CN105646229B - A kind of method that ester exchange prepares phthalic acid high-carbon alcohol ester - Google Patents
A kind of method that ester exchange prepares phthalic acid high-carbon alcohol ester Download PDFInfo
- Publication number
- CN105646229B CN105646229B CN201410730031.2A CN201410730031A CN105646229B CN 105646229 B CN105646229 B CN 105646229B CN 201410730031 A CN201410730031 A CN 201410730031A CN 105646229 B CN105646229 B CN 105646229B
- Authority
- CN
- China
- Prior art keywords
- phthalic acid
- ester
- carbon alcohol
- alcohol ester
- titanate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
The present invention relates to a kind of method that ester exchange prepares phthalic acid high-carbon alcohol ester, with repefral, diethylester, the O-phthalic such as dibutyl ester acid low carbon alcohol ester and isononyl alcohol, isodecanol, the higher alcohols such as 2 propyl enanthols are raw material, with titanium potassium oxalate, aluminium titanates, potassium titanate, magnesium titanate, calcium titanate, zirconia titanate, barium titanate, alchlor, antimony trichloride, titanium tetrachloride, zirconium chloride, four methanol titaniums, four (2 propyl enanthol) titaniums, four isononyl alcohol titaniums, one or more in four isodecanol titaniums are catalyst, 160~200 DEG C of 2~6h of reaction, O-phthalic acid low carbon alcohol ester conversion ratio and phthalic acid high-carbon alcohol ester selectively up to more than 99%.The present invention has process cleans energy-conservation, raw material accumulating stability good and the advantages such as charging is convenient, catalytic erosion is small, reaction condition is gentle, side reaction is few, consumption of raw materials is low.
Description
Technical field
The invention belongs to organic synthesis field, and in particular to a kind of ester exchange prepares the side of phthalic acid high-carbon alcohol ester
Method.
Background technology
Plasticizer is the essential auxiliary agents of product such as production plastics, rubber and polyester, and effect is to weaken polymer point
Sub- intermolecular forces, increase the mobility of strand, reduce crystallinity, improve processability, plasticity, pliability and the drawing of polymer
The combination properties such as stretching property.
China is mainly using low sides such as dibutyl phthalate (abbreviation DBP), dioctyl phthalates (abbreviation DOP)
Plasticizer.The meeting migration precipitation of these plasticizer, environment influence greatly, to have been produced and made by limitation on the U.S., Japan, European Union and other places
With mainly by diisononyl phthalate (abbreviation DINP), diisooctyl phthalate (abbreviation DIDP), O-phthalic
The phthalic acid high-carbon alcohol esters such as acid two (2- propyl group heptan) ester (abbreviation DPHP) substitute.The phthalic acids such as DINP, DIDP, DPHP
The steam of high-carbon alcohol ester forces down, volatility is small, small toxicity, ageing-resistant performance are good, there is the development trend for substituting DBP, DOP.Wherein
It is particularly superior with DPHP combination property, it is mainly manifested in:(1) steam forces down, not volatile, and applied at elevated temperature security is good, increases
Molding product temperature resistant grade is high;(2) small toxicity, it is one of the main environment-friendly plasticizer kind on the ground such as the U.S., Japan, European Union;(3) phase
Capacitive:It is good with the compatibility such as PVC, NC Nitroncellulose, polystyrene, ethyl cellulose, nitrile rubber, neoprene, it is not easy to analyse
Go out;(4) durability, anti-fog property:It is suitable with DIDP, better than DOP and DINP;(5) weather resisteant, colour stability:Better than DIDP,
DINP and DOP;(6) Plastic Rubber Products:Surface is smooth, flexibility is good, is not easily broken, and service life length, heating loss is few, 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).DBP、DOP、
DINP, DIDP and DPHP structural formula are as follows:
The phthalic acid high-carbon such as DINP, DIDP, DPHP alcohol ester passes through phthalic anhydride mainly using sulfuric acid as catalyst
The higher alcohols such as (abbreviation phthalic anhydride) and isononyl alcohol, isodecanol, 2- propyl enanthols occur esterification and are made, and have the following disadvantages:(1)
By-product and the equimolar water of phthalic anhydride are reacted, is not only moisturized from cost, and waste water can be produced;(2) raw material phthalic anhydride normal temperature is normal
Depress as solid, accumulating stability is poor, and easy moisture absorption caking, charging is inconvenient, and strong to human body excitant;(3) sulfuric acid is used
Deng strong acid catalyst, etching apparatus, and react and carried out under the harsh conditions such as high temperature, higher alcohols are easily dehydrated, are etherified
Side reaction, consumption of raw materials height (Jiang Pingping, Zhang Shuyuan, cold inflammation, Dong Yuming, Zhang Pingbo, chemical industry progress, 2012,31 (5), 953~
963)。
The content of the invention
It can be produced to solve the phthalic acid high-carbon alcohol ester processes such as the current preparation of phthalic anhydride esterification process DIDP, DINP, DPHP
Raw technique waste water, raw material phthalic anhydride accumulating stability is poor, charging is inconvenient and strong to human body excitant, and catalytic erosion is strong,
Side reaction is more, the outstanding problem such as consumption of raw materials height, and the purpose of the present invention is:Develop a kind of ester exchange prepare DIDP, DINP and
The method of the phthalic acid high-carbon alcohol ester such as DPHP, has advantages below:(1) process cleans save:Anhydrous generation is reacted, not only
Water separating energy consumption can be reduced, and the generation and discharge of technique waste water can be avoided;(2) using repefral, diethyl
The O-phthalic such as ester, dibutyl ester acid low carbon alcohol ester replaces phthalic anhydride, and accumulating stability is good, and reaction feed is convenient;(3) research and develop
Ester exchange catalyst is small to corrosion of equipment or corrosion-free, and reaction condition is gentle, and side reaction is few, and consumption of raw materials is lower.
To achieve the above object, the technical solution adopted by the present invention is shown below:
O-phthalic acid low carbon alcohol ester described in formula be repefral, diethylester, one kind in dibutyl ester or
More than one.The higher alcohols are more than one or both of isononyl alcohol, isodecanol, 2- propyl enanthols.
According to the present invention, catalyst is to O-phthalic acid low carbon alcohol ester conversion ratio, phthalic acid high-carbon alcohol ester selectivity
Influence extremely big.During without catalyst, O-phthalic acid low carbon alcohol ester conversion ratio and phthalic acid high-carbon alcohol ester selectivity are all non-
It is often low.When catalyst activity is low, O-phthalic acid low carbon alcohol ester conversion ratio is low, and primary product is phthalic acid list high-carbon
Alcohol ester.When catalyst activity is high, O-phthalic acid low carbon alcohol ester high conversion could be obtained and phthalic acid high-carbon alcohol ester is high
Selectivity.
The present invention researchs and develops the catalyst for ester exchange reaction as titanium potassium oxalate, aluminium titanates, potassium titanate, magnesium titanate, titanium
Sour calcium, zirconia titanate, barium titanate, alchlor, antimony trichloride, titanium tetrachloride, zirconium chloride, four methanol titaniums, four (2- propyl group heptan
Alcohol) titanium, four isononyl alcohol titaniums, it is more than one or both of four isodecanol titaniums.
According to the present invention, ester exchange reaction is reversible reaction, to make reaction to generation phthalic acid high-carbon alcohol ester direction
Carry out, the higher alcohols such as isononyl alcohol, isodecanol, 2- propyl enanthols are excessive, higher alcohols and repefral, diethylester, two
The mol ratio of the O-phthalic acid low carbon alcohol ester such as butyl ester is more than 2.However, the mol ratio of higher alcohols and O-phthalic acid low carbon alcohol ester
When too high, the energy consumption of separation and recovery higher alcohols can be increased.The mol ratio of higher alcohols of the present invention and O-phthalic acid low carbon alcohol ester is excellent
Select 2.1~4.0.On the other hand, to make reaction be carried out to generation phthalic acid high-carbon alcohol ester direction, the methanol of by-product, ethanol,
The low-carbon alcohols such as butanol isolate reaction system in time by water knockout drum.
According to the present invention, catalyst amount is preferably the 0.1~1.0% of O-phthalic acid low carbon alcohol ester quality, reaction temperature
Preferably 160~200 DEG C of degree, reaction time preferably 2~6h.
Beneficial effects of the present invention
1. the ester of the ester conversion rates of phthalic acid low-carbon alcohols and phthalic acid higher alcohols selectively up to 99% with
On.
2. the present invention has, process cleans energy-conservation, raw material accumulating stability are good and charging is convenient, catalytic erosion is small, anti-
Answer the advantages such as mild condition, side reaction are few, consumption of raw materials is low.
Embodiment
The following example helps to understand the present invention, but present invention is not limited thereto.
The reaction condition and result of table 1, ester exchange phthalic acid high-carbon alcohol ester
Embodiment 1
By 19.4 grams of repefrals (abbreviation DMP, 0.1 mol), 47.5 grams of 2- propyl enanthols (0.3 mol),
0.2 gram of titanium potassium oxalate (for the 1.0% of DMP mass) is added in two mouthfuls of round-bottomed flasks of 100 ml equipped with water knockout drum, on water knockout drum
Condenser pipe is connected, is stirred, 200 DEG C is warming up to and reacts 5 hours, mixture is entered by gas chromatography-mass spectrography after reaction
Row qualitative analysis, and quantitative analysis is carried out by gas-chromatography, DMP conversion ratios and DPHP selectivity are all up to more than 99%.
Embodiment 2
Catalyst blank assay:Catalyst is not added with, other conditions are same as Example 1, DMP conversion ratios only up to 50%,
DPHP selectively only 5%.
Embodiment 3~21
The specific practice of embodiment 3~21 is similar to Example 1, and specific reaction condition and result are as shown in table 1.
It was found from catalyst blank assay, DMP and 2- propyl enanthols in 200 DEG C of heating responses 5 hours, DMP conversion ratios and
DPHP selectivity all very low (embodiment 2).The concentrated sulfuric acid occurs esterification preparation DPHP with phthalic anhydride to 2- propyl enanthols and urged
Change effect is fine, and phthalic anhydride conversion ratio and DPHP are selectively all up more than 99%.However, the concentrated sulfuric acid is used to be catalyzed DMP and 2-
The ester exchange reaction of propyl enanthol, although DMP conversion ratios selectively only have 80% (embodiment up to more than 99%, DPHP
3).Attempt using tin titan as catalyst, reaction result (embodiment 4) as catalyst blank assay under the same terms.With titanium
Sour iron is catalyst, and DMP conversion ratios slightly raise under the same terms, but DPHP selectivity still very low (embodiment 5).However,
Using aluminium titanates, potassium titanate, magnesium titanate, calcium titanate, zirconia titanate, barium titanate as catalyst, repefral, diethylester,
Ester exchange reaction occurs for the higher alcohols such as the O-phthalic such as dibutyl ester acid low carbon alcohol ester and 2- propyl enanthols, isononyl alcohol, isodecanol, adjacent
Phthalic acid ester of low-carbon alcohol conversion ratio and phthalic acid high-carbon alcohol ester are selectively all up more than 90% (embodiment 6~11).
When especially using potassium titanate as catalyst, DMP conversion ratios and DPHP are selectively all up more than 99% (embodiment 7).
Using ferric trichloride and zinc chloride as catalyst, DMP conversion ratios and DPHP selectivity not high (embodiment 12~13).
However, using alchlor, antimony trichloride, titanium tetrachloride, zirconium chloride as catalyst, repefral, diethylester, two
Ester exchange reaction, adjacent benzene occur for the higher alcohols such as the O-phthalic such as butyl ester acid low carbon alcohol ester and 2- propyl enanthols, isononyl alcohol, isodecanol
Diformazan acid low carbon alcohol ester conversion ratio and phthalic acid high-carbon alcohol ester are selectively all up more than 90% (embodiment 14~17).Especially
When it is using antimony trichloride as catalyst, DMP conversion ratios and DPHP are selectively all up more than 99% (embodiment 15).
Using four methanol titaniums as catalyst, DMP and 2- propyl enanthols are in 200 DEG C of heating responses 5 hours, DMP conversion ratios
90%, DPHP selectivity are 88% (embodiment 18).Using four (2- propyl enanthols) titaniums, four isononyl alcohol titaniums, four isodecanol titaniums to urge
It is the O-phthalic such as agent, repefral, diethylester, dibutyl ester acid low carbon alcohol ester and 2- propyl enanthols, isononyl alcohol, different
Ester exchange reaction, O-phthalic acid low carbon alcohol ester conversion ratio and phthalic acid high-carbon alcohol ester selectivity occur for the higher alcohols such as decyl alcohol
It is all up more than 99% (embodiment 19~21).
Described in summary, the present invention uses ester-interchange method phthalic acid high-carbon alcohol ester, compared with phthalic anhydride esterification process, this
Invention saves with process cleans, raw material accumulating stability is good and charging is convenient, catalytic erosion is small, reaction condition is gentle,
The advantages such as side reaction is few, consumption of raw materials is low.
Claims (3)
1. a kind of method that ester exchange prepares phthalic acid high-carbon alcohol ester, it is characterised in that:With O-phthalic acid low carbon alcohol ester
It is raw material with higher alcohols, under catalyst action, prepares phthalic acid high-carbon alcohol ester, reaction equation is as follows:
The O-phthalic acid low carbon alcohol ester is repefral, diethyl phthalate or the fourth of phthalic acid two
It is more than one or both of ester;
The higher alcohols are more than one or both of isononyl alcohol, isodecanol or 2- propyl enanthols;
The catalyst be titanium potassium oxalate, aluminium titanates, potassium titanate, magnesium titanate, calcium titanate, zirconia titanate, barium titanate, alchlor,
It is more than one or both of antimony trichloride, titanium tetrachloride or zirconium chloride.
2. the method as described in claim 1, it is characterised in that:The mol ratio of higher alcohols and O-phthalic acid low carbon alcohol ester is
2.1 ~ 4.0, catalyst amount is the 0.1 ~ 1.0% of O-phthalic acid low carbon alcohol ester quality.
3. the method as described in claim 1, it is characterised in that:Reaction temperature is 160 ~ 200oC, reaction time are 2 ~ 6h.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201410730031.2A CN105646229B (en) | 2014-12-04 | 2014-12-04 | A kind of method that ester exchange prepares phthalic acid high-carbon alcohol ester |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201410730031.2A CN105646229B (en) | 2014-12-04 | 2014-12-04 | A kind of method that ester exchange prepares phthalic acid high-carbon alcohol ester |
Publications (2)
Publication Number | Publication Date |
---|---|
CN105646229A CN105646229A (en) | 2016-06-08 |
CN105646229B true CN105646229B (en) | 2018-01-02 |
Family
ID=56480796
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201410730031.2A Active CN105646229B (en) | 2014-12-04 | 2014-12-04 | A kind of method that ester exchange prepares phthalic acid high-carbon alcohol ester |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN105646229B (en) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
CN108976126B (en) * | 2017-06-02 | 2021-02-02 | 中国科学院大连化学物理研究所 | Method for preparing methyl ethyl carbonate through ester exchange reaction |
US11111203B2 (en) * | 2019-04-04 | 2021-09-07 | Lg Chem, Ltd. | System and method for manufacturing ester-based composition |
CN113209957B (en) * | 2021-04-26 | 2022-09-20 | 万华化学集团股份有限公司 | Catalyst and application thereof in production of special ester products |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2003238479A (en) * | 2002-02-13 | 2003-08-27 | Mitsubishi Chemicals Corp | Method for producing higher alcohol terephthalic acid ester |
CN101925571A (en) * | 2008-01-28 | 2010-12-22 | 赢创奥克森诺有限责任公司 | Mixtures of diisononyl esters of terephthalic acid, method for production thereof and use thereof |
-
2014
- 2014-12-04 CN CN201410730031.2A patent/CN105646229B/en active Active
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2003238479A (en) * | 2002-02-13 | 2003-08-27 | Mitsubishi Chemicals Corp | Method for producing higher alcohol terephthalic acid ester |
CN101925571A (en) * | 2008-01-28 | 2010-12-22 | 赢创奥克森诺有限责任公司 | Mixtures of diisononyl esters of terephthalic acid, method for production thereof and use thereof |
Non-Patent Citations (2)
Title |
---|
酯交换反应催化剂的研究与应用;沈国良,李森林;《工业催化》;20081031;第16卷(第10期);4-5 * |
酯交换法合成邻苯二甲酸二异辛酯;刘霞;《河南化工》;20041231(第7期);11-13 * |
Also Published As
Publication number | Publication date |
---|---|
CN105646229A (en) | 2016-06-08 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN105646229B (en) | A kind of method that ester exchange prepares phthalic acid high-carbon alcohol ester | |
CN102924279B (en) | A kind of process for catalytic synthesis of trioctyl trimellitate | |
CN103113617B (en) | Novel plasticizer and preparation method thereof | |
KR101099127B1 (en) | Method of preparing of 60% or more cis-di(C4-C20)alkyl cyclohexane-1,4-dicarboxylate | |
CN109516971A (en) | A kind of synthetic method of LITHIUM BATTERY sulfuric acid vinyl ester | |
TW201815933A (en) | Plasticizer composition and resin composition including the same | |
CN105344341B (en) | A kind of preparation method of solid catalyst for Synthesis of dimethyl carbonate | |
CN104370743B (en) | The preparation method of plasticizer triethylene glycol two tricaprylates | |
CN104418747B (en) | One prepares the method for phthalic acid two (2-propyl group heptan) ester | |
CN104151164A (en) | Method for preparing methyl chloroacetate | |
CN101376631B (en) | Environment-protective preparation method of diglycol ethylene dibenzoate plasticiser | |
EP3281977B1 (en) | Plasticizer composition, resin composition, and methods for preparing same | |
JP2010018629A5 (en) | ||
CN102219688A (en) | Method for improving thermal stability of dibutyl/diisobutyl phthalate | |
CA2861603C (en) | Methods for preparing acrylic acid from biobased starting materials | |
TWI529159B (en) | Method for continuously preparing carboxylic acid esters | |
CN108976117B (en) | Method for preparing high-carbon alcohol phthalate through ester exchange continuous reaction | |
CN104045555B (en) | A kind of preparation method of triglycol dicarboxylic ester | |
CN103664618A (en) | Novel synthesis process of octyl 2-propylheptyl phthalate | |
JP6010787B2 (en) | Catalyst for acetylation of alcohol, and method for producing acetylated product of alcohol using the catalyst | |
CN102643198A (en) | Preparation method of tripalmitin citrate | |
CN108976116B (en) | Method for preparing phthalic acid high carbon alcohol ester by titanium chelate catalysis ester exchange | |
CN107029692A (en) | A kind of preparation method of ester exchange synthesizing diphenyl carbonate CNT Quito phase catalyst | |
CN101485998B (en) | Application of organic phosphonic acid as esterification reaction catalyst | |
CN105753665A (en) | Process method for catalytic synthesis of 1,1,1,3,3,3-hexafluoro isopropyl methyl ether |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |