl red concentration is 0.03 mg/L, removing Efficiency>99%.
Embodiment two
It is that a kind of water-soluble quadripolymer molecular brush dyestuff catches sedimentation agent, is prepared by following steps：
Step 1 synthesizes PHEMAA main polymer chains
Take 1 part 2- isobutyl ethyl bromides initiator, 1 part CuBr and 1 part of 4,4- bipyridyls（BPy）, 100 parts of ethoxy third Acrylamide（HEMAA）, 100 part methanol, 60 DEG C carry out polymerisation 5 hours under nitrogen protection, obtain the degree of polymerization（DP）For 200 poly-hydroxyethyl acrylamide（PHEMAA）；
Step 2 synthesizing cationic type polymer side chain PDMC-COOH, anionic polymer side chain precursor polymer PtBMA-COOH and functional polymer side chain precursor polymer PNVF-COOH
Cationic high-molecular side chain PDMC-COOH synthesis：Take 1 part azo dicyano valeric acid initiator, 200 parts of methyl Acrylyl oxy-ethyl-trimethyl salmiac（DMC）With 100 parts of water, 60 DEG C carry out Raolical polymerizable 10 under nitrogen protection Hour, obtain the degree of polymerization（DP）For 120 PDMC-COOH；
Anionic polymer side chain precursor polymer PtBMA-COOH synthesis：1 part of azo dicyano valeric acid is taken to trigger Agent, 300 parts of Tert-butyl Methacrylate（tBMA）, 100 parts of toluene, under nitrogen protection 70 DEG C to carry out radical polymerizations anti- Answer 20 hours, obtain the degree of polymerization（DP）For 130 PtBMA-COOH；
Functional polymer side chain precursor polymer PNVF-COOH synthesis：Take 1 part azo dicyano valeric acid initiator, 200 The N- vinyl formamides of part（NVF）With 100 parts of water, 70 DEG C carry out Raolical polymerizable 10 hours under nitrogen protection, Obtain the degree of polymerization（DP）For 110 PNVF-COOH；
Step 3 synthesis 1,2- 1,2-diaminocyclohexane tetraacetic acids dianhydride (CDTAD)
10 parts of CDTA and 10 parts of acetic anhydride are dissolved in 30 parts of pyridine, are controlled in 70 DEG C, instead Answer 40 hours, obtain CDTA dianhydride；
Step 4 synthesis PHEMAA-g- (PDMC-r-PMAANa-r-PVACDTANa-r-PVACS2Na)
By 2 parts of poly-hydroxyethyl acrylamide resulting in step 1（PHEMAA）With 40 parts of sun resulting in step 2 Ionic polymer side chain PDMC-COOH, 40 parts of anionic polymer side chain precursor polymer PtBMA-COOH and 10 The functional polymer side chain precursor polymer PNVF-COOH mixing of part is dissolved in 300 parts of dimethylformamides（DMF）In solvent, The catalyst for adding 3 parts is that n-hydroxysuccinimide (NHS) and 3 parts 1- ethyls -3- (3- dimethylamino-propyls) carbon two are sub- Amine iodomethane salt (EDCCH3I), temperature control carries out esterification 40 hours in 65 DEG C, makes each unit of main polymer chain Hydroxyl functional groups and the carboxylic cationic high-molecular side chain PDMC-COOH in end, the carboxylic anionic in end are high Molecular side chain precursor polymer PtBMA and the carboxylic functional polymer side chain precursor polymer PNVF in end are randomly sent out Raw esterification, obtains poly-hydroxyethyl acrylamide-grafting-（Polymethyl acyloxyethyl trimethyl ammonium chloride-random-poly- Tert-butyl Methacrylate-random-polyvinylformamide）(PHEMAA-g-(PDMC-r-PtBMA-r-PNVF))；Again plus 5 The potassium hydroxide of part, temperature control is in 60 DEG C, to grafting on main polymer chain anionic polymer side chain precursor polymer PtBMA And reaction 24 hours is hydrolyzed in functional polymer side chain precursor polymer PNVF, poly-hydroxyethyl acrylamide-grafting-is obtained （Polymethyl acyloxyethyl trimethyl ammonium chloride-random-sodium polymethacrylate-is random-polyvinylamine）（PHEMAA-g- (PDMC-r-PMAANa-r-PVA）)；Add 10 parts synthesized in step 3 of 1,2- 1,2-diaminocyclohexane tetraacetic acid dianhydrides (CDTAD), acylation reaction 12 hours, acylation degree 75%, poly-hydroxyethyl acrylamide-grafting-is obtained（Polymethyl acyl Random-polyvinylamine basic ring hexamethylene tetraacetic acid the sodium-of oxy-ethyl-trimethyl salmiac-random-sodium polymethacrylate-is random- Polyvinylamine）(PHEMAA-g-(PDMC-r-PMAANa-r-PVACDTANa-r-PVA))；Add 5 parts of carbon disulfide, temperature control In 30 DEG C, addition reaction 2 hours is carried out, it is final to obtain water-soluble poly hydroxyethyl acrylamide-grafting-（Polymethyl acyl-oxygen Ethyl-trimethyl salmiac-random-polyvinylamine basic ring hexamethylene tetraacetic acid sodium-of random-sodium polymethacrylate-is random-poly- Ethene amido nabam）(PHEMAA-g-(PDMC-r-PMAANa-r-PVACDTANa-r-PVACS2Na)) i.e. Water-soluble quadripolymer molecular brush dyestuff catches sedimentation agent.Using nmr determination PDMC, PMAANa, PVACDTANa And PVACS2The grafting rate of Na side chains is respectively 26%, 24%, 6% and 2%.
In the present embodiment, water-soluble quadripolymer molecular brush dyestuff catches the application of sedimentation agent
Take the water-soluble quadripolymer molecular brush dyestuff of the present embodiment to catch sedimentation agent and do waste water from dyestuff test, take 500 parts Waste water containing the mg/L of rhodamine B 60, Congo red 60 mg/L, cadmium ion 3mg/L and the mg/L of citric acid 0.5, is added to 0.5 part Water-soluble quadripolymer molecular brush dyestuff catch sedimentation agent, stir 3 minutes under normal temperature, using the regulation of 0.1 mol/L hydrochloric acid PH value of waste water adds 0.05 part and helps sedimentation agent ferric trichloride to 5.0, stirs that to generate particle diameter in 1 minute, 2 seconds big under normal temperature Precipitated in 420 μm of flcos, filtering, filtrate is determined using Ultravioblet spectrophotometer and atomic absorption spectrophotometer respectively Middle rhodamine B concentration is 0.05 mg/L, Congo red concentration is 0.03mg/L and Cd2+Ion concentration is 0.03 mg/L, removing effect Rate>99%.
Embodiment three
It is that a kind of water-soluble quadripolymer molecular brush dyestuff catches sedimentation agent, is prepared by following steps：
Step 1 synthesizes PHEMAA main polymer chains
Take 1 part 2- isobutyl ethyl bromides initiator, 1 part CuBr and 1 part of 4,4- bipyridyls（BPy）, 400 parts of ethoxy third Acrylamide（HEMAA）, 100 part methanol, 70 DEG C carry out polymerisation 10 hours under nitrogen protection, obtain the degree of polymerization（DP）For 300 poly-hydroxyethyl acrylamide（PHEMAA）；
Step 2 synthesizing cationic type polymer side chain PDMC-COOH, anionic polymer side chain precursor polymer PtBMA-COOH and functional polymer side chain precursor polymer PNVF-COOH
Cationic high-molecular side chain PDMC-COOH synthesis：Take 1 part azo dicyano valeric acid initiator, 300 parts of methyl Acrylyl oxy-ethyl-trimethyl salmiac（DMC）With 100 parts of water, 60 DEG C carry out Raolical polymerizable 12 under nitrogen protection Hour, obtain the degree of polymerization（DP）For 190 PDMC-COOH；
Anionic polymer side chain precursor polymer PtBMA-COOH synthesis：1 part of azo dicyano valeric acid is taken to trigger Agent, 400 parts of Tert-butyl Methacrylate（tBMA）, 100 parts of toluene, under nitrogen protection 70 DEG C to carry out radical polymerizations anti- Answer 15 hours, obtain the degree of polymerization（DP）For 250 PtBMA-COOH；
Functional polymer side chain precursor polymer PNVF-COOH synthesis：Take 1 part azo dicyano valeric acid initiator, 400 The N- vinyl formamides of part（NVF）With 100 parts of water, 60 DEG C carry out Raolical polymerizable 18 hours under nitrogen protection, Obtain the degree of polymerization（DP）For 350 PNVF-COOH；
Step 3 synthesis 1,2- 1,2-diaminocyclohexane tetraacetic acids dianhydride (CDTAD)
20 parts of CDTA and 20 parts of acetic anhydride are dissolved in 20 parts of pyridine, are controlled in 60 DEG C, instead Answer 30 hours, obtain CDTA dianhydride；
Step 4 synthesis PHEMAA-g- (PDMC-r-PMAANa-r-PVACDTANa-r-PVACS2Na)
By 3 parts of poly-hydroxyethyl acrylamide resulting in step 1（PHEMAA）With 50 parts of sun resulting in step 2 Ionic polymer side chain PDMC-COOH, 50 parts of anionic polymer side chain precursor polymer PtBMA-COOH and 15 The functional polymer side chain precursor polymer PNVF-COOH mixing of part is dissolved in 500 parts of dimethylformamides（DMF）In solvent, The catalyst for adding 5 parts is that n-hydroxysuccinimide (NHS) and 5 parts 1- ethyls -3- (3- dimethylamino-propyls) carbon two are sub- Amine iodomethane salt (EDCCH3I), temperature control carries out esterification 10 hours in 50 DEG C, makes each unit of main polymer chain Hydroxyl functional groups and the carboxylic cationic high-molecular side chain PDMC-COOH in end, the carboxylic anionic in end are high Molecular side chain precursor polymer PtBMA and the carboxylic functional polymer side chain precursor polymer PNVF in end are randomly sent out Raw esterification, obtains poly-hydroxyethyl acrylamide-grafting-（Polymethyl acyloxyethyl trimethyl ammonium chloride-random-poly- Tert-butyl Methacrylate-random-polyvinylformamide）(PHEMAA-g-(PDMC-r-PtBMA-r-PNVF))；Again plus 10 parts of potassium hydroxide, temperature control is in 50 DEG C, to grafting on main polymer chain anionic polymer side chain precursor polymer PtBMA and functional polymer side chain precursor polymer PNVF, which is hydrolyzed, to react 12 hours, and acquisition poly-hydroxyethyl acrylamide- Grafting-（Polymethyl acyloxyethyl trimethyl ammonium chloride-random-sodium polymethacrylate-is random-polyvinylamine） （PHEMAA-g-(PDMC-r-PMAANa-r-PVA）)；Add 20 parts of the 1,2- 1,2-diaminocyclohexane tetraacetic acids synthesized in step 3 Dianhydride (CDTAD), acylation reaction 5 hours, acylation degree control are 69%, obtain poly-hydroxyethyl acrylamide-grafting-（Poly- methyl Acrylyl oxy-ethyl-trimethyl salmiac-random-polyvinylamine basic ring hexamethylene tetraacetic acid the sodium-of random-sodium polymethacrylate- Randomly-polyvinylamine）(PHEMAA-g-(PDMC-r-PMAANa-r-PVACDTANa-r-PVA))；Add 10 parts of curing Carbon, temperature control carries out addition reaction 3 hours in 20 DEG C, final to obtain water-soluble poly hydroxyethyl acrylamide-grafting-（Poly- methyl-prop Alkene acyloxyethyl trimethyl ammonium chloride-random-sodium polymethacrylate-is random-polyvinylamine basic ring hexamethylene tetraacetic acid sodium-nothing Rule-polyethylene amido nabam）(PHEMAA-g-(PDMC-r-PMAANa-r-PVACDTANa-r- PVACS2Na it is)) that water-soluble quadripolymer molecular brush dyestuff catches sedimentation agent.Using nmr determination PDMC, PMAANa, PVACDTANa and PVACS2The grafting rate of Na side chains is respectively 35%, 36%, 11% and 5%.
In the present embodiment, water-soluble quadripolymer molecular brush dyestuff catches the application of sedimentation agent
Take the water-soluble quadripolymer molecular brush dyestuff of the present embodiment to catch sedimentation agent and do waste water from dyestuff test, take 1000 parts Waste water containing the mg/L of crystal violet 30, the mg/L of methyl orange 30, lead ion 4mg/L and citric acid 0.2mg/L, the water of 1.0 parts of addition Dissolubility quadripolymer molecular brush dyestuff is caught in sedimentation agent, is stirred 5 minutes under normal temperature, is adjusted using 0.1 mol/L potassium hydroxide PH value of waste water is saved to 9.0,0.1 part is added and helps sedimentation agent alchlor, generation particle diameter in 1 minute, 5 seconds stir under normal temperature big Precipitated in 200 μm of flcos, filtering, filter is determined using Ultravioblet spectrophotometer and atomic absorption spectrophotometer respectively In liquid crystal violet concentration be 0.06 mg/L, methyl orange concentration be 0.05 mg/L and Pb2+Ion concentration is 0.04 mg/L, removing Efficiency>99%.
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment Limitation, other any Spirit Essences without departing from the present invention with made under principle change, modification, replacement, combine, simplification, Equivalent substitute mode is should be, is included within protection scope of the present invention.

Claims (6)

1. a kind of water-soluble quadripolymer molecular brush dyestuff catches sedimentation agent, it is characterised in that includes 1~10 part of polymer Main chain poly-hydroxyethyl acrylamide（PHEMAA）, 20~50 parts of the carboxylic poly- methyl-prop of cationic high-molecular side chain terminal Alkene acyloxyethyl trimethyl ammonium chloride（PDMC-COOH）, 20~50 parts of anionic polymer side chain precursor polymer end Hold carboxylic polymethyl tert-butyl acrylate (PtBMA-COOH), 5~15 parts of functional polymer side chain precursor polymer The carboxylic polyvinylformamide in end（PNVF-COOH）, 100~500 parts of dimethylformamide（DMF）Solvent, 1~ 5 parts of catalyst is n-hydroxysuccinimide (NHS), 1~5 part 1- ethyls -3- (3- dimethylamino-propyls) carbodiimide Iodomethane salt (EDCCH3I), 1~10 part of potassium hydroxide, 1~20 part of 1,2- 1,2-diaminocyclohexane tetraacetic acids dianhydride (CDTAD) And 1~10 part of carbon disulfide；It is mass fraction above.
2. water-soluble quadripolymer molecular brush dyestuff according to claim 1 catches sedimentation agent, it is characterised in that：
The main polymer chain poly-hydroxyethyl acrylamide（PHEMAA）Pass through general radical polymerization or controllable living polymerization Synthesize PHEMAA main polymer chains；
It is common free that the cationic high-molecular side chain PDMC-COOH mainly uses azo dicyano valeric acid to pass through for initiator Base polymerization synthesizes the carboxylic polymethyl acyloxyethyl trimethyl ammonium chloride in end（PDMC-COOH）Polymer；
The anionic macromolecule precursor polymer PtBMA-COOH mainly uses azo dicyano valeric acid to lead to for initiator Cross the general radical polymerization synthesis carboxylic polymethyl tert-butyl acrylate in end（PtBMA-COOH）Polymer；
The functional polymer side chain precursor polymer PNVF-COOH mainly uses azo dicyano valeric acid to pass through for initiator The general radical polymerization synthesis carboxylic polyvinylformamide in end（PNVF-COOH）Polymer；
The synthetic method of the 1,2- 1,2-diaminocyclohexane tetraacetic acids dianhydride (CDTAD) is：By 5~20 parts of 1,2- cyclohexanediamine four Acetic acid and 5~20 parts of acetic anhydride are dissolved in 10~30 parts of pyridine, are controlled in 50~70 DEG C, are reacted 20~40 hours, are obtained Obtain 1,2- 1,2-diaminocyclohexane tetraacetic acid dianhydrides.
3. a kind of water-soluble quadripolymer molecular brush dyestuff catches the preparation method of sedimentation agent, it is characterised in that by 1~10 part Main polymer chain poly-hydroxyethyl acrylamide（PHEMAA）, 20~50 parts cationic high-molecular side chain terminal it is carboxylic Polymethyl acyloxyethyl trimethyl ammonium chloride（PDMC-COOH）, 20~50 parts of anionic polymer side chain presoma The carboxylic polymethyl tert-butyl acrylate of polymer ends (PtBMA-COOH) and 5~15 parts of functional polymer side chain forerunner The carboxylic polyvinylformamide of body polymer ends（PNVF-COOH）Mixing is dissolved in 100~500 parts of dimethyl formyl Amine（DMF）In solvent, the catalyst for adding 1~5 part is the 1- ethyl -3- (3- of n-hydroxysuccinimide (NHS) and 1~5 part Dimethylamino-propyl) carbodiimide iodomethane salt (EDCCH3I), it is small to carry out esterification 10~70 in 50~80 DEG C for temperature control When, obtain poly-hydroxyethyl acrylamide-grafting-（Polymethyl acyloxyethyl trimethyl ammonium chloride-random-polymethyl Tert-butyl acrylate-random-polyvinylformamide）(PHEMAA-g-(PDMC-r-PtBMA-r-PNVF))；Add 1~10 part Potassium hydroxide, in 50~80 DEG C reaction is hydrolyzed 12~48 hours in temperature control, obtains poly-hydroxyethyl acrylamide-grafting- （Polymethyl acyloxyethyl trimethyl ammonium chloride-random-sodium polymethacrylate-is random-polyvinylamine）（PHEMAA-g- (PDMC-r-PMAANa-r-PVA）)；1~20 part of CDTA dianhydride (CDTAD) is added, carries out acyl group Change reaction 5~24 hours, acylation degree scope control is 60~99%, obtains poly-hydroxyethyl acrylamide-grafting-（Polymethyl Acyloxyethyl trimethyl ammonium chloride-random-sodium polymethacrylate-is random-polyvinylamine basic ring hexamethylene tetraacetic acid sodium-nothing Rule-polyvinylamine）(PHEMAA-g-(PDMC-r-PMAANa-r-PVACDTANa-r-PVA))；Add 1~10 part of two sulphur Change carbon, temperature control carries out addition reaction 1~3 hour in 20~40 DEG C, final to obtain poly-hydroxyethyl acrylamide-grafting-（Poly- first Base acrylyl oxy-ethyl-trimethyl salmiac-random-sodium polymethacrylate-is random-polyvinylamine basic ring hexamethylene tetraacetic acid Sodium-random-polyethylene amido nabam）(PHEMAA-g-(PDMC-r-PMAANa-r-PVACDTANa-r- PVACS2Na it is)) that water-soluble quadripolymer molecular brush dyestuff catches sedimentation agent, is mass fraction above.
4. the preparation method of water-soluble quadripolymer molecular brush according to claim 3, it is characterised in that the poly- hydroxyl Ethyl acrylamide（PHEMAA）The degree of polymerization be 10~500, the cationic high-molecular side chain PDMC-COOH, anion Type polymer side chain precursor polymer PtBMA-COOH and functional polymer side chain precursor polymer PNVF-COOH polymerization Degree is 10~500, and cationic high-molecular side chain PDMC grafting rates are that 1~40%, cationic high-molecular side chain PMAANa connects Branch rate is 1~40%, chelating type side chain PVACDTANa grafting rates are 1~15% and help sedimentation type side chain PVACS2Na grafting rate For 1~5%.
5. a kind of water-soluble quadripolymer molecular brush dyestuff catches the application of sedimentation agent, it is characterised in that by 0.1~1 part of water Dissolubility quadripolymer molecular brush dyestuff catches sedimentation agent and is added in 100~1000 parts of waste water, and 1~5 point is stirred under normal temperature Clock, adjusts pH to 2~9, and Wastewater Dyes molecule catches the cation of sedimentation agent with water-soluble quadripolymer molecular brush dyestuff Electrostatic Absorption, heavy metal ions in wastewater and water-soluble quadripolymer occur for type side chain PDMC and anionic side chain PMAANa Chelating absorption occurs for the chelating type side chain PVACDTANa that molecular brush dyestuff catches sedimentation agent, and it is heavy to add 0.01~0.1 part help Depressant prescription, stir 1 minute under normal temperature, help the metal ion of sedimentation agent quickly will catch with water-soluble quadripolymer molecular brush dyestuff Sedimentation agent helps sedimentation side chain PVACS2Chemical precipitation reaction occurs for Na, and flco of the particle diameter more than 100 μm is generated in 10 seconds and is precipitated, The dye of positive ion, anionic dye and the solvay-type heavy metal ion removed in waste water can be quickly realized, goes out water colorless, reaches state Family's discharge standard, is mass fraction above.
6. water-soluble quadripolymer molecular brush dyestuff catches sedimentation agent according to claim 5, it is characterised in that described to help Sedimentation agent is calcium chloride, magnesium sulfate, frerrous chloride, ferric trichloride, one or more kinds of any combination of alchlor.
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