CN112552170A - Preparation method of low-color tri (C8-10 alcohol) trimellitate - Google Patents
Preparation method of low-color tri (C8-10 alcohol) trimellitate Download PDFInfo
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- CN112552170A CN112552170A CN202011278651.9A CN202011278651A CN112552170A CN 112552170 A CN112552170 A CN 112552170A CN 202011278651 A CN202011278651 A CN 202011278651A CN 112552170 A CN112552170 A CN 112552170A
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 125000005591 trimellitate group Chemical group 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 239000000047 product Substances 0.000 claims abstract description 29
- 238000001914 filtration Methods 0.000 claims abstract description 24
- 239000002253 acid Substances 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 claims abstract description 18
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000011949 solid catalyst Substances 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 14
- 238000005886 esterification reaction Methods 0.000 claims abstract description 12
- 238000005086 pumping Methods 0.000 claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- 230000032050 esterification Effects 0.000 claims abstract description 10
- 239000003513 alkali Substances 0.000 claims abstract description 7
- 230000003647 oxidation Effects 0.000 claims abstract description 7
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000706 filtrate Substances 0.000 claims abstract description 6
- 238000001179 sorption measurement Methods 0.000 claims abstract description 6
- 239000003463 adsorbent Substances 0.000 claims abstract description 5
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims description 28
- 239000012295 chemical reaction liquid Substances 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 21
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 9
- 150000002148 esters Chemical class 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- GWHJZXXIDMPWGX-UHFFFAOYSA-N 1,2,4-trimethylbenzene Chemical compound CC1=CC=C(C)C(C)=C1 GWHJZXXIDMPWGX-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical compound [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 claims description 4
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 3
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 3
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 3
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 3
- 239000011736 potassium bicarbonate Substances 0.000 claims description 3
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 239000001119 stannous chloride Substances 0.000 claims description 3
- 235000011150 stannous chloride Nutrition 0.000 claims description 3
- 239000003930 superacid Substances 0.000 claims description 3
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 2
- 239000004927 clay Substances 0.000 claims description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 235000011181 potassium carbonates Nutrition 0.000 claims description 2
- 238000005070 sampling Methods 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000012824 chemical production Methods 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000002351 wastewater Substances 0.000 abstract description 2
- 239000012024 dehydrating agents Substances 0.000 abstract 1
- 239000007800 oxidant agent Substances 0.000 abstract 1
- 230000001590 oxidative effect Effects 0.000 abstract 1
- 238000011084 recovery Methods 0.000 abstract 1
- 238000001514 detection method Methods 0.000 description 7
- 239000004014 plasticizer Substances 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000010292 electrical insulation Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- CJGYQECZUAUFSN-UHFFFAOYSA-N oxygen(2-);tin(2+) Chemical compound [O-2].[Sn+2] CJGYQECZUAUFSN-UHFFFAOYSA-N 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- -1 n-octyl n-decyl Chemical group 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000009182 swimming Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000005691 triesters Chemical class 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
- C07C67/56—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
-
- 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
- C07C67/58—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
-
- 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
- C07C67/60—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to chemical modification
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of low-color-number tri (C8-10 alcohol) trimellitate, and relates to the technical field of organic chemical production. The method comprises the following steps: esterification: putting the raw materials into a reaction kettle, adding a water-carrying agent and a solid catalyst for reaction; dealcoholizing: opening vacuum, and pumping out most of excessive C8-10 alcohol; and (3) filtering: filtering while the solution is hot to recover the solid catalyst; and (3) oxidation: adding hydrogen peroxide; alkali washing: adding an alkaline reagent solution, standing for layering, and removing a water phase in the solution; dealcoholizing: pumping out residual water and C8-10 alcohol; adsorption: adding adsorbent and filter aid diatomite; and (3) filtering: filtering the decolored solution while the decolored solution is hot to obtain a filtrate, namely the finished product of trimellitic acid tri (C8-10 alcohol). The invention has the advantages that: by adopting the solid catalyst, the dehydrating agent and the oxidant, high-quality products with low color number, low acid value and high volume resistivity can be obtained, the generated wastewater is less, the recovery of the catalyst can be realized, and the aims of green, environmental protection and clean production are fulfilled.
Description
Technical Field
The invention relates to the technical field of organic chemical production, in particular to a preparation method of low-color-number tri (C8-10 alcohol) trimellitate.
Background
The trimellitic triester plasticizer is a plastic processing aid with very excellent performance, and the esters have the advantages of small volatility, extraction resistance, migration resistance and the like of polyester plasticizers, and have the characteristics of both monomer plasticizers and polyester plasticizers because the compatibility, the processability, the low-temperature performance and the like of the esters are similar to monomer phthalate. The heat-resistant and durable plasticizer is widely used in industrial and civil applications, and has been widely used in developed countries such as the united states and germany, and the plasticizer has been used not only in the plastic industry but also in automobile manufacturing and civil entertainment and sports fields.
The tri (C8-10 alcohol) trimellitate is also called tri (n-octyl n-decyl) trimellitate, has comprehensive performance superior to that of the traditional plasticizer, and can endow the product with good light resistance, heat resistance, aging resistance and electrical insulation performance. The product produced by the product has the characteristics of good water resistance and extraction resistance, low toxicity, aging resistance and excellent electrical insulation performance, so the product is widely applied to the industrial fields of toy films, wire and cable insulation materials, automobile interior decoration materials, refrigerator sealing strips, swimming pool decoration materials and the like, and the product comprehensively meets all strict requirements of REACH detection.
At present, strong acids such as sulfuric acid and sulfonic acid are mostly adopted as catalysts in the process of synthesizing trimellitic acid tri (C8-10 alcohol) ester reported in literature, although the catalytic activity is high, the esterification temperature is low, the cost is low, the corrosion to equipment is serious, and impurities generated by side reactions during esterification are many, so that the problems of deepening the color and luster of products, higher acid value, lower volume resistivity and the like are caused, thereby affecting the product quality.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of low-color tri (C8-10 alcohol) trimellitate, which can solve the problems of serious corrosion to equipment when strong acid is used as a catalyst, more impurities generated by side reaction during esterification, deepened product color, higher acid value, lower volume resistivity and influence on product quality.
In order to solve the technical problems, the technical scheme of the invention is as follows: the method comprises the following steps:
s1, esterification: the method comprises the following steps of mixing trimellitic anhydride and C8-10 alcohol according to a molar ratio of 1: 3.5-5.0, putting into a reaction kettle, putting under the protection of nitrogen, adding a water-carrying agent, heating to 120-130 ℃ under stirring until solid trimellitic anhydride is completely dissolved, starting to discharge water from the reaction liquid when the temperature is raised to 170 ℃, adding a solid catalyst after keeping the liquid discharge for 15-90 min, wherein the using amount of the solid catalyst is 0.01-0.2% of the total mass of the reaction charge, finally heating to 190-210 ℃, starting timing and heat preservation, detecting the acid value of the reaction liquid after 2 hours, sampling once every 0.5 hour or 1 hour until the acid value is less than 0.1mgKOH/g, and finishing the esterification reaction;
s2, dealcoholization: stopping heating, starting vacuum at the vacuum degree of-0.095 MPa, pumping out most of excessive C8-10 alcohol by using the residual temperature of the reaction liquid under stirring, and vacuumizing for 0.5-1.5 h;
s3, filtering: when the temperature of the reaction solution is reduced to 115-125 ℃, filtering and recovering the solid catalyst while the reaction solution is hot;
s4, oxidation: adding pre-prepared 12% hydrogen peroxide into the filtered reaction solution at 70-100 ℃, and stirring for 0.5-1.5 h;
s5, alkali washing: adding a prepared alkaline reagent solution at the temperature, stirring for 0.5-1.5 h, standing for layering, and removing a water phase in the solution;
s6, dealcoholization: slowly heating the product phase to 170-180 ℃, stirring under negative pressure, and pumping out residual water and C8-10 alcohol;
s7, adsorption: cooling the reaction liquid to 70-90 ℃, adding an adsorbent accounting for 0.1-1.0% of the product amount and filter aid diatomite into the reaction liquid, and uniformly stirring and decoloring for 0.5-3 h;
s8, filtering: filtering the decolored solution while the decolored solution is hot to obtain a filtrate, namely the finished product of trimellitic acid tri (C8-10 alcohol).
The weight ratio of the components in the reaction system is as follows:
further, the solid catalyst of S1 in the step is sodium bisulfite, stannous oxide, stannous chloride, solid super acid SO4 2-/ZrO、SO4 2-/ZnO、SO4 2-/Fe3O4The water-carrying agent is one or more of toluene, xylene, pseudocumene and mesitylene.
Further, the alkaline agent in step S5 is one or more of potassium carbonate, potassium bicarbonate, sodium carbonate, and sodium bicarbonate.
Further, the adsorbent in step S7 is one or more of activated carbon, clay, and activated alumina.
The invention has the advantages that: the catalyst replaces the traditional concentrated sulfuric acid and sulfonic acid catalysts with solid catalysts, so that side reactions can be reduced, the solid catalysts can be directly recycled in the subsequent treatment process, less waste water is generated, and the aims of environmental protection and clean production are fulfilled;
because the molecular weight of the raw material C8-10 alcohol is larger, the boiling point is higher, the esterification can be completed at lower temperature under the action of a small amount of water-carrying agent, the reaction time is shortened, the energy is saved, and the acid value and the color number of the product are reduced;
hydrogen peroxide is added in the post-treatment step, and the color of the product can be further reduced to No. 15-20 mainly by virtue of the oxidation and decoloration effects of the hydrogen peroxide, so that the product quality is improved;
and (3) extracting and layering the water phase obtained by alkali washing in the post-treatment step to remove salts dissolved in the water phase, so that the product has the characteristic of high volume resistivity, and the product quality is improved.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to specific embodiments. The following examples are presented to enable one of ordinary skill in the art to more fully understand the present invention and are not intended to limit the scope of the embodiments described herein.
Example one
(1) Esterification: putting 115.3g of trimellitic anhydride and 389.44g of C8-10 alcohol as raw materials into a reaction kettle, putting under the protection of nitrogen, adding 50g of dimethylbenzene as a water-carrying agent, heating to 120 ℃ under stirring to completely dissolve solid trimellitic anhydride, heating to 170 ℃ to enable reaction liquid to begin to produce water, keeping the reaction liquid for 30min, adding 0.5g of stannous oxide, finally heating to 195 ℃, keeping the temperature for 3h at the beginning of timing, and measuring the acid value of the reaction liquid to be 0.056 mgKOH/g;
(2) dealcoholizing: stopping heating, starting vacuum at the vacuum degree of-0.095 MPa, pumping out most of excessive C8-10 alcohol by using the residual temperature of the reaction solution under stirring, and vacuumizing for 1 h;
(3) and (3) filtering: when the temperature of the reaction solution is reduced to about 120 ℃, filtering and recovering the solid catalyst while the reaction solution is hot;
(4) and (3) oxidation: adding 20.0g of pre-prepared 12% hydrogen peroxide into the filtered reaction solution at the temperature of 80 ℃, and stirring for 0.5 h;
(5) alkali washing: adding 20.0g of prepared sodium bicarbonate solution with the mass fraction of 2% at the temperature, stirring for 0.5h, standing for layering, and removing a water phase in the solution;
(6) dealcoholizing: slowly heating the product phase to 180 ℃, stirring under negative pressure and pumping out residual water and C8-10 alcohol;
(7) adsorption: cooling the reaction liquid to 80 ℃, adding 3.5g of argil and 3.5g of diatomite into the reaction liquid, and uniformly stirring the mixture for decoloring for 0.5 h;
(8) and (3) filtering: filtering the decolored solution while the decolored solution is hot to obtain filtrate, namely the finished product of trimellitic acid tri (C8-10 alcohol) ester, wherein the acid value is 0.028mgKOH/g (the acid value detection method is determined according to the method of GB/T1668-9Omega m (detection according to GB/T1672-1988).
Example two
(1) Esterification: putting 115.3g of trimellitic anhydride and 346.2g of C8-10 alcohol into a reaction kettle, putting under the protection of nitrogen, adding 60g of trimellitic anhydride as a water-carrying agent, heating to about 120 ℃ under stirring to completely dissolve solid trimellitic anhydride, discharging reaction liquid at about 170 ℃, keeping the liquid discharged for 60min, and then adding solid super acid SO4 2-1.0g of ZrO, finally heating to 200 ℃, and measuring the acid value of the reaction solution to be 0.045mgKOH/g when the time and the heat preservation are started for 4 hours;
(2) dealcoholizing: stopping heating, starting vacuum at a vacuum degree of-0.095 MPa, pumping out most of excessive C8-10 alcohol by using the residual temperature of the reaction solution under stirring, and vacuumizing for 0.5 h;
(3) and (3) filtering: when the temperature of the reaction solution is reduced to about 120 ℃, filtering and recovering the solid catalyst while the reaction solution is hot;
(4) and (3) oxidation: adding 15.0g of pre-prepared 12% hydrogen peroxide into the filtered reaction solution at 90 ℃, and stirring for 0.5 h;
(5) alkali washing: at the temperature, 20.0g of prepared sodium carbonate solution with the mass fraction of 1 percent is added, stirred for 0.5h, stood for demixing, and the water phase in the mixture is removed;
(6) dealcoholizing: slowly heating the product phase to 180 ℃, and pumping out residual water and C8-10 alcohol under the condition of negative pressure stirring;
(7) adsorption: cooling the reaction liquid to 90 ℃, adding 3.0g of activated carbon and 3.0g of diatomite into the reaction liquid, and uniformly stirring the mixture for decoloring for 0.5 h;
(8) and (3) filtering: filtering the decolored solution while the decolored solution is hot to obtain filtrate, namely the finished product of trimellitic acid tri (C8-10 alcohol) ester, the acid value is 0.020mgKOH/g (the acid value detection method is determined according to the method of GB/T1668-9Omega m (detection according to GB/T1672-1988).
EXAMPLE III
(1) Esterification: putting 115.3g of raw material trimellitic anhydride and 302.9g of C8-10 alcohol into a reaction kettle, putting under the protection of nitrogen, adding 70g of mesitylene as a water-carrying agent, heating to about 120 ℃ under stirring to completely dissolve the solid trimellitic anhydride, starting to discharge water from reaction liquid at about 170 ℃, keeping the liquid for 45min, then adding 0.8g of solid stannous chloride, finally heating to 205 ℃, starting to time and preserve heat for 3.5h, and measuring the acid value of the reaction liquid to be 0.062 mgKOH/g;
(2) dealcoholizing: stopping heating, starting vacuum at a vacuum degree of-0.095 MPa, pumping out most of excessive C8-10 alcohol by using the residual temperature of the reaction solution under stirring, and vacuumizing for 0.5 h;
(3) and (3) filtering: when the temperature of the reaction solution is reduced to about 120 ℃, filtering and recovering the solid catalyst while the reaction solution is hot;
(4) and (3) oxidation: adding 10.0g of pre-prepared 12% hydrogen peroxide into the filtered reaction solution at 85 ℃, and stirring for 0.5 h;
(5) alkali washing: at the temperature, 20.0g of prepared potassium bicarbonate solution with the mass fraction of 2 percent is added, stirred for 1 hour, stood for demixing, and the water phase in the solution is removed;
(6) dealcoholizing: slowly heating the product phase to 180 ℃, and pumping out residual water and C8-10 alcohol under the condition of negative pressure stirring;
(7) adsorption: cooling the reaction liquid to 85 ℃, adding 3.5g of activated alumina and 3.5g of diatomite into the reaction liquid, and uniformly stirring the mixture for decoloring for 0.5 h;
(8) and (3) filtering: filtering the decolorized solution while it is hot to obtain filtrate (trimellitic acid)Acid tri (C8-10 alcohol) ester, acid value of 0.030mgKOH/g (the acid value detection method is determined according to the method of GB/T1668-2008), color number of 20 (determined according to the regulation of GB/T1664-1995), volume resistivity of 14.3 x 109Omega m (detection according to GB/T1672-1988).
TABLE 1 comparison of the masses of the components of examples 1 to 3
To compare the properties of the tri (C8-10 alcohol) trimellitate prepared using the above formulation, it was subjected to the relevant tests, and the test results are shown in Table 2.
TABLE 2 test results of tri (C8-10 alcohol) trimellitate prepared in examples 1 to 3
| Item | Example 1 | Example 2 | Example 3 |
| Acid value in the reaction | 0.056mgKOH/g | 0.045mgKOH/g | 0.062mgKOH/g |
| Acid value of the finished product | 0.028mgKOH/g | 0.020mgKOH/g | 0.030mgKOH/g |
| Color number | Number 15 | Number 15 | No. 20 |
| Volume resistivity | 15.2×109Ωm | 17.2××109Ωm | 14.3××109Ωm |
As can be seen from the table above, the prepared trimellitic acid tri (C8-10 alcohol) ester has low color number and acid value, high volume resistivity and high product quality, and in addition, compared with examples 1 to 3, the performances of example 2 are better than those of the other two examples, so that example 2 is the best example.
The foregoing shows and describes the general principles and features of the present invention, together with the advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (5)
1. A preparation method of low-color trimellitic acid tri (C8-10 alcohol) ester is characterized by comprising the following steps: the method comprises the following steps:
s1, esterification: the method comprises the following steps of mixing trimellitic anhydride and C8-10 alcohol according to a molar ratio of 1: 3.5-5.0, putting into a reaction kettle, putting under the protection of nitrogen, adding a water-carrying agent, heating to 120-130 ℃ under stirring until solid trimellitic anhydride is completely dissolved, starting to discharge water from the reaction liquid when the temperature is raised to 170 ℃, adding a solid catalyst after keeping the liquid discharge for 15-90 min, wherein the using amount of the solid catalyst is 0.01-0.2% of the total mass of the reaction charge, finally heating to 190-210 ℃, starting timing and heat preservation, detecting the acid value of the reaction liquid after 2 hours, sampling once every 0.5 hour or 1 hour until the acid value is less than 0.1mgKOH/g, and finishing the esterification reaction;
s2, dealcoholization: stopping heating, starting vacuum at the vacuum degree of-0.095 MPa, pumping out most of excessive C8-10 alcohol by using the residual temperature of the reaction liquid under stirring, and vacuumizing for 0.5-1.5 h;
s3, filtering: when the temperature of the reaction solution is reduced to 115-125 ℃, filtering and recovering the solid catalyst while the reaction solution is hot;
s4, oxidation: adding pre-prepared 12% hydrogen peroxide into the filtered reaction solution at 70-100 ℃, and stirring for 0.5-1.5 h;
s5, alkali washing: adding a prepared alkaline reagent solution at the temperature, stirring for 0.5-1.5 h, standing for layering, and removing a water phase in the solution;
s6, dealcoholization: slowly heating the product phase to 170-180 ℃, stirring under negative pressure, and pumping out residual water and C8-10 alcohol;
s7, adsorption: cooling the reaction liquid to 70-90 ℃, adding an adsorbent accounting for 0.1-1.0% of the product amount and filter aid diatomite into the reaction liquid, and uniformly stirring and decoloring for 0.5-3 h;
s8, filtering: filtering the decolored solution while the decolored solution is hot to obtain a filtrate, namely the finished product of trimellitic acid tri (C8-10 alcohol).
2. The process according to claim 1 for the preparation of low color tri (C8-10 alcohol) trimellitate in the form of a mixture comprising: the weight ratio of the components in the reaction system is as follows:
3. according to the rightThe process for producing a low-color tri (C8-10 alcohol) trimellitate according to claim 1 or 2, wherein: the solid catalyst of S1 in the step is sodium bisulfite, stannous oxide, stannous chloride, solid super acid SO4 2-/ZrO、SO4 2-/ZnO、SO4 2-/Fe3O4The water-carrying agent is one or more of toluene, xylene, pseudocumene and mesitylene.
4. The process for producing a low-color tri (C8-10 alcohol) trimellitate according to claim 1 or 2, wherein: the alkaline reagent in the step S5 is one or more of potassium carbonate, potassium bicarbonate, sodium carbonate and sodium bicarbonate.
5. The process for producing a low-color tri (C8-10 alcohol) trimellitate according to claim 1 or 2, wherein: the adsorbent in the step S7 is one or more of activated carbon, pottery clay and activated alumina.
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| CN114805928A (en) * | 2022-03-10 | 2022-07-29 | 江苏森禾化工科技有限公司 | Metabenzene bio-based plasticizer |
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