CN104418747B - One prepares the method for phthalic acid two (2-propyl group heptan) ester - Google Patents
One prepares the method for phthalic acid two (2-propyl group heptan) ester Download PDFInfo
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- CN104418747B CN104418747B CN201310374032.3A CN201310374032A CN104418747B CN 104418747 B CN104418747 B CN 104418747B CN 201310374032 A CN201310374032 A CN 201310374032A CN 104418747 B CN104418747 B CN 104418747B
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- 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
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Abstract
The present invention relates to the method that one prepares phthalic acid two (2 propyl group heptan) ester (DPHP).Preparing DPHP with phthalic acid and 2 propyl enanthols for raw material, reaction is carried out by the one in following two ways: (1) with toluene, dimethylbenzene or the mixture of the two as water entrainer, with charcoal sulfonic acid, SO3H functionalized ion liquid, sulfonate resin, benzenesulfonic acid, LOMAR PWA EINECS 246-676-2, trifluoromethanesulfonic acid, phosphorus heteropoly tungstic acid, silicotungstic heteropolyacid, phosphato-molybdic heteropolyacid, SO4 2‑/MxOyOr S2O8 2‑/MxOyOne or more in solid super-strong acid are catalyst, react 2～6 hours at 110～140 DEG C；(2) both without additional water entrainer also without extra catalyst under the conditions of, 220～240 DEG C react 4～6h.The esterification yield of two ways phthalic acid is the highest is all up more than 99%.The present invention has the advantages such as reaction condition is gentle, operation is the most convenient.
Description
Technical field
The present invention relates to the method that one prepares phthalic acid two (2-propyl group heptan) ester.
Background technology
The high molecular polymer such as plastics, rubber must use plasticizer in producing, weakens polymer molecule
Intermolecular forces, increases the mobility of strand, reduces the crystallinity of strand, thus it is poly-to reach improvement
The purpose of the plasticity of compound, pliability, draftability and processing characteristics.Current domestic mainly with adjacent benzene
Dioctyl phthalate dioctyl ester (DOP) is plasticizer.Cause is big to the harm of human body and environment, sends out in the U.S. etc.
Reach country, the production of DOP and use the most restricted, and by phthalic acid two (2-propyl group heptan)
The Novel high-end plasticizers such as ester (DPHP) replace.DPHP safety non-toxic, excellent combination property, with
The compatibility of plastics etc. is good, be difficult to precipitation, and end plastic product surface is smooth, flexibility good, resistance to
The aspects such as long property, weatherability, anti-fog properties, stability are all better than the using effect of DOP.
DPHP, mainly with sulphuric acid as catalyst, with phthalic anhydride and 2-propyl enanthol is
Raw material prepares, and there is the problems such as catalyst is serious to equipment corrosion, environmental pollution is big.Although in recent years
There is document report to react DPHP processed with titanate esters catalysis phthalic anhydride and 2-propyl enanthol, can subtract to a certain extent
The pollution of this process light (1. Wei Guofeng, Liu Naiqing, Wang Shuo, Zhang Long, Speciality Petrochemicals, 2007,
24 (4), 10～13；2. Cheng Zhengyong, CN201010291275.7), but, phthalic anhydride is by o-Dimethylbenzene
At high temperature being prepared by gaseous oxidation, easy over oxidation or decarboxylation produce CO2, energy consumption and adjacent diformazan
Benzene raw materials consumes height, and reacts and carry out in explosive range, poor stability.With gaseous oxidation legal system
Phthalic anhydride is compared, o-Xylene Oxidation in Liquid Phase phthalic acid reaction condition gentleness, consumption of raw materials and energy
Consume low, safety good.But, compared with phthalic anhydride, phthalic acid reacts generation with 2-propyl enanthol
More water, is unfavorable for that reaction is carried out, and makes the resistance to water of catalyst require higher, titanate esters
This reaction is not suitable for Deng catalyst more sensitive to water.
Summary of the invention
In order to solve, catalytic erosion in current DPHP preparation process is serious, environmental pollution big, and makes
It is raw material with phthalic anhydride, and the outstanding problem such as phthalic anhydride preparation process consumption of raw materials and energy consumption height, poor stability,
It is an object of the invention to: developing a kind of phthalic acid is the method that DPHP prepared by raw material, have anti-
Answer mild condition, operate the outstanding advantages such as the most convenient.
For achieving the above object, the technical solution used in the present invention is shown below:
According to the present invention, often generate 1 mole of DPHP, 2 mole of water can be produced simultaneously, it is contemplated that be adjacent
Phthalic acid and the reaction of 2-propyl enanthol are reversible reaction, and the water of generation is removed reaction system in time has
Being beneficial to reaction carry out, the preferred toluene of the present invention, dimethylbenzene or the mixture of the two are water entrainer, or
The 2-propyl enanthol using excess takes the water of generation out of reaction system in time.
During with toluene, dimethylbenzene or the mixture of the two for water entrainer, the selection of catalyst is to adjacent benzene two
Formic acid high conversion, that height is selectively converted to DPHP is of crucial importance.The present invention is with band SO3H group
One or more in organic acid, heteropoly acid, solid super-strong acid are catalyst.Described band SO3H
Group organic acid preferred charcoal sulfonic acid, SO3H functionalized ion liquid, sulfonate resin, benzenesulfonic acid, naphthalene sulphur
Acid, one or more in trifluoromethanesulfonic acid；The preferred phosphorus heteropoly tungstic acid of described heteropoly acid, silicon tungsten
One or more in heteropoly acid, phosphato-molybdic heteropolyacid；Described solid super-strong acid is SO4 2-/MxOy
Or S2O8 2-/MxOyIn one or more, wherein MxOyIt is preferably TiO2、ZrO2、SnO2、
Fe2O3、Al2O3In one or more.
According to the present invention, during with toluene, dimethylbenzene or the mixture of the two for water entrainer, 2-propyl group heptan
The mol ratio of alcohol and phthalic acid preferably 2.0～2.1, water entrainer is preferred with the mass ratio of phthalic acid
0.5:1～2.0:1, catalyst amount is preferably the 0.1～2.0% of phthalic acid quality, and reaction temperature is preferred
110～140 DEG C, the response time preferably 2～6h.
According to the present invention, it is contemplated that under normal pressure, the boiling point of 2-propyl enanthol is close to 220 DEG C, and adjacent benzene
The boiling point of dioctyl phthalate and product DPHP thereof is higher, under the conditions of not using additional water entrainer, and reaction temperature
Degree can be raised to more than 220 DEG C, does not use extra catalyst, esterification process at a temperature of present invention discover that this
Also can carry out, high yield prepares target product DPHP, and this is possibly due to phthalic acid self and rises
The effect of catalyst.
According to the present invention, both without additional water entrainer also without extra catalyst under the conditions of, 2-propyl enanthol
With the mol ratio preferably 2.1～3.0 of phthalic acid, reaction temperature preferably 220～240 DEG C, response time
Preferably 4～6h.
Detailed description of the invention
The following example contributes to understanding the present invention, but present invention is not limited thereto.
Embodiment 1:
By 16.6 grams of phthalic acids (0.1mol), 33.2 grams of 2-propyl enanthols (2-PH, 0.21mol),
8.3 grams of dimethylbenzene and 0.332 gram of carbon sulfonic acid add 100ml equipped with in two mouthfuls of round-bottomed flasks of water knockout drum,
Water knockout drum filled toluene and connects condensing tube, stirring, being warming up to 140 DEG C and react 6 hours；
Distillation recovery dimethylbenzene and the 2-propyl enanthol of excess；Take debris after 2ml distillation, use 0.05mol/l
NaOH solution titration；The esterification yield calculating phthalic acid is 99%.Product passes through gas chromatogram
-GC-MS carries out qualitative analysis.
Embodiment 2～14:
The specific practice of embodiment 2～14 is similar to Example 1, concrete reaction condition and the results are shown in Table 1.
Embodiment 15:
By 16.6 grams of phthalic acids (0.1mol), 39.6 grams of 2-propyl enanthols (2-PH, 0.25mol)
100ml is equipped with in two mouthfuls of round-bottomed flasks of water knockout drum in addition, fills 2-propyl enanthol and connect in water knockout drum
Connect condensing tube, stir, be warming up to 230 DEG C and react 6 hours；The 2-propyl group of Distillation recovery excess
Enanthol；Take debris after 2ml distillation, titrate by the NaOH solution of 0.05mol/l；Calculate adjacent benzene
The esterification yield of dioctyl phthalate is 99%.Product carries out qualitative analysis by gas chromatograph-mass spectrometer (GC-MS).
Embodiment 16～20:
The specific practice of embodiment 16～20 is similar to Example 15, concrete reaction condition and the results are shown in Table
1。
The reaction condition of table 1, phthalic acid and 2-propyl enanthol and result
Can be seen that from above example, with toluene, dimethylbenzene or the mixture of the two as water entrainer, with
Band SO described in table 13One or more in H group organic acid, heteropoly acid, solid super-strong acid
For catalyst, at 110～140 DEG C, phthalic acid can react with 2-propyl enanthol and prepare DPHP,
Esterification yield reaches as high as more than 99%.This process prepares DPHP, adjacent benzene with phthalic acid for raw material
Dioctyl phthalate can be prepared by liquid phase oxidation by o-Dimethylbenzene, and mild condition, energy consumption and o-Dimethylbenzene disappear
Consume low, safety good；And this esterification process has the advantage that reaction condition is gentle.With dimethylbenzene it is
Water entrainer, during without catalyst, the esterification yield that phthalic acid reacts with 2-propyl enanthol is the lowest.So
And, both without additional water entrainer also without extra catalyst under the conditions of, 2-propyl enanthol and phthalic acid
When mol ratio is 2.1～3.0, reaction temperature is increased to 220～240 DEG C, the esterification yield of phthalic acid
Reaching as high as more than 99%, the method is not required to use catalyst, is also not required to use additional water entrainer, tool
There is the succinct advantage easily of operation.
Claims (2)
1. the method preparing phthalic acid two (2-propyl group heptan) ester, it is characterised in that: with phthalic acid and 2-
Propyl enanthol is that phthalic acid two (2-propyl group heptan) ester prepared by raw material, and reaction equation is as follows:
Reaction is with toluene, dimethylbenzene or the mixture of the two as water entrainer, with phosphorus heteropoly tungstic acid, silicotungstic heteropolyacid, phosphorus molybdenum
Heteropoly acid, SO4 2-/MxOyOr S2O8 2-/MxOyOne or more in solid super-strong acid are catalyst；Described MxOy
For TiO2、ZrO2、SnO2、Fe2O3、Al2O3In one or more.
2. the method for claim 1, it is characterised in that: the mol ratio of 2-propyl enanthol and phthalic acid is preferred
2.0～2.1, catalyst amount is preferably the quality of the 0.1～2.0% of phthalic acid quality, water entrainer and phthalic acid
Preferred 0.5:1～2.0:1 of ratio, reaction temperature preferably 110～140 DEG C, the response time preferably 2～6h.
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| CN108976116B (en) * | 2017-06-02 | 2021-02-02 | 中国科学院大连化学物理研究所 | Method for preparing phthalic acid high carbon alcohol ester by titanium chelate catalysis ester exchange |
| CN108976117B (en) * | 2017-06-02 | 2021-01-26 | 中国科学院大连化学物理研究所 | Method for preparing high-carbon alcohol phthalate through ester exchange continuous reaction |
| CN108997123B (en) * | 2018-09-11 | 2021-04-09 | 山东元利科技股份有限公司 | Method for synthesizing phthalate by catalytic oxidation product of o-xylene or naphthalene |
| CN110330428B (en) * | 2019-07-31 | 2022-05-03 | 浙江建业化工股份有限公司 | Method for preparing diisobutyl phthalate |
| CN114436829A (en) * | 2020-11-02 | 2022-05-06 | 杭州千泰生物科技有限公司 | Preparation method of phenyl salicylate |
| CN113828330A (en) * | 2021-09-24 | 2021-12-24 | 南京师范大学 | Mesoporous solid acid S2O82-/ZrO2-TiO2-La2O3Preparation method and application of |
| CN114471705A (en) * | 2022-02-16 | 2022-05-13 | 润泰化学（泰兴）有限公司 | Preparation method and application of catalyst for preparing cyclohexane-1, 2-diisononyl diformate from hexahydrophthalic anhydride and isononyl alcohol |
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| BR0112172A (en) * | 2000-07-05 | 2003-05-06 | Basf Ag | Process for the preparation of mixtures of phthalic acid diesters with decanols and tridecanols, mixture of phthalic acid diesters, use thereof, and mixture of isomeric tridecanols |
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| US2921089A (en) * | 1957-11-27 | 1960-01-12 | Eastman Kodak Co | 2-propylheptanol and its esters |
| DE10147776A1 (en) * | 2001-09-27 | 2003-07-03 | Oxeno Olefinchemie Gmbh | Process for the preparation of alicyclic polycarboxylic acid esters from partial esters of aromatic polycarboxylic acids |
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