CN105056842A - Reaction apparatus and application thereof in synthesizing borate - Google Patents
Reaction apparatus and application thereof in synthesizing borate Download PDFInfo
- Publication number
- CN105056842A CN105056842A CN201510438222.6A CN201510438222A CN105056842A CN 105056842 A CN105056842 A CN 105056842A CN 201510438222 A CN201510438222 A CN 201510438222A CN 105056842 A CN105056842 A CN 105056842A
- Authority
- CN
- China
- Prior art keywords
- reactor
- preheater
- reaction
- heating plate
- valve
- 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.)
- Granted
Links
Abstract
A reaction apparatus and application thereof in synthesizing borate relate to a reaction apparatus. The reaction apparatus is provided with a preheater, a reactor, a product tank, a condenser, a byproduct tank and a vacuum system, wherein the outlet of the preheater is connected with the inlet of the reactor through a first valve; the first outlet of the reactor is connected with the product tank through a second valve; the second outlet of the reactor is connected with the inlet of the condenser; and the outlet of the condenser is connected with the byproduct tank; the preheater is connected with the vacuum system through a third valve, and the byproduct tank is connected with the vacuum system through a fourth valve. The method applying the reaction apparatus to synthesize borate comprises: reaction raw materials are firstly preheated in the preheater; and the raw materials in the preheater are continuously conveyed to the reactor by way of a liquid pump, a pressure difference or a potential difference, a feed liquid is dispersed on a heating plate in the reactor through a reaction liquid distributor to form a liquid thin film, a reaction byproduct is continuously output at the tail end outlet of the reactor and is collected in the product tank, and the byproduct is extracted from the top of the reactor and enters into the byproduct tank.
Description
Technical field
The present invention relates to reaction unit, especially relate to a kind of reaction unit and the application in synthesis borate thereof.
Background technology
Borate type braking fluid has excellent high temperature performance, is " water non-sensitive type " brake fluid, has become the high-performing car brake fluid competitively developed our times various countries.Borate is the of paramount importance component of boric acid ester automobile braking fluid, and the minor amount of water that it can be caught in system makes it stablize with associated forms, thus ensures that high-temperature behavior is unaffected.Industrial production borate generally adopts boric acid and alcohol ether esterification to generate, and it is a reversible reaction that acid esterification generates borate, in order to promote that the forward reacted carries out, needs in time byproduct of reaction water to be shifted out reaction system.
Patent CN101735254B as the esterification of the inorganic boric acid of catalysts and solvents catalysis and alcohol, obtains borate using acidity from liquid.Patent CN102796600A is with high polyalcohol ether, boric acid, propane diols for raw material, and two sections of esterification process have synthesized a kind of hexatomic ring borate of low-viscosity, improve dry equilibrium boiling point and the hydrolytic stability of brake fluid.Need nitrogen protection, toluene band water, esterification time is 2-4h.The problems such as these methods all use solvent, there is cost high, and later separation step is complicated, industrial applications is more difficult.
Patent CN102031179B proposes a kind of method preparing borate in non-isothermal transformation dynamic response technique, the method utilizes non-isothermal transformation dynamic response condition that in boric acid three boron oxygen keys are progressively combined with many glycol ethers of different molecular weight, synthesizes the borate with three different ester group groups.Boric acid and the alcohol ether passed into continuously are carried out esterification by patent CN103333188A, vacuumize, and obtain distillate and the borate of separation.Water is separated with alcohol ether by distillation by distillate.Ethylene glycol mono-ether, ethylene glycol or polyethylene glycol, boric acid, diluent, pH adjusting agent and corrosion inhibiter drop in reactor by patent CN102618354B in proportion, open vavuum pump and heater, respectively 1h is incubated at 60-100 DEG C and 140-160 DEG C of temperature section, pump reaction of moisture to terminate, obtain faint yellow borate.These patents are all in batch still, first carry out the reaction of a period of time at a lower temperature, then from reaction system, extract water byproduct out under high temperature high vacuum condition.The method pumps in the process of water byproduct and some lower boiling alcohol ether materials can be caused to be drawn out of reaction system together under high temperature high vacuum condition, seriously reduce the yield of reaction, and to obtain the higher borate product of dry wet boiling point, product also needs to purify through rectifying column, have that energy consumption is high, reaction time length, the shortcoming such as product jaundice, seriously constrain the development of borate-type basal liquid and high-performance brake fluid.
Summary of the invention
The object of the present invention is to provide and can realize esterification rapidly, continuously, and obtain stable prod, augmenting response and dehydration area, a kind of reaction unit that realization response is carried out with point water simultaneously.
Another object of the present invention is to provide the application of described reaction unit in synthesis borate.
Described reaction unit is provided with preheater, reactor, products pot, condenser, byproduct tank, vacuum system: preheater outlet connects reactor inlet by the first valve, reactor first exports and connects products pot by the second valve, reactor second outlet connects condenser inlet, and condensator outlet connects byproduct tank; Preheater connects vacuum system by the 3rd valve, and byproduct tank connects vacuum system by the 4th valve.
Described preheater can adopt still preheater.
Being provided with in described reactor can the heating plate of temperature control, and heating plate connects vacuum system, forms vacuum.And heating plate can variable inclinations as required, thus change the flowing (comprising as the time of staying, reactant liquor film thickness) of reaction liquid material above heating plate.
Described heating plate can be provided with fin, groove etc., be uniformly distributed on hot plate for reactant liquor; Described heating plate can adopt electric boiling plate or reaction bed, and described reaction bed tiles solid catalyst.
The method applying described reaction unit synthesis borate comprises the following steps:
1) reaction raw materials first carries out preheating in preheater;
2) preheater Raw is delivered continuously to inside reactor in modes such as liquor pump, pressure differential or potential differences, feed liquid is scatter by reaction liquid distributor and forms one deck fluid film on the heating plate of inside reactor, product is collected in products pot in the continuous output of reactor end outlet, accessory substance is then extracted out from reactor head, enters byproduct tank.
In step 1) in, described reaction raw materials is boric acid and all kinds of alcohol ether or alcohol-ether mixture, wherein alcohol ether can be selected from many gylcol ethers or polyalcohols ethers etc., described many gylcol ethers can be selected from the one in triethylene glycol methyl ether, triethylene glycol butyl ether etc., the optional one in polyethylene glycol, methoxypolyethylene glycol etc. of described polyalcohols ethers; The mol ratio of alcohol ether and boric acid can be (2 ~ 5): 1; Described preheater can be normal pressure or vacuum state, and the temperature of described preheating can be 50 ~ 150 DEG C.
In step 2) in, described heating plate can be provided with fin, groove etc., be uniformly distributed on hot plate for reactant liquor; Described heating plate can adopt electric boiling plate or reaction bed, and described reaction bed tiles solid catalyst; The temperature of heating plate can be 140 ~ 250 DEG C; The vacuum of described reactor can be 0.08 ~ 0.1MPa.
In order to realize esterification rapidly, continuously, and obtain stable prod.The present invention proposes the method for a kind of continuous reaction device synthesis borate: liquid reactions material enters into tubular reactor after preheating, form one deck fluid film in the reactor, increase reaction and dehydration area, the continuous esterification that realization response is carried out with point water simultaneously.
Utilize this reaction unit, serialization carries out quick esterification and the new technique for synthesizing of point water.Also be, allow raw material first through preheating, again by the high-temperature heating plate in reactor, raw material disperses on hot plate and forms one deck reaction liquid film, thus improve reactant liquor degree of being heated evenly and augmenting response liquid disengagement area, the water byproduct that esterification is produced can easilier be separated from reaction system, and then realizes quick esterification and continuous prodution.
The present invention utilizes reaction unit to carry out the method for esterification, dehydration.Described reaction unit is furnished with controllable temperature heating plate, and heating plate is provided with the reaction liquid such as fin, groove distributor and can has catalyst, thus reactant liquor thermally equivalent is reacted, and augmenting response area greatly.The cavity of the certain space size above reaction liquid level can vacuumize, and makes the moisture content be evaporated in reactant liquor etc. realize removing fast because disengagement area is large.More than design ensure that carrying out fast of esterification, and can realize the continuous prodution from being fed to discharging.The invention solves the lactate synthesis process reaction process of batch reactor that tradition adopts and rely on the shortcomings such as strong stirring, energy consumption is high, reaction time is long, inequality of being heated causes poor product quality, Lipase absobed technique has significant advantage and application prospect.
Maximum feature of the present invention makes reaction mass form one deck liquid film in the reactor to react; increase response area; make that accessory substance is easier to be separated from reaction system; improve reaction conversion ratio; improve reaction efficiency; decrease product at high temperature time of contact, provide product quality, and can the serialization of implementation procedure, scale.
Accompanying drawing explanation
Fig. 1 is the structure composition schematic diagram of reaction unit of the present invention.
In FIG, be respectively labeled as: E-1 reactor (dash area is heating plate); E-2 still preheater; E-3 products pot; E-4 byproduct tank; E-5 condenser; P1 pressure display table; T1 first temperature controls and display list, T2 second temperature control and display list; V-1 first valve, V-2 second valve, V-3 the 3rd valve, V-4 the 4th valve, A vacuum system.
Detailed description of the invention
Below in conjunction with embodiment, the invention will be further described, but the present invention protects content to be not limited only to this.
See Fig. 1, described reaction unit embodiment is provided with still preheater E-2, reactor E-1, products pot E-3, condenser E-5, byproduct tank E-4, vacuum system A: still preheater E-2 outlet connects reactor E-1 entrance by the first valve V-1, reactor E-1 first exports and meets products pot E-3 by the second valve V-2, reactor E-1 second outlet connects condenser E-5 entrance, and condenser E-5 outlet meets byproduct tank E-4; Still preheater E-2 meets vacuum system A by the 3rd valve V-3, and byproduct tank E-4 meets vacuum system A by the 4th valve V-4.
Being provided with in described reactor can the heating plate of temperature control, and heating plate connects vacuum system, forms vacuum.And heating plate can variable inclinations as required, thus change the flowing (comprising as the time of staying, reactant liquor film thickness) of reaction liquid material above heating plate.
Described heating plate can be provided with fin, groove etc., be uniformly distributed on hot plate for reactant liquor; Described heating plate can adopt electric boiling plate or reaction bed, and described reaction bed tiles solid catalyst.
Below provide the embodiment of the method for application described reaction unit synthesis borate:
Embodiment 1
Medicine: triethylene glycol methyl ether (Jiangsu Tianyin chemical Co., Ltd, technical grade), boric acid (Guangzhou Sui Xin Chemical Co., Ltd., purity >=99.0%).
Preparation work: by 9.7g boric acid and the mixing of 90.3g triethylene glycol methyl ether, 80 DEG C of constant temperature stir 30min in still preheater.
The first step keeps tubular reaction vessel vacuum to be 0.098MPa, and in tubular reaction vessel, temperature of heating plate is 160 DEG C, by liquor pump, reaction mass is got to (feed rate is about 10mL/min) in reactor from still preheater.
Second step, by observing liquid film state in tubular reaction vessel, carries out continuous blowing.
The index that reacted product detects is as follows: dry boiling point: 283 DEG C, wet boiling point: 205 DEG C ,-40 DEG C of kinematic viscosity: 1249mm
2/ s.
Embodiment 2
Medicine: triethylene glycol methyl ether (Jiangsu Tianyin chemical Co., Ltd, technical grade), boric acid (Guangzhou Sui Xin Chemical Co., Ltd., purity >=99.0%).
The present embodiment adopts the step the same with embodiment 1, unlike: in the first step, in tubular reaction vessel, temperature of heating plate is 180 DEG C.
The index that reacted product detects is as follows: dry boiling point: 289 DEG C, wet boiling point: 208 DEG C ,-40 DEG C of kinematic viscosity: 1257mm
2/ s.
Embodiment 3
Medicine: triethylene glycol methyl ether (Jiangsu Tianyin chemical Co., Ltd, technical grade), boric acid (Guangzhou Sui Xin Chemical Co., Ltd., purity >=99.0%).
The present embodiment adopts the step the same with embodiment 1, and unlike: preparation work still preheater is 60 DEG C.
The index that reacted product detects is as follows: dry boiling point: 271 DEG C, wet boiling point: 199 DEG C ,-40 DEG C of kinematic viscosity: 1196mm
2/ s.
Embodiment 4
Medicine: triethylene glycol methyl ether (Jiangsu Tianyin chemical Co., Ltd, technical grade), boric acid (Guangzhou Sui Xin Chemical Co., Ltd., purity >=99.0%).
The present embodiment adopts the step the same with embodiment 1, unlike: the feed rate in the first step is 18mL/min, and temperature of heating plate is 200 DEG C.
The index that reacted product detects is as follows: dry boiling point: 279 DEG C, wet boiling point: 203 DEG C ,-40 DEG C of kinematic viscosity: 1233mm
2/ s.
Embodiment 5
Medicine: triethylene glycol methyl ether (Jiangsu Tianyin chemical Co., Ltd, technical grade), boric acid (Guangzhou Sui Xin Chemical Co., Ltd., purity >=99.0%).
The present embodiment adopts the step the same with embodiment 1, unlike: in the first step, the vacuum of tubular reaction vessel is 0.096MPa.
The index that reacted product detects is as follows: dry boiling point: 280 DEG C, wet boiling point: 203 DEG C ,-40 DEG C of kinematic viscosity: 1235mm
2/ s.
Embodiment 6
Medicine: triethylene glycol butyl ether (Jiangsu Tianyin chemical Co., Ltd, technical grade), boric acid (Guangzhou Sui Xin Chemical Co., Ltd., purity >=99.0%).
The present embodiment adopts the step the same with embodiment 1, unlike: the raw material reacted in preparation work is triethylene glycol butyl ether, and addition is 113g.
The index that reacted product detects is as follows: dry boiling point: 290 DEG C, wet boiling point: 201 DEG C ,-40 DEG C of kinematic viscosity: 1280mm
2/ s.
Embodiment 7
Medicine: polyethylene glycol (Jiangsu Tianyin chemical Co., Ltd, technical grade), boric acid (Guangzhou Sui Xin Chemical Co., Ltd., purity >=99.0%).
The present embodiment adopts the step the same with embodiment 1, unlike: the raw material reacted in preparation work is polyethylene glycol, and addition is 120g.
The index that reacted product detects is as follows: dry boiling point: 310 DEG C, wet boiling point: 209 DEG C ,-40 DEG C of kinematic viscosity: 1410mm
2/ s.
Claims (10)
1. a reaction unit, it is characterized in that being provided with preheater, reactor, products pot, condenser, byproduct tank, vacuum system: preheater outlet connects reactor inlet by the first valve, reactor first exports and connects products pot by the second valve, reactor second outlet connects condenser inlet, and condensator outlet connects byproduct tank; Preheater connects vacuum system by the 3rd valve, and byproduct tank connects vacuum system by the 4th valve.
2. a kind of reaction unit as claimed in claim 1, is characterized in that described preheater adopts still preheater.
3. a kind of reaction unit as claimed in claim 1, it is characterized in that being provided with in described reactor can the heating plate of temperature control, and heating plate connects vacuum system, forms vacuum.
4. a kind of reaction unit as claimed in claim 3, is characterized in that described heating plate is provided with fin, groove.
5. a kind of reaction unit as described in claim 3 or 4, it is characterized in that described heating plate adopts electric boiling plate or reaction bed, described reaction bed tiles solid catalyst.
6. application such as described reaction unit arbitrary in Claims 1 to 5 synthesizes the method for borate, it is characterized in that comprising the following steps:
1) reaction raw materials first carries out preheating in preheater;
2) preheater Raw is delivered continuously to inside reactor in modes such as liquor pump, pressure differential or potential differences, feed liquid is scatter by reaction liquid distributor and forms one deck fluid film on the heating plate of inside reactor, product is collected in products pot in the continuous output of reactor end outlet, accessory substance is then extracted out from reactor head, enters byproduct tank.
7. method as claimed in claim 6, it is characterized in that in step 1) in, described reaction raw materials is boric acid and all kinds of alcohol ether or alcohol-ether mixture, wherein alcohol ether is selected from many gylcol ethers or polyalcohols ethers, described many gylcol ethers are selected from the one in triethylene glycol methyl ether, triethylene glycol butyl ether, and described polyalcohols ethers is selected from the one in polyethylene glycol, methoxypolyethylene glycol.
8. method as claimed in claim 7, is characterized in that the mol ratio of alcohol ether and boric acid is for (2 ~ 5): 1.
9. method as claimed in claim 6, it is characterized in that described preheater is normal pressure or vacuum state, the temperature of described preheating can be 50 ~ 150 DEG C.
10. method as claimed in claim 6, is characterized in that in step 2) in, the temperature of described heating plate is 140 ~ 250 DEG C; The vacuum of described reactor can be 0.08 ~ 0.1MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510438222.6A CN105056842B (en) | 2015-07-23 | 2015-07-23 | A kind of reaction unit and its application in borate is synthesized |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510438222.6A CN105056842B (en) | 2015-07-23 | 2015-07-23 | A kind of reaction unit and its application in borate is synthesized |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105056842A true CN105056842A (en) | 2015-11-18 |
| CN105056842B CN105056842B (en) | 2017-12-15 |
Family
ID=54486481
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510438222.6A Active CN105056842B (en) | 2015-07-23 | 2015-07-23 | A kind of reaction unit and its application in borate is synthesized |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105056842B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111558358A (en) * | 2020-04-07 | 2020-08-21 | 宜昌苏鹏科技有限公司 | Thin film reactor and process for continuous production of alkyl anthraquinone by using same |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1048542A (en) * | 1989-07-03 | 1991-01-16 | 天津石油化工公司化工厂 | A kind of production method of dimethyl terephthalate (DMT) |
| CN1764682A (en) * | 2003-03-31 | 2006-04-26 | 大赛璐化学工业株式会社 | Lactone polyester polyols and process for production thereof |
| CN101265184A (en) * | 2007-03-12 | 2008-09-17 | 中国石油天然气股份有限公司 | Process for preparing dibasic acid ester |
| CN101318969A (en) * | 2007-06-07 | 2008-12-10 | 南通鸿志化工有限公司 | Distillation method for preparing high-purity trimethyl borate |
| CN101575347A (en) * | 2009-06-16 | 2009-11-11 | 江苏龙蟠石化有限公司 | Method for preparing bridge borate lubricating agent |
| CN102618354A (en) * | 2012-03-08 | 2012-08-01 | 中国船舶重工集团公司第七一八研究所 | Method for preparing borate synthetic brake fluid |
| US20130066115A1 (en) * | 2011-09-14 | 2013-03-14 | Dow Agrosciences Llc | Methods and systems for forming boronic acids and intermediates thereof |
| CN103073728A (en) * | 2012-04-01 | 2013-05-01 | 张曦 | Boron-containing polyester, and synthesizing method and applications thereof |
| CN103333188A (en) * | 2013-07-25 | 2013-10-02 | 中国石油化工股份有限公司 | Boric acid ester production method |
| CN203768336U (en) * | 2014-04-09 | 2014-08-13 | 南京华阜尚研能源科技有限公司 | Efficient esterification and interesterification reaction device |
-
2015
- 2015-07-23 CN CN201510438222.6A patent/CN105056842B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1048542A (en) * | 1989-07-03 | 1991-01-16 | 天津石油化工公司化工厂 | A kind of production method of dimethyl terephthalate (DMT) |
| CN1764682A (en) * | 2003-03-31 | 2006-04-26 | 大赛璐化学工业株式会社 | Lactone polyester polyols and process for production thereof |
| CN101265184A (en) * | 2007-03-12 | 2008-09-17 | 中国石油天然气股份有限公司 | Process for preparing dibasic acid ester |
| CN101318969A (en) * | 2007-06-07 | 2008-12-10 | 南通鸿志化工有限公司 | Distillation method for preparing high-purity trimethyl borate |
| CN101575347A (en) * | 2009-06-16 | 2009-11-11 | 江苏龙蟠石化有限公司 | Method for preparing bridge borate lubricating agent |
| US20130066115A1 (en) * | 2011-09-14 | 2013-03-14 | Dow Agrosciences Llc | Methods and systems for forming boronic acids and intermediates thereof |
| CN102618354A (en) * | 2012-03-08 | 2012-08-01 | 中国船舶重工集团公司第七一八研究所 | Method for preparing borate synthetic brake fluid |
| CN103073728A (en) * | 2012-04-01 | 2013-05-01 | 张曦 | Boron-containing polyester, and synthesizing method and applications thereof |
| CN103333188A (en) * | 2013-07-25 | 2013-10-02 | 中国石油化工股份有限公司 | Boric acid ester production method |
| CN203768336U (en) * | 2014-04-09 | 2014-08-13 | 南京华阜尚研能源科技有限公司 | Efficient esterification and interesterification reaction device |
Non-Patent Citations (1)
| Title |
|---|
| 刘峰等: "制动液用环状硼酸酯的研制", 《石油化工高等学校学报》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111558358A (en) * | 2020-04-07 | 2020-08-21 | 宜昌苏鹏科技有限公司 | Thin film reactor and process for continuous production of alkyl anthraquinone by using same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105056842B (en) | 2017-12-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104262174B (en) | A kind of preparation method of high-performance grinding aid monomer diisopropanol monoethanolamine | |
| CN102964245A (en) | Preparation method of high-quality glycerin monostearate | |
| CN102875493A (en) | Method for preparing epoxidized fatty acid methyl esters in continuous flow microchannel reactor | |
| CN106631720B (en) | Method for directly synthesizing polymethoxy dimethyl ether by taking dilute formaldehyde and methylal as raw materials | |
| CN102079799B (en) | Preparation method of binary polymer wax oil pour point reducer | |
| CN106278836A (en) | Intermediate concentration formaldehyde and the apparatus and method of methylal synthesis polymethoxy dimethyl ether | |
| CN106117025B (en) | The secondary butyl ester transfer hydrogenation of sec-butyl alcohol Dichlorodiphenyl Acetate produces the process of methyl ethyl ketone simultaneously | |
| CN105056842A (en) | Reaction apparatus and application thereof in synthesizing borate | |
| CN104130107A (en) | Preparation method for synthesizing 3-methyl-3-butene-1-ol by using formaldehyde hemiacetal | |
| CN105017019A (en) | Energy-saving method for preparing isopropyl acetate | |
| CN102351652B (en) | Method for preparing dihydrodicyclopentadiene through continuous reaction | |
| CN102728403B (en) | Organic solid base catalyst for synthesizing alpha-cyanoethyl cinnamate, and preparation method and application thereof | |
| CN105503784A (en) | Method and device for producing tetrahydrofurfuryl alcohol diethyl ether through industrialized ultrasonic wave reaction | |
| CN102464633B (en) | Synthetic method for (methyl) glycidyl acrylate | |
| CN103936556B (en) | A kind of method preparing methyl alcohol from biomass single stage method | |
| CN105439823B (en) | A kind of method for synthesizing the alcohol of 3 methyl, 3 butylene 1 | |
| CN106824269A (en) | A kind of pyrazoles [5,4 b] γ pyran derivates and preparation method thereof and catalyst for preparing | |
| CN104140350A (en) | Method for preparing adamantane compound from non-cyclic olefin | |
| CN101049571B (en) | Complex type molecular sieve catalyst, preparation method, and application in preparing crylic acid | |
| CN104140352A (en) | Method for preparing adamantane compound from alcohol raw material | |
| CN102701968B (en) | Coupling production process for preparing methyl acetate and butyl acetate | |
| CN104592283A (en) | Synthetic method of silane coupling agent Si-69 | |
| CN206438059U (en) | A kind of equipment for producing antioxidant | |
| CN104557394A (en) | Method for producing ethylene | |
| CN105523880B (en) | A kind of method by acetate ethene |
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 | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20190613 Address after: 361000 Mao Xue Guangshe 398, Yongyao Village, Haicang District, Xiamen City, Fujian Province Patentee after: XIAMEN WONRKA LUBRICANT CO., LTD. Address before: Xiamen City, Fujian Province, 361005 South Siming Road No. 422 Co-patentee before: XIAMEN WONRKA LUBRICANT CO., LTD. Patentee before: Xiamen University |
|
| TR01 | Transfer of patent right |