CN108976117A - A kind of method that transesterification successive reaction prepares phthalic acid high-carbon alcohol ester - Google Patents
A kind of method that transesterification successive reaction prepares phthalic acid high-carbon alcohol ester Download PDFInfo
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- CN108976117A CN108976117A CN201710408372.1A CN201710408372A CN108976117A CN 108976117 A CN108976117 A CN 108976117A CN 201710408372 A CN201710408372 A CN 201710408372A CN 108976117 A CN108976117 A CN 108976117A
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- phthalic acid
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
- B01J23/04—Alkali metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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Abstract
The present invention relates to a kind of methods that transesterification successive reaction prepares phthalic acid high-carbon alcohol ester, in fixed bed reactors, with repefral, diethyl phthalate, the O-phthalics such as dibutyl phthalate acid low carbon alcohol ester and isononyl alcohol, isodecanol, the higher alcohols such as 2- propyl enanthol are raw material, with magnesium aluminate calcium, sodium silicoaluminate, potassium aluminosilicate, aluminosilicate magnesium, ca aluminosilicate, aluminum magnesium titanate, magnesium titanate calcium, the above are catalyst for one of zirconic acid magnalium or two kinds, higher alcohols and O-phthalic acid low carbon alcohol ester molar ratio 2.1~4.0, 160~220 DEG C of reaction temperature, 0.5~2h of volume space velocity‑1, O-phthalic acid low carbon alcohol ester conversion ratio and 99% or more phthalic acid high-carbon alcohol ester selectivity highest.The invention has the following advantages that raw material storage and transportation stability is good, charging is convenient；Side reaction is few, consumption of raw materials is low；Catalyst is corrosion-free and can be used continuously；Process cleans energy conservation, no waste water generates and discharge；Reaction is carried out continuously in fixed bed reactors, high-efficient.
Description
Technical field
The invention belongs to organic chemical industry fields, and in particular to a kind of transesterification successive reaction prepares phthalic acid higher alcohols
The method of ester.
Background technique
Plasticizer is the necessary assistant for producing the products such as polyester, plastics and rubber, for weakening active force between macromolecule, is increased
Bonus point subchain mobility reduces crystallinity, so that it is comprehensive to improve the plasticity of high molecular polymer, flexibility and draftability etc.
Energy.China mainly uses dibutyl phthalate (Dibutyl Phthalate, abbreviation DBP), dioctyl phthalate
The precipitation easy to migrate such as (Dioctyl Phthalate, abbreviation DOP), environment influence big low side plasticizer.DBP, DOP etc. are in day
The ground such as beauty, European Union are produced and are used by limitation, mainly by diisononyl phthalate (Diisononyl
Phthalate, abbreviation DINP), diisooctyl phthalate (Didecyl Phthalate, abbreviation DIDP), phthalic acid
The phthalic acids high-carbon alcohol ester substitution such as two (2- propyl heptan) esters (Di-2-propylheptyl Phthalate, abbreviation DPHP).
The structural formula of DBP, DOP, DINP, DIDP and DPHP are as shown below:
Wherein the comprehensive performance of DPHP is especially superior, has the advantage that (1) steam forces down, not volatile, product heatproof
Grade is high；(2) small toxicity is one of the main plasticizer kind on the ground such as Japan-US, European Union；(3) with polyvinyl chloride, polystyrene,
The compatibilities such as nitrocellulose, nitrile rubber, neoprene are good, are not easy to be precipitated；(4) durability, anti-fog property, weatherability, face
Color stability is good；(5) the Plastic Rubber Products surface of addition DPHP is smooth, flexibility is good, is not easily broken, and long service life is anti-aging
Property it is excellent, volume resistance is high, and water resistant, grease resistance are good (Zhang Li, Zhao Wenming, plastic additive, 2012,1,51~52).
The phthalic acids high-carbon such as DINP, DIDP, DPHP alcohol ester passes through neighbour mainly with sulfuric acid, titanate esters etc. for catalyst
The higher alcohols such as phthalate anhydride (phthalic anhydride) and isononyl alcohol, isodecanol, 2- propyl enanthol occur esterification and are made, and lack there are following
Point: (1) raw material phthalic anhydride storage and transportation stability is poor, and easy moisture absorption agglomeration, charging is inconvenient, and strong to human body irritation；(2) sulphur is used
The strong acid catalysts such as acid, equipment seriously corroded, and easily occur isononyl alcohol, isodecanol, the dehydration of higher alcohols such as 2- propyl enanthol,
The side reactions such as etherificate, consumption of raw materials are high；(3) reaction by-product and the equimolar water of phthalic anhydride, not only moisturize from cost, Er Qiehui
Generate waste water；(4) catalyst such as sulfuric acid, titanate esters cannot be recycled, and need to remove using the modes such as alkali cleaning and washing after reaction,
Generate a large amount of waste water；(5) use gap still reaction, low efficiency (Huang Yizheng, Xu Jie, Gao Jin, Miao Hong, Sun Ying, it is a kind of to prepare neighbour
The method of phthalic acid two (2- propyl heptan) ester, ZL201310374032.3).
Summary of the invention
In order to solve the phthalic acids higher alcohols ester plasticiser mistakes such as the current preparation of phthalic anhydride esterification process DINP, DIDP, DPHP
Raw material phthalic anhydride storage and transportation stability is poor in journey, it is inconvenient and strong to human body irritation to feed；Side reaction is more, and consumption of raw materials is high；It urges
Agent corrosivity is strong and cannot be recycled, and needs the processes such as alkali cleaning, washing to remove, generates a large amount of waste water；Reaction be gap reaction,
The outstanding problems such as low efficiency, the purpose of the present invention is: develop the neighbours such as a kind of preparation of transesterification successive reaction DINP, DIDP, DPHP
The method of phthalic acid high-carbon alcohol ester, have the advantage that (1) using repefral, diethyl phthalate,
It is raw material that the O-phthalics acid low carbon alcohol ester such as dibutyl phthalate, which replaces phthalic anhydride, and storage and transportation stability is good, and charging is convenient；(2)
Using ester-interchange method phthalic acid high-carbon alcohol ester, anhydrous generation is reacted, can not only reduce water separating energy consumption, but also can keep away
Exempt from the generation and discharge of technique waste water；(3) ester exchange catalyst researched and developed, corrosion-free and can be used continuously, side reaction is few,
Consumption of raw materials is low；(4) reaction is carried out continuously in fixed bed reactors, high-efficient.
To achieve the above object, the technical solution adopted by the present invention are as follows: it is shown below, in fixed bed reactors, with
O-phthalic acid low carbon alcohol ester and higher alcohols are raw material, in the presence of a catalyst, are prepared by transesterification successive reaction adjacent
Phthalic acid high-carbon alcohol ester.
The O-phthalic acid low carbon alcohol ester is repefral, diethyl phthalate and phthalic acid
One of dibutyl ester or two kinds or more；The higher alcohols are one of isononyl alcohol, isodecanol and 2- propyl enanthol or two kinds
More than；The phthalic acid high-carbon alcohol ester is diisononyl phthalate, diisooctyl phthalate, phthalic acid
One of two (2- propyl heptan) esters or two kinds or more
According to the present invention, catalyst is of crucial importance.When without catalyst, O-phthalic acid low carbon alcohol ester conversion ratio and adjacent benzene two
Formic acid high-carbon alcohol ester selectivity is all very low.When catalyst activity is low, O-phthalic acid low carbon alcohol ester conversion ratio is low, and main
Product is phthalic acid list low-carbon alcohols list high-carbon alcohol ester.When catalyst activity is high, O-phthalic acid low carbon alcohol ester could be obtained
High conversion and phthalic acid high-carbon alcohol ester it is highly selective.Reaction carries out in fixed bed reactors, and catalyst must
Reactant, product, intermediate product and by-product must not be dissolved in, and can be used continuously.The ester that the present invention researchs and develops is handed over
Change catalysts be magnesium aluminate calcium, sodium silicoaluminate, potassium aluminosilicate, aluminosilicate magnesium, ca aluminosilicate, aluminum magnesium titanate, magnesium titanate calcium,
One of zirconic acid magnalium or two kinds or more.
According to the present invention, ester exchange reaction is reversible reaction, to make reaction to generation phthalic acid high-carbon alcohol ester direction
It carries out, the higher alcohols such as isononyl alcohol, isodecanol, 2- propyl enanthol are slightly excessive, and the methanol, ethyl alcohol, butanol etc. for reacting generation
Low-carbon alcohols isolate reaction system using its low boiling point in time.The molar ratio of higher alcohols and O-phthalic acid low carbon alcohol ester is 2.1
~4.0, preferably 3.0~4.0.
According to the present invention, 160~220 DEG C of reaction temperature, preferably 200~220 DEG C；0.5~2.0h of reaction volume air speed-1,
It is preferred that 0.5~1.0h-1。
Beneficial effects of the present invention:
(1) ester-interchange method phthalic acid high-carbon alcohol ester is used, has the advantage that raw material storage and transportation stability is good,
Charging is convenient；Side reaction is few, consumption of raw materials is low；Process cleans energy conservation, no waste water generates and discharge；Catalyst is corrosion-free and can connect
It is continuous to use；Reaction is carried out continuously in fixed bed reactors, high-efficient.
(2) O-phthalic acid low carbon alcohol ester conversion ratio and phthalic acid high-carbon alcohol ester selectively up to 99% or more.
Specific embodiment
The following example helps to understand the present invention, but the content of present invention is not limited thereto.
Table 1, transesterification successive reaction phthalic acid high-carbon alcohol ester
Embodiment 1
100ml magnesium aluminate calcium catalyst is packed into fixed bed reactors to be pumped into and rub after reaction tube temperature is raised to 220 DEG C
You are than 2- propyl enanthol/repefral (DMP) mixed liquor for 3, flow set 100ml/h (volume space velocity 1h-1),
React continuous operation 4h after, sampling, by gas chromatography-mass spectrography carry out qualitative and quantitative analysis, raw material DMP conversion ratio with
And product DPHP selectivity is all up to 99% or more.After reacting continuous operation for 24 hours, sampling analysis again, DMP conversion ratio and DPHP
Selectivity is all up to 99% or more.
Embodiment 2~10
2~10 specific practice of embodiment is similar to Example 1, and reaction is tied afterwards for 24 hours for specific reaction condition and continuous operation
Fruit is as shown in table 1.With sodium silicoaluminate, potassium aluminosilicate, aluminosilicate magnesium, ca aluminosilicate, aluminum magnesium titanate, magnesium titanate calcium, zirconic acid magnalium,
Magnesium aluminate calcium is catalyst, the O-phthalics such as repefral, diethyl phthalate, dibutyl phthalate
Ester exchange reaction, higher alcohols and phthalic acid occur for the higher alcohols such as acid low carbon alcohol ester and 2- propyl enanthol, isononyl alcohol, isodecanol
The molar ratio of ester of low-carbon alcohol be 2.1~4.0,160~220 DEG C of reaction temperature, 0.5~2h of volume space velocity-1, phthalic acid low-carbon
Alcohol ester conversion rate and phthalic acid high-carbon alcohol ester are selectively all up 90% or more.
Comparative example 11~17
For the influence that the group of Study of Catalyst is reacted in pairs, comparative experiments has been carried out.It is original with DMP and 2- propyl enanthol
Material, with aluminium oxide, magnesia, calcium oxide, magnesium aluminate, calcium aluminate etc. for catalyst, carries out under the same conditions as example 1
Reaction, specific practice is similar to Example 1, and the results are shown in Table 2.
Table 2, transesterification successive reaction DPHP comparative example reaction result
Reaction condition: 2- propyl enanthol/DMP molar ratio be 3,220 DEG C of reaction temperature, volume space velocity 1.0h-1。
Embodiment 1 is using magnesium aluminate calcium as catalyst, and DMP conversion ratio and DPHP selectivity are all up to 99% or more.However, according to
Comparative example 11~14 is it is found that either individually using aluminium oxide, magnesia or calcium oxide as catalyst, or with its mixture
For catalyst, under same reaction conditions, the result of DMP conversion ratio and DPHP selectivity all than embodiment 1 is much lower.According to right
Than embodiment 15~17 it is found that either individually using magnesium aluminate or calcium aluminate as catalyst, or using its mixture as catalyst,
Under same reaction conditions, the result of DMP conversion ratio and DPHP selectivity also all than embodiment 1 is much lower, shows catalyst
Reaction result influence of the present invention is very big in pairs for group.
Described in summary, the present invention is in fixed bed reactors, with magnesium aluminate calcium, sodium silicoaluminate, potassium aluminosilicate, aluminosilicate
The above are catalyst, phthalic acids two for one of magnesium, ca aluminosilicate, aluminum magnesium titanate, magnesium titanate calcium, zirconic acid magnalium or two kinds
The O-phthalics such as methyl esters, diethyl phthalate, dibutyl phthalate acid low carbon alcohol ester and isononyl alcohol, isodecanol, 2-
Ester exchange reaction, O-phthalic acid low carbon alcohol ester conversion ratio and phthalic acid high-carbon alcohol ester occur for the higher alcohols such as propyl enanthol
Selectivity reaches as high as 99% or more.The invention has the following advantages that raw material storage and transportation stability is good, charging is convenient；Side reaction is few,
Consumption of raw materials is low；Catalyst is corrosion-free and can be used continuously；Process cleans energy conservation, no waste water generates and discharge；Reaction is in fixation
It is carried out continuously in bed reactor, it is high-efficient.
Claims (3)
1. a kind of method that transesterification successive reaction prepares phthalic acid high-carbon alcohol ester, it is characterised in that: in fixed bed reaction
In device, using O-phthalic acid low carbon alcohol ester and higher alcohols as raw material, in the presence of a catalyst, phthalic acid high-carbon is prepared
Alcohol ester；
The O-phthalic acid low carbon alcohol ester is two fourth of repefral, diethyl phthalate and phthalic acid
One of ester or two kinds or more；The higher alcohols are one of isononyl alcohol, isodecanol and 2- propyl enanthol or two kinds or more；
The phthalic acid high-carbon alcohol ester is diisononyl phthalate, diisooctyl phthalate, two (2- of phthalic acid
Propyl heptan) one of ester or two kinds or more；The catalyst be magnesium aluminate calcium, sodium silicoaluminate, potassium aluminosilicate, aluminosilicate magnesium,
One of ca aluminosilicate, aluminum magnesium titanate, magnesium titanate calcium, zirconic acid magnalium or two kinds or more.
2. the method as described in claim 1, it is characterised in that: in fixed bed reactors, higher alcohols and phthalic acid are low
The molar ratio of carbon alcohol ester is 2.1~4.0, preferably 3.0~4.0；160~220 DEG C of reaction temperature, preferably 200~220 DEG C；Reaction
0.5~2.0h of volume space velocity-1, preferably 0.5~1.0h-1。
3. method according to claim 1 or 2, it is characterised in that: reaction equation is as follows:
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112547037A (en) * | 2019-09-24 | 2021-03-26 | 中国石油化工股份有限公司 | Use of aluminosilicate compounds as catalysts in the preparation of dimethyl carbonate |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3507905A (en) * | 1965-06-09 | 1970-04-21 | Rhone Poulenc Sa | Continuous preparation of glycol phthalates |
| CN102675102A (en) * | 2012-04-27 | 2012-09-19 | 孝感市易生新材料有限公司 | Continuous production method of high-content high-optical-purity lactate |
| CN104418747A (en) * | 2013-08-22 | 2015-03-18 | 中国科学院大连化学物理研究所 | Method for preparation of phthalate di(2-propyl heptyl) ester |
| CN105646229A (en) * | 2014-12-04 | 2016-06-08 | 中国科学院大连化学物理研究所 | Method used for preparing higher aliphatic phthalates via ester exchange |
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2017
- 2017-06-02 CN CN201710408372.1A patent/CN108976117B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3507905A (en) * | 1965-06-09 | 1970-04-21 | Rhone Poulenc Sa | Continuous preparation of glycol phthalates |
| CN102675102A (en) * | 2012-04-27 | 2012-09-19 | 孝感市易生新材料有限公司 | Continuous production method of high-content high-optical-purity lactate |
| CN104418747A (en) * | 2013-08-22 | 2015-03-18 | 中国科学院大连化学物理研究所 | Method for preparation of phthalate di(2-propyl heptyl) ester |
| CN105646229A (en) * | 2014-12-04 | 2016-06-08 | 中国科学院大连化学物理研究所 | Method used for preparing higher aliphatic phthalates via ester exchange |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112547037A (en) * | 2019-09-24 | 2021-03-26 | 中国石油化工股份有限公司 | Use of aluminosilicate compounds as catalysts in the preparation of dimethyl carbonate |
| CN112547037B (en) * | 2019-09-24 | 2023-07-04 | 中国石油化工股份有限公司 | Use of aluminosilicate compounds as catalysts in the preparation of dimethyl carbonate |
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