CN107778175A - The synthesis technique of the tricaprylate of Isosorbide-5-Nitrae cyclohexanedimethanol two - Google Patents
The synthesis technique of the tricaprylate of Isosorbide-5-Nitrae cyclohexanedimethanol two Download PDFInfo
- Publication number
- CN107778175A CN107778175A CN201610737186.8A CN201610737186A CN107778175A CN 107778175 A CN107778175 A CN 107778175A CN 201610737186 A CN201610737186 A CN 201610737186A CN 107778175 A CN107778175 A CN 107778175A
- Authority
- CN
- China
- Prior art keywords
- reaction
- hydrogenation
- synthesis
- tricaprylate
- acid
- 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.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a kind of method of synthesizing ester, more particularly to a kind of tricaprylate of synthesis Isosorbide-5-Nitrae cyclohexanedimethanol two.Preparation process includes：At a temperature of superatmospheric pressure, 250 400 DEG C, add in a kettle to phenylenediacetic Acid with（4 methylcyclohexyls）Methanol, after stirring, fully reaction, obtain double to phenylenediacetic Acid（4 methylcyclohexyls）Methyl esters；Zn Ge/C catalyst is added into reaction system, it is passed through hydrogen, it is filled with hydrogen and carries out hydrogenation, during hydrogenation, controls hydrogenation rate, the temperature in reactor is maintained at 100 150 DEG C and be maintained at 1 3Mpa with pressure, after hydrogenation reaction terminates, 90 100 DEG C are cooled to, slowly opens exhaust outlet, obtain Isosorbide-5-Nitrae cyclohexanedimethanol；Isosorbide-5-Nitrae cyclohexanedimethanol prepared by step 1 and isooctyl acid are added in reaction vessel, then add super acidic catalyst SO4 2‑/TiO2/ Ce, 100 200 DEG C of reaction temperature react 5 15 h, and reaction terminates stopping heating and obtains crude product；The post processing of product.The synthetic route is adapted to industrialized production.
Description
Technical field
The present invention relates to a kind of method of synthesizing ester, more particularly to a kind of synthesis isooctyl acid of 1,4-CHDM two
The technique of ester.
Background technology
The tricaprylate of 1,4-CHDM two has good heat endurance and antioxidant, is widely used in being plasticized
Agent, cosmetics, senior lubricant etc., for example, it can be used as prepare jet engine senior lubricant.Because branched chain fatty acid is deposited
In steric hindrance so that reaction is more difficult to be carried out completely, therefore exploitation is suitable for the 1,4-CHDM two of industrialized production
The synthesis technique of tricaprylate is necessary.
Existing synthetic route is generally divided into three steps, and first two step hydrogenations prepare 1,4-CHDM, then general
The tricaprylate of 1,4-CHDM two is synthesized in organic solvent.Process route is complicated, and production cost is high, does not meet green
The technical requirements of chemistry, easily cause environmental pollution in hydriding process.And metal oxide, sulfuric acid etc. are typically chosen to urge
Agent, the defects of reagent is more expensive, and corrosivity is larger, potential safety hazard is big, yield is relatively low be present in reagent production, be unfavorable for industry
Production.As can be seen here, existing synthetic route, is not easy to industrialized production.Need badly and seek a kind of easy to operate, reaction condition
The preparation method of the gentle tricaprylate of 1,4-CHDM two.
The content of the invention
Present invention aims at solve above-mentioned technical problem present in prior art, there is provided one kind synthesis Isosorbide-5-Nitrae-hexamethylene
The method of the tricaprylate of dimethanol two.
In order to solve the above-mentioned technical problem, the present invention adopts the following technical scheme that.
A kind of method for synthesizing the tricaprylate of 1,4-CHDM two, preparation process include.
Step 1: the synthesis of 1,4 cyclohexane dimethanol.
1. at a temperature of superatmospheric pressure, 250-400 DEG C, add in a kettle to phenylenediacetic Acid with（4- methyl rings
Hexyl）Methanol, after stirring, fully reaction, obtain double to phenylenediacetic Acid（4- methylcyclohexyls）Methyl esters.
2. adding Zn-Ge/C catalyst into reaction system, hydrogen is passed through, hydrogen is filled with and carries out hydrogenation, hydrogenating
During reaction, hydrogenation rate is controlled, the temperature in reactor is maintained at 100-150 DEG C and is maintained at 1-3Mpa with pressure, be hydrogenated with
After reaction terminates, 90-100 DEG C is cooled to, slowly opens exhaust outlet, obtains 1,4- cyclohexanedimethanols.
Step 2: the synthesis of the tricaprylate of 1,4-CHDM two.
1. 1,4- cyclohexanedimethanols prepared by step 1 and isooctyl acid are added in reaction vessel, then add superpower
Acid catalyst SO4 2-/TiO2/ Ce, 100-200 DEG C of reaction temperature, 5-15 h are reacted, it is anti-that reaction end stopping heating obtaining crude product
Answer liquid.
Step 3: the post processing of product.
By reacting liquid filtering, catalyst is filtered out by washing, reclaims and uses after drying.Filtrate is washed with 5% NaOH solution
4 times.Organic phase be washed with water, saturated common salt water washing, anhydrous sodium sulfate drying, the pale yellow oily liquid of vacuum distillation.
It is described to phenylenediacetic Acid with（4- methylcyclohexyls）Methanol is with 1:1 molar ratio reaction.
Described hydrogen is with being 2 to the mol ratio of phenylenediacetic Acid:1.
Described 1,4- cyclohexanedimethanols are with isooctyl acid with 1:2 molar ratio reaction.
Described Zn-Ge/C catalyst, is by ZnCl2And GeCl2With simple substance carbon in molar ratio 2:3:2 are mixed with and form.
Described super acidic catalyst SO4 2-/TiO2/ Ce preparation methods are specially：Take TiCl4The aqueous solution is hydrolyzed with weak aqua ammonia
In alkalescence（PH=9-11）, filtered after standing 24 h, wash, obtain a large amount of white depositions.Solid is ground after 110-130 DEG C of drying
Clay into power.It is then added in the concentrated sulfuric acid solution of 0.5 M cerous sulfates, after reaction 8-14 h, filtration drying, is placed in muffle furnace
Roasting, produces super acidic catalyst SO4 2-/TiO2/Ce。
Beneficial effects of the present invention.
In the present invention, by two-step reaction can synthesis material 1,4-CHDM, first in superatmospheric pressure bar
Synthesis is double to phenylenediacetic Acid under part（4- methylcyclohexyls）Methyl esters, then in the higher Zn-Ge/C catalysts of catalytic activity
Under the conditions of, then hydrogenation is carried out, produce 1,4-CHDM.The synthesis technique of the raw material is relative to existing stage
Hydrogenation synthesis, technique is simple, and reaction condition does not need HTHP, easily controllable.
Raw material 1,4 cyclohexane dimethanol can make the sufficient super acidic catalyst SO of organic reaction with isooctyl acid4 2-/
TiO2The tricaprylate of 4- cyclohexanedimethanols two is synthesized under/Ce1 catalytic conditions, synthetic route is simple, mild condition, process route
It is green.Raw material sources enrich, and price is low, can reduce production cost, and finished product per ton can save 1500 yuan or so.What is synthesized is different
Sad vinyl acetate purity is higher than 99%, and yield reaches 80%, is adapted to large-scale industrial production.
Embodiment
Technical solution of the present invention is described in further detail below in conjunction with specific embodiment.
Embodiment 1.
A kind of method for synthesizing the tricaprylate of 1,4-CHDM two, preparation process include.
Step 1: the synthesis of 1,4 cyclohexane dimethanol.
1. at a temperature of superatmospheric pressure, 250-400 DEG C, add in a kettle to phenylenediacetic Acid 50mol with（4- first
Butylcyclohexyl）Methanol 50mol, after stirring, fully reaction, obtain double to phenylenediacetic Acid（4- methylcyclohexyls）Methyl esters.
2. adding Zn-Ge/C catalyst into reaction system, hydrogen 100mol is passed through, hydrogen is filled with and hydrogenate instead
Should, during hydrogenation, hydrogenation rate is controlled, the temperature in reactor is maintained at 150 DEG C and is maintained at 3Mpa with pressure, add
After hydrogen reaction terminates, 90 DEG C are cooled to, slowly opens exhaust outlet, obtains 1,4- cyclohexanedimethanols.
Step 2: the synthesis of the tricaprylate of 1,4-CHDM two.
1. 1,4- cyclohexanedimethanols prepared by step 1 and isooctyl acid are added in reaction vessel, then add superpower
Acid catalyst SO4 2-/TiO2/ Ce, 150 DEG C of reaction temperature react 10 h, and reaction terminates stopping heating and obtains crude product.
Step 3: the post processing of product.
By reacting liquid filtering, catalyst is filtered out by washing, reclaims and uses after drying.Filtrate is washed with 5% NaOH solution
4 times.Organic phase be washed with water, saturated common salt water washing, anhydrous sodium sulfate drying, the pale yellow oily liquid of vacuum distillation.
Embodiment 2.
A kind of method for synthesizing the tricaprylate of 1,4-CHDM two, preparation process include.
Step 1: the synthesis of 1,4 cyclohexane dimethanol.
1. at a temperature of superatmospheric pressure, 400 DEG C, add in a kettle to phenylenediacetic Acid 70mol with（4- methyl
Cyclohexyl）Methanol 70mol, after stirring, fully reaction, obtain double to phenylenediacetic Acid（4- methylcyclohexyls）Methyl esters.
2. adding Zn-Ge/C catalyst into reaction system, hydrogen 140mol is passed through, hydrogen is filled with and hydrogenate instead
Should, during hydrogenation, hydrogenation rate is controlled, the temperature in reactor is maintained at 180 DEG C and is maintained at 1Mpa with pressure, add
After hydrogen reaction terminates, 100 DEG C are cooled to, slowly opens exhaust outlet, obtains 1,4- cyclohexanedimethanols.
Step 2: the synthesis of the tricaprylate of 1,4-CHDM two.
1. 1,4- cyclohexanedimethanols prepared by step 1 and isooctyl acid are added in reaction vessel, then add superpower
Acid catalyst SO4 2-/TiO2/ Ce, 100 DEG C of reaction temperature react 15 h, and reaction terminates stopping heating and obtains crude product.
Step 3: the post processing of product.
By reacting liquid filtering, catalyst is filtered out by washing, reclaims and uses after drying.Filtrate is washed with 5% NaOH solution
4 times.Organic phase be washed with water, saturated common salt water washing, anhydrous sodium sulfate drying, the pale yellow oily liquid of vacuum distillation.
One, is analyzed the raw material fraction of Zn-Ge/C catalyst, and analysis result is shown in Table 1.
The ZnCl of table 12And GeCl2With the C influences to the 1,4 cyclohexane dimethanol yield of embodiment 1 in molar ratio.
As can be seen here, in 1,4-CHDM Material synthesis technique, the proportionate relationship of raw material is set to 2:3:When 2,
Yield highest.
The tricaprylate of 1,4-CHDM two of this synthesis route synthesis, up to 82%, purity is higher than high income
99%, and there is good heat endurance and antioxidant, it is widely used in plasticizer, cosmetics, senior lubricant etc., wherein,
It can be as the valable starting materials for preparing jet engine senior lubricant lubricating esters.
Claims (5)
1. a kind of synthesis technique of the tricaprylate of 1,4-CHDM two, it is characterised in that preparation process includes：Step
First, the synthesis of 1,4 cyclohexane dimethanol：
1. at a temperature of superatmospheric pressure, 250-400 DEG C, add in a kettle to phenylenediacetic Acid with（4- methylcyclohexyls）
Methanol, after stirring, fully reaction, obtain double to phenylenediacetic Acid（4- methylcyclohexyls）Methyl esters；
Zn-Ge/C catalyst is added into reaction system, is passed through hydrogen, hydrogen is filled with and carries out hydrogenation, in the hydrogenation phase
Between, hydrogenation rate is controlled, the temperature in reactor is maintained at 100-150 DEG C and is maintained at 1-3Mpa, hydrogenation reaction knot with pressure
Shu Hou, 90-100 DEG C is cooled to, slowly opens exhaust outlet, obtain 1,4- cyclohexanedimethanols；
Step 2: the synthesis of the tricaprylate of 1,4-CHDM two：
1. 1,4- cyclohexanedimethanols prepared by step 1 and isooctyl acid are added in reaction vessel, then add super acids and urge
Agent SO4 2-/TiO2/ Ce, 100-200 DEG C of reaction temperature react 5-15 h, and reaction terminates stopping heating and obtains crude product；
Step 3: the post processing of product：
By reacting liquid filtering, catalyst is filtered out by washing, reclaims and uses after drying；Filtrate is washed 4 times with 5% NaOH solution；
Organic phase be washed with water, saturated common salt water washing, anhydrous sodium sulfate drying, the pale yellow oily liquid of vacuum distillation.
2. synthetic method as claimed in claim 1, it is characterised in that it is described to phenylenediacetic Acid with（4- methylcyclohexyls）First
Alcohol is with 1:1 molar ratio reaction.
3. synthesis technique as claimed in claim 1, it is characterised in that described hydrogen is with being 2 to the mol ratio of phenylenediacetic Acid:
1。
4. synthesis technique as claimed in claim 1, it is characterised in that described 1,4- cyclohexanedimethanols and isooctyl acid with
1:2 molar ratio reaction.
5. synthesis technique as claimed in claim 1, it is characterised in that described Zn-Ge/C catalyst, is by ZnCl2With
GeCl2With simple substance carbon in molar ratio 2:3:2 are mixed with and form.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610737186.8A CN107778175A (en) | 2016-08-29 | 2016-08-29 | The synthesis technique of the tricaprylate of Isosorbide-5-Nitrae cyclohexanedimethanol two |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610737186.8A CN107778175A (en) | 2016-08-29 | 2016-08-29 | The synthesis technique of the tricaprylate of Isosorbide-5-Nitrae cyclohexanedimethanol two |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107778175A true CN107778175A (en) | 2018-03-09 |
Family
ID=61439899
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610737186.8A Pending CN107778175A (en) | 2016-08-29 | 2016-08-29 | The synthesis technique of the tricaprylate of Isosorbide-5-Nitrae cyclohexanedimethanol two |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107778175A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110551321A (en) * | 2017-06-13 | 2019-12-10 | Hu革新株式会社 | Environment-friendly plasticizer and resin composition containing same |
| KR20190141854A (en) * | 2018-06-15 | 2019-12-26 | (주)휴이노베이션 | Cyclohexanedimethanol Pitch-based Plasticizer and Resin Composition Comprising the Same |
| CN111269119A (en) * | 2018-12-04 | 2020-06-12 | 南亚塑胶工业股份有限公司 | Hydrogenation method for improving yield of cyclohexane-1, 4-dioctyl phthalate |
| KR20220150063A (en) * | 2021-05-03 | 2022-11-10 | (주)네오 | Novel dicyclohexyl ester composition and preparation thereof |
-
2016
- 2016-08-29 CN CN201610737186.8A patent/CN107778175A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110551321A (en) * | 2017-06-13 | 2019-12-10 | Hu革新株式会社 | Environment-friendly plasticizer and resin composition containing same |
| CN110551321B (en) * | 2017-06-13 | 2021-05-14 | Hu革新株式会社 | Environment-friendly plasticizer and resin composition containing same |
| KR20190141854A (en) * | 2018-06-15 | 2019-12-26 | (주)휴이노베이션 | Cyclohexanedimethanol Pitch-based Plasticizer and Resin Composition Comprising the Same |
| KR102092457B1 (en) * | 2018-06-15 | 2020-05-22 | (주)휴이노베이션 | Cyclohexanedimethanol Pitch-based Plasticizer and Resin Composition Comprising the Same |
| CN111269119A (en) * | 2018-12-04 | 2020-06-12 | 南亚塑胶工业股份有限公司 | Hydrogenation method for improving yield of cyclohexane-1, 4-dioctyl phthalate |
| CN111269119B (en) * | 2018-12-04 | 2022-06-28 | 南亚塑胶工业股份有限公司 | Hydrogenation method for improving yield of cyclohexane-1, 4-dioctyl phthalate |
| KR20220150063A (en) * | 2021-05-03 | 2022-11-10 | (주)네오 | Novel dicyclohexyl ester composition and preparation thereof |
| KR102520601B1 (en) | 2021-05-03 | 2023-04-12 | (주)네오 | Novel dicyclohexyl ester composition and preparation thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107778175A (en) | The synthesis technique of the tricaprylate of Isosorbide-5-Nitrae cyclohexanedimethanol two | |
| CN103785408B (en) | A kind of prepared by dimethyl oxalate plus hydrogen is for catalyst and the synthetic method of methyl glycollate | |
| CN107445830B (en) | Method for producing glyoxylic ester by oxidative dehydrogenation of glycolate | |
| CN103922931B (en) | A kind of method of a step catalytically synthesizing glycol ether acetate | |
| CN101560183B (en) | Method for preparing 5-bromo-2-methylpyridine | |
| CN102417445B (en) | Method for synthesizing succinic acid from maleic acid | |
| CN101157615A (en) | Method for producing plasticizer phthalic acid dinonyl | |
| CN104190401A (en) | Molybdenum-based composite metal oxide catalyst for synthesizing propenyl alcohol by glycerol and preparation method of molybdenum-based composite metal oxide catalyst | |
| CN104529935B (en) | Method for synthesizing ethyl 2-(3-aldehyde-4-isobutyloxyphenyl)-4-methylthiazole-5-formate | |
| CN104892389B (en) | Technique for preparing oxalic acid by performing continuous reaction rectification hydrolysis on dimethyl oxalate | |
| CN103387495B (en) | Method for the continuous production of carboxylic acid esters | |
| CN109305912B (en) | Method for preparing 2,2, 4-trimethyl-1, 3-pentanediol monoisobutyrate by condensing isobutyraldehyde | |
| CN107325890B (en) | Method for synthesizing epoxy plasticizer based on perrhenate ionic liquid | |
| CN102259008A (en) | Solid acid catalyst for esterification reaction and preparation method thereof | |
| CN102070693A (en) | Method for preparing ursodesoxycholic acid by chiral catalytic hydrogenation of 7-ketodesoxycholic acid | |
| CN104926610B (en) | The preparation method of dihydromyrcenol | |
| CN109569595B (en) | Catalytic system for preparing cyclohexene Ru through benzene selective hydrogenation, and preparation method and application thereof | |
| CN107778151B (en) | Method for preparing methyl ethyl ketone by sec-butyl alcohol dehydrogenation | |
| CN102836711A (en) | Catalyst for preparing cyclohexene via selective hydrogenation of benzene and preparation method thereof | |
| CN108947810B (en) | Method for preparing succinic acid by carbonylation of acetylene | |
| CN102351699A (en) | Gulonate and preparation method thereof | |
| CN102633624B (en) | Method for preparing methylcinnamic acid | |
| CN106582744A (en) | Preparation method of catalyst capable of increasing yield of maleic anhydride prepared through n-butane oxidation | |
| CN107185571B (en) | Cobalt catalyst, preparation method thereof and application thereof in catalytic synthesis of 2,3, 5-trimethylbenzoquinone | |
| CN110627641A (en) | Preparation method of isoamyl lactate based on supported sodium bisulfate catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20180309 |
|
| WD01 | Invention patent application deemed withdrawn after publication |