CN106008218A - Method for synthesizing tri (2-ethylhexyl) trimellitate - Google Patents
Method for synthesizing tri (2-ethylhexyl) trimellitate Download PDFInfo
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- CN106008218A CN106008218A CN201610336676.7A CN201610336676A CN106008218A CN 106008218 A CN106008218 A CN 106008218A CN 201610336676 A CN201610336676 A CN 201610336676A CN 106008218 A CN106008218 A CN 106008218A
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- ester
- trimellitate
- ethyl hexyl
- methanol
- tri trimellitate
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- 238000000034 method Methods 0.000 title claims abstract description 23
- 230000002194 synthesizing effect Effects 0.000 title abstract 2
- KRADHMIOFJQKEZ-UHFFFAOYSA-N Tri-2-ethylhexyl trimellitate Chemical compound CCCCC(CC)COC(=O)C1=CC=C(C(=O)OCC(CC)CCCC)C(C(=O)OCC(CC)CCCC)=C1 KRADHMIOFJQKEZ-UHFFFAOYSA-N 0.000 title description 9
- 150000002148 esters Chemical class 0.000 claims abstract description 86
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 72
- -1 2-ethylhexyl Chemical group 0.000 claims abstract description 48
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000005886 esterification reaction Methods 0.000 claims abstract description 18
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 238000007670 refining Methods 0.000 claims abstract description 7
- MJHNUUNSCNRGJE-UHFFFAOYSA-N trimethyl benzene-1,2,4-tricarboxylate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C(C(=O)OC)=C1 MJHNUUNSCNRGJE-UHFFFAOYSA-N 0.000 claims description 48
- 125000005591 trimellitate group Chemical group 0.000 claims description 44
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 230000015572 biosynthetic process Effects 0.000 claims description 10
- 150000007524 organic acids Chemical class 0.000 claims description 10
- 238000003786 synthesis reaction Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 230000018044 dehydration Effects 0.000 claims description 5
- 238000006297 dehydration reaction Methods 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 5
- 238000000605 extraction Methods 0.000 claims description 5
- 238000009413 insulation Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000000376 reactant Substances 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 230000004044 response Effects 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 12
- 239000004808 2-ethylhexylester Substances 0.000 abstract description 9
- 230000032050 esterification Effects 0.000 abstract description 6
- 239000013067 intermediate product Substances 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract 2
- NPSJHQMIVNJLNN-UHFFFAOYSA-N 2-ethylhexyl 4-nitrobenzoate Chemical compound CCCCC(CC)COC(=O)C1=CC=C([N+]([O-])=O)C=C1 NPSJHQMIVNJLNN-UHFFFAOYSA-N 0.000 abstract 1
- 238000005809 transesterification reaction Methods 0.000 abstract 1
- JNXDCMUUZNIWPQ-UHFFFAOYSA-N trioctyl benzene-1,2,4-tricarboxylate Chemical compound CCCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCC)C(C(=O)OCCCCCCCC)=C1 JNXDCMUUZNIWPQ-UHFFFAOYSA-N 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000004014 plasticizer Substances 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 3
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000003808 methanol extraction Methods 0.000 description 3
- 238000009835 boiling Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 1
- 102000004882 Lipase Human genes 0.000 description 1
- 108090001060 Lipase Proteins 0.000 description 1
- 239000004367 Lipase Substances 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 1
- 239000002649 leather substitute Substances 0.000 description 1
- 235000019421 lipase Nutrition 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000019635 sulfation Effects 0.000 description 1
- 238000005670 sulfation reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 125000005590 trimellitic acid group 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
- C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
-
- 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
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
The invention relates to a method for synthesizing trioctyl trimellitate (2-ethylhexyl) by methyl esterification of trimellitic anhydride, which comprises the steps of taking trimellitic anhydride and methanol as raw materials, rectifying after the methyl esterification reaction to obtain a trimethyl ester intermediate product with high purity and low color number, then carrying out transesterification reaction on trimethyl ester and 2-ethylhexyl ester, and finally refining to obtain a trioctyl ester product with high purity and low color number. The invention has the advantages that: the requirements on the content and color number of the raw material trimellitic anhydride are low, the content of the obtained trioctyl ester is high, the color number is low, and the quality of the obtained trioctyl ester is better than that of the trioctyl ester obtained by directly esterifying trimellitic anhydride and 2-ethylhexanol.
Description
Technical field
The invention belongs to the safety in production field of organic solvent, particularly to the method for one synthesis tri trimellitate (2-ethyl hexyl) ester.
Background technology
Tri trimellitate (2-ethyl hexyl) ester (TOTM) is a kind of trimellitic acid esters developed by the U.S. end of the sixties, is a kind of electrical property and the most excellent plasticizer of hot property.Its volatility is low, and resistance to ag(e)ing, resistance to extractable and heat resistance are good, and has good insulating properties, therefore can be used for 105 DEG C of level heat proof cable material and the production of 10kV polyvinyl chloride cable material.In addition, it also is used as pulse and the impregnated material of low voltage power capacitor and synthetic leather plasticizer etc..In the U.S., having the TOTM of 78% for wires and cables industry, account for the 13% of electric wire plasticizer total amount, traditional dioctyl phthalate (DOP) the most only accounts for the 6% of total consumption.China's wires and cables industry currently integrates with international standard, supporting in the urgent need to this high-performance plasticizer of TOTM, and traditional DOP, DBP cannot meet requirement at a lot of aspects.
Abroad, the production and consumption of TOTM increases quickly, and it is one of fastest-rising kind in U.S.'s plasticizer, has many producers all to have TOTM to produce, such as Meng Shan all, BASF, USS etc..China only has minimal amount of TOTM and produces, and raw material depends on greatly import, continues to use backward Sulfation technique, and the quality of product and quantity far from can meet user's request.Although the production technology of the primary raw material trimellitic anhydride of TOTM has started to research as far back as the end of the sixties, but on producing, reality is almost blank so far.Therefore, develop and produce TOTM and trimellitic anhydride for Appropriate application petroleum resources, promote the development of fine chemistry industry, adapt to the needs of the industrial departments such as motor, electric power, plastics, aerospace, there is huge realistic meaning and far-reaching significance.
Current employing trimellitic anhydride and 2-Ethylhexyl Alcohol direct esterification generate tri trimellitate (2-ethyl hexyl) ester, and final refining produces.It is difficult to tri trimellitate (2-ethyl hexyl) ester product is played decisive influence by raw material trimellitic anhydride in the existing product mode of production, in trimellitic anhydride, weight composition impurity is mainly phthalic anhydride, M-phthalic acid, p-phthalic acid, pyromellitic dianhydride, benzene-1 etc., also corresponding monooctyl ester can be generated with 2-Ethylhexyl Alcohol reaction, and boiling point is higher cannot be removed by rectification, ester content is between 95-96% to generally yield tri trimellitate (2-ethyl hexyl), and content is relatively low.Trimellitic anhydride color number is high, increases refined material activated carbon dosage, and cannot effectively reduce the color number of tri trimellitate (2-ethyl hexyl) ester.
For the deficiency in terms of the process that industry exists when producing tri trimellitate (2-ethyl hexyl) ester and to difficult problems such as raw material trimellitic anhydride prescription are high, it is necessary to invent a kind of new tri trimellitate (2-ethyl hexyl) Lipase absobed method to overcome disadvantages mentioned above.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of method of new synthesis tri trimellitate (2-ethyl hexyl) ester, product tri trimellitate (2-ethyl hexyl) ester content can be improved, effectively reduce tri trimellitate (2-ethyl hexyl) ester color number, and refined material activated carbon dosage can be reduced.
For solving above-mentioned technical problem, a kind of method that the technical scheme is that synthesis tri trimellitate (2-ethyl hexyl) ester, its innovative point is: with trimellitic anhydride and methanol as raw material, first pass through trimellitic anhydride and methanol under catalyst, carry out esterification reaction of organic acid generation trimethyl trimellitate, then obtained the trimethyl trimellitate of the low color number of high-purity by rectification, finally the trimethyl trimellitate after rectification and 2-Ethylhexyl Alcohol are carried out ester exchange and by being refining to obtain tri trimellitate (2-ethyl hexyl) ester product.
Further, described method specifically comprises the following steps that
(1) esterification reaction of organic acid: trimellitic anhydride, methanol and catalyst tetraisopropyl titanate are added reactor with mass ratio 100:100:0.3, it is heated to 60-65 DEG C under normal pressure, the first alcohol and water of generation being distilled out reactor, adds fresh methanol simultaneously and enter reactor, the response time is 3 hours；
(2) rectification: esterification reaction of organic acid liquid is squeezed in airtight rectifying still, under vacuum conditions, is slowly heated this tower bottoms, at tower reactor state 180～205 DEG C, 500Pa, tower top state 193～195 DEG C, 150pa, carries out rectification under conditions of reflux ratio 1:2～2:1；Trimethyl trimellitate is extracted by rectification；
(3) ester exchange: by trimethyl trimellitate, 2-Ethylhexyl Alcohol and catalyst tetraisopropyl titanate join in ester interchange vessel according to mass ratio 100:100-500:0.1-1, are slowly heated under normal pressure, are heated to 220 DEG C from room temperature, insulation 2.5h, ester exchange reaction terminates；
(4) desolventizing: under not heated condition, gradually steps up ester interchange vessel vacuum to 500Pa, and temperature solvent removal in time being down to 150 DEG C for 220 DEG C completes；
(5) hydrolyst: under normal temperature and pressure, adds the distilled water of reactant liquor quality 1% in ester interchange vessel, reacts 2h, and hydrolyst terminates；Then being evacuated to 500Pa, when being heated to 100 DEG C, dehydration terminates；
(6) refined: in ester interchange vessel, to add proper amount of active carbon and kieselguhr, stir 30min, filtered while hot when 50 DEG C, obtain tri trimellitate (2-ethyl hexyl) ester product.
Further, in described step (1), methanol is added pipe and should be extended below reaction liquid level, and methanol additional amount should keep consistent with produced quantity, makes liquid level in still keep balance.
Further, applying nitrogen that replacement of oxygen in still falls temperature reaction again in described step (3) before ester exchange reaction, reaction temperature-rise period can not be too fast, is to slowly warm up to 220 DEG C in 2.5h.
Further, in described step (6), extraction temperature is in the range of positive and negative 5 DEG C of 50 DEG C, and beyond temperature range, too conference of fluctuating affects refining effect.
Further, described tri trimellitate (2-ethyl hexyl) ester content can reach more than 99.0%, color 10#-15#.
It is an advantage of the current invention that:
(1) method that the present invention synthesizes tri trimellitate (2-ethyl hexyl) ester, can use the trimellitic anhydride that content is relatively low and color number is poor as the raw materials for production of tri trimellitate (2-ethyl hexyl) ester, trimellitic anhydride defective work is carried out effective recycling；Meanwhile, the synthetic method of the present invention can improve product tri trimellitate (2-ethyl hexyl) ester content, effectively reduces tri trimellitate (2-ethyl hexyl) ester color number, and can reduce refined material activated carbon dosage；
(2) method that the present invention synthesizes tri trimellitate (2-ethyl hexyl) ester, utilize the advantage that the trimethyl trimellitate boiling point of trimellitic anhydride and methanol esterification reaction generation is relatively low, trimethyl trimellitate and other weight composition impurities can be separated by rectification, also reduce trimethyl trimellitate color number while improving content, then obtained tri trimellitate (2-ethyl hexyl) ester of the low color number of high-load by ester exchange.
Detailed description of the invention
A kind of method that three monooctyl esters are prepared in trimellitic anhydride esterification, with trimellitic anhydride and methanol as raw material, by obtaining the trimethyl trimellitate intermediate product of the low color number of high-purity after rectification after esterification reaction of organic acid, then by trimethyl trimellitate and 2-Ethylhexyl Alcohol ester exchange reaction, finally by tri trimellitate (2-ethyl hexyl) the ester product being refining to obtain the low color number of high-purity.
The following examples can make professional and technical personnel that the present invention is more fully understood, but the most therefore limits the present invention among described scope of embodiments.
Embodiment
1
The method of tri trimellitate (2-ethyl hexyl) ester is prepared in one trimellitic anhydride esterification, and it specifically comprises the following steps that
The first step, successively joins in reactor by trimellitic anhydride 300g, methanol 300g and catalyst tetraisopropyl titanate 0.9g, reacting by heating still is heated to 65 DEG C, and reactant liquor seethes with excitement, by the water generated and methanol extraction, add fresh methanol simultaneously, make methanol additional amount keep consistent with produced quantity.Response time 3h, the conversion ratio obtaining trimethyl trimellitate is 97%；
Second step, rectification: esterification reaction of organic acid liquid is squeezed in airtight rectifying still.Under vacuum conditions, it is slowly heated this tower bottoms, at tower reactor state 180～205 DEG C, 500Pa, tower top state 193～195 DEG C, 150pa, under conditions of reflux ratio 1:2～2:1, carries out rectification；Trimethyl trimellitate intermediate product, trimethyl extraction ratio 97% is obtained by rectification；
3rd step, ester exchange: trimethyl trimellitate 390g, 2-Ethylhexyl Alcohol 1170g and catalyst tetraisopropyl titanate 1.2g are joined in ester interchange vessel, displace with nitrogen and be slowly heated under air in still, normal pressure, be heated to 220 DEG C from room temperature, insulation 2.5h, ester exchange reaction terminates；
4th step, desolventizing: under not heated condition, gradually step up ester interchange vessel vacuum to 500Pa, temperature solvent removal in time being down to 150 DEG C for 220 DEG C completes；
5th step, hydrolyst: under normal temperature and pressure, ester interchange vessel adds 7.5g distilled water, stirs 2h, hydrolyst terminates.Being evacuated to 500Pa, when being heated to 100 DEG C, dehydration terminates；
6th step, refined: in ester interchange vessel, to add 4g activated carbon and 2g kieselguhr, stir 30min, filtered while hot when 50 DEG C ± 5 DEG C, obtain tri trimellitate (2-ethyl hexyl) ester product.
In the present embodiment, tri trimellitate (2-ethyl hexyl) ester content 99.2% prepared, color 12#, the industrial department use requirements to tri trimellitate (2-ethyl hexyl) ester such as motor, electric power, plastics, aerospace can be met.
Embodiment
2
The method of tri trimellitate (2-ethyl hexyl) ester is prepared in one trimellitic anhydride esterification, and it specifically comprises the following steps that
The first step, successively joins in reactor by trimellitic anhydride 300g, methanol 600g and catalyst tetraisopropyl titanate 1.2g, reacting by heating still is heated to 60 DEG C, and reactant liquor seethes with excitement, by the water generated and methanol extraction, add fresh methanol simultaneously, make methanol additional amount keep consistent with produced quantity.Response time 3h, the conversion ratio obtaining trimethyl trimellitate is 96%；
Second step, rectification: esterification reaction of organic acid liquid is squeezed in airtight rectifying still.Under vacuum conditions, it is slowly heated this tower bottoms, at tower reactor state 180～205 DEG C, 500Pa, tower top state 193～195 DEG C, 150pa, under conditions of reflux ratio 1:2～2:1, carries out rectification；Trimethyl trimellitate intermediate product, trimethyl extraction ratio 96% is obtained by rectification；
3rd step, ester exchange: trimethyl trimellitate 390g, 2-Ethylhexyl Alcohol 800g and catalyst tetraisopropyl titanate 1.5g are joined in ester interchange vessel, displace with nitrogen and be slowly heated under air in still, normal pressure, be heated to 220 DEG C from room temperature, insulation 2.5h, ester exchange reaction terminates；
4th step, desolventizing: under not heated condition, gradually step up ester interchange vessel vacuum to 500Pa, temperature solvent removal in time being down to 150 DEG C for 220 DEG C completes；
5th step, hydrolyst: under normal temperature and pressure, ester interchange vessel adds 7.5g distilled water, stirs 1.5h, hydrolyst terminates.Being evacuated to 500Pa, when being heated to 100 DEG C, dehydration terminates；
6th step, refined: in ester interchange vessel, to add 4g activated carbon and 2g kieselguhr, stir 1h, filtered while hot when 50 DEG C ± 5 DEG C, obtain tri trimellitate (2-ethyl hexyl) ester product.
In the present embodiment, tri trimellitate (2-ethyl hexyl) ester content 99.4% prepared, color 12#, the industrial department use requirements to tri trimellitate (2-ethyl hexyl) ester such as motor, electric power, plastics, aerospace can be met.
Embodiment
3
The method of tri trimellitate (2-ethyl hexyl) ester is prepared in one trimellitic anhydride esterification, and it specifically comprises the following steps that
The first step, successively joins in reactor by trimellitic anhydride 300g, methanol 400g and catalyst tetraisopropyl titanate 0.9g, reacting by heating still is heated to 65 DEG C, and reactant liquor seethes with excitement, by the water generated and methanol extraction, add fresh methanol simultaneously, make methanol additional amount keep consistent with produced quantity.Response time 3h, the conversion ratio obtaining trimethyl trimellitate is 97%；
Second step, rectification: esterification reaction of organic acid liquid is squeezed in airtight rectifying still.Under vacuum conditions, it is slowly heated this tower bottoms, at tower reactor state 180～205 DEG C, 500Pa, tower top state 193～195 DEG C, 150pa, under conditions of reflux ratio 1:2～2:1, carries out rectification；Trimethyl trimellitate intermediate product, trimethyl extraction ratio 97% is obtained by rectification；
3rd step, ester exchange: trimethyl trimellitate 390g, 2-Ethylhexyl Alcohol 1400g and catalyst tetraisopropyl titanate 1.5g are joined in ester interchange vessel, displace with nitrogen and be slowly heated under air in still, normal pressure, be heated to 220 DEG C from room temperature, insulation 2h, ester exchange reaction terminates；
4th step, desolventizing: under not heated condition, gradually step up ester interchange vessel vacuum to 500Pa, temperature solvent removal in time being down to 150 DEG C for 220 DEG C completes；
5th step, hydrolyst: under normal temperature and pressure, ester interchange vessel adds 7.5g distilled water, stirs 1h, hydrolyst terminates.Being evacuated to 500Pa, when being heated to 100 DEG C, dehydration terminates；
6th step, refined: in ester interchange vessel, to add 4g activated carbon and 2g kieselguhr, stir 30min, filtered while hot when 50 DEG C ± 5 DEG C, obtain tri trimellitate (2-ethyl hexyl) ester product.
In the present embodiment, tri trimellitate (2-ethyl hexyl) ester content 99.5% prepared, color 12#, the industrial department use requirements to tri trimellitate (2-ethyl hexyl) ester such as motor, electric power, plastics, aerospace can be met.
The ultimate principle of the present invention and principal character and advantages of the present invention have more than been shown and described.Skilled person will appreciate that of the industry; the present invention is not restricted to the described embodiments; the principle that the present invention is simply described described in above-described embodiment and description; without departing from the spirit and scope of the present invention; the present invention also has various changes and modifications, and these changes and improvements both fall within scope of the claimed invention.Claimed scope is defined by appending claims and equivalent thereof.
Claims (6)
1. the method for synthesis tri trimellitate (2-ethyl hexyl) ester, it is characterized in that: with trimellitic anhydride and methanol as raw material, first pass through trimellitic anhydride and methanol under catalyst, carry out esterification reaction of organic acid generation trimethyl trimellitate, then obtained the trimethyl trimellitate of the low color number of high-purity by rectification, finally the trimethyl trimellitate after rectification and 2-Ethylhexyl Alcohol are carried out ester exchange and by being refining to obtain tri trimellitate (2-ethyl hexyl) ester product.
The method of synthesis tri trimellitate the most according to claim 1 (2-ethyl hexyl) ester, it is characterised in that: described method specifically comprises the following steps that
(1) esterification reaction of organic acid: trimellitic anhydride, methanol and catalyst tetraisopropyl titanate are added reactor with mass ratio 100:100:0.3, it is heated to 60-65 DEG C under normal pressure, the first alcohol and water of generation being distilled out reactor, adds fresh methanol simultaneously and enter reactor, the response time is 3 hours；
(2) rectification: esterification reaction of organic acid liquid is squeezed in airtight rectifying still, under vacuum conditions, is slowly heated this tower bottoms, at tower reactor state 180～205 DEG C, 500Pa, tower top state 193～195 DEG C, 150pa, carries out rectification under conditions of reflux ratio 1:2～2:1；Trimethyl trimellitate is extracted by rectification；
(3) ester exchange: by trimethyl trimellitate, 2-Ethylhexyl Alcohol and catalyst tetraisopropyl titanate join in ester interchange vessel according to mass ratio 100:100-500:0.1-1, are slowly heated under normal pressure, are heated to 220 DEG C from room temperature, insulation 2.5h, ester exchange reaction terminates；
(4) desolventizing: under not heated condition, gradually steps up ester interchange vessel vacuum to 500Pa, and temperature solvent removal in time being down to 150 DEG C for 220 DEG C completes；
(5) hydrolyst: under normal temperature and pressure, adds the distilled water of reactant liquor quality 1% in ester interchange vessel, reacts 2h, and hydrolyst terminates；Then being evacuated to 500Pa, when being heated to 100 DEG C, dehydration terminates；
(6) refined: in ester interchange vessel, to add proper amount of active carbon and kieselguhr, stir 30min, filtered while hot when 50 DEG C, obtain tri trimellitate (2-ethyl hexyl) ester product.
The method of synthesis tri trimellitate the most according to claim 2 (2-ethyl hexyl) ester, it is characterised in that: in described step (1), methanol is added pipe and should be extended below reaction liquid level, and methanol additional amount should keep consistent with produced quantity, makes liquid level in still keep balance.
The method of synthesis tri trimellitate the most according to claim 2 (2-ethyl hexyl) ester, it is characterized in that: described step (3) is applied nitrogen replacement of oxygen in still is fallen temperature reaction again before ester exchange reaction, reaction temperature-rise period can not be too fast, is to slowly warm up to 220 DEG C in 2.5h.
The method of synthesis tri trimellitate the most according to claim 2 (2-ethyl hexyl) ester, it is characterised in that: in described step (6), extraction temperature is in the range of positive and negative 5 DEG C of 50 DEG C, and beyond temperature range, too conference of fluctuating affects refining effect.
The method of synthesis tri trimellitate the most according to claim 1 and 2 (2-ethyl hexyl) ester, it is characterised in that: described tri trimellitate (2-ethyl hexyl) ester content can reach more than 99.0%, color 10#-15#.
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| CN108892612A (en) * | 2018-08-15 | 2018-11-27 | 南通百川新材料有限公司 | Method for preparing trioctyl trimellitate by ester exchange method |
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| WO2020019271A1 (en) * | 2018-07-27 | 2020-01-30 | 南通百川新材料有限公司 | Method for preparing trimellitic acid triester by means of continuous esterification method |
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| CN108752202A (en) * | 2018-07-04 | 2018-11-06 | 南通百川新材料有限公司 | Method for preparing trimellitic acid triester by continuous esterification method |
| WO2020019271A1 (en) * | 2018-07-27 | 2020-01-30 | 南通百川新材料有限公司 | Method for preparing trimellitic acid triester by means of continuous esterification method |
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| US11365357B2 (en) | 2019-05-24 | 2022-06-21 | Eastman Chemical Company | Cracking C8+ fraction of pyoil |
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| US12031091B2 (en) | 2019-05-24 | 2024-07-09 | Eastman Chemical Company | Recycle content cracked effluent |
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