CN1667007A - Starch-base macromolecules environmental protection flocculant, process for preparing same and use thereof - Google Patents
Starch-base macromolecules environmental protection flocculant, process for preparing same and use thereof Download PDFInfo
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- CN1667007A CN1667007A CN 200510059924 CN200510059924A CN1667007A CN 1667007 A CN1667007 A CN 1667007A CN 200510059924 CN200510059924 CN 200510059924 CN 200510059924 A CN200510059924 A CN 200510059924A CN 1667007 A CN1667007 A CN 1667007A
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Abstract
This invention relates to a starch group macromolecule series environment protection flocculant, its method and use. One of corn starch and carboxymethyl starch is the material of environment protection flocculant, two of acrylamide, acrylic acid and dimethyl diols propyl ammonium chloride are monomer, ammonium persulphate/ redactor is compound initiator. Flocculant ZMS1 is got through ternary polymerization of solution or out phase emulsion polymerization. Otherwise, ZMS1 is reacted with formaldehyde and dimethylamine to get flocculant ZMS2. The features are adsorption, emulsion breaking, broad spectrum, high efficiency, small dosage, non-toxic, non- secondary pollution, sterilization, alga destroy, deodorization and heavy metal, heat resisting, salt resisting, shearing resisting. It can be mixed with unorganic flocculant, and doesn't corrupt pipe. The materials are easy to get, cost is low and no release of the three wastes. The use of flocculant is to propose waste water contain oil, printing sewage, water clarificant and antimicrobial, sludge dehydrating agent and heavy metal scavenger.
Description
Technical field
The invention belongs to environmental friendly material, it relates to, and (carboxymethyl starch (CMS) is a raw material with W-Gum and derivative thereof, with acrylamide (AM), dimethyl diallyl ammonium chloride (DMDAAC), vinylformic acid vinyl compounds such as (AA) is monomer, under the efficient composite initiator effect of self-control, by solution polymerization or reversed-phase emulsion (reverse micro emulsion) polymerization, carry out chemistry and physical modification then and the prescription of the ternary graft copolymer that makes, processing condition, product performance and main technology such as application.
Background technology
Natural polymer grafting vinyl monomers flocculation agent is the novel organic polymer coargulator of having developed since the seventies, raw material sources are wide, cheap, the product biodegrade but this class natural macromolecule flocculating agent has, in characteristics such as occurring in nature can circulate benignly, thereby gain great popularity in the research of flocculation agent with in producing.At present, the ammonia cyanogen company of the U.S., national starch chemical company, general abrasive material chemical company, all there is the production and selling of like product in the Mayhall company of Britain etc.Be accompanied by the urgent need of enviromarketing, its development is accelerated day by day.
China is in the starting stage to the research and development of natural macromolecule modification flocculation agent.It is that the research of the natural macromolecule modification flocculation agent tandem product of base material reached more than 15 years that the inventor is engaged in starch, Mierocrystalline cellulose and derivative thereof, has has researched and developed three generations's series product.First-generation product was identified by scientific payoffs in nineteen ninety-five, regarded as transformation of scientific and technical result key popularized project by State Environmental Protection Administration in 1997, achievement transformed in 1999,2000 by new product evaluation, calendar year 2001 is identified as Daliang City's new high-tech product, is regarded as national product innovation by State Economic and Trade Commission in 2002.S-generation product: " H.F.AM natural macromolecule modification flocculation agent series product " were listed in the great scientific research and development project in Liaoning Province in 1999,2002 by the evaluation of Liaoning Province's scientific payoffs, calendar year 2001 is rated as Daliang City's scientific-technical progress second prize, is rated as Liaoning Province's scientific-technical progress second prize in 2003.Third generation product is in development, and its scientific and technological content has the leading level in the world.Current these series product continue the advantage of performance cooperation between school and enterprise as the leading product of Dalian Minsheng Environmental Protection Technology Co., Ltd., will obtain the better development space.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art part, and provide the source abundant, with low cost natural reproducible raw material, adopt homemade efficient composite initiator, by the method for different polymerization means and physics, chemically modified, preparation different ions characteristic, the environment-friendly starch-based macromolecule serial flocculating agent of difference in functionality, preparation method and its usage.
The object of the invention can realize by following measure: new environment-friendly starch-based macromolecule serial flocculating agent, with a kind of in W-Gum, the carboxymethyl starch is raw material, 2 kinds in acrylamide, vinylformic acid, the dimethyl diallyl ammonium chloride is monomer, under ammonium persulphate/reductive agent composite initiator effect, adopt solution polymerization process or inverse emulsion polymerization method, single stage method is carried out terpolymer, gets multipolymer environment-friendly starch-based macromolecule serial flocculating agent ZMS1; Or copolymer flocculant ZMS1 carries out Mannich reaction with formaldehyde and dimethylamine again, get quaternary strong cation and weak anionic amphoteric starch based high molecular series environmental protection flocculant ZMS2, comprise flocculation agent ZMS1 and flocculation agent ZMS2 among the flocculation agent ZMS, its general formula ZMS is:
x＝20000～35000，y＝20000～30000
The residual monomer 0.1% of-flocculation agent ZMS, intrinsic viscosity 300-800ml.g
-1, anionization degree 1.5-3%, cation ionization degree 5-35%.
The preparation method of environment-friendly starch-based macromolecule serial flocculating agent, with W-Gum, a kind of in the carboxymethyl starch is raw material, acrylamide, vinylformic acid, 2 kinds in the dimethyl diallyl ammonium chloride is monomer, wherein, any two kinds of monomer mass proportionings 1: 1～4: 1, raw material and monomer mass were than 1: 1～1: 1.5, under ammonium persulphate/reductive agent composite initiator effect, adopt solution polymerization or inverse emulsion polymerization method, 40～60 ℃ of temperature of reaction, reaction pressure-0.08～+ 0.15Mpa, reaction times 4～10hr, under the nitrogen protection condition, single stage method is carried out three-component grafted copolymerization, gets multipolymer environment-friendly starch-based macromolecule serial flocculating agent ZMS1; Then, multipolymer carries out Mannich reaction (mol ratio: 1: (0.8～1): (1～1.5)) with formaldehyde and dimethylamine again, 40～80 ℃ of temperature of reaction, reaction times 4～8hr gets quaternary strong cation and weak anionic amphoteric starch based high molecular series environmental protection flocculant ZMS2.
Ammonium persulphate/reductive agent composite initiator is ammonium persulphate/urea, ammonium persulphate/sulphur urine, ammonium persulphate/S-WAT, ammonium persulphate/V-Brite B; Ammonium persulphate and urea, sulphur urine, S-WAT, V-Brite B mass ratio are 1: 1～6.
Reversed emulsion polymerization is: be skeleton with starch, with AM, AA, DMDAAC is grafted monomer, with ammonium persulphate-reductive agent is catalyzer, with Span series is emulsifying agent, with the whiteruss is solvent, in organic solvent-emulsifying agent external phase that constitutes and the disperse phase that constitutes with water-starch-AM slurries, the multi-grafted copolyreaction of the starch base of carrying out and the structure environmental protection flocculant that obtains tempering toughness with gentleness.
The purposes of new environment-friendly starch-based macromolecule serial flocculating agent, this product are used to handle oily(waste)water, dyeing and printing sewage, water scavengine agent and sterilant, sludge dehydrating agent and heavy metal scavenging agent.
The concrete preparation method of new environment-friendly starch-based macromolecule serial flocculating agent is presented below:
1, W-Gum, AM, the DMDAAC of certain mass ratio, under the effect of composite initiators such as ammonium persulphate, urea, at 45～55 ℃, after keeping solution polymerization 4～6h, under the effect of Mono Chloro Acetic Acid and sodium hydroxide, make the starch graft copolymer flocculation agent ZMS1 of certain viscosity, certain monomer conversion, certain percentage of grafting, its chemical equation is:
2, the carboxymethyl starch of certain mass ratio and AM, DMDAAC can make copolymer flocculant ZMS1 under initiator and reaction conditions identical with 1, and its chemical equation is:
3, the said products and formaldehyde and dimethylamine are proceeded Mannich reaction, strong cation both sexes product flocculation agent ZMS2, its chemical equation is:
Behind the starch-grafted AM, two step method Mannich reaction (adding dimethylamine after adding aldehyde earlier) changed into single stage method in the past, has eliminated smell and dark colour that single stage method is brought to environment basically, and the molecular weight of product is increased.
4, adopting W-Gum is raw material, cause with ammonium persulphate-urea, ammonium persulphate-composite initiators such as sulphur urine, adopt solution polymerization or monomers such as reversed emulsion polymerization and AM, AA to carry out three-component grafted copolymerization, get product flocculation agent ZMS1, its chemical equation is:
5, in the starch copolyreaction, particularly in the inverse emulsion polymerization process, initial reaction stage, speed of response is too fast, the characteristics that heat release is violent have worked out at a lower temperature, realize the initiator system of normal graft polymerization reaction: ammonium persulphate-urea, ammonium persulphate-sulphur urine, ammonium persulphate-V-Brite B, potassium permanganate-EDTA-sulfuric acid and azo-bis-isobutyrate hydrochloride (AIBA) etc., control speed of response, reached ideal monomer conversion and higher molecular weight.
Key of the present invention is the selecting for use of renewable natural high moleculer eompound W-Gum, carboxymethyl starch and the formulating of recipe of carrying out terpolymer with other raw material, the development of the low-cost initiator of composite highly effective, and the selection of the best friendly process condition of reaction such as inverse emulsion polymerization and the utilisation technology of variant production.
Reversed emulsion polymerization is that emulsification is scattered in (in the organic solvent) in the oil by water-in-oil-type (W/O) emulsifying agent, by water-soluble or oil-soluble initiator initiated polymerization, obtains the w/o type aqueous colloidal dispersion of water swollen polymer particle in oil.
Adopt the three-component grafted copolyreaction of starch base that reversed emulsion polymerization carries out and the structure that obtains tempering toughness with gentleness, the emulsion of solid content 30～40% and 95% solid phase prod.But this product positively charged ion can also be an amphoteric, and highly concentrated oil-bearing wastewater and sludge dewatering are had excellent treatment effect.
With ferrous sulfate (FeSO
4) be coagulant aids, with ZMS flocculation agent, dyeing waste water is carried out coagulating treatment can obtain the ideal treatment effect.
The present invention compares other flocculant product, has following advantage:
1, having multiple effects such as absorption, surface bonding, breakdown of emulsion, charge neutrality, compression double electric layer and bridge formation flocculation, is a kind of environment-friendly type water treatment agent of practicality.
2, wide spectrum, efficient, consumption is few, nontoxic, degradable, non-secondary pollution, in the performance throwing out, have sterilization, algae removal, deodorizing again and remove in the sewage function such as heavy metal, for the recovery and reuse of water provide assurance.
3, the amphiphilic polymers of hard and soft structure has better heat-resisting, salt tolerant, anti-shear ability, aspect oil field breakdown of emulsion, flocculation, oily water separation and raising tertiary oil recovery efficient, is just paid much attention to.
4, can and multiple inorganic flocculating agent composite, bring into play better water treatment effect, and not corrosion pipeline and equipment.
5, raw material be easy to get, with low cost, the multistep chemical reaction of solution polymerization can be finished in same polymeric kettle, raw materials used 100% is converted into product, the whole process of production three-waste free discharge.
6, these series product have good environment, economic and social benefit.
Embodiment
According to the characteristics of these series product, enumerate 4 examples by different polymerization processs, the present invention is further specified, but the present invention is not only limited to these examples.
The starch graft acrylamide multipolymer is the macromolecular material that a class has premium properties, adopts different polymerization processs can obtain the product of various trait, and wherein solution polymerization and inverse emulsion polymerization method are the most characteristic.These series product have adopted different polymerization route and polymerization process respectively, four kinds of products have been obtained, product has functions such as environmental protection, efficient, inhibition, sterilization algae removal, decolouring, deodorizing, removal heavy metal ion when using as flocculation agent, be the environmental protection organic floculant of a class excellent performance.In addition, product also can be used as industry auxiliary agents uses such as papermaking, petrochemical complex.
(1) solution polymerization process
Example one
Reaction conditions
Temperature of reaction: 45～85 ℃;
Reaction pressure :-0.08～+ 0.15MPa
Reaction times: 4～10hr
Produce feeding intake of 1000 parts of products:
Material name charging capacity (mass fraction)
W-Gum 30
Polymerization single polymerization monomer 1 (AM) 50
Polymerization single polymerization monomer 2 (aqueous solution of 60%DMDAAC) 35
Ammonium persulphate 0.15
Urea 0.4
Sodium hydroxide (40% aqueous solution) 7
Mono Chloro Acetic Acid (75% aqueous solution) 5
-deionized water surplus
Wherein: (need total amount of water 70%) dropped in the reactor in the W-Gum back of need pulling an oar;
AM dissolves (density of solution is about 1.12) in dissolving tank;
Polymerization single polymerization monomer 2 is a liquid, in adding reactor after the AM aqueous solution;
Technological process:
1) presses charge ratio, under the condition of stirring and logical nitrogen, in having dissolved the solution of W-Gum, spray into ammonium persulphate and aqueous solution of urea (10mg/ml).
2) after 10 minutes, spray into the AM and the DMDAAC aqueous solution simultaneously, temperature of reaction is controlled at 45～50 ℃ and stirred 4～6 hours, obtains product I (solid content is 10%).
3) product I is made into 5% solution, under logical nitrogen and stirring condition, add sodium hydroxide solution in room temperature, behind the 5min, spray into Mono Chloro Acetic Acid, reacted 4 hours down at 30～35 ℃, then be warming up to 60～65 ℃ and reacted 1 hour down, 70～75 ℃ were reacted 1 hour, 80～85 ℃ were reacted 2 hours down, are cooled to room temperature and get product flocculation agent ZMS1.
The product performance index
1) residual monomer content (%)＜0.1
2) intrinsic viscosity (mlg
-1)＞650
3) anionization degree (%)＞3
4) cation ionization degree (%)＞20
The product application effect
As flocculation agent, this product is mainly used in waste water, sewage disposals such as oil field, meat connection, industrial and mineral and life, its COD (chemical oxygen demand) clearance and SS (suspended solid) clearance can reach more than 90%, and functions such as dehydration, deodorizing, removal heavy metal ion are arranged simultaneously.The composite use of this product and inorganic flocculating agent, effect is better.
Example two
Reaction conditions
Temperature of reaction: 40～60 ℃;
Reaction pressure :-0.08～+ 0.15MPa
Reaction times: 4～10hr
Produce feeding intake of 1000 parts of products:
Material name charging capacity (mass fraction)
Carboxymethyl starch (substitution value 0.1～0.3) 30
Polymerization single polymerization monomer 1 (AM) 50
Polymerization single polymerization monomer 2 (60% the DMDAAC aqueous solution) 30
Ammonium persulphate 0.15
Urea 0.4
Disodium ethylene diamine tetraacetate (EDTA, 0.2% aqueous solution) 0.8
The deionized water surplus
Wherein: (need total amount of water 70%) dropped in the reactor in the carboxymethyl starch back of need pulling an oar;
AM dissolves (density of solution is about 1.12) in dissolving tank;
Polymerization single polymerization monomer 2 is a liquid, in adding reactor after the AM aqueous solution;
Technological process:
1) under logical nitrogen and agitation condition, in the solution that dissolves carboxymethyl starch, adds EDTA solution by charge ratio, and spray into ammonium persulphate and urea soln that concentration is 10mg/ml.
2) after 10 minutes, add AM and DMDAAC in reactor, temperature of reaction remains on 40～60 ℃, 4～10 hours, obtains solid content and be 10% product flocculation agent ZMS1.
The product performance index
1) residual monomer content (%)＜0.1
2) intrinsic viscosity (mlg
-1)＞300
3) anionization degree (%)＞1.5
4) cation ionization degree (%)＞18
The product application effect
Product can be used as the flocculation agent of various useless, sewage, and its COD clearance and BOD (biological oxygen demand) clearance can reach more than 90%, and functions such as dehydration, decolouring, deodorizing, removal heavy metal ion are arranged simultaneously.The composite use of this product and inorganic flocculating agent, effect is better.
Example three
Reaction conditions
Temperature of reaction: 40～80 ℃;
Reaction pressure :-0.08～+ 0.15MPa
Reaction times: 4～8hr
Produce feeding intake of 1000 parts of products:
Material name charging capacity (mass fraction)
The product 30 of example two
Formaldehyde (36% aqueous solution) 2
Dimethylamine (30% aqueous solution) 4
The deionized water surplus
Technological process:
1, two-step process process
1) presses charge ratio, the product of example two is mixed with 3.5% solution, under agitation condition, be warming up to 70 ℃, regulate pH=9～10, be incubated 10 minutes.
2) be cooled to 45～50 ℃, add formaldehyde solution, insulation reaction 2 hours then is warming up to 80 ℃, adds dimethylamine agueous solution, and insulation reaction is after 4 hours, solid content is about 3.5% product.
2, one-step technology process
Press charge ratio, in reactor, add formaldehyde and dimethylamine agueous solution, under agitation condition, be warming up to 40～45 ℃, kept 1 hour, join in the product of example two, continue to be warming up to 50～55 ℃, reacted 3 hours, get product flocculation agent ZMS2.
The product performance index
1) residual monomer content (%)＜0.1
2) intrinsic viscosity (mlg
-1)＞800
3) anionization degree (%)＞1.5
4) cation ionization degree (%)＞35
The product application effect
The product application scope is with the product of example two, and to wastewater treatments such as printing and dyeing, meat connection, its COD clearance and SS clearance can reach more than 90%, and dewatering rate can reduce to 75%.The composite use of this product and inorganic flocculating agent, effect is better.
(2) reversed emulsion polymerization
Example four
Reaction conditions
Temperature of reaction: 40～60 ℃;
Reaction pressure :-0.08～+ 0.15MPa.
Catalyst type: 1, FHCY-3; Ammonium persulphate/urea (mass ratio is 1: 0.5～6)
2, FHCS-2; Ammonium persulphate/sulphur urine (mass ratio is 1: 0.5～6)
3, FHCSS-1; Ammonium persulphate/S-WAT (mass ratio is 1: 1～6)
4, FHC2S-1; Ammonium persulphate/V-Brite B (mass ratio is 1: 0.5～5)
Catalyst levels: 5～12mol/m
3
Reaction times: 4～10hr
Produce feeding intake of 1000 parts product (emulsions):
Material name charging capacity (mass fraction)
W-Gum 80
Polymerization single polymerization monomer 1 (AM) 120
Polymerization single polymerization monomer 2 (AA) 40
Whiteruss 400
Emulsifying agent (SPAN-20; SPAN-40, SPAN20-TWEEN-60) 15
The deionized water surplus
Wherein: (need total amount of water 70%) dropped in the reactor in the W-Gum back of need pulling an oar;
AM dissolves (density of solution is about 1.12) in dissolving tank;
Polymerization single polymerization monomer 2 is a liquid, in adding reactor after the AM aqueous solution;
Emulsifying agent needs to dissolve in whiteruss.
Technological process:
1) initiator 1 and initiator 2 are used 2000 times of deionized water dissolvings respectively, stand-by.
2) reactor is cleaned down, use deionized water rinsing 2 times.
3) starch paste after will pulling an oar adds in the reactor, notes the starch sedimentation blocking pipeline.
4) with emulsifiers dissolve in whiteruss, after stirring evenly the whiteruss solution of emulsifying agent is added in the reactor.
5) pass is covered, is tightened flange, makes the reactor sealing, drives vacuum pump, and being evacuated to residual voltage is 0.01～0.015Mpa, keeps 5～10 minutes, feeds ordinary nitrogen to normal pressure.Vacuumize for the second time, to residual voltage be 0.01～0.015Mpa, kept 5～10 minutes, the feeding ordinary nitrogen is to normal pressure.Vacuumize for the third time, to residual voltage be 0.01～0.015Mpa, kept 5～10 minutes, feed high pure nitrogen to normal pressure.When leading to nitrogen, be warming up to 35～40 ℃.
6) continue to feed high pure nitrogen, when the amount (standard volume) that feeds high pure nitrogen is about 3～4 times of reactor volume, add the initiator for preparing in advance.
7) add polymerization single polymerization monomer solution (in 30 minutes, adding).The reaction beginning.
8) continue reaction 4～6 hours, to reacting completely.
9) emulsion after reaction is finished is put into the breakdown of emulsion jar.
10) produce the gel-like prod of 50% content, leave standstill 2～3 hours after, from the top oil-yielding stratum, product flows out (extrusion) from outlet down.
11) if produce 95% solid phase prod, under agitation add the ethanol (adding in 20 minutes) of 0.8～1.2 side rice in the breakdown of emulsion still, continue to stir 1 hour, product is separated out the back standing demix.From the top oil-yielding stratum, water is from outlet outflow (extrusion) down.
12) water after filtration, dry content is greater than 95% solid phase prod flocculation agent ZMS1.
13) filtrate is distilled recovery ethanol.
The product performance index
1) residual monomer content (%)＜0.1
2) intrinsic viscosity (mlg
-1)＞600
3) anionization degree (%)＞3
The product application effect
Be mainly used in waste water, sewage disposals such as oil-containing, meat connection, industrial and mineral and life as this product of flocculation agent, its COD clearance and SS clearance can reach more than 90%, and functions such as deodorizing, sterilization algae removal, inhibition are arranged simultaneously.The composite use of this product and inorganic flocculating agent, effect is better.Especially thick-oil waste water and sludge dewatering there is excellent treatment effect.
Every processing condition of table 1 sintetics
| Raw material | Initiator | Temperature of reaction (℃) | Reaction times (h) | |
| Example one product | W-Gum 3g; AM5g; DMDAAC (60%) 3.5g; NaOH (40%) 0.7g; Mono Chloro Acetic Acid (75%) 0.5g; Deionized water 87.3g | Ammonium persulphate 0.015g; Urea 0.04g | ????45～85 | ????4～10 |
| Example two products | Carboxymethyl starch (substitution value 0.1～0.3) 3g; AM5g; DMDAAC (60%) 3g; EDTA (0.2%) 0.08g; Deionized water 88.9g | Ammonium persulphate 0.015g; Urea 0.04g | ????40～60 | ????4～10 |
| The example three products | The product 3g of example two; Formaldehyde (36%) 0.2g; Dimethylamine (30%) 0.4g; Deionized water 96.4g | ?-- | ????40～80 | ????4～8 |
| The example four-product | W-Gum 8g; AM12g; AA4g; Whiteruss 40g; Emulsifying agent 1.5g, deionized water 34.5g | Ammonium persulphate/urea (mass ratio 1: 0.5～6) 5～12mol/m 3 | ????40～60 | ????4～10 |
Every performance index of table 2 sintetics
| Residual monomer content (%) | Intrinsic viscosity (mlg -1) | Anionization degree (%) | Cation ionization degree (%) | |
| Example one product example two product example three products example four-products | ????＜0.1 ????＜0.1 ????＜0.1 ????＜0.1 | ????＞650 ????＞300 ????＞800 ????＞600 | ????＞3 ????＞1.5 ????＞1.5 ????＞3 | ????＞20 ????＞18 ????＞35 ????＞5 |
(3) initiator system
Initiator is one of most important component in the inverse emulsion polymerization reaction, and the kind of initiator and effect directly influence the speed of reaction and the quality product of graft polymerization reaction.Character according to initiator can be divided into it oil-soluble initiator and water soluble starter.The polyreaction that adopts oil-soluble initiator to carry out in reversed-phase emulsion is the notion of initial inverse emulsion polymerization, and thereafter, people are used for inverse emulsion polymerization with water soluble starter again, are the extensions of original notion.
Carrying out the reaction that monomers such as starch graft acrylamide carry out copolymerization in reversed-phase emulsion, is thermopositive reaction.Because reacting material concentration is higher, speed of reaction is bigger, carries out graft copolymerization under comparatively high temps, when the heat of reaction generation can not in time shift out, will cause the reaction of the hot scission of link of a large amount of monomers, liberated heat again can fast reaction speed, makes polyreaction be difficult to control; And kick off temperature is low excessively, can make the entire reaction required time long again, and reaction is difficult to carry through to the end.So, initiation reaction is carried out with the speed that can regulate and control under lower temperature, be the problem that this patent emphasis will solve.
Experimental technique
W-Gum (commercially available, as to use preceding) through vacuum-drying, AM (industrial goods, biological process production are carried out recrystallization with acetone before using), other reagent is analytical pure.
Elicitation procedure is carried out in the four-hole boiling flask of stirring is housed, and adds after starch is pulled an oar in water, polymerization single polymerization monomer is made into certain density solution adds, and emulsifiers dissolve adds in whiteruss, and logical nitrogen is stirred to temperature required, adds initiator.The primary condition that causes is: whiteruss is the oil phase solvent, and SPAN-20 is an emulsifying agent; The water massfraction is 30～50%, wherein m (W-Gum): m (AM)=1: 0.8～1: 1.5; Profit phase volume ratio V (oil): V (water)=1.0: 1～1.5: 1.
Initiator type: 1, FHCY-3; Ammonium persulphate/urea (mass ratio is 1: 0.5～6)
2, FHCS-2; Ammonium persulphate/sulphur urine (mass ratio is 1: 0.5～6)
3, FHCSS-1; Ammonium persulphate/S-WAT (mass ratio is 1: 1～6)
4, FHC2S-1; Ammonium persulphate/V-Brite B (mass ratio is 1: 0.5～5)
Initiator amount: 5～12mol/m
3
The product ethanol sedimentation, washing with acetone, 40～60 ℃ of vacuum-dryings get crude product.Crude product is put into apparatus,Soxhlet's, remove homopolymer with the mixed solution extracting of V (ethylene glycol): V (Glacial acetic acid)=6: 4, monomer conversion (C) is calculated in vacuum-drying.
C%=[(m
1-m
0)/m
nM in] * 100% formula
0Be W-Gum quality (g); m
nBe monomer mass (g); m
1Be thick quality product (g).
To in the aqueous hydrochloric acid of 1mol/L, carry out the hydrolysis of starch through the purified grafts, ooze out chlorion with ion permeable membrane, the NaNO of hydrolyzed solution furnishing 1mol/L
3The aqueous solution filters, and adopts the η of each dilution point of dark type viscometer working sample
Sp, return estimated performance viscosity number [η].Measure the intrinsic viscosity [η] of graft copolymer simultaneously.
Table 3 different initiator system optimum processing condition and experimental result
| Initiator system | Ammonium persulphate/urea | Ammonium persulphate/sulphur urine | Ammonium persulphate/S-WAT | Ammonium persulphate/V-Brite B | Potassium permanganate/EDTA/ sulfuric acid |
| Kick off temperature (℃) | ??45～55 | ??40～50 | ????40～50 | ????35～50 | ????40～50 |
| M (W-Gum)/m (monomer) g/g | ??1∶1～ ??1∶1.5 | ??1∶0.8～ ??1∶1.5 | ????1∶0.8～ ????1∶1.5 | ????1∶1～1∶1.5 | ????1∶1～1∶1.5 |
| V (oil)/V (water) ml/ml | ??1.2∶1 | ??1.5∶1 | ????1.4∶1 | ????1∶1 | ????1.4∶1 |
| W (water) % | ??40～45 | ??45～50 | ????45～50 | ????45～50 | ????40～45 |
| Monomer conversion (%) | ??≥99.9 | ??≥99.9 | ????≥99.9 | ????≥99.9 | ????≥99.9 |
| Intrinsic viscosity (ml.g -1) | ??500～800 | ??600～900 | ????600～900 | ????700～1000 | ????600～900 |
As shown in Table 3, the initiator system of five series is applicable to different polymerization temperatures respectively, and the variant production performance requriements is the suitable initiator system of monomer polymerization reactions such as starch graft acrylamide in the inverse emulsion polymerization.
The purposes of the environment-friendly starch-based macromolecule serial flocculating agent that the present invention is new is used to handle oily(waste)water, dyeing and printing sewage, water scavengine agent and sterilant, sludge dehydrating agent and heavy metal scavenging agent.
Claims (5)
1, new environment-friendly starch-based macromolecule serial flocculating agent, it is characterized in that with a kind of in W-Gum, the carboxymethyl starch be raw material, 2 kinds in acrylamide, vinylformic acid, the dimethyl diallyl ammonium chloride is monomer, under the effect of ammonium persulphate composite initiator, adopt solution polymerization process or inverse emulsion polymerization method, single stage method is carried out terpolymer, gets multipolymer environment-friendly starch-based macromolecule serial flocculating agent ZMS1; Or copolymer flocculant ZMS1 carries out Mannich reaction with formaldehyde and dimethylamine again, get quaternary strong cation and weak anionic amphoteric starch based high molecular series environmental protection flocculant ZMS2, comprise flocculation agent ZMS1 and flocculation agent ZMS2 among the flocculation agent ZMS, its ZMS general formula is:
St-OH is a W-Gum:
N=1000～6000
R
1：-CH
2COONa，-H；
R
2：
R
3：-COOH，
x＝20000～35000，y＝20000～30000
Residual monomer is 0～0.1% among the flocculation agent ZMS, intrinsic viscosity is 300-800ml.g
-1, anionization degree 1.5-3%, cation ionization degree 5-35%.
2, the preparation method of the described environment-friendly starch-based macromolecule serial flocculating agent of a kind of claim 1, it is characterized in that with W-Gum, a kind of in the carboxymethyl starch is raw material, acrylamide, vinylformic acid, 2 kinds in the dimethyl diallyl ammonium chloride is monomer, wherein, any two kinds of monomer mass proportionings 1: 1～4: 1, raw material and monomer mass were than 1: 1～1: 1.5, under ammonium persulphate/reductive agent composite initiator effect, adopt solution polymerization, the inverse emulsion polymerization method, 40～60 ℃ of temperature of reaction, reaction pressure-0.08～+ 0.15Mpa, reaction times 4～10hr, under the nitrogen protection condition, single stage method is carried out terpolymer, gets multipolymer environment-friendly starch-based macromolecule serial flocculating agent ZMS1; Perhaps, multipolymer carries out Mannich reaction with formaldehyde and dimethylamine again, its mol ratio: 1: 0.8～1: 1～1.5, and 40～80 ℃ of temperature of reaction, reaction times 4～8hr gets quaternary strong cation and weak anionic amphoteric starch based high molecular series environmental protection flocculant ZMS2.
3, the preparation method of environment-friendly starch-based macromolecule serial flocculating agent according to claim 2 is characterized in that described ammonium persulphate/reductive agent composite initiator is ammonium persulphate/urea, ammonium persulphate/sulphur urine, ammonium persulphate/S-WAT, ammonium persulphate/V-Brite B; Ammonium persulphate and urea, sulphur urine, S-WAT, V-Brite B mass ratio are 1: 1～6.
4, the preparation method of environment-friendly starch-based macromolecule serial flocculating agent according to claim 2, it is characterized in that described reversed emulsion polymerization is: be skeleton with starch, with acrylamide, vinylformic acid, dimethyl diallyl ammonium chloride is a grafted monomer, with ammonium persulphate/reductive agent compound substance is catalyzer, with Span series is emulsifying agent, with the whiteruss is solvent, organic solvent-emulsifying agent the external phase that constitutes, in the disperse phase that constitutes with water-starch-acrylamide slurries, the three-component grafted copolyreaction of the starch base of carrying out and the structure environmental protection flocculant that obtains tempering toughness with gentleness.
5, the purposes of the described new environment-friendly starch-based macromolecule serial flocculating agent of claim 1, this product is used to handle oily(waste)water, dyeing and printing sewage, water scavengine agent and sterilant, sludge dehydrating agent and heavy metal scavenging agent.
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