CN107954863A - The preparation method of phenolic ester type antioxidant - Google Patents
The preparation method of phenolic ester type antioxidant Download PDFInfo
- Publication number
- CN107954863A CN107954863A CN201711327223.9A CN201711327223A CN107954863A CN 107954863 A CN107954863 A CN 107954863A CN 201711327223 A CN201711327223 A CN 201711327223A CN 107954863 A CN107954863 A CN 107954863A
- Authority
- CN
- China
- Prior art keywords
- butyl
- isooctanol
- preparation
- tert
- hydroxy phenyl
- 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
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
- C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
- C10M129/68—Esters
- C10M129/76—Esters containing free hydroxy or carboxyl groups
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/283—Esters of polyhydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
Abstract
The invention discloses a kind of preparation method of phenolic ester type antioxidant, including：Using zinc acetate as catalyst, isooctanol and 4 hydroxy-phenylpropionic acid methyl esters of the desired amount of 3,5 di-t-butyl are added in flask and carry out esterification；After the completion of esterification unreacted isooctanol is removed using vacuum distillation；Sodium hydrate aqueous solution is added into reaction product and is stirred；Reaction product is dehydrated and is filtered, β (3,5 di-t-butyl, 4 hydroxy phenyl) propionic acid isooctanol ester is made.By technical scheme, manufactured β (3,5 di-t-butyl, 4 hydroxy phenyl) propionic acid isooctanol esters product purity is high, yield is high, appearance transparent, and technique is simple, while is produced substantially without waste water, is conducive to environmental protection.
Description
Technical field
The present invention relates to anti-oxidation tech field, more particularly to a kind of preparation method of phenolic ester type antioxidant.
Background technology
β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid isooctanol ester is a kind of common phenolic ester type antioxidant.Its property
Can be superior, with thermostability is good, antioxygenic property is prominent under the high temperature conditions, oil-soluble is good, the compatibility with other additives
Property it is good and ashless the features such as, can be widely used for various high-grade IC engine lubricating oils, conduction oil, high-temperature chain oil, hydraulic oil, gear
In the industrial lubricants such as oil, steam turbine oil and various lubricating grease and fuel oil.
The preparation method of existing a variety of β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid isooctanol ester at present.Such as：It is beautiful
State patent US5892097, using organotin as catalyst, 3,5- di-tert-butyl-hydroxy phenyl methyl propionates and isooctanol carry out
Ester exchange reaction, reaction is easy to carry out, but tin catalyst is not easy to remove, and residual can cause product appearance muddy in the product,
And tin catalyst adversely affects environment.
US5481023 provides one kind using aluminium isopropoxide as catalyst, 3,5- di-tert-butyl-hydroxy phenyl methyl propionates
Ester exchange reaction, which is carried out, with isooctanol obtains the preparation method of β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid isooctanol ester,
Although this method is needed pickling, washing in last handling process, is produced a large amount of waste water, be unfavorable for using non-tin catalyst
Environmental protection.
US4716244 is using zinc acetate as catalyst, at reduced pressure conditions, 3,5- di-tert-butyl-hydroxy phenyl propionic acid first
Ester and isooctanol carry out ester exchange reaction, and reaction temperature is controlled at 140-190 DEG C, but this method is not because taking any method to destroy
Catalyst, causes product appearance muddy, after long-term placement, has precipitation to produce.
The content of the invention
At least one of regarding to the issue above, the present invention provides a kind of preparation method of phenolic ester type antioxidant, it is made
β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid isooctanol ester product purity it is high, yield is high, appearance transparent, and technique letter
It is single, while produced substantially without waste water, be conducive to environmental protection.
To achieve the above object, the present invention provides a kind of preparation method of phenolic ester type antioxidant, it is used to prepare β-(3,5-
Di-tert-butyl-hydroxy phenyl) propionic acid isooctanol ester, including：Using zinc acetate as catalyst, by isooctanol and the desired amount of 3,5-
Di-tert-butyl-hydroxy phenyl methyl propionate adds in flask and carries out esterification, wherein 3,5- di-tert-butyl-hydroxy phenyls
Molar ratio between methyl propionate and isooctanol is 1:1.2-1:1.6, the quality of zinc acetate is 3,5- di-t-butyl -4- hydroxy benzenes
The 0.4%-0.6% of base methyl propionate quality；After the completion of esterification unreacted isooctanol is removed using vacuum distillation；To anti-
Answer and sodium hydrate aqueous solution is added in product and is stirred, wherein, the molar ratio between zinc acetate and sodium hydroxide is 1:1-1:2,
The mass concentration of sodium hydrate aqueous solution is 1%-5%；Reaction product is dehydrated and is filtered, β-(3,5- bis- tertiary fourths are made
Base -4- hydroxy phenyls) propionic acid isooctanol ester.
In the above-mentioned technical solutions, it is preferable that the flask is four-hole boiling flask, and mechanical agitation dress is configured on the flask
Put, thermometer, distillation condenser pipe and nitrogen device.
In the above-mentioned technical solutions, it is preferable that the reaction temperature of the esterification is 170 DEG C -180 DEG C, the reaction time
For 6-12 it is small when.
In the above-mentioned technical solutions, it is preferable that the vapo(u)rizing temperature of the vacuum distillation process is 180 DEG C -200 DEG C, vacuum
Spend for -0.07~-0.1MPa.
In the above-mentioned technical solutions, it is preferable that described that sodium hydrate aqueous solution is added into reaction product and is stirred specific
Including：Sodium hydrate aqueous solution is added at being 70 DEG C -90 DEG C in reaction product temperature, and is stirred 10-30 minutes.
Compared with prior art, beneficial effects of the present invention are：Pass through a kind of phenolic ester type antioxidant provided by the invention
Preparation method, manufactured β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid isooctanol ester product purity is high, yield is high, appearance
It is transparent, and technique is simple, while produced substantially without waste water, be conducive to environmental protection.
Brief description of the drawings
Fig. 1 is the flow diagram of the preparation method of phenolic ester type antioxidant disclosed in an embodiment of the present invention.
Embodiment
To make the purpose, technical scheme and advantage of the embodiment of the present invention clearer, below in conjunction with the embodiment of the present invention
In attached drawing, the technical solution in the embodiment of the present invention is clearly and completely described, it is clear that described embodiment is
The part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, ordinary skill people
Member's all other embodiments obtained on the premise of creative work is not made, belong to the scope of protection of the invention.
The present invention is described in further detail below in conjunction with the accompanying drawings：
As shown in Figure 1, a kind of preparation method of the phenolic ester type antioxidant provided according to the present invention, is used to prepare β-(3,5-
Di-tert-butyl-hydroxy phenyl) propionic acid isooctanol ester, including：Using zinc acetate as catalyst, by isooctanol and the desired amount of 3,5-
Di-tert-butyl-hydroxy phenyl methyl propionate adds in flask and carries out esterification, wherein 3,5- di-tert-butyl-hydroxy phenyls
Molar ratio between methyl propionate and isooctanol is 1:1.2-1:1.6, the quality of zinc acetate is 3,5- di-t-butyl -4- hydroxy benzenes
The 0.4%-0.6% of base methyl propionate quality；After the completion of esterification unreacted isooctanol is removed using vacuum distillation；To anti-
Answer and sodium hydrate aqueous solution is added in product and is stirred, wherein, the molar ratio between zinc acetate and sodium hydroxide is 1:1-1:2,
The mass concentration of sodium hydrate aqueous solution is 1%-5%；Reaction product is dehydrated and is filtered, β-(3,5- bis- tertiary fourths are made
Base -4- hydroxy phenyls) propionic acid isooctanol ester.
In the above embodiment, it is preferable that flask is four-hole boiling flask, mechanical stirring device, thermometer, steaming are configured on flask
Evaporate condenser pipe and nitrogen device.
In the above embodiment, it is preferable that the reaction temperature of esterification is 170 DEG C -180 DEG C, reaction time 6-12
Hour.
In the above embodiment, it is preferable that the vapo(u)rizing temperature of vacuum distillation process be 180 DEG C -200 DEG C, vacuum for -
0.07~-0.1MPa.
Specifically included in the above embodiment, it is preferable that adding sodium hydrate aqueous solution into reaction product and stirring：
Reaction product temperature is to add sodium hydrate aqueous solution at 70 DEG C -90 DEG C, and is stirred 10-30 minutes.
In the above-described embodiments, being reacted under normal pressure as reaction vessel with four-hole boiling flask, isooctanol is excessive, and 3,
5- di-tert-butyl-hydroxy phenyl methyl propionates：Isooctanol molar ratio is 1:1.2-1:1.6, zinc acetate dosage is 3,5-, bis- uncles
The 0.4-0.6% of butyl -4- hydroxy-phenylpropionic acid methyl esters quality, reaction temperature is 170-180 DEG C, when reaction time 6-12 is small.
The methanol distillated in order to prevent in esterification reaction process can take away a part of isooctanol, therefore add the different of excess in initial reaction stage
Octanol, and decompression steams unreacted isooctanol, 180-200 DEG C of vapo(u)rizing temperature, vacuum -0.07 after esterification
~-0.1MPa.After vacuum distillation, sodium hydrate aqueous solution is added in reaction product at 70-90 DEG C, stirs 10-
30 minutes, you can catalyst neutralisation, zinc acetate：Sodium hydroxide molar ratio is 1:1-1:2, sodium hydrate aqueous solution mass concentration is
1%-5%.Then finished product is obtained after being dehydrated, filtering.The moisture of removing can be used as next secondary response configuration sodium hydroxide solution
Use.
Specifically, the preparation side with the following example to β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid isooctanol ester
Method is specifically described：
Embodiment one：
Equipped with mechanical agitation, thermometer, distillation condenser pipe, nitrogen inlet 500mL four-hole boiling flasks in add 3,5- bis-
Tert-butyl-hydroxy phenyl methyl propionate 116.96g (0.4mol), isooctanol 78.14g (0.6mol), zinc acetate 0.585g
(0.0027mol), is gradually heating to 170 DEG C, when reaction 8 is small, has methanol to distillate during reaction, reaction terminates under nitrogen protection
Afterwards, decompression steams the complete isooctanol of unreacted, subtracts and steams 190 DEG C, vacuum -0.09MPa of temperature, and 90 are cooled to after subtracting steaming
DEG C, the sodium hydroxide solution 10.80g that mass concentration is 1% is added into flask, is stirred 15 minutes, then decompression steams moisture,
Water sample transparency liquid 153.11g is obtained by filtration, is product.β made from the embodiment-(3,5- di-t-butyl -4- hydroxy benzenes
Base) propionic acid isooctanol ester yield be 98.00%, product purity 99.20%.
Embodiment two：
Equipped with mechanical agitation, thermometer, distillation condenser pipe, nitrogen inlet 500mL four-hole boiling flasks in add 3,5- bis-
Tert-butyl-hydroxy phenyl methyl propionate 116.96g (0.4mol), isooctanol 72.93g (0.56mol), zinc acetate 0.585g
(0.0027mol), is gradually heating to 175 DEG C, when reaction 7 is small, has methanol to distillate during reaction, reaction terminates under nitrogen protection
Afterwards, decompression steams the complete isooctanol of unreacted, subtracts and steams 195 DEG C, vacuum -0.09MPa of temperature, and 90 are cooled to after subtracting steaming
DEG C, the sodium hydroxide solution 10.80g that mass concentration is 1% is added into flask and (prepares the water embodiment of sodium hydroxide solution
One water steamed, not enough supplements new water), stir 10 minutes, then decompression steams moisture, and water sample transparency liquid is obtained by filtration
152.10g it is product.The yield of β made from the embodiment-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid isooctanol ester
For 97.35%, product purity 99.15%.
Embodiment three：
Equipped with mechanical agitation, thermometer, distillation condenser pipe, nitrogen inlet 500mL four-hole boiling flasks in add 3,5- bis-
Tert-butyl-hydroxy phenyl methyl propionate 116.96g (0.4mol), isooctanol 78.14g (0.6mol), zinc acetate 0.585g
(0.0027mol), is gradually heating to 180 DEG C, when reaction 6 is small, has methanol to distillate during reaction, reaction terminates under nitrogen protection
Afterwards, decompression steams the complete isooctanol of unreacted, subtracts and steams 200 DEG C, vacuum -0.095MPa of temperature, and 80 are cooled to after subtracting steaming
DEG C, the sodium hydroxide solution 16.20g that mass concentration is 1% is added into flask, is stirred 15 minutes, then decompression steams moisture,
Water sample transparency liquid 153.27g is obtained by filtration, is product.β made from the embodiment-(3,5- di-t-butyl -4- hydroxy benzenes
Base) propionic acid isooctanol ester yield be 98.10%, product purity 99.31%.
Example IV：
Equipped with mechanical agitation, thermometer, distillation condenser pipe, nitrogen inlet 500mL four-hole boiling flasks in add 3,5- bis-
Tert-butyl-hydroxy phenyl methyl propionate 116.96g (0.4mol), isooctanol 72.93g (0.56mol), zinc acetate 0.585g
(0.0027mol), is gradually heating to 180 DEG C, when reaction 7 is small, has methanol to distillate during reaction, reaction terminates under nitrogen protection
Afterwards, decompression steams the complete isooctanol of unreacted, subtracts and steams 200 DEG C, vacuum -0.095MPa of temperature, and 80 are cooled to after subtracting steaming
DEG C, the sodium hydroxide solution 16.20g that mass concentration is 1% is added into flask and (prepares the water embodiment of sodium hydroxide solution
Three water steamed, not enough supplement new water), stir 15 minutes, then decompression steams moisture, and water sample transparency liquid is obtained by filtration
152.33g it is product.The yield of β made from the embodiment-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid isooctanol ester
For 97.50%, product purity 99.23%.
Understood in above-described embodiment, β-(3,5- bis- uncles made from the preparation method proposed by technical scheme
Butyl -4- hydroxy phenyls) propionic acid isooctanol ester product, its appearance is bright, and yield is high, and purity is high, solves prior art presence
The problem of turbid appearance；And the aftertreatment technology economy of the preparation method is simple, is produced substantially without waste water, be conducive to protection ring
Border.
The above is embodiments of the present invention, it is contemplated that catalyst residual causes product in the product in the prior art
Turbid appearance, long-term be placed with precipitate generation, last handling process complexity, the technical problem for producing a large amount of waste water, present invention proposition
A kind of preparation method of phenolic ester type antioxidant, manufactured β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid isooctanol ester production
Product purity is high, yield is high, appearance transparent, and technique is simple, while is produced substantially without waste water, is conducive to environmental protection.
It these are only the preferred embodiment of the present invention, be not intended to limit the invention, for those skilled in the art
For member, the invention may be variously modified and varied.Any modification within the spirit and principles of the invention, being made,
Equivalent substitution, improvement etc., should all be included in the protection scope of the present invention.
Claims (5)
1. a kind of preparation method of phenolic ester type antioxidant, it is different pungent to be used to prepare β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid
Alcohol ester, it is characterised in that including：
Using zinc acetate as catalyst, isooctanol and the desired amount of 3,5- di-tert-butyl-hydroxy phenyl methyl propionates are added and burnt
Esterification is carried out in bottle, wherein the molar ratio between 3,5- di-tert-butyl-hydroxy phenyl methyl propionates and isooctanol is 1:
1.2-1:1.6, the quality of zinc acetate is the 0.4%-0.6% of 3,5- di-tert-butyl-hydroxy phenyl methyl propionate quality；
After the completion of esterification unreacted isooctanol is removed using vacuum distillation；
Sodium hydrate aqueous solution is added into reaction product and is stirred, wherein, the molar ratio between zinc acetate and sodium hydroxide is
1:1-1:2, the mass concentration of sodium hydrate aqueous solution is 1%-5%；
Reaction product is dehydrated and is filtered, β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid isooctanol ester is made.
2. the preparation method of phenolic ester type antioxidant according to claim 1, it is characterised in that the flask is four mouthfuls of burnings
Bottle, mechanical stirring device, thermometer, distillation condenser pipe and nitrogen device are configured on the flask.
3. the preparation method of phenolic ester type antioxidant according to claim 1, it is characterised in that the reaction of the esterification
Temperature is 170 DEG C -180 DEG C, when the reaction time is 6-12 small.
4. the preparation method of phenolic ester type antioxidant according to claim 1, it is characterised in that the vacuum distillation process
Vapo(u)rizing temperature is 180 DEG C -200 DEG C, and vacuum is -0.07~-0.1MPa.
5. the preparation method of phenolic ester type antioxidant according to claim 1, it is characterised in that described to add into reaction product
It is hydrogenated with aqueous solution of sodium oxide and stirs and specifically includes：
Sodium hydrate aqueous solution is added at being 70 DEG C -90 DEG C in reaction product temperature, and is stirred 10-30 minutes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711327223.9A CN107954863A (en) | 2017-12-13 | 2017-12-13 | The preparation method of phenolic ester type antioxidant |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711327223.9A CN107954863A (en) | 2017-12-13 | 2017-12-13 | The preparation method of phenolic ester type antioxidant |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107954863A true CN107954863A (en) | 2018-04-24 |
Family
ID=61958771
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711327223.9A Pending CN107954863A (en) | 2017-12-13 | 2017-12-13 | The preparation method of phenolic ester type antioxidant |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107954863A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110938239A (en) * | 2019-12-12 | 2020-03-31 | 梁山新翔新材料有限公司 | Hindered phenol antioxidant and synthesis method thereof |
| CN113264830A (en) * | 2021-05-27 | 2021-08-17 | 新乡市瑞丰新材料股份有限公司 | Preparation method of phenolic ester type antioxidant |
| CN116332757A (en) * | 2023-03-10 | 2023-06-27 | 南雄志一精细化工有限公司 | Preparation method of liquid hindered phenol antioxidant |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1364753A (en) * | 2001-01-18 | 2002-08-21 | 中国石油化工股份有限公司 | Process for preparing hydroxyphenyl carboxylic ester |
| US20060110807A1 (en) * | 2002-10-10 | 2006-05-25 | Reinhold Ohrlein | Process for the preparation of phenolic carboxylic acid derivaties by enzymatic catalysis |
| CN101168508A (en) * | 2007-06-07 | 2008-04-30 | 上海金海雅宝精细化工有限公司 | Method for preparing liquid hindered phenol antioxidants |
-
2017
- 2017-12-13 CN CN201711327223.9A patent/CN107954863A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1364753A (en) * | 2001-01-18 | 2002-08-21 | 中国石油化工股份有限公司 | Process for preparing hydroxyphenyl carboxylic ester |
| US20060110807A1 (en) * | 2002-10-10 | 2006-05-25 | Reinhold Ohrlein | Process for the preparation of phenolic carboxylic acid derivaties by enzymatic catalysis |
| CN101168508A (en) * | 2007-06-07 | 2008-04-30 | 上海金海雅宝精细化工有限公司 | Method for preparing liquid hindered phenol antioxidants |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110938239A (en) * | 2019-12-12 | 2020-03-31 | 梁山新翔新材料有限公司 | Hindered phenol antioxidant and synthesis method thereof |
| CN113264830A (en) * | 2021-05-27 | 2021-08-17 | 新乡市瑞丰新材料股份有限公司 | Preparation method of phenolic ester type antioxidant |
| CN116332757A (en) * | 2023-03-10 | 2023-06-27 | 南雄志一精细化工有限公司 | Preparation method of liquid hindered phenol antioxidant |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107954863A (en) | The preparation method of phenolic ester type antioxidant | |
| CN101386562B (en) | Method for preparing policosanol mixture by nonsolvent reduction method | |
| CN102513163B (en) | Water-soluble catalytic cracking metal passivator and preparation method thereof | |
| CN103861596B (en) | A kind of preparation method of nickel-base hydrogenation catalyst | |
| CN105602604A (en) | Method for preparing long-chain alkane from gutter oil through hydrolysis and in-situ hydrogenation and decarboxylation | |
| CN106675789A (en) | Method for preparing biodiesel with low sulfur content from gutter oil | |
| CN103160336A (en) | Catering industry waste oil-based biological alcohol oil and preparation method thereof | |
| Pereira et al. | SnSO 4 as catalyst for simultaneous transesterification and esterification of acid soybean oil | |
| CN101294093B (en) | Integrated preparation method for biological diesel oil and isolated plant | |
| CN102433223B (en) | Method for preparing conjugate linoleate by using vegetable oil | |
| CN100523129C (en) | Production of biological diesel-oil | |
| CN104450209A (en) | Method for reducing acid value of crude rice bran oil through solid super acid catalysis | |
| CN102276810B (en) | Method for preparing alkyd resin from modified leftovers of vegetable oil | |
| CN101318892B (en) | Method for preparing sebacic acid with ricinus oil compounds | |
| WO2014063581A1 (en) | Alkaline compound ionic liquid and biodiesel preparation method | |
| CN106699624B (en) | A kind of production method of lutein | |
| CN101113349A (en) | Method for producing biodiesel with convenient post-treatment | |
| Salvi | Transesterification methods | |
| TWI590868B (en) | Solid metal oxide catalyst application on the transesterification and interesterification reactions | |
| CN104592169B (en) | With the method that waste oil prepares epoxy aliphatic acid methyl ester for raw material | |
| CN104592170A (en) | Method for producing epoxy fatty acid methyl ester by taking illegal cooking oil as raw material | |
| CN106518679A (en) | Method for preparing di-n-butyl adipate | |
| CN101338006A (en) | Acrylic resin with self-crosslinking characteristic and method for preparing same | |
| CN103804130A (en) | Method for preparing policosanol through beeswax normal-pressure reduction method | |
| TWI496881B (en) | Method for preparing bio - diesel by cycle |
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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180424 |
|
| RJ01 | Rejection of invention patent application after publication |