CN101830571A - Itaconic acid copolymer antisludging agent and microwave synthetic method thereof - Google Patents
Itaconic acid copolymer antisludging agent and microwave synthetic method thereof Download PDFInfo
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- CN101830571A CN101830571A CN201010198966A CN201010198966A CN101830571A CN 101830571 A CN101830571 A CN 101830571A CN 201010198966 A CN201010198966 A CN 201010198966A CN 201010198966 A CN201010198966 A CN 201010198966A CN 101830571 A CN101830571 A CN 101830571A
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- succinic acid
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/04—Polymerisation in solution
- C08F2/10—Aqueous solvent
Abstract
The invention discloses a novel itaconic acid copolymer antisludging agent and a microwave synthetic method thereof. The antisludging agent comprises a chain link structure shown in the formula [I]. The synthetic method comprises the following steps of: using the itaconic acid as a main raw material; and carrying out copolymerization on the itaconic acid, maleic anhydride, sulfonate and the like in the presence of an initiator to prepare a terpolymer. The molecular weight of the itaconic acid copolymer prepared by the invention is 2,000-3,000, and the color of the copolymer is light yellow or brown yellow. The novel itaconic acid copolymer antisludging agent belongs to an environment-friendly chemical-industrial product, and can be used as an antisludging agent, an anti-corrosion agent, a dispersing agent and the like. The invention has the advantages of simple process, high synthesis speed, low energy consumption and less pollution.
Description
Technical field
The invention belongs to polymkeric substance polymer and water-treatment technology field, be specifically related to a kind of novel itaconic acid copolymer antisludging agent and microwave synthesis method thereof.
Background technology
The industry of fast development needs recirculated cooling water mostly, and the scale formation of industrial water system has a strong impact on heat transfer efficiency, increases energy consumption, the corrosion of acceleration equipment.Because Freshwater resources is in short supply day by day, the scale inhibition of process water is handled and is more and more come into one's own.Utilization adds Scale inhibitors, and to carry out that scale inhibition handles be convenient relatively and high-efficiency method in numerous method of scale inhibition.Natural polymer class Scale inhibitors source is wide, cheaply be easy to get, but scale inhibition effect is poor the foreign matter content height; Phosphorous Scale inhibitors scale inhibition effect is better, but easily causes body eutrophication, brings very big destruction to water surrounding.Therefore exploitation is used low-phosphorous, without phosphorus green scale inhibitor has become the inexorable trend of domestic and international water treatment field, existing in the market polyacrylic acid, non-phosphorus scale agent such as polymethyl acrylic acid, but because its scale inhibition functional group is single, processing power is limited, synthetic complicated, production cost is higher, so binary, the terpolymer Scale inhibitors produces thereupon, and this analog copolymer contains carboxyl more, hydroxyl, sulfonic group, multiple scale inhibition such as amino functional group, different group matched combined, both can prevent effectively that the slightly water-wet group from generating the calcium gel of indissoluble, helped dissolving again, effectively antiscale.Methylene-succinic acid derives from biofermentation technique, and raw material is easy to get, and has avoided phosphorous Scale inhibitors potential to pollute.In the methylene-succinic acid molecule, not only contain the carbon double bond functional group of Raolical polymerizable needs, and be connected with a hydroxy-acid group respectively in the both sides of two keys, the latter give the good negative electricity dispersing property of itaconic acid copolymer and with the ability of other ion complexation.The synthesis technique of methylene-succinic acid (IA)-vinylformic acid (AA) copolymer aqueous solution has been studied and to CaCO in Wang Guang river etc. in the prior art
3Scale inhibition effect, experimental result shows that the IA-AA multipolymer is to CaCO
3Scale inhibition effect good, the adaptive temperature wide ranges can obtain significant scale inhibition effect under the less situation of multipolymer consumption, but the experiment in vinylformic acid cost an arm and a leg, increased the production cost of multipolymer.Chinese patent publication number CN03112046.6 has synthesized methylene-succinic acid, (methyl) propene sulfonic acid salt, (methyl) vinylformic acid hydroxyl ester multipolymer scale inhibiting agent, scale inhibition effect is good, and is of many uses, but the technological process more complicated, required time is longer, and energy consumption is bigger, has hindered its suitability for industrialized production.Compare with traditional method, carry out microwave radiation heating can improve thousands of times of speed of reaction, and easy to operate, at present the microwave-assisted synthesis about itaconic acid copolymer antisludging agent rarely has patent report, and the involutory one-tenth methylene-succinic acid of people, maleic anhydride, Sulfonates multipolymer more do not have bibliographical information.
Summary of the invention
Purpose of the present invention is intended to simplify technological process, improves speed of reaction, provides a kind of and has contained sulfonic group and carboxylic acid group functional group simultaneously and to CaCO on molecular chain
3The water conditioner itaconic acid copolymer and the microwave preparation scheme thereof of good scale-inhibiting properties are arranged, studied each reaction conditions emphatically the copolymer anti-scale Effect on Performance.This method technology is simple, and is convenient, and microwave is introduced experiment, has shortened the reaction times greatly, has improved chemical reaction rate, and product property is stable.
To achieve these goals, the present invention takes following technical solution: a kind of itaconic acid copolymer antisludging agent, and this Scale inhibitors is formed by the feedstock production of following mass fraction:
60 parts of methylene-succinic acids;
9 parts of maleic anhydrides;
8～14 parts in sulfonate;
100～120 parts of deionized waters;
5～20 parts of initiators;
6～15 parts of chain-transfer agents;
1～2 part of catalyzer.
Described sulfonate is selected from sodium allylsulfonate, propene sulfonic acid potassium, methylpropene sodium sulfonate, methacrylic potassium sulfonate, ethyl propylene sodium sulfonate, ethyl propylene potassium sulfonate, Sodium styrene sulfonate, styrene sulfonic acid potassium, phenyl sodium allylsulfonate or phenyl propene sulfonic acid potassium.
Preferred sodium allylsulfonate of described sulfonate or propene sulfonic acid potassium.
Described initiator is a redox class initiator: mass ratio be 1: 1 hydrogen peroxide (30%) with the mixture of sodium bisulfite (30%).
Described chain-transfer agent is analytically pure Virahol.
Described catalyzer is a ferrous ammonium sulphate.
Described Scale inhibitors according to following mass fraction preferred version is: methylene-succinic acid is 60 parts, and maleic anhydride is 9 parts, and sulfonate is 10 parts, and deionized water is 100 parts, and initiator is 15 parts, and chain-transfer agent is 12 parts, and catalyzer is 1 part.
The present invention gives the synthetic method of this methylene-succinic acid terpolymer Scale inhibitors, and this method is synthesized by following concrete steps:
Be respectively 60 parts methylene-succinic acid with mass fraction, the sulfonate of 9 parts maleic anhydride and 8～14 parts is raw material, with 100～120 parts of deionized water dissolvings, add 5～20 parts of mass ratioes and be 1: 1 hydrogen peroxide (30%) with the mixture of sodium bisulfite (30%), 6～15 parts of analytically pure Virahols and 1～2 part of catalyst sulfuric acid ferrous ammonium, applied microwave synthetic technology (XH-100A type computer microwave catalysis/synthetic abstraction instrument), be to heat under the condition of 700W～900W at microwave power, stir, reflux, radiation temperature is 50～90 ℃, and microwave irradiation time is 20～60min, obtains light yellow or pale brown look viscosity itaconic acid copolymer solution;
The remainder chain-transfer agent was told in underpressure distillation (underpressure distillation pressure is 0.8kPa) after product solution added 50～150mL washing with acetone 3～5 times, was cooled to the room temperature discharging, promptly got end product methylene-succinic acid terpolymer Scale inhibitors.
The mixture of described initiator hydrogen peroxide and sodium bisulfite and the adding mode of chain-transfer agent Virahol are slow dropping.
End product methylene-succinic acid terpolymer Scale inhibitors structural formula is:
In the formula, R
1Expression H
+Or low alkyl group, R
2Expression SO
3H, SO
3Na or SO
3K etc., m, n, q are respectively arbitrary integer in 1～50.
Characteristics such as the present invention has shortened the reaction times by the microwave chemical technology, has simplified synthesis technique, and it is simple that this technology has process, and resultant velocity is fast, and is energy-conservation.Product scale inhibition performance height, calcium there is very high tolerance, and good timeliness and very strong thermotolerance arranged, can avoid favorable environment protection being arranged because the body eutrophication problem that the discharging of phosphorus causes alleviates environmental pollution, can be widely used in recirculating cooling water system, feedwater, oil-field water, aspects such as sea water desalinization.This multipolymer Phosphateless environmentally friendly can be used as pure water, softening water, boiler feed water, the Scale inhibitors of systems such as industrial circulating cooling water, inhibiter etc.
Embodiment
The microwave synthesis method of novel itaconic acid copolymer antisludging agent of the present invention, be to be raw material with methylene-succinic acid, maleic anhydride, sulfonate, under the microwave field condition (XH-100A type computer microwave catalysis/synthetic abstraction instrument), add initiator and chain-transfer agent, irradiation for some time gets methylene-succinic acid terpolymer solution at a certain temperature.Concrete grammar is: the methylene-succinic acid that is respectively 60 parts with mass fraction, the sulfonate of 9 parts maleic anhydride and 8～14 parts is raw material, with 100～120 parts of deionized water dissolvings, add 5～20 parts of initiators, 6～15 parts of chain-transfer agents and 1～2 part of catalyzer, use XH-100A type computer microwave catalysis/synthetic abstraction instrument, be to heat under the condition of 700W～900W at microwave power, stir, reflux, microwave irradiation time is 20～60min, and radiation temperature is 50～90 ℃, obtains light yellow or pale brown look viscosity itaconic acid copolymer solution.Product solution is added underpressure distillation (pressure is 0.8kPa) behind 50～150mL washing with acetone 3～5 times, tell the remainder chain-transfer agent, be cooled to the room temperature discharging and promptly get end product methylene-succinic acid terpolymer.Can obtain under the different condition faint yellow, pale brown look or henna product, molecular weight distribution is 2000～30000.
Above-mentioned sulfonate is selected from sodium allylsulfonate (potassium), methylpropene sodium sulfonate (potassium), ethyl propylene sodium sulfonate (potassium), Sodium styrene sulfonate (potassium) or phenyl sodium allylsulfonate (potassium), preferred sodium allylsulfonate of the present invention or propene sulfonic acid potassium.
Above-mentioned initiator is a redox class initiator: mass ratio be 1: 1 hydrogen peroxide (30%) with the mixture of sodium bisulfite (30%), chain-transfer agent is the analytical pure Virahol, catalyzer is a ferrous ammonium sulphate.
The best in quality umber of above-mentioned methylene-succinic acid, maleic anhydride, sulfonate is respectively 60 parts, and 9 parts, 10 parts, deionized water best in quality umber is 100 parts, and initiator best in quality umber is 15 parts, and chain-transfer agent best in quality umber is 12 parts; Catalyzer best in quality umber is 1 part.
The adding mode of above-mentioned initiator hydrogen peroxide and sodium bisulfite and chain-transfer agent Virahol is slow dropping.
Further describe the present invention below by a series of embodiment, these embodiment are the more excellent examples of the present invention, and the present invention does not limit to these embodiment.In an embodiment, CaCO
3The measuring method of scale-inhibiting properties adopts the standard GB/T16632-1996 " mensuration of water conditioner scale-inhibiting properties---CaCO
3Sedimentation ".
Embodiment 1:(is according to every part of 1/10g meter of mass fraction)
In there-necked flask, add the 6.0g methylene-succinic acid, 0.9g maleic anhydride, and a certain amount of sodium allylsulfonate, each component chemical metering is than seeing Table 1 (these three kinds of proportion of raw materials are monomer ratio), use the 10mL deionized water dissolving, add 0.1g catalyst sulfuric acid ferrous ammonium, be placed on (XH-100A type computer microwave catalysis/synthetic abstraction instrument) under the microwave field of 2450MHz, microwave power is 700W, by certain speed slowly drip the 0.5g initiator (mass ratio be 1: 1 hydrogen peroxide (30%) with the mixture of sodium bisulfite (30%)) and 1.5g chain-transfer agent Virahol, the applied microwave synthetic technology, stir, reflux, microwave irradiation time is 30min, temperature of reaction is 70 ℃, obtains light yellow transparent solution.The remainder chain-transfer agent was told in underpressure distillation (pressure is 0.8kPa) after product added 150mL washing with acetone 4 times, was cooled to the room temperature discharging and promptly got end product methylene-succinic acid terpolymer.
Table 1: monomer ratio is to the influence of methylene-succinic acid terpolymer scale inhibition performance
| The monomer mass proportioning | Suppress CaCO 3??Ca 2+Concentration (mg/L) | Scale inhibitors concentration (mg/L) | Scale inhibition performance (%) |
| ??6∶0.9∶0.8 | ??500 | ??10 | ??55.38 |
| ??6∶0.9∶0.9 | ??500 | ??10 | ??65.14 |
| ??6∶0.9∶1.0 | ??500 | ??10 | ??77.03 |
| ??6∶0.9∶1.1 | ??500 | ??10 | ??70.25 |
| ??6∶0.9∶1.2 | ??500 | ??10 | ??59.49 |
| ??6∶0.9∶1.4 | ??500 | ??10 | ??53.93 |
The foregoing description can be found out: when monomer ratio is 6: 0.9: 1.0, and initiator 0.5g, chain-transfer agent 1.5g, microwave irradiation time 30min, during 70 ℃ of temperature of reaction, its scale inhibition performance the best.
Sodium allylsulfonate or take propene sulfonic acid potassium to substitute in the foregoing description 1.
Embodiment 2:(is according to every part of 1/10g meter of mass fraction)
In there-necked flask, add the 6.0g methylene-succinic acid respectively, 0.9g maleic anhydride and 1.0g methylpropene sodium sulfonate, use the 10mL deionized water dissolving, add 0.1g catalyst sulfuric acid ferrous ammonium, be placed under the microwave field of 2450MHz (the same), microwave power is 700W, by certain speed slowly drip a certain amount of initiator (mass ratio be 1: 1 hydrogen peroxide (30%) with the mixture of sodium bisulfite (30%)) and 1.2g chain-transfer agent Virahol, the initiator add-on sees Table 2, the applied microwave synthetic technology, stir, reflux, microwave irradiation time is 40min, temperature of reaction is 80 ℃, obtains light yellow transparent solution.The remainder chain-transfer agent was told in underpressure distillation after product added 100mL washing with acetone 4 times, was cooled to the room temperature discharging and promptly got end product methylene-succinic acid terpolymer.
Table 2: initiator amount is to the influence of methylene-succinic acid terpolymer scale inhibition performance
| Initiator add-on (g) | Suppress CaCO 3??Ca 2+Concentration (mg/L) | Scale inhibitors concentration (mg/L) | Scale inhibition performance (%) |
| ??0.5 | ??500 | ??10 | ??62.01 |
| ??1.0 | ??500 | ??10 | ??77.11 |
| ??1.5 | ??500 | ??10 | ??84.44 |
| ??2.0 | ??500 | ??10 | ??79.05 |
The foregoing description adds initiator 1.5g as can be seen when monomer ratio 6: 0.9: 1.0, chain-transfer agent 1.2g, and microwave irradiation time 40min, during 80 ℃ of temperature of reaction, its scale inhibition performance be the best.
Methylpropene sodium sulfonate or take the methacrylic potassium sulfonate to substitute in the foregoing description 2.
Embodiment 3:(is according to every part of 1/10g meter of mass fraction)
In there-necked flask, add the 6.0g methylene-succinic acid respectively, 0.9g maleic anhydride and 1.0g ethyl propylene sodium sulfonate, use the 10mL deionized water dissolving, add 0.1g catalyst sulfuric acid ferrous ammonium, be placed under the microwave field of 2450MHz (the same), microwave power is 800W, by certain speed slowly drip 1.0g initiator (mass ratio be 1: 1 hydrogen peroxide (30%) with the mixture of sodium bisulfite (30%)) and a certain amount of chain-transfer agent Virahol, the chain-transfer agent add-on sees Table 3, the applied microwave synthetic technology, stir, reflux, microwave irradiation time is 50min, temperature of reaction is 60 ℃, obtains light yellow transparent solution.The remainder chain-transfer agent was told in underpressure distillation after product added 150mL washing with acetone 3 times, was cooled to the room temperature discharging and promptly got end product methylene-succinic acid terpolymer.
Table 3: the chain-transfer agent consumption is to the influence of methylene-succinic acid terpolymer scale inhibition performance
| Chain-transfer agent add-on (g) | Suppress CaCO 3??Ca 2+Concentration (mg/L) | Scale inhibitors concentration (mg/L) | Scale inhibition performance (%) |
| ??0.6 | ??500 | ??10 | ??42.36 |
| ??0.9 | ??500 | ??10 | ??51.18 |
| ??1.2 | ??500 | ??10 | ??69.00 |
| ??1.5 | ??500 | ??10 | ??60.32 |
The foregoing description when monomer ratio is 6: 0.9: 1.0, adds chain-transfer agent Virahol 1.2g as can be seen, initiator 1.0g, and microwave irradiation time 50min, during 60 ℃ of temperature of reaction, its scale inhibition performance the best.
Ethyl propylene sodium sulfonate or take the ethyl propylene potassium sulfonate to substitute in the foregoing description 3.
Embodiment 4:(is according to every part of 1/10g meter of mass fraction)
In there-necked flask, add the 6.0g methylene-succinic acid respectively, 0.9g maleic anhydride and 1.4g Sodium styrene sulfonate, use the 12mL deionized water dissolving, add 0.2g catalyst sulfuric acid ferrous ammonium, be placed under the microwave field of 2450MHz (the same), microwave power is 800W, by certain speed slowly drip the 1.5g initiator (mass ratio be 1: 1 hydrogen peroxide (30%) with the mixture of sodium bisulfite (30%)) and 0.9g chain-transfer agent Virahol, the applied microwave synthetic technology, stir, reflux, microwave irradiation time sees Table 4, and temperature of reaction is 90 ℃, obtains pale brown look clear solution.The remainder chain-transfer agent was told in underpressure distillation after product added 100mL washing with acetone 4 times, was cooled to the room temperature discharging and promptly got end product methylene-succinic acid terpolymer.
Table 4: radiated time is to the influence of methylene-succinic acid terpolymer scale inhibition performance
| Radiated time (min) | Suppress CaCO 3??Ca 2+Concentration (mg/L) | Scale inhibitors concentration (mg/L) | Scale inhibition performance (%) |
| ??20 | ??500 | ??10 | ??58.32 |
| Radiated time (min) | Suppress CaCO 3??Ca 2+Concentration (mg/L) | Scale inhibitors concentration (mg/L) | Scale inhibition performance (%) |
| ??30 | ??500 | ??10 | ??67.26 |
| ??40 | ??500 | ??10 | ??74.88 |
| ??50 | ??500 | ??10 | ??71.54 |
| ??60 | ??500 | ??10 | ??68.64 |
The foregoing description when monomer ratio is 6: 0.9: 1.4, adds initiator 1.5g as can be seen, chain-transfer agent 0.9g, and microwave irradiation time 40min, during 90 ℃ of temperature of reaction, its scale inhibition performance be the best.
Sodium styrene sulfonate or take styrene sulfonic acid potassium to substitute in the foregoing description 4.
Embodiment 5:(is according to every part of 1/10g meter of mass fraction)
In there-necked flask, add the 6.0g methylene-succinic acid respectively, 0.9g maleic anhydride and 1.0g phenyl sodium allylsulfonate, use the 11mL deionized water dissolving, add 0.1g catalyst sulfuric acid ferrous ammonium, be placed under the microwave field of 2450MHz (the same), microwave power is 900W, by certain speed slowly drip the 2.0g initiator (mass ratio be 1: 1 hydrogen peroxide (30%) with the mixture of sodium bisulfite (30%)) and 0.6g chain-transfer agent Virahol, the applied microwave synthetic technology, stir, reflux, microwave irradiation time is 60min, and temperature of reaction sees Table 5, obtains light yellow transparent solution.The remainder chain-transfer agent was told in underpressure distillation after product added 50mL washing with acetone 5 times, was cooled to the room temperature discharging and promptly got end product methylene-succinic acid terpolymer.
Table 5: temperature of reaction is to the influence of methylene-succinic acid terpolymer scale inhibition performance
| Temperature of reaction (℃) | Suppress CaCO 3??Ca 2+Concentration (mg/L) | Scale inhibitors concentration (mg/L) | Scale inhibition performance (%) |
| ??50 | ??500 | ??10 | ??43.44 |
| ??60 | ??500 | ??10 | ??62.95 |
| ??70 | ??500 | ??10 | ??75.50 |
| ??80 | ??500 | ??10 | ??84.18 |
| ??90 | ??500 | ??10 | ??81.25 |
The foregoing description when monomer ratio is 6: 0.9: 1.0, adds initiator 2.0g as can be seen, chain-transfer agent 0.6g, and microwave irradiation time 60min, when temperature of reaction is 80 ℃, its scale inhibition performance the best.
Phenyl sodium allylsulfonate or take phenyl propene sulfonic acid potassium to substitute in the foregoing description 5.
Claims (10)
1. methylene-succinic acid terpolymer Scale inhibitors is characterized in that this Scale inhibitors has following link configuration:
Wherein, R
1Expression H
+Or low alkyl group, R
2Expression SO
3H, SO
3Na or SO
3K, m, n, q are respectively arbitrary integer in 1～50.
2. a kind of methylene-succinic acid terpolymer Scale inhibitors as claimed in claim 1 is characterized in that described Scale inhibitors is formed by the feedstock production of following mass fraction:
60 parts of methylene-succinic acids;
9 parts of maleic anhydrides;
8～14 parts in sulfonate;
100～120 parts of deionized waters;
5～20 parts of initiators;
6～15 parts of chain-transfer agents;
1～2 part of catalyzer.
3. methylene-succinic acid terpolymer Scale inhibitors as claimed in claim 2, it is characterized in that described sulfonate is selected from sodium allylsulfonate, propene sulfonic acid potassium, methylpropene sodium sulfonate, methacrylic potassium sulfonate, ethyl propylene sodium sulfonate, ethyl propylene potassium sulfonate, Sodium styrene sulfonate, styrene sulfonic acid potassium, phenyl sodium allylsulfonate or phenyl propene sulfonic acid potassium.
4. methylene-succinic acid terpolymer Scale inhibitors as claimed in claim 2 is characterized in that, preferred sodium allylsulfonate of described sulfonate or propene sulfonic acid potassium.
5. methylene-succinic acid terpolymer Scale inhibitors as claimed in claim 2 is characterized in that, described initiator is a redox class initiator: mass ratio is the mixture of the sodium bisulfite of 1: 1 30% hydrogen peroxide and 30%.
6. methylene-succinic acid terpolymer Scale inhibitors as claimed in claim 2 is characterized in that described chain-transfer agent is analytically pure Virahol.
7. methylene-succinic acid terpolymer Scale inhibitors as claimed in claim 2 is characterized in that described catalyzer is a ferrous ammonium sulphate.
8. methylene-succinic acid terpolymer Scale inhibitors as claimed in claim 2, it is characterized in that, described Scale inhibitors according to following mass fraction preferred version is: methylene-succinic acid is 60 parts, maleic anhydride is 9 parts, sulfonate is 10 parts, and deionized water is 100 parts, and initiator is 15 parts, chain-transfer agent is 12 parts, and catalyzer is 1 part.
9. the synthetic method of a methylene-succinic acid terpolymer Scale inhibitors, it is characterized in that, synthesize by following concrete steps: the methylene-succinic acid that is respectively 60 parts with mass fraction, the sulfonate of 9 parts maleic anhydride and 8～14 parts is raw material, with 100～120 parts of deionized water dissolvings, add 5～20 parts of mass ratioes and be 1: 1 30% the hydrogen peroxide and the mixture of 30% sodium bisulfite, 6～15 parts of analytically pure Virahols and 1～2 part of catalyst sulfuric acid ferrous ammonium, use under the condition that the catalysis of XH-100A type computer microwave/synthetic abstraction instrument is 700W～900W at microwave power and heat, stir, reflux, radiation temperature is 50～90 ℃, microwave irradiation time is 20～60min, obtains light yellow or pale brown look viscosity itaconic acid copolymer solution;
Behind product solution adding 50～150mL washing with acetone 3～5 times, be to tell the remainder chain-transfer agent under the 0.8kPa condition at underpressure distillation pressure, be cooled to the room temperature discharging, promptly get end product methylene-succinic acid terpolymer Scale inhibitors.
10. the preparation method of methylene-succinic acid terpolymer Scale inhibitors as claimed in claim 9 is characterized in that, the adding mode of described initiator and chain-transfer agent is slow dropping.
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| CN117263405A (en) * | 2023-11-23 | 2023-12-22 | 山东上远环保科技有限公司 | Protective agent for circulating water pipeline |
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