CN107721846B - Preparation method of heat-resistant rare earth composite organic carboxylate - Google Patents
Preparation method of heat-resistant rare earth composite organic carboxylate Download PDFInfo
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Abstract
The invention discloses a preparation method of heat-resistant rare earth composite organic carboxylate, belonging to the field of organic synthesis and material preparation. The preparation method comprises (1) fatty acid soap synthesis; (2) synthesizing fatty acid rare earth salt; (3) synthesizing fatty acid and polybasic aromatic carboxylic acid composite rare earth salt. The heat-resistant rare earth composite organic carboxylate is particularly suitable for nylon thermoplastic extrusion, spinning and injection molding processing processes, and improves the thermal oxidation stability of the nylon in the thermoplastic processing processes.
Description
Technical Field
The invention relates to a preparation method of heat-resistant rare earth composite organic carboxylate, belonging to the field of organic synthesis and material preparation.
Background
The high molecular material heat stabilizer is an additive capable of improving the stability of plastics, films and fibers in the thermoplastic processing process and eliminating or delaying the thermal degradation and the thermal oxidative degradation of a macromolecular chain. The heat stabilizer commonly used in industry mainly comprises lead salt, metal soap, organic tin, organic antimony, organic rare earth, pure organic compound hindered amine, hindered phenol and the like. Due to the special electronic structure and good coordination ability, the rare earth stabilizer has excellent thermal stability, electrical insulation property and non-toxic safety, and becomes an important direction for research and development of heat stabilizers. The rare earth thermal stability additive is mainly used for improving the thermal stability of PVC.
Polyamide or nylon is one of five major engineering plastics in the world at present, and nylon is easy to react with oxygen to form hydroperoxide to generate thermal oxidative degradation at the thermoplastic processing temperature, but the types of thermal oxidation stabilizers suitable for nylon are few, and the thermal oxidation stabilizers are mainly hindered phenol and copper salts. The effect of the hindered phenol antioxidant alone is not ideal, and excessive copper salts also color nylon. The rare earth heat stabilizer opens up a new way for improving the thermal stability of nylon. Although the lanthanum stearate long-chain fatty acid has the functions of both a lubricant and a heat stabilizer and has an obvious effect on the modification of the thermal stability of the polyvinyl chloride, the use temperature of the lanthanum stearate long-chain fatty acid is relatively low, and the lanthanum stearate long-chain fatty acid is difficult to meet the application in the thermoplastic forming and processing process of nylon.
The preparation of organic carboxylic acid rare earth mainly includes double decomposition method and saponification method. In the traditional double decomposition process, fatty acid and caustic soda are firstly subjected to saponification reaction to prepare fatty acid sodium saponification solution, and then the saponification solution is reacted with water-soluble rare earth salt solution to prepare the organic acid rare earth heat stabilizer. The saponification method is to convert rare earth salt into rare earth hydroxide and then react with fatty acid. In the two reaction processes, the long-chain fatty acid and the salt thereof have poor solubility in water, while the rare earth inorganic salt generally has good water solubility, and when the reaction is carried out in an aqueous solution, the chemical reaction efficiency is low, and the conversion rate of the organic carboxylic acid rare earth salt is low.
At present, organic acid rare earth salt is mainly of a pure fatty acid type, and the rare earth heat stabilizer is mainly applied to improving the heat stability of polyvinyl chloride, increasing the heat distortion temperature of cast nylon and the like. Rare earth naphthenate is used to raise the thermal deformation temperature of cast nylon by 30 deg.C (Zhang Yong, CN 1323848A). In the early research work, the thermal stability of the aromatic acid rare earth is obviously superior to that of the fatty acid rare earth, the high-temperature thermal oxidation stability of nylon can be obviously improved by the pure aromatic acid rare earth thermal stabilizer, but the addition amount of the pure aromatic acid rare earth thermal stabilizer is large, so that the high-temperature thermoplastic spinning and film forming process of nylon can be influenced. Therefore, the novel composite rare earth salt with the fatty acid and aromatic acid mixed structure is developed, the lubricating effect of the fatty acid rare earth is maintained, the thermal stability effect of the aromatic acid rare earth is achieved, and the high-temperature thermal stability processability of the nylon is expected to be improved.
Disclosure of Invention
The purpose is as follows: in order to overcome the defects in the prior art, the invention provides a preparation method of heat-resistant rare earth composite organic carboxylate.
The technical scheme is as follows: in order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a preparation method of heat-resistant rare earth composite organic carboxylate is characterized in that a two-phase ultrasonic and mechanical stirring mixing method is adopted to promote chemical reaction, and comprises the following steps:
(1) synthesis of fatty acid soap: under the conditions of ultrasonic and mechanical double mixing, dispersing and activating, fatty acid organic solvent solution and inorganic base or carbonate aqueous solution react at a two-phase microdroplet interface formed by the organic solvent and the aqueous solution to form fatty acid soap;
(2) synthesis of rare earth salts of fatty acids: adding a rare earth inorganic salt aqueous solution into the dispersion liquid obtained in the step (1), and continuously carrying out the reaction of the rare earth inorganic salt and the fatty acid soap on a two-phase interface under the combined action of ultrasonic waves and mechanical stirring to form fatty acid rare earth salt;
(3) synthesis of fatty acid and polybasic aromatic carboxylic acid composite rare earth salt: and (3) adding a polybasic aromatic acid salt aqueous solution into the dispersion liquid obtained in the step (2), and continuously reacting with fatty acid rare earth salt under the combined action of ultrasonic waves and mechanical stirring to obtain the fatty acid and polybasic aromatic carboxylic acid composite rare earth salt.
The step (1) specifically comprises the following steps: respectively adding a fatty acid organic solvent solution and an inorganic base or a carbonate aqueous solution into a three-neck flask, installing a reflux condenser tube and a self-made heating device, forming fatty acid soap under the combined action of ultrasonic waves and mechanical stirring, and reacting on a two-phase interface, wherein the reaction temperature is controlled to be 50-80 ℃, and the reaction time is 1.0-4.0 hours; the equivalent ratio of the fatty acid to the inorganic base or the carbonate is 1 (1.00-1.15).
The step (2) specifically comprises the following steps: on the basis of the synthesized fatty acid soap, pumping a certain amount of rare earth inorganic salt aqueous solution into a reaction solution of a three-neck flask at a constant speed, continuously carrying out the reaction on a two-phase interface under the combined action of ultrasonic waves and mechanical stirring, controlling the reaction temperature to be between 50 and 80 ℃, and continuously reacting for 1.0 to 5.0 hours after the rare earth inorganic salt is added; the equivalent ratio of the fatty acid soap to the rare earth salt is (1.00-1.20): 3.
The step (3) specifically comprises the following steps: pumping the polybasic aromatic acid salt water solution into the reaction liquid of the three-neck flask at a constant speed, controlling the reaction temperature to be between 50 and 80 ℃, and continuing to react for 1.0 to 5.0 hours after the polybasic aromatic acid salt is added; the equivalent ratio of the polybasic aromatic acid salt to the rare earth salt is (2.00-2.20): 3.
The preparation method of the heat-resistant rare earth composite organic carboxylate is characterized by comprising the following steps: the method also comprises the following processing steps: standing and layering the reaction solution obtained in the step (3), washing the upper layer 1 liquid with a dilute alkali aqueous solution, standing and layering to obtain a second upper layer 2 solution; heating and concentrating the lower layer 1 aqueous solution, extracting and separating by using a non-water-soluble organic solvent, and distilling the extract and the solution of the upper layer 2 under reduced pressure to obtain the heat-resistant rare earth composite organic carboxylate. The aqueous solution is all by-products.
Further, the water-insoluble organic solvent is toluene, xylene, chloroform or heptane.
Preferably, the fatty acid comprises a monobasic fatty acid selected from stearic acid, palmitic acid, myristic acid, lauric acid, perfluoroheptanoic acid, perfluorooctanoic acid.
Preferably, the rare earth inorganic salt is rare earth nitrate, rare earth hydrochloride or rare earth sulfate.
Preferably, the polybasic aromatic acid is phthalic acid/anhydride, pyromellitic acid/anhydride, N ' -p-phenylene-bis (1 ", 2" -imido) -bis (4 ", 5") -phthalic acid/anhydride (see molecular formula 1), 4, 4' -etheroxy-diphenyl-bis- (1 ", 2") -imide-bis- (4 ", 5") -phthalic acid/anhydride (see molecular formula 2), 4, 4' -methylene-diphenyl-bis- (1 ", 2") -imide-bis- (4 ", 5") -phthalic acid/anhydride (see molecular formula 3).
Preferably, the inorganic base is sodium hydroxide or potassium hydroxide; the carbonate is sodium carbonate, sodium bicarbonate, potassium carbonate, or potassium bicarbonate.
Has the advantages that: the invention provides a preparation method of heat-resistant rare earth composite organic carboxylate, which comprises the following steps of (1) reacting at a two-phase microdroplet interface formed by an organic solvent and an aqueous solution under the double dispersion and activation of ultrasound and machinery, particularly accelerating the contact and chemical reaction of the two-phase interface by the activation of the ultrasound, and increasing the contact area of the reaction by the contact of the two-phase microdroplet structure. (2) The obtained fatty acid and aromatic acid composite rare earth salt has both the lubricating effect of fatty acid rare earth and the thermal stability effect of aromatic acid rare earth.
Drawings
FIG. 1 is an infrared spectrum of lanthanum diterellitate monostearate;
FIG. 2 is a graph showing the thermogravimetric loss of lanthanum diterephthalate;
FIG. 3 is a chart of the infrared spectrum of 4, 4' -methylene-diphenyl-bis- (1 ',2 ') -imide-bis- (4 ',5 ') -phthalic acid;
FIG. 4 is an infrared spectrum of 4, 4' -methylene-diphenyl-bis- (1 ',2 ') -imide-bis- (4 ',5 ') -lanthanum bis-phthalate bis-distearate;
FIG. 5 is a graph showing the thermogravimetric plot of lanthanum bis-phthalate-4, 4' -methylene-diphenyl-bis- (1 ',2 ') -imide-bis- (4 ',5 ') -bis-stearate.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
(1) 156.2 parts of stearic acid and 24 parts of sodium hydroxide were weighed, respectively, and the stearic acid was dispersed in 600 parts of a toluene solvent and charged into a 2500 parts three-necked flask, while the sodium hydroxide was dissolved in 200 parts of deionized water at room temperature, and then an aqueous sodium hydroxide solution was charged into the flask.
(2) Installing a reflux condenser and a mechanical stirring device, placing the reflux condenser and the mechanical stirring device in an ultrasonic dispersion system for ultrasonic dispersion, heating the ultrasonic dispersion system by using a self-made electric heating system, controlling the reaction temperature to be 50-80 ℃, and performing ultrasonic and mechanical stirring dispersion and reaction for 1 hour to obtain a sodium stearate two-phase dispersion system.
(3) 170 parts of lanthanum chloride is put into a beaker, 250 parts of deionized water is added, and the solution is stirred and dissolved.
(4) And (3) continuing to start the ultrasonic dispersion and heating reaction system, controlling the reaction temperature to be 50-80 ℃, adding the lanthanum chloride aqueous solution into the three-neck flask at a constant speed through a peristaltic pump under the action of mechanical stirring, and continuing to react for 1 hour after the dropwise addition is finished.
(5) 40 parts of sodium hydroxide is dissolved in 400 parts of deionized water, 58 parts of pyromellitic dianhydride is slowly added under the action of magnetic stirring, after full dissolution and reaction, sodium pyromellitic dianhydride aqueous solution is pumped into the three-neck flask by a peristaltic pump under the action of ultrasonic waves and mechanical stirring, and the reaction is continued for 3 hours after the dropwise addition is finished.
(6) Standing and layering the reaction solution, washing the upper layer 1 of the solution with a small amount of dilute sodium hydroxide aqueous solution, standing and layering to obtain a second upper layer 2 of the solution; heating and concentrating the lower layer 1 water solution, extracting and separating with toluene, distilling the extract and the upper layer 2 solution under reduced pressure, drying in a 120 deg.C oven, and grinding. The target product of lanthanum bis (monostearate) pyromellitic acid is obtained, and the conversion rate is 88 percent. FIG. 1 is an infrared spectrum of lanthanum diterellitate monostearate; FIG. 2 is a graph showing the thermal weight loss of lanthanum diterephthalate.
Example 2
(1) A palmitic acid soap and a lanthanum palmitate solution were prepared according to the steps (1) to (5) of example 1, wherein the palmitic acid was used in an amount of 141 parts, the sodium bicarbonate was used in an amount of 50 parts, and the organic solvent was toluene.
(2) 40 parts of sodium hydroxide is dissolved in 400 parts of deionized water, 77 parts of phthalic anhydride is slowly added under the action of magnetic stirring, after full dissolution and reaction, sodium phthalate aqueous solution is injected into the three-neck flask by a peristaltic pump under the action of ultrasonic and mechanical stirring, and the reaction is continued for 2.5 hours after the dropwise addition is finished.
(3) Standing and layering the reaction solution, washing the upper layer 1 of the solution with a small amount of dilute sodium hydroxide aqueous solution, standing and layering to obtain a second upper layer 2 of the solution; heating and concentrating the lower layer 1 water solution, extracting and separating with toluene, distilling the extract and the upper layer 2 solution under reduced pressure, drying in a 120 deg.C oven, and grinding. The target product lanthanum monostearate is obtained, and the conversion rate is 85%.
Example 3
(1) A perfluoroheptanoic acid soap was prepared according to the step (1) of example 1, wherein perfluoroheptanoic acid was used in an amount of 100 parts, potassium carbonate was used in an amount of 18 parts, and an organic solvent was xylene and was used in an amount of 500 parts.
(2) Installing a reflux condenser and a mechanical stirring device, placing the reflux condenser and the mechanical stirring device in an ultrasonic dispersion system for ultrasonic dispersion, heating the ultrasonic dispersion system by using a self-made electric heating system, controlling the reaction temperature to be 50-80 ℃, and performing ultrasonic and mechanical stirring dispersion and reaction for 1 hour to obtain a perfluoro potassium heptanoate two-phase dispersion system.
(3) 86 parts of lanthanum chloride is weighed into a beaker, and 150 parts of deionized water is added for dissolution.
(4) Starting an ultrasonic dispersion and heating reaction system, controlling the reaction temperature to be 50-80 ℃, uniformly adding the lanthanum chloride aqueous solution into the three-neck flask through the peristaltic pump under the action of mechanical stirring, and continuing to react for 2 hours after the dropwise addition is finished.
(5) Dissolving 32 parts of potassium hydroxide in 250 parts of deionized water at room temperature, slowly adding 29 parts of pyromellitic dianhydride under the action of magnetic stirring, after full dissolution and reaction, pumping the aqueous solution into the three-neck flask by using a peristaltic pump under the action of ultrasonic waves and mechanical stirring simultaneously, and continuing to react for 3 hours after the dropwise addition is finished.
(6) Standing and layering the reaction solution, washing the upper layer 1 of the solution with a small amount of dilute potassium hydroxide aqueous solution, standing and layering to obtain a second upper layer 2 of the solution; heating and concentrating the lower layer 1 water solution, extracting and separating with xylene, distilling the extractive solution and the upper layer 2 solution under reduced pressure, oven drying in a 120 deg.C oven, and grinding. The target product of the bis-perfluoroheptanoic acid mono-lanthanum pyromellitic acid is obtained, and the conversion rate is 82%.
Example 4
(1) A soap of stearic acid and a lanthanum stearate solution were prepared according to the steps (1) to (5) of example 1, the organic solvent also being toluene.
(2) 40 parts of sodium hydroxide is dissolved in 600 parts of deionized water, 168.5 parts of 4, 4' -methylene-diphenyl-di- (1 ',2 ') -imide-di- (4 ',5 ') -phthalic acid (the reagent is synthesized by applicant laboratories) is slowly added under the action of magnetic stirring, after the sodium hydroxide is fully dissolved and reacted, the sodium hydroxide is injected into the three-neck flask by a peristaltic pump under the action of ultrasonic waves and mechanical stirring simultaneously, and the reaction is continued for 3 hours after the dropwise addition is finished. FIG. 3 is an infrared spectrum of 4, 4' -methylene-diphenyl-bis- (1 ',2 ') -imide-bis- (4 ',5 ') -phthalic acid.
(3) Standing and layering the reaction solution, washing the upper layer 1 of the solution with a small amount of dilute sodium hydroxide aqueous solution, standing and layering to obtain a second upper layer 2 of the solution; heating and concentrating the lower layer 1 water solution, extracting and separating with toluene, distilling the extract and the upper layer 2 solution under reduced pressure, drying in a 120 deg.C oven, and grinding. The target product, bis (4, 4' -methylene-diphenyl-bis- (1 ',2 ') -imide-bis- (4 ',5 ') -lanthanum bis (phthalate) was obtained with a 83% conversion. FIG. 4 is an infrared spectrum of lanthanum bis (4, 4' -methylene-diphenyl-bis- (1 ',2 ') -imide-bis- (4 ',5 ') -phthalate. FIG. 5 is a graph showing the thermogravimetric plot of lanthanum bis-phthalate-4, 4' -methylene-diphenyl-bis- (1 ',2 ') -imide-bis- (4 ',5 ') -bis-stearate.
The above description is only of the preferred embodiments of the present invention, and it should be noted that: it will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the principles of the invention and these are intended to be within the scope of the invention.
Claims (8)
1. A preparation method of heat-resistant rare earth composite organic carboxylate is characterized in that a two-phase ultrasonic and mechanical stirring mixing method is adopted to promote chemical reaction, and comprises the following steps:
(1) synthesis of fatty acid soap: under the conditions of ultrasonic and mechanical double mixing, dispersing and activating, fatty acid organic solvent solution and inorganic base or carbonate aqueous solution react at a two-phase microdroplet interface formed by the organic solvent and the aqueous solution to form fatty acid soap; the reaction is carried out on a two-phase interface, the reaction temperature is controlled to be 50-80 ℃, and the reaction time is 1.0-4.0 hours; the fatty acid is monobasic fatty acid selected from one or more of stearic acid, palmitic acid, myristic acid, lauric acid, perfluoroheptanoic acid and perfluorooctanoic acid;
(2) synthesis of rare earth salts of fatty acids: adding a rare earth inorganic salt aqueous solution into the dispersion liquid obtained in the step (1), and continuously carrying out the reaction of the rare earth inorganic salt and the fatty acid soap on a two-phase interface under the combined action of ultrasonic waves and mechanical stirring to form fatty acid rare earth salt; controlling the reaction temperature between 50 and 80 ℃, and continuing to react for 1.0 to 5.0 hours after the rare earth inorganic salt is added;
(3) synthesis of fatty acid and polybasic aromatic carboxylic acid composite rare earth salt: adding a polybasic aromatic acid salt aqueous solution into the dispersion liquid obtained in the step (2), continuously reacting with fatty acid rare earth salt under the combined action of ultrasonic waves and mechanical stirring to obtain fatty acid and polybasic aromatic carboxylic acid composite rare earth salt, controlling the reaction temperature to be between 50 and 80 ℃, and continuously reacting for 1.0 to 5.0 hours after the polybasic aromatic acid salt is added;
the polybasic aromatic acid salt is prepared from polybasic aromatic acid/anhydride and sodium hydroxide or potassium hydroxide, the polybasic aromatic acid/anhydride is phthalic acid/anhydride, pyromellitic acid/anhydride, N ' -p-phenylene-bis (1 ' ',2' ' -imido) -bis (4 ' ',5' ') -phthalic acid/anhydride, 4, 4' -etheroxy-diphenyl-bis- (1 ' ',2' ') -imide-bis- (4 ' ',5' ') -phthalic acid/anhydride, 4, 4' -methylene-diphenyl-bis- (1 ' ',2' ') -imido-bis- (4 ' ',5' ') -phthalic acid/anhydride.
2. The method for producing a heat-resistant rare earth complex organic carboxylate according to claim 1, characterized in that: the step (1) specifically comprises the following steps: respectively adding a fatty acid organic solvent solution and an inorganic base or a carbonate aqueous solution into a three-neck flask, installing a reflux condenser tube and a self-made heating device, and forming fatty acid soap under the combined action of ultrasonic waves and mechanical stirring.
3. The method for producing a heat-resistant rare earth complex organic carboxylate according to claim 1, characterized in that: the step (2) specifically comprises the following steps: on the basis of the synthesized fatty acid soap, a certain amount of rare earth inorganic salt aqueous solution is pumped into a reaction solution of a three-neck flask at a constant speed, the reaction is still carried out on a two-phase interface under the combined action of ultrasonic waves and mechanical stirring, the reaction temperature is controlled between 50 and 80 ℃, and the reaction is continuously carried out for 1.0 to 5.0 hours after the rare earth inorganic salt is added.
4. The method for producing a heat-resistant rare earth complex organic carboxylate according to claim 3, characterized in that: the step (3) specifically comprises the following steps: pumping the polybasic aromatic acid salt water solution into the reaction liquid of the three-neck flask at a constant speed, controlling the reaction temperature to be between 50 and 80 ℃, and continuing to react for 1.0 to 5.0 hours after the polybasic aromatic acid salt is added.
5. The method for producing a heat-resistant rare earth complex organic carboxylate according to claim 1, characterized in that: the method also comprises the following processing steps: standing and layering the reaction solution obtained in the step (3), washing the upper layer 1 liquid with a dilute alkali aqueous solution, standing and layering to obtain a second upper layer 2 solution; heating and concentrating the lower layer 1 aqueous solution, extracting and separating by using a non-water-soluble organic solvent, and distilling the extract and the solution of the upper layer 2 under reduced pressure to obtain the heat-resistant rare earth composite organic carboxylate.
6. The method for producing a heat-resistant rare earth composite organic carboxylate according to claim 5, characterized in that: the water-insoluble organic solvent is one or more of toluene, xylene, chloroform and heptane.
7. The method for producing a heat-resistant rare earth complex organic carboxylate according to claim 1, characterized in that: the rare earth inorganic salt is rare earth nitrate, rare earth hydrochloride or rare earth sulfate.
8. The method for producing a heat-resistant rare earth complex organic carboxylate according to claim 1, characterized in that: the inorganic alkali is sodium hydroxide or potassium hydroxide; the carbonate is sodium carbonate, sodium bicarbonate, potassium carbonate, or potassium bicarbonate.
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| CN88102641A (en) * | 1988-04-29 | 1988-12-07 | 吕福森 | Fatty acid rare earth compound and its technology |
| CN1052846A (en) * | 1989-12-28 | 1991-07-10 | 潘宏 | One-step nonaqueous synthesizing process of stearate |
| CN104327494A (en) * | 2014-09-11 | 2015-02-04 | 苏州大学 | Thermal oxidation stabilizing additive for polyamide |
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| CN88102641A (en) * | 1988-04-29 | 1988-12-07 | 吕福森 | Fatty acid rare earth compound and its technology |
| CN1052846A (en) * | 1989-12-28 | 1991-07-10 | 潘宏 | One-step nonaqueous synthesizing process of stearate |
| CN104327494A (en) * | 2014-09-11 | 2015-02-04 | 苏州大学 | Thermal oxidation stabilizing additive for polyamide |
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