CN110372504B - Method for producing polybasic acid ester by recovering light components from side product of meta-anhydride - Google Patents
Method for producing polybasic acid ester by recovering light components from side product of meta-anhydride Download PDFInfo
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- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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Abstract
The invention belongs to the technical field of organic compound preparation, and particularly discloses a method for producing polybasic acid ester by recovering light components from a by-product of metanhydride, which comprises the steps of introducing nitrogen into a reaction kettle, mixing crushed metanhydride light component residues and isooctyl alcohol serving as reaction raw materials, and adding activated carbon and soft water; and then carrying out initial heating, reaction, acid measurement, negative pressure dealcoholization, neutralization treatment, negative pressure impurity removal and detection. The method for synthesizing the polybasic acid ester plasticizer comprises the steps of esterification, acid measurement and neutralization, dealcoholization, low-boiling-point substance removal and the like, and the obtained plasticizer has the characteristics of light color and high quality, and is low in acid value and low in water content; meanwhile, the operation process flow is short, simple and feasible, no corrosion is caused to equipment, the reaction time is short, and the method is environment-friendly, safe and easy for industrial production.
Description
Technical Field
The invention belongs to the technical field of organic compound preparation, and particularly relates to a method for producing polybasic acid ester by recovering light components from a side product of meta-anhydride, which is a synthetic route of polybasic acid anhydride in refined residue of the meta-anhydride and relates to a preparation method of mixed polybasic acid ester plasticizer synthesized by esterification of light component residue at the top of a rectifying tower of the meta-anhydride and polyhydric alcohol.
Background
Plasticizers are polymeric additives that are widely used in industry. The plasticizer is used in plastic processing, and can modify or soften the plastic and increase the plasticity, flexibility, stretchability or expansibility and the like of the plastic. At present, the plasticizer industry has been developed into a plasticizer based on petrochemical industry and taking phthalate as a core, which is widely applied to the plastic and paint industries. However, the phthalate-containing plastic products can cause the dissolution of phthalate and have certain harm in the processes of processing, heating, packaging and containing.
The trimellitate plasticizer has a plurality of excellent performances such as compatibility, electrical property, plasticizing performance, low-temperature performance, migration resistance, water extraction resistance, thermal stability and the like, and the plasticizing efficiency and the processing performance are similar to those of phthalate plasticizers. The product is widely used for 105 ℃ and 125 ℃ heat-resistant wire and cable materials, automotive interior materials and other products requiring heat resistance and durability, such as plates, sheets, gaskets and the like.
Therefore, research and development of more trimellitate plasticizers with excellent performance have very important significance in the future plastic manufacturing industry.
Disclosure of Invention
The invention aims to provide a method for producing polybasic acid ester by recycling light components from a by-product of partial anhydride, which is used for producing a mixed polybasic acid ester plasticizer with better performance indexes such as acid value, heating decrement, resistivity and the like, and has simple process flow and low raw material cost.
In order to solve the technical problem, the invention provides a method for producing polybasic acid ester by recovering light components from a side product of meta-anhydride, which comprises the following steps:
s1, a feeding stage: introducing nitrogen into a reaction kettle, mixing the crushed light-component metaanhydride residue and isooctanol serving as reaction raw materials, and adding active carbon and soft water;
s2, an initial heating stage: heating to 120-130 ℃, stirring and refluxing for 1.5h to completely dissolve polybasic acid anhydride in isooctyl alcohol;
s3, reaction stage: heating to 160-180 ℃ within 10-30 minutes, adding tetraisopropyl titanate, stirring at constant temperature for reflux reaction for 1-1.5h, and simultaneously separating out water generated in the esterification process;
s4, sampling and detecting acidity: taking the reaction liquid for acid ester detection, and finishing the esterification reaction when the acid value is less than 0.1 percent;
s5, negative pressure dealcoholization: closing octanol reflux, carrying out negative pressure dealcoholization, continuously heating to 210-215 ℃, keeping the temperature unchanged, and refluxing for 1.5-2.5 h;
s6, cooling and neutralizing treatment: after dealcoholization is finished, introducing nitrogen, cooling to 90 ℃ under normal pressure, adding a sodium carbonate solution, and stirring for 0.5h;
s7, negative pressure impurity removal: after neutralization, stopping introducing nitrogen, vacuumizing, heating to 150-160 ℃, and removing the mixed ester and the dicarboxylic acid ester in the reaction system under negative pressure for 1.5 hours;
s8, sampling and detecting: and then stopping vacuumizing, introducing nitrogen, stopping heating when the system is recovered to the normal pressure state, starting cooling, sampling, and detecting the index of the product.
Furthermore, the activated carbon in the S1 accounts for 0.3-0.8% of the light component, and the soft water accounts for 0.1-0.15% of the light component.
Specifically, the tetraisopropyl titanate in S3 accounts for 0.05-0.15% of the light component.
Further, the reflux amount of octanol in S3 is 8-10m 3 /h。
Furthermore, the sodium carbonate solution in S6 accounts for 0.05-0.1% of the light components.
Furthermore, the indexes of the product in S8 are that the chroma is less than or equal to 40, the acid value (calculated by KOH)/(mg/g) is less than or equal to 0.15, the volume resistivity/(109 omega. M) is more than or equal to 10, and the water content is less than or equal to 0.1 percent.
The beneficial effects of the invention are: the method for synthesizing the polybasic acid ester plasticizer comprises the steps of esterification, acid measurement and neutralization, dealcoholization, low-boiling-point substance removal and the like, and the obtained plasticizer has the characteristics of light color and high quality, and is low in acid value and low in water content; meanwhile, the operation process flow is short, simple and feasible, no corrosion is caused to equipment, the reaction time is short, and the method is environment-friendly, safe and easy for industrial production.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
In the embodiment of the invention, the method for producing the polybasic acid ester by recovering the light components by using the side product of the metaanhydride specifically comprises the following steps:
s1, a feeding stage: introducing nitrogen into a reaction kettle, mixing crushed light-component metaanhydride residues and isooctyl alcohol serving as reaction raw materials, wherein the molar ratio is 1:3 to 4.5, simultaneously adding active carbon accounting for 0.3 to 0.8 percent of the light component and soft water accounting for 0.1 to 0.15 percent of the light component;
s2, an initial heating stage: heating to 120-130 ℃, stirring and refluxing for 1.5h to completely dissolve the polybasic acid anhydride in the isooctyl alcohol;
s3, a reaction stage: heating to 160-180 ℃ within 10-30 minutes, adding tetraisopropyl titanate accounting for 0.05-0.15% of the light component, and controlling the reflux of octanol to 8-10m 3 Stirring at constant temperature for reflux reaction for 1-1.5h, and simultaneously separating out water generated in the esterification process;
s4, sampling and detecting acidity: taking the reaction liquid for acid ester detection, and finishing the esterification reaction when the acid value is less than 0.1 percent;
s5, negative pressure dealcoholization: closing octanol reflux, carrying out negative pressure dealcoholization, continuously heating to 210-215 ℃, keeping the temperature unchanged, and refluxing for 1.5-2.5 h;
s6, cooling and neutralizing treatment: after the dealcoholization is finished, introducing nitrogen, reducing the temperature to 90 ℃ under normal pressure, adding 0.05-0.1% of sodium carbonate solution, and stirring for about 0.5h;
s7, negative pressure impurity removal: after neutralization, stopping introducing nitrogen, vacuumizing, heating to 150-160 ℃, and removing the mixed ester and the dicarboxylic acid ester in the reaction system under negative pressure for 1.5 hours;
s8, sampling and detecting: stopping vacuumizing, introducing nitrogen, stopping heating when the system is recovered to the normal pressure state, starting cooling, sampling, and detecting the index of the product, wherein the index of the product is that the chromaticity is less than or equal to 40; the acid value (calculated by KOH)/(mg/g) is less than or equal to 0.15; the volume resistivity/(109 omega. M) is more than or equal to 10; the water content is less than or equal to 0.1 percent.
Example one
(1) A feeding stage: introducing nitrogen into a reaction kettle, taking crushed light-component metaanhydride residues and isooctyl alcohol as reaction raw materials, and reacting according to the weight ratio of 1:3, and simultaneously adding activated carbon accounting for 0.3 percent of the light component and soft water accounting for 0.1 percent of the light component;
(2) An initial heating stage: heating to 120-130 ℃, stirring and refluxing for 1.5h to completely dissolve the polybasic acid anhydride in the isooctyl alcohol;
(3) A reaction stage: heating to 160-180 ℃ within 10-30 minutes, adding tetraisopropyl titanate accounting for 0.05 percent of the light component, and controlling the reflux quantity of octanol to be 8-10m 3 Stirring at constant temperature for reflux reaction for 1-1.5h, and simultaneously separating out water generated in the esterification process;
(4) Sampling and detecting acidity: taking the reaction liquid for acid ester detection, and finishing the esterification reaction when the acid value is less than 0.1 percent;
(5) Negative pressure dealcoholization: closing octanol reflux, carrying out negative pressure dealcoholization, continuously heating to 210-215 ℃, keeping the temperature unchanged, and refluxing for 1.5-2.5 h;
(6) Cooling and neutralizing treatment stage: after dealcoholization is finished, introducing nitrogen, cooling to 90 ℃ under normal pressure, adding 0.05 sodium carbonate solution, and stirring for about 0.5h;
(7) Negative pressure impurity removal: after neutralization, stopping introducing nitrogen, vacuumizing, heating to 150-160 ℃, and removing the mixed ester and the dicarboxylic acid ester in the reaction system under negative pressure for 1.5 hours;
(8) Sampling and detecting: and then stopping vacuumizing, introducing nitrogen, stopping heating when the system is recovered to the normal pressure state, starting cooling, sampling, and detecting the indexes of the product, wherein the indexes of the obtained product are 35% of chroma, 0.08% of acid value, 12.4% of resistivity and 0.034% of moisture.
Example two
(1) A feeding stage: introducing nitrogen into a reaction kettle, taking crushed light-component metaanhydride residues and isooctanol as reaction raw materials, and mixing the raw materials according to the proportion of 1:4, simultaneously adding activated carbon accounting for 0.5 percent of the light component and soft water accounting for 0.12 percent of the light component;
(2) An initial heating stage: heating to 120-130 ℃, stirring and refluxing for 1.5h to completely dissolve the polybasic acid anhydride in the isooctyl alcohol;
(3) A reaction stage: heating to 160-180 ℃ within 10-30 minutes, adding tetraisopropyl titanate accounting for 0.1 percent of the light component, and controlling the reflux quantity of octanol to be 8-10m 3 Stirring at constant temperature for reflux reaction for 1-1.5h, and simultaneously separating out water generated in the esterification process;
(4) Sampling and detecting acidity: taking the reaction liquid for acid ester detection, and completing the esterification reaction when the acid value is less than 0.1%;
(5) Negative pressure dealcoholization: closing octanol reflux, carrying out negative pressure dealcoholization, continuously heating to 210-215 ℃, keeping the temperature unchanged, and refluxing for 1.5-2.5 h;
(6) Cooling and neutralizing treatment stage: after the dealcoholization is finished, introducing nitrogen, cooling to 90 ℃ under normal pressure, adding 0.08% sodium carbonate solution, and stirring for about 0.5h;
(7) Negative pressure impurity removal: after neutralization, stopping introducing nitrogen, vacuumizing, heating to 150-160 ℃, and removing the mixed ester and the dicarboxylic acid ester in the reaction system under negative pressure for 1.5 hours;
(8) Sampling and detecting: and then stopping vacuumizing, introducing nitrogen, stopping heating when the system is recovered to the normal pressure state, starting cooling, sampling, and detecting the indexes of the product, wherein the indexes of the obtained product are 30% of chroma, 0.051 of acid value, 14.6% of resistivity and 0.025% of moisture.
EXAMPLE III
(1) A feeding stage: introducing nitrogen into a reaction kettle, taking crushed light-component metaanhydride residues and isooctyl alcohol as reaction raw materials, and reacting according to the weight ratio of 1:4.5, and simultaneously adding activated carbon accounting for 0.8 percent of the light component and soft water accounting for 0.15 percent of the light component;
(2) An initial heating stage: heating to 120-130 ℃, stirring and refluxing for 1.5h to completely dissolve the polybasic acid anhydride in the isooctyl alcohol;
(3) A reaction stage: heating to 160-180 ℃ within 10-30 minutes, adding tetraisopropyl titanate accounting for 0.15 percent of the light component, and controlling the reflux amount of octanol to 8-10m 3 H, stirring at constant temperatureReflux reaction is carried out for 1-1.5h, and water generated in the esterification process is separated out;
(4) Sampling and detecting acidity: taking the reaction liquid for acid ester detection, and finishing the esterification reaction when the acid value is less than 0.1 percent;
(5) Negative pressure dealcoholization: closing octanol reflux, carrying out negative pressure dealcoholization, continuously heating to 210-215 ℃, keeping the temperature unchanged, and refluxing for 1.5-2.5 h;
(6) Cooling and neutralizing treatment stage: after the dealcoholization is finished, introducing nitrogen, cooling to 90 ℃ under normal pressure, adding 0.1% sodium carbonate solution, and stirring for about 0.5h;
(7) Negative pressure impurity removal: after neutralization, stopping introducing nitrogen, vacuumizing, heating to 150-160 ℃, and removing the mixed ester and the dicarboxylic acid ester in the reaction system under negative pressure for 1.5 hours;
(8) Sampling and detecting: and then stopping vacuumizing, introducing nitrogen, stopping heating when the system is recovered to the normal pressure state, starting cooling, sampling, and detecting the indexes of the product, wherein the indexes of the obtained product are 30% of chroma, 0.03% of acid value, 16.89% of resistivity and 0.02% of moisture.
The above disclosure is only one preferred embodiment of the present invention, and certainly should not be construed as limiting the scope of the invention, which is defined by the claims and their equivalents.
Claims (5)
1. A method for producing polybasic acid ester by using light components recovered from a by-product of partial anhydride is characterized by comprising the following steps:
s1, feeding: introducing nitrogen into a reaction kettle, mixing crushed light-component metaanhydride residue and isooctanol serving as reaction raw materials, and simultaneously adding activated carbon and soft water, wherein the activated carbon accounts for 0.3-0.8% of the light components, and the soft water accounts for 0.1-0.15% of the light components;
s2, an initial heating stage: heating to 120-130 ℃, stirring and refluxing for 1.5h to completely dissolve the polybasic acid anhydride in the isooctyl alcohol;
s3, reaction stage: heating to 160-180 ℃ within 10-30 minutes, adding tetraisopropyl titanate, stirring at constant temperature for reflux reaction for 1-1.5h, and simultaneously separating out water generated in the esterification process;
s4, sampling and detecting acidity stage: taking the reaction liquid for acid ester detection, and completing the esterification reaction when the acid value is less than 0.1%;
s5, a negative pressure dealcoholization stage: closing octanol reflux, carrying out negative pressure dealcoholization, continuously heating to 210-215 ℃, keeping the temperature unchanged, and refluxing for 1.5-2.5 h;
s6, cooling and neutralizing treatment: after dealcoholization is finished, introducing nitrogen, cooling to 90 ℃ under normal pressure, adding a sodium carbonate solution, and stirring for 0.5h;
s7, negative pressure impurity removal stage: after neutralization, stopping introducing nitrogen, vacuumizing, heating to 150-160 ℃, and removing the mixed ester and the dicarboxylic acid ester in the reaction system under negative pressure for 1.5 hours;
s8, sampling detection: and then stopping vacuumizing, introducing nitrogen, stopping heating when the system is recovered to the normal pressure state, starting cooling, sampling, and detecting the index of the product.
2. The method for producing polybasic acid esters from light components recovered as by-products of partial anhydride according to claim 1, wherein the tetraisopropyl titanate in S3 is 0.05 to 0.15% of the light components.
3. The method for producing polybasic acid ester by using light components recovered from by-product of metaanhydride as claimed in claim 1, wherein the reflux amount of isooctanol in S3 is 8-10m 3 /h。
4. The method for producing polybasic acid esters using a light component recovered as a by-product of a partial anhydride according to claim 1, wherein the sodium carbonate solution in S6 is 0.05 to 0.1% of the light component.
5. The method for producing polybasic acid ester by using the light component recovered from the by-product of the partial anhydride as claimed in claim 1, wherein the index chroma of the product in S8 is less than or equal to 40, and the volume resistivity/(10) 9 Omega m) is more than or equal to 10, and the water content is less than or equal to 0.1 percent.
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