CN101429126B - Method for producing trioctyl trimellitate with trimellitic acid - Google Patents
Method for producing trioctyl trimellitate with trimellitic acid Download PDFInfo
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- CN101429126B CN101429126B CN2008102435290A CN200810243529A CN101429126B CN 101429126 B CN101429126 B CN 101429126B CN 2008102435290 A CN2008102435290 A CN 2008102435290A CN 200810243529 A CN200810243529 A CN 200810243529A CN 101429126 B CN101429126 B CN 101429126B
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- esterification
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- methyl alcohol
- trimellitic acid
- trimellitate
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- 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 title claims abstract description 46
- 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 title claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 69
- 238000005886 esterification reaction Methods 0.000 claims abstract description 36
- 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 abstract description 30
- 230000032050 esterification Effects 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 15
- -1 2-ethyl Chemical group 0.000 claims abstract description 14
- 150000002148 esters Chemical group 0.000 claims abstract description 8
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 26
- 239000000047 product Substances 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 239000002253 acid Substances 0.000 claims description 22
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 20
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 11
- 235000021050 feed intake Nutrition 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000005303 weighing Methods 0.000 claims description 7
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 6
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 6
- 150000007524 organic acids Chemical class 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 239000004408 titanium dioxide Substances 0.000 claims description 6
- 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 6
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 3
- 238000005809 transesterification reaction Methods 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- 239000002351 wastewater Substances 0.000 claims description 3
- 239000006227 byproduct Substances 0.000 claims description 2
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 abstract description 7
- 238000005516 engineering process Methods 0.000 abstract description 4
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 abstract 2
- 239000013067 intermediate product Substances 0.000 abstract 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract 1
- 125000005591 trimellitate group Chemical group 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000000926 separation method Methods 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 238000009835 boiling Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000004811 liquid chromatography Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000004902 Softening Agent Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 230000009182 swimming Effects 0.000 description 1
Abstract
The invention relates to a method for producing trioctyl trimellitate through using trimellitic acid. Intermediate products of trimellitic acid and methanol in the process of producing the trimellitic anhydride are esterified to generate trimethyl trimellitate; the trimethyl trimellitate and 2-ethylhexanol (commonly called asoctanol) are subjected to ester exchange to produce trimellitate (2-ethyl) trihexyl ester (trioctyl trimellitate). The method of methyl esterification and ester exchange can reduce requirement on a technology and equipment so that the intermediate product of the trimellitic acid in the process of producing the trimellitic anhydride is flexibly utilized.
Description
(1) technical field
The present invention relates to a kind of production method of trioctyl trimellitate.Belong to organic chemical industry's product technical field.
(2) background technology
Trioctyl trimellitate is a kind of softening agent with good heat-resistant quality, can improve the temperature resistant grade of PVC plastics, rubber, resin etc. significantly, can be used as the CABLE MATERIALS of 105 ℃ and 125 ℃ levels.It is also having application aspect automobile decoration material, swimming pool waterproof layer, the capacitor impregnation wet goods.
The method of present industrial production trioctyl trimellitate generally is to carry out direct esterification with trimellitic acid 1,2-anhydride and octanol to produce.Industrially under liquid phase state, after atmospheric oxidation, make trimellitic acid, become acid anhydride, just can make content through the high temperature high vacuum rectification again and surpass 95% trimellitic acid 1,2-anhydride through high temperature dehydration by unsym-trimethyl benzene.High temperature, high vacuum rectification to the requirement of technology, equipment than higher, and because the molecule of octanol is bigger, when the direct esterification method, be difficult to realize fully three esterifications, therefore always there are a spot of mono-esterification and double esterification impurity to be mixed in the trioctyl trimellitate finished product, very difficult economy easily with the purpose product separation, referring to Chinese patent ZL 200510095365.8.
(3) summary of the invention
The objective of the invention is to overcome above-mentioned deficiency, provide a kind of requirement to technology, equipment lower, with in the trimellitic acid 1,2-anhydride production process in the middle of product---trimellitic acid is produced the method for trioctyl trimellitate.
The object of the present invention is achieved like this: a kind of method of producing trioctyl trimellitate with trimellitic acid is characterized in that described method mainly comprises following technological process:
Step 1, will after weighing, drop into the pretreated trimellitic acid of overcooling, crystallization, filtration and washing in the esterification reaction of organic acid device, add and to account for trimellitic acid and feed intake the dimethylbenzene of 2.0～3.0 times of weight as the band aqua, add again and account for the feed intake catalyzer of weight 0.1～1.0% of trimellitic acid, stir, heat temperature raising to 100 ℃ ± 5 ℃, take by weighing and account for the feed intake methyl alcohol of 0.5～2.0 times of weight of weight of trimellitic acid, add in the dropping funnel, slowly, step by step methyl alcohol is added in the reactor with the speed of 1.5～2.5L/min; Continuation is warming up to 120～130 ℃ with reactor, at this moment can see that the dimethylbenzene that steams is after layering, obviously there is water layer to separate out, the adding speed of control methyl alcohol, feasible water distilled speed with the esterification by-product keeps balance, continue reaction Deng methyl alcohol after all dripping, the moisture that generates until reaction all distillates, esterification product I; Distilled dimethylbenzene etc. is collected in the transparent water trap, and after the cut layering, the water layer of telling send waste water processing station to handle after reclaiming organism, and dimethylbenzene is with after methyl alcohol send solvent tower to separate, and reuse makes to be with the raw material of aqua and esterification respectively;
Step 2, the esterification product I that step 1 is obtained neutralize with sig water, and with 50～60 ℃ warm water washing after-filtration, to pH be 6～8, do not have insolubles in the oil phase, esterification product II;
Step 3, the esterification product II that step 2 is obtained change in the rectifying still, use heat-conducting oil heating, under the vacuum condition of 1000～2000Pa, carry out rectifying, and the cut between collecting 185～200 ℃ obtains content and be the trimethyl trimellitate more than 99%;
Change in the transesterification reactor after step 4, the trimethyl trimellitate weighing that step 3 is obtained, add and to account for the feed intake octanol of 1.6～2.0 times of weight of trimethyl trimellitate, add and to account for the feed intake catalyzer of weight 0.05～1.0% of trimethyl trimellitate, stir heating; When being heated to 140～160 ℃, the methyl alcohol that has transesterify to go out distillates, and continuation stirring intensification has excessive octanol again and distillates, and to 240～260 ℃, no longer includes cuts such as methyl alcohol, octanol and distillates, and the low-boiling-point substance that forms in the production process also is removed; Separate in solvent tower behind the fraction collection that distills out, the raw material of esterification and transesterify is made in reuse;
Step 5, the ester exchange offspring that step 4 is obtained neutralize with sig water, and with 50～60 ℃ warm water washing after-filtration, to pH be 6～8, remove residual catalyzer;
Product after step 6, the washing that step 5 is obtained aspirates under vacuum condition, and residual moisture when removing washing can get content and be the trioctyl trimellitate more than 98%.
The catalyzer that uses in the above-mentioned steps one can be following a kind of: the vitriol oil, tosic acid, tetrabutyl titanate, metatitanic acid four isobutyl esters, titanium isopropylate, metatitanic acid metatitanic acid tetramethyl ester, titanium dioxide, zirconium white and zirconic acid tetramethyl ester.
The catalyzer that uses in the above-mentioned steps four can be following a kind of: Dibutyltin oxide, the vitriol oil, sodium methylate, tetrabutyl titanate, metatitanic acid four isobutyl esters, titanium isopropylate, metatitanic acid metatitanic acid tetramethyl ester, titanium dioxide, zirconium white and zirconic acid tetramethyl ester.
Control under the proper situation in condition, in the product that unsym-trimethyl benzene forms after atmospheric oxidation, the content of trimellitic acid can account for more than 90%.Product just can be used for carrying out esterification reaction of organic acid like this after cooling, crystallization, filtration.After the esterification, the fusing point of trimethyl trimellitate and some other impurity methyl esters things, boiling point all obviously reduce, this has reduced technologic trouble for separation purification trimethyl trimellitate, the purity of the trimethyl trimellitate after the purification can be reached more than 99%, and this has created condition for next step makes highly purified trioctyl trimellitate by transesterify.
Compared with prior art, though the present invention's operational path is longer, have following advantage:
1) distillation after the transesterify can be carried out under normal pressure, and temperature is not harsh yet, to equipment require low;
2) first esterification transesterify again can be avoided the steric effect that exists in the direct esterification process effectively, reduces octanol monoesters and double esterification impurity in the product;
3) with after the trimellitic acid esterification, can reduce the treatment temp of purified product, also no longer harsh to the vacuum tightness requirement of rectifying separation, make industrialized difficulty reduce;
4) can reasonably utilize the middle product trimellitic acid that generates after the unsym-trimethyl benzene oxidation along with Market Situation, this processing method is for enterprise's particularly advantageous of originally producing trimellitic acid 1,2-anhydride.
The method that the present invention carries out transesterify after by esterification again, make in the trimellitic acid 1,2-anhydride production process in the middle of the product trimellitic acid obtain flexible utilization, produce trioctyl trimellitate.The trioctyl trimellitate that the present invention makes can satisfy the service requirements of downstream industry.
Embodiment:
Certain batch is through the pretreated trimellitic acid of overcooling, crystallization, filtration and washing, and the sampling back is separated, detected with liquid chromatography, and the content of trimellitic acid is 91.3%.
Get above-mentioned trimellitic acid 1000kg, being put into volume is 10M
3The esterification reaction of organic acid still in, the dimethylbenzene that adds 2500kg is as the band aqua, the vitriol oil that adds 5kg again stirs as catalyzer, heating makes still temperature rise to 100 ℃.Taking by weighing 800kg methyl alcohol, add in the dropping funnel on still top, also is that the speed of 1.5kg/min adds reactor with methyl alcohol with 1.9L/min.
The temperature of reactor is increased to 125 ℃, in a transparent water trap on still top, collects the cut that reaction steams.After having water layer to separate out in the water trap, water layer is in time separated.After methyl alcohol all drips, continue reaction half an hour, the moisture that generates until reaction all distillates.
The water layer of telling recycles organism in recovery tower after, send waste water processing station to handle.The organic phase that water trap is told is sent solvent tower, carries out separating of methyl alcohol and dimethylbenzene.Methyl alcohol is back to esterification reaction of organic acid, and the band aqua of esterification reaction of organic acid is made in the dimethylbenzene reuse.
The product that esterification is made is with 10% sodium hydroxide solution neutralization, washs after-filtration with 50～60 ℃ warm water then, and the product pH value that obtains is 7, and it is transparent that oil phase becomes.
The product of esterification is changed in the rectifying still, use heat-conducting oil heating, the vacuum tightness of keeping distillation system is 1500～1700Pa, and collecting boiling point is the interior cuts of 190～198 ℃ of scopes, obtains 1015kg trimethyl trimellitate product.The liquid chromatography separation detection is used in sampling, and content is 99.38%.
The trimethyl trimellitate product that obtains is changed in the transesterification reactor, add the 1800kg octanol, add the 5kg Dibutyltin oxide, stir, heating.
When being heated to 145 ℃, begin to have methyl alcohol to distillate, be collected in the tundish.Continue to stir, obviously reduce until distilled methyl alcohol.Continuation heats up to ester interchange vessel, begins to have excessive octanol to distillate to 182 ℃, changes tundish in addition and collects.After octanol distillates obvious minimizing, continue ester interchange vessel is warming up to 250 ℃, the low-boiling-point substance that forms in production process also is removed.
The cut that transesterify obtains needs further to separate in solvent tower, and the methyl alcohol that reclaims out is as the raw material of esterification, and octanol is as the raw material of transesterify.
The product that transesterify is obtained with 50～60 ℃ warm water washing after-filtration, is removed catalyzer then with 10% sodium hydroxide solution neutralization, and filtrate change is clarified, and the pH value adjusts to 7.
Product after the washing is aspirated under the perfect vacuum of 2000Pa, obtain the trioctyl trimellitate of 2127kg.Sampling, working sample after the saponification, getting ester content is 98.6%.
The catalyzer of above esterification can also be following a kind of: a kind of in the vitriol oil, tosic acid, tetrabutyl titanate, metatitanic acid four isobutyl esters, titanium isopropylate, metatitanic acid metatitanic acid tetramethyl ester, titanium dioxide, zirconium white and the zirconic acid tetramethyl ester.
The catalyzer of above transesterify can also be following a kind of: Dibutyltin oxide, the vitriol oil, sodium methylate, tetrabutyl titanate, metatitanic acid four isobutyl esters, titanium isopropylate, metatitanic acid metatitanic acid tetramethyl ester, titanium dioxide, zirconium white and zirconic acid tetramethyl ester.
Claims (1)
1. method of producing trioctyl trimellitate with trimellitic acid is characterized in that described method mainly comprises following technological process:
Step 1, the trimellitic acid back of weighing is dropped in the esterification reaction of organic acid device, add and to account for trimellitic acid and feed intake the dimethylbenzene of 2.0～3.0 times of weight as the band aqua, add again and account for the feed intake catalyzer of weight 0.1～1.0% of trimellitic acid, stir, heat temperature raising to 100 ℃ ± 5 ℃, take by weighing and account for the feed intake methyl alcohol of 0.5～2.0 times of weight of weight of trimellitic acid, add in the dropping funnel, slowly, step by step methyl alcohol is added in the reactor with the speed of 1.5～2.5L/min; Continuation is warming up to 120～130 ℃ with reactor, the adding speed of control methyl alcohol, feasible water distilled speed with the esterification by-product keeps balance, continue reaction Deng methyl alcohol after all dripping, the moisture that generates until reaction all distillates, get esterification product I, distilled dimethylbenzene etc. is collected in the transparent water trap, after the cut layering, the water layer of telling send waste water processing station to handle after reclaiming organism, dimethylbenzene is with after methyl alcohol send solvent tower to separate, and the raw material of band aqua and esterification is made in reuse respectively;
Step 2, the esterification product I that step 1 is obtained neutralize with sig water, and with 50～60 ℃ warm water washing after-filtration, to pH be 6～8, do not have insolubles in the oil phase, esterification product II;
Step 3, the esterification product II that step 2 is obtained change in the rectifying still, use heat-conducting oil heating, under the vacuum condition of 1000～2000Pa, carry out rectifying, the cut between collecting 185～200 ℃, trimethyl trimellitate;
Change in the transesterification reactor after step 4, the trimethyl trimellitate weighing that step 3 is obtained, add and to account for the feed intake octanol of 1.6～2.0 times of weight of trimethyl trimellitate, add and to account for the feed intake catalyzer of weight 0.05～1.0% of trimethyl trimellitate, stir heating; When being heated to 140～160 ℃, the methyl alcohol that has transesterify to go out distillates, and continue to stir heats up to have excessive octanol again and distillate, and to 240～260 ℃, no longer includes methyl alcohol, the octanol cut distillates, and the low-boiling-point substance that forms in the production process also is removed; Separate in solvent tower behind the fraction collection that distills out, the raw material of esterification and transesterify is made in reuse;
Step 5, the ester exchange offspring that step 4 is obtained neutralize with sig water, and with 50～60 ℃ warm water washing after-filtration, to pH be 6～8;
Product after step 6, the washing that step 5 is obtained aspirates under condition of negative pressure, trioctyl trimellitate,
The catalyzer that uses in the above-mentioned steps one is following a kind of: the vitriol oil, tosic acid, tetrabutyl titanate, metatitanic acid four isobutyl esters, titanium isopropylate, metatitanic acid tetramethyl ester, titanium dioxide, zirconium white and zirconic acid tetramethyl ester,
The catalyzer that uses in the above-mentioned steps four is following a kind of: Dibutyltin oxide, the vitriol oil, sodium methylate, tetrabutyl titanate, metatitanic acid four isobutyl esters, titanium isopropylate, metatitanic acid tetramethyl ester, titanium dioxide, zirconium white and zirconic acid tetramethyl ester.
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| CN102030652B (en) * | 2010-11-23 | 2013-04-10 | 无锡双象化学工业有限公司 | Industrialized production method for synthesizing trioctyl trimellitate through composite catalysis |
| CN102477021B (en) * | 2010-11-25 | 2015-02-18 | 上海市合成树脂研究所 | Preparation method of di(4-trimellitic anhydride) glycol ester |
| CN102617351B (en) * | 2012-03-09 | 2013-03-27 | 无锡百川化工股份有限公司 | Method for recovering trioctyl trimellitate |
| CN105001448A (en) * | 2015-06-18 | 2015-10-28 | 张家港市大能塑料制品有限公司 | High-temperature-resisting plasticizer |
| CN106008218A (en) * | 2016-05-20 | 2016-10-12 | 百川化工(如皋)有限公司 | Method for synthesizing trioctyl trimellitate |
| CN109153630A (en) | 2016-05-25 | 2019-01-04 | 沙特基础工业全球技术有限公司 | The synthesis of triphen alkyl formate |
| CN106008204B (en) * | 2016-05-31 | 2019-02-22 | 南通百川新材料有限公司 | A method of synthesis tri trimellitate ester |
| 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 |
| CN108892612A (en) * | 2018-08-15 | 2018-11-27 | 南通百川新材料有限公司 | A kind of method of three monooctyl ester of ester-interchange method trimellitic acid |
| CN111960943A (en) * | 2020-08-27 | 2020-11-20 | 江苏正丹化学工业股份有限公司 | Process for producing dioctyl terephthalate by semi-continuous method |
| CN113200859A (en) * | 2021-04-29 | 2021-08-03 | 南京威尔生物科技有限公司 | Preparation method of malate with low chroma and low acid value |
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| CN1769260A (en) * | 2005-11-08 | 2006-05-10 | 江南大学 | Trimellitic tri(C8-9 ol)ester preparation method |
| CN100999590A (en) * | 2006-01-12 | 2007-07-18 | 奥克森诺奥勒芬化学股份有限公司 | Dialkyl terephthalates and their use |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1769260A (en) * | 2005-11-08 | 2006-05-10 | 江南大学 | Trimellitic tri(C8-9 ol)ester preparation method |
| CN100999590A (en) * | 2006-01-12 | 2007-07-18 | 奥克森诺奥勒芬化学股份有限公司 | Dialkyl terephthalates and their use |
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