CN107879451A - The water-soluble ter-polymers molecular brush dye of positive ion catches sedimentation agent and preparation method thereof and its application - Google Patents

The water-soluble ter-polymers molecular brush dye of positive ion catches sedimentation agent and preparation method thereof and its application Download PDF

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CN107879451A
CN107879451A CN201711127247.XA CN201711127247A CN107879451A CN 107879451 A CN107879451 A CN 107879451A CN 201711127247 A CN201711127247 A CN 201711127247A CN 107879451 A CN107879451 A CN 107879451A
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water
side chain
polymer
parts
phemaa
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CN107879451B (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
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/308—Dyes; Colorants; Fluorescent agents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/30—Nature of the water, waste water, sewage or sludge to be treated from the textile industry

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

Abstract

The present invention relates to a kind of water-soluble ter-polymers molecular brush dye of positive ion to catch sedimentation agent and preparation method thereof and its application,Feature is by main polymer chain poly-hydroxyethyl acrylamide,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,Catalyst is N HOSu NHSs,1 ethyl 3 (3 dimethylamino-propyl) carbodiimide iodomethane salt,Sodium hydroxide,1,2 1,2-diaminocyclohexane tetraacetic acid dianhydrides and carbon disulfide prepare the water-soluble ter-polymers molecular brush dye of positive ion and catch sedimentation agent,And the water-soluble ter-polymers molecular brush dye of positive ion 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.It has that trapping ability is good, sinking speed speed, the defects of handling complexation heavy metal ion, can capture the dye of positive ion and solvay-type heavy metal ion within the several seconds, the big aggregation of fast-growth, the advantages that realizing the purpose of quick separating dyestuff.

Description

The water-soluble ter-polymers molecular brush dye of positive ion catches sedimentation agent and its preparation side Method and its application
Technical field
The invention belongs to water technology and polymer-function material field, and in particular to a kind of ter-polymers molecular brush The dye of positive ion catches sedimentation agent and preparation method thereof and its application, what it mainly gave off in Dyestuff synthesis or dyeing and finishing process Applied in waste water from dyestuff and art coatings waste water, the water-soluble ter-polymers molecular brush dye of positive ion catches sedimentation agent and can realized The dye of positive ion molecule and solvay-type heavy metal ion of waste water from dyestuff are removed simultaneously.
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 be overcome the deficiencies in the prior art and provide a kind of water-soluble ter-polymers molecular brush sun from Sub- dyestuff catches sedimentation agent and preparation method thereof and its application, and trapping ability is good, sinking speed speed, can handle complexing heavy metal The defects of ion, the dye of positive ion and solvay-type heavy metal ion can be captured within the several seconds, the big aggregation of fast-growth, is realized The purpose of quick separating dyestuff, there are efficiently seizure and rapid subsidence function.
In order to achieve the above object, the water-soluble ter-polymers molecular brush dye of positive ion of the invention catches sedimentation agent Technical scheme, which is achieved in that, is characterized in that the main polymer chain poly-hydroxyethyl acrylamide for including 1~10 part （PHEMAA）, 20~100 parts of the carboxylic polymethylacrylic acid uncle in anionic polymer side chain precursor polymer end Butyl ester (PtBMA-COOH), 5~30 parts of the carboxylic poly N-vinyl first in functional polymer side chain precursor polymer end Acid amides（PNVF-COOH）, 100~500 parts of dimethylformamide（DMF）, 1~5 part of catalyst be N- hydroxysuccinimidyls acyl Asia Amine (NHS), 1~5 part of 1- ethyls -3- (3- dimethylamino-propyls) carbodiimide iodomethane salt (EDCCH3I), 1~10 part Sodium hydroxide, 1~20 part of 1,2- 1,2-diaminocyclohexane tetraacetic acids dianhydride (CDTA) and 1~10 part of carbon disulfide；It is above Mass fraction.
In the technical program, the main polymer chain poly-hydroxyethyl acrylamide（PHEMAA）It is to pass through general radical Polymerization or controllable living polymerization synthesis PHEMAA main polymer chains；
Anionic polymer side chain precursor polymer PtBMA-COOH and functional polymer the side chain precursor polymer PNVF-COOH mainly uses azo dicyano valeric acid to be synthesized for initiator by general radical polymerization, and end is carboxylic to gather Tert-butyl Methacrylate（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 (CDTA) is：By 5~20 parts of 1,2- cyclohexanediamine tetrems Acid and 5~20 parts of acetic anhydrides are dissolved in 10~30 parts of pyridine, are controlled in 50~70 DEG C, are reacted 20~40 hours, obtain 1, 2- 1,2-diaminocyclohexane tetraacetic acid dianhydrides.
In order to achieve the above object, the water-soluble ter-polymers molecular brush dye of positive ion of the invention catches sedimentation agent The technical scheme of preparation method, which is achieved in that, is characterized in that 1~10 part of main polymer chain poly-hydroxyethyl acryloyl Amine（PHEMAA）, 20~100 parts of the carboxylic polymethylacrylic acid in anionic polymer side chain precursor polymer end The tert-butyl ester (PtBMA-COOH) and 5~30 parts of the carboxylic poly N-vinyl in functional polymer side chain precursor polymer end Formamide（PNVF-COOH）Mixing is dissolved in 100~500 parts of dimethylformamide（DMF）In solvent, 1~5 part of catalysis is added Agent is 1- ethyls -3- (3- dimethylamino-propyls) carbodiimide iodomethane salt of n-hydroxysuccinimide (NHS) and 1~5 part (EDC·CH3I), temperature control carries out esterification 10~70 hours in 50~80 DEG C, obtains poly-hydroxyethyl acrylamide-grafting- （Polymethyl tert-butyl acrylate-random-polyvinylformamide）(PHEMAA-g-(PtBMA-r-PNVF))；Add 1~ In 50~80 DEG C reaction is hydrolyzed 12~48 hours in 10 part sodium hydroxide, temperature control, acquisition poly-hydroxyethyl acrylamide-connect Branch-（Sodium polymethacrylate-random-polyvinylamine）（PHEMAA-g-(PMAANa-r-PVA）)；The 1 of 1~20 part is added, 2- 1,2-diaminocyclohexane tetraacetic acids dianhydride (CDTA), acylation reaction 5~24 hours, acylation degree scope control are 60~99%, are gathered Hydroxyethyl acrylamide-grafting-（Sodium polymethacrylate-random-polyvinylamine basic ring hexamethylene tetraacetic acid sodium-random-poly- second Enamine）(PHEMAA-g-(PMAANa-r-PVACDTANa-r-PVA))；Add 1~10 part of carbon disulfide, temperature control in 20~ 40 DEG C, addition reaction 1~3 hour is carried out, it is final to obtain water-soluble poly hydroxyethyl acrylamide-grafting-（Polymethylacrylic acid Sodium-random-polyvinylamine basic ring hexamethylene tetraacetic acid sodium-is random-polyethylene amido nabam）(PHEMAA-g- ( PMAANa-r-PVACDTANa-r-PVACS2Na it is)) that the water-soluble ter-polymers molecular brush dye of positive ion catches sedimentation Agent；It is mass fraction above.
In the technical program, the poly-hydroxyethyl acrylamide（PHEMAA）The degree of polymerization be 10~200, it is described it is cloudy from Subtype polymer side chain precursor polymer PtBMA-COOH's and functional polymer side chain precursor polymer PNVF-COOH is poly- Right is 10~200, and cationic high-molecular side chain PMAANa grafting rate is 1~80%, chelating type polymer side chain PVACDTANa grafting rate 1~20% and help sedimentation polymer side chain PVACS2Na grafting rate is 1~5%.
In order to achieve the above object, the water-soluble ter-polymers molecular brush dye of positive ion of the invention catches sedimentation agent The technical scheme of application, which is achieved in that, is characterized in that 0.1~1 part of water-soluble poly hydroxyethyl acrylamide-grafting- （Sodium polymethacrylate-random-polyvinylamine basic ring hexamethylene tetraacetic acid sodium-is random-polyethylene amido aminodithioformic acid Sodium）(PHEMAA-g-(PMAANa-r-PVACDTANa-r-PVACS2Na)) it is added in 100~1000 parts of waste water, under normal temperature Stirring 1~5 minute, adjust pH to 6~9, waste water cationic dye molecule and water-soluble poly hydroxyethyl acrylamide-grafting- （Sodium polymethacrylate-random-polyvinylamine basic ring hexamethylene tetraacetic acid sodium-is random-polyethylene amido aminodithioformic acid Sodium）（PHEMAA-g-(PMAANa-r-PVACDTANa-r-PVACS2Na)）Anionic side chain PAANa occur Electrostatic Absorption, Heavy metal ions in wastewater and ter-polymers molecular brush (PHEMAA-g- (PMAANa-r-PVACDTANa-r-PVACS2Na)) Chelating side chain PVACDTANa chelating absorption occurs, add 0.01~0.1 part of the sedimentation agent that helps, stirred 1 minute under normal temperature, Help sedimentation agent metal ion will quickly with water-soluble ter-polymers molecular brush (PHEMAA-g- (PMAANa-r- PVACDTANa-r-PVACS2Na sedimentation side chain PVACS is helped on))2Chemical precipitation reaction occurs for Na, and it is big that particle diameter is generated in 10 seconds In 100 μm flcos precipitate, can quickly realize remove waste water in the dye of positive ion and solvay-type heavy metal ion, the above it is equal For mass fraction.
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.
In the technical program, take 1~5 part of flco to precipitate, add 1~5 part of water, adjust pH to 2, flco precipitation can It is inverse to be dissolved in the water, so as to realize recovery and concentrate dyestuff and heavy metal ion purpose.
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, and it contains The polymer side chain of three kinds of difference in functionalitys is anionic polymer side chain PMAANa, chelating side chain PVACDTANa and helps sedimentation Side chain PVACS2Na；Anionic polymer side chain PMAANa has good Electrostatic Absorption ability to the dye of positive ion, chelating Chelating absorption occurs for side chain PVACDTANa heavy metals ion, is helping sedimentation side chain PVACS2Under Na synergy, PVACS2Na polymer side chains reach with helping sedimentation agent metal ion that chemical precipitation reaction quickly occurs and efficiently catch and quickly sink Function drops, and the water-soluble ter-polymers molecular brush dye of positive ion, which catches sedimentation agent, has efficiently seizure dye of positive ion ability, Water outlet is substantially colorless；
2nd, the present invention can occur chelating precipitation reaction, big aggregation quickly generated in the several seconds, produce in the case where helping sedimentation agent on a small quantity Sludge quantity it is few.The flco precipitation of generation can be realized invertible dissolution, reach and reclaim and concentrate dyestuff further by adjusting pH value With heavy metal ion purpose；
3rd, the present invention has dual-use function, can catch dyestuff and heavy metal ion simultaneously, solving traditional flocculant can not be handled 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 ter-polymers molecular brush dye of positive ion catches sedimentation agent, is prepared by following steps：
Step 1 synthesizes PHEMAA main polymer chains
Take 1 part azodiisobutyronitrile initiator, 200 parts of hydroxyethyl acrylamide（HEMAA）, 400 part methanol, in nitrogen Protect lower 80 DEG C to carry out polymerisation 2 hours, obtain the degree of polymerization（DP）For 30 poly-hydroxyethyl acrylamide（PHEMAA）；
Step 2 synthetic anionic polymer side chain precursor polymer PtBMA-COOH and functional polymer side chain presoma Polymer P NVF-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 10 hours, obtain the degree of polymerization（DP）For 50 PtBMA-COOH；
Functional polymer side chain precursor polymer PNVF-COOH synthesis：Take 1 part azo dicyano valeric acid initiator, 300 The N- vinyl formamides of part（NVF）With 600 parts of water, 50 DEG C carry out Raolical polymerizable 4 hours under nitrogen protection, obtain To the degree of polymerization（DP）For 40 PNVF-COOH；
Step 3 synthesis 1,2- 1,2-diaminocyclohexane tetraacetic acids dianhydride (CDTA)
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- (PMAANa-r-PVACDTANa-r-PVACS2Na)
1 part of poly-hydroxyethyl acrylamide PHEMAA obtained by taking in step 1 with step 2 obtained by 20 parts it is cloudy from Subtype polymer side chain precursor polymer PtBMA-COOH and 5 parts of functional polymer side chain precursor polymer PNVF- COOH mixing is dissolved in 100 parts of dimethylformamide（DMF）In solvent, add 1 part n-hydroxysuccinimide (NHS) and 1 part of 1- ethyls -3- (3- dimethylamino-propyls) carbodiimide iodomethane salt (EDCCH3I), react 10 hours at 50 DEG C, obtain Obtain water-soluble ter-polymers molecular brush PHEMAA-g- (PtBMA-r-PNVF)；1 part of sodium hydroxide is added, temperature control is in 50 DEG C, reaction 48 hours is hydrolyzed, obtains poly-hydroxyethyl acrylamide-grafting-（Polymethylacrylic acid receives-random-polyethylene Amine）（PHEMAA-g-(PMAANa-r-PVA）)；5 parts of 1,2- 1,2-diaminocyclohexane tetraacetic acids two obtained by adding in step 3 Acid anhydride (CDTA), temperature control carry out acylation reaction 24 hours in 50 DEG C, acylation degree 80%, acquisition poly-hydroxyethyl acrylamide-connect Branch-（Sodium polymethacrylate-random-polyvinylamine basic ring hexamethylene tetraacetic acid sodium-is random-polyvinylamine）(PHEMAA-g- (PMAANa-r-PVACDTANa-r-PVA))；1 part of carbon disulfide is added, temperature control carries out addition reaction 1 hour in 20 DEG C, It is final to obtain water-soluble poly hydroxyethyl acrylamide-grafting-（Sodium polymethacrylate-random-polyvinylamine basic ring hexamethylene diamine four Sodium acetate-random-polyethylene amido nabam）(PHEMAA-g-( PMAANa-r-PVACDTANa-r- PVACS2Na it is)) that the water-soluble ter-polymers molecular brush dye of positive ion catches sedimentation agent, using nmr determination PMAANa, PVACDTANa and PVACS2The grafting rate of Na side chains is respectively 19%, 4% and 1%.
In the present embodiment, the water-soluble ter-polymers molecular brush dye of positive ion catches the application of sedimentation agent
Take the water-soluble ter-polymers molecular brush dye of positive ion of the present embodiment to catch sedimentation agent and do waste water from dyestuff test, take 100 parts of the mg/L containing methylene blue 50 waste water, it is added to 0.1 part of the water-soluble ter-polymers molecular brush dye of positive ion Catch in sedimentation agent, stirred 1 minute under normal temperature, pH value of waste water is adjusted to 6.0 using 0.1 mol/L hydrochloric acid, adds 0.01 part Help sedimentation agent calcium chloride, stirred under normal temperature in 1 minute, 10 seconds generate particle diameter more than 120 μm flco precipitate, filter, use Ultravioblet spectrophotometer measure filtrate Methylene Blue concentration is 0.01 mg/L, removal efficiency>99%.
The flco precipitation of 1 part of generation is taken, adds 1 part of water, adjusts pH to 2, flco precipitates invertible dissolution in water, so as to Realize and reclaim and concentrate methylene blue purpose.
Embodiment two
It is that a kind of water-soluble ter-polymers molecular brush dye of positive ion catches sedimentation agent, is prepared by following steps：
Step 1 synthesizes PHEMAA main polymer chains
Take 2 parts 2- isobutyl ethyl bromides initiator, CuBr and 3 of 3 parts part of 4,4- bipyridyls（BPy）, 100 parts of ethoxy Acrylamide（HEMAA）, 200 part methanol, 60 DEG C carry out polymerisation 10 hours under nitrogen protection, obtain the degree of polymerization（DP） For 100 poly-hydroxyethyl acrylamide（PHEMAA）；
Step 2 synthetic anionic polymer side chain precursor polymer PtBMA-COOH and functional polymer side chain presoma Polymer P NVF-COOH
Anionic polymer side chain precursor polymer PtBMA-COOH synthesis：3 parts of azo dicyano valeric acid is taken to trigger Agent, 200 parts of Tert-butyl Methacrylate（tBMA）, 100 parts of toluene, under nitrogen protection 60 DEG C to carry out radical polymerizations anti- Answer 20 hours, obtain the degree of polymerization（DP）For 110 PtBMA-COOH；
Functional polymer side chain precursor polymer PNVF-COOH synthesis：Take 2 parts azo dicyano valeric acid initiator, 300 The N- vinyl formamides of part（NVF）With 100 parts of water, 70 DEG C carry out Raolical polymerizable 7 hours under nitrogen protection, obtain To the degree of polymerization（DP）For 110 PNVF-COOH；
Step 3 synthesis 1,2- 1,2-diaminocyclohexane tetraacetic acids dianhydride (CDTA)
10 parts of CDTA and 10 parts of acetic anhydrides are dissolved in 30 parts of pyridine, are controlled in 70 DEG C, reaction 40 hours, obtain CDTA dianhydride；
Step 4 synthesis PHEMAA-g- (PMAANa-r-PVACDTANa-r-PVACS2Na)
3 parts of poly-hydroxyethyl acrylamide PHEMAA obtained by taking in step 1 with step 2 obtained by 40 parts it is cloudy from Subtype polymer side chain precursor polymer PtBMA-COOH and 15 parts of functional polymer side chain precursor polymer PNVF- COOH mixing is dissolved in 300 parts of dimethylformamide（DMF）In solvent, add 3 parts n-hydroxysuccinimide (NHS) and 3 parts of 1- ethyls -3- (3- dimethylamino-propyls) carbodiimide iodomethane salt (EDCCH3I), react 50 hours at 70 DEG C, obtain Water-soluble ter-polymers molecular brush PHEMAA-g- (PtBMA-r-PNVF)；；5 parts of sodium hydroxide is added, temperature control is in 70 DEG C, reaction 36 hours is hydrolyzed, obtains poly-hydroxyethyl acrylamide-grafting-（Polymethylacrylic acid receives-random-polyethylene Amine）（PHEMAA-g-(PMAANa-r-PVA）)；10 parts of 1,2- 1,2-diaminocyclohexane tetraacetic acids two obtained by adding in step 3 Acid anhydride (CDTA), temperature control acylation reaction 12 hours, acylation degree 70%, obtain poly-hydroxyethyl acrylamide-grafting-in 70 DEG C （Sodium polymethacrylate-random-polyvinylamine basic ring hexamethylene tetraacetic acid sodium-is random-polyvinylamine）(PHEMAA-g- (PMAANa-r-PVACDTANa-r-PVA))；5 parts of carbon disulfide is added, temperature control carries out addition reaction 2 hours in 30 DEG C, It is final to obtain water-soluble poly hydroxyethyl acrylamide-grafting-（Sodium polymethacrylate-random-polyvinylamine basic ring hexamethylene diamine four Sodium acetate-random-polyethylene amido nabam）(PHEMAA-g-( PMAANa-r-PVACDTANa-r- PVACS2Na be)) that the water-soluble ter-polymers molecular brush dye of positive ion catches sedimentation agent, using NMR PMAANa, PVACDTANa and PVACS2The grafting rate of Na side chains is respectively 32%, 7% and 3%.
In the present embodiment, the water-soluble ter-polymers molecular brush dye of positive ion catches the application of sedimentation agent
Take the water-soluble ter-polymers molecular brush dye of positive ion of the present embodiment to catch sedimentation agent and do waste water from dyestuff test, take 500 parts of the waste water containing the mg/L of rhodamine B 60, cadmium ion 5mg/L and the mg/L of citric acid 0.5, the water solubility of 0.5 part of addition The ter-polymers molecular brush dye of positive ion is caught in sedimentation agent, is stirred 3 minutes under normal temperature, using 0.1 mol/L sodium hydroxides PH value of waste water is adjusted to 8.0, add 0.05 part and help sedimentation agent iron, stir under normal temperature and generated in 1 minute, 6 seconds Flco of the particle diameter more than 320 μm precipitates, and filtering, is distinguished using Ultravioblet spectrophotometer and atomic absorption spectrophotometer It is 0.05 mg/L and Cd to determine rhodamine B concentration in filtrate2+Ion concentration is 0.02 mg/L, removal efficiency>99%.
The flco precipitation of 2 parts of generations is taken, adds 2 parts of water, adjusts pH to 2, flco precipitates invertible dissolution in water, so as to Realize and reclaim and concentrate rhdamine B and Cd2+Ion purpose.
Embodiment three
It is that a kind of water-soluble ter-polymers molecular brush dye of positive ion catches sedimentation agent, is prepared by following steps：
Step 1 synthesizes PHEMAA main polymer chains
Take 1 part 2- isobutyl ethyl bromides initiator, CuBr and 1 of 1 part part of 4,4- bipyridyls（BPy）, 100 parts of ethoxy Acrylamide（HEMAA）, 100 part methanol, 70 DEG C carry out polymerisation 5 hours under nitrogen protection, obtain the degree of polymerization（DP） For 195 poly-hydroxyethyl acrylamide PHEMAA；
Step 2 synthetic anionic polymer side chain precursor polymer PtBMA-COOH and functional polymer side chain presoma Polymer P NVF-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 10 hours, obtain the degree of polymerization（DP）For 190 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, 60 DEG C carry out Raolical polymerizable 15 hours under nitrogen protection, Obtain the degree of polymerization（DP）For 180 PNVF-COOH；
Step 3 synthesis 1,2- 1,2-diaminocyclohexane tetraacetic acids dianhydride (CDTA)
8 parts of CDTA and 8 parts of acetic anhydride are dissolved in 20 parts of pyridine, are controlled in 60 DEG C, reaction 30 hours, obtain CDTA dianhydride；
Step 4 synthesis PHEMAA-g- (PMAANa-r-PVACDTANa-r-PVACS2Na)
5 parts of poly-hydroxyethyl acrylamide PHEMAA and 100 parts the moon resulting in step 2 obtained by taking in step 1 Ionic polymer side chain precursor polymer PtBMA-COOH and 30 parts of functional polymer side chain precursor polymer PNVF- COOH mixing is dissolved in 300 parts of dimethylformamide（DMF）In solvent, add 5 parts n-hydroxysuccinimide (NHS) and 5 parts of 1- ethyls -3- (3- dimethylamino-propyls) carbodiimide iodomethane salt (EDCCH3I), react 70 hours at 80 DEG C, obtain Obtain water-soluble ter-polymers molecular brush PHEMAA-g- (PtBMA-r-PNVF)；；Add 10 parts of sodium hydroxide, temperature control in 80 DEG C, reaction 12 hours is hydrolyzed, obtains poly-hydroxyethyl acrylamide-grafting-（Polymethylacrylic acid receives-random-polyethylene Amine）（PHEMAA-g-(PMAANa-r-PVA）)；20 parts of 1,2- 1,2-diaminocyclohexane tetraacetic acids two obtained by adding in step 3 Acid anhydride (CDTA), temperature control carry out acylation reaction 5 hours in 80 DEG C, acylation degree 71%, acquisition poly-hydroxyethyl acrylamide-connect Branch-（Sodium polymethacrylate-random-polyvinylamine basic ring hexamethylene tetraacetic acid sodium-is random-polyvinylamine）(PHEMAA-g- (PMAANa-r-PVACDTANa-r-PVA))；10 parts of carbon disulfide are added, temperature control carries out addition reaction 3 hours in 40 DEG C, It is final to obtain water-soluble poly hydroxyethyl acrylamide-grafting-（Sodium polymethacrylate-random-polyvinylamine basic ring hexamethylene diamine four Sodium acetate-random-polyethylene amido nabam）(PHEMAA-g-( PMAANa-r-PVACDTANa-r- PVACS2Na be)) that the water-soluble ter-polymers molecular brush dye of positive ion catches sedimentation agent, using NMR PMAANa, PVACDTANa and PVACS2The grafting rate of Na side chains is respectively 67%, 12% and 5%.
In the present embodiment, the water-soluble ter-polymers molecular brush dye of positive ion catches the application of sedimentation agent
Take the water-soluble ter-polymers molecular brush dye of positive ion of the present embodiment to catch sedimentation agent and do waste water from dyestuff test, take 1000 parts of the waste water containing the mg/L of crystal violet 30, lead ion 2mg/L and citric acid 0.2mg/L, it is added to 1.0 parts of water solubility The ter-polymers molecular brush dye of positive ion is caught in sedimentation agent, is stirred 5 minutes under normal temperature, using 0.1 mol/L sodium hydroxides PH value of waste water is adjusted to 9.0, add 0.1 part and help sedimentation agent alchlor, stirred under normal temperature in 1 minute, 3 seconds and generate particle diameter Flco precipitation more than 300 μm, filtering, is determined respectively using Ultravioblet spectrophotometer and atomic absorption spectrophotometer Crystal violet concentration is 0.04 mg/L and Pb in filtrate2+Ion concentration is 0.02 mg/L, removal efficiency>99%.
Taking the flco of 4 parts of generation to precipitate, add 4 parts of water, adjust pH to 2, flco precipitates invertible dissolution in water, from And realize and reclaim and concentrate dye methyl violet and Pb2+Ion purpose.
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 (7)

1. a kind of water-soluble ter-polymers molecular brush dye of positive ion catches sedimentation agent, it is characterised in that including 1~10 part Main polymer chain poly-hydroxyethyl acrylamide（PHEMAA）, 20~100 parts of anionic polymer side chain precursor polymer The carboxylic polymethyl tert-butyl acrylate in end (PtBMA-COOH), the polymerization of 5~30 parts of functional polymer side chain presoma The carboxylic polyvinylformamide in thing end（PNVF-COOH）, 100~500 parts of dimethylformamide（DMF）, 1~5 The catalyst of part is n-hydroxysuccinimide (NHS), 1~5 part 1- ethyls -3- (3- dimethylamino-propyls) carbodiimide iodine Methane salt (EDCCH3I), 1~10 part of sodium hydroxide, 1~20 part of 1,2- 1,2-diaminocyclohexane tetraacetic acids dianhydride (CDTA) and 1 ~10 parts of carbon disulfide；It is mass fraction above.
2. the water-soluble ter-polymers molecular brush dye of positive ion according to claim 1 catches sedimentation agent, its feature exists In：
The main polymer chain poly-hydroxyethyl acrylamide（PHEMAA）It is by general radical polymerization or controllable living polymerization Method synthesizes PHEMAA main polymer chains；
Anionic polymer side chain precursor polymer PtBMA-COOH and functional polymer the side chain precursor polymer PNVF-COOH mainly uses azo dicyano valeric acid to be synthesized for initiator by general radical polymerization, and end is carboxylic to gather Tert-butyl Methacrylate（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 (CDTA) is：By 5~20 parts of 1,2- cyclohexanediamine tetrems Acid and 5~20 parts of acetic anhydrides are dissolved in 10~30 parts of pyridine, are controlled in 50~70 DEG C, are reacted 20~40 hours, obtain 1, 2- 1,2-diaminocyclohexane tetraacetic acid dianhydrides.
3. a kind of water-soluble ter-polymers molecular brush dye of positive ion catches the preparation method of sedimentation agent, it is characterised in that by 1 ~10 parts of main polymer chain poly-hydroxyethyl acrylamide（PHEMAA）, 20~100 parts of anionic polymer side chain forerunner Before the carboxylic polymethyl tert-butyl acrylate of body polymer ends (PtBMA-COOH) and 5~30 parts of functional polymer side chain Drive the carboxylic polyvinylformamide of body polymer ends（PNVF-COOH）Mixing is dissolved in 100~500 parts of dimethyl methyl Acid amides（DMF）In solvent, the catalyst for adding 1~5 part is the 1- ethyls -3- of n-hydroxysuccinimide (NHS) and 1~5 part (3- dimethylamino-propyls) carbodiimide iodomethane salt (EDCCH3I), temperature control carries out esterification 10~70 in 50~80 DEG C Hour, obtain poly-hydroxyethyl acrylamide-grafting-（Polymethyl tert-butyl acrylate-random-polyvinylformamide） (PHEMAA-g-(PtBMA-r-PNVF))；1~10 part sodium hydroxide is added, reaction is hydrolyzed in 50~80 DEG C in temperature control 12~48 hours, obtain poly-hydroxyethyl acrylamide-grafting-（Sodium polymethacrylate-random-polyvinylamine）（PHEMAA-g- (PMAANa-r-PVA）)；1~20 part of CDTA dianhydride (CDTA) is added, acylation reaction 5~24 is small When, acylation degree scope control is 60~99%, obtains poly-hydroxyethyl acrylamide-grafting-（Sodium polymethacrylate-random-poly- Vinylamine basic ring hexamethylene tetraacetic acid sodium-random-polyvinylamine）(PHEMAA-g-(PMAANa-r-PVACDTANa-r-PVA))； 1~10 part of carbon disulfide is added, temperature control carries out addition reaction 1~3 hour, finally obtain water-soluble poly in 20~40 DEG C Hydroxyethyl acrylamide-grafting-（Sodium polymethacrylate-random-polyvinylamine basic ring hexamethylene tetraacetic acid sodium-random-poly- second Enamine base nabam）(PHEMAA-g-( PMAANa-r-PVACDTANa-r-PVACS2Na)) i.e. water-soluble three First polymer molecule brush dye of positive ion catches sedimentation agent；It is mass fraction above.
4. the water-soluble ter-polymers molecular brush dye of positive ion according to claim 3 catches the preparation side of sedimentation agent Method, it is characterised in that the poly-hydroxyethyl acrylamide（PHEMAA）The degree of polymerization be 10~200, the anionic macromolecule Side chain precursor polymer PtBMA-COOH and functional polymer side chain precursor polymer the PNVF-COOH degree of polymerization are 10 ~200, cationic high-molecular side chain PMAANa grafting rate are connecing for 1~80%, chelating type polymer side chain PVACDTANa Branch rate 1~20% and help sedimentation polymer side chain PVACS2Na grafting rate is 1~5%.
5. a kind of water-soluble ter-polymers molecular brush dye of positive ion catches the application of sedimentation agent, it is characterised in that by 0.1~1 Water-soluble poly hydroxyethyl acrylamide-the grafting-of part（Sodium polymethacrylate-random-polyvinylamine basic ring hexamethylene tetraacetic acid Sodium-random-polyethylene amido nabam）(PHEMAA-g-(PMAANa-r-PVACDTANa-r-PVACS2Na)) It is added in 100~1000 parts of waste water, is stirred 1~5 minute under normal temperature, adjusts pH to 6~9, waste water cationic dyestuff point Son and water-soluble poly hydroxyethyl acrylamide-grafting-（Sodium polymethacrylate-random-polyvinylamine basic ring hexamethylene tetraacetic acid Sodium-random-polyethylene amido nabam）（PHEMAA-g-(PMAANa-r-PVACDTANa-r-PVACS2Na)） Anionic side chain PAANa Electrostatic Absorption, heavy metal ions in wastewater and ter-polymers molecular brush (PHEMAA-g- occurs (PMAANa-r-PVACDTANa-r-PVACS2Chelating absorption occurs for chelating side chain PVACDTANa Na)), add 0.01~ 0.1 part is helped sedimentation agent, is stirred 1 minute under normal temperature, help sedimentation agent metal ion will quickly with water-soluble ter-polymers point Son brush (PHEMAA-g- (PMAANa-r-PVACDTANa-r-PVACS2Na sedimentation side chain PVACS is helped on))2It is heavy that chemistry occurs for Na Form sediment reaction, flco of the particle diameter more than 100 μm generated in 10 seconds and is precipitated, can quickly realize remove the dye of positive ion in waste water and Solvay-type heavy metal ion, it is mass fraction above.
6. the water-soluble ter-polymers molecular brush dye of positive ion catches the application of sedimentation agent according to claim 5, it is special Sign helps sedimentation agent as calcium chloride, magnesium sulfate, frerrous chloride, ferric trichloride, the one or more of alchlor described in being Any combination.
7. the water-soluble ter-polymers molecular brush dye of positive ion catches the application of sedimentation agent according to claim 5, it is special Sign is to take 1~5 part of flco to precipitate, and adds 1~5 part of water, adjusts pH to 2, and flco precipitates invertible dissolution in water, so as to Realize and reclaim and concentrate dyestuff and heavy metal ion purpose.
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