CN100369954C - Aspartate copolymer and method for preparing same - Google Patents
Aspartate copolymer and method for preparing same Download PDFInfo
- Publication number
- CN100369954C CN100369954C CNB2006100129183A CN200610012918A CN100369954C CN 100369954 C CN100369954 C CN 100369954C CN B2006100129183 A CNB2006100129183 A CN B2006100129183A CN 200610012918 A CN200610012918 A CN 200610012918A CN 100369954 C CN100369954 C CN 100369954C
- Authority
- CN
- China
- Prior art keywords
- hydroxyl
- organic amine
- reaction
- maleic anhydride
- aspartate copolymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Polyamides (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The present invention relates to a polyaspartic acid copolymer and a preparing method thereof. The present invention belongs to high molecular material and the technical field of water treatment. The present invention is the polyaspartic acid copolymer simultaneously containing sulfonic acid group, hydroxyl and a carboxyl functional group and the preparing method of the polyaspartic acid copolymer. A brittle solid obtained by means of thin layer reaction between maleic anhydride and ammonium salt is added to mixed water solution composed of organic amine containing sulfonic acid group and organic amine containing hydroxyl to react. Then, the product is hydrolyzed to make the polyaspartic acid copolymer simultaneously containing the sulfonic acid group, the hydroxyl and the carboxyl functional group. The preparing process combines ammonia absorption reaction and ammonia polycondensation reaction to be implemented in one step. The sulfonic acid group and the hydroxyl are introduced in one step. The prepared polyaspartic acid copolymer has properties of sludge resistance, corrosion inhibition and biodegradability.
Description
Technical field
A kind of aspartate copolymer of the present invention and preparation method thereof, belong to macromolecular material and water-treatment technology field, be specifically related to a kind of aspartate copolymer of sulfonic group, hydroxyl and carboxyl functional group and preparation method thereof that contains when being used for water conditioner.
Background technology
Poly aspartic acid is a kind of novel green chemical, and purposes is very widely arranged, and at industrial circulating water, is used as Scale inhibitors in water coolant and the oil-field flooding; Be used as detergent additive in the day chemical industry; Be used for chemical fertilizer as dietetic alimentation auxiliary agent etc.But its topmost Application Areas concentrates on the field that is used as Scale inhibitors in industrial circulating water, water coolant and the oil-field flooding at present.At present mostly the poly aspartic acid preparation method who announces is with maleic anhydride or fumaric acid anhydride with the ammoniacal liquor prepared in reaction, after patent CN1267673A has promptly adopted maleic acid or fumaric acid and ammoniacal liquor reaction to generate an ammonium salt or di-ammonium salts, polymerization prepares poly aspartic acid under acid catalysis, need transpiring moisture in the reaction process, energy dissipation is serious, simultaneously, can in use enter into the use system and influence its use properties because catalyzer is difficult to separate from product; Patent CN1398799A has announced that with maleic anhydride and ammoniacal liquor be the method that main raw material prepares the environment-friendly type poly aspartic acid, at first water is hydrolyzed to toxilic acid with maleic anhydride, generate the amine salt of toxilic acid then with the ammoniacal liquor reaction, the amine salt of toxilic acid is being obtained the poly-succinic diamide aqueous solution to carrying out polycondensation under the fixed temperature, this solution is carried out drying treatment isolate poly-succinic diamide, cyclization generation polysuccinimide is carried out in dehydration under suitable temperature then, and being hydrolyzed at last is prepared into poly aspartic acid.Because poly aspartic acid itself is all relatively poor to the scale-inhibiting properties and the corrosion mitigating effect of calcium phosphate scale, therefore in the prior art poly aspartic acid is carried out study on the modification, patent CN1569922A has announced a kind of modified polyaspartic acid with poly aspartic acid, phosphorus trichloride and formaldehyde to be feedstock production contain on end group phosphonate group; Patent CN1487003A has announced a kind of preparation method of modified polyaspartic acid, preparation process is to be main raw material with maleic anhydride, 25%～30% ammoniacal liquor and amidosulfonic acid, at high temperature dewater after in having the reactor of agitator, reacting certain hour, with the reaction that is hydrolyzed of organic bases and mineral alkali, obtain the poly aspartic acid of modification then.
Summary of the invention
The purpose of a kind of aspartate copolymer of the present invention and preparation method thereof is, provide a kind of on molecular chain, contain sulfonic group, hydroxyl and carboxylic acid group functional group simultaneously not only lime carbonate and calcium sulfate are had good scale-inhibiting properties, and the technical scheme that calcium phosphate is also had scale-inhibiting properties preferably and has good water conditioner aspartate copolymer of the over-all properties of good dispersing iron oxide performance and preparation method thereof.
A kind of aspartate copolymer, it is characterized in that it being maleic anhydride and the ammonium salt mixture that in the disc type reactor, is paved into certain thickness of thin layer through grinding, reacting back gained withered yellow brittle solid product under differing temps joins in the organic amine mixed aqueous solution that contains sulfonic organic amine and hydroxyl with buffer reagent regulator solution pH value after crushed, react at a certain temperature, add the aqueous solution contain mineral alkali then and continue that reaction is resulting to contain sulfonic group simultaneously on a molecular chain, the aspartate copolymer of hydroxyl and carboxyl functional group, used each component and stoichiometric ratio thereof are: maleic anhydride: ammonium salt: contain sulfonic organic amine: the organic amine of hydroxyl is 1: 0.5～2: 0.05～0.4: 0.05～0.4; The mol ratio of carboxyl, sulfonic group and hydroxy functional group is 0.2～0.9: 0.05～0.4 in the aspartate copolymer: 0.05～0.4.
The preparation method who contains the aspartate copolymer of sulfonic group, hydroxyl and carboxyl functional group simultaneously is characterized in that preparation may further comprise the steps:
I, will stoichiometric ratio be that 1: 0.5～2 maleic anhydride and ammonium salt mixture are paved into 1～10cm thin layer in the disc type reactor, at 30～70 ℃ of reaction 0.5～2h down through grinding;
II, intensification continue reaction 0.5～2h at 175～250 ℃, get the withered yellow brittle solid, pulverize;
III, the organic amine that will contain sulfonic organic amine and hydroxyl are soluble in water, the consumption of water is 2～5 times of maleic anhydride quality, after being 6～12 with pH damping fluid regulator solution pH value, the Step II product is joined in this mixing solutions, used each component and stoichiometric ratio thereof are maleic anhydride: contain sulfonic organic amine: the organic amine of hydroxyl is 1: 0.05～0.4: 0.05～0.4, at 20～65 ℃ of reaction 0.5～25h, obtain sorrel liquid;
The aqueous solution that IV, adding contain mineral alkali continues hydrolysis 1～4h, regulates pH=7 with hydrochloric acid, obtains a kind of aspartate copolymer that contains sulfonic group, hydroxyl and carboxyl functional group.
The preparation method of above-mentioned aspartate copolymer is characterized in that it being that used ammonium salt comprises volatile salt, bicarbonate of ammonia, ammonium chloride, ammonium nitrate or ammonium sulfate.
The preparation method of above-mentioned aspartate copolymer is characterized in that it being that the organic amine of described hydroxyl comprises azanol, Monoethanolamine MEA BASF, N-(2-hydroxyethyl)-quadrol or 2-(2-(amino)-oxyethyl group)-ethanol; Describedly contain sulfonic organic amine and comprise thionamic acid, aniline sulfonic acid or amidoalkylsulfonic acid.
The preparation method of above-mentioned aspartate copolymer is characterized in that it being that described buffer reagent is boric acid-borate buffer solution, borax-sodium hydrate buffer solution, phosphate buffered saline buffer, glycine-sodium hydrate buffer solution, potassium primary phosphate-sodium hydrate buffer solution, Veronal sodium-hydrochloride buffer, Tris-hydrochloride buffer or yellow soda ash-sodium bicarbonate buffer liquid.
The preparation method of above-mentioned aspartate copolymer is characterized in that it being that the used inorganic alkali solution of described hydrolysis is sodium hydroxide or potassium hydroxide.
The advantage of a kind of aspartate copolymer of the present invention and preparation method thereof is, on molecular chain, contain sulfonic group simultaneously, hydroxyl and carboxyl functional group, not only lime carbonate and calcium sulfate had good scale-inhibiting properties, calcium phosphate also had scale-inhibiting properties preferably, but also good water conditioner aspartate copolymer of the over-all properties with good dispersing iron oxide performance and preparation method thereof, owing to adopt ammonia to absorb and one step of polycondensation thin layer reaction, saved and used ammoniacal liquor to synthesize the process of necessary transpiring moisture in the past, hydroxyl and one step of sulfonic group introduce, make and contain sulfonic group simultaneously on the molecular chain, hydroxyl and carboxyl functional group, thereby make that the technological process of this invention is simple, save energy, and improved the over-all properties of product.
Embodiment
Further specify the present invention with concrete embodiment below.
Embodiment 1.
With joining in the disc type reactor behind 9.8kg maleic anhydride and the 7.9kg bicarbonate of ammonia mixed grinding, be paved into the thin layer of 1cm, place baking oven, 55 ℃ of reaction 0.5h; Heat up, continue reaction 2h, get the withered yellow brittle solid at 175 ℃; 1.25kg taurine and 0.61kg thanomin are dissolved in the 35kg water; with Veronal sodium-hydrochloride buffer regulator solution pH value is 8; to join in this mixing solutions after the pulverizing of withered yellow brittle solid; stir; at 20 ℃ of reaction 25h, obtain sorrel liquid, add and contain 3.2kg aqueous sodium hydroxide solution continuation hydrolysis 1h; regulate pH=7 with hydrochloric acid, obtain a kind of aspartate copolymer that contains sulfonic group, hydroxyl and carboxyl functional group.
Embodiment 2. joins 9.8kg maleic anhydride and 6.5kg volatile salt ground and mixed in the disc type reactor, is paved into the thin layer of 5cm, places baking oven, 62 ℃ of reaction 1h; Heat up, continue reaction 1h, get the withered yellow brittle solid at 185 ℃; 6.92kg aniline sulfonic acid and 1.32kg azanol are dissolved in the 35kg water, with borax-sodium hydrate buffer solution regulator solution pH value is 9, to join in this mixing solutions after the pulverizing of withered yellow brittle solid, stir, at 35 ℃ of reaction 12h, obtain sorrel liquid, add the solution that contains 0.8kg sodium hydroxide and continue hydrolysis 2h, regulate pH=7 with hydrochloric acid, obtain a kind of aspartate copolymer that contains sulfonic group, hydroxyl and carboxyl functional group.
Embodiment 3. joins 9.8kg maleic anhydride and 8.56kg ammonium chloride ground and mixed in the disc type reactor, is paved into the thin layer of 10cm, places baking oven, 70 ℃ of reaction 2h; Heat up, continue reaction 0.5h, get the withered yellow brittle solid at 245 ℃; 1.94kg thionamic acid and 6.25kgN-(2-hydroxyethyl)-quadrol are dissolved in the 45kg water, with yellow soda ash-sodium bicarbonate buffer agent regulator solution pH value is 10, to join in this mixing solutions after the pulverizing of withered yellow brittle solid, stir, at 65 ℃ of reaction 0.5h, obtain sorrel liquid, add and contain 1.04kg potassium hydroxide solution continuation hydrolysis 4h, regulate pH=7 with hydrochloric acid, obtain a kind of aspartate copolymer that contains sulfonic group, hydroxyl and carboxylic acid functional.
Embodiment 4. joins in the disc type reactor after with 9.8kg maleic anhydride and 7.9kg bicarbonate of ammonia mixed grinding, is paved into the thin layer of 1cm, places baking oven, 55 ℃ of reaction 0.5h; Heat up, continue reaction 2h, get the withered yellow brittle solid at 175 ℃; 0.7kg aminopropanesulfonic acid and 0.61kg thanomin are dissolved in the 48kg water, with Veronal sodium-hydrochloride buffer regulator solution pH value is 8, to join in this mixing solutions after the pulverizing of withered yellow brittle solid, stir, at 35 ℃ of reaction 25h, obtain sorrel liquid, add and contain 3.2kg aqueous sodium hydroxide solution continuation hydrolysis 1h, regulate pH=7 with hydrochloric acid, obtain a kind of aspartate copolymer that contains sulfonic group, hydroxyl and carboxyl functional group.
Embodiment 5. joins 9.8kg maleic anhydride and 6.5kg volatile salt ground and mixed in the disc type reactor, is paved into the thin layer of 5cm, places baking oven, 62 ℃ of reaction 1h; Heat up, continue reaction 1h, get the withered yellow brittle solid at 185 ℃; Amino fourth sulfonic acid of 3kg and 1.32kg azanol are dissolved in the 25kg water, with borax-sodium hydrate buffer solution regulator solution pH value is 9, to join in this mixing solutions after the pulverizing of withered yellow brittle solid, stir, at 25 ℃ of reaction 12h, obtain sorrel liquid, add the solution that contains 0.8kg sodium hydroxide and continue hydrolysis 2h, regulate pH=7 with hydrochloric acid, obtain a kind of aspartate copolymer that contains sulfonic group, hydroxyl and carboxyl functional group.
Claims (6)
1. aspartate copolymer, it is characterized in that it being to adopt maleic anhydride and one step of ammonium salt thin layer reaction, the resulting aspartate copolymer that on a molecular chain, contains sulfonic group, hydroxyl and carboxyl functional group simultaneously of organic amine one step modification through containing sulfonic organic amine and hydroxyl, each component and stoichiometric ratio thereof are: maleic anhydride: ammonium salt: contain sulfonic organic amine: the organic amine of hydroxyl is 1: 0.5～2: 0.05～0.4: 0.05～0.4; The mol ratio of carboxyl, sulfonic group and hydroxy functional group is 0.2～0.9: 0.05～0.4 in the aspartate copolymer: 0.05～0.4.
2. the preparation method of the described a kind of aspartate copolymer of claim 1, it is characterized in that at maleic anhydride and the ammonium salt mixture of disc type reactor middle berth one deck through grinding, reacting back gained withered yellow brittle solid product under differing temps joins after crushed in the organic amine mixed aqueous solution that contains sulfonic organic amine and hydroxyl with buffer reagent regulator solution pH value and reacts, add mineral alkali then and continue the method that reaction obtains multipolymer, its concrete steps are:
I, will stoichiometric ratio be that 1: 0.5～2 maleic anhydride and ammonium salt mixture are paved into 1～10cm thin layer in the disc type reactor, at 30～70 ℃ of reaction 0.5～2h down through grinding;
II, intensification continue reaction 0.5～2h at 175～250 ℃, get the withered yellow brittle solid, pulverize;
III, the organic amine that will contain sulfonic organic amine and hydroxyl are soluble in water, the consumption of water is 2～5 times of maleic anhydride quality, after being 6～12 with pH damping fluid regulator solution pH value, the Step II product is joined in this mixing solutions, used each component and stoichiometric ratio thereof are maleic anhydride: contain sulfonic organic amine: the organic amine of hydroxyl is 1: 0.05～0.4: 0.05～0.4, at 20～65 ℃ of reaction 0.5～25h, obtain sorrel liquid;
The aqueous solution that IV, adding contain mineral alkali continues hydrolysis 1～4h, regulates pH=7 with hydrochloric acid, obtains a kind of aspartate copolymer that contains sulfonic group, hydroxyl and carboxyl functional group.
3. the preparation method of aspartate copolymer according to claim 2 is characterized in that it being that used ammonium salt comprises volatile salt, bicarbonate of ammonia, ammonium chloride, ammonium nitrate or ammonium sulfate.
4. the preparation method of aspartate copolymer according to claim 2 is characterized in that it being that the organic amine of described hydroxyl comprises azanol, Monoethanolamine MEA BASF, N-(2-hydroxyethyl)-quadrol or 2-(2-(amino)-oxyethyl group)-ethanol; Describedly contain sulfonic organic amine and comprise thionamic acid, aniline sulfonic acid or amidoalkylsulfonic acid.
5. the preparation method of aspartate copolymer according to claim 2 is characterized in that it being that described buffer reagent is boric acid-borate buffer solution, borax-sodium hydrate buffer solution, phosphate buffered saline buffer, glycine-sodium hydrate buffer solution, potassium primary phosphate-sodium hydrate buffer solution, Veronal sodium-hydrochloride buffer, tris-HCI buffer or yellow soda ash-sodium bicarbonate buffer liquid.
6. the preparation method of aspartate copolymer according to claim 2 is characterized in that it being that the used mineral alkali of described hydrolysis is sodium hydroxide or potassium hydroxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100129183A CN100369954C (en) | 2006-07-05 | 2006-07-05 | Aspartate copolymer and method for preparing same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100129183A CN100369954C (en) | 2006-07-05 | 2006-07-05 | Aspartate copolymer and method for preparing same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1876696A CN1876696A (en) | 2006-12-13 |
| CN100369954C true CN100369954C (en) | 2008-02-20 |
Family
ID=37509273
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006100129183A Expired - Fee Related CN100369954C (en) | 2006-07-05 | 2006-07-05 | Aspartate copolymer and method for preparing same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100369954C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101428912B (en) * | 2008-12-10 | 2010-11-10 | 河北省能源研究所 | Biodegradable scale inhibitor-carboxylic acid base-containing poly-asparagic acid derivant and method for producing the same |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102381724A (en) * | 2010-09-01 | 2012-03-21 | 中国科学院化学研究所 | Preparation method of shape controllable monodisperse barium sulfate crystal particles |
| CN102173936A (en) * | 2011-01-21 | 2011-09-07 | 青岛德佳生物技术有限公司 | Polyaspartic acid fertilizer additive, and preparation method and application thereof |
| CN104530428A (en) * | 2014-12-22 | 2015-04-22 | 安徽大学 | Preparation method of modified polyaspartic acid copolymer |
| CN113527679B (en) * | 2020-04-15 | 2023-03-31 | 中国石油化工股份有限公司 | Polyaspartic acid/2-amino-4, 6-dimethoxypyrimidine graft copolymer and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5219952A (en) * | 1992-09-18 | 1993-06-15 | Donlar Corporation | Production of high molecular weight polysuccinimide and high molecular weight polyaspartic acid from maleic anhydride and ammonia |
| CN1194027C (en) * | 2003-06-03 | 2005-03-23 | 中国石油兰州炼油化工总厂 | Modified polyaspartate and its prepn process |
-
2006
- 2006-07-05 CN CNB2006100129183A patent/CN100369954C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5219952A (en) * | 1992-09-18 | 1993-06-15 | Donlar Corporation | Production of high molecular weight polysuccinimide and high molecular weight polyaspartic acid from maleic anhydride and ammonia |
| CN1194027C (en) * | 2003-06-03 | 2005-03-23 | 中国石油兰州炼油化工总厂 | Modified polyaspartate and its prepn process |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101428912B (en) * | 2008-12-10 | 2010-11-10 | 河北省能源研究所 | Biodegradable scale inhibitor-carboxylic acid base-containing poly-asparagic acid derivant and method for producing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1876696A (en) | 2006-12-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100369954C (en) | Aspartate copolymer and method for preparing same | |
| CN103554361B (en) | A kind of preparation method of high-efficiency calcium phosphate scale inhibitor | |
| CN101700937B (en) | Composite scale inhibitor | |
| CN101768268B (en) | Method for preparing polyaspartic acid by crystal condensation | |
| CN100478288C (en) | Biodegradable composite corrosion and scale inhibitor and method for preparing same | |
| CN102583792A (en) | Method for preparing composite industrial circulating cooling water scale inhibitor | |
| CN102146161A (en) | Polyaspartic acid complex for scale inhibitor | |
| CN105482117B (en) | Poly-aspartate/urea graft copolymer and its preparation method and application | |
| CN102167451B (en) | Composite multiple dirt dispersion agent for oilfield flooding treatment and preparation method thereof | |
| CN102174197B (en) | Microwave synthesis method for hydroxyl modified polyaspartic acid | |
| CN106543436A (en) | High molecular organic amine and maleic anhydride modified polyaspartic acid salts and its preparation method | |
| CN102153749B (en) | Microwave synthesis method for sulfonic group modified polyaspartic acid | |
| CN109019887A (en) | A kind of environmental Water Treatment Chemicals having both inhibition, scale-inhibiting properties | |
| CN104530428A (en) | Preparation method of modified polyaspartic acid copolymer | |
| CN109264876B (en) | Non-phosphorus reverse osmosis scale inhibitor EDA-PAMAM and preparation method thereof | |
| CN103601401A (en) | Preparation method of sulfonated bisphenol A-formaldehyde condensate superplasticizer | |
| CN105439299A (en) | Method for preparing hyperbranched polyethyleneimine copolymer water treatment agent and application of hyperbranched polyethyleneimine copolymer water treatment agent | |
| CN101767883A (en) | Method for synthesizing barium strontium scale inhibitor | |
| CN105154007B (en) | Preparation method and usage method for slag grinding aid mother liquor | |
| CN102391491A (en) | Biodegradable water treatment agent p-sulfonicphenylaminopolyepoxysuccinic acid and preparation method thereof | |
| CN103553218A (en) | Composite corrosion inhibitor | |
| CN102786156A (en) | Sulfonic acid group-containing attapulgite corrosion and scale inhibitor and preparation method as well as application thereof | |
| CN105060516A (en) | Method for scale inhibition of blasting condensation high hardness circulating water in coking plant | |
| CN105174506B (en) | A kind of scale inhibitor for circulating cooling water and preparation method thereof | |
| CN104556431A (en) | Preparation method of modified polyaspartic acid scale inhibitor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |