CN103007920A - Catalyst for synthesizing trioctyl trimellitate from trimellitic anhydride or trimellitic acid and octanol through esterification and application thereof - Google Patents
Catalyst for synthesizing trioctyl trimellitate from trimellitic anhydride or trimellitic acid and octanol through esterification and application thereof Download PDFInfo
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- CN103007920A CN103007920A CN2012103922967A CN201210392296A CN103007920A CN 103007920 A CN103007920 A CN 103007920A CN 2012103922967 A CN2012103922967 A CN 2012103922967A CN 201210392296 A CN201210392296 A CN 201210392296A CN 103007920 A CN103007920 A CN 103007920A
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- trioctyl trimellitate
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Abstract
The invention discloses a catalyst for synthesizing trioctyl trimellitate from trimellitic anhydride or trimellitic acid and octanol through esterification and application thereof. The catalyst is a solid oxide and has excellent catalytic effect so that prepared trioctyl trimellitate is shallow in color and has high volume resistance. Furthermore, as the catalyst is a non-acid catalyst, no neutralizing water washing operation is needed in the production process; therefore, the posttreatment procedure is simplified; no wastewater is discharged in the production process and no pollution is caused on the environment; and the production process is clean and meet the national related industrial policy requirements for energy saving and emission reduction of the chemical engineering industry.
Description
Technical field
The present invention relates to a kind of catalyst and application thereof, belong to catalyst technical field.
Background technology
Trioctyl trimellitate (TOTM) is the plasticizer of function admirable, compare with phthalic ester plasticizer, have the advantages such as low, the anti-solvent of flash-point height, volatility is extracted out, animal migration is little, molecular weight is large, simultaneously particularly the compatibility of pvc material is good because of the high specific insulation of trioctyl trimellitate (TOTM) and with polymer, not only can be used as universal plasticizer, can also be widely used in 105 ℃ of level CABLE MATERIALS, the 125 ℃ of materials such as CABLE MATERIALS, automotive interior material, medical device and polyvinyl chloride, thereby have broad application prospects.But generally adopt lewis acid as catalyst in the prior art in the synthetic method of trioctyl trimellitate (TOTM), such as sulfuric acid, butyl titanate etc. as catalyst, the washing operation just can be removed acid contained in the product or be hydrolyzed and be removed titanate esters so that building-up process need to neutralize, thereby so that produce a large amount of waste water in the production process, environment is caused pollution, do not met country to the related industry policy requirements of chemical industry energy-saving and emission-reduction.
Summary of the invention
The object of the invention is to overcome defective of the prior art, a kind of catalyst and application thereof for trimellitic anhydride or trimellitic acid and the synthetic trioctyl trimellitate (TOTM) of octanol esterification is provided, catalyst of the present invention is applied to can be so that produce without waste water in the production process in the reaction of trimellitic anhydride or trimellitic acid and the synthetic trioctyl trimellitate (TOTM) of octanol esterification, can be to environment, and the trioctyl trimellitate (TOTM) lighter color that makes, have high specific insulation.
The present invention is achieved by the following technical programs.
A kind of catalyst for trimellitic anhydride or trimellitic acid and the synthetic trioctyl trimellitate (TOTM) of octanol esterification, described catalyst is soild oxide, described soild oxide is ZrO
2, TiO
2, ZnO, NiO
2, SiO
2, one or more the mixture among the SnO.
Above-mentioned a kind of catalyst for trimellitic anhydride or trimellitic acid and the synthetic trioctyl trimellitate (TOTM) of octanol esterification, wherein, described soild oxide is SnO.
The application of above-mentioned a kind of catalyst for trimellitic anhydride or trimellitic acid and the synthetic trioctyl trimellitate (TOTM) of octanol esterification, with trimellitic anhydride or trimellitic acid, octanol and catalyst add in the reaction kettle of the esterification, the control reaction temperature is at 160-220 ℃, stirring and refluxing reaction 3-8 hour, through the synthetic trioctyl trimellitate (TOTM) of esterification, trimellitic anhydride or Pian benzene San Suan ︰ octanol mol ratio are 1 ︰ 3.4-4.5, catalyst amount is the 0.05-0.2% of reaction raw materials gross mass, the binary azeotrope that the water that generates in the esterification process and excessive octanol are formed shifts out the esterification system, esterification is constantly carried out to the positive reaction direction, when the conversion ratio of trimellitic anhydride or trimellitic acid is higher than 99.5%, the system acid number is when 0.05mgKOH/g is following, finish esterification, the solids removed by filtration catalyst, esterification products is removed octanol under vacuum, vacuum is 0.05-0.1MPa, can obtain trioctyl trimellitate (TOTM).
The application of above-mentioned a kind of catalyst for trimellitic anhydride or trimellitic acid and the synthetic trioctyl trimellitate (TOTM) of octanol esterification, wherein, trimellitic anhydride or Pian benzene San Suan ︰ octanol mol ratio are 1 ︰ 4.
The application of above-mentioned a kind of catalyst for trimellitic anhydride or trimellitic acid and the synthetic trioctyl trimellitate (TOTM) of octanol esterification, wherein, catalyst amount is 0.1% of reaction raw materials gross mass.
The application of above-mentioned a kind of catalyst for trimellitic anhydride or trimellitic acid and the synthetic trioctyl trimellitate (TOTM) of octanol esterification wherein, when the system acid number is 0.03mgKOH/g, finishes esterification.
The present invention a kind of catalyst and application thereof for trimellitic anhydride or trimellitic acid and the synthetic trioctyl trimellitate (TOTM) of octanol esterification, described catalyst is soild oxide, catalytic effect is good, so that the trioctyl trimellitate (TOTM) lighter color that makes has high specific insulation.And catalyst is non-acid catalyst, so that the washing operation that do not need in the production process to neutralize, thereby simplified postprocessing working procedures, discharge without waste water in the production process, environmentally safe is process for cleanly preparing, meets country encourages energy-saving and emission-reduction to chemical industry related industry policy requirements.
The specific embodiment
Embodiment 1
With trimellitic anhydride, octanol and SnO add in the reaction kettle of the esterification, the control reaction temperature is at 160 ℃, stirring and refluxing reaction 4 hours, through the synthetic trioctyl trimellitate (TOTM) of esterification, Pian benzene three Suan Gan ︰ octanol mol ratios are 1 ︰ 3.5, catalyst amount is 0.1% of reaction raw materials gross mass, the binary azeotrope that the water that generates in the esterification process and excessive octanol are formed shifts out the esterification system, esterification is constantly carried out to the positive reaction direction, when the conversion ratio of trimellitic anhydride is higher than 99.5%, acid-base titration is measured and is finished esterification when the system acid number is 0.05mgKOH/g, remove by filter SnO, esterification products is removed octanol under vacuum, vacuum is 0.08MPa, can obtain trioctyl trimellitate (TOTM).246 ℃ of trioctyl trimellitate (TOTM) product flash-points, ester content 99.5%, acid value 0.16 mgKOH/g, platinum-cobalt colorimetric color and luster are 40(APHA), specific insulation 1.2 * 10
12Ω cm.
Embodiment 2
With trimellitic anhydride, octanol and ZrO
2Add in the reaction kettle of the esterification, the control reaction temperature is at 180 ℃, stirring and refluxing reaction 3 hours, through the synthetic trioctyl trimellitate (TOTM) of esterification, Pian benzene three Suan Gan ︰ octanol mol ratios are 1 ︰ 3.9, catalyst amount is 0.15% of reaction raw materials gross mass, the binary azeotrope that the water that generates in the esterification process and excessive octanol are formed shifts out the esterification system, esterification is constantly carried out to the positive reaction direction, when the conversion ratio of trimellitic anhydride is higher than 99.5%, acid-base titration is measured and finished esterification when the system acid number is 0.04mgKOH/g, remove by filter ZrO
2, esterification products is removed octanol under vacuum, vacuum is 0.05MPa, can obtain trioctyl trimellitate (TOTM).245 ℃ of trioctyl trimellitate (TOTM) product flash-points, ester content 99.4%, acid value 0.15 mgKOH/g, platinum-cobalt colorimetric color and luster are 40(APHA), specific insulation 1.0 * 10
12Ω cm.
Embodiment 3
With trimellitic acid, octanol, TiO
2Add in the reaction kettle of the esterification with ZnO, the control reaction temperature is at 200 ℃, stirring and refluxing reaction 8 hours, through the synthetic trioctyl trimellitate (TOTM) of esterification, Pian benzene San Suan ︰ octanol mol ratio is 1 ︰ 4.0, catalyst amount is 0.2% of reaction raw materials gross mass, the binary azeotrope that the water that generates in the esterification process and excessive octanol are formed shifts out the esterification system, esterification is constantly carried out to the positive reaction direction, when the conversion ratio of trimellitic acid is higher than 99.5%, acid-base titration is measured and finished esterification when the system acid number is 0.03mgKOH/g, remove by filter TiO
2And ZnO, esterification products is removed octanol under vacuum, vacuum is 0.1MPa, can obtain trioctyl trimellitate (TOTM).245 ℃ of trioctyl trimellitate (TOTM) product flash-points, ester content 99.5%, acid value 0.18 mgKOH/g, platinum-cobalt colorimetric color and luster are 40(APHA), specific insulation 1.3 * 10
12Ω cm.
Embodiment 4
With trimellitic acid, octanol, NiO
2And SiO
2Add in the reaction kettle of the esterification, the control reaction temperature is at 220 ℃, stirring and refluxing reaction 6 hours, through the synthetic trioctyl trimellitate (TOTM) of esterification, Pian benzene San Suan ︰ octanol mol ratio is 1 ︰ 4.5, catalyst amount is 0.05% of reaction raw materials gross mass, the binary azeotrope that the water that generates in the esterification process and excessive octanol are formed shifts out the esterification system, esterification is constantly carried out to the positive reaction direction, when the conversion ratio of trimellitic acid is higher than 99.5%, acid-base titration is measured and finished esterification when the system acid number is 0.02mgKOH/g, remove by filter NiO
2And SiO
2, esterification products is removed octanol under vacuum, vacuum is 0.06MPa, can obtain trioctyl trimellitate (TOTM).246 ℃ of trioctyl trimellitate (TOTM) product flash-points, ester content 99.5%, acid value 0.16 mgKOH/g, platinum-cobalt colorimetric color and luster are 40(APHA), specific insulation 1.2 * 10
12Ω cm.
Here description of the invention and application is illustrative, is not to want that therefore, the present invention is not subjected to the restriction of present embodiment with scope restriction of the present invention in the above-described embodiments, and the technical scheme that any employing equivalence replacement obtains is all in the scope of protection of the invention.
Claims (6)
1. a catalyst that is used for trimellitic anhydride or trimellitic acid and the synthetic trioctyl trimellitate (TOTM) of octanol esterification is characterized in that described catalyst is soild oxide, and described soild oxide is ZrO
2, TiO
2, ZnO, NiO
2, SiO
2, one or more the mixture among the SnO.
2. a kind of catalyst for trimellitic anhydride or trimellitic acid and the synthetic trioctyl trimellitate (TOTM) of octanol esterification as claimed in claim 1 is characterized in that described soild oxide is SnO.
3. application that is used for the catalyst of trimellitic anhydride or trimellitic acid and the synthetic trioctyl trimellitate (TOTM) of octanol esterification, it is characterized in that, with trimellitic anhydride or trimellitic acid, octanol and catalyst add in the reaction kettle of the esterification, the control reaction temperature is at 160-220 ℃, stirring and refluxing reaction 3-8 hour, through the synthetic trioctyl trimellitate (TOTM) of esterification, trimellitic anhydride or Pian benzene San Suan ︰ octanol mol ratio are 1 ︰ 3.4-4.5, catalyst amount is the 0.05-0.2% of reaction raw materials gross mass, the binary azeotrope that the water that generates in the esterification process and excessive octanol are formed shifts out the esterification system, esterification is constantly carried out to the positive reaction direction, when the conversion ratio of trimellitic anhydride or trimellitic acid is higher than 99.5%, the system acid number is when 0.05mgKOH/g is following, finish esterification, the solids removed by filtration catalyst, esterification products is removed octanol under vacuum, vacuum is 0.05-0.1MPa, can obtain trioctyl trimellitate (TOTM).
4. the application of a kind of catalyst for trimellitic anhydride or trimellitic acid and the synthetic trioctyl trimellitate (TOTM) of octanol esterification as claimed in claim 3 is characterized in that trimellitic anhydride or Pian benzene San Suan ︰ octanol mol ratio are 1 ︰ 4.
5. the application of a kind of catalyst for trimellitic anhydride or trimellitic acid and the synthetic trioctyl trimellitate (TOTM) of octanol esterification as claimed in claim 3 is characterized in that catalyst amount is 0.1% of reaction raw materials gross mass.
6. the application of a kind of catalyst for trimellitic anhydride or trimellitic acid and the synthetic trioctyl trimellitate (TOTM) of octanol esterification as claimed in claim 3 is characterized in that, when the system acid number is 0.03mgKOH/g, finishes esterification.
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| CN201210392296.7A CN103007920B (en) | 2012-10-16 | 2012-10-16 | Catalyst for synthesizing trioctyl trimellitate from trimellitic anhydride or trimellitic acid and octanol through esterification and application thereof |
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| CN201210392296.7A CN103007920B (en) | 2012-10-16 | 2012-10-16 | Catalyst for synthesizing trioctyl trimellitate from trimellitic anhydride or trimellitic acid and octanol through esterification and application thereof |
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Cited By (7)
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|---|---|---|---|---|
| CN102924279A (en) * | 2012-10-16 | 2013-02-13 | 江苏正丹化学工业股份有限公司 | Catalytic synthesis method of tri-octyl tri-meta-benzoate |
| CN103214372A (en) * | 2013-05-10 | 2013-07-24 | 范强 | Synthesis method of tridecyl trimellitate |
| CN103864620A (en) * | 2014-04-04 | 2014-06-18 | 百川化工(如皋)有限公司 | Production method of trioctyl trimellate |
| CN106975475A (en) * | 2017-04-26 | 2017-07-25 | 中国石油化工股份有限公司 | It is a kind of for catalyst of synthesizing trimethylol propane ester and preparation method thereof and application |
| CN107413383A (en) * | 2017-07-07 | 2017-12-01 | 江苏正丹化学工业股份有限公司 | The just pungent positive last of the ten Heavenly stems Lipase absobed catalyst of tri trimellitate and its application method |
| US10640446B2 (en) | 2016-05-25 | 2020-05-05 | Sabic Global Technologies B.V. | Synthesis of alkyl tribenzanoate |
| CN111606803A (en) * | 2020-06-20 | 2020-09-01 | 南通百川新材料有限公司 | Production method of trioctyl trimellitate plasticizer with high volume resistivity |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102924279A (en) * | 2012-10-16 | 2013-02-13 | 江苏正丹化学工业股份有限公司 | Catalytic synthesis method of tri-octyl tri-meta-benzoate |
| 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 |
| CN103214372A (en) * | 2013-05-10 | 2013-07-24 | 范强 | Synthesis method of tridecyl trimellitate |
| CN103864620A (en) * | 2014-04-04 | 2014-06-18 | 百川化工(如皋)有限公司 | Production method of trioctyl trimellate |
| 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) |
| US10640446B2 (en) | 2016-05-25 | 2020-05-05 | Sabic Global Technologies B.V. | Synthesis of alkyl tribenzanoate |
| CN106975475A (en) * | 2017-04-26 | 2017-07-25 | 中国石油化工股份有限公司 | It is a kind of for catalyst of synthesizing trimethylol propane ester and preparation method thereof and application |
| CN106975475B (en) * | 2017-04-26 | 2019-12-20 | 中国石油化工股份有限公司 | Catalyst for synthesizing trimethylolpropane ester and preparation method and application thereof |
| CN107413383A (en) * | 2017-07-07 | 2017-12-01 | 江苏正丹化学工业股份有限公司 | The just pungent positive last of the ten Heavenly stems Lipase absobed catalyst of tri trimellitate and its application method |
| CN107413383B (en) * | 2017-07-07 | 2019-10-29 | 江苏正丹化学工业股份有限公司 | The just pungent positive last of the ten Heavenly stems Lipase absobed catalyst of tri trimellitate and its application method |
| CN111606803A (en) * | 2020-06-20 | 2020-09-01 | 南通百川新材料有限公司 | Production method of trioctyl trimellitate plasticizer with high volume resistivity |
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