CN106565470B - A kind of preparation method of hexamethylene -1,2- dioctyl phthalate dinonyl - Google Patents
A kind of preparation method of hexamethylene -1,2- dioctyl phthalate dinonyl Download PDFInfo
- Publication number
- CN106565470B CN106565470B CN201510656238.4A CN201510656238A CN106565470B CN 106565470 B CN106565470 B CN 106565470B CN 201510656238 A CN201510656238 A CN 201510656238A CN 106565470 B CN106565470 B CN 106565470B
- Authority
- CN
- China
- Prior art keywords
- hexamethylene
- dioctyl phthalate
- temperature
- residence time
- alcohol
- 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
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Prepare hexamethylene -1, the method of 2- dioctyl phthalate dinonyl, it include: 1) by hexahydro phthalic anhydride and isononyl alcohol, acetic anhydride while to be added in reaction kettle, wherein hexahydro phthalic anhydride and isononyl alcohol molar ratio are 1:2 ~ 5, acetic anhydride additional amount is the 1% ~ 10% of hexahydro phthalic anhydride quality, 180 ~ 300 DEG C are heated to, 2 ~ 5 h of stirring dehydration；2) pass through falling film evaporator, flash distillation removes excessive alcohol under -0.02MPa ~ 0.096MPa negative pressure, and the residence time is 0.001 ~ 0.05 h；3) it is passed through vapor in stripping tank and nitrogen is bubbled, steam low molecular weight impurities in material 2；4) active carbon that 3 mass 1% ~ 10% of material is added in decoloration kettle stirs decoloration, and filtering obtains final products hexamethylene -1,2- dioctyl phthalate dinonyl, yield reaches 98.5%, and purity reaches 99.8%.Using single step high temperature esterification method technique, the reaction time is greatly shortened；Vacuum flashing alcohol excess, reduces energy consumption, avoids emulsion；Without neutralizing, washing, is generated without alkaline waste water, be suitble to large-scale industrial production.
Description
Technical field
It is a kind of to prepare novel environment-friendlyplasticizer plasticizer hexamethylene -1,2- diformazan the invention belongs to Field of Fine Chemicals scope
The novel method of sour dinonyl.
Background technique
Hexamethylene -1,2- dioctyl phthalate dinonyl (alias: hexahydro phthalic acid dinonyl, referred to as: DINCH) it is a kind of
Emerging safety and environmental protection plasticizer has and diisononyl phthalate (DINP) and dioctyl phthalate (DOP) class
As structure and performance, be mainly used for: Medicines, food packaging, toy for children and child care product, it is often more important that its increase
The product of modeling in the natural environment can be voluntarily biodegradable, does not cause environmental pollution, what is be beneficial to man is safe and healthy, is benzene carboxylic
The favorable substitutes of acid ester type plasticizer.Therefore, develop efficient, nontoxic, degradable plasticizer new product substitution traditional category
At trend of the times.
Currently, the main method of synthesizing cyclohexane 1 alkane -1,2- dioctyl phthalate dinonyl (DINCH) include directed hydrogenation, it is straight
Connect esterification process and ester-interchange method.
The production technology of external DINCH is directed hydrogenation, is existed using precious metal catalysts such as nickel, platinum, palladium, rhodium, rutheniums
It is hexamethylene -1,2- dioctyl phthalate dinonyl that directly diisononyl phthalate (DINP), which is hydrogenated, under high temperature, high pressure
(DINCH).The processing technology routine is simple, cleaning, but very high to equipment and catalyst requirement, and investment is big.
United States Patent (USP) US628917 and US6888021 disclose the process of hydrogenation method, right using hydrogenation as manufacturing method
Diisononyl phthalate carries out hydrogenation, and 50 ~ 250 DEG C of reaction temperature, 20 ~ 300bar of pressure, catalyst includes to be applied to
The metal of at least one the VIIIth race of periodic table transition containing huge hole support body individually or at least one periodic table transition the Ith or VIII race
Metal together as active metal catalyst.Although this legal system, which makes DINCH, to need High Pressure Hydrogen to avoid three-waste pollution
Change, the reaction time is long, at high cost, hydrogenation high-tension apparatus is expensive.
Direct esterification has a two lines, and one is first with lower temperature (120 ~ 160 DEG C) by hexahydro-phthalic acid
Acid anhydride and isononyl alcohol carry out single-esterification, generate the different nonyl ester of intermediate species hexamethylene -1- formic acid -2- formic acid, rear to improve temperature extremely
250 DEG C and add catalyst carry out dehydration esterification (Fig. 1)；Another route is esterified with (250 DEG C) of the direct high temperature of single step
(Fig. 2).The present invention makes the reaction time shorten to 5 h by 16 h using single step high temperature esterification method, is effectively shortened processing procedure
Time saves the energy.
The manufacturing method of esterification is disclosed in United States Patent (USP) US6310235, is deposited in the metal solvents such as titanium system or tin system
In lower carry out esterification, esterification is reacted in two stages, first with (120 ~ 160 DEG C) progress single-esterifications of lower temperature,
Temperature is improved afterwards to 250 DEG C and adds catalyst and carries out double esterification reaction, after the reaction was completed with the hydrogen-oxygen of alkali or alkaline earth metal
Compound aqueous solution carries out neutralization reaction, the rear removing for carrying out excessive response alcohol, and dry, filtering is prepared into the esterification of plasticizer
Object, this technological reaction time are up to 16 h.
Chinese patent CN1962736A discloses different with single step high temperature esterification method synthesizing cyclohexane 1 alkane 1,2- dioctyl phthalate two
The method of nonyl ester, this method is using tetra isopropyl titanate as catalyst, and 250 DEG C of reaction temperature, 5 h reaction pressure 5 of reaction time ~
760 mbar remove moisture；Then pass through neutralization, washing, dealcoholysis, filtering, decoloration, obtain product DINCH.
The country is suitble to use esterification process, and compared to high-pressure hydrogenation, equipment requirement is low, and catalyst is at low cost, and the reaction time is short.
Domestic device uses for reference the single step high temperature esterification method of CN1962736, greatly shortens the reaction time, but first neutralizes and take off again
Alcohol, consumption is big and ester and water are easy emulsification, is unfavorable for being layered, product coloration is high.It is stringent with environmental requirement, it is a large amount of in
Very big burden is also increased to enterprise with washing waste water.
Summary of the invention
For overcome the deficiencies in the prior art, the purpose of the present invention is to provide one kind, low energy consumption, at low cost, raw material utilizes
The method of rate height, good product quality, environmental-friendly synthesizing cyclohexane 1 alkane -1,2- dioctyl phthalate dinonyl.
The present invention uses single step high temperature esterification method, i.e., by raw material hexahydro phthalic anhydride, isononyl alcohol and urges
Agent is added under reaction kettle normal pressure carries out heating esterification simultaneously, and border ring dehydration in side can effectively shorten esterification time；It is de-
After water, direct dealcoholysis relies on the heat contained by itself using falling film evaporator under reduced pressure, and alcohol excess is fallen in flash vaporization,
Alcohol is evaporated from tower top to be discharged, and is used through condenser condensation cycle, the thick ester after dealcoholysis is flowed out from bottom；Then it is refined, is made
It is bubbled with vapor and nitrogen, low molecular weight impurities steam under negative pressure；Finally, active carbon, which is added, carries out adsorption bleaching, filter
To final products, synthesis technology flow diagram is shown in that Fig. 3, device figure are shown in Fig. 4.
A kind of method preparing hexamethylene -1,2- dioctyl phthalate dinonyl using single step high temperature esterification method is specific to walk
It is rapid as follows:
1) hexahydro phthalic anhydride and isononyl alcohol, acetic anhydride are added in reaction kettle simultaneously, wherein hexahydro neighbour benzene
Dicarboxylic acid anhydride and isononyl alcohol molar ratio are 1:2 ~ 5, and acetic anhydride additional amount is the 1% ~ 10% of hexahydro phthalic anhydride quality, are added
Heat is to 200 ~ 260 DEG C, and stirring 2 ~ 6 h of dehydration obtain material 1, and material 1 is hexamethylene -1,2- dioctyl phthalate dinonyl crude product；
2) material 1 is passed through into falling film evaporator, flash distillation removes excessive alcohol under -0.02MPa ~ 0.096MPa negative pressure,
Residence time is 0.001 ~ 0.01 h, obtains material 2, into stripping tank；
3) it is passed through vapor in stripping tank and nitrogen is bubbled, steam low molecular weight impurities in material 2, obtain material 3, into
Enter the kettle that decolourizes.Pressure tank control is stripped in -0.02MPa ~ 0.096MPa, strips the control of tank temperature degree at 40 ~ 90 DEG C, material 2 is in vapour
The residence time for mentioning tank controls in 0.5 ~ 1 h；
4) active carbon of 3 mass 1% ~ 10% of material is added in decoloration kettle, it is de- in 50 ~ 90 DEG C of temperature 0.5 ~ 3.5 h of stirring
Color, filtering, obtains final products hexamethylene -1,2- dioctyl phthalate dinonyl.
In the step (1), preferred hexahydro phthalic anhydride and isononyl alcohol molar ratio are 1:2 ~ 3, preferred second
Acid anhydrides additional amount is the 1% ~ 5% of hexahydro phthalic anhydride quality, not 220 ~ 250 DEG C of preferred heating temperature, is preferably stirred
Mixing dewatering time is 3 ~ 4 h.
In the step (2), preferred negative pressure be -0.04MPa ~ 0.096MPa, the preferred residence time be 0. 001 ~
0.01 h。
In the step (3), the preferred pressure tank that strips is -0.06MPa ~ 0.08MPa, and preferred temperature is 60 ~ 90 DEG C,
The preferred residence time is 0.5 ~ 1 h.
In the step (4), preferred active carbon additional amount is the 1% ~ 3% of 3 mass of material, and preferred temperature is 70 ~ 90
DEG C, the preferred residence time is 0.5 ~ 1 h, and preferred filter is filter centrifugal.
Using preferred condition, the yield of final products can reach 98.5%, and purity reaches 99.8%
The present invention has the advantage that compared with hydrogenation technique
It 1) the use of acetic anhydride is catalyst, it is cheap and easy to get, catalytic activity is good, non-environmental-pollution, it avoids using noble metal
Catalyst has saved cost；
2) synthesis under normal pressure, it is easy to operate, without additional equipment investment；
3) the not exclusively generated benzene homologues residual of hydrogenation reaction is avoided, it is safer；
The present invention has the advantage that compared with traditional esterifications technique
1) single step high temperature esterification method is used, acid anhydrides generates acetic acid with reaction water and promotes to react to the shifting of positive reaction direction
Dynamic, the reaction time foreshortens to 2 ~ 5 h by 16 h of two-step method, greatly shortens the reaction time；
2) heat contained by itself is relied at reduced pressure conditions, and flash vaporization alcohol excess reduces energy consumption；
3) alcohol reprocessing process is first steamed compared with first neutralizing washing and steaming alcohol again, is avoided emulsion, is alleviated post-processing
Pressure；
4) low boiling impurity is removed using vapor and nitrogen stripping method for refining, does not have to neutralize, wash, without alkaline waste water
It generates, achievees the effect that energy-saving and emission-reduction, reduce environmental protection pressure.
5) centrifugal type filter is used, production efficiency and yield can be improved, be suitble to large-scale industrial production.
Detailed description of the invention
Fig. 1 is double esterification method synthetic route；Fig. 2 is single step esterification process synthetic route；Fig. 3 is that embodiment DINCH is closed
At process flow diagram；Fig. 4 is embodiment DINCH synthesis technology schematic device.
Specific embodiment
Embodiment 1
It is put in proportion into hexahydro phthalic anhydride, isononyl alcohol, catalyst acetic acid acid anhydride in a kettle, in which: hexahydro
The molar ratio of phthalic anhydride and isononyl alcohol is 1:2.3, and acetic anhydride additional amount is the 5% of hexahydrophthalic anhydride quality, and heating stirring under normal pressure rises
Temperature starts timing to 180 DEG C of reflux, continues temperature reaction, and material 1 is obtained after 230 DEG C of 3 h of maintenance, and material 1 is hexamethylene -1,
2- dioctyl phthalate dinonyl crude product；Material 1 is passed through into falling film evaporator, flash distillation removing is excessive under the negative pressure of -0.06MPa
Alcohol, residence time are 0.002 h, obtain material 2, into stripping tank；It is passed through vapor in stripping tank and nitrogen is bubbled, steams
Low molecular weight impurities in material 2 obtain material 3, into decoloration kettle.Pressure tank control is stripped in -0.05MPa, strips tank temperature degree
At 80 ~ 90 DEG C, material 2 is controlled in the residence time of stripping tank in 0.5 h for control；4) 3 mass 3% of material is added in decoloration kettle
Active carbon, decolourize in 90 DEG C of temperature 1.5 h of stirring, filtering obtains final products hexamethylene -1,2- dioctyl phthalate dinonyl,
Product is colourless transparent oil liquid, yield 98.5%, purity 99.8%.
Comparative example 1
Esterification is carried out with two stages difference processing procedure, the first stage first carries out single-esterification, first by 1 mole before reaction
154 g and 2.6 moles of 370 g of isononyl alcohol of hexahydro phthalic anhydride are added in 1000 ml four-hole boiling flasks, and catalyst is not added,
With 140 DEG C of progress single-esterifications, monoesters can be formed completely after 1 h.Second stage carry out double esterification reaction, by temperature by
140 DEG C of 0.5% 26 g of tetra isopropyl titanate for being promoted to 230 DEG C and adding raw materials gross mass, reaction 16 h dehydration are completed.
Comparative example 2
With single step high temperature esterification method, by 1 mole of hexahydro phthalic anhydride, 154 g and 2.6 moles of isononyl alcohols 370
2.6 g of g and catalyst tetra isopropyl titanate, while being added in 1000 ml four-hole boiling flasks, it is warming up to 180 DEG C and starts to flow back
Timing is dehydrated after 5 h and completes.
Embodiment 2
It is put in proportion into hexahydro phthalic anhydride, isononyl alcohol, catalyst acetic acid acid anhydride in a kettle, in which: hexahydro
The molar ratio of phthalic anhydride and isononyl alcohol is 1:2.1, and acetic anhydride additional amount is the 2% of hexahydrophthalic anhydride quality, and heating stirring under normal pressure rises
Temperature starts timing to 180 DEG C of reflux, continues temperature reaction, and material 1 is obtained after 220 DEG C of 3 h of maintenance, and material 1 is hexamethylene -1,
2- dioctyl phthalate dinonyl crude product；Material 1 is passed through into falling film evaporator, flash distillation removing is excessive under the negative pressure of -0.08MPa
Alcohol, residence time are 0.001 h, obtain material 2, into stripping tank；It is passed through vapor in stripping tank and nitrogen is bubbled, steams
Low molecular weight impurities in material 2 obtain material 3, into decoloration kettle.Pressure tank control is stripped in -0.04MPa, strips tank temperature degree
At 70 ~ 80 DEG C, material 2 is controlled in the residence time of stripping tank in 1 h for control；4) 3 mass 10% of material is added in decoloration kettle
Active carbon decolourizes in 90 DEG C of temperature 1.5 h of stirring, and filtering obtains final products hexamethylene -1,2- dioctyl phthalate dinonyl, produces
Product are colourless transparent oil liquid, yield 95.2%, purity 99.8%.
Embodiment 3
It is put in proportion into hexahydro phthalic anhydride, isononyl alcohol, catalyst acetic acid acid anhydride in a kettle, in which: hexahydro
The molar ratio of phthalic anhydride and isononyl alcohol is 1:2.5, and acetic anhydride additional amount is the 6% of hexahydrophthalic anhydride quality, and heating stirring under normal pressure rises
Temperature starts timing to 180 DEG C of reflux, continues temperature reaction, and material 1 is obtained after 250 DEG C of 5 h of maintenance, and material 1 is hexamethylene -1,
2- dioctyl phthalate dinonyl crude product；Material 1 is passed through into falling film evaporator, flash distillation removing is excessive under the negative pressure of -0.096MPa
Alcohol, residence time are 0.001 h, obtain material 2, into stripping tank；It is passed through vapor in stripping tank and nitrogen is bubbled, steams
Low molecular weight impurities in material 2 obtain material 3, into decoloration kettle.Pressure tank control is stripped in -0.08MPa, strips tank temperature degree
At 60 ~ 70 DEG C, material 2 is controlled in the residence time of stripping tank in 1 h for control；4) 3 mass 1% of material is added in decoloration kettle
Active carbon decolourizes in 90 DEG C of temperature 1.5 h of stirring, and filtering obtains final products hexamethylene -1,2- dioctyl phthalate dinonyl, produces
Product are colourless transparent oil liquid, yield 96.5%, purity 99.6%.
Embodiment 4
It is put in proportion into hexahydro phthalic anhydride, isononyl alcohol, catalyst acetic acid acid anhydride in a kettle, in which: hexahydro
The molar ratio of phthalic anhydride and isononyl alcohol is 1:2.7, and acetic anhydride additional amount is the 5% of hexahydrophthalic anhydride quality, and heating stirring under normal pressure rises
Temperature starts timing to 180 DEG C of reflux, continues temperature reaction, and material 1 is obtained after 240 DEG C of 3 h of maintenance, and material 1 is hexamethylene -1,
2- dioctyl phthalate dinonyl crude product；Material 1 is passed through into falling film evaporator, flash distillation removing is excessive under the negative pressure of -0.06MPa
Alcohol, residence time are 0.001 h, obtain material 2, into stripping tank；It is passed through vapor in stripping tank and nitrogen is bubbled, steams
Low molecular weight impurities in material 2 obtain material 3, into decoloration kettle.Pressure tank control is stripped in -0.05MPa, strips tank temperature degree
At 80 ~ 90 DEG C, material 2 is controlled in the residence time of stripping tank in 1.5 h for control；4) 3 mass 5% of material is added in decoloration kettle
Active carbon, decolourize in 90 DEG C of temperature 0.5 h of stirring, filtering obtains final products hexamethylene -1,2- dioctyl phthalate dinonyl,
Product is colourless transparent oil liquid, yield 97.5%, purity 99.2%.
Protection scope of the present invention is not limited only to above embodiments, mention on all claims and this field
The deformation that technical staff can be extrapolated to is in protection scope.
Claims (5)
1. a kind of method of hexamethylene -1,2- dioctyl phthalate dinonyl, feature is the following steps are included: 1) by hexahydro neighbour benzene two
Formic anhydride and isononyl alcohol, catalyst acetic acid acid anhydride are added in reaction kettle simultaneously, and wherein hexahydro phthalic anhydride and isononyl alcohol rub
, than being 1:2 ~ 5, catalyst acetic acid acid anhydride additional amount is the 1% ~ 5% of hexahydro phthalic anhydride quality for you, is heated to 200 ~ 260
DEG C, stirring 2 ~ 5 h of dehydration obtain material 1, and material 1 is hexamethylene -1,2- dioctyl phthalate dinonyl crude product；2) material 1 is passed through
Falling film evaporator, flash distillation removes excessive alcohol under -0.02MPa ~ -0.096MPa negative pressure, and the residence time is 0.001 ~ 0.05
H obtains material 2, into stripping tank；3) it is passed through vapor in stripping tank and nitrogen is bubbled, it is miscellaneous to steam low molecular weight in material 2
Matter obtains material 3, and into decoloration kettle, the control of stripping pressure tank strips the control of tank temperature degree 40 in -0.02MPa ~ -0.096MPa
~ 90 DEG C, material 2 is controlled in the residence time of stripping tank in 0.5 ~ 1 h；4) 3 mass 1% ~ 10% of material is added in decoloration kettle
Active carbon, decolourizes in 50 ~ 90 DEG C of temperature 0.5 ~ 3.5 h of stirring, and it is different to obtain final products hexamethylene -1,2- dioctyl phthalate two for filtering
Nonyl ester.
2. according to the method described in claim 1, it is characterized in that in the step (1), hexahydro phthalic anhydride and different nonyl
Alcohol molar ratio is 1:2 ~ 3, and 220 ~ 250 DEG C of heating temperature, stirring dewatering time is 3 ~ 4 h.
3. according to the method described in claim 1, negative pressure is -0.04MPa ~ -0.096MPa it is characterized in that in the step (2),
Residence time is 0. 001 ~ 0.01 h.
4. according to the method described in claim 1, it is characterized in that in the step (3), stripping pressure tank be -0.06MPa ~ -
0.08MPa, temperature are 60 ~ 90 DEG C, and the residence time is 0.5 ~ 1 h.
5. according to the method described in claim 1, it is characterized in that active carbon additional amount is 3 mass of material in the step (4)
1% ~ 3%, temperature is 70 ~ 90 DEG C, and the residence time is 0.5 ~ 1 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510656238.4A CN106565470B (en) | 2015-10-12 | 2015-10-12 | A kind of preparation method of hexamethylene -1,2- dioctyl phthalate dinonyl |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510656238.4A CN106565470B (en) | 2015-10-12 | 2015-10-12 | A kind of preparation method of hexamethylene -1,2- dioctyl phthalate dinonyl |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106565470A CN106565470A (en) | 2017-04-19 |
| CN106565470B true CN106565470B (en) | 2019-08-02 |
Family
ID=58508099
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510656238.4A Active CN106565470B (en) | 2015-10-12 | 2015-10-12 | A kind of preparation method of hexamethylene -1,2- dioctyl phthalate dinonyl |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106565470B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114014758B (en) * | 2021-10-26 | 2023-12-29 | 中石化南京化工研究院有限公司 | Decoloring method of plasticizer DINCH product |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101417950A (en) * | 2008-10-27 | 2009-04-29 | 中国科学院大连化学物理研究所 | Method for preparing 1,2-cyclohexane cyclohexanedimethanol dibasic ester |
| CN101774919A (en) * | 2010-02-04 | 2010-07-14 | 江南大学 | Method for preparing cyclohexane 1,2-dicarboxylate using organic acid as catalyst |
| CN102701980A (en) * | 2012-06-29 | 2012-10-03 | 太仓市新星轻工助剂厂 | Synthetic method of environmental-friendly plasticizer hexahydrobenzene diisononyl phthalate |
-
2015
- 2015-10-12 CN CN201510656238.4A patent/CN106565470B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101417950A (en) * | 2008-10-27 | 2009-04-29 | 中国科学院大连化学物理研究所 | Method for preparing 1,2-cyclohexane cyclohexanedimethanol dibasic ester |
| CN101774919A (en) * | 2010-02-04 | 2010-07-14 | 江南大学 | Method for preparing cyclohexane 1,2-dicarboxylate using organic acid as catalyst |
| CN102701980A (en) * | 2012-06-29 | 2012-10-03 | 太仓市新星轻工助剂厂 | Synthetic method of environmental-friendly plasticizer hexahydrobenzene diisononyl phthalate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106565470A (en) | 2017-04-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPS6025478B2 (en) | Production method of fatty acid lower alcohol ester | |
| CN108558659A (en) | The high-selectivity synthesis method of glycerine monofatty ester | |
| CN111960943A (en) | Process for producing dioctyl terephthalate by semi-continuous method | |
| CN103086891A (en) | Preparation method of plasticizer diethylene glycol dibenzoate | |
| CN101812044A (en) | Method and system for extracting and separating natural VE from plant oil deodorizing distillate | |
| CN108129423A (en) | A kind of method for preparing α-acetyl-gamma-butyrolacton | |
| CN106565470B (en) | A kind of preparation method of hexamethylene -1,2- dioctyl phthalate dinonyl | |
| CN106565662B (en) | Macrocyclic musk-pentadacanolide method is prepared using Malania Oleifera Oil | |
| CN101318880B (en) | Green synthesis process for bornyl alcohol | |
| CN102863408B (en) | Preparation method of andrographolide | |
| CN101585827A (en) | Method for preparing lactide with high yield | |
| CN108047175A (en) | A kind of synthetic method of furanone | |
| CN107903224A (en) | Acidic catalyst and hydrogenation catalyst concerted catalysis carbohydrate one kettle way prepare γ valerolactones | |
| CN106748774B (en) | Refining method of cyclohexane diformate plasticizer | |
| CN102633640B (en) | Integrated production technique of acetyl tributyl citrate (ATBC) | |
| CN103524525B (en) | The method extracting arteannuinic acid and derivative thereof waste is produced from Artemisinin | |
| CN103387495B (en) | Method for the continuous production of carboxylic acid esters | |
| CN105315158B (en) | A kind of combined technique for preparing cyclohexane cyclohexanedimethanodibasic dibasic ester | |
| CN104450209A (en) | Method for reducing acid value of crude rice bran oil through solid super acid catalysis | |
| CN107573237B (en) | Method for preparing high-purity gossypol acetate in cotton oil refining process | |
| CN104945357A (en) | Refining method of dehydroandrographolide succinate | |
| CN103992223A (en) | Preparation method of methyl acetylricinolate | |
| CN109456172B (en) | Method for purifying dodecanedioic acid in water phase | |
| CN109704958B (en) | Method for preparing ethyl butyrate and catalyst used in method | |
| CN112538036A (en) | Method for producing methyl thioglycolate based on sodium hydrosulfide method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP01 | Change in the name or title of a patent holder |
Address after: Liuhe District of Nanjing City, Jiangsu province 210048 geguan Road No. 699 Patentee after: China Petroleum & Chemical Corp. Patentee after: SINOPEC NANJING CHEMICAL RESEARCH INSTITUTE Co.,Ltd. Address before: Liuhe District of Nanjing City, Jiangsu province 210048 geguan Road No. 699 Patentee before: China Petroleum & Chemical Corp. Patentee before: Nanhua Group Research Institute |
|
| CP01 | Change in the name or title of a patent holder |