CN108178731A - Green synthesis method for preparing AMP-95 by one-pot method - Google Patents

Abstract

The invention discloses a green synthesis method for preparing AMP-95 by a one-pot method, comprising the following steps: S1, in an alcohol solution, acetone, hydrogen peroxide and ammonia are catalyzed by a catalyst to generate 2-nitropropane; S2, the In the S1 step, the reaction solution directly reacts with formaldehyde or paraformaldehyde under alkaline conditions without purification to generate 2-nitro-2-methyl-1-propanol; in S3, the reaction product in the S2 step is not purified The product 2-amino-2-methyl-1-propanol (AMP-95) is obtained by direct hydrogenation, and the purity reaches more than 99.5% through rectification. The invention has cheap and easy-to-obtain raw materials, simple reaction steps, little environmental pollution, low cost, high yield, easy purification of products, and is suitable for industrialized production.

Description

A Green Synthetic Method for One-Pot Preparation of AMP-95

technical field

The invention relates to the technical field of synthesis and preparation of fine chemical products, in particular to a green synthesis method for preparing AMP-95 by a one-pot method.

Background technique

2-Amino-2-methyl-1-propanol is called AMP-95 for short. It is white crystal or colorless viscous liquid, miscible with water and soluble in ethanol. AMP-95 is a well-known multifunctional additive widely used in industries such as coating ink, metalworking fluid, personal care and pharmaceutical intermediates. As a primary amine, AMP-95 has a higher pH value due to its high pKa value. At the same time, because it is an organic base, it is relatively soft and has good compatibility with various emulsions. The performance impact is minor. Compared with other organic bases such as ammonia, trimethylamine, and triethylamine, AMP-95 has good stability, is not easy to yellow, and has low toxicity and is not volatile. It can reduce the odor of the system, reduce corrosion and flash rust, and belongs to Environmentally friendly conditioner. At present, the top ten coating companies in the world are using AMP-95TM as a pH regulator and formulation optimization aid. AMP-95TM has helped them improve the performance of their products while reducing costs. In China's paint market, AMP-95TM is also the first choice of paint manufacturers, and the market coverage of AMP-95TM is greater than 80%. Well-known domestic paint manufacturers have been using this product since the 1990s, and the stability and superiority of AMP-95TM have won unanimous praise from customers.

There are many existing synthesis methods of 2-amino-2-methyl-1-propanol. In US20110224460, 2-nitropropane reacts with formaldehyde solution to generate 2-nitro-2-methyl-1-propanol. Alcohol, and then carry out hydrogenation reaction under the metal nickel catalyst, and separate to obtain 2-amino-2-methyl-1-propanol. The method has the disadvantages of high raw material cost, high risk, difficult storage and transportation, large investment in production equipment, and low product purity. Chinese patent CN1810767 uses isopropanol to react with sodium nitrite and paraformaldehyde at 0-25°C, then extracts, washes and distills to obtain 2-nitro-2-methyl-1-propanol, and then catalyzes Hydrogen gives the product. The synthesis conditions of this method are complex, the reaction time is long, and the post-processing is difficult. Chinese patent CN1911899 discloses a method for preparing 2-amino-2-methyl-1-propanol through the Ritter process of isobutylene. The method has many kinds of reaction raw materials, complicated preparation steps, and low yield, which is 50-70%. Chinese patent CN201310152527 introduces a method for obtaining 2-amino-2-methyl-1-propanol in one step by hydrogenolysis and reduction reaction of an alcohol solution of alkyl α-aminoisobutyrate with hydrogen in the presence of a metal catalyst. The raw material cost of the method is high, the steps are cumbersome, the environmental pollution is large, the yield is low, and the product is difficult to purify, so it is not suitable for industrial production.

Contents of the invention

(1) Solved technical problems

Aiming at the deficiencies of the prior art, the present invention provides a green synthesis method for preparing AMP-95 by a one-pot method, which solves the problem that the traditional method has high cost of raw materials, cumbersome steps, great environmental pollution, low yield, and the product is not easy Purification is not suitable for industrial production.

(2) Technical solution

To achieve the above object, the present invention provides the following technical solutions:

A green synthetic method for preparing AMP-95 by a one-pot method, comprising the following steps:

S1, in the alcohol solution, acetone, hydrogen peroxide and ammonia generate 2-nitropropane under the catalysis of the catalyst;

Wherein, the conditions required for preparing 2-nitropropane in the S1 step are: under a certain temperature range and time range, the catalyst is a porous skeleton metal hybrid catalyst, and the skeleton of the porous skeleton metal hybrid catalyst is mainly Silicon, oxygen and hybrid metals, wherein the hybrid metals are one or two combinations of titanium, zirconium, vanadium and molybdenum, the ratio of silicon to hybrid metal atoms is 20-100:1, and the molar ratio of hybrid double metals 1:20～1:100; the configuration of the catalyst is one of ZSM-5, MCM-41, SBA-15, and its micropore-mesoporous composite structure and mesoporous-macropore composite structure. The dosage is 0.001-10% of the total amount of materials;

S2, the reaction solution in the S1 step is directly reacted with formaldehyde or paraformaldehyde under alkaline conditions without purification to generate 2-nitro-2-methyl-1-propanol;

Wherein, the conditions required for the preparation of 2-nitro-2-methyl-1-propanol in the S2 step are: under a certain temperature range and time range, the alkali is sodium hydroxide, potassium hydroxide, hydroxide One or more of calcium, magnesium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, dimethylamine, triethylamine, diethylamine, pyridine and ammonia water, the amount of alkali is 2-nitrate 0.001-2 of the mass of propane;

S3, the reaction product in the step S2 is directly hydrogenated without purification to obtain the product 2-amino-2-methyl-1-propanol (AMP-95), and the purity reaches more than 99.5% through rectification;

Wherein, the conditions required for preparing AMP-95 by hydrogenation of 2-nitro-2-methyl-1-propanol in the S3 step are: under a certain temperature range, time range and hydrogenation pressure range, hydrogenation The hydrogenation catalyst is palladium carbon or Raney nickel, and the amount of hydrogenation catalyst is 0.001-30% of 2-nitro-2-methyl-1-propanol.

Preferably, in the S1 step, the molar ratio of hydrogen peroxide to acetone is 0.1:1 to 5:1, the molar ratio of acetone to ammonia is 1:0.01 to 1:3, and the reaction temperature range is 20-120°C, and the reaction time is The range is 0.5-5h.

Preferably, in the S1 step, the alcohol solution is water or one or more of methanol, ethanol, n-butanol, isobutanol, propanol, isopropanol, tert-butanol, ethylene glycol and propylene glycol.

Preferably, the temperature range required for the reaction in the S2 step is 10-120°C, and the time range required for the reaction is 0.5-12h, and the molar ratio of formaldehyde or paraformaldehyde to 2-nitropropane is 1: 1-5:1.

Preferably, in the step S3, the hydrogenation pressure ranges from 0.1-10 MPa, the reaction temperature ranges from 10-120° C., and the reaction time ranges from 0.5-10 h.

(3) Beneficial effects

The invention provides a green synthesis method for preparing AMP-95 by a one-pot method, which has the following beneficial effects:

(1) The raw materials of the present invention are cheap and easy to obtain, the reaction steps are simple, the environmental pollution is small, the cost is low, the yield is high, the product is easy to purify, and is suitable for industrial production.

Detailed ways

The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some of the embodiments of the present invention, but not all of them. Based on the embodiments of the present invention, all other embodiments obtained by persons of ordinary skill in the art without making creative efforts belong to the protection scope of the present invention.

The invention provides a technical solution:

A green synthetic method for preparing AMP-95 by a one-pot method, comprising the following steps:

S1, in the alcohol solution, acetone, hydrogen peroxide and ammonia generate 2-nitropropane under the catalysis of the catalyst;

Among them, the conditions required for the preparation of 2-nitropropane in step S1 are: the reaction temperature range is 20-120°C, and the reaction time range is 0.5-5h, the catalyst is a porous framework metal hybrid catalyst, a porous framework metal hybrid catalyst Its skeleton is mainly silicon, oxygen and hybrid metal, wherein the hybrid metal is one or two combinations of titanium, zirconium, vanadium and molybdenum, the ratio of silicon to hybrid metal atoms is 20-100:1, and the hybrid The bimetallic molar ratio is 1:20～1:100; the configuration of the catalyst is one of ZSM-5, MCM-41, SBA-15, and its microporous-mesoporous composite structure and mesopore-macroporous composite structure , wherein the amount of catalyst used is 0.001-10% of the total amount of materials, the molar ratio of hydrogen peroxide to acetone is 0.1:1-5:1, the molar ratio of acetone to ammonia is 1:0.01-1:3, and the alcohol solution is water or methanol, One or more of ethanol, n-butanol, isobutanol, propanol, isopropanol, tert-butanol, ethylene glycol and propylene glycol;

In the steps S2 and S1, the reaction solution directly reacts with formaldehyde or paraformaldehyde under alkaline conditions without purification to generate 2-nitro-2-methyl-1-propanol;

Wherein, the conditions required for the preparation of 2-nitro-2-methyl-1-propanol in step S2 are: the temperature range required for the reaction is 10-120°C, and the time range required for the reaction is 0.5-12h, The alkali is one of sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, dimethylamine, triethylamine, diethylamine, pyridine and ammonia One or several kinds, the amount of alkali is 0.001-2 of the mass of 2-nitropropane, and the molar ratio of formaldehyde or paraformaldehyde to 2-nitropropane is 1:1-5:1;

In steps S3 and S2, the reaction product is directly hydrogenated without purification to obtain the product 2-amino-2-methyl-1-propanol (AMP-95), and the purity reaches more than 99.5% through rectification;

Wherein, the conditions required for the preparation of AMP-95 by hydrogenation of 2-nitro-2-methyl-1-propanol in step S3 are: the range of hydrogenation pressure is 0.1-10MPa, the range of reaction temperature is 10-120°C, and The reaction time range is 0.5-10h, the hydrogenation catalyst is palladium carbon or Raney nickel, and the hydrogenation catalyst consumption is 0.001-30% of 2-nitro-2-methyl-1-propanol.

And the catalyst used in the present invention is the porous framework metal hybrid catalyst mentioned in the patent No. ZL201510866441.4.

Embodiment one

Add 10g of catalyst (Ti-V-ZSM-5), 58.08g of acetone, and 20g of ammonia water into 400ml of methanol, raise the temperature to 70°C, slowly add 226.7g of hydrogen peroxide (35%) dropwise, and maintain the temperature at 65- React at 75°C for 1 hour to obtain 2-nitropropane reaction solution; filter, add 5g of sodium hydroxide to the reaction solution, heat up to 35°C, add formaldehyde (40% aqueous solution) dropwise, and continue to react for 3 hours after the dropwise addition to obtain 2-nitropropane -Methyl-2-nitro-propanol reaction solution; put the reaction solution into the autoclave, add 14g of Raney nickel, the reaction temperature is 75°C, the reaction pressure is 3MPa, and the reaction is 4h to obtain 2-methyl-2-amino- The crude product of 1-propanol was rectified to obtain 44.6g of product (AMP-95).

Embodiment two

Add 10g of catalyst (Zr-V-SBA-15), 58.08g of acetone, and 20g of ammonia water into 400ml of methanol, raise the temperature to 70°C, slowly add 226.7g of hydrogen peroxide (35%) dropwise, and maintain the temperature at 65- React at 75°C for 2 hours to obtain a 2-nitropropane reaction solution; filter, add 5g of sodium hydroxide to the reaction solution, heat up to 35°C, add formaldehyde (40% aqueous solution) dropwise, and continue the reaction for 3 hours after the dropwise addition to obtain 2-nitropropane -Methyl-2-nitro-propanol reaction solution; put the reaction solution into the autoclave, add 14g of Raney nickel, the reaction temperature is 75°C, the reaction pressure is 3MPa, and the reaction is 4h to obtain 2-methyl-2-amino- The crude product of 1-propanol was rectified to obtain 53.4g of product (AMP-95).

Embodiment three

Add 10g of catalyst (Zr-Mo-MCM-41), 58.08g of acetone, and 20g of ammonia water into 400ml of methanol, raise the temperature to 70°C, slowly add 226.7g of hydrogen peroxide (35%) dropwise, and maintain the temperature at 65- React at 75°C for 1 hour to obtain 2-nitropropane reaction solution; filter, add 5g of sodium hydroxide to the reaction solution, heat up to 35°C, add formaldehyde (40% aqueous solution) dropwise, and continue to react for 3 hours after the dropwise addition to obtain 2-nitropropane -Methyl-2-nitro-propanol reaction solution; put the reaction solution into the autoclave, add 14g of Raney nickel, the reaction temperature is 75°C, the reaction pressure is 3MPa, and the reaction is 4h to obtain 2-methyl-2-amino- The crude product of 1-propanol was rectified to obtain 50.9 g of the product (AMP-95).

Embodiment four

Add 10g of catalyst (titanium-zirconium-doped mesoporous-macroporous composite catalyst), 58.08g of acetone, and 20g of ammonia water into 400ml of methanol, heat up to 70°C, slowly add 226.7g of hydrogen peroxide (35%) dropwise, and keep The temperature is 65-75°C, react for 1h to obtain 2-nitropropane reaction liquid; filter, add 5g sodium hydroxide to the reaction liquid, raise the temperature to 35°C, add formaldehyde (40% aqueous solution) dropwise, and continue the reaction after the dropwise addition 3h, to obtain 2-methyl-2-nitro-propanol reaction solution; put the reaction solution into the autoclave, add 14g of Raney nickel, reaction temperature 75 ° C, reaction pressure 3MPa, reaction 4h, 2-methyl- The crude product of 2-amino-1-propanol was rectified to obtain 57.5 g of the product (AMP-95).

Embodiment five

Add 10g of catalyst (titanium-zirconium-doped mesoporous-macroporous composite catalyst), 58.08g of acetone, and 20g of ammonia water into 400ml of methanol, heat up to 70°C, slowly add 226.7g of hydrogen peroxide (35%) dropwise, and keep The temperature was 65-75°C, reacted for 1h, and obtained 2-nitropropane reaction liquid; filtered, added 5g of sodium hydroxide to the reaction liquid, raised the temperature to 35°C, added 20g of paraformaldehyde in batches, continued the reaction for 3h, and obtained 2- Methyl-2-nitro-propanol reaction solution; put the reaction solution into an autoclave, add 14g of Raney nickel, reaction temperature 75°C, reaction pressure 3MPa, reaction for 4h to obtain 2-methyl-2-amino-1 - propanol crude product, rectification obtains product (AMP-95) 55.9g.

Embodiment six

Add 10g of catalyst (titanium-zirconium-doped mesoporous-macroporous composite catalyst), 58.08g of acetone, and 10g of ammonia water into 400ml of methanol, heat up to 70°C, slowly add 226.7g of hydrogen peroxide (35%) dropwise, and keep The temperature was 65-75°C, reacted for 1h, and obtained 2-nitropropane reaction liquid; filtered, added 5g of sodium hydroxide to the reaction liquid, raised the temperature to 35°C, added 20g of paraformaldehyde in batches, continued the reaction for 3h, and obtained 2- Methyl-2-nitro-propanol reaction solution; put the reaction solution into an autoclave, add 14g of Raney nickel, reaction temperature 75°C, reaction pressure 3MPa, reaction for 4h to obtain 2-methyl-2-amino-1 - propanol crude product, rectification obtains product (AMP-95) 40.6g.

Embodiment seven

Add 10g of catalyst (titanium-zirconium-doped mesoporous-macroporous composite catalyst), 58.08g of acetone, and 20g of ammonia water into 400ml of methanol, raise the temperature to 50°C, slowly add 226.7g of hydrogen peroxide (35%) dropwise, and maintain the temperature after the dropwise addition React at 50-60°C for 2 hours to obtain 2-nitropropane reaction solution; filter, add 5g of sodium hydroxide to the reaction solution, raise the temperature to 35°C, add 20g of paraformaldehyde in batches, continue the reaction for 4h after the dropwise addition, Obtain 2-methyl-2-nitro-propanol reaction solution; put the reaction solution into the autoclave, add 14g of Raney nickel, the reaction temperature is 75°C, the reaction pressure is 3MPa, and the reaction is 4h to obtain 2-methyl-2- The crude product of amino-1-propanol was rectified to obtain 50.1 g of the product (AMP-95).

Embodiment Eight

Add 20g of catalyst (titanium-zirconium-doped mesoporous-macroporous composite catalyst), 58.08g of acetone, and 20g of ammonia water into 400ml of methanol, raise the temperature to 70°C, slowly add 226.7g of hydrogen peroxide (35%) dropwise, and maintain the temperature after the dropwise addition React at 65-75°C for 1 hour to obtain 2-nitropropane reaction solution; filter, add 5g of sodium hydroxide to the reaction solution, raise the temperature to 35°C, add 20g of paraformaldehyde in batches, continue the reaction for 4 hours after the dropwise addition, Obtain 2-methyl-2-nitro-propanol reaction solution; put the reaction solution into the autoclave, add 14g of Raney nickel, the reaction temperature is 75°C, the reaction pressure is 3MPa, and the reaction is 4h to obtain 2-methyl-2- The crude product of amino-1-propanol was rectified to obtain 59.1 g of the product (AMP-95).

Embodiment nine

Add 20g of catalyst (titanium-zirconium-doped mesoporous-macroporous composite catalyst), 58.08g of acetone, and 20g of ammonia into 400ml of methanol, raise the temperature to 70°C, slowly add 226.7g of hydrogen peroxide (35%) dropwise, and maintain the temperature after the dropwise addition is completed React at 65-75°C for 1 hour to obtain 2-nitropropane reaction solution; filter, add 10g of sodium hydroxide to the reaction solution, raise the temperature to 55°C, add 20g of paraformaldehyde in batches, continue the reaction for 2 hours after the dropwise addition, Obtain 2-methyl-2-nitro-propanol reaction solution; put the reaction solution into the autoclave, add 14g of Raney nickel, the reaction temperature is 75°C, the reaction pressure is 3MPa, and the reaction is 4h to obtain 2-methyl-2- The crude product of amino-1-propanol was rectified to obtain 53.6g of product (AMP-95).

Embodiment ten

Add 20g of catalyst (titanium-zirconium-doped mesoporous-macroporous composite catalyst), 58.08g of acetone, and 20g of ammonia water into 400ml of methanol, raise the temperature to 70°C, slowly add 326.7g of hydrogen peroxide (35%) dropwise, and maintain the temperature after the dropwise addition React at 65-75°C for 1 hour to obtain 2-nitropropane reaction solution; filter, add 10g of sodium hydroxide to the reaction solution, raise the temperature to 55°C, add 20g of paraformaldehyde in batches, continue the reaction for 2 hours after the dropwise addition, Obtain 2-methyl-2-nitro-propanol reaction solution; put the reaction solution into the autoclave, add 14g of Raney nickel, the reaction temperature is 75°C, the reaction pressure is 3MPa, and the reaction is 4h to obtain 2-methyl-2- The crude product of amino-1-propanol was rectified to obtain 54.9 g of the product (AMP-95).

In summary, the present invention has cheap and easy-to-obtain raw materials, simple reaction steps, less environmental pollution, low cost, high yield, easy purification of the product, and is suitable for industrial production.

Although the embodiments of the present invention have been shown and described, those skilled in the art can understand that various changes, modifications and substitutions can be made to these embodiments without departing from the principle and spirit of the present invention. and modifications, the scope of the invention is defined by the appended claims and their equivalents.

Claims (5)

1. a kind of one kettle way prepares the green synthesis method of AMP-95, which is characterized in that includes the following steps：

S1, in alcoholic solution, acetone, hydrogen peroxide and ammonia generate 2- nitropropanes under the catalytic action of catalyst；

Wherein, the required condition of 2- nitropropanes is prepared in the S1 steps is：In certain temperature range and time range Under, the catalyst is stephanoporate framework metal hybrid catalyst, its skeleton of stephanoporate framework metal hybrid catalyst is mainly silicon, oxygen And hybridized metal, wherein hybridized metal be titanium, zirconium, vanadium and molybdenum one kind or combination of two, the ratio of silicon and hybridized metal atom is 20~100：1, and hydridization bimetallic molar ratio is 1:20~1:100；The catalyst is configured as ZSM-5, MCM-41, SBA- 15 and its one of micropore-mesopore composite construction and mesopore-macropore composite construction, the wherein dosage of catalyst is material total amount 0.001~10%；

The not purified direct and formaldehyde under alkaline condition of reaction solution or polyformaldehyde reaction generation 2- nitre in S2, the S1 steps Base -2- methyl-1s-propyl alcohol；

Wherein, 2- nitros -2- methyl-1s-required condition of propyl alcohol is prepared in the S2 steps is：In certain temperature range Under time range, alkali for sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, One or more of saleratus, dimethylamine, triethylamine, diethylamine, pyridine and ammonium hydroxide, the dosage of alkali is 2- nitropropane matter The 0.001-2 of amount；

The not purified direct hydrogenation of reaction product obtains product 2-amino-2-methyl-1-propanol (AMP- in S3, the S2 steps 95), reach more than 99.5% through rectifying purity；

Wherein, 2- nitros -2- methyl-1s-propyl alcohol Hydrogenation is for the required conditions of AMP-95 in the S3 steps：Certain Temperature range, under time range and under hydrogenation pressure range, hydrogenation catalyst is palladium carbon or Raney's nickel, hydrogenation catalyst dosage 0.001-30% for 2- nitros -2- methyl-1s-propyl alcohol.

2. one kettle way according to claim 1 prepares the green synthesis method of AMP-95, it is characterised in that：The S1 steps In, hydrogen peroxide and acetone molar ratio are 0.1:1~5:1, acetone and ammonia molar ratio are 1:0.01~1:3, and range of reaction temperature It it is 20-120 DEG C, and reaction time range is 0.5-5h.

3. a kind of one kettle way according to claim 1 prepares the green synthesis method of AMP-95, it is characterised in that：The S1 In step, alcoholic solution is water or methanol, ethyl alcohol, n-butanol, isobutanol, propyl alcohol, isopropanol, the tert-butyl alcohol, ethylene glycol and propylene glycol One or more of.

4. one kettle way according to claim 1 prepares the green synthesis method of AMP-95, it is characterised in that：The S2 steps The middle required temperature range of reaction is 10-120 DEG C, and reacts required time range for 0.5-12h, and formaldehyde or poly The molar ratio of formaldehyde and 2- nitropropanes is 1:1-5:1.

5. one kettle way according to claim 1 prepares the green synthesis method of AMP-95, it is characterised in that：The S3 steps Middle hydrogenation pressure ranging from 0.1-10MPa, range of reaction temperature are 10-120 DEG C, and reaction time range is 0.5-10h.