CN101717509A - Method for synthesizing polyaspartic acid by utilizing ionic liquid - Google Patents
Method for synthesizing polyaspartic acid by utilizing ionic liquid Download PDFInfo
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Abstract
The invention provides a method for synthesizing polyaspartic acid by utilizing ionic liquid, which relates to a method for synthesizing polyaspartic acid. The invention solves the problems that catalysts used in the prior liquid-phase polymerization method are easy to cause environmental pollution and organic solvents are easy to volatilize and lose and poor in safety during synthesis. The method comprises: 1, the preparation of ionic liquid; 2, polymerization; 3, product separation; and 4, the purification of polyaspartic acid. The method has the advantage of adopting the ionic liquid as a catalyst which is safe, nontoxic and incapable of polluting environment.
Description
Technical field
The present invention relates to a kind of method for synthesizing polyaspartic acid derivatives.
Background technology
Advantages such as poly aspartic acid (PASP) is a kind of environmentally friendly Scale inhibitors, and the much more existing liquid polymerization methods that adopt are made poly aspartic acids, and this method has that temperature of reaction is low, homogeneous heating, reaction times weak point, products molecule clear in structure, linearity are better.Liquid polymerization method is that aspartic acid high temperature in organic solvent (trimethylbenzene, tetramethylene sulfone etc.) carries out polyreaction, this method organic solvent dissolution aspartic acid ability a little less than, need extra catalyst (phosphoric acid etc.) to realize the making of poly aspartic acid.In making processes, organic solvent is volatile, loss, contaminate environment, and phosphoric acid is the principal pollutant of body eutrophication, the thermostability of organic solvent is relatively poor when high temperature, causes accident, poor stability easily.Therefore traditional liquid polymerization method is difficult to industrial applications always.
Summary of the invention
The present invention causes easily in order to solve the employed catalyzer of existing liquid polymerization method that organic solvent in environmental pollution and the building-up process is volatile, the problem of loss and poor stability, and a kind of ionic liquid method for synthesizing polyaspartic acid derivatives of utilizing is provided
The present invention utilizes the ionic liquid method for synthesizing polyaspartic acid derivatives to carry out according to following steps: one, ion liquid preparation: under nitrogen protection, Triethylammonium chloride is added in the three-necked bottle, temperature is risen to 60～100 ℃, and then Aluminum chloride anhydrous joined three-necked bottle, stir and promptly obtained ionic liquid in 1～3 hour, wherein the mol ratio of Aluminum chloride anhydrous and Triethylammonium chloride is 1～3: 1; Two, polyreaction: under nitrogen protection, the ionic liquid of 47～53ml is put into three-necked bottle, the L-aspartic acid that adds 8～12g then carries out stirring reaction, is that 160～240 ℃, mixing speed are to react 1～3h under the condition of 80～120r/min promptly to obtain polymkeric substance in temperature; Three, separate purification: the deionized water and stirring that adds 200～300ml in polymkeric substance is even, leaves standstill then to be cooled to room temperature, and suction filtration is isolated solid, promptly obtains the polysuccinimide intermediate 2～4 times with 60～100 ℃ deionized water wash solids; Four, adding mass concentration in the polysuccinimide intermediate is that 15%～25% sodium hydroxide solution carries out the titration hydrolysis, until the pH value of solution value is promptly to obtain the poly aspartic acid sodium salt solution at 8.5～9.5 o'clock, be that 70～98% ethanol mixes precipitating according to 1: 11～13 volume ratio then with poly aspartic acid sodium salt solution and mass concentration, be drying to obtain poly aspartic acid then.
The inventive method utilizes ionic liquid to prepare synthesizing polyaspartic acid, does not need extra catalyst, and ionic liquid safety non-toxic used in the present invention, and manufacturing conditions gentleness of the present invention, temperature of reaction is low, and security is good, can not cause environmental pollution, method of the present invention.The molecular mass that the inventive method is made the poly aspartic acid that obtains is 1000～5000, the inventive method is made the scale-inhibiting properties excellence of the poly aspartic acid that obtains, by static-state scale inhibition performance test (GBT 16632-2008 tosca method) as can be known, it is 70%～94% that the inventive method is made the poly aspartic acid scale inhibition performance that obtains, compare with traditional liquid polymerization method, the inventive method is made the poly aspartic acid scale inhibition performance that obtains and has been improved about 5%.
Description of drawings
Fig. 1 is the infrared spectrum of poly aspartic acid, the infrared spectrum of " I " expression poly aspartic acid mark product among the figure, and " II " expression embodiment 21 is made the infrared spectrum of the poly aspartic acid that obtains; Fig. 2 is the molecular weight GPC spectrum curve of poly aspartic acid.
Embodiment
Technical solution of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: present embodiment utilizes the ionic liquid method for synthesizing polyaspartic acid derivatives to carry out according to following steps: one, ion liquid preparation: under nitrogen protection, Triethylammonium chloride is added in the three-necked bottle, temperature is risen to 60～100 ℃, and then Aluminum chloride anhydrous joined three-necked bottle, stir and promptly obtained ionic liquid in 1～3 hour, wherein the mol ratio of Aluminum chloride anhydrous and Triethylammonium chloride is 1～3: 1; Two, polyreaction: under nitrogen protection, the ionic liquid of 47～53ml is put into three-necked bottle, the L aspartic acid that adds 8～12g then carries out stirring reaction, is that 160～240 ℃, mixing speed are to react 1～3h under the condition of 80～120r/min promptly to obtain polymkeric substance in temperature; Three, separate purification: the deionized water and stirring that adds 200～300ml in polymkeric substance is even, leaves standstill then to be cooled to room temperature, and suction filtration is isolated solid, promptly obtains the polysuccinimide intermediate 2～4 times with 60～100 ℃ deionized water wash solids; Four, adding mass concentration in the polysuccinimide intermediate is that 15%～25% sodium hydroxide solution carries out the titration hydrolysis, until the pH value of solution value is promptly to obtain the poly aspartic acid sodium salt solution at 8.5～9.5 o'clock, be that 70～98% ethanol mixes precipitating according to 1: 11～13 volume ratio then with poly aspartic acid sodium salt solution and mass concentration, be drying to obtain poly aspartic acid then.
Make the ionic liquid that obtains in the present embodiment step 1 and form the yellow-green colour ionic liquid.
Thermometer and agitator and nitrogen protection device are housed in the three-necked bottle in the present embodiment step 2.
Under agitation condition, add the L-aspartic acid in the present embodiment step 2 and carry out polyreaction.
Polymkeric substance in the present embodiment step 2 is the brown viscous liquid.
The isolated solid of suction filtration is a tawny in the present embodiment step 3.
The polysuccinimide intermediate is a tawny in the present embodiment step 3.
Adding mass concentration in the present embodiment step 4 and be 20% sodium hydroxide in the polysuccinimide intermediate, to carry out the resulting solution of titration hydrolysis be the reddish-brown transparent liquid.
Drying is to handle 4～6h under 80～120 ℃ of conditions in the present embodiment step 4.
Dripped 0.5～2mL in the present embodiment step 4 during titration hydrolysis in per 1～2 second.
Ionic liquid described in the present embodiment has Lewis acidity, and the L-aspartic acid is had solvability, and the poly aspartic acid polyreaction is had the effect of solvent-induced acceleration polymeric.
The result shows by infrared analysis, and present embodiment is made the product that obtains and had the constitutional features of poly aspartic acid.
Present embodiment is made the poly aspartic acid that obtains and is had good scale-inhibiting properties, the inventive method is made the poly aspartic acid scale inhibition performance that obtains and is reached 90%～94%, compare with traditional liquid polymerization method, under identical synthesis condition, improved about 5% than the scale inhibition performance of organic liquid phase polymerisate.
Embodiment two: what present embodiment and embodiment one were different is: in the step 1 temperature is risen to 70～90 ℃, churning time is 1.5～2.5 hours.Other step and parameter are identical with embodiment one.
Embodiment three: what present embodiment and embodiment one were different is: in the step 1 temperature is risen to 70 ℃, churning time is 2.5 hours.Other step and parameter are identical with embodiment one.
Embodiment four: what present embodiment and embodiment one were different is: in the step 1 temperature is risen to 90 ℃, churning time is 1.5 hours.Other step and parameter are identical with embodiment one.
Embodiment five: what present embodiment and embodiment one were different is: in the step 1 temperature is risen to 80 ℃, churning time is 2 hours.Other step and parameter are identical with embodiment one.
Embodiment six: what present embodiment and embodiment one to five were different is: the mol ratio of Aluminum chloride anhydrous and Triethylammonium chloride is 1.5～2.5: 1 in the step 1.Other step and parameter are identical with embodiment one to five.
Embodiment seven: what present embodiment and embodiment one to five were different is: the mol ratio of Aluminum chloride anhydrous and Triethylammonium chloride is 1.5: 1 in the step 1.Other step and parameter are identical with embodiment one to five.
Embodiment eight: what present embodiment and embodiment one to five were different is: the mol ratio of Aluminum chloride anhydrous and Triethylammonium chloride is 2.5: 1 in the step 1.Other step and parameter are identical with embodiment one to five.
Embodiment nine: what present embodiment and embodiment one to five were different is: the mol ratio of Aluminum chloride anhydrous and Triethylammonium chloride is 2: 1 in the step 1.Other step and parameter are identical with embodiment one to five.
Embodiment ten: what present embodiment and embodiment one to nine were different is: in the step 2 ionic liquid of 49～51ml is put into three-necked bottle, add the L-aspartic acid of 9～11g then.Other step and parameter are identical with embodiment one to nine.
Embodiment 11: what present embodiment and embodiment one to nine were different is: in the step 2 ionic liquid of 49ml is put into three-necked bottle, add the L-aspartic acid of 9g then.Other step and parameter are identical with embodiment one to nine.
Embodiment 12: what present embodiment and embodiment one to nine were different is: in the step 2 ionic liquid of 51ml is put into three-necked bottle, add the L-aspartic acid of 11g then.Other step and parameter are identical with embodiment one to nine.
Embodiment 13: what present embodiment and embodiment one to nine were different is: in the step 2 ionic liquid of 50ml is put into three-necked bottle, add the L-aspartic acid of 10g then.Other step and parameter are identical with embodiment one to nine.
Embodiment 14: what present embodiment and embodiment one to 13 were different is: be that 200～220 ℃, mixing speed are to react 1～3h under the condition of 90～110r/min in temperature in the step 2.Other step and parameter are identical with embodiment one to 13.
Embodiment 15: what present embodiment and embodiment one to 13 were different is: be that 200 ℃, mixing speed are to react 1～3h under the condition of 90r/min in temperature in the step 2.Other step and parameter are identical with embodiment one to 13.
Embodiment 16: what present embodiment and embodiment one to 13 were different is: be that 220 ℃, mixing speed are to react 1～3h under the condition of 110r/min in temperature in the step 2.Other step and parameter are identical with embodiment one to 13.
Embodiment 17: what present embodiment and embodiment one to 13 were different is: be that 210 ℃, mixing speed are to react 1～3h under the condition of 100r/min in temperature in the step 2.Other step and parameter are identical with embodiment one to 13.
Embodiment 18: what present embodiment and embodiment one to 17 were different is: in the step 3 with 70～90 ℃ deionized water wash solid 3 times.Other step and parameter are identical with embodiment one to 13.
Embodiment 19: what present embodiment and embodiment one to 17 were different is: in the step 3 with 70 ℃ deionized water wash solid 4 times.Other step and parameter are identical with embodiment one to 13.
Embodiment 20: what present embodiment and embodiment one to 17 were different is: in the step 3 with 90 ℃ deionized water wash solid 2 times.Other step and parameter are identical with embodiment one to 13.
Embodiment 21: present embodiment utilizes the ionic liquid method for synthesizing polyaspartic acid derivatives to carry out according to following steps: one, ion liquid preparation: under nitrogen protection, Triethylammonium chloride is added in the three-necked bottle, temperature is risen to 80 ℃, and then Aluminum chloride anhydrous joined three-necked bottle, stir and promptly obtained ionic liquid in 2 hours, wherein the mol ratio of Aluminum chloride anhydrous and Triethylammonium chloride is 2.2: 1; Two, polyreaction: under nitrogen protection, the ionic liquid of 50ml is put into three-necked bottle, the L aspartic acid that adds 10g then carries out stirring reaction, is that 200 ℃, mixing speed are that reaction 2h promptly obtains polymkeric substance under the condition of 100r/min in temperature; Three, separate purification: the deionized water and stirring that adds 250ml in polymkeric substance is even, leaves standstill then and is cooled to room temperature, and suction filtration is isolated solid, promptly obtains the polysuccinimide intermediate 3 times with 80 ℃ deionized water wash solids; Four, adding mass concentration in the polysuccinimide intermediate is that 20% sodium hydroxide solution carries out the titration hydrolysis, until the pH value of solution value is promptly to obtain the poly aspartic acid sodium salt solution at 9 o'clock, be that 85% ethanol mixes precipitating according to 1: 12 volume ratio then with poly aspartic acid sodium salt solution and mass concentration, be drying to obtain poly aspartic acid then.
Drying is to handle 4h under 80 ℃ of conditions in the present embodiment step 4.
Dripped 0.5～2mL in the present embodiment step 4 during titration hydrolysis in per 1～2 second.
The infrared spectrum that present embodiment is made the poly aspartic acid obtain as shown in Figure 1, the infrared spectrum of " I " expression poly aspartic acid mark product among the figure, the infrared spectrum of the poly aspartic acid that 21 making of " II " expression embodiment obtain.As can be seen from the figure, 3416cm
-1Be the flexible absorption peak of the N Nv key in the secondary acid amides, illustrate to contain a large amount of secondary amido linkages in the polymkeric substance; At 1656cm
-1Be the acid amides I band of amide group absorption peak, i.e. the absorption peak of carbonyl in the acid amides is at 1531cm
-1And 1280cm
-1Be amide group δ
NHAnd v
C-NBetween coupling cause phthalein amine II, III band, show behind the polymkeric substance hydrolysis and have a secondary amide structure.1720cm
-1And 1392cm
-1The absorption peak at place is respectively antisymmetric stretching vibration and the symmetrical stretching vibration absorption peak that the C=O vibrational coupling produces among carboxylate radical-COO-, and empirical tests present embodiment synthetic poly aspartic acid has the PASP constitutional features
Simultaneous test: the poly aspartic acid that the poly aspartic acid that present embodiment obtains and traditional liquid polymerization method obtain detects scale inhibition performance as Scale inhibitors, and detection method detects scale inhibition performance with reference to GBT 16632-2008 tosca method, takes by weighing the Ca of 50mL respectively
2+And HCO
3 -The ion water sample adds 20ml borax buffer solution and Scale inhibitors and mixes, and at 80 ± 1 ℃ of constant temperature 6h, takes out testing liquid and is cooled to room temperature, gets supernatant liquid, with EDTA complexometric titration Ca
2+Ionic concn.By formula calculation result: scale inhibition performance=(V
1-V
0)/(V
2-V
0) * 100% is in the formula: V
1For adding the mL number that the PASP water sample consumes EDTA; V
2For not adding the mL number that the PASP water sample consumes EDTA; V
0For adding medicine water sample (blank) not consumes the EDTAmL number.Ca wherein
2+Concentration is respectively 250mgL
-1, 300mgL
-1, 350mgL
-1, 400mgL
-1, detected result is as shown in table 1.
Table 1
| ??Ca 2+Concentration/mgL -1 | ??250 | ??300 | ??350 | ??400 |
| |
??93.8 | ??88.6 | ??83.5 | ??79.3 |
| ??Ca 2+Concentration/mgL -1 | ??250 | ??300 | ??350 | ??400 |
| Tradition liquid polymerization method scale inhibition performance (%) | ??88.8 | ??82.6 | ??75.3 | ??71.0 |
From the data of table 1 as can be seen, the scale inhibition performance height of the poly aspartic acid that present embodiment obtains, scale inhibition effect is good.
Embodiment 22: what present embodiment and embodiment 21 were different is: the mol ratio of Aluminum chloride anhydrous and Triethylammonium chloride is 1.5: 1 in the step 1.Other step and parameter are identical with embodiment 21.
The scale inhibition performance of present embodiment poly aspartic acid is 72.7%.
Embodiment 23: what present embodiment and embodiment 21 were different is: the mol ratio of Aluminum chloride anhydrous and Triethylammonium chloride is 2.0: 1 in the step 1.Other step and parameter are identical with embodiment 21.
The scale inhibition performance of present embodiment poly aspartic acid is 90.1%.
Embodiment 24: what present embodiment and embodiment 21 were different is: the mol ratio of Aluminum chloride anhydrous and Triethylammonium chloride is 2.5: 1 in the step 1.Other step and parameter are identical with embodiment 21.
The scale inhibition performance of present embodiment poly aspartic acid is 92.5%.
Embodiment 25: what present embodiment and embodiment 21 were different is: temperature of reaction is 160 ℃ in the step 2.Other steps and parameter are identical with embodiment 21.
The scale inhibition performance of present embodiment poly aspartic acid is 72.6%.
Embodiment 26: what present embodiment and embodiment 21 were different is: temperature of reaction is 180 ℃ in the step 2.Other steps and parameter are identical with embodiment 21.
The scale inhibition performance of present embodiment poly aspartic acid is 83.2%.
Embodiment 27: what present embodiment and embodiment 21 were different is: temperature of reaction is 220 ℃ in the step 2.Other steps and parameter are identical with embodiment 21.
The scale inhibition performance of present embodiment poly aspartic acid is 93.8%.
Embodiment 28: what present embodiment and embodiment 21 were different is: temperature of reaction is 240 ℃ in the step 2.Other steps and parameter are identical with embodiment 21.
The scale inhibition performance of present embodiment poly aspartic acid is 94%.
Embodiment 30: what present embodiment and embodiment 21 were different is: the L-aspartic acid that adds 6g in the step 2 carries out stirring reaction.Other steps and parameter are identical with embodiment 21.
The scale inhibition performance of present embodiment poly aspartic acid is 84.5%.
The molecular weight of present embodiment poly aspartic acid is 1167.
The embodiment hentriaconta-: what present embodiment and embodiment 21 were different is: the L-aspartic acid that adds 8g in the step 2 carries out stirring reaction.Other steps and parameter are identical with embodiment 21.
The scale inhibition performance of present embodiment poly aspartic acid is 90.2%.
The molecular weight of present embodiment poly aspartic acid is 1984.
Embodiment 32: what present embodiment and embodiment 21 were different is: the L-aspartic acid that adds 12g in the step 2 carries out stirring reaction.Other steps and parameter are identical with embodiment 21.
The scale inhibition performance of present embodiment poly aspartic acid is 92.5%.
The molecular weight of present embodiment poly aspartic acid is 3037.
Embodiment 33: what present embodiment and embodiment 21 were different is: the L-aspartic acid that adds 12g in the step 2 carries out stirring reaction.Other steps and parameter are identical with embodiment 21.
The scale inhibition performance of present embodiment poly aspartic acid is 90.1%.
The molecular weight of present embodiment poly aspartic acid is 2789.
Claims (5)
1. one kind is utilized the ionic liquid method for synthesizing polyaspartic acid derivatives, it is characterized in that utilizing the ionic liquid method for synthesizing polyaspartic acid derivatives to carry out: one, ion liquid preparation: under nitrogen protection according to following steps, Triethylammonium chloride is added in the three-necked bottle, temperature is risen to 60～100 ℃, and then Aluminum chloride anhydrous joined three-necked bottle, stir and promptly obtained ionic liquid in 1～3 hour, wherein the mol ratio of Aluminum chloride anhydrous and Triethylammonium chloride is 1～3: 1; Two, polyreaction: under nitrogen protection, the ionic liquid of 47～53ml is put into three-necked bottle, the L-aspartic acid that adds 8～12g then carries out stirring reaction, is that 160～240 ℃, mixing speed are to react 1～3h under the condition of 80～120r/min promptly to obtain polymkeric substance in temperature; Three, separate purification: the deionized water and stirring that adds 200～300ml in polymkeric substance is even, leaves standstill then to be cooled to room temperature, and suction filtration is isolated solid, promptly obtains the polysuccinimide intermediate 2～4 times with 60～100 ℃ deionized water wash solids; Four, adding mass concentration in the polysuccinimide intermediate is that 15%～25% sodium hydroxide solution carries out the titration hydrolysis, until the pH value of solution value is promptly to obtain the poly aspartic acid sodium salt solution at 8.5～9.5 o'clock, be that 70～98% ethanol mixes precipitating according to 1: 11～13 volume ratio then with poly aspartic acid sodium salt solution and mass concentration, be drying to obtain poly aspartic acid then.
2. a kind of ionic liquid method for synthesizing polyaspartic acid derivatives of utilizing according to claim 1 is characterized in that in the step 1 temperature being risen to 70～90 ℃, and churning time is 1.5～2.5 hours.
3. a kind of ionic liquid method for synthesizing polyaspartic acid derivatives of utilizing according to claim 1 and 2 is characterized in that in the step 2 ionic liquid of 49～51ml being put into three-necked bottle, adds the L-aspartic acid of 9～11g then.
4. a kind of ionic liquid method for synthesizing polyaspartic acid derivatives of utilizing according to claim 3 is characterized in that in the step 2 in temperature being that 200～220 ℃, mixing speed are to react 1～3h under the condition of 80～120r/min.
5. according to claim 1,2 or 4 described a kind of ionic liquid method for synthesizing polyaspartic acid derivatives of utilizing, it is characterized in that adding in polymkeric substance in the step 3 200～300ml deionized water mixes, leave standstill, cool off the back and separate, use 70～90 ℃ deionized water wash solid 3 times again.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102250352A (en) * | 2011-05-19 | 2011-11-23 | 黑龙江大学 | Method for catalytic synthesis of polyaspartic acid by using imidazole type ionic liquid |
| CN103304815A (en) * | 2013-06-13 | 2013-09-18 | 扬州大学 | Preparation method for synthesizing polyaspartic acid by using ionic liquid |
| CN111116910A (en) * | 2019-12-24 | 2020-05-08 | 苏州美瑞姿生物科技有限公司 | Preparation method of polyaspartic acid sodium salt aqueous solution |
| CN111908626A (en) * | 2020-06-03 | 2020-11-10 | 山东省食品发酵工业研究设计院 | Production method of high-adaptability green scale inhibitor and composite scale inhibitor thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0866084A3 (en) * | 1997-03-21 | 2002-02-27 | Mitsui Chemicals, Inc. | Production process of cross-linked polyaspartic acid resin |
| CN100465155C (en) * | 2004-10-11 | 2009-03-04 | 北京大学 | Ion liquid of amino acid ester cation and its preparation method |
| CN101177482A (en) * | 2007-09-30 | 2008-05-14 | 华东师范大学 | Alpha, beta-poly(L- aspartate)-aminophenol derivatives and preparation thereof |
-
2009
- 2009-11-27 CN CN2009103105644A patent/CN101717509B/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102250352A (en) * | 2011-05-19 | 2011-11-23 | 黑龙江大学 | Method for catalytic synthesis of polyaspartic acid by using imidazole type ionic liquid |
| CN102250352B (en) * | 2011-05-19 | 2012-07-25 | 黑龙江大学 | Method for catalytic synthesis of polyaspartic acid by using imidazole type ionic liquid |
| CN103304815A (en) * | 2013-06-13 | 2013-09-18 | 扬州大学 | Preparation method for synthesizing polyaspartic acid by using ionic liquid |
| CN111116910A (en) * | 2019-12-24 | 2020-05-08 | 苏州美瑞姿生物科技有限公司 | Preparation method of polyaspartic acid sodium salt aqueous solution |
| CN111116910B (en) * | 2019-12-24 | 2022-07-12 | 苏州美瑞姿生物科技有限公司 | Preparation method of polyaspartic acid sodium salt aqueous solution |
| CN111908626A (en) * | 2020-06-03 | 2020-11-10 | 山东省食品发酵工业研究设计院 | Production method of high-adaptability green scale inhibitor and composite scale inhibitor thereof |
| CN111908626B (en) * | 2020-06-03 | 2023-05-12 | 山东省食品发酵工业研究设计院 | Production method of high-adaptability green scale inhibitor and composite scale inhibitor thereof |
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