CN105838477B - Method for preparing polyvinyl ether lubricating oil base oil - Google Patents
Method for preparing polyvinyl ether lubricating oil base oil Download PDFInfo
- Publication number
- CN105838477B CN105838477B CN201610280952.2A CN201610280952A CN105838477B CN 105838477 B CN105838477 B CN 105838477B CN 201610280952 A CN201610280952 A CN 201610280952A CN 105838477 B CN105838477 B CN 105838477B
- Authority
- CN
- China
- Prior art keywords
- polyvinyl ether
- vinyl ether
- lubricating oil
- catalyst
- ether compound
- 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
Images
Classifications
-
- 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
- C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
- C10M107/20—Lubricating compositions characterised by the base-material being a macromolecular compound containing oxygen
- C10M107/22—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C10M107/24—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an alcohol, aldehyde, ketonic, ether, ketal or acetal radical
-
- 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
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/04—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an alcohol or ester thereof; bound to an aldehyde, ketonic, ether, ketal or acetal radical
- C10M2209/043—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an alcohol or ester thereof; bound to an aldehyde, ketonic, ether, ketal or acetal radical used as base material
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Lubricants (AREA)
Abstract
The invention provides a method for preparing a polyvinyl ether lubricating oil foundation, belonging to the technical field of industrial catalysis. Reacting calcium carbide with alcohol under the action of an alkali metal catalyst to generate a vinyl ether compound monomer and calcium alkoxide, collecting and purifying the vinyl ether compound by a distillation method, carrying out polymerization reaction on the vinyl ether compound monomer after distillation and purification in a polymerization kettle under the action of an aluminum trichloride complex catalyst to generate a polyvinyl ether crude product, filtering the polyvinyl ether crude product to remove the aluminum trichloride complex catalyst, feeding the filtered polyvinyl ether crude product into a reduced pressure distillation tower, carrying out gas-liquid separation on a product at the top of the reduced pressure distillation tower to obtain an oligomer and an unreacted vinyl ether compound monomer, and feeding the unreacted vinyl ether compound monomer into the polymerization kettle again to carry out polymerization reaction; and (3) carrying out catalytic hydrogenation impurity removal on the crude product of the polyvinyl ether to obtain the polyvinyl ether lubricating oil base oil. The method is simple, the purity of the prepared vinyl ether compound monomer is high, and the kinematic viscosity of the polyvinyl ether lubricating oil base oil is adjustable.
Description
Technical Field
The invention belongs to the field of lubricating oil synthesis, and relates to a method for preparing polyvinyl ether lubricating oil base oil.
Background
The polyether is used as a lubricant and is mainly characterized in that: the lubricating oil has the characteristics of excellent viscosity-temperature property and no coking at high temperature, and can be used as lubricating oil for high-temperature parts of machinery; has excellent low temperature resistance and is suitable for hydrogen and ethyleneThe alkene and the natural gas have the characteristics of low solubility and good intersolubility with Freon gas, and can be used as gas compressor oil, refrigerator oil, vacuum pump oil and the like; the lubricating oil has good lubricity, has good dissolving and precipitating effects, can keep the interior of an engine clean, does not leave residues when completely combusted, and is suitable for totally-enclosed internal combustion engine oil, gear oil, winter and summer gear oil and the like; has good thickening effect and good anti-shearing performance, does not generate sediment and paint-like substances under high pressure, and is suitable for being used as base oil of flame-retardant hydraulic oil. Vinyl ether compounds are important as monomers of organic synthesis intermediates and polymers, and homopolymers and copolymers thereof are widely used in many fields such as adhesives, paints, lubricants, plasticizers, insecticides, and surface protective materials, and thus, the vinyl ether compounds have been receiving great attention. The preparation method of the vinyl ether compound comprises the following steps: the acetylene process, the general reaction formula is as follows:
the alcohol and acetylene gas are directly reacted at high temperature and high pressure to prepare the catalyst, but the explosion limit range of acetylene is wide (the volume ratio of the acetylene to air is 2.5-81 percent) due to the use of high-temperature and high-pressure equipment, and the operation can cause explosion by carelessness.
Dehydrohalogenation, the general reaction formula is as follows:
the reaction conditions of the method are milder than that of an acetylene method, but the method has requirements on the structure of a raw material for reaction, because a vinyl ether compound cannot be prepared by a general ether synthesis method, and a synthesized target product is limited to a certain extent.
Thermal acetal decomposition method, the reaction general formula is as follows:
the decomposition system includes a gas phase system and a liquid phase system. The gas phase cracking method uses metal as a catalyst, and acetal steam is cracked by passing through a catalyst layer at high temperature. The acetal is cleaved in the presence of a liquid medium and a suitable catalyst. It has the advantages of simple equipment, uniform reaction condition, easy control, etc. The key to this is the choice of medium and catalyst and how to separate the olefinic ether produced by the cleavage from the reaction system and prevent recombination with the alcohol produced by the cleavage.
The above 3 methods are each characterized, and are compared below with respect to various factor lists.
Aiming at the problems of high risk and difficulty in preparing synthetic monomers of the base oil of the polyvinyl ether lubricating oil, difficulty in hydrogenation and impurity removal of the base oil of the polyvinyl ether lubricating oil and the like. We open another way to replace CaC2As a cocatalyst for mild reaction conditions without directly using acetylene gas. CaC2The principle of reaction with alcohols to form vinyl ether compounds is as follows:in the mixed product, the vinyl ether compound can be collected by distillation, and the by-product Ca (OR)2The product is stable and remains, and the purity of the product is not influenced. The vinyl ether compound monomer after distillation and purification is subjected to polymerization reaction in a polymerization kettle under the action of an aluminum trichloride complex catalyst to generate a polyvinyl ether crude product, and the polymerization principle is as follows:
filtering the crude product of the polyvinyl ether to remove the aluminum trichloride complex catalyst, feeding the filtered crude product of the polyvinyl ether into a distillation tower, carrying out gas-liquid separation on the product at the top of the distillation tower to obtain an oligomer and an unreacted vinyl ether compound monomer, and feeding the unreacted vinyl ether compound monomer into a polymerization kettle again to carry out polymerization reaction. The product at the bottom of the distillation tower is hydrogenated to remove impurities to obtain the polyvinyl ether lubricating oil base oil which is improved to be water white in color phase and has good thermal stability. The following known techniques all have some disadvantages:
chinese patent, publication No.: CN100590110C discloses a method for producing vinyl ethers, which adopts acetal thermal decomposition method to prepare vinyl ethers compounds. The prepared vinyl ether compound contains alcohol, unreacted dibutyl acetal, low-boiling-point substances and water, so that the vinyl ether compound has low purity and great influence on subsequent polymerization reaction.
Disclosure of Invention
The invention discloses a method for preparing polyvinyl ether lubricating oil base oil, belonging to the field of lubricating oil synthesis. The method comprises the steps of reacting calcium carbide with alcohol under the action of an alkali metal catalyst to generate a vinyl ether compound monomer, carrying out distillation and purification, and polymerizing to obtain a polyvinyl ether crude product, and carrying out catalytic hydrogenation and impurity removal on the polyvinyl ether crude product to obtain the polyvinyl ether lubricating oil base oil. The method is simple, the purity of the prepared vinyl ether compound monomer is high, and the kinematic viscosity of the polyvinyl ether lubricating oil base oil is adjustable.
The technical scheme of the invention is as follows:
a method for preparing polyvinyl ether lubricating oil base oil comprises the following steps:
the method comprises the steps of reacting calcium carbide and alcohol in a reaction kettle under the action of an alkali metal catalyst to generate a vinyl ether compound monomer and calcium alcohol, collecting and purifying the vinyl ether compound by a distillation method because the calcium alcohol is relatively stable, carrying out polymerization reaction on the vinyl ether compound monomer after distillation and purification in a polymerization kettle under the action of an aluminum trichloride complex catalyst to generate a polyvinyl ether crude product, filtering the polyvinyl ether crude product to remove the aluminum trichloride complex catalyst, feeding the filtered polyvinyl ether crude product into a reduced pressure distillation tower, carrying out gas-liquid separation on the top product of the reduced pressure distillation tower to obtain an oligomer and an unreacted vinyl ether compound monomer, and feeding the unreacted vinyl ether compound monomer into the polymerization kettle again to carry out polymerization reaction. The bottom product of the reduced pressure distillation tower is pressurized and mixed with hydrogen to directly enter a hydrogenation tower filled with a hydrogenation catalyst, the feeding temperature is 150-170 ℃, the hydrogen partial pressure is 15-18MPa, and the volume space velocity is 0.4-0.6h-1Hydrogen-oil volume ratio 400: 1; hydrogenation catalystThe catalyst is an eggshell type Pd catalyst, and polyvinyl ether lubricating oil base oil is prepared by catalytic hydrogenation and impurity removal.
The alcohol is one or more of methanol, ethanol, propanol and isopropanol;
the molar ratio of the calcium carbide to the alcohol is more than 3, and the optimal range is 3.5-5;
the alkali metal catalyst is one or a mixture of more than two of K, KOH, Na and NaOH;
the operating pressure of the reduced pressure distillation tower is 10-30 KPa.
The eggshell type Pd catalyst is used for the fixed bed continuous hydrogenation of the base oil of the polyvinyl ether lubricating oil, firstly, the base oil of the polyvinyl ether lubricating oil is diluted by a solvent, the proportion of the base oil of the polyvinyl ether lubricating oil is 50%, and then, the eggshell type Pd catalyst is mixed with hydrogen to carry out hydrogenation and impurity removal to remove double bonds and acetal in the base oil of the polyvinyl ether lubricating oil, so that the further reaction of a target product is avoided, and the selectivity of an intermediate product in the irreversible series reaction process can be improved. And reduces the dosage of the noble metal palladium of the catalyst. The catalyst cost is effectively reduced, the amplification production is facilitated, the hue of the hydrogenated and impurity-removed base oil of the polyvinyl ether lubricating oil is improved to be water white, the thermal stability is improved, and the viscosity is slightly reduced.
The invention has simple process, high purity of the prepared vinyl ether compound monomer, adjustable kinematic viscosity of the polyvinyl ether lubricating oil base oil and good industrial application prospect.
Drawings
FIG. 1 is a schematic process flow diagram of the present invention.
In the figure: 1, a synthesis kettle; 2, an atmospheric distillation tower; 3, a polymerization kettle; 4, a filter; 5, a reduced pressure distillation tower;
6 a hydrogenation tower; 7 gas-liquid separation tank.
Detailed Description
The following further describes the specific embodiments of the present invention with reference to the technical solutions and the accompanying drawings.
Example 1: the calcium carbide and alcohol react under the action of an alkali metal catalyst to generate a vinyl ether compound monomer. An alkali metal catalyst is used as a catalyst, the amount of the catalyst is 10% of the weight of the calcium carbide, and the vinyl ether compound monomer is prepared by directly reacting alcohol and the calcium carbide at high temperature and high pressure. And (3) investigating the influence of the types of the alcohols, the molar ratio of the alcohols to the calcium carbide and the types of the alkali metal catalysts on the monomer yield of the vinyl ether compound. Table 1 shows the yields of vinyl ether compounds obtained from different ratios of methanol to calcium carbide in different base catalysts.
Table 2 shows the yields of vinyl ether compounds obtained from different ratios of ethanol to calcium carbide in different base catalysts.
Table 3 shows the yields of vinyl ether compounds from different ratios of propanol to calcium carbide in different base catalysts.
Table 4 shows the yields of vinyl ether compounds obtained from different ratios of isopropyl alcohol to calcium carbide in different base catalysts.
Example 2: distilling the purified vinyl ether compound monomer. The vinyl ether compound prepared by using K as an alkali metal catalyst with the molar ratio of ethanol to calcium carbide being 5 is taken as an example. The operating temperature of the distillation tower is 40-45 ℃.
Example 3: vinyl ether compound monomers are polymerized to generate crude polyvinyl ether products. The mol ratio of ethanol to calcium carbide is 5, K is used as an alkali metal catalyst, a vinyl ether compound after distillation and purification is used as a monomer, aluminum trichloride is used as a polymerization catalyst, and the polymerization temperature is 200-260 ℃. The polymerization catalyst may also be boron trifluoride.
Example 4: and filtering the crude product of the polyvinyl ether to remove the polymerization catalyst. On the basis of example 3, the crude polyvinyl ether product was filtered through a 200-mesh 800-mesh screen to remove the polymerization catalyst.
Example 5: and (5) distilling and purifying a crude product of polyvinyl ether. On the basis of the embodiment 4, the crude product of the filtered polyvinyl ether enters a reduced pressure distillation tower, the product at the top of the reduced pressure distillation tower is subjected to gas-liquid separation to obtain an oligomer and an unreacted vinyl ether compound monomer, and the unreacted vinyl ether compound monomer enters a polymerization kettle again for polymerization reaction. The operating pressure of the reduced pressure distillation tower is 10-30Kpa, and the theoretical plate number is more than 40.
Example 6: and (3) carrying out catalytic hydrogenation impurity removal on the polyvinyl ether after reduced pressure distillation and purification to obtain the polyvinyl ether lubricating oil base oil. Firstly, diluting a product at the bottom of a reduced pressure distillation tower by using a solvent, wherein the ratio of the polyvinyl ether lubricating oil base oil is 50%, then mixing the product with hydrogen to remove double bonds and acetals in the polyvinyl ether lubricating oil base oil through hydrogenation and impurity removal, and directly feeding the mixture into a hydrogenation tower filled with a hydrogenation catalyst through pressurization and mixing with hydrogen, wherein the feeding temperature is 150--1Hydrogen-oil volume ratio 400: 1; the hydrogenation catalyst is an eggshell type Pd catalyst, and the polyvinyl ether lubricating oil base oil prepared by catalytic hydrogenation impurity removal has improved hue to water white, slightly reduced viscosity and good high-temperature thermal stability. The vinyl ether compound prepared by the process has high monomer purity, and the polyvinyl ether lubricating oil base oil has adjustable kinematic viscosity, thereby having good industrial application prospect.
Claims (5)
1. A method for preparing polyvinyl ether lubricating oil base oil is characterized by comprising the following steps:
reacting calcium carbide and alcohol in a reaction kettle under the action of an alkali metal catalyst to generate a vinyl ether compound monomer and calcium alkoxide, collecting and purifying the vinyl ether compound monomer by a distillation method, carrying out a polymerization reaction on the distilled and purified vinyl ether compound monomer in a polymerization kettle under the action of an aluminum trichloride complex catalyst to generate a polyvinyl ether crude product, and filtering the polyvinyl ether crude product to remove trichloro chlorideThe crude product of polyvinyl ether after filtration enters a reduced pressure distillation tower, the product at the top of the reduced pressure distillation tower is subjected to gas-liquid separation to obtain an oligomer and an unreacted vinyl ether compound monomer, and the unreacted vinyl ether compound monomer enters a polymerization kettle again for polymerization reaction; the bottom product of the reduced pressure distillation tower is pressurized and mixed with hydrogen to directly enter a hydrogenation tower filled with a hydrogenation catalyst, the feeding temperature is 150-170 ℃, the hydrogen partial pressure is 15-18MPa, and the volume space velocity is 0.4-0.6h-1Hydrogen-oil volume ratio 400: 1; the hydrogenation catalyst is an eggshell type Pd catalyst, and polyvinyl ether lubricating oil base oil is prepared by catalytic hydrogenation and impurity removal; the molar ratio of the calcium carbide to the alcohol is more than 3;
the eggshell type Pd catalyst is used for the fixed bed continuous hydrogenation of the base oil of the polyvinyl ether lubricating oil, firstly, the base oil of the polyvinyl ether lubricating oil is diluted by a solvent, the proportion of the base oil of the polyvinyl ether lubricating oil is 50 percent, and then the eggshell type Pd catalyst is mixed with hydrogen to carry out hydrogenation and impurity removal to remove double bonds and acetal in the base oil of the polyvinyl ether lubricating oil;
the alkali metal catalyst is K, Na one or two mixtures.
2. The method according to claim 1, wherein the molar ratio of the calcium carbide to the alcohol is 3.5-5.
3. The method according to claim 1 or 2, characterized in that: the alcohol is one or more of methanol, ethanol, propanol and isopropanol.
4. The process according to claim 1 or 2, wherein the operating pressure of the vacuum distillation column is 10 to 30 KPa.
5. The process of claim 3, wherein the vacuum distillation column is operated at a pressure of from 10 to 30 KPa.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610280952.2A CN105838477B (en) | 2016-04-28 | 2016-04-28 | Method for preparing polyvinyl ether lubricating oil base oil |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610280952.2A CN105838477B (en) | 2016-04-28 | 2016-04-28 | Method for preparing polyvinyl ether lubricating oil base oil |
Publications (2)
Publication Number | Publication Date |
---|---|
CN105838477A CN105838477A (en) | 2016-08-10 |
CN105838477B true CN105838477B (en) | 2021-04-20 |
Family
ID=56590408
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201610280952.2A Active CN105838477B (en) | 2016-04-28 | 2016-04-28 | Method for preparing polyvinyl ether lubricating oil base oil |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN105838477B (en) |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107033260A (en) * | 2017-04-14 | 2017-08-11 | 上海欧勒奋生物科技有限公司 | A kind of method that PAO9 base oils are synthesized based on the Aluminium Trichloride as Catalyst that Loprazolam is modified |
CN106916238A (en) * | 2017-04-14 | 2017-07-04 | 上海欧勒奋生物科技有限公司 | A kind of method that PAO15 base oils are synthesized based on the modified alchlor of laurate |
CN107082831A (en) * | 2017-04-14 | 2017-08-22 | 上海欧勒奋生物科技有限公司 | A kind of synthetic method of top-grade lubricating oil PAO22 for automobile engine |
CN110551522B (en) * | 2018-05-31 | 2021-12-17 | 中国石油化工股份有限公司 | Method for preparing lubricating oil base oil |
CN110607199B (en) * | 2018-06-14 | 2022-07-15 | 中国石油化工股份有限公司 | Method for removing impurities by hydrogenating polyvinyl ether |
CN112126503B (en) * | 2019-06-24 | 2022-12-09 | 中国石油化工股份有限公司 | Method for removing impurities from polyvinyl ether by liquid-phase hydrogenation |
CN112125993B (en) * | 2019-06-24 | 2022-10-21 | 中国石油化工股份有限公司 | Method for liquid-phase hydrofining of polyvinyl ether |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3341606A (en) * | 1965-10-22 | 1967-09-12 | Air Reduction | Process for producing vinyl ethers |
CN1339561A (en) * | 2000-08-22 | 2002-03-13 | 中国石油化工股份有限公司 | Hydrorefining catalyst |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4302613A (en) * | 1980-08-22 | 1981-11-24 | Conoco Inc. | Inorganic catalyst for alkoxylation of alcohols |
CN100590110C (en) * | 2007-09-19 | 2010-02-17 | 山西三维集团股份有限公司 | Production method for vinyl ethers |
CN103521221B (en) * | 2013-10-18 | 2016-04-06 | 大连理工大学 | A kind of load type gold-platinum bimetallic alloy Catalysts and its preparation method, application |
-
2016
- 2016-04-28 CN CN201610280952.2A patent/CN105838477B/en active Active
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3341606A (en) * | 1965-10-22 | 1967-09-12 | Air Reduction | Process for producing vinyl ethers |
CN1339561A (en) * | 2000-08-22 | 2002-03-13 | 中国石油化工股份有限公司 | Hydrorefining catalyst |
Non-Patent Citations (2)
Title |
---|
乙烯基醚;化工百科全书编委会;《树脂与塑料.化工百科全书专业卷》;20030131;第1585页 * |
乙烯基醚;汪伟志;《湖北化工》;20001231;全文 * |
Also Published As
Publication number | Publication date |
---|---|
CN105838477A (en) | 2016-08-10 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN105838477B (en) | Method for preparing polyvinyl ether lubricating oil base oil | |
TWI324991B (en) | Process for producing alcohol | |
GB2483325A (en) | Method for preparing polymethoxy dimethyl ethers by acetalization reaction of formaldehyde and methanol | |
CN101565353B (en) | Preparation method for 2-propyl enanthol | |
CN102206336B (en) | Saturated cardanol polyoxyethylene ether and preparation method thereof | |
JP3925940B2 (en) | Method for producing ether compound | |
CN106866366A (en) | Dihydroxylic alcohols or polyol impurities and the method for increasing production ethylene glycol in a kind of removal ethylene glycol | |
CN102504891A (en) | Preparation method of glyceryl biological fuel additives | |
CN106565945A (en) | Preparation method of perfluoropolyether alcohol | |
CN105085165A (en) | Ethylene glycol and diethylene glycol separation method | |
US2397514A (en) | Preparation of diethers of the glycols | |
US3429936A (en) | Novel polyalkyl alcohols | |
CN114105744A (en) | Method for catalyzing Claisen rearrangement at lower temperature | |
JP4466050B2 (en) | Method for producing alcohol | |
CN113816839B (en) | Method for synthesizing glyoxal through acetylene double hydroformylation | |
CN112479858A (en) | Methanol carbonylation enhanced reaction system and process with aldehyde recovery function | |
CN1840528A (en) | Process for preparing N-formyl morpholine | |
CN110563580A (en) | synthesis method of high-purity propyl propionate | |
CN210237494U (en) | Multi-stage reaction rectification synthesis process device for polymethoxy dimethyl ether | |
JP4110844B2 (en) | Method for producing hydroxyaldehydes | |
WO2019165636A1 (en) | Preparation method for fluorine-containing 1,3-dioxacycloalkane olefin | |
CN104341294B (en) | A kind of method being prepared 4-methoxyl group methyl valerate by γ-valerolactone | |
CN114478203B (en) | Preparation method of vinyl low-carbon alcohol for polyether initiator | |
CN1508108A (en) | Combined process for synthesizing amylene alcohol | |
CN114213560B (en) | Synthesis method of renewable polycycloolefin material |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |