CN103319658B - A kind of containing phosphino-and sulfonic polymerization of itaconic acid thing and preparation method thereof - Google Patents
A kind of containing phosphino-and sulfonic polymerization of itaconic acid thing and preparation method thereof Download PDFInfo
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- CN103319658B CN103319658B CN201310271996.5A CN201310271996A CN103319658B CN 103319658 B CN103319658 B CN 103319658B CN 201310271996 A CN201310271996 A CN 201310271996A CN 103319658 B CN103319658 B CN 103319658B
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F14/00—Inhibiting incrustation in apparatus for heating liquids for physical or chemical purposes
- C23F14/02—Inhibiting incrustation in apparatus for heating liquids for physical or chemical purposes by chemical means
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/173—Macromolecular compounds
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Abstract
A kind of containing phosphino-and sulfonic polymerization of itaconic acid thing and preparation method thereof, belong to technical field of chemical products.It take methylene-succinic acid as principal monomer, and introduce sulfonic acid group and phosphino-, by aqueous solution polymerization, redox initiation system, synthesizes a kind of multifunctional anti-incrustation corrosion inhibitor simultaneously possessing scale inhibition, inhibition, dispersing property.The present invention is a kind of low-phosphorous, efficient, have the medicament of good scale prevention ability, and this product has good corrosion inhibiting ability in high rigidity, high alkalinity water quality.This polymkeric substance readily biodegradable, the biological degradability after 28 days can reach 70%, belongs to environmentally friendly product.
Description
Technical field
The present invention relates to a kind of containing phosphino-and sulfonic polymerization of itaconic acid thing and preparation method thereof, belong to technical field of chemical products.
Background technology
In the industrial production, recirculated cooling water almost along with the whole process of producing, plays a very important role.Good recirculating cooling water system is the prerequisite of enterprise's production equipment steady running.Improve water technology level, extension device work-ing life and plant running cycle, realizing water-saving consumption-reduction is the important channel of improving enterprise overall economic benefit.As far back as the sixties in 20th century, people adopt the method for adding chemical agent to alleviate the scale problems of the industrial circulating cooling waters such as refinery, chemical plant, fertilizer plant with regard to starting.Because the scale-inhibiting properties of multipolymer is better than homopolymer, the parent that copolymer antisludging agent more and more receives user in recent years looks at.
Methylene-succinic acid (IA), also known as methylene-succinic acid, mostly adopt fermentation method to produce both at home and abroad, biological degradability is strong.In circulating water cooling treatment field, the multipolymer of methylene-succinic acid and other reactive monomers starts there is patent report (WalinskySW. (Meth) acrylicacid/itaconicacidcopolymers, theirpreparationanduseasantiscalants [P] .US5032646.1991-07) in the nineties in 20th century.In recent years, Chinese scholar had carried out extensive research to itaconic acid homopolymers and multipolymer.Zhang Yanhe etc. have synthesized itaconic acid homopolymers, and it has excellent biodegradability.Adopt evaporation concentration test determination scale-inhibiting properties, cycles of concentration is 1.5, Ca
2+for 250mg/L is (with CaCO
3meter), HCO
3 -for 250mg/L is (with CaCO
3meter), result shows: itaconic acid homopolymers has excellent scale-inhibiting properties.Yu Yueqin etc. for monomer with methylene-succinic acid (IA) and vinylformic acid (AA), adopt aqueous free radical polyreaction, have synthesized IA/AA polymkeric substance, and determined optimum synthesis condition.Land man red horse etc. have studied synthesis and the scale-inhibiting properties of polymer antisludging agent IA/SSS, and to its modified synthesis IA/SSS/MA, compare the difference in both performances, the scale-inhibiting properties of the latter is better than the former.Zhao Zhanglin etc. with methylene-succinic acid (IA), 2-acrylamide-2-methyl propane sulfonic (AMPS), Propylene glycol monoacrylate (HPA) for monomer, pass through solution polymerization process, synthetic polymer IA-AMPS-HPA, and determine optimum synthesis condition.Along with the rise of oil price, like product such as the price such as vinylformic acid, toxilic acid significantly improves, and methylene-succinic acid is because taking starch as raw material, can biological degradation, and price is relatively stable, therefore develops methylene-succinic acid analog copolymer Scale inhibitors very necessary.
Current Scale inhibitors is just towards environmental protection, efficient and polyfunctional future development.Sulfonic acid group is introduced on the basis of carboxylic acid type polymkeric substance, effectively can prevent polymkeric substance and water intermediate ion from reacting and producing insoluble polymkeric substance calcium gel, and can effectively improve dispersing iron oxide performance.Phosphorus-containing carboxylic acid multipolymer is the high molecular polymer simultaneously containing phosphino-and hydroxy-acid group in a kind of molecular structure, and the existence of phosphino-can make this base polymer have good corrosion inhibition.Original polymerization of itaconic acid thing is not containing phosphino-, and corrosion inhibition is poor, needs to carry out composite with other inhibiter, complicated operation in actual procedure when using as water conditioner.Not poor containing sulfonic polymerization of itaconic acid thing dispersing property.So exploitation one is principal monomer with methylene-succinic acid, the multifunctional anti-incrustation corrosion inhibitor simultaneously introducing sulfonic group and phosphino-is significant.This polymkeric substance has good scale-inhibiting properties in high rigidity, high alkalinity water quality, and dispersing iron oxide better performances, there is good corrosion inhibition to A3 carbon steel, can use, without the need to composite as water conditioner separately.
Summary of the invention
It is principal monomer with methylene-succinic acid that technical problem to be solved by this invention is to provide a kind of, integrate the multipolymer of carboxylic acid group, sulfonic group, phosphino-, and this multipolymer has good scale inhibition, inhibition, dispersing property.
The technical scheme that the present invention takes is as follows:
One, a kind of containing phosphino-and sulfonic polymerization of itaconic acid thing, its special feature is it take methylene-succinic acid as principal monomer, introduce sulfonic acid group and phosphino-, pass through aqueous solution polymerization, redox initiation system, synthesizes a kind of multifunctional anti-incrustation corrosion inhibitor simultaneously possessing scale inhibition, inhibition, dispersing property.
Wherein methylene-succinic acid: sodium allylsulfonate: the mass ratio of inferior sodium phosphate is 45-55:10-20:5-20.
Redox initiation system comprises ferrous ammonium sulphate, massfraction 30% hydrogen peroxide, inferior sodium phosphate, and the mass ratio of they and methylene-succinic acid is methylene-succinic acid: ferrous ammonium sulphate: 30% hydrogen peroxide: inferior sodium phosphate=45-55:1-2:22-44:5-20.
Two, described a kind of preparation method containing phosphino-and sulfonic polymerization of itaconic acid thing, its concrete grammar step is as follows:
45-55:10-20:1-2:1-3:30-50:22-44:5-20 gets methylene-succinic acid, sodium allylsulfonate, ferrous ammonium sulphate, Virahol, water, 30% hydrogen peroxide and inferior sodium phosphate in mass ratio, first methylene-succinic acid, sodium allylsulfonate, ferrous ammonium sulphate, Virahol, water are added successively the four-hole boiling flask that reflux exchanger, dropping funnel, thermometer, whipping appts are housed, be warming up to 85-95 DEG C, then drip hydrogen peroxide and inferior sodium phosphate simultaneously, within 1.5-3 hour, dropwise, be warming up to 102-105 DEG C, back flow reaction 1.5-2.5h; After completion of the reaction, cool to room temperature discharging, reaction product is containing phosphino-and sulfonic polymerization of itaconic acid thing.
The present invention adopts the beneficial effect of technique scheme as follows:
The present invention is directed to existing Scale inhibitors needs the problem of composite use to improve in water treatment procedure, its major advantage is embodied in following several aspect compared with existing water conditioner: 1. the present invention is that one is low-phosphorous, efficient, multifunctional anti-incrustation disperses inhibiter, and have good scale prevention ability in high rigidity, high alkalinity water quality.2. this polymkeric substance readily biodegradable, measure through shaking table laboratory method, the biological degradability after 28 days can reach about 70%, belongs to environmentally friendly product.3. this product has good corrosion inhibiting ability.
The present invention measures respectively to the scale inhibition of this polymkeric substance, inhibition, dispersing property.Scale-inhibiting properties measures with reference to GB/T16632-2008 " mensuration-tosca method of water conditioner scale-inhibiting properties ", and in configuration water, the concentration of calcium ion is that 600mg/L(is with CaCO
3meter), the concentration of bicarbonate ion is that 1200mg/L(is with CaCO
3meter).Biological degradability, with reference to the mensuration of biodegradable in " synthesis of green bio polymeric polyaspartic acid and scale-inhibiting properties research " literary compositions such as " Treatment of Industrial Water " the 21st volume first phase Xiong Rongchun, adopts THZ-82 gas bath constant temperature oscillator to carry out shaking table laboratory method mensuration.Corrosion inhibition test, with reference to GB/T18175-2000 " mensuration-rotary hanging plate method of water conditioner corrosion inhibition ", adopts ZJ dip etching experiment instrument to carry out corrosion inhibition test, temperature 40 DEG C, rotating speed 75r/min, not pre-film lacing film, time 75h, A3 carbon steel coupon (50mmX25mmX2mm).Corrosion inhibition test water is Hebei Academy of Sciences tap water, and condition of water quality is as table 1.
Table 1 corrosion inhibition test water Analysis Results of Water Quality
| Total hardness/mgL -1 | [Ca 2+]/mg·L -1 | Total alkalinity/mgL -1 | [Cl -]/mg·L -1 |
| 293.5 | 186.8 | 134.6 | 96.2 |
Embodiment
Following examples are for illustration of the present invention:
Embodiment 1:
52:13:2:1.5:50:22:13 gets methylene-succinic acid, sodium allylsulfonate, ferrous ammonium sulphate, Virahol, water, 30% hydrogen peroxide and ortho phosphorous acid sodium solution in mass ratio, first methylene-succinic acid, sodium allylsulfonate, ferrous ammonium sulphate, Virahol, water are added successively the four-hole boiling flask that reflux exchanger, dropping funnel, thermometer, whipping appts are housed, be warming up to 90 DEG C and keep temperature 90 ± 1 DEG C, then drip hydrogen peroxide and ortho phosphorous acid sodium water solution simultaneously, within 1.5 hours, dropwise, be warming up to 102 ± 1 DEG C, back flow reaction 2h.After completion of the reaction, cool to room temperature discharging, reaction product is containing phosphino-and sulfonic polymerization of itaconic acid thing.Carry out performance test to this polymkeric substance, test-results shows: when chemical feeding quantity is 20mg/L, scale inhibition performance can reach 93.21%.When chemical feeding quantity is 30mg/L, transmittance is only 65.7%.When chemical feeding quantity is 50mg/L, be 0.01882/a to the corrosion rate of carbon steel, corrosion inhibition rate is 95.42%; Degradation rate after 28 days is 70.5%.
Embodiment 2:
55:11:2:1.5:40:22:13 gets methylene-succinic acid, sodium allylsulfonate, ferrous ammonium sulphate, Virahol, water, 30% hydrogen peroxide and ortho phosphorous acid sodium solution in mass ratio, first methylene-succinic acid, sodium allylsulfonate, ferrous ammonium sulphate, Virahol, water are added successively the four-hole boiling flask that reflux exchanger, dropping funnel, thermometer, whipping appts are housed, be warming up to 90 DEG C and keep temperature 90 ± 1 DEG C, then drip hydrogen peroxide and ortho phosphorous acid sodium water solution simultaneously, within 1.5 hours, dropwise, be warming up to 102 ± 1 DEG C, back flow reaction 2h.After completion of the reaction, cool to room temperature discharging, reaction product is containing phosphino-and sulfonic polymerization of itaconic acid thing.Carry out performance test to this polymkeric substance, test-results shows: when chemical feeding quantity is 20mg/L, scale inhibition performance can reach 91.60%.When chemical feeding quantity is 30mg/L, transmittance is only 69.2%.When chemical feeding quantity is 50mg/L, be 0.02823/a to the corrosion rate of carbon steel, corrosion inhibition rate is 93.13%; Degradation rate after 28 days is 70.9%.
Embodiment 3:
50:16:2:1.5:40:33:9 gets methylene-succinic acid, sodium allylsulfonate, ferrous ammonium sulphate, Virahol, water, 30% hydrogen peroxide and ortho phosphorous acid sodium solution in mass ratio, first methylene-succinic acid, sodium allylsulfonate, ferrous ammonium sulphate, Virahol, water are added successively the four-hole boiling flask that reflux exchanger, dropping funnel, thermometer, whipping appts are housed, be warming up to 90 DEG C and keep temperature 90 ± 1 DEG C, then drip hydrogen peroxide and ortho phosphorous acid sodium water solution simultaneously, within 1.5 hours, dropwise, be warming up to 102 ± 1 DEG C, back flow reaction 2h.After completion of the reaction, cool to room temperature discharging, reaction product is containing phosphino-and sulfonic polymerization of itaconic acid thing.Carry out performance test to this polymkeric substance, test-results shows: when chemical feeding quantity is 20mg/L, scale inhibition performance can reach 92.34%.When chemical feeding quantity is 30mg/L, transmittance is only 63.2%.When chemical feeding quantity is 50mg/L, be 0.03653/a to the corrosion rate of carbon steel, corrosion inhibition rate is 91.11%; Degradation rate after 28 days is 70.6%.
Embodiment 4:
45:10:1:1:30:22:5 gets methylene-succinic acid, sodium allylsulfonate, ferrous ammonium sulphate, Virahol, water, 30% hydrogen peroxide and ortho phosphorous acid sodium solution in mass ratio, first methylene-succinic acid, sodium allylsulfonate, ferrous ammonium sulphate, Virahol, water are added successively the four-hole boiling flask that reflux exchanger, dropping funnel, thermometer, whipping appts are housed, be warming up to 85 DEG C and keep temperature 85 ± 1 DEG C, then drip hydrogen peroxide and ortho phosphorous acid sodium water solution simultaneously, within 1.5 hours, dropwise, be warming up to 105 ± 1 DEG C, back flow reaction 1.5h.After completion of the reaction, cool to room temperature discharging, reaction product is containing phosphino-and sulfonic polymerization of itaconic acid thing.Carry out performance test to this polymkeric substance, test-results shows: when chemical feeding quantity is 20mg/L, scale inhibition performance can reach 88.23%.When chemical feeding quantity is 30mg/L, transmittance is 70.3%.When chemical feeding quantity is 50mg/L, be 0.05369/a to the corrosion rate of carbon steel, corrosion inhibition rate is 86.93%; Degradation rate after 28 days is 72.4%.
Embodiment 5:
52:20:1.5:3:50:44:20 gets methylene-succinic acid, sodium allylsulfonate, ferrous ammonium sulphate, Virahol, water, 30% hydrogen peroxide and ortho phosphorous acid sodium solution in mass ratio, first methylene-succinic acid, sodium allylsulfonate, ferrous ammonium sulphate, Virahol, water are added successively the four-hole boiling flask that reflux exchanger, dropping funnel, thermometer, whipping appts are housed, be warming up to 95 DEG C and keep temperature 95 ± 1 DEG C, then drip hydrogen peroxide and ortho phosphorous acid sodium water solution simultaneously, within 3 hours, dropwise, be warming up to 102 ± 1 DEG C, back flow reaction 2.5h.After completion of the reaction, cool to room temperature discharging, reaction product is containing phosphino-and sulfonic polymerization of itaconic acid thing.Carry out performance test to this polymkeric substance, test-results shows: when chemical feeding quantity is 20mg/L, and scale inhibition performance is 86.35%.When chemical feeding quantity is 30mg/L, transmittance is 68.4%.When chemical feeding quantity is 50mg/L, be 0.05812/a to the corrosion rate of carbon steel, corrosion inhibition rate is 85.85%; Degradation rate after 28 days is 70.1%.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.
Claims (1)
1. contain a preparation method for phosphino-and sulfonic polymerization of itaconic acid thing, it is characterized in that it carries out according to the following steps:
45-55:10-20:1-2:1-3:30-50:22-44:5-20 gets methylene-succinic acid, sodium allylsulfonate, ferrous ammonium sulphate, Virahol, water, 30% hydrogen peroxide and inferior sodium phosphate in mass ratio, first methylene-succinic acid, sodium allylsulfonate, ferrous ammonium sulphate, Virahol, water are added successively the four-hole boiling flask that reflux exchanger, dropping funnel, thermometer, whipping appts are housed, be warming up to 85-95 DEG C, then drip hydrogen peroxide and inferior sodium phosphate simultaneously, within 1.5-3 hour, dropwise, be warming up to 102-105 DEG C, back flow reaction 1.5-2.5h; After completion of the reaction, cool to room temperature discharging, reaction product is containing phosphino-and sulfonic polymerization of itaconic acid thing.
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Citations (3)
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| CN1454909A (en) * | 2003-03-25 | 2003-11-12 | 青岛琅琊台集团股份有限公司 | Itaconic acid copolymer and preparation method and application thereof |
| KR100805649B1 (en) * | 2000-04-01 | 2008-02-26 | 키네티큐 리미티드 | Novel copolymers, their preparation and their use |
| CN101786731A (en) * | 2010-04-08 | 2010-07-28 | 山东省特种设备检验研究院淄博分院 | Ether-based itaconic acid sulfonate type multi-copolymer scale inhibitor and method for preparing same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR100805649B1 (en) * | 2000-04-01 | 2008-02-26 | 키네티큐 리미티드 | Novel copolymers, their preparation and their use |
| CN1454909A (en) * | 2003-03-25 | 2003-11-12 | 青岛琅琊台集团股份有限公司 | Itaconic acid copolymer and preparation method and application thereof |
| CN101786731A (en) * | 2010-04-08 | 2010-07-28 | 山东省特种设备检验研究院淄博分院 | Ether-based itaconic acid sulfonate type multi-copolymer scale inhibitor and method for preparing same |
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| "醚基衣康酸多元共聚物阻垢剂合成条件研究";张文辉等;《广州化工》;20120531;第40卷(第10期);第56-59页 * |
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