CN111217998A - Method for synthesizing polyaspartic acid by adopting catalytic system - Google Patents
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- CN111217998A CN111217998A CN201811415389.0A CN201811415389A CN111217998A CN 111217998 A CN111217998 A CN 111217998A CN 201811415389 A CN201811415389 A CN 201811415389A CN 111217998 A CN111217998 A CN 111217998A
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Abstract
The invention provides a method for synthesizing polyaspartic acid by adopting a catalytic system, belonging to the field of organic synthesis. The method takes a titanium polymer as a catalyst, is used in the reaction of synthesizing polysuccinimide, further improves the yield of polyaspartic acid, improves the scale inhibition performance, and is easy to recover and can be recycled. The catalytic system is applied to the reaction, the operation is simple and convenient, and the polysuccinimide prepared by the method is used for synthesizing the polyaspartic acid, so that the scale inhibition performance of the polyaspartic acid is obviously improved.
Description
Technical Field
The invention belongs to the field of organic synthesis, and particularly relates to a method for synthesizing polyaspartic acid by adopting a catalytic system.
Background
The polyaspartic acid has good biocompatibility and biodegradability besides the property of water-soluble carboxylic acid, and the final degradation products are ammonia, carbon dioxide and water which are harmless to the environment, so that the polyaspartic acid is a water-soluble high polymer material which has excellent performance, is nontoxic, pollution-free and extremely easy to degrade, and has easily available raw materials and low price.
The environment-friendly chemical is widely applied to the fields of water treatment agents, detergents, cosmetics, bacteriostats, dispersing agents, chelating agents, tanning, medicines, pesticides, hydrogel, agricultural fertilizers and the like in recent years, and is an internationally recognized environment-friendly green chemical which has wide application, no toxicity, no pollution and easy degradation. At present, 2 methods are mainly used for synthesizing polyaspartic acid, namely 1) synthesizing N-carboxylic anhydride (NCA) by taking aspartic acid as a raw material; 2) l-aspartic acid, D (L) -aspartic acid, maleic anhydride or fumaric acid are taken as raw materials, the polysuccinimide is generated through oligomerization or copolymerization, polyaspartate is obtained through hydrolysis, and the polyaspartic acid is obtained through separation and purification.
Disclosure of Invention
In order to improve the scale inhibition performance of polyaspartic acid, the invention provides a method for preparing polysuccinimide with high yield by using a titanium polymer as a catalyst in the reaction of synthesizing the polysuccinimide, so that the yield of the polyaspartic acid is improved, and the scale inhibition performance of the polyaspartic acid is improved.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: the catalyst system takes a titanium polymer as a catalyst, catalyzes aspartic acid in a solvent to generate polysuccinimide with high yield, and then hydrolyzes the polysuccinimide into the polyaspartic acid under the action of sodium hydroxide.
The invention utilizes a novel catalyst system to synthesize the polysuccinimide with high yield, thereby improving the content of polyaspartic acid, improving the scale inhibition rate and improving the application effect.
A method for synthesizing polyaspartic acid by adopting a catalytic system specifically comprises the following steps:
(1) preparation of titanium catalyst: under the protection of nitrogen, stirring titanium salt and a ligand in a molar ratio of 1:0.1-10 in a reaction medium for 0.5-2 hours, adding a certain amount of distilled water, continuing stirring for 3 hours, standing for liquid separation, concentrating an organic layer, adding n-hexane to precipitate a solid, filtering, and drying to obtain a titanium catalyst;
(2) adding 200-300 parts by weight of solvent into a reaction kettle, then adding 100-200 parts by weight of aspartic acid and 1-2 parts by weight of titanium catalyst, and reacting for 1-12 hours at 80-150 ℃;
(3) then cooling the system to 80 ℃, adding 400-600 parts by weight of ethanol into the reaction kettle, stirring for 1-3 hours at room temperature, filtering, washing the solid with 50 parts by weight of water, washing with 50 parts by weight of ethanol, and drying to obtain polysuccinimide;
(4) after the mother liquor is concentrated, adding 50-200 parts by weight of normal hexane into the kettle, stirring for 1-3 hours at room temperature, filtering, drying and recovering 0.5-2 parts by weight of titanium catalyst;
(5) adding 50 parts by weight of polysuccinimide into 100 parts by weight of 20% sodium hydroxide aqueous solution, and reacting for 2 hours at 40 ℃ to obtain polyaspartic acid.
The reaction medium in the step (1) is one or more than two of methanol, ethanol, toluene, benzene, xylene, dichloromethane, dichloroethane, diethyl ether, tetrahydrofuran or ethyl acetate.
The titanium salt in the step (1) is one or more than two of titanium tetrachloride, titanium trichloride, titanium oxide, tetraisopropanol, titanium tetrabromide and titanium tetraiodide.
The ligand in the step (1) is as follows:
in the formula, R1Is H, Cl, NO2、t-Bu、CH3One or more of phenyl and diphenylphosphine;
the titanium catalyst in the step (1) has the structure that:
in the formula, R1Is H, Cl, NO2、t-Bu、CH3One or more of phenyl and diphenylphosphine.
In the step (2), the solvent is 200 parts by weight, and the aspartic acid is 100 parts by weight.
The titanium catalyst in the step (2) is 1 part by weight, and the reaction time is 2-10 hours.
In the step (3), 400 parts by weight of ethanol is stirred at room temperature for 2 hours.
And (4) stirring the n-hexane in the step (4) for 1 hour, wherein the n-hexane accounts for 50 parts by weight.
The invention has the following positive effects:
the synthesis method of the polyaspartic acid has the advantages of high yield, simple operation, convenient operation and no environmental pollution, and the polyaspartic acid prepared by the method has excellent scale inhibition performance.
Drawings
FIG. 1 is an infrared absorption spectrum of polysuccinimide,
FIG. 2 shows the nuclear magnetic carbon spectrum of polyaspartic acid (sample 3),
FIG. 3 is a GPC chart of polyaspartic acid (sample 3),
FIG. 4 is a GPC chart of polyaspartic acid (commercial sample 1)
Detailed Description
The following examples further illustrate the invention but are not intended to limit the invention thereto.
The structural formula of L-1 used in the examples is shown below:
example 1
(1) Adding 14.7g (0.01mol) of ligand L into a reaction bottle under the protection of nitrogen, adding 20ml of dichloromethane, stirring until the ligand L is dissolved uniformly, adding 2.68g (0.01mol) of titanium tetraisopropoxide, stirring for 2 hours, adding 5ml of distilled water into the system, continuing stirring for 3 hours, standing for liquid separation, adding 10ml of n-hexane after an organic layer is concentrated, stirring for 5 minutes, filtering, and drying to obtain the titanium catalyst.
(2) 200g of sulfolane, 100g of aspartic acid and 1g of titanium catalyst were added to the reaction kettle, and the mixture was heated to 120 ℃ for reaction for 4 hours.
(3) And then cooling the system to 80 ℃, adding 400g of ethanol into the reaction kettle, stirring for 2 hours at room temperature, filtering, washing the solid with 50g of water and 50g of ethanol, and drying to obtain 70.7g of polysuccinimide with the yield of 97%.
(4) Concentrating the filtered mother liquor to dryness, adding 50g of n-hexane, stirring at room temperature for 1 hour, filtering and drying, recovering 0.937g of titanium catalyst, recovering 93.7 percent, and directly using the titanium catalyst in the next reaction.
(5) 50g of polysuccinimide is added into 200g of 20 percent sodium hydroxide aqueous solution, and the reaction is carried out for 2 hours at 40 ℃ to obtain the polyaspartic acid. (sample 3)
The infrared absorption spectrum of the polysuccinimide is shown in figure 1, and the obtained product has the same structure as the designed polysuccinimide from the aspect of spectrum. The NMR spectrum of sample 3 is shown in FIG. 2, with carbon absorption peaks at the carbonyl groups at. delta. ≈ 175-182 and methine (-CH) groups at. delta. ≈ 51-57-) and a methylene group (-CH) at. delta. apprxeq.38-432-) carbon absorption peak. The nuclear magnetic spectrum of the synthesized compound is consistent with the report in the literature, and the compound is proved to be polyaspartic acid. The GPC analysis spectrum is shown in FIG. 3, and the GPC analysis spectrum of commercial sample 1 is shown in FIG. 4. The results of scale inhibition tests performed on polyaspartic acid are shown in Table 1.
Example 2
(1) The preparation method of the titanium catalyst is the same as that of example 1
(2) 200g of sulfolane, 100g of aspartic acid and 1g of titanium catalyst were added to the reaction kettle, and the mixture was heated to 150 ℃ for reaction for 3 hours.
(3) And then cooling the system to 80 ℃, adding 400g of ethanol into the reaction kettle, stirring for 2 hours at room temperature, filtering, washing the solid with 50g of water and 50g of ethanol, and drying to obtain 56.9g of polysuccinimide with the yield of 78%.
(4) Concentrating the filtered mother liquor to dryness, adding 50g of n-hexane, stirring at room temperature for 1 hour, filtering and drying, recovering 0.935g of titanium catalyst, recovering 93.5 percent, and directly using in the next reaction.
(5) 50g of polysuccinimide is added into 200g of 20 percent sodium hydroxide aqueous solution, and the reaction is carried out for 2 hours at 40 ℃ to obtain the polyaspartic acid. (sample 9) the product was subjected to infrared absorption and nuclear magnetic carbon spectrum detection, and from the spectrum, the obtained product had the same structure as the designed polysuccinimide. The results of scale inhibition tests performed on polyaspartic acid are shown in Table 1.
Example 3
(1) The titanium catalyst was prepared in the same manner as in example 1.
(2) 200g of sulfolane, 100g of aspartic acid and 1g of titanium catalyst are added into the reaction kettle, and the mixture is heated to 80 ℃ for reaction for 8 hours.
(3) And then cooling the system to 80 ℃, adding 400g of ethanol into the reaction kettle, stirring for 2 hours at room temperature, filtering, washing the solid with 50g of water and 50g of ethanol, and drying to obtain 59.8g of polysuccinimide with the yield of 82%.
(4) Concentrating the filtered mother liquor to dryness, adding 50g of n-hexane, stirring at room temperature for 1 hour, filtering and drying, recovering 0.929g of titanium catalyst, recovering 92.9%, and directly using in the next reaction.
(5) 50g of polysuccinimide is added into 200g of 20 percent sodium hydroxide aqueous solution, and the reaction is carried out for 2 hours at 40 ℃ to obtain the polyaspartic acid. (sample 17) the product was subjected to infrared absorption and nuclear magnetic carbon spectrum detection, and from the spectrum, the obtained product had the same structure as the designed polysuccinimide. The results of scale inhibition tests performed on polyaspartic acid are shown in Table 1.
Example 4
The results of scale inhibition tests on the yields of Polysuccinimide (PSI) prepared at different polymerization temperatures and polymerization times and on the corresponding polyaspartic acid and on the market with the polyaspartic acid present are shown in table 1:
as can be seen from the data in Table 1, the scale inhibition performance of the sample of the invention is obviously superior to that of the existing products in the market.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
TABLE 1 polyaspartic acid Scale inhibition Performance test
Claims (10)
1. A method for synthesizing polyaspartic acid by adopting a catalytic system is characterized in that: the catalyst system takes a titanium polymer as a catalyst, catalyzes aspartic acid in a solvent to generate polysuccinimide with high yield, and then hydrolyzes the polysuccinimide into polyaspartic acid under the action of sodium hydroxide.
2. The method for synthesizing polyaspartic acid by using catalytic system as claimed in claim 1, wherein: the method comprises the following steps:
(1) preparation of titanium catalyst: under the protection of nitrogen, stirring titanium salt and a ligand in a molar ratio of 1:0.1-10 in a reaction medium for 0.5-2 hours, adding a certain amount of distilled water, continuing stirring for 3 hours, standing for liquid separation, taking an organic layer for concentration, adding n-hexane to precipitate a solid, filtering, and drying to obtain a titanium catalyst;
(2) adding 200-300 parts by weight of solvent into a reaction kettle, then adding 100-200 parts by weight of aspartic acid and 1-2 parts by weight of titanium catalyst, and reacting for 1-12 hours at 80-150 ℃;
(3) cooling the system to 80 ℃, adding 400-600 parts by weight of ethanol into the reaction kettle, stirring at room temperature for 1-3 hours, filtering, washing the solid with 50 parts by weight of water, washing with 50 parts by weight of ethanol, and drying to obtain polysuccinimide;
(4) after the mother liquor is concentrated, adding 50-200 parts by weight of normal hexane into the kettle, stirring for 1-3 hours at room temperature, filtering, drying and recovering 0.5-2 parts by weight of titanium catalyst;
(5) adding 50 parts by weight of polysuccinimide into 100 parts by weight of 20% sodium hydroxide aqueous solution, and reacting for 2 hours at 40 ℃ to obtain polyaspartic acid.
3. The method for synthesizing polyaspartic acid by using catalytic system as claimed in claim 2, wherein: the reaction medium in the step (1) is one or more than two of methanol, ethanol, toluene, benzene, xylene, dichloromethane, dichloroethane, diethyl ether, tetrahydrofuran or ethyl acetate.
4. The method for synthesizing polyaspartic acid using a catalytic system according to claim 2, wherein: the titanium salt in the step (1) is one or more than two of titanium tetrachloride, titanium trichloride, titanium oxide, titanium tetraisopropoxide, titanium tetrabromide and titanium tetraiodide.
5. The method for synthesizing polyaspartic acid using a catalytic system according to claim 2, wherein: the ligand in the step (1) is as follows:
in the formula, R1Is H, Cl, NO2、t-Bu、CH3One or more of phenyl and diphenylphosphine.
6. The method for synthesizing polyaspartic acid using a catalytic system according to claim 2, wherein: the titanium catalyst in the step (1) has the structure that:
in the formula, R1Is H, Cl, NO2、t-Bu、CH3One or more of phenyl and diphenylphosphine.
7. The method for synthesizing polyaspartic acid using a catalytic system according to claim 2, wherein: in the step (2), the solvent is 200 parts by weight, and the aspartic acid is 100 parts by weight.
8. The method for synthesizing polyaspartic acid using a catalytic system according to claim 2, wherein: the titanium catalyst in the step (2) is 1 part by weight, and the reaction time is 2-10 hours.
9. The method for synthesizing polyaspartic acid using a catalytic system according to claim 2, wherein: in the step (3), 400 parts by weight of ethanol is stirred at room temperature for 2 hours.
10. The method for synthesizing polyaspartic acid using a catalytic system according to claim 2, wherein: and (4) stirring the n-hexane in the step (4) for 1 hour, wherein the n-hexane accounts for 50 parts by weight.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1103411A (en) * | 1993-08-24 | 1995-06-07 | 三井东压化学株式会社 | Preparation process of polysuccinimide |
| CN1162603A (en) * | 1996-01-29 | 1997-10-22 | 拜尔公司 | Process for preparation of polymers having recurring succinyl units |
| CN101768268A (en) * | 2010-02-11 | 2010-07-07 | 山东省泰和水处理有限公司 | Method for preparing polyaspartic acid by crystal condensation |
-
2018
- 2018-11-26 CN CN201811415389.0A patent/CN111217998A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1103411A (en) * | 1993-08-24 | 1995-06-07 | 三井东压化学株式会社 | Preparation process of polysuccinimide |
| CN1162603A (en) * | 1996-01-29 | 1997-10-22 | 拜尔公司 | Process for preparation of polymers having recurring succinyl units |
| CN101768268A (en) * | 2010-02-11 | 2010-07-07 | 山东省泰和水处理有限公司 | Method for preparing polyaspartic acid by crystal condensation |
Non-Patent Citations (4)
| Title |
|---|
| KIM, JI-HEUNG: ""Synthesis and characterization of poly(aspartic acid) derivatives conjugated with various amino acids"", 《JOURNAL OF POLYMER RESEARCH》 * |
| 李风亭: ""聚天冬氨酸的合成及应用研究进展"", 《工业水处理》 * |
| 杨士林: "《聚天冬氨酸合成与阻垢技术》", 30 November 2009 * |
| 汪济奎: "《新型功能材料导论》", 31 October 2014 * |
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