CN107805207B - Preparation method of polyaspartic aspartate - Google Patents
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Abstract
The invention provides methods for synthesizing polyaspartic acid ester, which take tetraalkylammonium hydroxide as a catalyst, and react organic primary amine with unsaturated dibasic acid ester to obtain the product, wherein the tetraalkylammonium hydroxide is taken as organic strong base, can obviously improve the Michael addition reaction activity of the primary amine and the butenedioic acid ester, can completely remove the catalyst by simply heating after the reaction is finished, and cannot generate adverse effect on downstream application of the product.
Description
Technical Field
The invention relates to a preparation method of polyaspartic acid , in particular to a method for efficiently synthesizing polyaspartic acid polyaspartic acid ester under the catalysis of tetraalkylammonium hydroxide, wherein the method comprises the steps of polyaspartic acid polyaspartic acid ester.
Background
Polyaspartic acid (PAE) as a class of specific sterically hindered secondary amines, gel times with low viscosity isocyanate curing agents can be adjusted from minutes to hours due to steric hindrance and induction effects of the Ester groups.
Formula 1A schematic of the synthesis of PAE
PAE is synthesized by Michael addition reaction of organic primary diamine and diester of butylene diacid, PAE is a medium-low viscosity liquid with boiling point higher than 500 ℃, so that PAE can not be purified by rectification or crystallization, if excessive residual diester of butylene diacid in the product causes large odor of volatile matter during construction, mechanical property of PAE polyurea coating film is damaged due to plasticizing effect, and residual primary amine group in the product obviously shortens gelation time of PAE polyurea, therefore, improving conversion rate of raw materials as much as possible is which is a key factor for improving quality of PAE products.
The document (Advanced Materials research. Vol 875-877,2014, pp 165-170.) reports that the Michael addition reaction series for synthesizing PAE is 3, the rate of the later period of the PAE synthesis reaction is very slow, the satisfactory reaction conversion rate can be achieved only after the PAE synthesis reaction is placed at room temperature for half a year or even more than 1 year, the product supply efficiency is greatly reduced, the conversion rate is improved by raising the temperature and prolonging the reaction time, the byproducts are increased, the color of the amine high-temperature oxidation is sharply increased, and the product phase is influenced.
In order to improve the conversion rate of raw materials, patent US005821326A reports that a nitrogen-containing five-membered heterocycle, such as 1,2, 4-triazole, 3, 5-dimethyl-1, 2, 4-triazole and 3, 5-dimethylpyrazole is used for catalyzing the synthesis reaction of PAE, and liparix et al in journal of polyurethane industry 2005,20(4):16-19, preparation and research of polyaspartic aspartate polyurea reports that the conversion rate can be obviously improved by adding 0.05 wt% of a tertiary amine catalyst, catalysts in patent CN201310448660 adopt pyridine, 2,4, 6-tris (dimethylaminomethyl) phenol, triethylamine and triphenylphosphine as a catalyst to synthesize the polyetheramine PAE, and the catalysts are reacted at a high temperature of more than 100 ℃ for 20-30 hours and placed at room temperature for 3-4 months to reach 100% conversion rate, most of the catalysts reported in the documents cannot be used for catalysis, and cannot be remained in products, the downstream application may affect the performance, including the gel filtration of the pa, the gel performance of the pa is not adversely affected, the pa is filtered by adding a heterogeneous catalyst, and the catalytic conversion rate of a catalyst is improved by adding a centrifugal method of improving the rate of a tertiary glyceride by adding a catalyst, such as a catalyst, and the like, and the catalyst is reported that the catalyst is satisfactory method of adding a catalyst is capable of improving the catalyst of adding a catalyst of improving the catalyst of a catalyst.
In summary, the synthesis of PAE has a technical difficulty in avoiding adverse effects on product quality and downstream applications while increasing reaction rate.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides methods for synthesizing PAE by adopting tetraalkylammonium hydroxide catalysis, which have the characteristics of high production efficiency, simple and convenient operation, high product quality and easy industrialization.
In order to realize the purpose, the invention adopts the following technical scheme:
A process for the catalytic synthesis of PAE comprising the steps of:
(1) reacting organic primary amine with unsaturated dibasic acid ester under the catalysis of a catalyst to obtain a product;
(2) removing the catalyst from the product obtained in the step (1) to obtain a poly (aspartic acid ) ester product.
Preferably, in step (1), the apparatus used for the reaction is a reaction apparatus equipped with a mechanical stirring paddle, a thermometer, a constant pressure dropping funnel, with N attached2A gas path pipe and a three-mouth reactor of a bubbler, such as a three-mouth flask.
In the step (1), the reaction process is as follows: and (2) under the atmosphere of inert gas, dropwise adding the unsaturated dibasic acid ester into the mixture of the organic primary amine and the catalyst, heating and reacting after the dropwise adding is finished, and stopping the reaction after the target conversion rate is reached, wherein the inert gas is preferably nitrogen.
In the step (1), the inert gas is introduced into the reaction for 10-30 min, the stirring temperature is 10-40 ℃, the temperature is 30-70 ℃ after temperature rise, and the reaction time is 1-12 h.
In the step (1), the organic primary amine is or more selected from 2-methyl pentamethylene diamine, 4 ' -diaminodicyclohexyl methane, 3 ' -dimethyl-4, 4 ' -diaminodicyclohexyl methane, isophorone diamine and polyether amine.
In step (1), the catalyst is tetraalkylammonium hydroxide catalyst, preferably tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide and hydrates of these tetraalkylammonium hydroxides, or more in aqueous solution, more preferably tetramethylammonium hydroxide, in step (1), the amount of the catalyst is 0.005 to 0.5%, preferably 0.01 to 0.1%, based on the molar amount of primary amine groups in the primary organic amine.
In the step (1), the unsaturated dibasic acid ester is or more selected from maleic acid diester and fumaric acid diester.
The raw materials of the organic secondary amine and the unsaturated dibasic acid ester are selected from or more of diethyl fumarate, dipropyl fumarate, dibutyl fumarate and methylpropyl fumarate, the raw materials of the organic secondary amine and the unsaturated dibasic acid ester are selected from or more of diethyl maleate, dipropyl maleate, dibutyl maleate and methylpropyl maleate, and the feeding ratio of the unsaturated dibasic acid ester to the organic primary amine is that the molar ratio of C-C in the unsaturated dibasic acid ester to primary amine groups in the organic primary amine is 1: 1.
In the step (1), the reaction can be carried out in the absence of a solvent or in the presence of a solvent, the solvent is or more selected from methanol, ethanol, propanol, tert-butanol, acetone, tetrahydrofuran and acetonitrile, and the amount of the solvent is 0-90 wt% based on the total mass of the reactants and the solvent.
The product poly (aspartic acid ) in the step (1) has the following structural characteristics:
wherein x represents an organic group, R1And R2Are identical or different alkyl groups, n represents the secondary amine functionality of poly () aspartate and is an integer ≥ 2.
In the step (2), the method for removing the catalyst comprises the steps of heating the reaction device after the reaction is stopped, flowing nitrogen, and extracting the catalyst by a water pump. In the step (2), the temperature of the catalyst removal is 90-130 ℃, the removal gauge pressure is 0.001-0.02 MPa, and the extraction time is 20-40 min.
The chroma of the poly (aspartic acid ) ester prepared by the process condition can reach below 30 Hazen, the primary amine conversion rate of the product reaches 97 percent or above, and no catalyst residue exists, so that the construction pot life of the coating compounded with the isocyanate curing agent is better than the reported result.
Compared with the existing PAE synthesis method, the invention has the following advantages and beneficial effects:
(1) compared with other organic homogeneous catalysts, the tetraalkylammonium hydroxide catalyst has the advantages of strong basicity, higher catalytic activity, easy removal and no pollution to PAE products.
(2) Compared with an inorganic heterogeneous catalyst, the tetraalkylammonium hydroxide catalyst provided by the invention does not introduce metal ions, and the PAE product has excellent chromaticity.
(3) The tetraalkylammonium hydroxide catalyst of the invention can obtain PAE products with high primary amine conversion rate in a short time, and the gel time is obviously longer than that of products of comparative examples.
Drawings
FIG. 1 is the synthesis of PAE product of 4, 4' -diaminodicyclohexylmethane and diethyl maleate in CDCl in example 53In a reagent1H NMR spectrum, in which no peak of catalyst remaining was observed.
Detailed Description
The following examples will illustrate the process provided by the present invention at step , but the present invention is not limited to the examples listed, and should include any other known variations within the scope of the claims of the present invention.
Calculating the conversion rate: PAE products were subjected to Bruker 400MHz NMR1H NMR characterization, as shown in fig. 1, the double bond of the unreacted diethyl fumarate (dialkyl maleate isomerizes to dialkyl fumarate in the presence of amine) peaked at a single peak σ 6.85, the peak of the newly formed methine group attached to the secondary amine appeared at σ 3.5 to 3.8, while the peak ranging from 4.3 to 4.0 is subordinate to the methylene group attached to the oxygen atom in the ester group in the product and unreacted diethyl fumarate, and we set the area integral thereof to 8, the calculation formula of the conversion of diethyl maleate: and C is 1-A/4.
And (3) measuring the gel time: at 25 ℃, the obtained PAE and a Corsida low-viscosity HDI trimer curing agent N3600(NCO content 23%) are uniformly mixed at the molar ratio of NCO to NH of 1:1, the gel point is judged by a wire drawing method, and the gel time is measured by a stopwatch.
And (3) measuring the chromaticity: the Hazen chromaticity of the sample was measured with a quartz sample cell by means of a BYK model LCS IV colorimeter.
Medicine information: TCI is selected as the 2-methyl pentanediamine to produce a reagent with the purity of more than 98 percent; diethyl maleate adopts a reagent with Annaging purity of more than 99 percent; adopting a reagent with the purity of the dibutyl maleate being more than 99.5 percent; the diethyl fumarate adopts a reagent with the purity of the alatin being more than 98.5 percent; 4, 4' -diaminodicyclohexyl methane is an HMDA product with purity of more than 99.5 percent produced by Wanhua chemistry; 3,3 '-dimethyl-4, 4' -diaminodicyclohexyl methane is used as a reagent with TCI (trichloroacetic acid) production purity of more than 99%; the polyether amine D-2000 adopts a Jeffamine D-2000 industrial standard product of a Henschel company; the tetramethylammonium hydroxide and pentahydrate thereof are industrial grade products with purity of more than 99% from Jinan Hongtai industry commercial Limited company; the 25% aqueous solution of tetraethylammonium hydroxide was prepared using the reagent from Aladdin.
Example 1
(1) 174.31g (1.5mol) 2-methylpentamethylenediamine and 0.137g (1.5mmol) tetramethylammonium hydroxide catalyst were charged into a reaction vessel equipped with a mechanical stirring blade, thermometer, isobaric dropping funnel with N connection2In a 1L three-necked flask with an air line pipe and a bubbler, 516.54g (3.0mol) of diethyl maleate was added into a constant pressure dropping funnel, and N was introduced into the system2Replacing air in the system for 20 min; slowly dripping diethyl maleate into the mixture under the stirring condition of 25 ℃, heating the mixture to 40 ℃ after dripping, reacting for 2 hours, and stopping the reaction.
(2) Heating to 90 ℃, flowing nitrogen, and extracting by a water pump for 20min under the pressure of 0.001MPa to remove the tetramethylammonium hydroxide catalyst, thus obtaining the poly (aspartic acid ) aspartate PAE-1, wherein the structure is shown as the following formula:
(3) the characterization analysis result shows that the conversion rate of diethyl maleate is 99.7 percent, the Hazen chroma is 25, the gel time is 5min, X in PAE-1 is 2-methyl-1, 5-pentyl, R is1＝R2Is ethyl, n is 2.
Example 2
(1) 174.31g (1.5mol) 2-methylpentamethylenediamine and 0.044g (0.075mmol) 25% tetraethylammonium hydroxide aqueous solution were charged to a stirred vessel equipped with a mechanical stirrer, thermometer, isobaric dropping funnel with N attached2In a 1L three-necked flask with an air line pipe and a bubbler, 516.54g (3.0mol) of diethyl maleate was added into a constant pressure dropping funnel, and N was introduced into the system2Replacing air in the system for 10 min; slowly dripping diethyl maleate into the mixture under the stirring condition of 10 ℃, heating the mixture to 30 ℃ after dripping, reacting for 6 hours, and stopping the reaction.
(2) Heating to 130 ℃, flowing nitrogen, and extracting by a water pump for 40min under the pressure of 0.02MPa to remove the tetraethyl ammonium hydroxide catalyst and water, thus obtaining the poly (aspartic acid ) aspartate PAE-1.
(3) The characterization and analysis result shows that the conversion rate of diethyl maleate is 99%, the Hazen chroma is 28, the gel time is 4min, X in PAE-1 is 2-methyl-1, 5-pentyl, R is1＝R2Is ethyl, n is 2.
Example 3
(1) 174.31g (1.5mol) 2-methylpentamethylenediamine and 0.685g (7.5mmol) tetramethylammonium hydroxide catalyst were added to a reaction vessel equipped with a mechanical stirring blade, thermometer, isobaric dropping funnel with N attached2In a 1L three-necked flask equipped with a gas line and a bubbler, 516.54g (3.0mol) of diethyl fumarate was charged into the flask under a constant pressureIn the dropping funnel, N is introduced into the system2Replacing air in the system for 15 min; slowly dripping diethyl fumarate at 40 ℃ under the stirring condition, heating to 70 ℃ after dripping, reacting for 1h, and stopping the reaction.
(2) Heating to 120 ℃, flowing nitrogen, and extracting by a water pump for 30min under the pressure of 0.01MPa to remove the tetramethylammonium hydroxide catalyst, thus obtaining the poly (aspartic acid ) aspartate PAE-1.
(3) The characterization analysis result shows that the conversion rate of diethyl fumarate is 98.5%, the Hazen chroma is 29, the gel time is 4min, X in PAE-1 is 2-methyl-1, 5-pentyl, R is1＝R2Is ethyl, n is 2.
Example 4
(1) 174.31g (1.5mol) 2-methylpentamethylenediamine and 0.272g (1.5mmol) tetramethylammonium hydroxide pentahydrate were charged to a flask equipped with a mechanical stirring blade, thermometer, isobaric dropping funnel, connected with N2In a 1L three-neck flask with an air passage pipe and a bubbler, 684.78g (3.0mol) of dibutyl maleate is added into a constant-pressure dropping funnel, and N is introduced into the system2Replacing air in the system for 20 min; slowly dripping dibutyl maleate into the mixture under the stirring condition of 20 ℃, heating the mixture to 40 ℃ after dripping, reacting for 12 hours, and stopping the reaction.
(2) Heating to 120 ℃, flowing nitrogen, and extracting with a water pump under the pressure of 0.01MPa for 30min to remove tetramethyl ammonium hydroxide pentahydrate to obtain poly (aspartic ester) PAE-2, wherein the structure is shown as the following formula:
(3) the characterization analysis result shows that the dibutyl maleate conversion rate is 99 percent, the Hazen chroma is 24, the gel time is 20min, X in PAE-1 is 2-methyl-1, 5-amyl alkyl, R is1＝R2Is butyl, n is 2.
Example 5
(1) 315.54g (1.5mol) of 4, 4' -diaminodicyclohexylmethane and 0.137g (1.5mmol) of tetramethylammonium hydroxide catalyst were introduced into a reaction vessel equipped with a mechanical stirrer, thermometer, isobaric dropping funnel, N connection2A1L three-necked flask was placed in a gas line and a bubbler, and then 516 was added.54g (3.0mol) of diethyl maleate is added into a constant pressure dropping funnel, and N is introduced into the system2Replacing air in the system for 20 min; slowly dripping diethyl maleate into the mixture under the stirring condition of 25 ℃, heating the mixture to 50 ℃ after dripping, reacting for 7 hours, and stopping the reaction.
(2) Heating to 100 ℃, flowing nitrogen, and extracting with a water pump under the pressure of 0.01MPa for 30min to remove the tetramethylammonium hydroxide catalyst, thus obtaining the poly (aspartic acid ) aspartate PAE-3, wherein the structure is shown as the following formula:
(3) the characterization and analysis result shows that the conversion rate of diethyl maleate is 99%, the Hazen chroma is 20, the gel time is 90min, X in PAE-3 is 4, 4' -dicyclohexyl methane, R is1＝R2Is ethyl, n is 2.
Example 6
(1) 357.62g (1.5mol) of 3,3 '-dimethyl-4, 4' -diaminodicyclohexylmethane and 0.137g (1.5mmol) of tetramethylammonium hydroxide catalyst are introduced into a reaction vessel equipped with a mechanical stirrer, thermometer, isobaric dropping funnel, connected with an N connection2In a 1L three-necked flask with an air line pipe and a bubbler, 516.54g (3.0mol) of diethyl maleate was added into a constant pressure dropping funnel, and N was introduced into the system2Replacing air in the system for 20 min; slowly dripping diethyl maleate into the mixture under the stirring condition of 25 ℃, heating the mixture to 70 ℃ after dripping, reacting for 10 hours, and stopping the reaction.
(2) Heating to 100 ℃, flowing nitrogen, and extracting with a water pump under the pressure of 0.01MPa for 30min to remove the tetramethylammonium hydroxide catalyst, thus obtaining the poly (aspartic acid ) aspartate PAE-4, wherein the structure is shown as the following formula:
(3) the characterization and analysis result shows that the conversion rate of diethyl maleate is 97%, the Hazen chroma is 23, the gel time is 10h, X in PAE-4 is 3,3 '-dimethyl-4, 4' -dicyclohexyl methane, R is1＝R2Is ethyl, n is 2.
Example 7
(1) 3000g (1.5mol) of polyetheramine D-2000 and 0.884g (1.5mmol) of 25% aqueous tetraethylammonium hydroxide solution were added to a reaction vessel equipped with a mechanical stirring paddle, thermometer, isobaric dropping funnel with N attached2In a three-neck flask with an air passage pipe and a bubbler, 516.54g (3.0mol) of diethyl maleate is added into a constant-pressure dropping funnel, and N is introduced into the system2Replacing air in the system for 20 min; slowly dripping diethyl maleate into the mixture under the stirring condition of 25 ℃, heating the mixture to 50 ℃ after dripping, reacting for 12 hours, and stopping the reaction.
(2) Heating to 100 ℃, flowing nitrogen, and extracting with a water pump under the pressure of 0.01MPa for 30min to remove the tetraethyl ammonium hydroxide catalyst and water, thus obtaining the poly (aspartic acid ) PAE-5, wherein the structure is shown as the following formula:
(3) the characterization analysis result shows that the conversion rate of diethyl maleate is 98%, the Hazen chroma is 30, the gel time is 11h, X in PAE-5 is epoxypropane polyether with the average molecular weight of about 2000, R1＝R2Is ethyl, n is 2.
Comparative example 1
(1) 357.62g (1.5mol) of 3,3 '-dimethyl-4, 4' -diaminodicyclohexylmethane and 2.07g (2 mol%) of 1,2, 4-triazole catalyst were added to a reaction vessel equipped with a mechanical stirrer, thermometer, isobaric dropping funnel, N-connection2In a 1L three-necked flask with an air line pipe and a bubbler, 516.54g (3.0mol) of diethyl maleate was added into a constant pressure dropping funnel, and N was introduced into the system2Replacing air in the system for 20 min; slowly dripping diethyl maleate into the mixture under the stirring condition of 25 ℃, heating the mixture to 70 ℃ after dripping, reacting for 24 hours, and stopping the reaction.
(2) And the characterization analysis result shows that the conversion rate of diethyl maleate is 85%, the Hazen color is 96, and the gel time is 4 h.
Claims (14)
1, A method for synthesizing polyaspartic acid ester, comprising the following steps:
(1) reacting organic primary amine with unsaturated dibasic acid ester under the catalysis of a catalyst to obtain a product; the catalyst is tetraalkylammonium hydroxide;
(2) removing the catalyst from the product obtained in the step (1) to obtain a poly (aspartic acid ) ester product.
2. The method according to claim 1, wherein in step (1), the reaction is carried out by: and (3) under the atmosphere of inert gas, dropwise adding the unsaturated dibasic acid ester into the mixture of the organic primary amine and the catalyst, heating and reacting after the dropwise adding is finished, and stopping the reaction after the target conversion rate is reached.
3. The method of claim 2, wherein the inert gas is nitrogen.
4. The method according to claim 3, wherein in the step (1), the inert gas is introduced for 10-30 min, the stirring temperature is 10-40 ℃, the temperature after temperature rise is 30-70 ℃, and the reaction time is 1-12 h.
5. The process of any of , wherein in step (1), the primary organic amine is selected from 2-methylpentamethylenediamine, 4 ' -diaminodicyclohexylmethane, 3 ' -dimethyl-4, 4 ' -diaminodicyclohexylmethane, isophoronediamine, or or more polyetheramines.
6. The method according to claim 5, wherein in step (1), the catalyst is or more of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and hydrates, aqueous solutions of these tetraalkylammonium hydroxides,
7. the method of claim 6, wherein the catalyst is tetramethylammonium hydroxide.
8. The method according to claim 7, wherein in step (1), the unsaturated dibasic acid ester is selected from or more of maleic acid diester and fumaric acid diester, the fumaric acid diester is selected from or more of diethyl fumarate, dipropyl fumarate, dibutyl fumarate and methylpropyl fumarate, and the maleic acid diester is selected from or more of diethyl maleate, dipropyl maleate, dibutyl maleate and methylpropyl maleate.
9. The method according to claim 8, wherein in the step (1), the amount of the catalyst is 0.005-0.5% of the primary amine groups based on the molar amount of the primary amine groups in the organic primary amine, and the unsaturated dibasic acid ester is used in such an amount that the molar ratio of C ═ C to the primary amine groups in the unsaturated dibasic acid ester is 1: 1.
10. The method according to claim 9, wherein in the step (1), the catalyst is used in an amount of 0.01 to 0.1% based on the molar amount of the primary amine groups in the primary organic amine.
11. The method according to claim 10, wherein in step (1), the reaction is carried out in the absence of a solvent or in the presence of a solvent selected from or more of methanol, ethanol, propanol, tert-butanol, acetone, tetrahydrofuran and acetonitrile.
12. The method according to claim 11, wherein in the step (1), the reaction is carried out under a solvent-free condition.
13. The method as claimed in claim 12, wherein in the step (2), the temperature for removing the catalyst is 90-130 ℃, the removing pressure is 0.001-0.02 MPa, and the extraction time is 20-40 min.
14. The method of claim 13, wherein in step (2), the product polyaspartic acid ester has the following structural features:
wherein X represents an organic group, R1And R2Are identical or different alkyl groups, n represents the secondary amine functionality of poly (aspartic acid ) aspartate, n is greater than or equal to 2.
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