阅读说明：本技术 一种混合二元酸二酰肼及其制备方法与应用 (Mixed dibasic acid dihydrazide and preparation method and application thereof ) 是由 靳少华 丁可 胡江林 刘运海 赵欣 蒋玉鑫 陈永 宋延方 王磊 于丽丽 季成祥 于 2019-11-29 设计创作，主要内容包括：本发明公开了一种混合二元酸二酰肼及其制备方法与应用。本发明公开的混合二元酸二酰肼,以所述混合二元酸二酰肼的质量为100％计,包含丁二酸二酰肼15-25wt％、戊二酸二酰肼55-65wt％、己二酸二酰肼15-25wt％。本发明提供的混合二元酸二酰肼在PA乳液和水性漆应用中表现了优异的效果。(The invention discloses a mixed dibasic acid dihydrazide and a preparation method and application thereof. The mixed dibasic acid dihydrazide disclosed by the invention comprises 15-25 wt% of succinic dihydrazide, 55-65 wt% of glutaric dihydrazide and 15-25 wt% of adipic dihydrazide, wherein the mass of the mixed dibasic acid dihydrazide is 100%. The mixed dibasic acid dihydrazide provided by the invention has excellent effect in application of PA emulsion and water paint.)

1. The mixed dibasic acid dihydrazide comprises 15-25 wt% of succinic dihydrazide, 55-65 wt% of glutaric dihydrazide and 15-25 wt% of adipic dihydrazide, wherein the mass of the mixed dibasic acid dihydrazide is 100%.

2. The mixed dibasic acid dihydrazide of claim 1, wherein: the weight of the mixed dibasic acid dihydrazide is calculated as 100%, and the mixed dibasic acid dihydrazide comprises 15-20 wt% of succinic dihydrazide, 60-65 wt% of glutaric dihydrazide and 20-25 wt% of adipic acid dihydrazide.

3. A process for preparing the mixed dibasic acid dihydrazide of claim 1 or 2, comprising the steps of: carrying out esterification reaction on mixed dibasic acid and saturated monohydric alcohol with the carbon atom number of 1-4 to generate mixed dibasic acid diester, and then carrying out hydrazide reaction on the mixed dibasic acid diester and hydrazine hydrate to generate mixed dibasic acid dihydrazide;

wherein the mixed dibasic acid comprises 15-25 wt% of succinic acid, 55-65 wt% of glutaric acid and 15-25 wt% of adipic acid, wherein the mass of the mixed dibasic acid is 100%.

4. The method of claim 3, wherein: the mixed dibasic acid comprises 15-20 wt% of succinic acid, 60-65 wt% of glutaric acid and 20-25 wt% of adipic acid, wherein the mass of the mixed dibasic acid is 100%.

5. The method of claim 3, wherein: in the esterification reaction, the molar ratio of the mixed dibasic acid to the saturated monohydric alcohol is 1: 3-1: 5.

6. The method according to any one of claims 3-5, wherein: the mass percentage of the catalyst for the esterification reaction in the mixed dibasic acid is 5-20%;

the catalyst for the esterification reaction is preferably one or more of strong acid resin, acidic molecular sieve, acidic white clay, niobic acid and heteropoly acid.

7. The method according to any one of claims 3-6, wherein: the esterification reaction further comprises a water-carrying agent, and the molar ratio of the mixed dibasic acid to the water-carrying agent is 1: 0.3-1: 1;

the water-carrying agent is preferably one or more of cyclohexane, toluene and dichloromethane.

8. The method according to any one of claims 3-7, wherein: the temperature of the esterification reaction is 80-110 ℃, and the reaction time is 1-4 h; and/or

In the esterification reaction, fresh saturated monohydric alcohol is introduced into an esterification reaction kettle, a mixture of the saturated monohydric alcohol, the water-carrying agent and water is extracted from the kettle top, and the saturated monohydric alcohol is separated for recycling.

9. The method according to any one of claims 3-8, wherein: in the hydrazide reaction, the molar ratio of the mixed dibasic acid diester to hydrazine hydrate is 1: 1.5-1: 4, the hydrazide reaction temperature is 15-30 ℃, and the reaction time is 1-4 h; and/or

In the hydrazidation reaction, the step of continuously taking out the generated dihydrazide slurry is included.

10. Use of a mixed dibasic acid dihydrazide, as defined in claim 1 or 2, in the preparation of an aqueous coating.

Technical Field

The invention belongs to the field of chemical synthesis, and relates to a mixed dibasic acid dihydrazide and a preparation method and application thereof.

Background

Adipic Dihydrazide (ADH) is a white crystalline solid, is easily soluble in water, has a symmetrical molecular structure, and is a dual-functional group compound. ADH is a good cross-linking agent, can be cross-linked with carbonyl, is typically cross-linked with hyaluronic acid to be applied to medicine and pharmacology, and is cross-linked with diacetone acrylamide to be applied to the field of water-based paint. Along with the stricter and stricter limitation of environmental regulations on volatile organic substances in the coating, the water-based coating product is rapidly developed, and in many application fields, the water-based coating completely or partially replaces the solvent-based coating in the traditional sense, along with the improvement of the quality of life of people and the technical progress of industry, the production cost of the water-based coating is continuously reduced, and the development prospect is very wide.

At present, it is known from chinese patents CN109748815A and CN107963980A that the industrial synthesis method of adipic acid dihydrazide mainly adopts a two-step method, which includes esterification reaction and hydrazide reaction: the first step of esterification reaction is used for synthesizing adipic acid dimethyl/ethyl ester, and the second step of hydrazinolysis reaction is used for reacting ester with hydrazine hydrate to generate ADH. However, since the esterification reaction usually uses concentrated sulfuric acid as a catalyst, a large amount of acidic organic wastewater is generated, the salt content and the COD (chemical oxygen demand) content in the wastewater after the neutralization treatment with alkali are high, the wastewater treatment difficulty is high, the treatment cost is high, and the environmental pollution is easily caused due to the large discharge amount of waste. In addition, the market price of adipic acid is nearly ten thousand yuan per ton, which causes high ADH production cost, limits the use of the adipic acid in the field of water-based paint, and is not beneficial to the development of the paint from solvent type to water-based paint.

On the other hand, succinic acid and glutaric acid are by-produced in the production process of adipic acid. Because the binary acid has good solubility in water, the content of adipic acid, glutaric acid and succinic acid in the waste liquid generated by the adipic acid process is high, and the industrial common name of the mixed binary acid waste liquid is green or tawny. 60-70 kg of mixed dibasic acid by-product is produced for every 1 ton of adipic acid. Since these mixed dibasic acids have a very large content of impurities and moisture and are difficult to recycle, they are usually disposed of by incineration or landfill.

Disclosure of Invention

In order to solve the problems of high production cost and low production efficiency of the existing dihydrazide, the invention provides the mixed dibasic acid dihydrazide, which has simple preparation process and is easy for industrial amplification production.

In order to solve the technical problems, the invention provides a mixed dibasic acid dihydrazide, which comprises or consists of the following components by taking the mass of the mixed dibasic acid dihydrazide as 100 percent: 15-25 wt% of succinic dihydrazide, 55-65 wt% of glutaric dihydrazide and 15-25 wt% of adipic dihydrazide.

In some embodiments, the above-mentioned mixed dibasic acid dihydrazide comprises or consists of the following components, based on 100% by mass of the mixed dibasic acid dihydrazide: 15-20 wt% of succinic dihydrazide, 60-65 wt% of glutaric dihydrazide and 20-25 wt% of adipic dihydrazide.

In order to solve the above technical problems, the present invention further provides a method for preparing any one of the mixed dibasic acid dihydrazides described above, comprising the steps of: carrying out esterification reaction on mixed dibasic acid and saturated monohydric alcohol with the carbon atom number of 1-4 to generate mixed dibasic acid diester, and then carrying out hydrazide reaction on the mixed dibasic acid diester and hydrazine hydrate to generate mixed dibasic acid dihydrazide;

wherein the mixed dibasic acid comprises or consists of the following components in percentage by mass of 100 percent: 15-25 wt% of succinic acid, 55-65 wt% of glutaric acid and 15-25 wt% of adipic acid.

In some embodiments, in the above method, the mixed dibasic acid comprises or consists of the following components, based on 100% by mass of the mixed dibasic acid: 15-20 wt% of succinic acid, 60-65 wt% of glutaric acid and 20-25 wt% of adipic acid.

In some embodiments, in any of the above methods, the molar ratio of the mixed dibasic acid to the saturated monohydric alcohol in the esterification reaction is from 1:3 to 1: 5.

In some embodiments of any of the above methods, the esterification catalyst is 5 to 20 wt% of the mixed dibasic acid;

the catalyst for the esterification reaction is preferably one or more of strong acid resin, acidic molecular sieve, acidic argil, niobic acid and heteropoly acid, wherein the acidic molecular sieve is an HY molecular sieve or an H β molecular sieve.

In some embodiments, in any one of the above methods, the esterification reaction further comprises a water-carrying agent, and the molar ratio of the mixed dibasic acid to the water-carrying agent is 1: 0.3-1: 1;

the water-carrying agent is preferably one or more of cyclohexane, toluene and dichloromethane.

In some embodiments, in any of the above methods, the esterification reaction is performed at a temperature of 80 to 110 ℃ for 1 to 4 hours.

In some embodiments, in the method described in any one of the above, in the esterification reaction, fresh saturated monohydric alcohol is introduced into an esterification reaction kettle, a mixture of saturated monohydric alcohol, a water-carrying agent and water is extracted from the kettle top, and the saturated monohydric alcohol is separated for recycling, wherein the fresh saturated monohydric alcohol may be fed at a flow rate of 10 to 50ml/min, and the mixture of saturated monohydric alcohol, a water-carrying agent and water may be extracted at a kettle top flow rate of 10 to 50 ml/min.

In some embodiments, the method of any of the above, wherein the saturated monohydric alcohol is methanol or ethanol.

In some embodiments, in the method described in any one of the above, in the hydrazidation reaction, the molar ratio of the mixed dibasic acid dimethyl ester to the hydrazine hydrate is 1: 1.5-1: 4, the temperature of the hydrazidation reaction is 15-30 ℃, and the reaction time is 1-4 h.

In some embodiments, the method of any one of the above, comprising the step of continuously withdrawing the resulting dihydrazide slurry during the hydrazidation reaction.

In some embodiments, the above method further comprises the steps of filtering the continuously produced dihydrazide slurry, washing with methanol, and drying at 60-100 ℃ for 4-8h to obtain a filter cake, and then re-crushing the filter cake.

In order to solve the technical problems, the invention also provides an application of any one of the mixed dibasic acid dihydrazides in preparing water-based paint.

The invention has the following technical effects:

the performance evaluation of downstream PA emulsion and water paint shows that the mixed dibasic acid dihydrazide provided by the invention at least has the same grade of commodity index as adipic acid dihydrazide on the market, and is even better than the adipic acid dihydrazide in some characteristics, and meanwhile, the market price of the raw material mixed dibasic acid for preparing the mixed dibasic acid dihydrazide is lower than that of the adipic acid, so that the production cost of the dihydrazide can be effectively reduced, and the market popularization of the future paint water-based paint is facilitated; in addition, the continuous production method for preparing the mixed dibasic acid dihydrazide provided by the invention enables the conversion rate of the dibasic acid and the selectivity of the dihydrazide to be higher, can replace the conventional batch operation, and realizes the efficient continuous production of the dihydrazide product.

Drawings

FIG. 1 is a process flow diagram of the continuous production of mixed dibasic acid dihydrazide.

Detailed Description

The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.

Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.

The present invention will be further described with reference to the following examples. It should be understood that the following examples are illustrative only and are not intended to limit the scope of the present invention.

The mixed dibasic acid is a product of chemical industry Limited in Tangshan.

Adipic acid is a product of chemical industry, Inc. in Tangshan.

Methanol is a product of Shanghai Aladdin Biotechnology, Inc., and the catalog number is M116122.

Hydrazine hydrate is a product of Shanghai Aladdin Biotechnology GmbH, with the product catalog number H104021.

The strong acid type cation exchange resin is a product of special resin of Dandong Mingzhu, and the product catalog number is DA 330.

The HY molecular sieve is a product of catalyst factories of southern Kai university, the product catalog number is NKF-8, and the HY molecular sieve is an acidic molecular sieve.

The H β molecular sieve is a product of catalyst works of southern Kao university, catalog number NKF-6, and is an acidic molecular sieve.

The acid clay is a product of Liaoning Tianhua chemical industry Limited liability company.

The rest reagents used in the invention are conventional reagents in the field, and the purity specifications are analytical purity.

The conversion rate and yield calculation method related by the invention is as follows:

mixed diacid conversion rate (mixed diacid feed mass-mixed diacid residual mass)/mixed diacid feed mass

Yield of mixed dibasic acid dihydrazide-actual mass/theoretical mass of mixed dibasic acid dihydrazide

The invention adopts gas chromatography to detect the content of the mixed dibasic acid, and the detection conditions of the gas chromatography are as follows: the model of the chromatographic column is HP-5 (5% Phenyl Methyl Siloxan, 30m × 0.32mm × 0.25 μm), FID detector; the temperatures of the sample injector and the detector are both set to be 280 ℃; the chromatographic column adopts temperature programming, and the temperature programming is as follows: keeping at 100 deg.C for 2min, and heating to 280 deg.C at 10 deg.C/min; main pressure 8.5868 psi; the flow rate was 1.5 ml/min.

The invention adopts¹³C-NMR analysis of the productThe mass percent of dihydrazide and adipic acid dihydrazide,¹³the C-NMR analysis conditions were: 30mg of dihydrazide solid is weighed by adopting an AVANCE series 400MHz nuclear magnetic resonance spectrometer of Bruker company, dissolved in 2mL of deuterated chloroform, and a dissolved sample is put into a sample injector to start testing and perform spectrum analysis.

In the embodiment of the invention, the mixed dibasic acid dihydrazide is prepared by adopting the process flow of the continuous production of the mixed dibasic acid dihydrazide shown in figure 1.