CN106748790B - Method for preparing hindered phenol antioxidant 1010 - Google Patents
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- CN106748790B CN106748790B CN201611031948.9A CN201611031948A CN106748790B CN 106748790 B CN106748790 B CN 106748790B CN 201611031948 A CN201611031948 A CN 201611031948A CN 106748790 B CN106748790 B CN 106748790B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0279—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the cationic portion being acyclic or nitrogen being a substituent on a ring
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
- B01J31/0284—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member of an aromatic ring, e.g. pyridinium
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Abstract
The invention belongs to the technical field of fine chemical engineering, and particularly relates to a method for preparing hindered phenol antioxidant 1010, which is prepared by taking beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) methyl propionate and pentaerythritol as raw materials through ester exchange reaction in an alkaline ionic liquid catalytic system. The invention uses the alkaline ionic liquid as the catalyst, has high catalytic activity, the product content reaches more than 97.5 percent, and the yield reaches more than 95 percent. The ionic liquid catalyst has better performance than lithium acetate, sodium methoxide, potassium tert-butoxide, organic tin and other catalysts in 1010 esterification reaction. The ionic liquid catalytic reaction system is used, the environment is friendly, the catalyst can be recycled, the product is not easy to color, the yield is high, and no heavy metal is contained.
Description
Technical Field
The invention belongs to the technical field of fine chemical engineering, and particularly relates to a method for preparing hindered phenol antioxidant 1010.
Technical Field
The antioxidant has good oxidation resistance, stable oxidation stability and thermal stability, good compatibility with polymers, extremely low volatility and difficult loss caused by volatilization at high temperature. Can effectively prevent the damage of light, heat and oxygen to the polymer, obviously improve the performance of the polymer, effectively prolong the service life of the polymer, and has no pollution and no coloring. Can be widely applied to the industries of general plastics, engineering plastics, synthetic rubber, fiber, resin, printing ink, paint and the like.
Antioxidant 1010 (pentaerythrityl tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate) is a hindered phenol antioxidant with high molecular weight, low volatility, good extraction resistance, high thermal stability, long lasting effect, no coloring, no pollution and no toxicity, and is widely used in olefin resins, such as polyethylene, polypropylene, polyurethane, polyoxymethylene, ABS resin, polyvinyl acetal, synthetic rubber and petroleum products, and the common dosage is 0.1-0.5%. At present, the synthesis of the antioxidant 1010 is reported in documents and all is obtained by taking 3, 5-methyl ester and pentaerythritol as raw materials through ester exchange reaction. The main difference of the process is a catalyst and a reaction solvent, wherein the catalyst mainly comprises alkaloids (lithium acetate, sodium methoxide, potassium tert-butoxide, sodium hydroxide and the like) and organic gold tin. The former strong alkali easily causes the product color deepening, the equipment corrosion degree is large, and the post-treatment is complex; the organic tin catalyst has low reaction rate, difficult removal of organic metal, high metal content of the product and limited application range of the product; in addition, the introduction of the reaction solvent increases the difficulty of post-reaction treatment (solvent removal, post-treatment of waste liquid) and the production cost.
Disclosure of Invention
The invention aims to provide a method for preparing hindered phenol antioxidant 1010, which not only accelerates the reaction, but also has simple post-treatment process, recyclable catalyst, good product color, high yield and no heavy metal.
the method for preparing the hindered phenol antioxidant 1010 is prepared by taking beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) methyl propionate and pentaerythritol as raw materials through ester exchange reaction, wherein the ester exchange reaction is carried out in an alkaline ionic liquid catalytic system. The specific synthetic route is as follows:
The method comprises the following specific steps: adding beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) methyl propionate, pentaerythritol and ionic liquid into a reactor for reaction, adding an organic solvent into a reaction system while the reaction is hot after the reaction is finished, standing and layering, wherein the upper layer is an organic phase, the lower layer is an ionic liquid phase, the ionic liquid is recycled, and the organic phase is recrystallized to obtain the antioxidant 1010.
When the organic solvent is added, the temperature of the system is controlled to be 70-80 ℃, the organic solvent is prevented from volatilizing when the temperature is too high, and the organic solvent can be separated out too early when the temperature is too low of 1010 ℃. The amount of organic solvent added is 1.1-1.5 times of the theoretical mass of 1010. The organic solvent adopts ethanol.
The alkaline ionic liquid is 1-methyl-3-butylimidazole formate ([ Bmim ] HCOO) or 1-methyl-3-butylimidazole acetate ([ Bmim ] OAc) or 1-methyl-3-butylimidazole propionate ([ Bmim ] C 2 H 5 COO) or 1-methyl-3-butylimidazole carbonate ([ Bmim ] 2 CO 3) or 1-methyl-3-butylimidazole hydroxide ([ Bmim ] OH) or 1-butyl-3-methylimidazolyl proline ionic liquid ([ Bmim ] [ Pro ]) or tetramethylguanyl proline ionic liquid ([ TMG ] [ Pro ]).
The pH value of the alkaline ionic liquid aqueous solution is 12-14.
The dosage of the ionic liquid is 3-5% of the mass of the pentaerythritol. When the amount of the ionic liquid is too large, the treatment is difficult, and when the amount is too small, the reaction rate is slow and the reaction is incomplete.
The mass ratio of the beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) methyl propionate to the pentaerythritol is 4.5-5: 1. After-treatment of the beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) methyl propionate is difficult when the amount is too large, the reaction rate is slow when the amount is too small, and the pentaerythritol reaction is incomplete.
The transesterification reaction temperature is 170-190 ℃, the reaction time is 5-7 h, and the reaction pressure is 0.08-0.1 MPa. The pressure range is controlled to be 0.08 to-0.1 MPa, so that the generated methanol can be removed as soon as possible, the forward reaction is ensured, and meanwhile, the reaction solution can be protected from being oxidized and discolored under the negative pressure state; if the pressure is too high, the methanol removal rate is slow, which affects the reaction, and if the pressure is too low, the methanol removal rate does not have a large effect. Too high a temperature or too long a time may result in a darker product; the reaction is incomplete due to too low temperature or short time.
The ionic liquid catalyzed transesterification mechanism described in the present invention: under the heating condition, the alkaline ionic liquid M can abstract hydrogen atoms of pentaerythritol to form active intermediate negative ions A, the A attacks carbonyl carbon atoms of methyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate to form an intermediate B with a tetrahedral structure, then the intermediate B is decomposed into an ester C and methoxy negative ions, the methoxy negative ions abstract the hydrogen atoms on MH to generate a byproduct methanol and alkaline ionic liquid M negative ions, and the negative ions circularly catalyze the next ester exchange reaction. And (3) carrying out ester exchange reaction on the monoester C to obtain a diester, and sequentially carrying out ester exchange to finally obtain the tetraester antioxidant 1010. The catalytic mechanism is shown as follows:
The invention uses the alkaline ionic liquid as the catalyst, has high catalytic activity, the product content reaches more than 97.5 percent, and the yield reaches more than 95 percent. The ionic liquid catalyst has better performance than lithium acetate, sodium methoxide, potassium tert-butoxide, organic tin and other catalysts in 1010 esterification reaction. The ionic liquid catalytic reaction system is used, the environment is friendly, the catalyst can be recycled, the product is not easy to color, the yield is high, and no heavy metal is contained.
Detailed Description
The raw materials adopted by the invention are all commercially available, and in the following examples, methyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate is simply referred to as 3, 5-methyl ester. The technical solution of the present invention is not limited to the following specific embodiments, but includes any combination of the specific embodiments.
Example 1
4.63g of N-butyl chloride and 6.85g of N-methylimidazole are taken to be put in a four-mouth bottle and reacted for 12 hours at 50 ℃ under the protection of nitrogen, 100mL of ethyl acetate is added when the reaction is finished, the mixture is cooled and filtered to obtain white solid, and the white solid is recrystallized by using a mixed solvent of acetonitrile and ethyl acetate to obtain the ionic liquid [ Bmim ] Cl.
And (3) dissolving 8.75g of the ionic liquid in 50ml of dichloromethane, adding 2.0g of solid sodium hydroxide particles, stirring at room temperature for 10 hours, filtering to remove precipitates, and removing the solvent by rotary evaporation to obtain a crude ionic liquid [ Bmim ] OH. Washing the crude product with anhydrous ether for 3 times, evaporating to remove ether under reduced pressure, and vacuum drying at 80 deg.C to constant weight to obtain basic ionic liquid [ Bmim ] OH. .
Example 2
0.05mol of ionic liquid intermediate [ Bmim ] Cl was dissolved in 50ml of isopropanol, 2.5 times of KOAc was added thereto, and the mixture was stirred at 25 ℃ for 10 hours, and then insoluble matter was removed by filtration. The filtrate was evaporated to remove the solvent to give a pale yellow oil. Dissolving the crude product with dichloromethane, adding activated carbon powder, stirring for 10h, filtering, removing the solvent from the filtrate by rotary evaporation, and drying in vacuum to obtain colorless oily substance, namely the target product [ Bmim ] OAc.
Example 3
Dissolving 0.05mol of [ Bmim ] Cl in 50ml of isopropanol, adding 2 times of sodium carbonate, stirring and reacting for 8h at 60 ℃, filtering, performing rotary evaporation on filtrate to obtain oily liquid, and performing vacuum drying to obtain a final product [ Bmim ] 2 CO 3.
Example 4
Dissolving 0.06mol of solid potassium formate in 50ml of methanol, adding 0.05mol of [ Bmim ] Cl, stirring at room temperature for 24 hours, filtering to remove white precipitate, performing rotary evaporation on the filtrate at 45 ℃ under reduced pressure to remove the methanol solvent, adding diethyl ether for washing, separating out unreacted solid potassium formate precipitate, and performing rotary evaporation to remove the solvent to obtain colorless viscous liquid [ Bmim ] [ HCOO ].
example 5
0.05mol proline and 0.05mol sodium hydroxide solution in methanol were placed in a 100ml round bottom flask, then 60% methanol solution of [ Bmim ] Cl (0.05mol) was added to the solution, stirred at room temperature for 12h, filtered to remove the precipitate, the methanol solvent was removed under reduced pressure, and the potassium acetate was removed by washing with ether to obtain pure colorless liquid [ Bmim ] [ Pro ].
Example 6
0.05mol of proline and tetramethylguanidine (0.05mol) in methanol was placed in a flask, and stirred at room temperature for 4 hours to obtain colorless transparent oil [ TMG ] [ Pro ].
example 7
Adding 6.8g of pentaerythritol, 65.8g of 3, 5-methyl ester and 0.34g of ionic liquid catalyst [ Bmim ] OH into a four-mouth bottle, reacting at 185 ℃ for 7h under the reaction pressure of-0.1 MPa, adding 90ml of solvent when the reaction is finished (about 70 ℃), standing and layering, wherein the upper layer is an organic phase, the lower layer is an ionic liquid phase, the ionic liquid is recycled, and the organic phase is recrystallized to obtain the antioxidant 1010. HPLC shows that the content of the target product of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester can reach 98.6 percent, and the yield is 96.7 percent.
Example 8
Adding 6.8g of pentaerythritol, 65.8g of 3, 5-methyl ester and 0.34g of ionic liquid catalyst [ Bmim ] 2 CO 3 0.34 into a four-mouth bottle, reacting at the reaction pressure of-0.1 MPa and 190 ℃ for 7h, adding 85ml of solvent into the bottle when the reaction is finished (about 70 ℃), standing and layering, wherein the upper layer is an organic phase, the lower layer is an ionic liquid phase, the ionic liquid is recycled, and the organic phase is recrystallized to obtain the antioxidant 1010. HPLC shows that the content of the target product pentaerythritol tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] can reach 98.2%, and the yield is 96.0%.
Example 9
Adding 6.8g of pentaerythritol, 72.8g of 3, 5-methyl ester and 0.28g of ionic liquid catalyst [ Bmim ] 2 CO 3 0.28 into a four-mouth bottle, reacting at 185 ℃ for 6h under-0.1 MPa, adding 110ml of solvent when the reaction is finished (about 70 ℃) and standing for layering, wherein the upper layer is an organic phase, the lower layer is an ionic liquid phase, the ionic liquid is recycled, and the organic phase is recrystallized to obtain a product antioxidant 1010. HPLC shows that the content of a target product pentaerythritol tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] can reach 97.9%, and the yield is 95.7%.
Example 10
adding 6.8g of pentaerythritol, 71.4g of 3, 5-methyl ester and 0.28g of ionic liquid catalyst [ Bmim ] OH into a four-mouth bottle, reacting at 190 ℃ for 6.5h under the reaction pressure of-0.1 MPa, adding 100ml of solvent when the reaction is finished (about 70 ℃), standing and layering, wherein the upper layer is an organic phase, the lower layer is an ionic liquid phase, the ionic liquid is recycled, and the organic phase is recrystallized to obtain the antioxidant 1010. HPLC shows that the content of the target product of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester can reach 98.2 percent, and the yield is 95.8 percent.
Example 11
Adding 6.8g of pentaerythritol, 70g of 3, 5-methyl ester and 0.34g of ionic liquid catalyst [ Bmim ] OAc into a four-mouth bottle, reacting at 190 ℃ for 5.5h under the reaction pressure of-0.1 MPa, adding 95ml of solvent when the reaction is finished (about 70 ℃), standing and layering, wherein the upper layer is an organic phase, the lower layer is an ionic liquid phase, the ionic liquid is recycled, and the organic phase is recrystallized to obtain the antioxidant 1010. HPLC shows that the content of the target product of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester can reach 97.8 percent, and the yield is 95.2 percent.
Example 12
Adding 6.8g of pentaerythritol, 66.7g of 3, 5-methyl ester and 0.34g of ionic liquid catalyst [ Bmim ] [ Pro ] into a four-mouth bottle, reacting at the pressure of-0.1 MPa and the temperature of 170 ℃ for 5 hours, adding 90ml of solvent when the mixture is hot (about 70 ℃) after the reaction is finished, standing and layering, wherein the upper layer is an organic phase, the lower layer is an ionic liquid phase, the ionic liquid is recycled, and the organic phase is recrystallized to obtain the product antioxidant 1010. HPLC shows that the content of the target product of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester can reach 97.5 percent, and the yield is 95.2 percent.
Example 13
Adding 6.8g of pentaerythritol, 66.7g of 3, 5-methyl ester and 0.21g of ionic liquid catalyst [ Bmim ] HCOO into a four-mouth bottle, reacting at the temperature of 170 ℃ for 5h under the reaction pressure of 0.08MPa, adding 90ml of solvent when the solution is hot (about 70 ℃) after the reaction is finished, standing and layering, wherein the upper layer is an organic phase, the lower layer is an ionic liquid phase, the ionic liquid is recycled, and the organic phase is recrystallized to obtain the product antioxidant 1010. HPLC shows that the content of the target product of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester can reach 97.7 percent, and the yield is 95 percent.
Example 14
Adding 6.8g of pentaerythritol, 70.7g of 3, 5-methyl ester and 0.25g of ionic liquid catalyst [ TMG ] [ Pro ] into a four-mouth bottle, reacting at the reaction pressure of-0.1 MPa and at the temperature of 190 ℃ for 6h, adding 100ml of solvent when the mixture is hot (about 70 ℃) after the reaction is finished, standing and layering, wherein the upper layer is an organic phase, the lower layer is an ionic liquid phase, the ionic liquid is recycled, and the organic phase is recrystallized to obtain the antioxidant 1010. HPLC shows that the content of the target product of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester can reach 98.5 percent, and the yield is 96.1 percent.
Example 15
5.1g of pentaerythritol, 53.6g of 3, 5-methyl ester and 0.21g of the ionic liquid catalyst [ Bmim ] OH recovered in the example 10 are added into a four-mouth bottle, the reaction pressure is-0.1 MPa, the mixture reacts for 6.5 hours at 190 ℃, 80ml of solvent is added into the mixture when the mixture is hot (about 70 ℃) after the reaction is finished, the mixture is kept stand and layered, the upper layer is an organic phase, the lower layer is an ionic liquid phase, the ionic liquid is recovered and recycled, and the organic phase is recrystallized to obtain the product antioxidant 1010. HPLC shows that the content of the target product of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester can reach 98.0 percent, and the yield is 95.6 percent.
Example 16
Adding 3.4g of pentaerythritol, 35.7g of 3, 5-methyl ester and 0.14g of the ionic liquid catalyst [ Bmim ] OH recovered in example 13 into a four-mouth bottle, reacting at-0.1 MPa and 190 ℃ for 6.5h, adding 60ml of solvent into the mixture when the mixture is hot (about 70 ℃) after the reaction is finished, standing and layering the mixture, wherein the upper layer is an organic phase, the lower layer is an ionic liquid phase, the ionic liquid is recovered and recycled, and the organic phase is recrystallized to obtain the product antioxidant 1010. HPLC shows that the content of the target product of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester can reach 98.1 percent, and the yield is 95.3 percent.
Claims (5)
1. A method for preparing hindered phenol antioxidant 1010 is prepared by taking beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) methyl propionate and pentaerythritol as raw materials through ester exchange reaction, and is characterized in that: the ester exchange reaction is carried out in a basic ionic liquid catalytic system;
Adding beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) methyl propionate, pentaerythritol and ionic liquid into a reactor for reaction, adding an organic solvent into a reaction system while the reaction is hot after the reaction is finished, standing and layering, wherein the upper layer is an organic phase, the lower layer is an ionic liquid phase, the ionic liquid is recycled, and the organic phase is recrystallized to obtain a product antioxidant 1010;
The alkaline ionic liquid is 1-methyl-3-butylimidazole formate or 1-methyl-3-butylimidazole acetate or 1-methyl-3-butylimidazole propionate or 1-methyl-3-butylimidazole carbonate or 1-methyl-3-butylimidazole hydroxide or 1-butyl-3-methylimidazolyl proline ionic liquid or tetramethylguanadinyl proline ionic liquid;
The transesterification reaction temperature is 170-190 ℃, the reaction time is 5-7 h, and the reaction pressure is 0.08-0.1 MPa;
When the organic solvent is added, the mixture is hot, and the temperature of the system is controlled to be 70-80 ℃.
2. The method of claim 1, wherein the hindered phenol antioxidant 1010 is selected from the group consisting of: the dosage of the ionic liquid is 3-5% of the mass of the pentaerythritol.
3. The method of claim 1, wherein the hindered phenol antioxidant 1010 is selected from the group consisting of: the mass ratio of the beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) methyl propionate to the pentaerythritol is 4.5-5: 1.
4. The method of claim 2, wherein the hindered phenol antioxidant 1010 is prepared by: the organic solvent is ethanol.
5. The method of claim 2, wherein the hindered phenol antioxidant 1010 is prepared by: the pH value of the alkaline ionic liquid aqueous solution is 12-14.
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| CN108558719A (en) * | 2018-05-21 | 2018-09-21 | 烟台新秀化学科技股份有限公司 | A kind of preparation method of pentaerythritol ester |
| CN110343055B (en) * | 2019-05-27 | 2022-07-12 | 烟台新特路新材料科技有限公司 | Preparation method of high-purity pentaerythritol plastic additive |
| CN111072484A (en) * | 2019-12-30 | 2020-04-28 | 宁波福天新材料科技有限公司 | Optimized preparation method of hindered phenol antioxidant 1010 |
| CN111334300A (en) * | 2020-04-01 | 2020-06-26 | 辽宁石化职业技术学院 | Preparation method of double-effect antioxidant |
| CN112266531A (en) * | 2020-09-24 | 2021-01-26 | 句容市百事特复合材料有限公司 | Low-odor long fiber reinforced polypropylene granule composition and preparation method thereof |
| CN114957007B (en) * | 2022-06-15 | 2023-09-08 | 江苏极易新材料有限公司 | Method for recycling 3,5 methyl ester through alcoholysis of antioxidant 1010 |
| CN115193487A (en) * | 2022-08-22 | 2022-10-18 | 陕西艾科莱特新材料有限公司 | Efficient composite catalyst for synthesizing antioxidant 1010 and preparation method thereof |
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| CN101508644A (en) * | 2009-03-26 | 2009-08-19 | 北京极易化工有限公司 | Novel synthesis method for hindered phenol anti-oxidants |
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| CN101508644A (en) * | 2009-03-26 | 2009-08-19 | 北京极易化工有限公司 | Novel synthesis method for hindered phenol anti-oxidants |
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| 碱性离子液体催化合成碳酸二烷基酯的研究;潘素娟;《中国优秀硕士论文电子期刊工程科技I辑B016-48》;20150715;摘要、第29-30页2.5部分、第39-40页3.3.2部分、第42-43页3.3.2.2和3.3.2.3部分 * |
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