CN107903398A - Water-soluble ter-polymers molecular brush dyestuff catches sedimentation agent and preparation method thereof and its application - Google Patents

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

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CN107903398A
CN107903398A CN201711127101.5A CN201711127101A CN107903398A CN 107903398 A CN107903398 A CN 107903398A CN 201711127101 A CN201711127101 A CN 201711127101A CN 107903398 A CN107903398 A CN 107903398A
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side chain
polymer
cooh
sedimentation agent
water
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CN107903398B (en
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刘锋
陈燕舞
霍应鹏
洪丹
张浥琨
郭志杰
唐秋实
彭琦
邓荣治
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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
    • 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
    • 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
    • C02F1/5245—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using basic salts, e.g. of aluminium and iron
    • 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
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Water Supply & Treatment (AREA)
  • Environmental & Geological Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Hydrology & Water Resources (AREA)
  • Medicinal Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (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 ter-polymers molecular brush dyestuff to catch sedimentation agent and preparation method thereof and its application,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,Solvent dimethylformamide,Catalyst, that is, N HOSu NHSs,1 ethyl 3 (3 dimethylamino-propyl) carbodiimide iodomethane salt,Potassium hydroxide and carbon disulfide prepare water-soluble ter-polymers molecular brush dyestuff and catch sedimentation agent,And water-soluble ter-polymers 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.It is strong with trapping ability, and sinking speed is fast, can capture dye molecule and heavy metal ion in a few seconds, and fast-growth realizes the purpose of quick separating dyestuff and heavy metal ion into big sedimented particle, and easy to operate, processing cost is low, it is adaptable the advantages that.

Description

Water-soluble ter-polymers 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 ter-polymers 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 give up Applied in water and art coatings waste water, can realize while remove the cationic dyes molecule of waste water from dyestuff, anionic dye and Heavy metal ion.
Background technology
In recent years, the annual quantity of wastewater effluent in China is up to more than 390 hundred million tons, 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 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 can be directly discharged into water body with waste water, waste water from dyestuff has become 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 very much 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, 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 wastewater treatment method 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 at the same time His macromolecular suspended contaminant.The structural property of coagulant is depended primarily upon 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 stablized, and residue is few, to pH Value requirement is 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 heavy metal ion.
The content of the invention
A kind of water-soluble ter-polymers molecular brush dyestuff is provided the purpose of the present invention is overcome the deficiencies in the prior art Catch sedimentation agent preparation method, trapping ability is strong, and sinking speed is fast, can capture in a few seconds dye molecule and heavy metal from Son, fast-growth realizes the purpose of quick separating dyestuff and heavy metal ion into big sedimented particle, easy to operate, is processed into This is low, adaptable.
In order to achieve the above object, water-soluble ter-polymers molecular brush dyestuff of the invention catches the technical side of sedimentation agent Case is achieved in that the main polymer chain poly-hydroxyethyl acrylamide it is characterized by comprising 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, that is, N- hydroxysuccinimidyls acyl are sub- Amine (NHS), 1~5 part of 1- ethyls -3- (3- dimethylamino-propyls) carbodiimide iodomethane salt (EDCCH3I), 1~10 part Potassium hydroxide and 1~10 part of carbon disulfide；It is mass fraction above.
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；The cationic high-molecular side chain PDMC-COOH is main Azo dicyano valeric acid is used to synthesize the carboxylic polymethyl acyl-oxygen in end by general radical polymerization for initiator Ethyl-trimethyl salmiac（PDMC-COOH）Polymer；The anionic macromolecule precursor polymer PtBMA-COOH master Azo dicyano valeric acid is used to synthesize the carboxylic polymethylacrylic acid in end by general radical polymerization for initiator The tert-butyl ester（PtBMA-COOH）Polymer；The functional polymer side chain precursor polymer PNVF-COOH mainly uses azo Dicyano valeric acid polymerize the synthesis carboxylic polyvinylformamide in end for initiator by general radical（PNVF- COOH）Polymer.
In order to achieve the above object, water-soluble ter-polymers molecular brush dyestuff of the invention catches the preparation side of sedimentation agent The technical solution 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 dimethylformamides（DMF）In solvent, 1~5 part of catalyst is added N-hydroxysuccinimide (NHS) and 1~5 part of 1- ethyls -3- (3- dimethylamino-propyls) carbodiimide iodomethane salt (EDC CH3I), temperature control is in 50~80 DEG C, when progress esterification 10~70 is small, obtains poly-hydroxyethyl acrylamide-grafting-（Poly- methyl Acrylyl oxy-ethyl-trimethyl salmiac-random-polymethyl tert-butyl acrylate-is random-polyvinylformamide） (PHEMAA-g-(PDMC-r-PtBMA-r-PNVF))；1~10 part of potassium hydroxide is added, temperature control carries out water in 50~80 DEG C When solution reaction 12~48 is small, poly-hydroxyethyl acrylamide-grafting-is obtained（Polymethyl acyloxyethyl trimethyl ammonium chloride-nothing Rule-sodium polymethacrylate-random-polyvinylamine）（PHEMAA-g-(PDMC-r-PMAANa-r-PVA）)；Add 1~10 Part carbon disulfide, temperature control is in 20~40 DEG C, final to obtain poly-hydroxyethyl acrylamide-grafting-when progress addition reaction 1~3 is small （Polymethyl acyloxyethyl trimethyl ammonium chloride-random-sodium polymethacrylate-is random-polyethylene amido dithiocarbamates Sodium formate）(PHEMAA-g-(PDMC-r-PMAANa-r-PVACS2Na)) i.e. water-soluble ter-polymers molecular brush dyestuff is caught 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 degree of polymerization of side chain precursor polymer PNVF-COOH is 10~500, and the grafting rate of cationic high-molecular side chain PDMC is 1~50%, the grafting rate of cationic high-molecular side chain PMAANa is 1~50% and functional polymer side chain PVACS2The grafting of Na Rate is 1~5%.
In order to achieve the above object, water-soluble ter-polymers molecular brush dyestuff of the invention catches the application of sedimentation agent Technical solution, which is achieved in that, is characterized in that 0.1~1 part of water-soluble ter-polymers molecular brush dyestuff seizure sedimentation Agent is added in 100~1000 parts of waste water, is stirred 1~5 minute under room temperature, adjust pH to 2~9, Wastewater Dyes molecule with Water-soluble ter-polymers molecular brush dyestuff catches sedimentation agent cationic side chain PDMC and anionic side chain PMAANa and occurs Electrostatic Absorption, heavy metal ions in wastewater catch the functional form side chain of sedimentation agent with water-soluble ter-polymers molecular brush dyestuff PVACS2Chelating absorption occurs for Na, adds 0.01~0.1 part of the sedimentation agent that helps, is stirred 1 minute under room temperature, help sedimentation agent Metal ion will quickly with water-soluble ter-polymers molecular brush (PHEMAA-g- (PDMC-r-PMAANa-r-PVACS2Na on) Functional form 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, can be quick Realize the dye of positive ion, anionic dye and the heavy metal ion removed in waste water, 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.
Compared with prior art, the present invention having 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 Polymer side chain containing three kinds of difference in functionality, cationic high-molecular side chain PDMC have anionic dyes quiet well Electro Sorb ability, anionic polymer side chain PMAANa have good Electrostatic Absorption ability to cationic dyes, PVACS2Under the synergistic effect of Na functional polymer side chains, PVACS2Na polymer side chains are with helping sedimentation agent metal ion or a huge sum of money Belong to ion and chemical precipitation reaction quickly occurs, reach efficiently seizure and rapid subsidence function, water outlet is substantially colorless, reaches national row Put standard.
2nd, the present invention has the technical advantage of sinking speed, chelating precipitation reaction, number can occur in the case where helping sedimentation agent on a small quantity Big aggregation is quickly generated in second, the sludge quantity of generation is few；
3rd, the present invention has dual-use function, can catch dyestuff and heavy metal ion at the same time, solving traditional flocculant can not be handled 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 embodiments.
Embodiment one
It is that a kind of water-soluble ter-polymers molecular brush dyestuff catches sedimentation agent, is prepared by following steps：
Step 1 synthetic polymer main chain PHEMAA
Take 2 parts azodiisobutyronitrile initiator, 100 parts of hydroxyethyl acrylamide（HEMAA）, 100 part methanol, in nitrogen When protecting lower 70 DEG C of progress polymerisation 8 small, the degree of polymerization is obtained（DP）For 130 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
The synthesis of cationic high-molecular side chain PDMC-COOH：Take 1 part azo dicyano valeric acid initiator, 100 parts of methyl Acrylyl oxy-ethyl-trimethyl salmiac（DMC）With 100 parts of water, Raolical polymerizable 5 is carried out for 80 DEG C under nitrogen protection Hour, obtain the degree of polymerization（DP）For 110 cationic high-molecular side chain PDMC-COOH；
The synthesis of anionic polymer side chain precursor polymer PtBMA-COOH：1 part of azo dicyano valeric acid is taken to trigger Agent, 100 parts of Tert-butyl Methacrylate（tBMA）, 100 parts of toluene, under nitrogen protection 80 DEG C to carry out radical polymerizations anti- Answer 8 it is small when, obtain the degree of polymerization（DP）For 120 anionic polymer side chain precursor polymer PtBMA-COOH；
The synthesis of functional polymer side chain precursor polymer PNVF-COOH：Take 1 part azo dicyano valeric acid initiator, 100 The N- vinyl formamides of part（NVF）With 100 parts of water, under nitrogen protection 70 DEG C carry out Raolical polymerizables 12 it is small when, Obtain the degree of polymerization（DP）For 140 functional polymer side chain precursor polymer PNVF-COOH；
Step 3 synthesis PHEMAA-g- (PDMC-r-PMAANa-r-PVACS2Na)
By obtained 1 part in step 1 of poly-hydroxyethyl acrylamide（PHEMAA）With obtained 21 parts in step 2 of sun Ionic polymer side chain PDMC-COOH, 21 parts of anionic polymer side chain precursor polymer PtBMA-COOH and 6 parts Functional polymer side chain precursor polymer PNVF-COOH mixing be dissolved in 100 parts of dimethylformamide（DMF）In solvent, It is sub- to add 1 part catalyst, that is, n-hydroxysuccinimide (NHS) and 1 part 1- ethyls -3- (3- dimethylamino-propyls) carbon two Amine iodomethane salt (EDCCH3I), temperature control when progress esterification 65 is small, makes each unit of main polymer chain in 52 DEG C 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 2 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 functional polymer side chain precursor polymer PNVF be hydrolyzed reaction 48 it is small when, obtain poly-hydroxyethyl acrylamide-grafting- （Polymethyl acyloxyethyl trimethyl ammonium chloride-random-sodium polymethacrylate-is random-polyvinylamine）（PHEMAA-g- (PDMC-r-PMAANa-r-PVA）)；2 parts of carbon disulfide is added, temperature control is in 40 DEG C, when progress addition reaction 1 is small, finally Obtain water-soluble poly hydroxyethyl acrylamide-grafting-（Polymethyl acyloxyethyl trimethyl ammonium chloride-random-poly- methyl-prop Olefin(e) acid sodium-random-polyethylene amido nabam）(PHEMAA-g-(PDMC-r-PMAANa-r-PVACS2Na)) I.e. water-soluble ter-polymers molecular brush dyestuff catches sedimentation agent.Using nmr determination PDMC, PMAANa and PVACS2The grafting rate of Na side chains is respectively 17%, 16% and 2%.
In the present embodiment, water-soluble ter-polymers molecular brush dyestuff catches the application of sedimentation agent
Take the water-soluble ter-polymers molecular brush dyestuff of the present embodiment to catch sedimentation agent and do waste water from dyestuff test, take 100 parts Waste water containing 20 mg/L of 20 mg/L of methylene blue and methyl red, is added to 0.1 part of water-soluble ter-polymers molecular brush dye Material is caught in sedimentation agent, is stirred 1 minute under room temperature, is adjusted pH value of waste water to 2.0 using 0.1 mol/L hydrochloric acid, is added 0.01 Part helps sedimentation agent magnesium sulfate, is stirred under room temperature and flco precipitation of the particle diameter more than 150 μm is generated in 1 minute, 10 seconds, filtering, is adopted It is 0.08 mg/L with Ultravioblet spectrophotometer measure filtrate Methylene Blue concentration, methyl red concentration is 0.05mg/L, is taken off Except efficiency>99%.
Embodiment two
It is that a kind of water-soluble ter-polymers molecular brush dyestuff catches sedimentation agent, is prepared by following steps：
Step 1 synthetic polymer main chain PHEMAA
Take CuBr and 5 part of 4,4- bipyridyls of 5 parts of 5 parts of 2- isobutyl ethyl bromides initiator（BPy）, 100 parts of ethoxy Acrylamide（HEMAA）, 400 part methanol, under nitrogen protection 65 DEG C carry out polymerisations 2 it is small when, obtain the degree of polymerization（DP） For 40 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
The synthesis of cationic high-molecular side chain PDMC-COOH：Take 1 part azo dicyano valeric acid initiator, 100 parts of methyl Acrylyl oxy-ethyl-trimethyl salmiac（DMC）With 200 parts of water, Raolical polymerizable 1 is carried out for 75 DEG C under nitrogen protection Hour, obtain the degree of polymerization（DP）For 30 cationic high-molecular side chain PDMC-COOH；
The synthesis of anionic polymer side chain precursor polymer PtBMA-COOH：1 part of azo dicyano valeric acid is taken to trigger Agent, 100 parts of Tert-butyl Methacrylate（tBMA）, 200 parts of toluene, under nitrogen protection 75 DEG C to carry out radical polymerizations anti- Answer 3 it is small when, obtain the degree of polymerization（DP）For 30 anionic polymer side chain precursor polymer PtBMA-COOH；
The synthesis of functional polymer side chain precursor polymer PNVF-COOH：Take 1 part azo dicyano valeric acid initiator, 100 The N- vinyl formamides of part（NVF）With 200 parts of water, when 75 DEG C of progress Raolical polymerizables 1 are small under nitrogen protection, obtain To the degree of polymerization（DP）For 30 functional polymer side chain precursor polymer PNVF-COOH；
Step 3 synthesis PHEMAA-g- (PDMC-r-PMAANa-r-PVACS2Na)
By obtained 3 parts in step 1 of poly-hydroxyethyl acrylamide（PHEMAA）With obtained 35 parts in step 2 of sun Ionic polymer side chain PDMC-COOH, 35 parts of anionic polymer side chain precursor polymer PtBMA-COOH and 8 parts Functional polymer side chain precursor polymer PNVF-COOH mixing be dissolved in 300 parts of dimethylformamides（DMF）In solvent, add Enter 1- ethyls -3- (3- dimethylamino-propyls) carbodiimide iodine of 3 parts of catalyst i.e. n-hydroxysuccinimide (NHS) and 3 parts Methane salt (EDCCH3I), temperature control is in 65 DEG C, when progress esterification 35 is small, makes the hydroxyl of each unit of main polymer chain Functional group and the carboxylic cationic high-molecular side chain PDMC-COOH in end, the carboxylic anionic macromolecule in end Ester randomly occurs for side chain precursor polymer PtBMA and the carboxylic functional polymer side chain precursor polymer PNVF in end Change reaction, obtain poly-hydroxyethyl acrylamide-grafting-（Polymethyl acyloxyethyl trimethyl ammonium chloride-random-poly- methyl Tert-butyl acrylate-random-polyvinylformamide）(PHEMAA-g-(PDMC-r-PtBMA-r-PNVF))；Again plus 5 parts Potassium hydroxide, temperature control is in 60 DEG C, to grafting on main polymer chain anionic polymer side chain precursor polymer PtBMA and work( Can polymer side chain precursor polymer PNVF be hydrolyzed reaction 24 it is small when, obtain poly-hydroxyethyl acrylamide-grafting-（It is poly- MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride-random-sodium polymethacrylate-is random-polyvinylamine）（PHEMAA-g- (PDMC-r-PMAANa-r-PVA）)；5 parts of carbon disulfide is added, temperature control is in 30 DEG C, when progress addition reaction 2 is small, finally Obtain water-soluble poly hydroxyethyl acrylamide-grafting-（Polymethyl acyloxyethyl trimethyl ammonium chloride-random-poly- methyl-prop Olefin(e) acid sodium-random-polyethylene amido nabam）(PHEMAA-g-(PDMC-r-PMAANa-r-PVACS2Na)) I.e. water-soluble ter-polymers molecular brush dyestuff catches sedimentation agent.Using nmr determination PDMC, PMAANa and PVACS2The grafting rate of Na side chains is respectively 33%, 32% and 4%.
In the present embodiment, water-soluble ter-polymers molecular brush dyestuff catches the application of sedimentation agent
Take the water-soluble ter-polymers molecular brush dyestuff of the present embodiment to catch sedimentation agent and do waste water from dyestuff test, take 500 parts to contain The waste water of 40 mg/L of rhodamine B, Congo red 40 mg/L and cadmium ion 3mg/L, are added to 0.5 part of water-soluble binary polymerization Thing molecular brush dyestuff is caught in sedimentation agent, stir 3 minutes under room temperature, using 0.1 mol/L hydrochloric acid adjusting pH value of waste water to 5.0, Add 0.05 part and help sedimentation agent iron, stirred under room temperature and the flco that particle diameter is more than 350 μm is generated in 1 minute, 4 seconds Precipitation, filtering, rhodamine B concentration in filtrate is measured using Ultravioblet spectrophotometer and atomic absorption spectrophotometer respectively For 0.09 mg/L, Congo red concentration is 0.07mg/L and Cd2+Ion concentration is 0.01mg/L, removal efficiency>99%.
Embodiment three
It is that a kind of water-soluble ter-polymers molecular brush dyestuff catches sedimentation agent, is prepared by following steps：
Step 1 synthetic polymer main chain PHEMAA
Take 1 part 2- isobutyl ethyl bromides initiator, CuBr and 1 of 1 part part of 4,4- bipyridyls（BPy）, 400 parts of ethoxy Acrylamide（HEMAA）, 50 part methanol, under nitrogen protection 70 DEG C carry out polymerisations 5 it is small when, obtain the degree of polymerization（DP）For 350 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
The synthesis of cationic high-molecular side chain PDMC-COOH：Take 1 part azo dicyano valeric acid initiator, 300 parts of methyl Acrylyl oxy-ethyl-trimethyl salmiac（DMC）With 10 parts of water, Raolical polymerizable 16 is carried out for 78 DEG C under nitrogen protection Hour, obtain the degree of polymerization（DP）For 220 cationic high-molecular side chain PDMC-COOH；
The synthesis of anionic polymer side chain precursor polymer PtBMA-COOH：1 part of azo dicyano valeric acid is taken to trigger Agent, 400 parts of Tert-butyl Methacrylate（tBMA）, 10 parts of toluene, under nitrogen protection 79 DEG C to carry out radical polymerizations anti- Answer 17 it is small when, obtain the degree of polymerization（DP）For 330 anionic polymer side chain precursor polymer PtBMA-COOH；
The synthesis of functional polymer side chain precursor polymer PNVF-COOH：Take 1 part azo dicyano valeric acid initiator, 400 The N- vinyl formamides of part（NVF）With 10 parts of water, when 85 DEG C of progress Raolical polymerizables 14 are small under nitrogen protection, obtain To the degree of polymerization（DP）For 340 functional polymer side chain precursor polymer PNVF-COOH；
Step 3 synthesis PHEMAA-g- (PDMC-r-PMAANa-r-PVACS2Na)
By obtained 4 parts in step 1 of poly-hydroxyethyl acrylamide（PHEMAA）With obtained 50 parts in step 2 of sun 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, It is sub- to add 5 parts catalyst, that is, n-hydroxysuccinimide (NHS) and 5 parts 1- ethyls -3- (3- dimethylamino-propyls) carbon two Amine iodomethane salt (EDCCH3I), temperature control when progress esterification 15 is small, makes each unit of main polymer chain in 50 DEG C 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 be hydrolyzed reaction 12 it is small when, obtain poly-hydroxyethyl acrylamide- Grafting-（Polymethyl acyloxyethyl trimethyl ammonium chloride-random-sodium polymethacrylate-is random-polyvinylamine） （PHEMAA-g-(PDMC-r-PMAANa-r-PVA）)；10 parts of carbon disulfide is added, temperature control carries out addition reaction in 20 DEG C 3 it is small when, it is final to obtain water-soluble poly hydroxyethyl acrylamide-grafting-（Polymethyl acyloxyethyl trimethyl ammonium chloride-nothing Rule-sodium polymethacrylate-random-polyethylene amido nabam）(PHEMAA-g-(PDMC-r-PMAANa-r- PVACS2Na)) i.e. water-soluble ter-polymers molecular brush dyestuff catches sedimentation agent.Using nmr determination PDMC, PMAANa and PVACS2The grafting rate of Na side chains is respectively 42%, 43% and 5%.
In the present embodiment, water-soluble ter-polymers molecular brush dyestuff catches the application of sedimentation agent
Take the present embodiment water solubility ter-polymers molecular brush dyestuff to catch sedimentation agent and do waste water from dyestuff test, take 1000 parts to contain first 30 mg/L of base purple, the waste water of methyl orange 30 mg/L and lead ion 2mg/L, are added to 1.0 parts of water-soluble ter-polymers point Sub- brush dyestuff is caught in sedimentation agent, stir 5 minutes under room temperature, using 0.1 mol/L potassium hydroxide adjusting pH value of waste water to 9.0, Add 0.1 part and help sedimentation agent ferric trichloride, stirred under room temperature and flco of the particle diameter more than 500 μm is generated in 1 minute, 2 seconds sink Form sediment, filtering, use Ultravioblet spectrophotometer and atomic absorption spectrophotometer measure respectively in filtrate crystal violet concentration for 0.03 mg/L, methyl orange concentration are 0.02 mg/L and Pb2+Ion concentration is 0.02 mg/L, removal efficiency>99%.
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention and from 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 solubility ter-polymers 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, that is, n-hydroxysuccinimide (NHS), 1~5 part 1- ethyls -3- (3- dimethylamino-propyls) carbodiimide Iodomethane salt (EDCCH3I), 1~10 part of potassium hydroxide and 1~10 part of carbon disulfide；It is mass fraction above.
2. water solubility ter-polymers molecular brush dyestuff according to claim 1 catches sedimentation agent, it is characterised in that described Main polymer chain poly-hydroxyethyl acrylamide（PHEMAA）It is to be synthesized by general radical polymerization or controllable living polymerization PHEMAA main polymer chains；The cationic high-molecular side chain PDMC-COOH mainly uses azo dicyano valeric acid to trigger Agent synthesizes the carboxylic polymethyl acyloxyethyl trimethyl ammonium chloride in end by general radical polymerization（PDMC- COOH）Polymer；The anionic macromolecule precursor polymer PtBMA-COOH mainly use azo dicyano valeric acid for Initiator synthesizes the carboxylic polymethyl tert-butyl acrylate in end by general radical polymerization（PtBMA-COOH）Polymerization Thing；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.
3. a kind of water solubility ter-polymers 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 dimethylformamides （DMF）In solvent, 1~5 part of n-hydroxysuccinimide (NHS) of catalyst and 1~5 part of 1- ethyls -3- (3- dimethylamino are added Propyl group) carbodiimide iodomethane salt (EDCCH3I), temperature control when progress esterification 10~70 is small, is gathered in 50~80 DEG C Hydroxyethyl acrylamide-grafting-（Polymethyl acyloxyethyl trimethyl ammonium chloride-random-polymethyl tert-butyl acrylate- Randomly-polyvinylformamide）(PHEMAA-g-(PDMC-r-PtBMA-r-PNVF))；1~10 part of potassium hydroxide is added, Temperature control in 50~80 DEG C, be hydrolyzed reaction 12~48 it is small when, obtain poly-hydroxyethyl acrylamide-grafting-（Polymethyl acyl Oxy-ethyl-trimethyl salmiac-random-sodium polymethacrylate-is random-polyvinylamine）（PHEMAA-g-(PDMC-r- PMAANa-r-PVA）)；1~10 part of carbon disulfide is added, temperature control is in 20~40 DEG C, when progress addition reaction 1~3 is small, finally Obtain poly-hydroxyethyl acrylamide-grafting-（Polymethyl acyloxyethyl trimethyl ammonium chloride-random-polymethylacrylic acid Sodium-random-polyethylene amido nabam）(PHEMAA-g-(PDMC-r-PMAANa-r-PVACS2Na)) i.e. water Dissolubility ter-polymers molecular brush dyestuff catches sedimentation agent, is mass fraction above.
4. water solubility ter-polymers molecular brush dyestuff according to claim 3 catches the preparation method of sedimentation agent, it is special Sign is the poly-hydroxyethyl acrylamide（PHEMAA）The degree of polymerization be 10~500, the cationic high-molecular side chain PDMC-COOH, anionic polymer side chain precursor polymer PtBMA-COOH and the polymerization of functional polymer side chain presoma The degree of polymerization of thing PNVF-COOH is 10~500, and the grafting rate of cationic high-molecular side chain PDMC is 1~50%, cation The grafting rate of type polymer side chain PMAANa is 1~50% and functional polymer side chain PVACS2The grafting rate of Na is 1~5%.
5. a kind of water solubility ter-polymers molecular brush dyestuff catches the application of sedimentation agent, it is characterised in that by 0.1~1 part of water Dissolubility ter-polymers molecular brush dyestuff catches sedimentation agent and is added in 100~1000 parts of waste water, and 1~5 point is stirred under room temperature Clock, adjusts pH to 2~9, and Wastewater Dyes molecule catches sedimentation agent cationic with water-soluble ter-polymers molecular brush dyestuff Electrostatic Absorption, heavy metal ions in wastewater and water-soluble ter-polymers point occur for side chain PDMC and anionic side chain PMAANa Sub- brush dyestuff catches the functional form side chain PVACS of sedimentation agent2Chelating absorption occurs for Na, adds 0.01~0.1 part and helps sedimentation Agent, is stirred 1 minute under room temperature, help sedimentation agent metal ion will quickly with water-soluble ter-polymers molecular brush (PHEMAA-g- (PDMC-r-PMAANa-r-PVACS2Na the functional form side chain PVACS on)2Chemical precipitation reaction occurs for Na, and grain is generated in 10 seconds Footpath more than 100 μm flco precipitate, can quickly realize remove waste water in the dye of positive ion, anionic dye and heavy metal from Son, is mass fraction above.
6. water-soluble ter-polymers molecular brush dyestuff catches the application of sedimentation agent according to claim 5, it is characterised in that It is described help sedimentation agent for calcium chloride, magnesium sulfate, frerrous chloride, ferric trichloride, alchlor it is one or more kinds of any Combination.
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