CN100575391C - The corrosion inhibiting and descaling agent Epoxysuccinic acid/to acid/epoxy ethylbenzene sulfonic acid copolymer and preparation method thereof - Google Patents
The corrosion inhibiting and descaling agent Epoxysuccinic acid/to acid/epoxy ethylbenzene sulfonic acid copolymer and preparation method thereof Download PDFInfo
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- CN100575391C CN100575391C CN200810033181A CN200810033181A CN100575391C CN 100575391 C CN100575391 C CN 100575391C CN 200810033181 A CN200810033181 A CN 200810033181A CN 200810033181 A CN200810033181 A CN 200810033181A CN 100575391 C CN100575391 C CN 100575391C
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Abstract
The invention belongs to the industrial circulating cooling water processing technology field, be specifically related to a kind of corrosion inhibiting and descaling agent Epoxysuccinic acid/acid/epoxy ethylbenzene sulfonic acid copolymer and preparation method thereof.This multipolymer is a kind of carboxyl, sulfonic polyether compound of containing.The present invention is with toxilic acid, to behind the double bond epoxidation in the vinyl benzenesulfonic acid sodium, forms epoxy Succinic Acid/to oxyethane Phenylsulfonic acid multipolymer by the ionic polymerization mode again.Experiment showed, that this multipolymer can stop CaCO effectively
3, CaSO
4, BaSO
4, SrSO
4, Ca
3(PO
4)
2Deng the formation of dirt, and zine ion being had good stabilization, is a kind of polynary dirt dispersion agent; This multipolymer also has certain corrosion inhibition simultaneously; And without phosphorus, the no nitrogen of this multipolymer, biodegradable is a kind of environmental type corrosion inhibiting and descaling agent.
Description
Technical field
The invention belongs to the industrial circulating cooling water processing technology field, be specifically related to a kind of corrosion inhibiting and descaling agent Epoxysuccinic acid/to oxyethane Phenylsulfonic acid multipolymer and preparation method thereof, it is a kind of carboxyl, sulfonic polyether compound of containing, belong to without phosphorus, no nitrogen, biodegradable environmental type corrosion inhibiting and descaling agent, the inhibition and the scale inhibition that are used for water quality are handled.
Background technology
Though the recirculated cooling water treatment technology is for solving the technology that environmental problem grows up, to water saving, energy-saving and cost-reducing, guarantee the industrial installation safe and stable operation, solve the exhausted problem of global water resources and brought into play crucial effect that but the use of the medicament of circulating water treatment simultaneously also exerts a certain influence to environment.
As far back as phase early 1930s, just begin to adopt inorganic polyphosphate such as tripoly phosphate sodium STPP, Sodium hexametaphosphate 99, solve the fouling obstruction and the etching problem of water supply system, but scale inhibition and corrosion mitigating effect are not so good, high concentrations of phosphoric acid salt can cause the eutrophication of water body simultaneously.Therefore good chromic salt sour water treatment formulations and the nitrite sour water treatment formulations of corrosion mitigating effect was used widely in 40～fifties of century; but in view of the carcinogenic harm of chromic salt, nitrate to human body; environment is polluted; along with the increasingly stringent of legislations of environmental protection, the use of this type of medicament is subjected to strict restriction.Middle 1960s organic phospho acid salt inhibiter occurred and has had good scale inhibition and dispersion performance polycarboxylic acid polymkeric substance.Organic phosphoric acid (salt) class Scale inhibitors, polycarboxylic acid Scale inhibitors are compared them and are had good chemical stability, not facile hydrolysis, higher water temperature, hardness and the basicity of ability, to CaCO with inorganic polyphosphate class Scale inhibitors
3Dirt has extremely good restraining effect, and organic phosphonate has reduced the danger that forms calcium phosphate scale because Stability Analysis of Structures and phosphorus content are low simultaneously, has also alleviated the pressure of environment eutrophication.For reducing the discharging of phosphorus, this phosphorus system alkalescence prescription of the recirculated cooling water seventies in 20th century " poly-phosphate-organic phosphonate-polymeric dispersant " has obtained using widely.
Though phosphorus system alkalescence prescription has reduced phosphorus content, its poly-phosphate is still about 15mg/L.The eighties in 20th century, because the increasing of environment protection dynamics, the discharging of phosphorus restriction has become a kind of trend, and phosphine having occurred is all-organic formula " organic phospho acid (salt)-multipolymer ".Phosphine is that phosphonate inhibiter component is generally not high in the all-organic formula, and total phosphorus is about 4mg/L in the recirculated water in service, and corrosive control mainly leans against under the high basicity and moves, and competent OH is arranged in the cathodic area this moment
-, promoted negative electrode to turn usefulness into, provide corrosive environment slowly to steel surface; Ca in alkaline operation in addition
2+And HCO
3 -Generate skim CaCO at steel surface
3Film, the dispersion agent that use properties is good makes CaCO
3Film is very thin, realizes little dirt operation, stops the diffusion of oxygen in water.Phosphine is that all-organic formula is a corrosion inhibitor formula with the organic phosphonate, has reduced phosphorus content, up to the early 1990s this phosphorus be that all-organic formula still accounts for very big proportion.
Late 1980s phosphorous lower inhibiter such as PBTCA, hydroxyl phosphino-acetate organic phosphine carboxylic acid compounds such as (HPAA) have occurred to the beginning of the nineties.Various on the other hand high performance copolymer anti-scale dispersers constantly occur, especially contain multi-functional multipolymers such as sulfonic acid, phosphonic acids, carboxylic acid, because of its good performance causes common concern, owing to introduced sulfonic acid, phosphonyl group, improved it in the polyfunctional group multipolymer to the inhibition ability of calcium phosphate scale, zinc dirt and to the stabilization of iron.Therefore it is good corrosion inhibition to have occurred, " the phosphine carboxylic acid+polymkeric substance " that the scale inhibition dissemination is stronger, " phosphine carboxylic acid+sulfonic acid polymer ", the complete organic water treatment prescription all-organic formula of " phosphine carboxylic acid+phosphonic acids polymkeric substance " alkalescence.Further reduced phosphorus content, but the phosphine carboxylic acid after all also is the organic water conditioner of phosphorated, though become orthophosphoric acid salt because it is difficult for nature hydrolysis (or decomposition), once be considered to little, be nontoxic the pollution of water body, but because the complicacy of water body itself, organic phosphonate, phosphine carboxylic acid kind difference, hydrolysis (decomposition) time is variant, but can be decomposed into orthophosphoric acid salt eventually and influence water body, cause body eutrophication.
Though polymkeric substance such as polycarboxylic acid dirt dispersion agent such as polyacrylic acid, polymaleic anhydride once made water technology obtain breakthrough in addition.Since without phosphorus, once be considered to nontoxic, polluted very little, environmentally acceptable water treatment agent.But the water treatment agent lower or nontoxic to these toxicity ignored their long-term accumulated in environment and the potential hazard that causes.Because achievement in research in recent years shows: although most poly-to complete sour dirt dispersion agent toxicity lower, but they generally can't resolve into simple nontoxic material under the effect of microorganism and fungi, promptly can't biological degradation or can only be on a small quantity by biological degradation, if in the medium-term and long-term enrichment of water body, also with contaminate environment, especially at some to relatively stricter field of environmental requirement such as offshore oilfield etc.
Therefore enter the nineties in 20th century, well-known water treatment enterprises of several families such as the U.S., Japan, Germany all begin to be devoted to seek a kind of energy in succession and substitute poly carboxylic acid, when having good anticorrosion-antiscaling property, biodegradable again " environmental protection " type Water Treatment Chemicals.Along with the exploitation of without phosphorus, biodegradable corrosion inhibiting and descaling agent poly-epoxy succinic acid and poly aspartic acid, the notion of " green corrosion inhibiting and descaling agent " has become the developing direction of 21 century water treatment agent.
United States Patent (USP) usp5062962 and United States Patent (USP) usp5147555 show that poly-epoxy succinic acid is to CaCO
3, CaSO
4, BaSO
4Good scale inhibition effect is arranged, and have good corrosion inhibition, because its without phosphorus, no nitrogen, biodegradable belongs to green chemical truly.Though but United States Patent (USP) usp5147555 shows that also poly-epoxy succinic acid is to CaCO
3, CaSO
4, BaSO
4Good scale inhibition effect is arranged, but very poor to the scale inhibition effect of calcium phosphate.When poly-epoxy succinic acid and organic phosphine corrosion inhibiting and descaling agent carry out composite use, increased the sedimentary danger of calcium phosphate scale like this.
Can improve the restraining effect of polymkeric substance in view of in polymkeric substance, introducing sulfonic group to calcium phosphate scale, zinc dirt, and to the stabilization (Yan Yan of metallic iron, Yang Jiaoling. contain the present situation .[J of co-polymer of sulfonate as dirt dispersion agent] Treatment of Industrial Water, 1993, (4): 7～11.), because poly-epoxy succinic acid is the homopolymer of epoxy Succinic Acid, structure is single, therefore we have carried out modification with sulfonic group to poly-epoxy succinic acid, with the excellent more corrosion inhibiting and descaling agent of expectation obtained performance.
Summary of the invention
The objective of the invention is to overcome poly-epoxy succinic acid suppresses weak effect to calcium phosphate scale, zinc dirt weakness, poly-epoxy succinic acid is carried out modification, a kind of modified product of novel poly-epoxy succinic acid is proposed---Epoxysuccinic acid/to acid/epoxy ethylbenzene sulfonic acid copolymer, with and preparation method thereof.
The corrosion inhibiting and descaling agent Epoxysuccinic acid that the present invention proposes/oxyethane Phenylsulfonic acid multipolymer is with Epoxysuccinic acid and the oxyethane Phenylsulfonic acid is carried out ring opening copolymer, obtain Epoxysuccinic acid/to the multipolymer of oxyethane Phenylsulfonic acid, this multipolymer is a kind of carboxyl, sulfonic polyethers polymkeric substance of containing, and has following structure:
M is H in the formula
+Or water-soluble cationic Na
+, K
+, NH
4 +, (Ca
2+)
1/2In any; N represents the polymerization degree, is 1～50 integer; X be molecular fraction, the y of Epoxysuccinic acid in the molecule be in the molecule to the molecular fraction of acid/epoxy ethylbenzene sulfonic acid, establish x+y=100%, then the x value is 20%～99%, the y value is 1%～80%.
The corrosion inhibiting and descaling agent Epoxysuccinic acid that the present invention proposes/to the preparation method of oxyethane Phenylsulfonic acid multipolymer, concrete steps are as follows: with maleic anhydride, to vinyl benzenesulfonic acid is raw material, at first mix, and dissolve with proper amount of deionized water with the raw material maleic anhydride with to vinyl benzenesulfonic acid.The slow sodium hydroxide solution of Dropwise 5 0% in cooling and under stirring again is 6～7 until maleic anhydride with to the pH value of vinyl benzenesulfonic acid mixing solutions; In water-bath, be heated to 50 ℃～60 ℃ then, add 30% hydrogen peroxide in batches and carry out the epoxidation reaction of maleate, with the sodium wolframate is catalyzer, temperature of reaction is 60 ℃～70 ℃, the pH value of the sodium hydroxide solution control reaction mixture with 50% is 5-6, reaction times is 2～4 hours, Epoxysuccinic acid and to the mixing solutions of oxyethane Phenylsulfonic acid; After the epoxidation reaction without separation, again temperature is risen to 80 ℃～90 ℃, add a certain amount of calcium hydroxide or calcium oxide and carry out ring opening copolymer reaction, 2～5 hours reaction times, colourless or faint yellow sticking shape liquid, be Epoxysuccinic acid/to the multipolymer of oxyethane Phenylsulfonic acid.
Among the present invention, the mol ratio of raw material maleic anhydride and p styrene sulfonic acid is 1: 0.1～1: 4.
Among the present invention, the add-on of described hydrogen peroxide is that the ratio of mole number and the mole number sum of raw material maleic anhydride and p styrene sulfonic acid of hydrogen peroxide is 1: 1.03～1: 1.05.
Among the present invention, the add-on of catalyzer sodium wolframate is that the ratio of mole number and the mole number sum of raw material maleic anhydride and p styrene sulfonic acid of calcium hydroxide or calcium oxide is 1: 0.08～1: 0.15.
Among the present invention, the add-on of oxygen calcium oxide or calcium oxide is that the ratio of mole number and the mole number sum of raw material maleic anhydride and p styrene sulfonic acid of sodium wolframate is 1: 0.005～1: 0.02.
Synthetic route of the present invention can be described below:
The inventor is through discovering, when inserting in the molecular chain at poly-epoxy succinic acid to the oxyethane Phenylsulfonic acid, the new type copolymer of gained---Epoxysuccinic acid/to oxyethane Phenylsulfonic acid multipolymer, not only kept the scale-inhibiting properties of poly-epoxy succinic acid to lime carbonate, calcium sulfate, barium sulfate, and compare with poly-epoxy succinic acid, have the characteristic of good resistance calcium phosphate scale and zinc dirt, advantage is fairly obvious.
The inventor also finds after deliberation, Epoxysuccinic acid provided by the present invention/to oxyethane Phenylsulfonic acid multipolymer, to the scale inhibition ability of calcium phosphate scale and zinc dirt, increase along with sulfonic increase on the molecular chain.Explanation has been introduced sulfonic group on the polyether chain of poly-epoxy succinic acid, make to contain polyethers, carboxyl, sulfonic group simultaneously in the molecular structure, and the characteristic that product of the present invention has good resistance calcium phosphate scale and zinc dirt has been given in the interaction of these groups.
The inventor also finds after deliberation, Epoxysuccinic acid provided by the present invention/to oxyethane Phenylsulfonic acid multipolymer, scale inhibition ability to lime carbonate, the difference along with the difference of the shared percentage ratio of sulfonic acid group, when the molecular fraction shared＜25% to the oxyethane Phenylsulfonic acid, to the scale inhibition performance of lime carbonate and poly-epoxy succinic acid much at one, and the molecular fraction shared to the oxyethane Phenylsulfonic acid＞25% o'clock, its scale inhibition performance to lime carbonate has bigger decline along with the increase of sulfonic acid group.
The inventor also finds after deliberation, Epoxysuccinic acid provided by the present invention/to oxyethane Phenylsulfonic acid multipolymer, to the scale inhibition performance of calcium sulfate, barium sulfate, and to the corrosion inhibition rate of carbon steel, basically be not subjected to the influence of sulfonic acid group, similar with poly-epoxy succinic acid.
This product is not phosphorous, and biodegradable, is a kind of water treatment agent of environmental type.The preparation-obtained Epoxysuccinic acid of the present invention/oxyethane Phenylsulfonic acid multipolymer be can be used as corrosion and scale inhibition disperser can stop CaCO effectively
3, CaSO
4, BaSO
4, Ca
3(PO
4)
2, zinc salt deposition, be a kind of polynary dirt dispersion agent.
Embodiment
To further specify the advantage of this product by Comparative Examples and embodiment below.
Comparative Examples: the preparation of poly-epoxy succinic acid
In being furnished with the four neck flasks that stir prolong, stirring, thermometer, pH meter, dropping funnel, add 49.0g (0.50mol) maleic anhydride, and adding 60ml water dissolution, the aqueous sodium hydroxide solution 55g of slow Dropwise 5 0% under ice bath and stirring, this moment, the pH value of solution was 6.In 60 ℃～65 ℃ water-bath, heat then, when temperature rises to 50 ℃～60 ℃, add catalyzer 1.65g sodium wolframate and stirring.Dividing then and adding total amount five times is the epoxidizing agent hydrogen peroxide (0.511mol) of 58g 30%, added once every 30 minutes, after adding hydrogen peroxide at every turn, the pH that keeps reaction solution by the aqueous sodium hydroxide solution of Dropwise 5 0% is 6～7, epoxidised temperature maintenance is at 60 ℃～65 ℃ simultaneously, hydrogen peroxide all adds the back and continue reaction 2 hours under 60 ℃～65 ℃ temperature, gets the mixing solutions to the oxyethane Phenylsulfonic acid of Epoxysuccinic acid.Again temperature is risen to 80 ℃～90 ℃, adds 3.7g (0.04mol) calcium hydroxide, react 2.0 hours, the faint yellow shape liquid that glues clearly of certain solid content, be Epoxysuccinic acid/to the multipolymer of oxyethane Phenylsulfonic acid.
Embodiment 1: Epoxysuccinic acid/and to the preparation of oxyethane Phenylsulfonic acid multipolymer
In being furnished with the four neck flasks that stir prolong, stirring, thermometer, pH meter, dropping funnel, add 33.6g (0.34mol) (x=0.85) maleic anhydride and 11.7g (0.058mol) (y=0.15) to vinyl benzenesulfonic acid sodium, add the 50ml water dissolution again, the aqueous sodium hydroxide solution 34g of slow Dropwise 5 0% under ice bath and stirring, this moment, the pH value of solution was 6.In 60 ℃～65 ℃ water-bath, heat then, when temperature rises to 50 ℃～60 ℃, add catalyzer 1.32g sodium wolframate and stirring.Dividing then and adding total amount five times is the epoxidizing agent hydrogen peroxide (0.41mol) of 47g 30%, added once every 30 minutes, after adding hydrogen peroxide at every turn, the pH that keeps reaction solution by the aqueous sodium hydroxide solution of Dropwise 5 0% is 6～7, epoxidised temperature maintenance is at 60 ℃～65 ℃ simultaneously, hydrogen peroxide all adds the back and continue reaction 2 hours under 60 ℃～65 ℃ temperature, gets the mixing solutions to the oxyethane Phenylsulfonic acid of Epoxysuccinic acid.Again temperature is risen to 80 ℃～90 ℃, adds 2.96g (0.04mol) calcium hydroxide, react 2.0 hours, the faint yellow shape liquid that glues clearly of certain solid content, be Epoxysuccinic acid/to the multipolymer of oxyethane Phenylsulfonic acid.Its The performance test results sees Table 2.
Embodiment 2～11: Epoxysuccinic acid/and to the preparation of oxyethane Phenylsulfonic acid multipolymer
Embodiment 2～11 is other Epoxysuccinic acid/to the preparation of oxyethane Phenylsulfonic acid multipolymer, its preparation process is with embodiment 1, added reactant maleic anhydride (Maleic anhydride, hereinafter to be referred as MA), to vinyl benzenesulfonic acid (1,4-Styrene sulfonic sodium, hereinafter to be referred as SSS), hydrogen peroxide, the amount of catalyzer and product Epoxysuccinic acid/to Epoxysuccinic acid (Epoxy succinic acid in the oxyethane Phenylsulfonic acid multipolymer, hereinafter to be referred as ESA) and as shown in table 2 to the composition of acid/epoxy ethylbenzene sulfonic acid (4-Epoxyethyl benzenesulfonic acid is hereinafter to be referred as EBSA).The performance test results sees Table 2.
Table 1 preparation Epoxysuccinic acid/to the raw material and the composition of oxyethane Phenylsulfonic acid multipolymer
Embodiment 12: the performance test experiment
The product that obtains among Comparative Examples and the embodiment is carried out the static-state scale inhibition performance test of lime carbonate, and method is as follows:
" calcium phosphate sedimentation " in " water coolant analysis and the experimental technique " that the static-state scale inhibition performance test of lime carbonate is write with reference to Sinopec China PetroChemical Corporation (Sinopec press, 1993) carries out.
The testing method of the static-state scale inhibition performance of calcium sulfate is: 500ml contains certain density Scale inhibitors, 1800mgL with the deionized water preparation
-1Ca
2+, 4800mgL
-1SO
4 2-Solution, transferring pH is 7, places water bath with thermostatic control then, be incubated certain hour at a certain temperature after, cooling is filtered usefulness EDTA titration measuring Ca with the millipore filter of 0.22 μ m
2+Ionic concn is done blank assay simultaneously.Barium sulfate scale inhibition performance=(C
i-C
Empty)/(C
0-C
Empty) * 100%, wherein C
iSteady concentration for calcium ion in the solution after the solution thermostatically heating that adds Scale inhibitors; C
EmptyBe blank solution steady concentration of calcium ion in the solution under identical condition; C
0Be calcium ion concn in the solution before the thermostatically heating.
The testing method of the static-state scale inhibition performance of barium sulfate is: 500ml contains certain density Scale inhibitors, 60mgL with the deionized water preparation
-1Ba
2+, 100mgL
-1SO
4 2-Solution, transferring pH is 7, places water bath with thermostatic control then, be incubated certain hour at a certain temperature after, cooling is filtered with the millipore filter of 0.22 μ m, with atomic emission spectrometry (ICP) mensuration Ba
2+Ionic concn is done blank assay simultaneously.Barium sulfate scale inhibition performance=(C
i-C
Empty)/(C
0-C
Empty) * 100%, wherein C
iSteady concentration for calcium or barium ion in the solution after the solution thermostatically heating that adds Scale inhibitors; C
EmptyBe blank solution steady concentration of calcium or barium ion in the solution under identical condition; C
0Be calcium in the solution before the thermostatically heating or barium ion concentration.
" calcium phosphate sedimentation " in " water coolant analysis and the experimental technique " that the test of the static-state scale inhibition performance of calcium phosphate is write with reference to Sinopec China PetroChemical Corporation (Sinopec press, 1993) carries out.
" zinc salt sedimentation " that the stability of zine ion is tested in " water coolant analysis and experimental technique " (Sinopec press, 1993) of writing with reference to Sinopec China PetroChemical Corporation carries out.
The test of corrosion inhibition is with reference to " State Standard of the People's Republic of China GB/T18175-2000, the water conditioner corrosion inhibition mensuration-rotary hanging plate method ", adopt on the RCC-II type rotary hanging plate corrosion tester and carry out the corrosion inhibition experiment, 45 ℃ of temperature, rotating speed 75r/min, not pre-film lacing film, experimental period 72 hours; Carbon steel test piece: 20
#Carbon steel, 50mm * 25mm * 2mm.The inhibition experimental water is a Yangtze valley factory recirculating cooling water system make up water, and water-quality guideline is as shown in table 1; High-alkali, high hard water quality is selected in the scale inhibition experiment for use, and water-quality guideline is as shown in table 3.
Table 2: inhibition experiment water quality
| pH | Turbidity | Total hardness mgL -1 | Basicity mgL -1 | Ca 2+ mg·L -1 | Total Fe mgL -1 | Cl - mg·L -1 | SO 4 2- mg·L -1 | Total solids solute mgL -1 |
| 7.6 | 0.28 | 150 | 120 | 105 | ＜0.02 | 82 | 46 | 367 |
Annotate: total hardness, basicity, Ca
2+All with CaCO
3Meter, mgL
-1
The performance test experimental result sees Table 3, from the experimental result of table 3 as can be seen, and the prepared polymer ring oxydisuccinic acid of the present invention/, can stop CaCO effectively to oxyethane Phenylsulfonic acid multipolymer (ESA/EBSA)
3, CaSO
4, BaSO
4, Ca
3(PO
4)
2, zinc salt deposition, be a kind of polynary dirt dispersion agent, and have certain corrosion inhibition.
Table 3 Epoxysuccinic acid/to the composition and the The performance test results of oxyethane Phenylsulfonic acid multipolymer (ESA/EBSA)
Annotate: [a] lime carbonate scale inhibition experimental pharmacy concentration is 10mgL
-1[b] calcium sulfate scale inhibition experimental pharmacy concentration is 15mgL
-1[c] barium sulfate scale inhibition experimental pharmacy concentration is 5mgL
-1
[d] calcium phosphate scale inhibition experimental pharmacy concentration is 15mgL
-1[e] zinc salt sedimentation experiment drug concentration is 20mgL
-1[f] corrosion inhibition experimental pharmacy concentration is 150mgL
-1
Claims (2)
1, a kind of corrosion inhibiting and descaling agent Epoxysuccinic acid/, it is characterized in that this corrosion inhibiting and descaling agent has following structure to acid/epoxy ethylbenzene sulfonic acid copolymer:
M is H in the formula
+Or water-soluble cationic Na
+, K
+, NH
4 +, (Ca
2+)
1/2In any, n represents the polymerization degree, is 1～50 integer; X be molecular fraction, the y of Epoxysuccinic acid in the molecule be in the molecule to the molecular fraction of acid/epoxy ethylbenzene sulfonic acid, establish x+y=100%, then x is 20%～99%, y is 1%～80%.
2, a kind of corrosion inhibiting and descaling agent Epoxysuccinic acid as claimed in claim 1/to the preparation method of acid/epoxy ethylbenzene sulfonic acid copolymer, it is characterized in that raw material maleic anhydride and p styrene sulfonic acid are mixed, use deionized water dissolving, under ice bath and agitation condition, the sodium hydroxide solution of Dropwise 5 0%, the pH value of regulator solution is 6-7, then in 50-60 ℃ of water-bath, the hydrogen peroxide of adding 30% in solution, with the sodium wolframate is catalyzer, carry out the epoxidation reaction of maleate and p styrene sulfonic acid salt, temperature of reaction is 60-70 ℃, reaction times is 2-4 hour, is 5-6 with the pH value of 50% sodium hydroxide solution control reaction mixture, obtains Epoxysuccinic acid and to the mix products of acid/epoxy ethylbenzene sulfonic acid; Without separation, temperature is risen to 80-90 ℃ again after the epoxidation reaction, add calcium hydroxide or calcium oxide and directly carry out the ring opening copolymer reaction, the reaction times is 2-5 hour, obtains faint yellow sticking shape liquid, is Epoxysuccinic acid/to acid/epoxy ethylbenzene sulfonic acid copolymer; Wherein:
The mol ratio of raw material maleic anhydride and p styrene sulfonic acid is 1: 0.1～1: 4;
The add-on of described hydrogen peroxide is: the mole number of hydrogen peroxide is 1: 1.03～1: 1.05 with the ratio of the mole number sum of raw material maleic anhydride and p styrene sulfonic acid;
The add-on of oxygen calcium oxide or calcium oxide is: the mole number of calcium hydroxide or calcium oxide is 1: 0.08～1: 0.15 with the ratio of the mole number sum of raw material maleic anhydride and p styrene sulfonic acid;
The add-on of catalyzer sodium wolframate is: the mole number of sodium wolframate is 1: 0.005～1: 0.02 with the ratio of the mole number sum of raw material maleic anhydride and p styrene sulfonic acid.
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| US5378372A (en) * | 1993-06-09 | 1995-01-03 | Betz Laboratories, Inc. | Control of scale formation in aqueous systems |
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| US5866011A (en) * | 1997-04-25 | 1999-02-02 | Betzdearborn Inc. | Method of controlling scale formation in brine concentration and evaporation system |
| CN1375467A (en) * | 2002-04-29 | 2002-10-23 | 南京工业大学 | Water treating corrosion and scale inhibitor and its prepn. |
| CN1398798A (en) * | 2002-04-18 | 2003-02-26 | 同济大学 | Polyepoxysuccinic acid as environment protecting scale inhibitor and its prepn process |
| CN1524893A (en) * | 2003-02-28 | 2004-09-01 | 赵勇军 | Synthesis of poly epoxy succinate |
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2008
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4654159A (en) * | 1985-06-24 | 1987-03-31 | The Procter & Gamble Company | Ether hydroxypolycarboxylate detergency builders |
| US5468393A (en) * | 1993-04-23 | 1995-11-21 | Betz Paperchem, Inc. | Methods of controlling scale formation in the presence of metal ions in aqueous systems |
| US5378372A (en) * | 1993-06-09 | 1995-01-03 | Betz Laboratories, Inc. | Control of scale formation in aqueous systems |
| US5866011A (en) * | 1997-04-25 | 1999-02-02 | Betzdearborn Inc. | Method of controlling scale formation in brine concentration and evaporation system |
| CN1398798A (en) * | 2002-04-18 | 2003-02-26 | 同济大学 | Polyepoxysuccinic acid as environment protecting scale inhibitor and its prepn process |
| CN1375467A (en) * | 2002-04-29 | 2002-10-23 | 南京工业大学 | Water treating corrosion and scale inhibitor and its prepn. |
| CN1524893A (en) * | 2003-02-28 | 2004-09-01 | 赵勇军 | Synthesis of poly epoxy succinate |
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| CN101230132A (en) | 2008-07-30 |
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