CN102786623B - Fluorescent tracing non-phosphate polyether multifunctional water treatment agent and preparation method of water treatment agent - Google Patents
Fluorescent tracing non-phosphate polyether multifunctional water treatment agent and preparation method of water treatment agent Download PDFInfo
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Abstract
The invention relates to a fluorescent tracing non-phosphate polyether multifunctional water treatment agent (APEGYG), which is prepared from polyether monomers, monomers containing vinyl unsaturated double bonds and fluorescent monomers containing unsaturated double bonds through free radical copolymerization. The APEGYG has a structure formula shown as the accompanying drawing, wherein A is a repeated structure unit after polymerization of the monomers containing vinyl unsaturated double bonds, B is a repeated structure unit after polymerization of the fluorescent monomers containing unsaturated double bonds, G is -CH2-O- or -O-, the polymerization degree x is 5 to 5000, the polymerization degree y is 5 to 500, the polymerization degree z is 5 to 5000, and the repeated unit m is 5 to 100.
Description
Technical field
The present invention relates to a kind of fluorescent tracing phosphate-free polyether multifunctional water treating agent (APEGYG) and preparation method thereof, be a kind of be applicable to industrial circulating cooling water system without phosphorus, without nitrogen, biodegradable and can realize the multifunctional water treating agent of online detection and automatic chemical feeding, for the corrosion-mitigation scale-inhibition dispersion treatment of water quality, belong to water conditioner preparation and the utilisation technology of water-treatment technology field.
Background technology
In industrial circulating cooling water system, generally all need to add water treatment agent and to reach scale inhibition, disperse the effect of inhibition.The scale inhibition that effect is preferably traditional disperses corrosion inhibitor mostly to be phosphoric acid salt, as hydroxy ethylene diphosphonic acid (HEDP), PAPE (PAPE), Amino Trimethylene Phosphonic Acid (ATMP), 2-hydroxyl phosphoryl acetic acid (HPAA), 2 – phosphonic acids Ding Wan – 1, 2, 4 – tricarboxylic acid (PBTC), ethylenediamine tetramethylene phosphoric acid (EDTMP) and polyamino polyether base tetramethylene phosphoric acid (PAPEMP) etc., although this type of water conditioner has excellent inhibition tosca performance and good corrosion inhibition, but due to HEDP, PBTC, HPAA etc. are because relative molecular mass less (<800), functional group is also less, poor to the inhibition of calcium phosphate scale and ferric oxide particles and dissemination, less stable to zinc salt.The biocide oxygenolysis that these phosphoric acid salt water treatment agents are also easily hydrolyzed or are existed in system, generates PO
4 3-ion can easily form organic phosphoric acid calcium and the organic phosphoric acid iron that is insoluble in water in the water quality that contains high calcium and high ferro, has affected its application.Secondly phosphoric acid salt water conditioner is due to the phosphorous nutritive ingredient that can serve as bacterium and algae in water, and the eutrophication that easily causes water source causes the pollution of water resources.At present being widely used of phosphorous, nitrogenous water conditioner in a large number, has caused the amount reproduction of bacterium algae, therefore the problem of environmental pollutions such as eutrophication of water body develop without phosphorus Green Water treatment agent imperative.
Phosphate-free water treatment agent mostly is without phosphorus carboxylic-acid water conditioner as polyacrylic acid, poly-epoxy succinic acid resistance calcium phosphate and disperses Fe (III) ability undesirable now, and easily produces calcium gel under high calcium condition, and calcium tolerance is low; In addition the corrosion inhibition of this type of water conditioner is general.2002, U.S. Betz company releases the without phosphorus multipolymer of vinylformic acid/allyloxy polyethoxye sulfonate of new generation (AA/APES), owing to having adopted new allyloxy polyethoxye sulfonate comonomer, AA/APES has higher holding capacity to hardness, suspended substance, temperature, and the interference of ability iron ion, it hinders Ca
3(PO
4)
2efficiency is higher, and 2003 Nian， Betz companies have developed again the tripolymer of APES, is intended to further optimizing product performance and reduces production costs, though this class water treatment agent is without phosphorus, contains Shuifu County's nutrient nitrogen.In addition, thus the large shortcoming of phosphate-free water treatment agent one be not phosphorous in its structure cannot be with conventional ammonium molybdate spectrophotometry, thereby cannot detect online and automatic chemical feeding the concentration of water treatment agent.Fluorescence labelling polymkeric substance, owing to containing fluorophor in its structural molecule, can, by the mensuration of the material of fluorescence labelling is obtained very rapidly and easily to its drug concentration in system, detect with administration and control system thereby realize accurately.Therefore, develop a kind of can fluorescent tracing and there is the without phosphorus non-nitrogen environmental type water treatment agent that corrosion-mitigation scale-inhibition disperses can extensively be suitable for of multi-functional and industrial circulating water system, for the update of corrosion and scale inhibition disperser, there is important scientific meaning and great using value.
The present invention adopt polyether monomer and containing vinyl unsaturated double-bond monomer and containing the fluorescent monomer copolymerization of unsaturated double-bond prepared a kind of can fluorescent tracing and there is the phosphate-free polyether multifunctional water treating agent of excellent scale inhibition, inhibition and dispersing property.
Summary of the invention
Technical problem: the object of this invention is to provide a kind of fluorescent tracing phosphate-free polyether multifunctional water treating agent (APEGYG) and preparation method thereof, this water conditioner is biodegradable, and there is excellent scale inhibition, dispersion and corrosion inhibition, be a kind of eco-friendly polyethers water conditioner.
Technical scheme: fluorescent tracing phosphate-free polyether multifunctional water treating agent of the present invention (APEGYG) be with polyether monomer with containing the monomer of vinyl unsaturated double-bond and containing the fluorescent monomer of unsaturated double-bond, carry out free-radical polymerized and obtain, its general structure is:
Wherein: A is containing the repeated structural unit after vinyl unsaturated double-bond monomer polymerization, B is that G is-CH containing the repeated structural unit after the fluorescent monomer polymerization of unsaturated double-bond
2-O-or-O-, polymerization degree x is 5 ~ 5000, and polymerization degree y is 5 ~ 5000, and polymerization degree z is 5 ~ 5000, and repeating unit m is 5 ~ 100;
The preparation method of above-mentioned a kind of fluorescent tracing phosphate-free polyether multifunctional water treating agent is:
At N
2under atmosphere, take polyether monomer quality as benchmark, polyether monomer is added in reactor, temperature is adjusted to after 60 ~ 95 ℃, the monomer containing vinyl unsaturated double-bond that adds 0.1 ~ 5 times of polyether monomer quality, the fluorescent monomer containing unsaturated double-bond of 0.001 ~ 0.5 times of polyether monomer quality, the water of 0.1 ~ 5 times of polyether monomer quality, mix the inorganic initiator solution that rear dropping mass percentage concentration is 5%～60%, add-on without organic initiators is 0.01 ~ 0.5 times of polyether monomer quality, 0.5～5h drips off, drip off rear continuation and react 0.5～10h at 60 ~ 95 ℃, be chilled to room temperature, make 5 ~ 80wt% fluorescent tracing phosphate-free polyether multifunctional water treating agent.
Polyether monomer described in the preparation method of above-mentioned a kind of fluorescent tracing phosphate-free polyether multifunctional water treating agent is a kind of of allyl polyglycol monoether and vinyl polyoxyethylene glycol monoether or both combinations, described is vinylformic acid containing vinyl unsaturated double-bond monomer, methacrylic acid, maleic anhydride, toxilic acid, methylene-succinic acid, fumaric acid, vinylformic acid hydroxyl methyl esters, hydroxy methyl methacrylate, Hydroxyethyl acrylate, hydroxyethyl methylacrylate, Propylene glycol monoacrylate, Rocryl 410, vinylformic acid hydroxy butyl ester, the own ester of vinylformic acid hydroxyl, monomethyl maleate, ethyl maleate, toxilic acid list isopropyl ester, toxilic acid isobutyl ester, the toxilic acid list tert-butyl ester, the single rare propyl ester in Malaysia, monomethyl fumarate, monomethyl ester, fumaric acid list propyl ester, the combination of one or more of fumaric acid two hydroxypropyl acrylates or fumaric acid mono—n—butylester, the described fluorescent monomer containing unsaturated double-bond is 8-allyloxy-1,3,6-pyrene sodium trisulfonate and 8-(4-vinyl benzyloxy base)-1,3, the combination of a kind of in 6-pyrene sodium trisulfonate or two kinds, described without organic initiators be Sodium Persulfate, Potassium Persulphate, lay particular stress on-sulfinic acid sodium, lay particular stress on-sulfinic acid potassium, one or more combination in persulfonic acid sodium, persulfonic acid potassium or hydrogen peroxide.
Beneficial effect: fluorescent tracing phosphate-free polyether multifunctional water treating agent of the present invention (APEGYG) has following excellent properties:
(1) the eutrophy element such as not phosphorous, nitrogen of this polyethers water conditioner, has good biodegradability, is a kind of novel Green Water Treatment Reagents.Its preparation technology's green environment is friendly, and building-up process adopts environmental protection, inexpensive water as reaction solvent, and reaction process adopts " treating different things alike " mode, without separation, simple to operation, production cost is lower.
(2) in this polyethers water conditioner structure, contain the polyether group that wetting ability is strong, and can with the carboxylic acid ion of calcium ion, iron ion and Zinc Ions Chelated, the incrustation scales such as the calcium phosphate in industrial circulating cooling water system, calcium carbonate, calcium sulfate, ironic hydroxide and zinc hydroxide are had to efficient restraining effect.In addition also there is good corrosion inhibition.
(3) compatibleness of this polyethers water conditioner is good, can with the composite uses of water conditioner such as organophosphate, zinc salt inhibiter, also can be used alone.
(4) this polyethers water conditioner, owing to containing fluorophor in structure, can accurately detect the concentration of water treatment agent, thereby realizes online detection and automatic chemical feeding.
Static resistance Ca of the present invention
3(PO
4)
2dirt experiment is analyzed by the < < of China PetroChemical Corporation water coolant and experimental technique > > experiment 402(GB 50050-95) carry out; The calculating of the calcium carbonate in scale-inhibiting properties test experiments, calcium sulfate scale inhibition performance is carried out according to the oil and gas industry standard-SY/T5673-1993 > > of the < < People's Republic of China (PRC); At < < Treatment of Industrial Water > >, the < < cooling water treatment agent on 06 phase in 1991 disperses the evaluation > > of deposition of iron ability to carry out by Lu Jianmin to disperse Fe (III) sedimentation experiment, characterize disperseing Fe (III) performance with containing Fe(III) transmittance of solution represents, the lower expression of transmittance disperses the performance of Fe (III) better.The test of corrosion inhibition is with reference to < < State Standard of the People's Republic of China GB/T18175-2000, mensuration-rotary hanging plate method > > of water conditioner corrosion inhibition, carbon steel lacing film meets the regulation of HG/T3523.
Embodiment
Example 1: at N
2in the reactor of protection, add 100g allyl polyglycol monoether; temperature is adjusted to after 70 ℃; add 25g vinylformic acid, 0.5g8-allyloxy-1; 3,6-pyrene sodium trisulfonate, 350g water, mix rear dropping 5g Sodium Persulfate (being dissolved in 100g water); after 2h dropwises; be warming up to 85 ℃ and continue reaction 2h, be down to after room temperature, make fluorescent tracing phosphate-free polyether multifunctional water treating agent (APEGYG).
The APEGYG of gained is when dosage is 8mg/L, to Ca
3(PO
4)
2scale inhibition performance can reach 98.9%, to CaCO
3scale inhibition performance is 90.6%, to CaSO
4scale inhibition performance is 95.1%, characterize to disperse ferrum property containing Fe(III) transmittance of solution is 16.3%, to the corrosion inhibition rate of carbon steel, can reach 92.3%.
Example 2: at N
2in the reactor of protection, add 100g vinyl polyoxyethylene glycol monoether; temperature is adjusted to after 75 ℃; add 100g methylene-succinic acid, 5g8-allyloxy-1; 3,6-pyrene sodium trisulfonate, 260g water, mix rear dropping Potassium Persulphate (3g), Sodium Persulfate (3g) and lay particular stress on-sulfinic acid potassium (3g) mixture (being dissolved in 120g water); after 3.5h dropwises; be warming up to 90 ℃ and continue reaction 3.5h, be down to after room temperature, make fluorescent tracing phosphate-free polyether multifunctional water treating agent (APEGYG).
Gained APEGYG is when dosage is 8mg/L, to Ca
3(PO
4)
2scale inhibition performance can reach 98.7%, to CaCO
3scale inhibition performance is 89.9%, to CaSO
4scale inhibition performance is 91.3%., characterize to disperse ferrum property containing Fe(III) transmittance of solution is 15.9%, to the corrosion inhibition rate of carbon steel, can reach 92.6%.
Example 3: at N
2in the reactor of protection, add 110g allyl polyglycol monoether; temperature is adjusted to after 60 ℃; add 100g hydroxyethyl methylacrylate, 15g8-allyloxy-1; 3,6-pyrene sodium trisulfonate, 380g water, mix rear dropping 50g Sodium Persulfate (being dissolved in 80g water); after 4h dropwises; be warming up to 95 ℃ and continue reaction 2h, be down to after room temperature, make fluorescent tracing phosphate-free polyether multifunctional water treating agent (APEGYG).
Gained APEGYG is when dosage is 8mg/L, to Ca
3(PO
4)
2scale inhibition performance can reach 99.5%, to CaCO
3scale inhibition performance is 88.9%, to CaSO
4scale inhibition performance is 92.7%, characterize to disperse ferrum property containing Fe(III) transmittance of solution is 17.2%, to the corrosion inhibition rate of carbon steel, can reach 95.4%.
Example 4: at N
2in the reactor of protection, add 150g vinyl polyoxyethylene glycol monoether; temperature is adjusted to after 70 ℃; add 150g fumaric acid, 5g8-(4-vinyl benzyloxy base)-1; 3,6-pyrene sodium trisulfonate, 320g water, mix rear dropping 16g Sodium Persulfate (being dissolved in 150g water); after 5h dropwises; be warming up to 90 ℃ and continue reaction 7h, be down to after room temperature, make fluorescent tracing phosphate-free polyether multifunctional water treating agent (APEGYG).
Gained APEGYG is when dosage is 8mg/L, to Ca
3(PO
4)
2scale inhibition performance can reach 98.8%, to CaCO
3scale inhibition performance is 90.7%, to CaSO
4scale inhibition performance is 93.5%, characterize to disperse ferrum property containing Fe(III) transmittance of solution is 15.7%.To the corrosion inhibition rate of carbon steel, can reach 93.8%.
Example 5: at N
2in the reactor of protection, add 180g allyl polyglycol monoether; temperature is adjusted to after 85 ℃; add 180g Propylene glycol monoacrylate, 80g8-allyloxy-1; 3; 6-pyrene sodium trisulfonate, 280g water, mix rear dropping Sodium Persulfate (5g) and persulfonic acid potassium (5g) mixture (being dissolved in 100g water), and 2.5h dropwises rear continuation and react 2.5h at 85 ℃; be down to after room temperature, make fluorescence labelling phosphate-free polyether multifunctional water treating agent (APEGYG).
Gained APEGYG is when dosage is 8mg/L, to Ca
3(PO
4)
2scale inhibition performance can reach 96.9%, to CaCO
3scale inhibition performance is 88.1%, to CaSO
4scale inhibition performance is 92.5%, characterize to disperse ferrum property containing Fe(III) transmittance of solution is 18.3%, to the corrosion inhibition rate of carbon steel, can reach 92.3%.
Example 6: at N
2in the reactor of protection, add 100g vinyl polyoxyethylene glycol monoether; temperature is adjusted to after 65 ℃; add 200g toxilic acid, 20g8-(4-vinyl benzyloxy base)-1; 3,6-pyrene sodium trisulfonate, 360g water, mix rear dropping 20g Sodium Persulfate (being dissolved in 50g water); after 0.5h dropwises; be warming up to 80 ℃ and continue reaction 9h, be down to after room temperature, make fluorescent tracing phosphate-free polyether multifunctional water treating agent (APEGYG).
Gained APEGYG is when dosage is 8mg/L, to Ca
3(PO
4)
2scale inhibition performance can reach 99.7%, to CaCO
3scale inhibition performance is 92.6%, to CaSO
4scale inhibition performance is 94.6%, characterize to disperse ferrum property containing Fe(III) transmittance of solution is 15.5%.To the corrosion inhibition rate of carbon steel, can reach 94.7%.
Example 7: at N
2in the reactor of protection, add 120g allyl polyglycol monoether; temperature is adjusted to after 80 ℃; add 70g methacrylic acid, 80g Hydroxyethyl acrylate, 5g8-allyloxy-1; 3; 6-pyrene sodium trisulfonate, 5g8-(4-vinyl benzyloxy base)-1; 3; 6-pyrene sodium trisulfonate, 500g water; mix rear dropping 55g and lay particular stress on-sulfinic acid sodium (being dissolved in 80g water); after 1.5h dropwises; be warming up to 85 ℃ and continue reaction 10h, be down to after room temperature, make fluorescent tracing phosphate-free polyether multifunctional water treating agent (APEGYG).
Gained APEGYG is when dosage is 8mg/L, to Ca
3(PO
4)
2scale inhibition performance can reach 98.4%, to CaCO
3scale inhibition performance is 88.5%, to CaSO
4scale inhibition performance is 91.7%, characterize to disperse ferrum property containing Fe(III) transmittance of solution is 16.9%.To the corrosion inhibition rate of carbon steel, can reach 89.9%.
Example 8: at N
2in the reactor of protection, add 60g allyl polyglycol monoether and 60g vinyl polyoxyethylene glycol monoether; temperature is adjusted to after 60 ℃; add 50g vinylformic acid, 50g methylene-succinic acid, 60g hydroxyethyl methylacrylate, 10g8-allyloxy-1; 3; 6-pyrene sodium trisulfonate, 6g8-(4-vinyl benzyloxy base)-1; 3; 6-pyrene sodium trisulfonate, 480g water; mix rear dropping 40g persulfonic acid potassium (being dissolved in 100g water); after 0.5h dropwises; be warming up to 80 ℃ and continue reaction 4.7h, be down to after room temperature, make fluorescent tracing phosphate-free polyether multifunctional water treating agent (APEGYG).
Gained APEGYG is when dosage is 8mgL, to Ca
3(PO
4)
2scale inhibition performance can reach 97.1%, to CaCO
3scale inhibition performance is 89.2%, to CaSO
4scale inhibition performance is 91.1%, characterize to disperse ferrum property containing Fe(III) transmittance of solution is 17.9%.To the corrosion inhibition rate of carbon steel, can reach 91.5%.
Example 9: at N
2in the reactor of protection, add 80g allyl polyglycol monoether; temperature is adjusted to after 65 ℃, adds 50g vinylformic acid hydroxyl methyl esters, 5g8-allyloxy-1,3; 6-pyrene sodium trisulfonate, 10g8-(4-vinyl benzyloxy base)-1; 3,6-pyrene sodium trisulfonate, 360g water, mix rear dropping 16g Sodium Persulfate (being dissolved in 120g water); after 3.6h dropwises; be warming up to 80 ℃ and continue reaction 8.5h, be down to after room temperature, make fluorescent tracing phosphate-free polyether multifunctional water treating agent (APEGYG).
The APEGYG of gained is when dosage is 8mg/L, to Ca
3(PO
4)
2scale inhibition performance can reach 98.6%, to CaCO
3scale inhibition performance is 91.2%, to CaSO
4scale inhibition performance is 92.7%, characterize to disperse ferrum property containing Fe(III) transmittance of solution is 17.1%, to the corrosion inhibition rate of carbon steel, can reach 92.4%.
Example 10: at N
2in the reactor of protection, add 100g allyl polyglycol monoether; temperature is adjusted to after 75 ℃; add 60g methylene-succinic acid, 80g vinylformic acid hydroxyl methyl esters, 3g8-allyloxy-1; 3; 6-pyrene sodium trisulfonate, 6g8-(4-vinyl benzyloxy base)-1; 3; 6-pyrene sodium trisulfonate, 330g water; mix rear dropping Potassium Persulphate (3g), Sodium Persulfate (3g) and lay particular stress on-sulfinic acid potassium (5g) mixture (being dissolved in 180g water); after 1.5h dropwises; be warming up to 90 ℃ and continue reaction 9h, be down to after room temperature, make fluorescent tracing phosphate-free polyether multifunctional water treating agent (APEGYG).
Gained APEGYG is when dosage is 8mg/L, to Ca
3(PO
4)
2scale inhibition performance can reach 99.1%, to CaCO
3scale inhibition performance is 91.6%, to CaSO
4scale inhibition performance is 95.4%., characterize to disperse ferrum property containing Fe(III) transmittance of solution is 16.5%, to the corrosion inhibition rate of carbon steel, can reach 92.9%.
Example 11: at N
2in the reactor of protection, add 60g allyl polyglycol monoether and 100g vinyl polyoxyethylene glycol monoether, temperature is adjusted to after 85 ℃, add 80g hydroxyethyl methylacrylate, 80g monomethyl fumarate, 35g8-allyloxy-1, 3, 6-pyrene sodium trisulfonate, 35g8-(4-vinyl benzyloxy base)-1, 3, 6-pyrene sodium trisulfonate, 380g water, after mixing, mixing rear dropping massfraction is 17% aqueous hydrogen peroxide solution 100g, after 5h dropwises, be warming up to 95 ℃ and continue reaction 2.5h, be down to after room temperature, make fluorescent tracing phosphate-free polyether multifunctional water treating agent (APEGYG).
Gained APEGYG is when dosage is 8mg/L, to Ca
3(PO
4)
2scale inhibition performance can reach 97.8%, to CaCO
3scale inhibition performance is 90.2%, to CaSO
4scale inhibition performance is 92.6%, characterize to disperse ferrum property containing Fe(III) transmittance of solution is 16.7%, to the corrosion inhibition rate of carbon steel, can reach 93.5%.
Example 12: at N
2in the reactor of protection, add 240g allyl polyglycol monoether; temperature is adjusted to after 90 ℃; add 100g Propylene glycol monoacrylate, 100g fumaric acid two hydroxypropyl acrylates, 100g 8-(4-vinyl benzyloxy base)-1; 3; 6-pyrene sodium trisulfonate, 400g water; mix rear dropping Sodium Persulfate (25g) and persulfonic acid potassium (50g) mixture (being dissolved in 160g water); 3h dropwises rear continuation and react 3h at 90 ℃; be down to after room temperature, make fluorescent tracing phosphate-free polyether multifunctional water treating agent (APEGYG).
Gained APEGYG is when dosage is 8mg/L, to Ca
3(PO
4)
2scale inhibition performance can reach 99.3%, to CaCO
3scale inhibition performance is 92.2%, to CaSO
4scale inhibition performance is 95.8%, characterize to disperse ferrum property containing Fe(III) transmittance of solution is 15.6%, to the corrosion inhibition rate of carbon steel, can reach 95.1%.
Claims (6)
1. a fluorescent tracing phosphate-free polyether multifunctional water treating agent, is characterized in that this water conditioner is carry out free-radical polymerized and obtain with polyether monomer and monomer containing vinyl unsaturated double-bond and containing the fluorescent monomer of unsaturated double-bond, and its general structure is:
Wherein: A is containing the repeated structural unit after vinyl unsaturated double-bond monomer polymerization, B is that G is-CH containing the repeated structural unit after the fluorescent monomer polymerization of unsaturated double-bond
2-O-or-O-, polymerization degree x is 5～5000, and polymerization degree y is 5～5000, and polymerization degree z is 5～5000, and repeating unit m is 5～100.
2. a preparation method for fluorescent tracing phosphate-free polyether multifunctional water treating agent as claimed in claim 1, is characterized in that this preparation method is:
At N
2under atmosphere, take polyether monomer quality as benchmark, polyether monomer is added in reactor, temperature is adjusted to after 60～95 ℃, the monomer containing vinyl unsaturated double-bond that adds 0.1～5 times of polyether monomer quality, the fluorescent monomer containing unsaturated double-bond of 0.001～0.5 times of polyether monomer quality, the water of 0.1～5 times of polyether monomer quality, mix the inorganic initiator solution that rear dropping mass percentage concentration is 5%～60%, add-on without organic initiators is 0.01～0.5 times of polyether monomer quality, 0.5～5h drips off, drip off rear continuation and react 0.5～10h at 60～95 ℃, be chilled to room temperature, make 5～80wt% fluorescent tracing phosphate-free polyether multifunctional water treating agent.
3. the preparation method of a kind of fluorescent tracing phosphate-free polyether multifunctional water treating agent according to claim 2, is characterized in that the polyether monomer described in this preparation method is a kind of of allyl polyglycol monoether or vinyl polyoxyethylene glycol monoether or both combinations.
4. the preparation method of a kind of fluorescent tracing phosphate-free polyether multifunctional water treating agent according to claim 2, it is characterized in that described in this preparation method containing vinyl unsaturated double-bond monomer be fumaric acid, vinylformic acid hydroxyl methyl esters, hydroxy methyl methacrylate, Hydroxyethyl acrylate, hydroxyethyl methylacrylate, Propylene glycol monoacrylate, Rocryl 410, vinylformic acid hydroxy butyl ester, the own ester of vinylformic acid hydroxyl, monomethyl maleate, ethyl maleate, toxilic acid list isopropyl ester, toxilic acid isobutyl ester, the toxilic acid list tert-butyl ester, Malaysia monoene propyl ester, monomethyl fumarate, monomethyl ester, fumaric acid list propyl ester, the combination of one or more of fumaric acid two hydroxypropyl acrylates or fumaric acid mono—n—butylester.
5. the preparation method of a kind of fluorescent tracing phosphate-free polyether multifunctional water treating agent according to claim 2, it is characterized in that the fluorescent monomer containing unsaturated double-bond described in this preparation method is 8-allyloxy-1,3,6-pyrene sodium trisulfonate and 8-(4-vinyl benzyloxy base)-1, the combination of a kind of in 3,6-pyrene sodium trisulfonate or two kinds.
6. the preparation method of a kind of fluorescent tracing phosphate-free polyether multifunctional water treating agent according to claim 2, it is characterized in that described in this preparation method without organic initiators be Sodium Persulfate, Potassium Persulphate, lay particular stress on-sulfinic acid sodium, lay particular stress on-sulfinic acid potassium, one or more combination in persulfonic acid sodium, persulfonic acid potassium or hydrogen peroxide.
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