CN112724105B - Piperazine derivatives, their preparation and use - Google Patents
Piperazine derivatives, their preparation and use Download PDFInfo
- Publication number
- CN112724105B CN112724105B CN202110359391.6A CN202110359391A CN112724105B CN 112724105 B CN112724105 B CN 112724105B CN 202110359391 A CN202110359391 A CN 202110359391A CN 112724105 B CN112724105 B CN 112724105B
- Authority
- CN
- China
- Prior art keywords
- formula
- substance
- ester
- piperazine derivative
- piperazine
- 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
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
- C07D295/14—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D295/145—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals with the ring nitrogen atoms and the carbon atoms with three bonds to hetero atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings
- C07D295/15—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals with the ring nitrogen atoms and the carbon atoms with three bonds to hetero atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings to an acyclic saturated chain
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a piperazine derivative, the structural general formula of which is
Description
Technical Field
The invention relates to a heterocyclic compound, in particular to a piperazine derivative, and a preparation method and application thereof.
Background
Piperazine is an important cyclic amine compound and can be prepared by taking hydroxyethyl ethylenediamine as a raw material through cyclization. Piperazine as an organic amine compound belongs to a hydrophilic substance and cannot be dissolved in an ester substance, and the piperazine and a compound synthesized by the piperazine have a saponification effect on a solvent for synthesizing esters, cannot be independently applied to an ester system, and severely limits the application range of the piperazine. How to increase the lipid phase solubility of piperazine and widen the application range of piperazine is not reported at present.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a piperazine derivative with good fat solubility.
The second technical problem to be solved by the present invention is to provide a method for preparing the piperazine derivative.
The third technical problem to be solved by the invention is to provide the application of the piperazine derivative as a reaction substrate of an oil-soluble compound in washing, daily chemical industry, lubrication and metal processing.
In order to achieve the purpose, the invention adopts the technical scheme that:
the first aspect of the present invention provides a piperazine derivative, wherein the structural general formula of the piperazine derivative is represented by formula (1):
wherein, R is1Is (CH)2）7、（CH2）10、（CH2）11Any one of (1), the R2Is CH3、CH3CH2、CH（CH3）2、CH3（CH2）3Any one of (1), the R3Is CH3（CH2）7、CH3（CH2）4、CH3（CH2）5Any one of the above.
The piperazine derivative has good intermiscibility with oil and fat substances, and the imino structure also provides a reaction site for chemically modifying downstream products, thereby greatly enlarging the application range of the piperazine derivative.
Preferably, the piperazine derivative comprises one or more of the following structural formulas:
the second aspect of the invention provides a preparation method of a piperazine derivative, which comprises the steps of carrying out epoxidation reaction on a substance with a structural general formula shown as a formula (2) to obtain an epoxy ester substance, then reacting the epoxy ester substance with hydroxyethyl ethylenediamine to obtain a hydroxyethyl ethylenediamine derivative, and then reacting the hydroxyethyl ethylenediamine derivative in the presence of modified diatomite to obtain the piperazine derivative.
Preferably, the general structural formula of the substance shown in the formula (2) is
R in the formula (2)1、R2、R3And R in the formula (1)1、R2、R3The same is true.
According to some specific and preferred embodiments, the epoxidation reaction comprises the steps of: reacting the substance shown in the formula (2) with hydrogen peroxide in the presence of formic acid and sulfuric acid.
Wherein the chemical reaction formula of the epoxidation reaction is as follows:
further preferably, the feeding mass ratio of the substance shown in the formula (2), the formic acid and the sulfuric acid is 100: (5-10): (0.2 to 0.8), further 100: (8-10): (0.5-0.8).
More preferably, the addition amount of the hydrogen peroxide is 10-15 times of the mass of the formic acid.
Preferably, the mass concentration of the hydrogen peroxide is 30-50%, further 35-45%, and further 40-45%.
According to some further specific and preferred embodiments, in the epoxidation reaction, the hydrogen peroxide is added in a dropwise manner, the dropwise addition time is controlled to be 1-2 hours, and the reaction is continued for 1-3 hours after the dropwise addition is completed.
According to some specific and preferred embodiments, the temperature of the epoxidation reaction is controlled to be 40 to 70 ℃, preferably 50 to 70 ℃, further preferably 60 to 70 ℃, and more preferably 65 to 70 ℃.
According to some specific and preferred embodiments, the epoxy ester species is reacted with the hydroxyethylethylenediamine in the presence of zinc oxide.
Wherein, the zinc oxide is used as a catalyst, and the chemical reaction formula of the reaction of the epoxy ester substance and the hydroxyethyl ethylene diamine is as follows:
further preferably, the pressure in the reaction process is controlled to be 0.1-0.6 MPa, and the temperature is controlled to be 110-130 ℃.
Further preferably, the reaction time is controlled to be 0.5-1.5 h.
Further preferably, the feeding mass ratio of the epoxy ester substances, the hydroxyethyl ethylenediamine and the zinc oxide is 100: (70-80): (0.5 to 1), further 100: (70-75): (0.5-0.8).
Preferably, the method for preparing the hydroxyethylethylene diamine derivative further comprises the step of obtaining the hydroxyethylethylene diamine derivative by reduced pressure distillation after the reaction is finished.
According to some specific and preferred embodiments, the epoxy value of the epoxy ester is 1 to 5%, preferably 2 to 3%.
Preferably, the substance represented by the formula (2) comprises one or more of methyl oleate, soybean oil methyl ester, rapeseed oil methyl ester, ethyl oleate, soybean oil ethyl ester, rapeseed oil ethyl ester, isopropyl oleate, soybean oil isopropyl ester, rapeseed oil isopropyl ester, butyl oleate, soybean oil butyl ester and rapeseed oil butyl ester.
The raw materials of the methyl oleate, the soybean oil methyl ester, the rapeseed oil methyl ester and the like are derived from natural vegetable oil, and the hydroxyethyl ethylenediamine derivative synthesized by using the methyl oleate, the soybean oil methyl ester, the rapeseed oil methyl ester and the like as reactants and hydroxyethyl ethylenediamine has good fat solubility, is easy to degrade, has low toxicity, and is green and environment-friendly.
Preferably, the feeding mass ratio of the hydroxyethyl ethylenediamine derivative to the modified diatomite is controlled to be 100: (0.5 to 1).
Preferably, the reaction temperature of the hydroxyethyl ethylenediamine derivative for preparing the piperazine derivative in the presence of the modified diatomite is controlled to be 120-160 ℃, further 130-150 ℃, and further 140-145 ℃.
Preferably, the reaction pressure for preparing the piperazine derivative by using the hydroxyethyl ethylenediamine derivative in the presence of the modified diatomite is controlled to be 0.01 to 0.1MPa, further 0.02 to 0.07MPa, and further 0.03 to 0.05 MPa.
Preferably, the reaction time of the hydroxyethyl ethylene diamine derivative for preparing the piperazine derivative in the presence of the modified diatomite is controlled to be 2-4 h. Wherein, the modified diatomite is used as a catalyst, and the chemical reaction formula for synthesizing the piperazine derivative is as follows:
according to some specific and preferred embodiments, the mass content of the zinc element in the modified diatomite is 5% to 15%, preferably 5% to 10%, and further preferably 5% to 8%.
Preferably, the mass content of the copper element in the modified diatomite is 1% -9%, further 3% -7%, and further 5% -6%.
Preferably, the mass content of the nickel element in the modified diatomite is 1% -5%, and further 2% -3%.
Wherein, the zinc element, the copper element and the nickel element in the modified diatomite exist in the form of oxides.
According to some specific and preferred embodiments, the method for preparing the modified diatomaceous earth comprises: and soaking zinc nitrate, copper nitrate and nickel nitrate solution into diatomite and roasting to obtain the modified diatomite. Or, the modified diatomite is commercially available modified diatomite with zinc element, copper element and nickel element meeting the requirements of the application.
In a third aspect of the present invention, there is provided use of a piperazine derivative and/or a piperazine derivative prepared by the above-mentioned preparation method as a reaction substrate for an oil-soluble compound in washing, daily chemicals, lubrication, and metal working.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
1) the invention takes natural oil ester and derivatives thereof as reaction raw materials to construct active epoxy groups, and utilizes the high-activity amino group of the hydroxyethyl ethylenediamine to synthesize the hydroxyethyl ethylenediamine derivative with imino structure of alkyl ester side chain.
2) The piperazine derivative is polymerized by the hydroxyethyl ethylenediamine derivative to synthesize the piperazine derivative with the alkyl ester group, and the piperazine derivative has good compatibility with oil ester substances, thereby greatly expanding the application of the piperazine structure.
Drawings
FIG. 1 is a hydrogen spectrum of a piperazine derivative in example 1;
fig. 2 is a nuclear magnetic carbon spectrum of the piperazine derivative in example 1.
Detailed Description
The present invention will be further described with reference to the following examples. However, the present invention is not limited to the following examples. The implementation conditions adopted in the embodiments can be further adjusted according to different requirements of specific use, and the implementation conditions not mentioned are conventional conditions in the industry. The technical features of the embodiments of the present invention may be combined with each other as long as they do not conflict with each other.
In the present invention, "wt%" means a mass percentage content, normal pressure is 1 atmosphere, room temperature means 15 to 25 ℃, and "plural" means 2 or more, unless otherwise specified.
Example 1
1. Mixing methyl oleate, formic acid and sulfuric acid according to a mass ratio of 100: 8: 0.5, adding into a reaction kettle, stirring uniformly, heating to 70 ℃, adding 40wt% hydrogen peroxide which is 10 times of the mass of formic acid at a constant speed, dropwise adding within 1-2 h, continuing to react for 3h, and distilling to obtain epoxy methyl oleate with the epoxy value of 2%.
2. Epoxy methyl oleate, hydroxyethyl ethylenediamine and zinc oxide are mixed according to the mass ratio of 100: 75: 0.8, putting the mixture into a pressure reaction kettle, heating the mixture to 120 ℃, reacting the mixture at a constant temperature for 1 hour, pouring the mixture into a distillation flask after the pressure is zero, and distilling the mixture at the negative pressure of 0.4-0.5MPa and the temperature of 210 ℃ and 230 ℃ to obtain a fraction, namely the hydroxyethyl ethylenediamine derivative.
3. Mixing hydroxyethyl ethylenediamine derivative and modified diatomite (the modified diatomite contains 5wt% of zinc, 5wt% of copper and 2wt% of nickel) according to a mass ratio of 100: 0.5, adding the mixture into a reaction kettle, heating the mixture to 140 ℃, keeping the pressure at 0.05MPa, reacting for 2 to 4 hours, and filtering the mixture while the mixture is hot to obtain the piperazine derivative (product 1), wherein the structural formula of a main product in the product is shown in the specification
The related spectrogram is shown in figures 1 and 2.
Example 2
1. Mixing methyl oleate, formic acid and sulfuric acid according to a mass ratio of 100: 10: 0.8, adding into a reaction kettle, uniformly stirring, heating to 65 ℃, adding 40wt% hydrogen peroxide which is 15 times of formic acid in mass at a constant speed, dropwise adding within 1-2 h, continuing to react for 3h, and distilling to obtain epoxy methyl oleate with the epoxy value of 2.3%.
2. Epoxy methyl oleate, hydroxyethyl ethylenediamine and zinc oxide are mixed according to the mass ratio of 100: 70: 0.5, putting the mixture into a pressure reaction kettle, heating the mixture to 120 ℃, reacting the mixture at a constant temperature for 1.5h, pouring the mixture into a distillation flask after the pressure is zero, and distilling the mixture at the negative pressure of 0.4-0.5MPa and the temperature of 210 ℃ and 230 ℃ to obtain the fraction, namely the hydroxyethyl ethylenediamine derivative.
3. Mixing hydroxyethyl ethylenediamine derivative and modified diatomite (the modified diatomite contains 8wt% of zinc, 5wt% of copper and 3wt% of nickel) according to a mass ratio of 100: 0.8, adding the mixture into a reaction kettle, heating the mixture to 140 ℃, reacting for 2 to 4 hours under the pressure of 0.05MPa, and filtering the mixture while the mixture is hot to obtain the piperazine derivative (product 2). The main product in the product has the structural formula
。
Comparative example 1
1. Mixing methyl oleate and hydroxyethyl ethylenediamine according to a mass ratio of 100: 75, putting the mixture into a normal-pressure reaction kettle, heating the mixture to 120 ℃, reacting the mixture for 1 hour at a constant temperature, and cooling the reactant to room temperature to obtain a reactant 1;
2. mixing the reactant 1 and modified diatomite (the modified diatomite contains 8wt% of zinc, 5wt% of copper and 3wt% of nickel) according to a mass ratio of 100: 0.8, adding the mixture into a reaction kettle, heating to 140 ℃, reacting for 2 to 4 hours under the pressure of 0.05MPa, and filtering while the mixture is hot to obtain a product 3.
Comparative example 2
1. Epoxy methyl oleate and hydroxyethyl ethylene diamine are mixed according to the mass ratio of 100: putting 75 parts of the mixture into a normal-pressure reaction kettle, heating to 120 ℃, reacting for 1 hour at constant temperature, and cooling the reactant to room temperature to obtain a reactant 2;
2. mixing the reactant 2 and modified diatomite (the modified diatomite contains 8wt% of zinc, 5wt% of copper and 3wt% of nickel) according to the mass ratio of 100: 0.8, adding the mixture into a reaction kettle, heating to 140 ℃, reacting for 2 to 4 hours under the pressure of 0.05MPa, and filtering while the mixture is hot to obtain a product 4.
The appearance of the products obtained in each example and comparative example at room temperature was observed, and each product was added to water, methyl oleate, and white oil, respectively, to prepare systems having product concentrations of 10wt%, respectively, to compare the solubility properties of each product in each solvent, and the appearance and solubility properties of each product at room temperature are shown in table 1.
The present invention has been described in detail in order to enable those skilled in the art to understand the invention and to practice it, and it is not intended to limit the scope of the invention, and all equivalent changes and modifications made according to the spirit of the present invention should be covered by the present invention.
Claims (8)
1. Preparation of piperazine derivativeThe preparation method is characterized by comprising the following steps: carrying out epoxidation reaction on a substance with a structural general formula shown in a formula (2) to obtain an epoxy ester substance, then reacting the epoxy ester substance with hydroxyethyl ethylenediamine to obtain a hydroxyethyl ethylenediamine derivative, reacting the hydroxyethyl ethylenediamine derivative in the presence of modified diatomite to obtain a piperazine derivative, and controlling the reaction pressure of the epoxy ester substance and the hydroxyethyl ethylenediamine to be 0.1-0.6 MPa; wherein the general structural formula of the substance shown in the formula (2) is
The general structural formula of the epoxy ester substance is
The structural general formula of the hydroxyethyl ethylenediamine derivative is
The structural general formula of the piperazine derivative is shown as the formula (1):
wherein R in the formula (1), the formula (2), the epoxy ester substance and the hydroxyethyl ethylene diamine1Is (CH)2）7、（CH2）10、（CH2）11Any one of (1), R2Is CH3、CH3CH2、CH（CH3）2、CH3（CH2）3Any one of (1), R3Is CH3（CH2）7、CH3（CH2）4、CH3（CH2）5Any one of the above modified diatomaceous earth contains zinc, copper and nickel.
2. The process for producing a piperazine derivative according to claim 1, wherein: the piperazine derivative comprises one or more of the following substances shown in the structural formula:
3. the process for producing a piperazine derivative according to claim 1, wherein: the epoxidation reaction comprises the following steps: reacting the substance shown in the formula (2) with hydrogen peroxide in the presence of formic acid and sulfuric acid; wherein the feeding mass ratio of the substance shown in the formula (2), the formic acid and the sulfuric acid is 100: (5-10): (0.2-0.8); the adding mass of the hydrogen peroxide is 10-15 times of that of the formic acid, and the mass concentration of the hydrogen peroxide is 30-50%; and controlling the temperature of the epoxidation reaction to be 40-70 ℃.
4. The process for producing a piperazine derivative according to claim 1, wherein: the epoxy ester substance and the hydroxyethyl ethylene diamine react in the presence of zinc oxide, and the temperature is controlled to be 110-130 ℃ in the reaction process.
5. The process for producing a piperazine derivative according to claim 4, wherein: the feeding mass ratio of the epoxy ester substance, the hydroxyethyl ethylenediamine and the zinc oxide is 100: (70-80): (0.5 to 1).
6. The process for producing a piperazine derivative according to claim 1, wherein: controlling the feeding mass ratio of the hydroxyethyl ethylenediamine derivative to the modified diatomite to be 100: (0.5-1), controlling the reaction temperature to be 120-160 ℃, the reaction pressure to be 0.01-0.1 MPa, and the reaction time to be 2-4 h.
7. The process for producing a piperazine derivative according to claim 1, wherein: the substance shown in the formula (2) comprises one or more of methyl oleate, soybean oil methyl ester, rapeseed oil methyl ester, ethyl oleate, soybean oil ethyl ester, rapeseed oil ethyl ester, isopropyl oleate, soybean oil isopropyl ester, rapeseed oil isopropyl ester, butyl oleate, soybean oil butyl ester and rapeseed oil butyl ester.
8. The process for producing a piperazine derivative according to claim 1, wherein: the modified diatomite comprises 5-15% by mass of zinc element, 1-9% by mass of copper element and 1-5% by mass of nickel element.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110359391.6A CN112724105B (en) | 2021-04-02 | 2021-04-02 | Piperazine derivatives, their preparation and use |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110359391.6A CN112724105B (en) | 2021-04-02 | 2021-04-02 | Piperazine derivatives, their preparation and use |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112724105A CN112724105A (en) | 2021-04-30 |
| CN112724105B true CN112724105B (en) | 2021-08-06 |
Family
ID=75596415
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110359391.6A Active CN112724105B (en) | 2021-04-02 | 2021-04-02 | Piperazine derivatives, their preparation and use |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112724105B (en) |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3843667A (en) * | 1973-09-12 | 1974-10-22 | M Cupery | N-imidazole compounds and their complex metal derivatives |
| CN1413991A (en) * | 2002-10-09 | 2003-04-30 | 天津大学 | Method of fixed bed continuous synthetising piperazine series compound |
| CN1634896A (en) * | 2003-12-30 | 2005-07-06 | 天津大学 | Method for continuous synthesis of piperazine compounds by fixed bed |
| ES2547220T3 (en) * | 2004-04-20 | 2015-10-02 | Dendritic Nanotechnologies, Inc. | Dendritic polymers with enhanced amplification and interior functionality |
| CN100334078C (en) * | 2005-03-22 | 2007-08-29 | 建德市新化化工有限责任公司 | Method for synthesizing piperazine |
| CN109438675B (en) * | 2018-10-15 | 2021-06-15 | 广州市白云化工实业有限公司 | Modified epoxy resin curing agent and preparation method thereof |
| CN111321027B (en) * | 2020-04-01 | 2023-07-14 | 苏州丰倍生物科技股份有限公司 | Environment-friendly lubricant for water-soluble metal working fluid and synthetic method thereof |
-
2021
- 2021-04-02 CN CN202110359391.6A patent/CN112724105B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN112724105A (en) | 2021-04-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI331612B (en) | Method for preparation of spherical support for olefin polymerization catalyst | |
| EP3347339B1 (en) | Ether amine compounds and use thereof as flotation collector | |
| CN111995497B (en) | Preparation method of allyl alcohol | |
| CN110818733B (en) | Method for preparing boric acid ester by using disilylamine rare earth complex to catalyze hydroboration reaction of imine and borane | |
| CN112724105B (en) | Piperazine derivatives, their preparation and use | |
| CN112300212A (en) | Use of borane-pyridine complexes for the preparation of NK-1 receptor antagonists | |
| CN109364952B (en) | Catalyst for synthesizing imine from aromatic nitro compound and benzaldehyde or furfural and derivatives thereof, preparation method and application | |
| CN112300029B (en) | Preparation method of 3-hydroxypropionitrile | |
| JP2011506383A5 (en) | ||
| CN113387822B (en) | Method for synthesizing polyoxyethylene ether alkylamine cationic surfactant | |
| CN112794805A (en) | Alkyl ester base salt derivative, preparation method and application thereof | |
| CN106111203A (en) | The application in catalysis aldehyde and borine hydroboration of two (beta diimine base) ytterbium | |
| CN107999073B (en) | Preparation method of formaldehyde ethynylation reaction catalyst | |
| CN112552345A (en) | Preparation method of NK-1 receptor antagonist | |
| CN112480172A (en) | Use of borane-pyridine complexes for the preparation of pharmaceutical compounds | |
| CN113461557B (en) | Hydroxyethyl ethylenediamine derivative, fatty acid ester derivative and preparation method of hydroxyethyl ethylenediamine derivative and fatty acid ester derivative | |
| CN112521421A (en) | Preparation method of pharmaceutical compound | |
| JPH04234367A (en) | Process for producing 1-hydroxymethylpyrazoles | |
| CN110354902B (en) | Process for preparing phosphine guanidine compound | |
| CN110292948B (en) | Application of imines-functionalized imidazole chloride salt as catalyst in preparation of aromatic heterocyclic formate compounds | |
| KR102399171B1 (en) | Copper catalyst compound, method for producing same, and method for producing triazole compound using the same | |
| KR102702951B1 (en) | Asymmetric amidine compound and method for preparing the same | |
| CN108586365A (en) | A kind of preparation method of high-purity 4- methyl benzotriazazoles | |
| CN115894374A (en) | Preparation method and application of fluorocarbonitrile | |
| CN109517157B (en) | Special catalyst for synthesizing high molecular weight polyoxyethylene and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP03 | Change of name, title or address | ||
| CP03 | Change of name, title or address |
Address after: 215000 No. 1, Donghai Road, Jiangsu Yangtze River International Chemical Industry Park, Zhangjiagang City, Suzhou City, Jiangsu Province (Fengbei biological) Patentee after: Suzhou Fengbei Biotechnology Co.,Ltd. Address before: 215600 room 346b, building a, emerging industry development center, Zhangjiagang Free Trade Zone, Suzhou City, Jiangsu Province (Fengbei Biology) Patentee before: SUZHOU FENGBEI BIOTECH Co.,Ltd. |