CN110128314B - Method for continuously producing 2, 2-bis (tert-butyl peroxide) butane - Google Patents
Method for continuously producing 2, 2-bis (tert-butyl peroxide) butane Download PDFInfo
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Abstract
The invention discloses a method for continuously producing 2, 2-bis (tert-butyl peroxide) butane, which comprises the following steps: (1) preparing an acid catalyst; (2) the acid catalyst and the tert-butyl peroxide enter the same precooling module of the microreactor to be mixed, and the methyl ethyl ketone enters the other precooling module of the microreactor to control the precooling temperature of the two precooling modules; (3) the three raw materials are precooled by the precooling module and then enter the reaction module to react, and the reaction temperature is kept consistent with the temperature of the precooling module; (4) after the reaction is finished, directly collecting the reaction liquid obtained from the outlet of the microchannel reactor, separating the liquid, washing an organic phase with alkali, and washing with water to obtain the solvent oil solution of the 2, 2-bis (tert-butyl peroxide) butane. Compared with the traditional kettle type reaction, the invention has the advantages of high heat exchange efficiency, uniform system heat exchange, high safety and suitability for industrial production, and the reaction temperature can be accurately controlled by utilizing the external heat exchanger, and the reaction can be started and stopped at any time without amplification effect.
Description
Technical Field
The invention belongs to the field of fine chemicals, and particularly relates to a method for continuously producing 2, 2-bis (tert-butyl peroxide) butane.
Background
The organic peroxide cross-linking agent is an important auxiliary agent of an organic high molecular polymer, can convert a linear or slightly branched organic high molecular chain into a three-dimensional network structure to limit relative movement between high molecular chains and between chain segments inside the high molecular chains, thereby improving certain properties of the organic high molecular polymer, and can obviously improve the properties of heat resistance, oil resistance, wear resistance, mechanical strength and the like after some high molecular polymers are cross-linked; some organic high molecular polymers, such as rubber, must be crosslinked to be of practical use.
We have generally used dicumyl peroxide as the organic peroxide crosslinking agent, but the use of this peroxide as the crosslinking agent, which produces acetophenone having an unpleasant odor upon crosslinking and remains in the finished product, makes this organic peroxide crosslinking agent unusable in many cases.
2, 2-bis (tert-butyl peroxide) butane is widely used as a substitute for a crosslinking agent of unsaturated polyester and silicon rubber, a polymerization initiator of a monomer, a polypropylene modifier and a rubber vulcanizing agent, can also be used as an inorganic synthetic raw material, is also applied to the paint industry, and is a common fine chemical.
As the initiator of the polymerization reaction, the method is mainly used for the polymerization reaction of the suspension method styrene and the copolymer of the styrene at the temperature of 90-130 ℃. Compared with thermal initiation polymerization, the initiation polymerization of 2, 2-bis (tert-butylperoxy) butane has the advantages of low single residue level, high conversion rate and high reaction rate.
The 2, 2-bis (tert-butyl peroxide) butane is mainly synthesized by tert-butyl peroxide and methyl ethyl ketone under the catalysis of acid. However, since this acid catalysis method does not use a solvent, the high-content peroxyketal product and a large amount of acid catalysts are liable to undergo a severe acid decomposition reaction, resulting in low product yield, deep color, even explosion accidents due to a large amount of heat release, and unsafe production.
The industrial production still uses the traditional intermittent method to produce, and its processing time such as feeding, unloading is long, and reation kettle is bulky, needs to occupy great factory building, and this reaction is exothermic reaction, needs lower temperature, and the heat is difficult to the effluvium, and traditional kettle-type reaction, and mass transfer heat transfer efficiency is lower, takes place the incident easily. To date, no research has been found for producing 2, 2-bis (t-butylperoxy) butane in a continuous manner.
Disclosure of Invention
The invention provides a method for continuously producing 2, 2-bis (tert-butyl peroxide) butane, which comprises the following steps:
(1) preparing an acid catalyst;
(2) respectively feeding the acid catalyst and tert-butyl peroxide into the same precooling module of the microreactor through a metering pump for mixing, feeding methyl ethyl ketone into the other precooling module of the microreactor through the metering pump, and controlling precooling temperatures of the two precooling modules;
(3) the three raw materials are precooled by the precooling module and then enter the reaction module to react, and the reaction temperature is kept consistent with the temperature of the precooling module;
(4) after the reaction is finished, directly flowing the reaction liquid obtained from the outlet of the microchannel reactor into a collector filled with solvent oil, after the reaction liquid stops flowing out, separating the liquid, and carrying out alkali washing and water washing on an organic phase to obtain the solvent oil solution of the 2, 2-bis (tert-butyl peroxide) butane.
Further, in the step (2), after the acidic catalyst and the tert-butyl peroxide are mixed in the pre-cooling module, a catalytic auxiliary agent is added into the pre-cooling module, wherein the catalytic auxiliary agent is a mixture of ruthenium sulfate and ethylene diamine tetraacetic acid, and the mixing mass ratio of the ruthenium sulfate to the ethylene diamine tetraacetic acid is ruthenium sulfate: ethylene diamine tetraacetic acid =1: 2-5; the mass of the catalytic auxiliary agent is 10-16% of that of the acidic catalyst.
Further, the acidic catalyst is one or a mixture of more of hydrochloric acid, sulfuric acid, phosphoric acid, perchloric acid, nitric acid, p-toluenesulfonic acid and sulfanilic acid.
Further, the acidic catalyst is sulfuric acid.
Further, the mass percentage of the solute in the acid catalyst is 45% -95%, and the solvent is water.
Further, the mass percentage of the solute in the acid catalyst is 60% -80%, and the solvent is water.
Further, in the reaction module, the molar ratio of the solute in the acidic catalyst, the methyl ethyl ketone and the tert-butyl alcohol peroxide to the solute in the acidic catalyst is: methyl ethyl ketone: tert-butyl peroxide = 0.4-1.2: 1: 2.
Further, the pre-cooling temperature and the reaction temperature are 6-15 ℃.
According to the technical scheme, the invention has the advantages that:
1. the invention provides a process route for continuously producing 2, 2-bis (tert-butyl peroxide) butane by utilizing tert-butyl peroxide and methyl ethyl ketone in a microchannel reactor in a continuous flow mode under catalysis. The process route has the advantages that the reaction temperature, the molar ratio of the raw materials, the residence time of the reaction and the like are accurately controlled, and the 2, 2-bis (tert-butyl peroxide) butane is obtained with high yield within the time from tens of seconds to several minutes. This provides a safe synthetic route for the production of 2, 2-bis (t-butylperoxy) butane that is easy to operate. And the invention adopts the method of continuous preparation in the microchannel reactor to continuously produce the 2, 2-bis (tert-butyl peroxide) butane, compared with the traditional kettle type reaction, the invention has the advantages of high heat exchange efficiency, uniform system heat exchange, accurate control of reaction temperature by utilizing an external heat exchanger, capability of starting and stopping the reaction at any time, no amplification effect, high safety and suitability for industrial production.
2. The invention further improves the catalytic efficiency by introducing the catalytic auxiliary agent under the catalytic system of the acid catalyst, obviously improves the purity of the 2, 2-bis (tert-butyl peroxide) butane product compared with the purity without the catalytic auxiliary agent, and has wide application prospect.
Drawings
FIG. 1 is a schematic flow diagram of the process of the present invention; wherein feed 1 represents an acidic catalyst; raw material 2 represents tert-butyl peroxide; feed 3 represents methyl ethyl ketone.
Detailed Description
The following is a detailed description with reference to examples:
example 1
A process for the continuous production of 2, 2-bis (t-butylperoxy) butane comprising the steps of:
(1) preparing sulfuric acid with solute mass fraction of 60%, and water as solvent;
(2) respectively feeding the prepared sulfuric acid and tert-butyl peroxide into the same precooling module of the microreactor through a metering pump for mixing, simultaneously feeding methyl ethyl ketone into the other precooling module of the microreactor through the metering pump, and controlling the precooling temperature of the two precooling modules to be 15 ℃;
(3) the three raw materials are precooled by a precooling module and then enter a reaction module for reaction, and the flow rate of a metering pump is adjusted, so that the molar ratio of sulfuric acid to methyl ethyl ketone to tert-butyl peroxide in the reaction module is sulfuric acid (solute in a sulfuric acid solution): methyl ethyl ketone: tert-butyl peroxide =0.8:1:2, reaction residence time 150 seconds; the reaction temperature is kept consistent with the temperature of the precooling module;
(4) after the reaction is finished, directly flowing the reaction liquid obtained from the outlet of the microchannel reactor into a collector filled with solvent oil, after the reaction liquid stops flowing out, separating the liquid, and carrying out alkali washing and water washing on an organic phase to obtain the solvent oil solution of the 2, 2-bis (tert-butyl peroxide) butane. The purity of the product 2, 2-bis (t-butylperoxy) butane in the miscella solution was determined to be 93.02%.
Example 2
A process for the continuous production of 2, 2-bis (t-butylperoxy) butane comprising the steps of:
(1) preparing sulfuric acid with solute mass fraction of 70%, and water as solvent;
(2) respectively feeding the prepared sulfuric acid and tert-butyl peroxide into the same precooling module of the microreactor through a metering pump for mixing, simultaneously feeding methyl ethyl ketone into the other precooling module of the microreactor through the metering pump, and controlling the precooling temperature of the two precooling modules to be 8 ℃;
(3) the three raw materials are precooled by a precooling module and then enter a reaction module for reaction, and the flow rate of a metering pump is adjusted, so that the molar ratio of sulfuric acid to methyl ethyl ketone to tert-butyl peroxide in the reaction module is sulfuric acid (solute in a sulfuric acid solution): methyl ethyl ketone: tert-butyl peroxide =0.6:1:2, reaction residence time 200 seconds; the reaction temperature is kept consistent with the temperature of the precooling module;
(4) after the reaction is finished, directly flowing the reaction liquid obtained from the outlet of the microchannel reactor into a collector filled with solvent oil, after the reaction liquid stops flowing out, separating the liquid, and carrying out alkali washing and water washing on an organic phase to obtain the solvent oil solution of the 2, 2-bis (tert-butyl peroxide) butane. The purity of the product 2, 2-bis (t-butylperoxy) butane in the miscella solution was determined to be 92.42%.
Example 3
A process for the continuous production of 2, 2-bis (t-butylperoxy) butane comprising the steps of:
(1) preparing sulfuric acid with solute mass fraction of 75%, and water as a solvent;
(2) respectively feeding the prepared sulfuric acid and tert-butyl peroxide into the same precooling module of the microreactor through a metering pump for mixing, simultaneously feeding methyl ethyl ketone into the other precooling module of the microreactor through the metering pump, and controlling the precooling temperature of the two precooling modules to be 6 ℃;
(3) the three raw materials are precooled by a precooling module and then enter a reaction module for reaction, and the flow rate of a metering pump is adjusted, so that the molar ratio of sulfuric acid to methyl ethyl ketone to tert-butyl peroxide in the reaction module is sulfuric acid (solute in a sulfuric acid solution): methyl ethyl ketone: tert-butyl peroxide =0.75:1:2, reaction residence time 100 seconds; the reaction temperature is kept consistent with the temperature of the precooling module;
(4) after the reaction is finished, directly flowing the reaction liquid obtained from the outlet of the microchannel reactor into a collector filled with solvent oil, after the reaction liquid stops flowing out, separating the liquid, and carrying out alkali washing and water washing on an organic phase to obtain the solvent oil solution of the 2, 2-bis (tert-butyl peroxide) butane. The purity of the product 2, 2-bis (t-butylperoxy) butane in the miscella solution was determined to be 92.35%.
Example 4
A process for the continuous production of 2, 2-bis (t-butylperoxy) butane comprising the steps of:
(1) preparing sulfuric acid with solute mass fraction of 80%, and water as solvent;
(2) respectively feeding the prepared sulfuric acid and tert-butyl peroxide into the same precooling module of the microreactor through a metering pump for mixing, simultaneously feeding methyl ethyl ketone into the other precooling module of the microreactor through the metering pump, and controlling the precooling temperature of the two precooling modules to be 10 ℃;
(3) the three raw materials are precooled by a precooling module and then enter a reaction module for reaction, and the flow rate of a metering pump is adjusted, so that the molar ratio of sulfuric acid to methyl ethyl ketone to tert-butyl peroxide in the reaction module is sulfuric acid (solute in a sulfuric acid solution): methyl ethyl ketone: tert-butyl peroxide =0.7:1:2, reaction residence time 85 seconds; the reaction temperature is kept consistent with the temperature of the precooling module;
(4) after the reaction is finished, directly flowing the reaction liquid obtained from the outlet of the microchannel reactor into a collector filled with solvent oil, after the reaction liquid stops flowing out, separating the liquid, and carrying out alkali washing and water washing on an organic phase to obtain the solvent oil solution of the 2, 2-bis (tert-butyl peroxide) butane. The purity of the product 2, 2-bis (t-butylperoxy) butane in the miscella solution was determined to be 93.03%.
Comparative example 1
A process for the continuous production of 2, 2-bis (t-butylperoxy) butane comprising the steps of:
(1) preparing sulfuric acid with solute mass fraction of 80%, and water as solvent;
(2) respectively feeding the prepared sulfuric acid and tert-butyl peroxide into the same precooling module of the microreactor through a metering pump to be mixed, simultaneously feeding methyl ethyl ketone into the other precooling module of the microreactor through the metering pump, controlling the precooling temperature of the two precooling modules to be 10 ℃, continuously adding a catalytic auxiliary agent into the precooling module mixed by the sulfuric acid and the tert-butyl peroxide while pumping the sulfuric acid and the tert-butyl peroxide, wherein the catalytic auxiliary agent is a mixture of ruthenium sulfate and ethylene diamine tetraacetic acid, and the mixing mass ratio of the ruthenium sulfate to the ethylene diamine tetraacetic acid is ruthenium sulfate: ethylenediaminetetraacetic acid =1: 5; controlling the addition of the catalytic adjuvant so that the mass of the catalytic adjuvant in the reaction module is 16% of the mass of the acidic catalyst (solute + solvent) in the reaction module;
(3) the raw materials are precooled by a precooling module and then enter a reaction module for reaction, and the flow rate of a metering pump is adjusted, so that the molar ratio of sulfuric acid, methyl ethyl ketone and tert-butyl peroxide to sulfuric acid (solute in a sulfuric acid solution): methyl ethyl ketone: tert-butyl peroxide =0.7:1:2, reaction residence time 85 seconds; the reaction temperature is kept consistent with the temperature of the precooling module;
(4) after the reaction is finished, directly flowing reaction liquid obtained from the outlet of the microchannel reactor into a collector filled with solvent oil, separating liquid after the reaction liquid stops flowing out, carrying out alkali washing on an organic phase, and removing a catalytic auxiliary agent by water washing to obtain the solvent oil solution of the 2, 2-bis (tert-butyl peroxide) butane. The purity of the product 2, 2-bis (t-butylperoxy) butane in the miscella solution was determined to be 97.57%.
Comparative example 2
A process for the continuous production of 2, 2-bis (t-butylperoxy) butane comprising the steps of:
(1) preparing sulfuric acid with solute mass fraction of 80%, and water as solvent;
(2) respectively feeding the prepared sulfuric acid and tert-butyl peroxide into the same precooling module of the microreactor through a metering pump to be mixed, simultaneously feeding methyl ethyl ketone into the other precooling module of the microreactor through the metering pump, controlling the precooling temperature of the two precooling modules to be 10 ℃, continuously adding a catalytic auxiliary agent into the precooling module mixed by the sulfuric acid and the tert-butyl peroxide while pumping the sulfuric acid and the tert-butyl peroxide, wherein the catalytic auxiliary agent is a mixture of ruthenium sulfate and ethylene diamine tetraacetic acid, and the mixing mass ratio of the ruthenium sulfate to the ethylene diamine tetraacetic acid is ruthenium sulfate: ethylenediaminetetraacetic acid =1: 2; controlling the addition of the catalytic adjuvant so that the mass of the catalytic adjuvant in the reaction module is 10% of the mass of the acidic catalyst (solute + solvent) in the reaction module;
(3) the raw materials are precooled by a precooling module and then enter a reaction module for reaction, and the flow rate of a metering pump is adjusted, so that the molar ratio of sulfuric acid, methyl ethyl ketone and tert-butyl peroxide to sulfuric acid (solute in a sulfuric acid solution): methyl ethyl ketone: tert-butyl peroxide =0.7:1:2, reaction residence time 85 seconds; the reaction temperature is kept consistent with the temperature of the precooling module;
(4) after the reaction is finished, directly flowing reaction liquid obtained from the outlet of the microchannel reactor into a collector filled with solvent oil, separating liquid after the reaction liquid stops flowing out, carrying out alkali washing on an organic phase, and removing a catalytic auxiliary agent by water washing to obtain the solvent oil solution of the 2, 2-bis (tert-butyl peroxide) butane. The purity of the product 2, 2-bis (t-butylperoxy) butane in the miscella solution was determined to be 96.42%.
Comparative examples 3 to 8
6 separate runs were conducted, each run prepared as described in example 4 for the continuous production of 2, 2-bis (t-butylperoxy) butane to obtain a 2, 2-bis (t-butylperoxy) butane in mineral spirits, except that: the type of acidic catalyst used in each run was different and the other process parameters were identical to those of example 4. The mass percentages of the acidic catalyst and its solute used in the examples are shown in table 1. The purity of the product 2, 2-bis (t-butylperoxy) butane was determined from the solvent oil solution of 2, 2-bis (t-butylperoxy) butane obtained in each example and is shown in table 1.
The technical solutions provided by the present invention are described in detail above, and for those skilled in the art, the ideas according to the embodiments of the present invention may be changed in the specific implementation manners and the application ranges, and in summary, the content of the present description should not be construed as limiting the present invention.
Claims (7)
1. A process for the continuous production of 2, 2-bis (t-butylperoxy) butane, comprising the steps of:
(1) preparing an acid catalyst;
(2) respectively feeding the acid catalyst and tert-butyl peroxide into the same precooling module of the microreactor through a metering pump for mixing, feeding methyl ethyl ketone into the other precooling module of the microreactor through the metering pump, and controlling precooling temperatures of the two precooling modules;
(3) the three raw materials are precooled by the precooling module and then enter the reaction module to react, and the reaction temperature is kept consistent with the temperature of the precooling module;
(4) after the reaction is finished, directly flowing the reaction liquid obtained from the outlet of the microchannel reactor into a collector filled with solvent oil, after the reaction liquid stops flowing out, separating the liquid, and carrying out alkali washing and water washing on an organic phase to obtain a solvent oil solution of the 2, 2-bis (tert-butyl peroxide) butane;
in the step (2), after the acidic catalyst and the tert-butyl peroxide are mixed in the precooling module, a catalytic auxiliary agent is added into the precooling module, wherein the catalytic auxiliary agent is a mixture of ruthenium sulfate and ethylene diamine tetraacetic acid, and the mixing mass ratio of the ruthenium sulfate to the ethylene diamine tetraacetic acid is as follows: ethylene diamine tetraacetic acid =1: 2-5; the mass of the catalytic auxiliary agent is 10-16% of that of the acidic catalyst.
2. The method for continuously producing 2, 2-bis (tert-butylperoxy) butane according to claim 1, wherein the acidic catalyst is one or more of hydrochloric acid, sulfuric acid, phosphoric acid, perchloric acid, nitric acid, p-toluenesulfonic acid and sulfanilic acid.
3. The method of claim 2, 2-bis (t-butylperoxy) butane, wherein the acidic catalyst is sulfuric acid.
4. The method for continuously producing 2, 2-bis (tert-butylperoxy) butane according to claim 1, wherein the acidic catalyst comprises 45-95% solute by mass and the solvent is water.
5. The method for continuously producing 2, 2-bis (tert-butylperoxy) butane according to claim 4, wherein the acidic catalyst comprises 60-80% solute by mass and the solvent is water.
6. The method for continuously producing 2, 2-bis (tert-butylperoxy) butane according to claim 1, wherein the molar ratio of the solute in the acidic catalyst, the methyl ethyl ketone and the tert-butyl hydroperoxide in the reaction module is: methyl ethyl ketone: tert-butyl peroxide = 0.4-1.2: 1: 2.
7. The method for continuously producing 2, 2-bis (tert-butylperoxy) butane according to claim 1, wherein the pre-cooling temperature and the reaction temperature are 6 ℃ to 15 ℃.
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| US2537853A (en) * | 1947-03-28 | 1951-01-09 | Shell Dev | Process for the manufacture of organic peroxides |
| JPS49110617A (en) * | 1973-03-10 | 1974-10-22 | ||
| NL7707887A (en) * | 1977-07-15 | 1979-01-17 | Akzo Nv | NEW METHOXYACETONE DERIVED PERCETALS. |
| ES2162955T3 (en) * | 1995-02-28 | 2002-01-16 | Mitsui Chemicals Inc | PROCEDURE FOR THE PREPARATION OF ARILO-ALQUILO-HIDROPEROXIDOS. |
| JP2006083159A (en) * | 2004-08-19 | 2006-03-30 | Sumitomo Chemical Co Ltd | Method for oxidizing cycloalkane |
| WO2019034006A1 (en) * | 2017-08-12 | 2019-02-21 | 上海惠和化德生物科技有限公司 | Online fully continuous flow production process for directly preparing organic peroxide from alcohol or alkane |
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