CN111574366B - Method for synthesizing triisodecyl trimellitate - Google Patents
Method for synthesizing triisodecyl trimellitate Download PDFInfo
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- CN111574366B CN111574366B CN202010570341.8A CN202010570341A CN111574366B CN 111574366 B CN111574366 B CN 111574366B CN 202010570341 A CN202010570341 A CN 202010570341A CN 111574366 B CN111574366 B CN 111574366B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
- B01J31/0275—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 also containing elements or functional groups covered by B01J31/0201 - B01J31/0269
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/49—Esterification or transesterification
Abstract
The invention relates to the technical field of triisodecyl trimellitate, and particularly discloses a method for synthesizing triisodecyl trimellitate, which comprises the following steps: esterification reaction, negative pressure dealcoholization, alkali washing and water washing, adsorption decoloration, hot filtration, oxidation decoloration, secondary adsorption decoloration and secondary hot filtration. The catalyst used in the invention is compound inorganic acid ester, which not only can improve the conversion efficiency of raw materials, but also the prepared triisodecyl trimellitate product has the characteristics of high ester content, transparent color and luster and stable quality; meanwhile, the obtained product is further decolored, so that the chromaticity of the product can be further reduced, the esterification temperature is obviously reduced, and the effects of reducing the acid value and reducing the energy consumption are well achieved.
Description
Technical Field
The invention relates to the technical field of triisodecyl trimellitate, in particular to a method for synthesizing triisodecyl trimellitate.
Background
Trimellitate plasticizers are essential plasticizers with high heat resistance and weather resistance. Due to the low volatility, the low migration property, the good electronic resistance and the advantages of processability, aging resistance, heat resistance, cold resistance and the like. Can be widely used for PVC products with high requirements on oil resistance, water resistance and heat resistance, can improve the processing performance of the products, and completely meets the requirements of green chemical industry and sustainable development.
With the increasing concern of various countries on the harm of the plasticizer to human bodies in recent years, the development of novel nontoxic environment-friendly plasticizers is becoming the key point of various countries. The traditional plasticizer, such as the phthalate plasticizer, has extremely high volatility and mobility, can be dissolved out in the processes of processing, heating, packaging and the like, and belongs to carcinogenic substances. The triisodecyl trimellitate has good performances in the aspects of volatility, migration resistance, low and high temperature resistance and electrical property, and is a novel nontoxic environment-friendly plasticizer. Therefore, the new environment-friendly plasticizer is used for replacing the traditional plasticizer, and is a necessary trend in the modern plasticizer industry.
Disclosure of Invention
The invention aims to provide a method for synthesizing triisodecyl trimellitate plasticizer, which has the advantages of simple process, safe and environment-friendly production process, and capability of synthesizing products with low chroma, low acid value and high ester content.
In order to solve the technical problem, the invention provides a method for synthesizing triisodecyl trimellitate, which is characterized by comprising the following steps of:
s1, esterification: raw materials of trimellitic anhydride and isodecyl alcohol are mixed according to a molar ratio of 1: 4.2-5.5, adding 65-90 g of water-carrying agent into the reaction kettle, uniformly stirring under the protection of nitrogen, heating to 115-140 ℃ to completely dissolve trimellitic anhydride in isodecyl alcohol to obtain a reaction solution, heating to 160-175 ℃ to start water discharge of the reaction solution, keeping the water discharge for 15-50 min, and then adding a catalyst with the amount of 0.04-0.1% of the feeding amount; finally, directly heating to 200-220 ℃ and preserving heat for 3-5 h; finishing esterification when the acid value of the reaction solution to be detected is less than or equal to 0.1 mgKOH/g;
s2, negative pressure dealcoholization: exhausting the isodecyl alcohol in the reaction system under the negative pressure vacuum condition at 190-210 ℃, wherein the negative pressure exhausting time is 1.5-2.5 h;
s3, alkali washing and water washing: cooling the reaction liquid after the negative pressure dealcoholization to 75-95 ℃, adding liquid caustic soda, and stirring for 0.5-1.5 h to destroy the unhydrolyzed catalyst;
s4, adsorption decoloring: cooling the reaction liquid to 70-90 ℃, adding 0.05-0.2% of adsorbent, and uniformly stirring for decoloring for 1.5-2.5 h;
s5, filtering while hot: filtering the decolored solution obtained in the step S4 while the decolored solution is hot, and adding a filter aid to obtain a filtrate which is a crude product;
s6, oxidation decoloring: adding an oxidant accounting for 1-3% of the total amount of the product at 70-100 ℃, oxidizing for 1.5-2.5 h, and then pumping out the residual water in the solution under the negative pressure vacuum condition;
s7, secondary adsorption decoloring: cooling the oxidized crude product of S6 to 70-90 ℃, adding 0.05-0.2% of adsorbent, and uniformly stirring and decoloring for 1.5-2.5 h;
s8, filtering the mixture twice while the mixture is hot: and (3) filtering the product subjected to secondary adsorption and decoloration while the product is hot, and adding a filter aid to obtain a filtrate, namely the triisodecyl trimellitate.
Further, the weight ratio of the raw materials and the auxiliary materials is as follows: trimellitic anhydride 15-20 wt%, isodecyl alcohol 55-80 wt%, water carrying agent 5-15 wt%, catalyst 0.04-0.1 wt%, alkali reagent 0.01-0.1 wt%, adsorbent 0.05-0.2 wt% and oxidant 0.5-1 wt%.
Further, the catalyst in S1 is one or more of tetraisopropyl titanate, tetrapropyl titanate, tetrabutyl titanate, and stannous chloride, and the water-carrying agent is one or more of pseudocumene, mesitylene, and xylene.
Further, the alkaline agent in S2 is one or more of sodium carbonate, sodium bicarbonate and potassium bicarbonate.
Further, the adsorbents in S4 and S7 are one or more of activated carbon, activated alumina and activated soil.
Further, the filter aids in the S5 and the S8 are both one or more of diatomite and perlite.
Further, the oxidant of S6 is one or more of hydrogen peroxide, ammonium persulfate, and sodium carbonate peroxide.
The invention has the beneficial effects that:
1. the catalyst used in the invention is compound inorganic acid ester, replaces the traditional concentrated sulfuric acid and sulfonic acid catalyst, not only can improve the conversion efficiency of raw materials, but also the prepared triisodecyl trimellitate product has the characteristics of high ester content, bright color and stable quality.
2. The obtained product is further decolored, so that the chroma of the product can be further reduced from original No. 50 to No. 15-20, and the effect is obvious.
3. Because the melting point of the 2-propyl-1-heptanol is higher, the bumping of the solution can occur, and after a small amount of water-carrying agent is added for buffering, the esterification temperature is obviously reduced, thereby well playing the role of reducing the acid value and reducing the energy consumption.
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 derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example one
Putting 121g of trimellitic anhydride into an esterification reaction kettle, adding 504g of 2-propyl-1-heptanol, adding 90g of mesitylene, heating to 115 ℃ for dissolution, heating to 160 ℃ for keeping liquid for 50min, adding 1g of tetrabutyl titanate, heating to 220 ℃ and keeping the temperature for 5h, and finishing esterification when the acid value of the reaction liquid to be detected is less than or equal to 0.1 mgKOH/g;
at the temperature of 195 ℃, the residual isodecyl alcohol in the reaction system is pumped out in vacuum at negative pressure, and the pumping time is 2 hours;
reducing the temperature to 75 ℃, preparing 0.1g of sodium bicarbonate solution dissolved in 21g of water, adding the solution into the reaction solution, and stirring for 0.5h to destroy the unhydrolyzed catalyst in the reaction solution;
then adding 0.5g of active soil, uniformly stirring and decoloring for 1.5h, then filtering, and adding a small amount of perlite as a filter aid during filtering to obtain a filtrate;
adding 5g of ammonium persulfate at 75 ℃, oxidizing for 2.5h, then pumping out water in the solution under the condition of negative pressure vacuum, then adding 0.5g of active soil, uniformly stirring and decoloring for 1.5h, then adding pearl salt, and filtering to finally obtain 206g of the target product of triisodecyl trimellitate.
The acid value of the obtained triisodecyl trimellitate was 0.09mgKOH/g (the acid value detection method was determined according to the method of GB 1668-2008), the color number was 15 (determined according to the specification of GB 1664-.
Example two
(1) Putting 115g of trimellitic anhydride into an esterification reaction kettle, adding 465g of 2-propyl-1-heptanol, adding 65g of trimellitic anhydride, heating to 140 ℃ to dissolve, heating to 175 ℃ to keep liquid out for 15min, adding 2g of tetrapropyl titanate, finally heating to 215 ℃ and preserving heat for 3h, and finishing esterification when the acid value of the reaction liquid to be detected is less than or equal to 0.1 mgKOH/g;
(2) under the condition of 200 ℃, vacuum pumping is carried out under negative pressure to completely pump out the residual isodecyl alcohol in the reaction system, and the pumping time is 1.5 h;
(3) reducing the temperature to 95 ℃, preparing a solution of 0.2g of sodium bicarbonate dissolved in 32g of water, adding the solution into the reaction solution, and stirring for 1 hour to destroy the unhydrolyzed catalyst in the reaction solution;
(4) then adding 1.5g of activated alumina, uniformly stirring and decoloring for 2h, and then adding a small amount of diatomite as a filter aid during filtering to obtain a filtrate;
(5) 4g of sodium carbonate peroxide is added at the temperature of 95 ℃ for oxidation for 2h, then water in the solution is extracted under the negative pressure vacuum condition, and then the operation (4) is carried out, so that 217g of the target product of the triisodecyl trimellitate, the acid value of 0.086mgKOH/g (the acid value detection method is determined according to the method of GB 1668-2008), the color number of 20 (determined according to the specification of GB 1664-.
EXAMPLE III
(1) Putting 109g of trimellitic anhydride into an esterification reaction kettle, adding 475g of 2-propyl-1-heptanol, adding 85g of xylene, heating to 130 ℃ to dissolve, heating to 165 ℃ to keep liquid out for 45min, adding 1.5g of tetraisopropyl titanate, finally heating to 205 ℃ and preserving heat for 3.5h, and finishing esterification when the acid value of the reaction liquid to be detected is less than or equal to 0.1 mgKOH/g;
(2) at the temperature of 195 ℃, the residual isodecyl alcohol in the reaction system is pumped out in vacuum at negative pressure, and the pumping time is 2.5 h;
(3) the temperature is reduced to 85 ℃, 0.15g of potassium bicarbonate dissolved in 35g of water is prepared and added into the reaction liquid, and the mixture is stirred for 1.5h to destroy the catalyst which is not hydrolyzed in the reaction liquid.
(4) Then adding 2g of activated carbon, uniformly stirring and decoloring for 2h, and then adding a small amount of diatomite as a filter aid during filtering to obtain a filtrate;
(5) adding 3.5g of hydrogen peroxide at 85 ℃, oxidizing for 1.5h, then extracting water in the solution under the negative pressure vacuum condition, and then carrying out the operation (4) to obtain 221g of the target product of the triisodecyl trimellitate, the acid value is 0.078mgKOH/g (the acid value detection method is determined according to the method of GB 1668-2008), the color number is No. 15 (determined according to the specification of GB 1664-.
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 (7)
1. A synthetic method of triisodecyl trimellitate is characterized by comprising the following steps:
s1, esterification: raw materials of trimellitic anhydride and isodecyl alcohol are mixed according to a molar ratio of 1: 4.2-5.5, adding 65-90 g of water-carrying agent into the reaction kettle, uniformly stirring under the protection of nitrogen, heating to 115-140 ℃ to completely dissolve trimellitic anhydride in isodecyl alcohol to obtain a reaction solution, heating to 160-175 ℃ to start water discharge of the reaction solution, keeping the water discharge for 15-50 min, and then adding a catalyst with the amount of 0.04-0.1% of the feeding amount; finally, directly heating to 200-220 ℃ and preserving heat for 3-5 h; finishing esterification when the acid value of the reaction solution to be detected is less than or equal to 0.1 mgKOH/g;
s2, negative pressure dealcoholization: exhausting the isodecyl alcohol in the reaction system under the negative pressure vacuum condition at 190-210 ℃, wherein the negative pressure exhausting time is 1.5-2.5 h;
s3, alkali washing and water washing: cooling the reaction liquid after the negative pressure dealcoholization to 75-95 ℃, adding liquid caustic soda, and stirring for 0.5-1.5 h to destroy the unhydrolyzed catalyst;
s4, adsorption decoloring: cooling the reaction liquid to 70-90 ℃, adding 0.05-0.2% of adsorbent, and uniformly stirring for decoloring for 1.5-2.5 h;
s5, filtering while hot: filtering the decolored solution obtained in the step S4 while the decolored solution is hot, and adding a filter aid to obtain a filtrate which is a crude product;
s6, oxidation decoloring: adding an oxidant accounting for 1-3% of the total amount of the product at 70-100 ℃, oxidizing for 1.5-2.5 h, and then pumping out the residual water in the solution under the negative pressure vacuum condition;
s7, secondary adsorption decoloring: cooling the oxidized crude product of S6 to 70-90 ℃, adding 0.05-0.2% of adsorbent, and uniformly stirring and decoloring for 1.5-2.5 h;
s8, filtering the mixture twice while the mixture is hot: and (3) filtering the product subjected to secondary adsorption and decoloration while the product is hot, and adding a filter aid to obtain a filtrate, namely the triisodecyl trimellitate.
2. The method for synthesizing triisodecyl trimellitate according to claim 1, wherein the weight ratio of the raw materials to the auxiliary materials is as follows: trimellitic anhydride 15-20 wt%, isodecyl alcohol 55-80 wt%, water carrying agent 5-15 wt%, catalyst 0.04-0.1 wt%, alkali reagent 0.01-0.1 wt%, adsorbent 0.05-0.2 wt% and oxidant 0.5-1 wt%.
3. The method for synthesizing triisodecyl trimellitate according to claim 1, wherein the catalyst in S1 is one or more of tetraisopropyl titanate, tetrapropyl titanate, tetrabutyl titanate and stannous chloride, and the water-carrying agent is one or more of pseudocumene, mesitylene and xylene.
4. The method for synthesizing triisodecyl trimellitate according to claim 1, wherein the basic reagent in S2 is one or more of sodium carbonate, sodium bicarbonate and potassium bicarbonate.
5. The method for synthesizing triisodecyl trimellitate according to claim 1, wherein the adsorbents in S4 and S7 are one or more of activated carbon, activated alumina and activated soil.
6. The method for synthesizing triisodecyl trimellitate according to claim 5, wherein the filter aid in S5 and S8 is one or more of diatomite and perlite.
7. The method for synthesizing triisodecyl trimellitate according to claim 1, wherein the oxidant of S6 is one or more of hydrogen peroxide, ammonium persulfate, and sodium carbonate peroxide.
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| CN113214079A (en) * | 2021-05-26 | 2021-08-06 | 浙江皇星化工股份有限公司 | Production method of DPHP |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102924280A (en) * | 2012-10-25 | 2013-02-13 | 浙江皇马科技股份有限公司 | Preparation method of trimellitate |
| CN103694121A (en) * | 2013-11-28 | 2014-04-02 | 浙江海利业科技有限公司 | Novel synthetic process of tris (2-propylheptyl) trimellitate |
| CN108892614A (en) * | 2018-08-30 | 2018-11-27 | 江苏正丹化学工业股份有限公司 | A kind of synthetic method of triisononyl trimellitate plasticizer |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102924280A (en) * | 2012-10-25 | 2013-02-13 | 浙江皇马科技股份有限公司 | Preparation method of trimellitate |
| CN103694121A (en) * | 2013-11-28 | 2014-04-02 | 浙江海利业科技有限公司 | Novel synthetic process of tris (2-propylheptyl) trimellitate |
| CN108892614A (en) * | 2018-08-30 | 2018-11-27 | 江苏正丹化学工业股份有限公司 | A kind of synthetic method of triisononyl trimellitate plasticizer |
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