CN101659605B - Method for synthesizing o-hydroxy benzophenone-rare earth coordination compound - Google Patents

Abstract

The invention discloses a method for synthesizing an o-hydroxy benzophenone-rare earth coordination compound. The synthesis method comprises the following steps: firstly, mixing o-hydroxy benzophenone, water soluble rare earth salt, alkali and water used as a reaction medium according to the stoichiometric ratio at a temperature below the melting point of the o-hydroxy benzophenone, then stirring, regulating the temperature, reacting, completing the reaction and obtaining a product of the o-hydroxy benzophenone-rare earth coordination compound by filtering, washing, dewatering and drying the obtained product. The invention realizes that the water is used as the reaction medium for synthesizing the o-hydroxy benzophenone-rare earth coordination compound by a one-step reaction; compared with the prior art requiring taking an organic solvent as the reaction medium, the operation is greatly simplified, the yield, the production efficiency, the environmental protection and the safety are obviously enhanced, and the production cost is correspondingly lowered.

Description

Synthetic method of o-hydroxybenzophenone-rare earth complex

technical field

The invention relates to a method for synthesizing o-hydroxybenzophenone-rare earth complexes, more specifically, the invention relates to a method for synthesizing o-hydroxybenzophenone-rare earth complexes in one step with water as the reaction medium.

Background technique

O-hydroxybenzophenone is a class of organic compounds whose core structure is shown in the following formula:

Because they can strongly absorb the solar ultraviolet rays that can cause polymer materials to degrade, and have a high degree of light resistance, they have been widely used as UV absorber light stabilizers for polymer materials (Genhut R, Miller H. Handbook of Plastic Additives. Translated by Cheng Guoxiang, Yao Kangde, etc. Beijing: Chemical Industry Press, 2000).

Recently, the patent literature (CN1730454) reported that the o-hydroxybenzophenone ultraviolet absorber can not only significantly improve the photostabilization performance of polymer materials by forming appropriate rare earth complexes, but also has the following advantages:

(1) The heat resistance is significantly higher than that of commonly used UV absorbers and hindered amine light stabilizers, and higher than its high molecular weight varieties;

(2) The tendency of blooming phenomenon is extremely small;

(3) It does not interact with sulfur-containing additives.

According to CN1730454, o-hydroxybenzophenone, soluble rare earth salt and neutralizing agent are stirred and reacted in lower alcohol or lower alcohol-water medium by stoichiometric ratio, and the precipitate generated by the reaction can be synthesized to obtain o-hydroxybenzophenone by filtering, washing and drying Benzophenone-rare earth complexes. It is a pity that adopting this method to synthesize o-hydroxybenzophenone-rare earth complexes requires the use of organic solvent lower alcohols as the reaction medium, so the application in industrial production has the following obvious disadvantages:

(1) Because the solubility of the o-hydroxybenzophenone-rare earth complex 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.

Contents of the invention

The object of the present invention is to provide a method for synthesizing o-hydroxybenzophenone-rare earth complexes that can effectively overcome the shortcomings of the background technology. O-hydroxybenzophenone-rare earth complex synthetic method of the present invention is as follows:

First, at a temperature lower than the melting point of o-hydroxybenzophenone, o-hydroxybenzophenone in a stoichiometric ratio (that is, the molar ratio is equal to the ratio of the stoichiometric number), a water-soluble rare earth salt, and an alkali are mixed with water as a reaction medium , then stirring, adjusting the temperature and reacting. After the reaction is completed, the resulting product is filtered, washed, dehydrated and dried to obtain the o-hydroxybenzophenone-rare earth complex product;

The structure of the o-hydroxybenzophenone is shown in formula (I):

Wherein, R is hydrogen or an alkyl group with 1 to 12 carbon atoms;

The structure of the o-hydroxybenzophenone-rare earth complex is shown in formula (II):

Wherein, R is hydrogen or an alkyl group with 1-12 carbon atoms; RE represents rare earth elements, including lanthanides except scandium, yttrium and promethium; n=1-3.

When using the method of the present invention to synthesize the o-hydroxybenzophenone-rare earth complex, the water-soluble rare earth salt is selected from rare earth chloride, rare earth nitrate, rare earth acetate, rare earth sulfate or mixtures thereof, wherein the rare earth includes scandium, yttrium and promethium except lanthanides.

The bases that can be used in the synthesis method of o-hydroxybenzophenone-rare earth complexes of the present invention include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, ammonia or mixtures thereof;

Synthesize the o-hydroxybenzophenone-rare earth complex with the method of the present invention, the water-soluble rare earth salt and the alkali are fed in the form of the substance itself or its aqueous solution, for the sake of accuracy, preferably in the form of an aqueous solution calibrated through the concentration; the medium water and the adjacent The feed ratio (mass ratio) of hydroxybenzophenone is 2:1-10:1, preferably 3:1-6:1.

With the method of the present invention to synthesize o-hydroxybenzophenone-rare earth complexes, the reaction temperature is different because of o-hydroxybenzophenones: during the synthesis of 2-hydroxyl-4-methoxybenzophenone-rare earth complexes, the reaction The temperature is from room temperature to 100°C; when synthesizing 2-hydroxy-4-n-octyloxybenzophenone-rare earth complex, the reaction temperature is from 60 to 100°C.

The present invention realizes the one-step reaction synthesis of o-hydroxybenzophenone-rare earth complex with water as the reaction medium, and has the following obvious advantages compared with the background technology:

(1) The operation is greatly simplified;

(2) Because the solubility of the o-hydroxybenzophenone-rare earth complex in water is very small, the yield is significantly improved;

(3) Since there is no need to configure a solvent recovery system, production equipment investment 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, 224.2g of 2-hydroxy-4-methoxybenzophenone (HMBP, 1mol), lanthanum chloride aqueous solution containing 81.8g (0.333mol) of LaCl ₃ and 40.0g (1mol) of NaOH were added to the reactor ) of sodium hydroxide aqueous solution, add water until the total mass of the solution is about 1000g, then stir, heat up to 40°C, control the constant temperature for 10min, the reaction product is filtered, washed with water and dehydrated, then dried at 105°C under normal pressure to constant weight , to obtain a yellow powder product with a yield of 99.3%. After analysis, the melting point of the product is: >300°C; the La, C, and H contents are 16.77%, 61.49%, and 4.68% respectively, which is consistent with the chemical formula La(MBP) ₃ (the calculated values of La, C, and H contents are respectively 16.92% , 61.40%, 4.75%).

Example 2

At room temperature, 224.2g 2-hydroxy-4-methoxybenzophenone (HMBP, 1mol), lanthanum chloride aqueous solution containing 122.7g (0.5mol) of _LaCl3 and 60.0g (1.5mol) of NaOH were added to the reactor. mol) of sodium hydroxide aqueous solution, add water until the total mass of the solution is about 1000g, then stir, heat up to 40°C, control the constant temperature reaction for 10min, the reaction product is filtered, washed and dehydrated, and dried at 105°C Weight, a yellow powdery product was obtained with a yield of 99.5%. After analysis and determination, the melting point of the product: > 300 ° C; La, C, H content is 23.27%, 22.59% and 4.07%, respectively, consistent with the chemical formula La (MBP) ₂ (OH) (La, C, H content calculation values are respectively 23.06%, 55.79%, 3.98%).

Example 3

At room temperature, add 224.2g 2-hydroxy-4-methoxybenzophenone (HMBP, 1mol), lanthanum chloride aqueous solution containing 245.4g (1mol) of _LaCl3 and 120.0g (3mol) of NaOH in the reactor Aqueous sodium hydroxide solution, add water until the total mass of the solution is about 1000g, then stir, heat up to 40°C, control the constant temperature reaction for 10min, the reaction product is filtered, washed with water and dehydrated, then dried at 105°C under normal pressure to constant weight, A yellow powdery product was obtained with a yield of 99.1%. Through analysis and determination, the melting point of the product: > 300 ℃; La, C, H content are respectively 34.95%, 42.49% and 3.15%, and chemical formula La (MBP) (OH) ₂ accord with (La, C, H content calculated value respectively 35.07%, 42.41%, 3.03%).

Example 4

At room temperature, 224.2g 2-hydroxy-4-methoxybenzophenone (HMBP, 1mol), samarium chloride aqueous solution containing 85.6g (0.33mol) of SmCl ₃ and 40.0g (1mol) of NaOH were added into the reactor ) of sodium hydroxide aqueous solution, add water until the total mass of the solution is about 1000g, then stir, heat up to 40°C, control the constant temperature reaction for 10min, and the reaction product is filtered, washed and dried to obtain a yellow powder product with a yield of 99.2% . After analysis and determination, the melting point of the product: > 300 ° C; Sm, C, H content are 17.97%, 60.69% and 4.66% respectively, consistent with the chemical formula Sm (MBP) ₃ (Sm, C, H content calculation value is 18.06% respectively , 60.55%, 4.68%).

Example 5

At room temperature, 224.2g of 2-hydroxy-4-methoxybenzophenone (HMBP, 1mol), thulium chloride aqueous solution containing 91.8g (0.333mol) of TmCl ₃ and 40.0g (1mol) of NaOH containing ) of sodium hydroxide aqueous solution, add water until the total mass of the solution is about 1000g, then stir, heat up to 40°C, control the constant temperature for 10min, the reaction product is filtered, washed with water and dehydrated, then dried at 105°C under normal pressure to constant weight , to obtain a yellow powder product with a yield of 99.3%. Through analysis and determination, the melting point of the product: > 300 ℃; Tm, C, H content are respectively 19.77%, 59.15% and 4.68%, and chemical formula Tm (MBP) ₃ accord with (Tm, C, H content calculated value is 19.85% respectively , 59.23%, 4.58%).

Example 6

At room temperature, 326.0g 2-hydroxy-4-n-octyloxybenzophenone (HOBP, 1mol), lanthanum chloride aqueous solution containing 81.8g (0.333mol) of _LaCl3 and 40.0g ( 1mol) of sodium hydroxide aqueous solution, add water until the total mass of the solution is about 1500g, then stir, heat up to 70°C, and control the constant temperature for 90min, the reaction product is filtered, washed and dehydrated, then dried at 50°C under normal pressure Weight, a yellow waxy product was obtained with a yield of 99.0%. It was determined by analysis that the contents of La, C, and H were 12.53%, 67.99%, and 6.88%, respectively, consistent with the chemical formula La(OBP) ₃ (calculated values of La, C, and H were 12.47%, 67.87%, and 7.00%, respectively).

Example 7

At room temperature, 326.0g of 2-hydroxy-4-n-octyloxybenzophenone (HOBP, 1mol), lanthanum chloride aqueous solution containing 122.7g (0.5mol) of _LaCl3 and 60.0g of NaOH ( 1.5mol) of sodium hydroxide aqueous solution, add water until the total mass of the solution is about 1500g, then stir, heat up to 70°C, control the constant temperature for 90min, the reaction product is filtered, washed with water and dehydrated, then dried at 50°C under normal pressure to Constant weight was obtained to obtain a yellow waxy product with a yield of 99.0%. After analysis, the contents of La, C, and H are 17.37%, 62.49%, and 6.48%, respectively, which are consistent with the chemical formula La(OBP) ₂ (OH) (calculated values of La, C, and H are 17.24%, 62.54%, 6.45%, respectively. %).

Example 8

At room temperature, add 326.0g 2-hydroxy-4-n-octyloxybenzophenone (HOBP, 1mol), lanthanum chloride aqueous solution containing 245.4g (1mol) of LaCl ₃ and 120.0g (3mol) of NaOH ) of sodium hydroxide aqueous solution, add water until the total mass of the solution is about 1500g, then stir, heat up to 70°C, control the constant temperature for 90min, the reaction product is filtered, washed with water and dehydrated, then dried at 50°C under normal pressure to constant weight , a yellow waxy product was obtained with a yield of 99.0%. After analysis, the content of La, C and H is 27.77%, 50.49% and 5.30% respectively, which is consistent with the chemical formula La(OBP)(OH) ₂ (calculated values of La, C and H are 27.90%, 50.61%, 5.22% respectively %).

Example 9

At room temperature, add 326.0g 2-hydroxyl-4-n-octyloxybenzophenone (HOBP, 1mol), samarium chloride aqueous solution containing 85.6g (0.33mol) of _SmCl3 and 40.0g ( 1mol) of sodium hydroxide aqueous solution, add water until the total mass of the solution is about 1500g, then stir, heat up to 70°C, and control the constant temperature for 90min, the reaction product is filtered, washed and dehydrated, then dried at 50°C under normal pressure Weight, a yellow waxy product was obtained with a yield of 99.3%. It was determined by analysis that the contents of Sm, C, and H were 13.27%, 67.30%, and 6.86%, respectively, consistent with the chemical formula Sm(OBP) ₃ (the calculated values of Sm, C, and H were 13.36%, 67.18%, and 6.93%, respectively).

Example 10

At room temperature, add 326.0g 2-hydroxyl-4-n-octyloxybenzophenone (HOBP, 1mol), thulium chloride aqueous solution containing _TmCl3 91.8g (0.333mol) and NaOH containing 40.0g ( 1mol) of sodium hydroxide aqueous solution, add water until the total mass of the solution is about 1500g, then stir, heat up to 70°C, and control the constant temperature for 90min, the reaction product is filtered, washed and dehydrated, then dried at 50°C under normal pressure Weight, a yellow waxy product was obtained with a yield of 99.4%. It was determined by analysis that the Tm, C, and H contents were 14.63%, 66.25%, and 6.88%, respectively, which was consistent with the chemical formula Tm(OBP) ₃ (the calculated values of Tm, C, and H contents were 14.77%, 66.09%, and 6.82%, respectively).

Claims (5)

1. a synthetic method of o-hydroxybenzophenone rare earth complex, is characterized in that: at first lower than the temperature of o-hydroxybenzophenone fusing point, the o-hydroxybenzophenone of stoichiometric ratio, water-soluble rare earth Mix the salt and alkali with water as the reaction medium, then stir and adjust the temperature to carry out the reaction. After the reaction is completed, the resulting product is filtered, washed, dehydrated and dried to obtain the o-hydroxybenzophenone rare earth complex product; The structure of the o-hydroxybenzophenone is shown in formula (I):

Wherein, R is an alkyl group with 1 to 12 carbon atoms; The structure of the rare earth complex of o-hydroxybenzophenone is shown in formula (II):

Wherein, R is an alkyl group with 1 to 12 carbon atoms; RE is a lanthanide element except scandium, yttrium and promethium; n=1 to 3; The above-mentioned stoichiometric ratio refers to a ratio in which the molar ratio is equal to the stoichiometric number. 2. the synthetic method of the rare earth complex of o-hydroxybenzophenone according to claim 1, is characterized in that: described water-soluble rare earth salt is rare earth chloride, rare earth nitrate, rare earth acetate, rare earth sulfate or its mixture, Among them, the rare earths are lanthanides except scandium, yttrium and promethium. 3. the synthetic method of the rare earth complex of o-hydroxybenzophenone according to claim 1, is characterized in that: described alkali is sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, ammonia or its mixture . 4. the synthetic method of the rare earth complex of o-hydroxybenzophenone according to claim 1, is characterized in that: described o-hydroxybenzophenone is 2-hydroxyl-4-methoxybenzophenone, The synthesis reaction temperature is from room temperature to 100°C. 5. the synthetic method of the rare earth complex of o-hydroxybenzophenone according to claim 1, is characterized in that: described o-hydroxybenzophenone is 2-hydroxyl-4-n-octyloxybenzophenone , The synthesis reaction temperature is 60-100°C.