Preparation method of phenyl diisopropanolamine

Abstract

The invention discloses a preparation method of phenyl diisopropanolamine, and belongs to the technical field of organic chemical synthesis. The preparation method comprises the following steps: adding aniline and a Na2SiO3 / D301 catalyst into a reaction kettle, heating, adding epoxypropane, carrying out a ring-opening addition reaction, carrying out a constant-temperature reaction until the pressure is not reduced any more, cooling, and filtering and separating the Na2SiO3 / D301 catalyst to obtain phenyl diisopropanolamine. The Na2SiO3 / D301 catalyst is adopted to catalyze the ring-opening addition reaction of aniline and epoxypropane, compared with a traditional autocatalysis method, reactants are more quickly activated, the reaction efficiency is higher, the reaction is more complete, the prepared phenyl diisopropanolamine is high in yield and purity, aniline residues are few, purification treatment is not needed, and the method is suitable for industrial production. The separation of the catalyst can be realized only by simple filtration, and the method is green, environment-friendly, simple in process flow and suitable for industrialization.

Description

Technical Field

[0001] This invention relates to the field of organic chemical synthesis technology, and specifically to a method for preparing phenyl diisopropanolamine. Background Technology

[0002] Phenyl diisopropanolamine is a colorless to pale yellow viscous liquid at room temperature and is non-toxic. When used as a chain extender in polyurethane products, phenyl diisopropanolamine not only has low viscosity, thus improving material flowability and good compatibility with other raw materials, but also exhibits different basicities due to the varying substitutions of nitrogen atoms, thus providing a certain catalytic effect on polyurethane synthesis. Furthermore, the presence of aromatic rings in the phenyl diisopropanolamine molecular chain allows it to participate in the polyurethane network structure along with the benzene ring during stepwise polymerization, resulting in polyurethane products with excellent mechanical properties. Therefore, phenyl diisopropanolamine not only excels in chain extension, vulcanization, and reinforcing effects but also possesses excellent overall performance, making it widely used in the automotive, construction, and electronics industries, and showing broad development prospects.

[0003] Currently, phenyl diisopropanolamine is typically prepared via a traditional autocatalytic method. For example, Chinese patent CN101200432A directly generates phenyl diisopropanolamine from aniline and propylene oxide. This method has few reaction steps and is easy to operate. However, because it involves direct autocatalytic generation, the reaction time is long, and the yield is low (around 95%). Furthermore, the product obtained by this method has low purity and requires purification, increasing costs.

[0004] Therefore, it is essential to develop a method for preparing phenyl diisopropanolamine that yields high output, produces low aniline residue, achieves high product purity, and involves simple procedures. Summary of the Invention

[0005] In order to overcome the shortcomings of the prior art, the present invention aims to provide a method for preparing phenyl diisopropanolamine, so as to solve the problems of low yield, low purity and increased cost due to purification treatment in the traditional autocatalytic method.

[0006] To solve the above problems, the technical solution adopted by the present invention is as follows: A method for preparing phenyl diisopropanolamine, wherein aniline is used as an initiator, and propylene oxide is introduced in the presence of Na2SiO3 / D3O1 catalyst to carry out a ring-opening addition reaction to obtain phenyl diisopropanolamine.

[0007] In a preferred embodiment of the present invention, the Na2SiO3 / D301 catalyst is a supported catalyst in which Na2SiO3 is supported on a weakly basic styrene-based ion exchange resin D301 with a macroporous structure.

[0008] As a preferred embodiment of the present application, the loading of Na2SiO3 in the Na2SiO3 / D301 catalyst is 18-20%.

[0009] As a preferred embodiment of the present application, the preparation method of the Na2SiO3 / D301 catalyst comprises the following steps: S1, washing the weakly basic styrene ion exchange resin D301 until the filtrate is colorless and transparent, and drying for standby; S2, dissolving Na2SiO3·9H2O in a mixed solvent prepared by mixing deionized water and anhydrous ethanol at a volume ratio of 2-4:1 to prepare a saturated Na2SiO3 solution with a concentration of 0.12-0.14 g / ml, and heating at 40-50°C for standby; S3, taking the Na2SiO3 solution prepared in step S2, adding the weakly basic styrene ion exchange resin D301 prepared in step S1, and after impregnation, standing, drying, and grinding, a Na2SiO3 / D301 catalyst with a loading of 18-20% is prepared.

[0010] As a preferred embodiment of the present application, the preparation method of the phenyl diisopropanolamine specifically comprises the following steps: putting aniline and Na2SiO3 / D301 catalyst into a reaction kettle, after warming, adding propylene oxide for ring-opening addition reaction, constant temperature reaction until the pressure no longer decreases, cooling and filtering to separate the Na2SiO3 / D301 catalyst, and the phenyl diisopropanolamine is obtained.

[0011] The reaction formula of the above ring-opening addition reaction is as follows: .

[0012] As a preferred embodiment of the present application, the amount of the Na2SiO3 / D301 catalyst is 0.2-0.5% of the total mass of aniline and propylene oxide.

[0013] Further preferably, the amount of the Na2SiO3 / D301 catalyst is 0.35% of the total mass of aniline and propylene oxide. As a preferred embodiment of the present application, the molar ratio of aniline to propylene oxide is 1:2.0-3.0.

[0014] Further preferably, the molar ratio of aniline to propylene oxide is 1:2.2.

[0015] As a preferred embodiment of the present application, the conditions of the ring-opening addition reaction are: reaction pressure ≤1.0 Mpa, and reaction temperature is 120-140°C.

[0016] As a preferred embodiment of the present application, the yield of the phenyl diisopropanolamine is ≥99%, the purity is ≥98%, and the residual amount of aniline raw material is <1000 ppm.

[0017] Compared with the prior art, the present application has the following advantages: The preparation method of the present application uses Na2SiO3 / D301 catalyst to catalyze the ring-opening addition reaction of aniline and propylene oxide. Compared with the traditional self-catalytic method, the reactant is activated faster, the reaction efficiency is higher, and the reaction is more complete, thus greatly improving the product yield (≥99%). Under the action of the Na2SiO3 / D301 catalyst, the prepared phenyl diisopropanolamine has high purity (≥98%) and low aniline residue (<1000 ppm), and does not need to be purified, thus simplifying the process flow and being suitable for industrialization. At the same time, the Na2SiO3 / D301 catalyst is a supported catalyst, which is easy to handle after treatment, can be separated by simple filtration, and can be reused, thus meeting the concept of green environmental protection. DETAILED DESCRIPTION

[0018] The present application will be further described in detail below in combination with specific embodiments.

[0019] The present application provides a preparation method of phenyl diisopropanolamine, which uses aniline as a starting agent and performs ring-opening addition reaction by introducing propylene oxide in the presence of Na2SiO3 / D301 catalyst to prepare phenyl diisopropanolamine. The Na2SiO3 / D301 catalyst is a supported catalyst in which Na2SiO3 is supported on a weakly basic styrene-based ion exchange resin D301 with a large pore structure. Its high-efficiency catalytic mechanism is as follows: the large pore structure of the D301 resin accelerates the mass transfer of the reactants; the SiO3 2- forms gradient basic sites to activate the amino hydrogen of aniline and promote the ring-opening of propylene oxide, respectively, to synergistically catalyze the reaction; the hydrophobic skeleton enriches aniline through π-π interaction, stabilizes the active components through bonding structure, and inhibits side reactions, so that the conversion rate of aniline is >99% and the selectivity is >98%.

[0020] Specifically, the preparation method of the above-mentioned phenyl diisopropanolamine specifically comprises the following steps: aniline and Na2SiO3 / D301 catalyst are put into a reaction kettle, propylene oxide is added after warming to perform ring-opening addition reaction, and the reaction is carried out at a reaction pressure ≤1.0 Mpa and a reaction temperature of 120-140℃ until the pressure no longer decreases, and then the Na2SiO3 / D301 catalyst is separated by filtration after cooling, to obtain phenyl diisopropanolamine with a yield ≥99%, a purity ≥98%, and a residual amount of aniline raw material <1000 ppm.

[0021] In the above method, the molar ratio of aniline to propylene oxide is 1:2.0-3.0, preferably 1:2.2; the amount of Na2SiO3 / D301 catalyst is 0.2-0.5% of the total mass of aniline and propylene oxide, preferably 0.35%. In some embodiments, the loading of Na2SiO3 in the Na2SiO3 / D301 catalyst is 18-20%. Specifically, the preparation method of the Na2SiO3 / D301 catalyst comprises the following steps: S1, washing the weakly basic styrene ion exchange resin D301 until the filtrate is colorless and transparent, and drying for standby; S2, dissolving Na2SiO3·9H2O in a mixed solvent prepared by mixing deionized water and anhydrous ethanol at a volume ratio of 2-4:1 to obtain a saturated Na2SiO3 solution with a concentration of 0.12-0.14 g / ml, and heating at 40-50°C for standby; S3, taking 500 mL of the Na2SiO3 solution prepared in step S2, adding 238-312 g of the weakly basic styrene ion exchange resin D301 prepared in step S1, and after impregnation, standing, drying, and grinding, a Na2SiO3 / D301 catalyst with a loading of 18-20% is prepared.

[0022] The application will be further described in conjunction with specific examples to facilitate those skilled in the art to better understand the application and implement it, but the listed examples are not limiting the application.

[0023] Example 1 A preparation method of phenyl diisopropanolamine, which comprises the following specific steps: Put 500 g of aniline and 2.250 g (loading of 18%) of Na2SiO3 / D301 catalyst into a reaction kettle, heat to 95°C, then continuously add 625 g of propylene oxide, control the reaction temperature at 130±2°C, and react until the pressure no longer decreases. Finally, cool to 60°C, separate the Na2SiO3 / D301 catalyst from the material through a filter, and obtain the product phenyl diisopropanolamine.

[0024] Example 2 A preparation method of phenyl diisopropanolamine, which comprises the following specific steps: Put 500 g of aniline and 3.938 g (loading of 20%) of Na2SiO3 / D301 catalyst into a reaction kettle, heat to 95°C, then continuously add 625 g of propylene oxide, control the temperature at 130±2°C, and react until the pressure no longer decreases. Finally, cool to 60°C, separate the Na2SiO3 / D301 catalyst from the material through a filter, and obtain the product phenyl diisopropanolamine.

[0025] Example 3 A preparation method of phenyl diisopropanolamine, the specific steps are as follows: 500g of aniline and 5.625g (loading capacity is 19%) Na2SiO3 / D301 catalyst are put into a reaction kettle, heated to 95℃, then 625g of propylene oxide is continuously added, the temperature is controlled at 130±2℃, and the reaction is carried out until the pressure does not decrease, finally, the temperature is cooled to 60℃, the Na2SiO3 / D301 catalyst is separated from the material by a filter, and the product phenyl diisopropanolamine is obtained.

[0026] Example 4 A preparation method of phenyl diisopropanolamine, the specific steps are as follows: 500g of aniline and 2.380g (loading capacity is 18%) Na2SiO3 / D301 catalyst are put into a reaction kettle, heated to 95℃, then 690g of propylene oxide is continuously added, the temperature is controlled at 130±2℃, and the reaction is carried out until the pressure does not decrease, finally, the temperature is cooled to 60℃, the Na2SiO3 / D301 catalyst is separated from the material by a filter, and the product phenyl diisopropanolamine is obtained.

[0027] Example 5 A preparation method of phenyl diisopropanolamine, the specific steps are as follows: 500g of aniline and 4.165g (loading capacity is 19%) Na2SiO3 / D301 catalyst are put into a reaction kettle, heated to 95℃, then 690g of propylene oxide is continuously added, the temperature is controlled at 130±2℃, and the reaction is carried out until the pressure does not decrease, finally, the temperature is cooled to 60℃, the Na2SiO3 / D301 catalyst is separated from the material by a filter, and the product phenyl diisopropanolamine is obtained.

[0028] Example 6 A preparation method of phenyl diisopropanolamine, the specific steps are as follows: 500g of aniline and 5.590g (loading capacity is 20%) Na2SiO3 / D301 catalyst are put into a reaction kettle, heated to 95℃, then 690g of propylene oxide is continuously added, the temperature is controlled at 130±2℃, and the reaction is carried out until the pressure does not decrease, finally, the temperature is cooled to 60℃, the Na2SiO3 / D301 catalyst is separated from the material by a filter, and the product phenyl diisopropanolamine is obtained.

[0029] Example 7 A preparation method of phenyl diisopropanolamine, the specific steps are as follows: Put 500g aniline and 2.872g (loading capacity of 20%) Na2SiO3 / D301 catalyst into the reaction kettle, heat to 95℃, then continuously add 936g propylene oxide, control the temperature at 130±2℃ until the pressure does not decrease, finally cool to 60℃, separate the catalyst by filter to get the product phenyl diisopropanolamine.

[0030] Example 8 A method for preparing phenyl diisopropanolamine, the specific steps are as follows: Put 500g aniline and 5.026g (loading capacity of 18%) Na2SiO3 / D301 catalyst into the reaction kettle, heat to 95℃, then continuously add 936g propylene oxide, control the temperature at 130±2℃ until the pressure does not decrease, finally cool to 60℃, separate the Na2SiO3 / D301 catalyst by filter to get the product phenyl diisopropanolamine.

[0031] Example 9 A method for preparing phenyl diisopropanolamine, the specific steps are as follows: Put 500g aniline and 7.180g (loading capacity of 19%) Na2SiO3 / D301 catalyst into the reaction kettle, heat to 95℃, then continuously add 936g propylene oxide, control the temperature at 130±2℃ until the pressure does not decrease, finally cool to 60℃, separate the Na2SiO3 / D301 catalyst by filter to get the product phenyl diisopropanolamine.

[0032] Comparative Example 1 A method for preparing phenyl diisopropanolamine, the specific steps are as follows: Put 500g aniline into the reaction kettle, heat to 95℃, then continuously add 625g propylene oxide, control the temperature at 130±2℃ until the pressure does not decrease, finally cool to 60℃ to get the product phenyl diisopropanolamine.

[0033] Comparative Example 2 A method for preparing phenyl diisopropanolamine, the specific steps are as follows: Put 500g aniline into the reaction kettle, heat to 95℃, then continuously add 690g propylene oxide, control the temperature at 130±2℃ until the pressure does not decrease, finally cool to 60℃ to get the product phenyl diisopropanolamine. Comparative Example 3 A method for preparing phenyl diisopropanolamine, the specific steps are as follows: 500g aniline was put into a reaction kettle, heated to 95℃, then 936g propylene oxide was continuously added, the temperature was controlled at 130±2℃ until the pressure did not decrease, finally cooled to 60℃, the product phenyl diisopropanolamine was obtained.

[0034] Product performance comparison experiment The phenyl diisopropanolamine products prepared in Examples 1-9 and Comparative Examples 1-3 were subjected to yield calculation, purity and aniline residue detection, and the results are shown in Table 1.

[0035] Table 1 is the preparation conditions and product performance parameters of Examples 1-9 and Comparative Examples 1-3

[0036] As can be seen from the data in Table 1, the addition reaction of aniline and propylene oxide catalyzed by Na2SiO3 / D301 catalyst in Examples 1-9 has good overall effect: the product yield is more than 99%, the purity is not less than 98%, and the aniline residue is less than 1000 ppm. Among them, the reaction effect of Example 5 is the best, and the product index is the best, in which the molar ratio of aniline to propylene oxide is 1:2.2, the dosage of Na2SiO3 / D301 catalyst is 0.35%, and the catalyst loading is 19%. As can be seen from Comparative Examples 2, 5, 8 and Comparative Examples 1, 2, 3, Examples 2, 5 and 8 use Na2SiO3 / D301 catalyst, which significantly improves the reaction effect, and the product yield and purity are much higher than those of Comparative Examples 1-3 without catalyst. And the aniline residue of the product after using Na2SiO3 / D301 catalyst also decreased significantly, which shows that the use of Na2SiO3 / D301 catalyst to catalyze the ring-opening addition reaction of aniline and propylene oxide is obviously better than the existing self-catalytic synthesis method.

[0037] The above embodiments are only preferred embodiments of the present application, and cannot be used to limit the scope of protection of the present application. Any non-essential changes and substitutions made by those skilled in the art based on the present application are within the scope of the present application.

Claims

1. A method for preparing phenyl diisopropanolamine, characterized in that: Using aniline as a starting agent, phenyl diisopropanolamine was prepared by ring-opening addition reaction of propylene oxide in the presence of Na2SiO3 / D3O1 catalyst.

2. The method for preparing phenyl diisopropanolamine according to claim 1, characterized in that: The Na2SiO3 / D301 catalyst is a supported catalyst in which Na2SiO3 is supported on a weakly basic styrene-based ion exchange resin D301 with a macroporous structure.

3. The method for preparing phenyldiisopropanolamine according to claim 1 or 2, characterized in that: The loading of Na2SiO3 in the Na2SiO3 / D3O1 catalyst is 18-20%.

4. The method for preparing phenyldiisopropanolamine according to claim 1 or 2, characterized in that: The preparation method of the Na2SiO3 / D3O1 catalyst includes the following steps: S1. Wash the weakly basic styrene-based ion exchange resin D301 until the filtrate is colorless and transparent, and then dry it for later use. S2. Dissolve Na2SiO3·9H2O in a mixed solvent of deionized water and anhydrous ethanol in a volume ratio of 2-4:1 to prepare a saturated Na2SiO3 solution with a concentration of 0.12-0.14 g / ml. Heat the solution at 40-50℃ for later use. S3. Take the Na2SiO3 solution obtained in step S2, add the weakly basic styrene-based ion exchange resin D301 obtained in step S1, and after impregnation, standing, drying and grinding, obtain a Na2SiO3 / D301 catalyst with a loading of 18-20%.

5. The method for preparing phenyldiisopropanolamine according to claim 1 or 2, characterized in that: Specifically, the following steps are included: Aniline and Na2SiO3 / D301 catalyst were added to a reactor, and after heating, propylene oxide was added to carry out a ring-opening addition reaction. The reaction was kept at a constant temperature until the pressure no longer decreased. After cooling, the Na2SiO3 / D301 catalyst was separated by filtration to obtain phenyl diisopropanolamine.

6. The method for preparing phenyl diisopropanolamine according to claim 5, characterized in that: The amount of the Na2SiO3 / D3O1 catalyst used is 0.2~0.5% of the total mass of aniline and propylene oxide.

7. The method for preparing phenyl diisopropanolamine according to claim 6, characterized in that: The amount of the Na2SiO3 / D3O1 catalyst used is 0.35% of the total mass of aniline and propylene oxide.

8. The method for preparing phenyl diisopropanolamine according to claim 5, characterized in that: The molar ratio of aniline to propylene oxide is 1:2.0~3.

0.

9. The method for preparing phenyl diisopropanolamine according to claim 8, characterized in that: The molar ratio of aniline to propylene oxide is 1:2.

2.

10. The method for preparing phenyl diisopropanolamine according to claim 5, characterized in that: The conditions for the ring-opening addition reaction are: reaction pressure ≤ 1.0 MPa and reaction temperature 120~140℃.

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