CN100363328C - Trimellitic tri(C8-9 ol)ester preparation method - Google Patents
Trimellitic tri(C8-9 ol)ester preparation method Download PDFInfo
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- CN100363328C CN100363328C CNB2005100953658A CN200510095365A CN100363328C CN 100363328 C CN100363328 C CN 100363328C CN B2005100953658 A CNB2005100953658 A CN B2005100953658A CN 200510095365 A CN200510095365 A CN 200510095365A CN 100363328 C CN100363328 C CN 100363328C
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- alcohol
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Abstract
The present invention relates to a trimellitic acid tri (C<8-10> alcohol) ester preparation method, which belongs to the technical field of plasticizing agent synthesis. The present invention relates to a synthetic method for trimellitic acid tri (2-ethyl) cyclohexyl, trimellitic acid tri nonyl and trimellitic acid tri decyl; trimellitic anhydride and C<8-10> alcohol are used as raw material; solid superacid or bivalent stannum oxide is used as a catalyst for esterification reaction; a new synthesis process without sulfuric acid catalysis and with a solventless aqueous method is used; the technological process of the present invention not only makes products have high ester content and high volume resistivity but also does not need neutralization and wash, a large amount of waste water is not generated, and the technical process has no environment pollution. The products can be widely used in 105 DEG C electric cable material, 125 DEG C electric cable material, automotive decorative material, high-grade spinning fiber oil, impregnating oil of a pulse low-pressure power capacitor, electric chemical industry and high-tech military products.
Description
Technical field
A kind of tri trimellitate (C
8-10Alcohol) preparation method of ester belongs to the synthesis technical field of softening agent.
Background technology
Tri trimellitate (C
8-10Alcohol) ester is compared with common plasticizer dioctyl phthalate (DOP) (DOP), dibutyl phthalate (DBP) and is had many advantages such as molecular weight is big, flash-point is high, volatility is low, anti-each kind solvent is extracted out, transport property is little.In addition, the tri trimellitate (C of this high ester content, high volume specific resistance
8-10Alcohol) particularly the consistency of PVC material is good with macromolecular material in polymer processing for ester plasticizer, and characteristics such as its processibility, low-temperature performance are similar to monomeric phthalic acid esters again, so have the advantage of monomeric plasticizer and polyester softening agent concurrently.It not only can be used as general primary plasticizer and uses in the product for civilian use, and can use 105 ℃ of level CABLE MATERIALS, 125 ℃ of level CABLE MATERIALS, automobile decoration material, senior spinning in fine finish, pulse low voltage power capacitor impregnation oils, electronics chemical industry and the high-tech war products widely.
Summary of the invention
The purpose of this invention is to provide a kind of tri trimellitate (C
8-10Alcohol) preparation method of ester.Production process of the present invention not only makes product have high ester content and high volume specific resistance, and does not have a large amount of waste water to produce, and environment is not polluted, and reaches the purpose of cleaner production.
Technical scheme of the present invention: by raw material trimellitic acid 1,2-anhydride (being called for short inclined to one side acid anhydride) and corresponding monobasic C
8-10Fatty Alcohol(C12-C14 and C12-C18) prepares by esterification under the effect of catalyzer.Preparation technology's flow process is: trimellitic acid 1,2-anhydride, Fatty Alcohol(C12-C14 and C12-C18) carry out esterification under the effect of catalyzer, make tri trimellitate (C through dealcoholysis, filtration, ion-exchange process again
8-10Alcohol) ester product.Reaction formula is
Inclined to one side acid anhydride of the first step and pure mono-esterification effect
Second step was double esterification reaction
The 3rd step was three esterification:
R：C
nH
2n+1，n：8-10
Reactant trimellitic acid 1,2-anhydride, high-carbon (C in the said process
8-10) alcohol, catalyzer adds esterification device with certain proportioning, temperature stirring and refluxing 5-6 hour, is carried out esterification, trimellitic acid 1,2-anhydride: C at 180-220 ℃
8-10The alcohol mol ratio is 1: 3.5-4.0, catalyst levels is the 0.01%-0.1% of reaction raw materials total mass, the hydrogen bond action of water generation reaction utilization and excessive alcohol is formed binary azeotrope shift out the esterification system fast, reaction is constantly carried out to forward, when the transformation efficiency of the inclined to one side acid anhydride of raw material greater than 99.5% the time, finish esterification, acid number is to 0.05mgKOH/g, in esterification system, slough excessive alcohol with vacuum, vacuum tightness is 0.5-0.1MPa, filtering product, final product carries out adsorption treatment through the multiple-hearth ion exchange column, obtains final tri trimellitate (C
8-10Alcohol) ester product.
Catalyzer is solid super-strong acid or Bivalent Tin oxide compound, and solid super-strong acid is SO
4 2-/ ZrO
2, SO
4 2-/ TiO
2Or SO
4 2-/ Fe
3O
4Solid super-strong acid is (as zirconium white ZrO by carrier
2, titanium oxide TiO
2Or Z 250 Fe
3O
4) in sulphuric acid soln, adsorbed SO through dipping
4 2-After, make through calcining again, be a kind of loaded catalyst.
Ion exchange resin in the multiple-hearth ion exchange column is that the resin cation (R.C.) by the resin anion(R.A) of macropore and macropore is composited.The softening agent kind that adopts the present invention to produce is: the own ester of tri trimellitate (2-ethyl), tri trimellitate ester in the ninth of the ten Heavenly Stems or tri trimellitate ester in the last of the ten Heavenly stems.The organic alcohol of raw material is C
8-10Fatty Alcohol(C12-C14 and C12-C18), can straight chain also can be the C of side chain
8-10Fatty Alcohol(C12-C14 and C12-C18).Catalyzer is a solid acid, and solid acid can be solid super-strong acid or Bivalent Tin oxide compound.The product of the present invention's preparation can be widely used in 105 ℃ of polyvinyl chloride wire cable materials and other the PVC plastics.
Beneficial effect of the present invention: the present invention adopts advanced no sulfuric acid catalysis new synthetic process, sulfuric acid catalysis that need not be traditional and with solid super-strong acid or Bivalent Tin oxide compound as catalyzer, its catalytic effect is better, and pollution-free.
Tri trimellitate (C
8-10Alcohol) the ester reaction is reversible reaction, need resultant water is constantly shifted out from reactive system to forward for helping reaction, to destroy the balance of esterification, the present invention adopts solvent-free band water law, utilizing the hydrogen bond action of alcohol and water to form binary azeotrope apace will generate water and deviate from reactive system, shorten the reaction times, so this technical process is short, investment is little, production cost is lower.
Because the reactive behavior of three carboxyls is inequalities in the molecular structure of trimellitic acid 1,2-anhydride, acid anhydride is after generating single, double ester partially, can make the reactive behavior, electronic effect of reactive group carboxyl on the phenyl ring, the change that sterically hindered generation is bigger, the reversibility of esterification is increased, some single, double esters that have are in various degree existed; Adopt solid acid catalyst and ion-exchange absorption to handle, can effectively reduce the by product and the refined product of product.
Embodiment
Embodiment 1
Adding reactant molar ratio in esterification device is 1: 3.5 trimellitic acid 1,2-anhydride and 2-Ethylhexyl Alcohol, and adds 0.1% solid acid SO of reaction raw materials total mass
4 2-/ Fe
3O
4Catalyzer, behind stirring and refluxing reaction 5h under 180～220 ℃ of conditions, measuring the thick ester acid value of esterification with neutralization titration is 0.05mgKOH/g, under vacuum 0.5-0.1MPa condition, slough excessive alcohol, after the filtration, through obtaining flash-point after the multiple-hearth treatment on ion exchange columns is that 245 ℃, ester content 99.5%, acid value 0.15mgKOH/g, color and luster are 60 (APHA), and volume resistivity is 1 * 10
12The finished product of Ω CM.APHA is platinum-cobalt colorimetric color and luster unit.
Embodiment 2
Adding reactant molar ratio in the esterification device of embodiment 1 is 1: 3.8 trimellitic acid 1,2-anhydride and nonyl alcohol, and adds 0.05% solid acid SO of reaction raw materials total mass
4 2-/ TiO
2Catalyzer, catalyzer divided for two steps added, for the first time add 75% solid acid of catalyzer total amount as catalysts, behind stirring and refluxing reaction 4h under 180～220 ℃ of conditions, in reactive system, add remaining 25% solid acid catalyst again, behind the restir back flow reaction 2h, measuring the thick ester acid value of esterification with neutralization titration is 0.04mgKOH/g, under vacuum tightness 0.5-0.1MPa condition, slough excessive alcohol, after the filtration, obtaining flash-point again after the multiple-hearth treatment on ion exchange columns is 245 ℃, ester content 99%, finished product acid value 0.1mgKOH/g, color and luster is 60 (APHA), and volume resistivity is 6 * 10
11Ω CM finished product
Embodiment 3
With embodiment 1 esterification device in to add reactant molar ratio be 1: 4.0 trimellitic acid 1,2-anhydride and decyl alcohol, and add 0.01% solid acid SO of reaction raw materials total mass
4 2-/ ZrO
2Catalyzer, behind stirring and refluxing reaction 5h under 180～220 ℃ of conditions, measuring the thick ester acid value of esterification with neutralization titration is 0.05mgKOH/g, under vacuum 0.5-0.1MPa condition, slough excessive alcohol, after the filtration, obtaining flash-point and be 245 ℃, ester content 99%, acid value 0.2mgKOH/g, color and luster after the multiple-hearth treatment on ion exchange columns is 60 (APHA), and volume resistivity is 1.5 * 10
12Ω CM finished product.
Embodiment 4
The adding reactant molar ratio is 1: 3.5 trimellitic acid 1,2-anhydride and a 2-Ethylhexyl Alcohol in esterification device, the 0.1%SnO that adds the reaction raw materials total mass is as catalysts, behind stirring and refluxing reaction 6h under 180～220 ℃ of conditions, measuring the thick ester acid value of esterification with neutralisation is 0.04mgKOH/g, under vacuum 0.5-0.1MPa condition, slough excessive alcohol, after filtering, obtaining flash-point and be 245 ℃, ester content 99%, finished product acid value 0.15mgKOH/g, color and luster after the multiple-hearth treatment on ion exchange columns is 60 (APHA), and volume resistivity is 8 * 10
11Ω CM finished product.
The comparative example 1
At 3.5M
3The adding reactant molar ratio is 1: 3.5 trimellitic acid 1,2-anhydride and a 2-Ethylhexyl Alcohol in the esterification device, total charging capacity 2500KG, with the tetrabutyl titanate of routine as catalysts, behind stirring and refluxing reaction 6h under 180～220 ℃ of conditions, measuring the thick ester acid value of esterification is 0.15mgKOH/g, carry out the neutralized crude esters product with 5% sodium carbonate solution 500GK then, behind the static minute lixiviating water layer, wash with the water of 500GK again, under vacuum condition, slough excessive alcohol behind the branch vibration layer, after filtering, obtaining flash-point is 240 ℃, ester content 98%, finished product acid value 0.3mgKOH/g, color and luster is 110 (APHA), and volume resistivity is 1 * 10
11Ω CM finished product.
Application example
Tri trimellitate (2-ethyl) own ester (TOTM) performance behind the polrvinyl chloride product prescription in being used for automobile is as follows.
TOTM is used for polrvinyl chloride product prescription in the automobile
The chemical constitution prescription accounts for weight in the prescription
Polyvinyl chloride 100.0
Filler 8.0
Stablizer 8.0
Lubricant 0.5
TOTM 50.0
The tri trimellitate ester plasticizer is used for polrvinyl chloride product performance in the automobile
| Trimellitate | Phthalic ester |
| TOTM | 9-11P 11P |
| Anti-mist degree begins luminosity reflectivity % and reclaimed recovery 88 in 36 16 hours in 1 hour | 27 34 71 100 |
| The minimum weight deposition, mg 4.8 | 4.6 9.8 |
| Temperature limit of brittleness, ℃-19 | -28 -34 |
| 85 ℃ after 100 hours; Elongation retention % 99 | 94 87 |
| 85 ℃ after 100 hours; Stretching strength retentivity % 104 | 69 91 |
Claims (3)
1. tri trimellitate C
8-10The preparation method of alcohol ester is characterized in that by raw material trimellitic acid 1,2-anhydride and corresponding monobasic C
8-10Alcohol by esterification preparation, after the esterification, makes through dealcoholysis, filtration, ion-exchange process under the effect of catalyzer again; Reactant trimellitic acid 1,2-anhydride, high-carbon C
8-10Alcohol, catalyzer add esterification device with certain proportioning, and temperature stirring and refluxing 5-6 hour, is carried out esterification, trimellitic acid 1,2-anhydride: C at 180-220 ℃
8-10The alcohol mol ratio is 1: 3.5-4.0, catalyst levels is the 0.01%-0.1% of reaction raw materials total mass, catalyzer is solid super-strong acid or Bivalent Tin oxide compound, when the transformation efficiency of the inclined to one side acid anhydride of raw material greater than 99.5% the time, finish esterification, acid number is to 0.05mgKOH/g, slough excessive alcohol with vacuum in esterification system, vacuum tightness is 0.5-0.1MPa, filtering product, final product carries out adsorption treatment through the multiple-hearth ion exchange column, obtains final tri trimellitate C
8-10The alcohol ester product.
2. preparation method according to claim 1 is characterized in that solid super acid catalyst is SO
4 2-/ ZrO
2, SO
4 2-/ TiO
2Or SO
4 2-/ Fe
3O
4
3. preparation method according to claim 1 is characterized in that the ion exchange resin in the multiple-hearth ion exchange column is to be composited by the resin anion(R.A) of macropore and the resin cation (R.C.) of macropore.
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| CNB2005100953658A CN100363328C (en) | 2005-11-08 | 2005-11-08 | Trimellitic tri(C8-9 ol)ester preparation method |
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| CN100363328C true CN100363328C (en) | 2008-01-23 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10640446B2 (en) | 2016-05-25 | 2020-05-05 | Sabic Global Technologies B.V. | Synthesis of alkyl tribenzanoate |
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| CN101429126B (en) * | 2008-12-22 | 2011-09-21 | 无锡百川化工股份有限公司 | Method for producing trioctyl trimellitate with trimellitic acid |
| CN101973884A (en) * | 2010-09-26 | 2011-02-16 | 昆山合峰化工有限公司 | Method for preparing triisononyl trimellitate (TINTM) |
| CN102924279B (en) * | 2012-10-16 | 2015-09-16 | 江苏正丹化学工业股份有限公司 | A kind of process for catalytic synthesis of trioctyl trimellitate |
| CN102924280B (en) * | 2012-10-25 | 2015-08-19 | 浙江皇马科技股份有限公司 | A kind of preparation method of trimellitate |
| JP2016141787A (en) * | 2015-02-05 | 2016-08-08 | 新日本理化株式会社 | Non-phthalic acid ester based plasticizer for vinyl chloride-based resin and vinyl chloride-based resin composition comprising the same |
| CN103864620B (en) * | 2014-04-04 | 2016-08-17 | 百川化工(如皋)有限公司 | A kind of production method of trioctyl trimellitate (TOTM) |
| US20170313851A1 (en) * | 2014-12-02 | 2017-11-02 | Emery Oleochemicals Gmbh | Ester plasticizers based on ethylhexanol and propylheptanol |
| CN107698449A (en) * | 2017-09-28 | 2018-02-16 | 江苏正丹化学工业股份有限公司 | A kind of synthetic method of the positive nonyl ester plasticiser of tri 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 |
| CN112552170A (en) * | 2020-11-16 | 2021-03-26 | 南通百川新材料有限公司 | Preparation method of low-color tri (C8-10 alcohol) trimellitate |
| CN112619689A (en) * | 2021-01-07 | 2021-04-09 | 江苏正丹化学工业股份有限公司 | Preparation and application method of catalyst for synthesizing triisononyl trimellitate |
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| US10640446B2 (en) | 2016-05-25 | 2020-05-05 | Sabic Global Technologies B.V. | Synthesis of alkyl tribenzanoate |
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Assignee: Yixing Yuxing Industrial And Trade Co., Ltd. Assignor: Jiangnan University Contract fulfillment period: 2008.9.21 to 2014.12.31 contract change Contract record no.: 2009320001208 Denomination of invention: Method for preparing amino acid three (C#-[8-10] alcohol) ester Granted publication date: 20080123 License type: Exclusive license Record date: 2009.7.23 |
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