CN101565364B - Synthetic method of Beta-diketone metal salt - Google Patents

Abstract

The invention discloses a synthesis method of β-diketone metal salt. The steps of the synthesis method are as follows: firstly, at a temperature lower than the melting point of β-diketone, stoichiometric ratio of β-diketone, water-soluble metal salt, Alkali is mixed with water as the reaction medium, then stirred, and the temperature is adjusted to react. After the reaction is completed, the resulting product is filtered, washed, dehydrated and dried to obtain a β-diketone metal salt product; Synthesis of β-diketone metal salt by reaction, compared with the prior art that requires an organic solvent as a reaction medium or does not require a reaction medium but can escape acid mist, the operation is greatly simplified, and the yield, production efficiency, and environmental protection The safety and safety are obviously improved, and the production cost is correspondingly reduced.

Description

The synthetic method of β-diketone metal salt

technical field

The invention relates to a method for synthesizing beta-diketone metal salts, more specifically, the invention relates to a method for synthesizing beta-diketone metal salts in one step with water as a reaction medium.

Background technique

β-diketones are a class of organic compounds whose structure can be represented by the general formula (A):

In formula (A), R ₁ and R ₂ may be the same or different groups.

β-diketones can be converted to the enol structure by isomerization:

(ketone form) (enol form)

Due to the acidity of the hydroxyl group in the enol structure, β-diketones can form metal salts [Formula (B)]:

In the formula (B), M represents a metal element, n is equal to the charge number of the metal ion in the metal salt, and 1≤m≤n.

Metal salts (also known as complexes) of β-diketones such as dibenzoylmethane [formula (C)] or fatty acylbenzoylmethane [formula (D)] are important heat stabilizers for polyvinyl chloride (PVC) (CN1517399, JP11060970, JP10308122, JP9255834), wherein, rare earth salts can also be used as transparent plastic ultraviolet filter (JP8012617) and polymer light stabilizer (CN1730522).

In formula (D), R ₃ is an alkyl group;

The synthesis of dibenzoylmethane and fatty acyloylmethane metal salts has been reported in the literature. For example, according to GB999234, zinc carbonate is added to the methanol solution of dibenzoylmethane and heated to reflux for several hours to obtain dibenzoylmethane zinc salt; according to US4003937, ytterbium halide and diphenylmethane Acylmethane reacts in tetrahydrofuran, ether, ketone or ester solution at a temperature of 20-60°C to synthesize dibenzoylmethane ytterbium; according to JP8012617, add ammonia water dropwise to the methanol solution of dibenzoylmethane and rare earth nitrate , and then reacted for 1 hour at 20～25°C, the basic dibenzoylmethane rare earth salt can be synthesized; Li Jianping (Hubei University Journal (Natural Science Edition), 1998, 20(1): 59～62) introduced, Dissolve dibenzoylmethane in ethanol, adjust the pH of the solution to 8.0-9.0 with 1:1 ammonia water, and slowly add the rare earth chloride solution with a stoichiometric ratio (that is, the molar ratio is equal to the stoichiometric ratio) dropwise under constant stirring , continue to stir for 2 hours, dibenzoylmethane rare earth can be synthesized; according to CN1730522, add sodium hydroxide aqueous solution to the ethanol solution of dibenzoylmethane or benzoylacetone at room temperature, stir and mix the reaction, and then add chlorine dropwise Thin the rare earth or calcium chloride aqueous solution and continue to stir and react for 1.5 hours, and the rare earth or calcium salt of dibenzoylmethane or benzoylacetone can be synthesized. Unfortunately, when adopting the above-mentioned method to synthesize β-diketone metal salt, it is required to use an organic solvent as a reaction medium, so the application in industrial production has the following obvious disadvantages:

(1) Because the solubility of β-diketone metal salts in organic solvents is relatively large, the yield is low;

(2) Since the organic solvent recovery system must be configured, the production equipment investment and production energy consumption are relatively high;

(3) Since the organic solvent is toxic, flammable and explosive, the environmental protection and safety risks are relatively large;

(4) Due to the low production rate, high production investment and production energy consumption, investment is required to solve environmental protection and safety risks, so the production cost is relatively high.

Lv Jingci et al. (Journal of Inorganic Chemistry, 1998, 14(3): 340-342) recently reported a method for synthesizing β-diketone rare earth salts without a reaction medium. According to this method, the dibenzoylmethane rare earth salt can be synthesized by grinding the mixture of dibenzoylmethane and rare earth acetate and heating at about 70° C. for about 4 hours. Unfortunately, although this method does not need organic solvent, there is a new problem of acetic acid gas mist escaping from the reaction process. This not only still has the problems of volatile organic compound recovery, environmental protection and safety risks, but also puts forward new requirements for the acid corrosion resistance of production equipment.

Contents of the invention

The object of the present invention is to provide a method for synthesizing β-diketone metal salts that can effectively overcome the shortcomings of the background technology. β-diketone metal salt synthetic method of the present invention is as follows:

First, at a temperature lower than the melting point of the β-diketone, the β-diketone of the stoichiometric ratio (that is, the molar ratio is equal to the ratio of the stoichiometric number), the water-soluble metal salt, and the alkali are mixed with water as a reaction medium, and then stirred, The reaction is carried out by adjusting the temperature. After the reaction is completed, the resulting product is filtered, washed, dehydrated and dried to obtain the product.

The structure of the β-diketone is shown in formula (I):

Wherein, R is a phenyl group or an alkyl group with 1 to 24 carbon atoms;

The structure of the β-diketone metal salt is shown in formula (II):

Wherein, R is a phenyl group or a linear alkyl group with 1 to 24 carbon atoms, M represents a metal element, n=2 or 3, and 0≤m≤3.

When the metal is calcium, the water-soluble metal salt is selected from calcium chloride, calcium nitrate, calcium acetate or a mixture thereof; when the metal is magnesium, the water-soluble metal salt is selected from magnesium sulfate, magnesium chloride, magnesium nitrate, acetic acid Magnesium or a mixture thereof; when the metal is zinc, the water-soluble metal salt is selected from zinc sulfate, zinc chloride, zinc nitrate, zinc acetate or a mixture thereof; when the metal is a rare earth, the water-soluble metal salt is selected from chlorine Rare earth oxides, rare earth nitrates, rare earth acetates, rare earth sulfates or mixtures thereof, wherein the rare earths include lanthanides other than scandium, yttrium and promethium.

The base that can be used in the synthesis method of β-diketone metal salt of the present invention includes sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, ammonia or a mixture thereof;

Synthesize β-diketone metal salt with the inventive method, water-soluble metal salt and alkali feed intake with this material itself or its aqueous solution form, for the sake of accuracy, preferably feed intake with the aqueous solution form of concentration calibration; Medium water and β-diketone The feeding ratio (mass ratio) is 2:1-10:1, preferably 3:1-6:1.

Synthesize β-diketone metal salt with the method of the present invention, reaction temperature and reaction time are different because of β-diketone: when β-diketone is dibenzoylmethane, reaction temperature is 76～100 ℃, and reaction time is 10 ～40min; when the β-diketone is stearylbenzoylmethane metal salt, the reaction temperature is 40～100°C, and the reaction time is 10～40min.

The present invention realizes the one-step reaction synthesis of β-diketone metal salt with water as the reaction medium, and has the following obvious advantages compared with the background technology:

(1) The operation is greatly simplified and the reaction time is obviously shortened;

(2) Since the solubility of the β-diketone metal salt in water is very small, the yield is significantly improved;

(3) Since there is no need to configure a solvent or acid mist recovery system, nor to use special acid-resistant equipment, the investment in production equipment and production energy consumption are reduced;

(4) Since the medium water is non-toxic, non-flammable and non-explosive, the environmental protection and safety are greatly improved;

(5) Due to the obvious shortening of the reaction time, the obvious increase of the yield, the investment in production equipment, environmental protection and safety, and the reduction of production energy consumption, the production cost is significantly reduced.

Detailed ways

The present invention will be further illustrated by specific but non-limiting examples below.

Example 1

At room temperature, add 224g dibenzoylmethane (HDBM, 1mol), calcium chloride aqueous solution containing _CaCl2 55.5g (0.5mol) and sodium hydroxide aqueous solution containing NaOH 40.0g (1mol) in the reactor, add water to The total mass of the solution is about 1000g, then stirred, heated to 80°C, controlled constant temperature reaction for 30min, the reaction product was filtered, washed with water and dehydrated, then dried to constant weight at 105°C under normal pressure to obtain a yellow powder product, the yield 99.3%. After analysis and determination, the melting point of the product is 227～228°C, and the contents of Ca, C, and H are respectively 8.18%, 74.15%, and 4.98%, which is consistent with the chemical formula Ca(DBM) ₂ (calculated values of Ca, C, and H are respectively 8.23 %, 74.07%, 4.93%).

Example 2

At room temperature, add 224g dibenzoylmethane (HDBM, 1mol), magnesium sulfate aqueous solution containing MgSO ₄ 60.2g (0.5mol) and sodium hydroxide aqueous solution containing NaOH 40.0g (1mol) in the reactor, add water to the solution The total mass is about 1000g, then stirred, heated to 80°C, controlled constant temperature reaction for 30min, the reaction product is filtered, washed with water and dehydrated, then dried to constant weight at 105°C under normal pressure to obtain a yellow powder product, the yield is 99.1%. After analysis and determination, the melting point of the product is 147-150°C, and the contents of Mg, C, and H are 5.25%, 76.79%, and 4.99% respectively, which is consistent with the chemical formula Mg(DBM) ₂ (the calculated values of Mg, C, and H are respectively 5.17 %, 76.55%, 5.10%).

Example 3

At room temperature, add 224g dibenzoylmethane (HDBM, 1mol), zinc sulfate aqueous solution containing 80.8g (0.5mol) of ZnSO ₄ and aqueous sodium hydroxide solution containing 40.0g (1mol) of NaOH in the reactor, add water to the solution The total mass is about 1000g, then stirred, heated to 80°C, controlled constant temperature reaction for 30min, the reaction product is filtered, washed with water and dehydrated, then dried to constant weight at 105°C under normal pressure to obtain a yellow powder product, the yield is 99.3%. After analysis and determination, the melting point of the product is 215-218°C, and the Zn, C, and H contents are respectively 12.87%, 70.49%, and 4.66%, which is consistent with the chemical formula Zn(DBM) ₂ (the calculated values of Zn, C, and H are respectively 12.79 %, 70.39%, 4.69%).

Example 4

At room temperature, add _224g dibenzoylmethane (HDBM, 1mol), lanthanum chloride aqueous solution containing 81.8g (0.33mol) of LaCl3 and aqueous sodium hydroxide solution containing 40.0g (1mol) of NaOH in the reactor, add water to The total mass of the solution is about 1000g, then stirred, heated to 80°C, controlled constant temperature reaction for 30min, the reaction product was filtered, washed with water and dehydrated, then dried to constant weight at 105°C under normal pressure to obtain a yellow powder product, the yield 99.5%. It is determined by analysis that the melting point of the product is 131-133°C, and the La, C, and H contents are 16.47%, 63.89%, and 4.33% respectively, which is consistent with the chemical formula La(DBM) ₃ 2H ₂ O (calculated from the La, C, and H contents The values are respectively 16.46%, 63.99%, 4.27%).

Example 5

At room temperature, add 224g dibenzoylmethane (HDBM, 1mol), samarium chloride aqueous solution containing SmCl _85.6g (0.33mol) and sodium hydroxide aqueous solution containing NaOH 40.0g (1mol) in the reactor, add water to The total mass of the solution is about 1000g, then stirred, heated to 80°C, controlled constant temperature reaction for 30min, the reaction product was filtered, washed with water and dehydrated, then dried to constant weight at 105°C under normal pressure to obtain a yellow powder product, the yield 99.3%. It is determined by analysis that the melting point of the product is 231-233°C, and the contents of Sm, C, and H are 17.67%, 63.24%, and 4.16%, respectively, which is consistent with the chemical formula Sm(DBM) ₃ ·2H ₂ O (calculated by the contents of Sm, C, and H The values are respectively 17.58%, 63.13%, 4.21%).

Example 6

At room temperature, add 386g stearoylbenzoylmethane (HSBM, 1mol), the calcium chloride aqueous solution containing CaCl _55.5g (0.5mol) and the sodium hydroxide aqueous solution containing NaOH 40.0g (1mol) in the reactor, Add water until the total mass of the solution is about 2000g, then stir, heat up to 65°C, and react at a constant temperature for 30 minutes. After the reaction product is filtered, washed with water and dehydrated, it is dried at 50°C under normal pressure to constant weight to obtain a beige waxy product , the yield was 99.0%. After analysis, the Ca, C, and H contents of the product are 4.87%, 76.89%, and 10.56% _respectively , which is consistent with the chemical formula Ca(SBM) (calculated values of Ca, C, and H contents are 4.94%, 77.04%, and 10.37% respectively. ).

Example 7

At room temperature, add 386g stearoylbenzoylmethane (HSBM, 1mol), magnesium sulfate aqueous solution containing MgSO _60.2g (0.5mol) and sodium hydroxide aqueous solution containing NaOH 40.0g (1mol) in the reactor, add water The total mass of the solution was about 2000g, then stirred, heated to 65°C, controlled constant temperature for 30 minutes, and the reaction product was filtered, washed with water and dehydrated, then dried at 50°C under normal pressure to constant weight to obtain a beige waxy product. The yield was 99.2%. After analysis and determination, the Mg, C, and H contents of the product are 3.15%, 78.39%, and 10.66% _respectively , consistent with the chemical formula Mg(SBM) (calculated values of Mg, C, and H contents are 3.06%, 78.56%, and 10.58% respectively. ).

Example 8

At room temperature, add 386g stearoylbenzoylmethane (HSBM, 1mol), zinc sulfate aqueous solution containing ZnSO ₄ 80.8g (0.5mol) and sodium hydroxide aqueous solution containing NaOH 40.0g (1mol) in the reactor, add water The total mass of the solution is about 2000g, then stirred, heated to 65°C, controlled constant temperature for 30 minutes, the reaction product was filtered, washed with water and dehydrated, then dried to constant weight at 50°C under normal pressure to obtain a beige waxy product. The yield was 99.3%. After analysis and determination, the Zn, C, and H contents of the product are 7.87%, 74.79%, and 10.16% _respectively , which is consistent with the chemical formula Zn(SBM) (calculated values of Zn, C, and H contents are respectively 7.83%, 74.70%, and 10.06% ).

Example 9

At room temperature, add 386g stearoylbenzoylmethane (HSBM, 1mol), the aqueous lanthanum chloride solution containing _81.8g (0.33mol) of LaCl and the aqueous sodium hydroxide solution containing 40.0g (1mol) of NaOH in the reactor, Add water until the total mass of the solution is about 2000g, then stir, heat up to 65°C, and react at a constant temperature for 30 minutes. After the reaction product is filtered, washed with water and dehydrated, it is dried at 50°C under normal pressure to constant weight to obtain a beige waxy product , the yield was 99.1%. After analysis and determination, the La, C, and H contents of the product are 10.87%, 72.45%, and 9.67% respectively, consistent with the chemical formula La(SBM) ₃ (calculated values of La, C, and H contents are 10.73%, 72.34%, and 9.74% ).

Example 10

At room temperature, add 386g stearoylbenzoylmethane (HSBM, 1mol), _SmCl3 85.6g (0.33mol) samarium chloride aqueous solution and NaOH 40.0g (1mol) sodium hydroxide aqueous solution in the reactor, Add water until the total mass of the solution is about 2000g, then stir, heat up to 65°C, and react at a constant temperature for 30 minutes. After the reaction product is filtered, washed with water and dehydrated, it is dried at 50°C under normal pressure to constant weight to obtain a beige waxy product , the yield was 99.2%. After analysis and determination, the Sm, C, and H contents of the product are 11.47%, 71.79%, and 9.71% _respectively , consistent with the chemical formula Sm(SBM) ).

Claims (8)

1. a synthetic method of β-diketone metal salt, is characterized in that: first under the temperature lower than β-diketone fusing point, the β-diketone of stoichiometric ratio, water-soluble metal salt, alkali and as reaction medium mixed with water, then stirred and adjusted the temperature to react, after the reaction was completed, the resulting product was filtered, washed, dehydrated and dried to obtain the β-diketone metal salt product; The structure of the β-diketone is shown in formula (I):

Wherein, R is a phenyl group or an alkyl group with 1 to 24 carbon atoms; The structure of the β-diketone metal salt is shown in formula (II):

Among them, R is a phenyl group or a straight-chain alkyl group with 1 to 24 carbon atoms, M represents a metal element, n=2 or 3, 0≤m≤3; The stoichiometric ratio refers to the ratio in which the molar ratio is equal to the stoichiometric number. 2. The synthetic method of β-diketone metal salt according to claim 1, characterized in that: the metal is calcium, and the water-soluble metal salt is selected from calcium chloride, calcium nitrate, calcium acetate or mixtures thereof. 3. The synthetic method of β-diketone metal salt according to claim 1, characterized in that: the metal is magnesium, and the water-soluble metal salt is selected from magnesium sulfate, magnesium chloride, magnesium nitrate, magnesium acetate or mixtures thereof. 4. the synthetic method of β-diketone metal salt according to claim 1 is characterized in that: described metal is zinc, and water-soluble metal salt is selected from zinc sulfate, zinc chloride, zinc nitrate, zinc acetate or its mixture . 5. the synthetic method of β-diketone metal salt according to claim 1 is characterized in that: described metal is rare earth, and water-soluble metal salt is selected from rare earth chloride, rare earth nitrate, rare earth acetate, rare earth sulfate or mixture thereof , where the rare earths include lanthanides other than scandium, yttrium and promethium. 6. the synthetic method of β-diketone metal salt according to claim 1 is characterized in that: described alkali is sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, ammonia or its mixture. 7. The synthetic method of β-diketone metal salt according to claim 1, characterized in that: the β-diketone is dibenzoylmethane, the synthesis reaction temperature is 76～100°C, and the reaction time is 10～ 40min. 8. the synthetic method of β-diketone metal salt according to claim 1 is characterized in that: described β-diketone is stearoylbenzoylmethane, and synthetic reaction temperature is 40～100 ℃, and the reaction time is 10-40min.