CN103145256B - Preparation method and application of ternary high polymer copolymer scale inhibitor - Google Patents
Preparation method and application of ternary high polymer copolymer scale inhibitor Download PDFInfo
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Abstract
The invention relates to a preparation method and application of a ternary high polymer copolymer scale inhibitor. The method comprises the following steps: 1) reacting cyclodextrin and maleic anhydride; 2) reacting styrene with the cyclodextrin modified by maleic anhydride; and 3) performing a sulfonation reaction on the copolymer obtained in the step 2), thereby obtaining the ternary high polymer copolymer scale inhibitor. The scale inhibitor has the common high-efficiency scale-inhibiting radicals such as carboxyl, sulfo group and the like, multiple hydrophilic hydroxyl are distributed on the outer wall and large opening end of the cavity of the introduced cyclodextrin, the scale inhibitor has the function of chelating calcium, magnesium and other metal ions; and therefore, the scale inhibitor has the good effect of promoting scale inhibition, formation of CaCO3 and CaSO4 can be effectively avoided, the scale inhibitor has excellent scale inhibition and has good dispersing performance on the iron, zinc and other metal ions, and the preparation process is feasible, high in practicality and low in environmental influence.
Description
Technical field
The present invention relates to industrial water supply processing and degree of depth water-treatment technology field, be specifically related to a kind of preparation method and application of ternary high-molecular copolymer Scale inhibitors.
Background technology
Scale inhibitors is that a class can stop and in water, causes dirty salt at the material of equipment surface deposition, normally due to Scale inhibitors to underwater gold belong to ion chelating, the effects such as the absorption dispersion of crystallite and character distortion are formed.Along with the continuous aggravation of worldwide water resources crisis, reasonably the reuse of water and water has become the important topic of industrial development in recent years.Recycling of water runs down water quality, aggravated the fouling of equipment, affects hot conduction and even likely causes an explosion accident, and causes huge financial loss, so be one of method preventing fouling to adding Scale inhibitors in recirculated water.
China's Scale inhibitors product has been obtained obvious progress through development after a while, and particularly polymer antisludging agent development is more rapid, is the focus of water treatment field research always.The current water coolant of China Scale inhibitors used be take the phosphorus line formulations such as inorganic phosphate, organic phospho acid and phosphonates as main, but this class Scale inhibitors structural instability, during use, because of hydrolysis generation ortho-phosphoric acid root, cause the formation of phosphoric acid salt crust, the eutrophication and the bacterium algae amount reproduction that when working concentration is higher, cause water body, form red tide contaminate environment.Along with people's environmental protection consciousness strengthens; many countries are the discharge of phosphorus restriction; promoted developing rapidly of low-phosphorous, phosphate-free water treatment agent, therefore design and synthesize out there is special construction, the novel non-phosphate Scale inhibitors that nontoxic, without phosphorus, anti-scaling property is good is particularly important.
Cyclodextrin is to act on by cyclodextrin glycosyltransferase one group of cyclic oligosaccharide that starch produces, and is a kind of natural green compound, and production cost is low, receives much concern in recent years.The most frequently used is beta-cyclodextrin, the tapered cylinder structure that it is formed by connecting with α-Isosorbide-5-Nitrae glycosidic link by 7 glucose units.The special molecular structure of its " interior hydrophobic; outer hydrophilic ", make cyclodextrin by the various effects such as ether-oxygen bond, Van der Waals force, hydrophobic interaction, charge transfer, to form inclusion complex with multiple guest molecule, simultaneously its molecule cavity outer wall and big opening end numerous wetting ability hydroxyls that distribute, have sequestering action to metal ion.
Cyclodextrin molecular is introduced in the main chain or side chain of polymer molecule, can build various containing cyclodextrin, this polymkeric substance has not only kept the peculiar inclusion of mother body cyclodextrin molecule, also shows unique polymer effect (as synergistic effect, neighboring group effect) etc.Being of wide application of cyclodextrin, as fluorescence identification, chipal compounds split and as GC stationary phase etc., in recent years the application at aspects such as food, medicine and water treatments constantly expands, but still few about the research report using cyclodextrin as Scale inhibitors.
Summary of the invention
The object of the present invention is to provide preparation method and the application of the ternary high-molecular copolymer Scale inhibitors that a kind of scale inhibition effect is good, preparation cost is low, nontoxic.
To achieve these goals, the technical solution adopted in the present invention is:
A preparation method for ternary high-molecular copolymer Scale inhibitors, is characterized in that, it comprises the following steps:
1) cyclodextrin and maleic acid anhydride reactant
Get cyclodextrin and MALEIC ANHYDRIDE that mol ratio is 0.01-0.02:0.23, termination reaction after reacting 8h after both grindings are mixed in 80 ℃ of thermostat water baths, after being cooled to room temperature, add acetone to smash to pieces, filter to obtain white powdery solid, then with acetone, soak, filter purifying, washing, dry, obtain through the cyclodextrin of maleic anhydride modified standby;
2) vinylbenzene and through the cyclodextrin reaction of maleic anhydride modified
Getting vinylbenzene and the resulting cyclodextrin through maleic anhydride modified of step 1) that mol ratio is 1:1 joins in reaction flask, add dry toluene, be slowly warming up to 40-70 ℃, be stirred well to completely and dissolve, then slowly drip the toluene solution of initiator dibenzoyl peroxide, described initiator dibenzoyl peroxide and cinnamic mol ratio are 0.004-0.005:1, keep 85 ℃ of reaction 2h of temperature, stop heating, cold filtration, obtain white powder multipolymer, washing, dry;
3) sulfonation reaction
By step 2) resulting multipolymer is dissolved in pyridine, control temperature at 50-55 ℃, slowly add wherein dry sulphur trioxide, described sulphur trioxide and step 2) mass ratio of resulting multipolymer is 1:2, add rear continuation reaction 2h, reaction finishes rear steaming except pyridine, and enriched material obtains final copolymerization product by dehydrated alcohol precipitating.
In such scheme, described cyclodextrin is beta-cyclodextrin.
The application of described ternary high-molecular copolymer Scale inhibitors in resistance calcium dirt.
In such scheme, it comprises the following steps: in the water sample of calcium ions, bicarbonate ion, add described Scale inhibitors, controlling water temperature is 70 ℃, and described inhibitor concentration is 2.5-20mg/L, and the reaction times is 8 h.
In such scheme, described inhibitor concentration is 7.5mg/L.
In such scheme, in described water sample, the concentration of calcium ion is 150-350mg/L, the concentration 150-400mg/L of bicarbonate ion.
Principle of the present invention is: adopt MALEIC ANHYDRIDE to carry out modification to beta-cyclodextrin, obtain the modified product that contains carboxyl, ester group and hydroxyl, under the condition that this modified product is existed at initiator with vinylbenzene, react, obtain white powder copolymerization product, this copolymerization product is dissolved in pyridine solution, add sulphur trioxide solid reaction under certain condition, finally obtain terpolymer Scale inhibitors.
Beneficial effect of the present invention is:
1) the object of the invention is nontoxic, cheap natural green cyclodextrin molecular to introduce in organic macromolecular copolymer, utilize its hydroxyl and cavity to the chelating of incrustation ion and coating function, the collaborative traditional good carboxyl of scale inhibition and dispersion performance and sulfonic group, prepares the ternary high-molecular copolymer Scale inhibitors effective, price is low, nontoxic;
2) this Scale inhibitors not only has the common efficient scale groups such as carboxyl, sulfonic group, cyclodextrin cavity outer wall and the big opening end introduced are distributed with numerous wetting ability hydroxyls simultaneously, the metal ions such as calcium magnesium are had to sequestering action, thereby scale inhibition is played to good promoter action, can effectively stop CaCO
3and CaSO
4the formation of dirt, it has good scale inhibition performance to calcium phosphate, and the metal ions such as iron, zinc are had to good dispersing property, and preparation technology easily goes, practical, little to environmental influence.
Embodiment
In order to understand better the present invention, below in conjunction with embodiment, further illustrate content of the present invention, but content of the present invention is not only confined to the following examples.
embodiment 1:
Get 0.010mol beta-cyclodextrin and 0.23mol MALEIC ANHYDRIDE, both are fully ground in mortar and mix, transfer in time in Erlenmeyer flask with a lid, being placed in 80 ℃ of thermostat water baths reacts, within every 5 minutes, stir once, mixture becomes thick liquid gradually, becomes white solid after 4h, continues to be incubated the termination reaction to 8h.After being cooled to room temperature, add acetone to smash to pieces, filter to obtain white powdery solid, rear with acetone immersion, filtration purifying, uses 95% washing with alcohol, and product is standby after 80 ℃ of vacuum-drying 12h.Get 0.1mol vinylbenzene and 0.1mol maleic anhydride modified cyclodextrin joins in reaction flask, add 100mL dry toluene, be slowly warming up to 55 ℃, be stirred well to after dissolving completely, then slowly drip the toluene solution 10mL that is dissolved with initiator 0.1g dibenzoyl peroxide, when strong heat release appears in reaction, note cooling, heat release keeps 85 ℃ of reaction 2h of temperature later, stops heating, cold filtration, obtain white powder multipolymer, with methanol solution washing, dry.The above-mentioned multipolymer of 10g is dissolved in 100mL pyridine, control temperature at 50-55 ℃, slowly add wherein dry 5g sulphur trioxide, add rear continuation reaction 2h, reaction finishes with Rotary Evaporators, to steam except pyridine afterwards, and enriched material obtains final copolymerization product by dehydrated alcohol precipitating.
embodiment 2:
Get 0.015mol beta-cyclodextrin and 0.23mol MALEIC ANHYDRIDE, both are fully ground in mortar and mix, transfer in time in Erlenmeyer flask with a lid, being placed in 80 ℃ of thermostat water baths reacts, within every 5 minutes, stir once, mixture becomes thick liquid gradually, becomes white solid after 4h, continues to be incubated the termination reaction to 8h.After being cooled to room temperature, add acetone to smash to pieces, filter to obtain white powdery solid, rear with acetone immersion, filtration purifying, uses 95% washing with alcohol, and product is standby after 80 ℃ of vacuum-drying 12h.Get 0.1mol vinylbenzene and 0.1mol maleic anhydride modified cyclodextrin joins in reaction flask, add 100mL dry toluene, be slowly warming up to 55 ℃, be stirred well to completely and dissolve, then slowly drip the toluene solution 10mL that is dissolved with initiator 0.1g dibenzoyl peroxide, when strong heat release appears in reaction, note cooling, heat release keeps 85 ℃ of reaction 2h of temperature later, stops heating, cold filtration, obtain white powder multipolymer, with methanol solution washing, dry.The above-mentioned multipolymer of 10g is dissolved in 100mL pyridine, control temperature at 50-55 ℃, slowly add wherein dry 5g sulphur trioxide, add rear continuation reaction 2h, reaction finishes with Rotary Evaporators, to steam except pyridine afterwards, and enriched material obtains final copolymerization product by dehydrated alcohol precipitating.
embodiment 3:
Get 0.020mol beta-cyclodextrin and 0.23mol MALEIC ANHYDRIDE, both are fully ground in mortar and mix, transfer in time in Erlenmeyer flask with a lid, being placed in 80 ℃ of thermostat water baths reacts, within every 5 minutes, stir once, mixture becomes thick liquid gradually, becomes white solid after 4h, continues to be incubated the termination reaction to 8h.After being cooled to room temperature, add acetone to smash to pieces, filter to obtain white powdery solid, rear with acetone immersion, filtration purifying, uses 95% washing with alcohol, and product is standby after 80 ℃ of vacuum-drying 12h.Get 0.1mol vinylbenzene and 0.1mol maleic anhydride modified cyclodextrin joins in reaction flask, add 100mL dry toluene, be slowly warming up to 55 ℃, be stirred well to completely and dissolve, then slowly drip the toluene solution 10mL that is dissolved with initiator 0.1g dibenzoyl peroxide, when strong heat release appears in reaction, note cooling, heat release keeps 85 ℃ of reaction 2h of temperature later, stops heating, cold filtration, obtain white powder multipolymer, with methanol solution washing, dry.The above-mentioned multipolymer of 10g is dissolved in 100mL pyridine, control temperature at 50-55 ℃, slowly add wherein dry 5g sulphur trioxide, add rear continuation reaction 2h, reaction finishes with Rotary Evaporators, to steam except pyridine afterwards, and enriched material obtains final copolymerization product by dehydrated alcohol precipitating.
embodiment 4:
Get 0.015mol beta-cyclodextrin and 0.23mol MALEIC ANHYDRIDE, both are fully ground in mortar and mix, transfer in time in Erlenmeyer flask with a lid, being placed in 80 ℃ of thermostat water baths reacts, within every 5 minutes, stir once, mixture becomes thick liquid gradually, becomes white solid after 4h, continues to be incubated the termination reaction to 8h.After being cooled to room temperature, add acetone to smash to pieces, filter to obtain white powdery solid, rear with acetone immersion, filtration purifying, uses 95% washing with alcohol, and product is standby after 80 ℃ of vacuum-drying 12h.Get 0.1mol vinylbenzene and 0.2mol maleic anhydride modified cyclodextrin joins in reaction flask, add 100mL dry toluene, be slowly warming up to 40 ℃, be stirred well to completely and dissolve, then slowly drip the toluene solution 10mL that is dissolved with initiator 0.1g dibenzoyl peroxide, when strong heat release appears in reaction, note cooling, heat release keeps 85 ℃ of reaction 2h of temperature later, stops heating, cold filtration, obtain white powder multipolymer, with methanol solution washing, dry.The above-mentioned multipolymer of 10g is dissolved in 100mL pyridine, control temperature at 50-55 ℃, slowly add wherein dry 5g sulphur trioxide, add rear continuation reaction 2h, reaction finishes with Rotary Evaporators, to steam except pyridine afterwards, and enriched material obtains final copolymerization product by dehydrated alcohol precipitating.
embodiment 5:
Get 0.015mol beta-cyclodextrin and 0.23mol MALEIC ANHYDRIDE, both are fully ground in mortar and mix, transfer in time in Erlenmeyer flask with a lid, being placed in 80 ℃ of thermostat water baths reacts, within every 5 minutes, stir once, mixture becomes thick liquid gradually, becomes white solid after 4h, continues to be incubated the termination reaction to 8h.After being cooled to room temperature, add acetone to smash to pieces, filter to obtain white powdery solid, rear with acetone immersion, filtration purifying, uses 95% washing with alcohol, and product is standby after 80 ℃ of vacuum-drying 12h.Get 0.2mol vinylbenzene and 0.1mol maleic anhydride modified cyclodextrin joins in reaction flask, add 100mL dry toluene, be slowly warming up to 70 ℃, be stirred well to completely and dissolve, then slowly drip the toluene solution 10mL that is dissolved with initiator 0.1g dibenzoyl peroxide, when strong heat release appears in reaction, note cooling, heat release keeps 85 ℃ of reaction 2h of temperature later, stops heating, cold filtration, obtain white powder multipolymer, with methanol solution washing, dry.The above-mentioned multipolymer of 10g is dissolved in 100mL pyridine, control temperature at 50-55 ℃, slowly add wherein dry 5g sulphur trioxide, add rear continuation reaction 2h, reaction finishes with Rotary Evaporators, to steam except pyridine afterwards, and enriched material obtains final copolymerization product by dehydrated alcohol precipitating.
The Scale inhibitors that embodiment 1 is prepared is measured its scale-inhibiting properties according to GB/T 16632-2008 by following contrived experiment, and specific experiment and result are as follows:
(1) impact of inhibitor concentration on resistance calcium carbonate scale performance
Fixedly water temperature is 70 ℃, and the time is 8 h, Ca
2+concentration is 200 mg/L, HCO
3 -concentration is 250mg/L, and while measuring different inhibitor concentration, the scale inhibition effect of calcium carbonate scale, the results are shown in Table 1.
Table 1
| Concentration (mg/L) | 2.5 | 5 | 7.5 | 10 | 20 |
| Scale inhibition performance (%) | 34 | 70 | 93 | 93 | 93 |
As seen from Table 1, along with the increase of inhibitor concentration, scale inhibition performance obviously promotes.When Scale inhibitors mass concentration is 7.5mg/L, resistance calcium carbonate scale rate reaches the highest.After this along with the increase of inhibitor concentration, it is constant that scale inhibition performance is tending towards.
(2) impact of calcium ion concn on resistance calcium carbonate scale performance
Fixedly water temperature is 70 ℃, and the time is 8 h, and inhibitor concentration is 7.5mg/L, HCO
3 -concentration is 250mg/L,, while measuring different calcium ionic concn, the scale inhibition effect of calcium carbonate scale, the results are shown in Table 2.
Table 2
| Concentration (mg/L) | 150 | 200 | 250 | 300 | 350 |
| Scale inhibition performance (%) | 86 | 89 | 94 | 83 | 78 |
As seen from Table 2, scale inhibition performance, along with the increase decline subsequently first in rising trend of calcium ion concn, reaches the highest when calcium ion concn is 250mg/L, and scale inhibition capacity reaches capacity thereafter, and therefore under higher calcium ion concn, scale inhibition performance reduces gradually.Can find out, within the scope of certain calcium ion concn, the scale inhibition effect of Scale inhibitors is remarkable simultaneously.
(3) impact of bicarbonate ion concentration on resistance calcium carbonate scale performance
Fixedly water temperature is 70 ℃, and the time is 8 h, and inhibitor concentration is 7.5mg/L, Ca
2+concentration is 250mg/L, and while measuring different bicarbonate ion concentration, the scale inhibition effect of calcium carbonate scale, the results are shown in Table 3.
Table 3
| Concentration (mg/L) | 150 | 200 | 250 | 300 | 400 |
| Scale inhibition performance (%) | 94 | 88 | 82 | 79 | 73 |
As seen from Table 3, scale inhibition performance declines along with the increase of bicarbonate ion concentration, and when bicarbonate ion concentration is 150mg/L, scale inhibition performance is the highest.And easily find out, in certain bicarbonate ion concentration range, the scale inhibition effect of Scale inhibitors is remarkable.
The Scale inhibitors that embodiment 2-5 is prepared is tested its scale-inhibiting properties with reference to above-mentioned experiment, and specific experiment is as follows: fixedly water temperature is 70 ℃, and the time is 8 h, and the concentration of the Scale inhibitors of embodiment 2-5 is 7.5mg/L, Ca
2+concentration is 250 mg/L, HCO
3 -concentration is 150mg/L, and the scale inhibition effect of the Scale inhibitors of mensuration embodiment 2-5 to calcium carbonate scale, the results are shown in Table 4.As can be seen from Table 4, scale inhibition effect is very good.
Table 4
| Scale inhibitors | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| Scale inhibition performance (%) | 96 | 90 | 91 | 90 |
Each cited raw material of the present invention can be realized the present invention, the bound value of each raw material with and interval value can realize the present invention, the bound value of processing parameter of the present invention (as proportioning, temperature, time etc.) with and interval value can realize the present invention, at this, do not enumerate embodiment.
Claims (6)
1. a preparation method for ternary high-molecular copolymer Scale inhibitors, is characterized in that, it comprises the following steps:
1) cyclodextrin and maleic acid anhydride reactant
Get cyclodextrin and MALEIC ANHYDRIDE that mol ratio is 0.01-0.02:0.23, termination reaction after reacting 8h after both grindings are mixed in 80 ℃ of thermostat water baths, after being cooled to room temperature, add acetone to smash to pieces, filter to obtain white powdery solid, then with acetone, soak, filter purifying, washing, dry, obtain through the cyclodextrin of maleic anhydride modified standby;
2) vinylbenzene and through the cyclodextrin reaction of maleic anhydride modified
Getting vinylbenzene and the resulting cyclodextrin through maleic anhydride modified of step 1) that mol ratio is 1:1 joins in reaction flask, add dry toluene, be slowly warming up to 40-70 ℃, be stirred well to completely and dissolve, then slowly drip the toluene solution of initiator dibenzoyl peroxide, described initiator dibenzoyl peroxide and cinnamic mol ratio are 0.004-0.005:1, keep 85 ℃ of reaction 2h of temperature, stop heating, cold filtration, obtain white powder multipolymer, washing, dry;
3) sulfonation reaction
By step 2) resulting multipolymer is dissolved in pyridine, control temperature at 50-55 ℃, slowly add wherein dry sulphur trioxide, described sulphur trioxide and step 2) mass ratio of resulting multipolymer is 1:2, add rear continuation reaction 2h, reaction finishes rear steaming except pyridine, and enriched material obtains final copolymerization product by dehydrated alcohol precipitating.
2. the preparation method of ternary high-molecular copolymer Scale inhibitors as claimed in claim 1, is characterized in that, described cyclodextrin is beta-cyclodextrin.
3. the application of the ternary high-molecular copolymer Scale inhibitors that the preparation method of ternary high-molecular copolymer Scale inhibitors as claimed in claim 1 prepares in resistance calcium dirt.
4. application as claimed in claim 3, is characterized in that, it comprises the following steps: in the water sample of calcium ions, bicarbonate ion, add described Scale inhibitors, controlling water temperature is 70 ℃, and described inhibitor concentration is 2.5-20mg/L, and the reaction times is 8 h.
5. application as claimed in claim 4, is characterized in that, described inhibitor concentration is 7.5mg/L.
6. application as claimed in claim 4, is characterized in that, in described water sample, the concentration of calcium ion is 150-350mg/L, the concentration 150-400mg/L of bicarbonate ion.
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| CN104556428B (en) * | 2013-10-14 | 2016-09-21 | 中国石油化工股份有限公司 | A kind of corrosion-mitigation scale-inhibition compositions and application thereof |
| CN104327198B (en) * | 2014-05-15 | 2016-11-02 | 中国农业科学院原子能利用研究所 | Maleic acid beta-schardinger dextrin-ester and preparation method thereof |
| CN105753182A (en) * | 2016-03-08 | 2016-07-13 | 佛山市聚成生化技术研发有限公司 | Styrene ketone-maleic anhydride-butadiene-butenol scale inhibitor and preparation method thereof |
| CN108706751A (en) * | 2018-07-18 | 2018-10-26 | 林文标 | A kind of research of non-phosphorus scale inhibitor and preparation method thereof |
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|---|---|---|---|---|
| US4128492A (en) * | 1976-12-21 | 1978-12-05 | Joh. A. Benckiser Gmbh | Process of producing a cyclohexane-1,2,3,4-tetracarboxylic acid-containing scale inhibitor |
| CN101864034A (en) * | 2010-06-06 | 2010-10-20 | 西北大学 | Application of acrylic acid cyclodextrin polymer in dyeing industrial waste water treatment |
| CN102464409A (en) * | 2010-11-04 | 2012-05-23 | 湖北中碧环保科技有限公司 | Preparation method of multielement composite scale inhibitor |
| CN102872836A (en) * | 2012-09-11 | 2013-01-16 | 安徽理工大学 | Cyclodextrin immobilized macromolecular polymer and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2000024691A (en) * | 1998-07-09 | 2000-01-25 | Jsr Corp | Water-soluble copolymer (salt) and scale inhibitor |
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Patent Citations (4)
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|---|---|---|---|---|
| US4128492A (en) * | 1976-12-21 | 1978-12-05 | Joh. A. Benckiser Gmbh | Process of producing a cyclohexane-1,2,3,4-tetracarboxylic acid-containing scale inhibitor |
| CN101864034A (en) * | 2010-06-06 | 2010-10-20 | 西北大学 | Application of acrylic acid cyclodextrin polymer in dyeing industrial waste water treatment |
| CN102464409A (en) * | 2010-11-04 | 2012-05-23 | 湖北中碧环保科技有限公司 | Preparation method of multielement composite scale inhibitor |
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