CN102381987A - Solvent-free synthesis method for octodecyl methyl dihydroxy ethyl ammonium bromide - Google Patents
Solvent-free synthesis method for octodecyl methyl dihydroxy ethyl ammonium bromide Download PDFInfo
- Publication number
- CN102381987A CN102381987A CN2011102566636A CN201110256663A CN102381987A CN 102381987 A CN102381987 A CN 102381987A CN 2011102566636 A CN2011102566636 A CN 2011102566636A CN 201110256663 A CN201110256663 A CN 201110256663A CN 102381987 A CN102381987 A CN 102381987A
- Authority
- CN
- China
- Prior art keywords
- dihydroxy ethyl
- amonio
- solvent
- reaction
- methyl dihydroxy
- 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.)
- Pending
Links
Images
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a solvent-free synthesis method for octodecyl methyl dihydroxy ethyl ammonium bromide, which includes that N-methyldiethanolamine and octadecyl bromide are mixed to react and synthesize the target product under the heating condition. The temperature range of the heating condition ranges from 80 DEG C to 100 DEG C, the variation range of reaction time ranges from 120min to 180min, the variation range of the molar ratio of N-methyldiethanolamine serving as raw materials to octadecyl bromide serving as raw materials ranges from 9:10 to 11:10, and the mixing speed is 200 r/min. Amplification experiments are carried out based on a preferred scheme by means of gradual amplification. The solvent-free synthesis method enables synthesis to be simpler, saves energy, prevents generation of waste and avoids harm and toxicity. The experimental scheme is improved by the aid of the amplification experiments, so that the solvent-free synthesis method can be applied to industrialized mass production.
Description
Technical field
The invention belongs to chemical field, be specifically related to a kind of no-solvent synthesis process of octadecyl methyl dihydroxy ethyl brometo de amonio.
Background technology
The Green Chemistry of rising the nineties in 20th century tries hard to overcome pollution on the environment in the process of production and use chemical substance.(the especially reaction of solid matter participation) with an organic solvent is comparatively general in the building-up process of organic chemicals, and these organic solvents can be lost in the environment and pollute.Green Chemistry is the important research field of 21 century chemical science development.Green Chemistry be utilize a series of principles to reduce or eliminate design in Chemicals, production and use in the using and producing of objectionable impurities.Some are arranged in many solvents commonly used is volatile organic cpds, when it is discharged in the atmosphere, will cause harmful smog.Solvent-free system has been eliminated harmful smog emission, has human health and the most significant advantage of environment, and be one of Green Chemistry research direction.
Solvent-free organic reaction is meant the organic reaction of not adopting solvent, and it can be the solid state reaction between the solid material, the liquid phase reaction between the liquid starting material, also can be the reaction of raw material under molten state, or the inhomogeneous reaction between the different phase raw material.The various countries chemist creates and has studied the Green Chemistry method of many replacement conventional organic solvents, as with water be medium with supercutical fluid (like CO
2) be solvent, with the ionic liquid at room temperature be method such as solvent and the most completely method be fully without the solvent-free organic synthesis of solvent.
At present, solvent-free organic synthesis research mainly concentrates in the fundamental research of laboratory realization response, to being advanced to the applied research of large-scale industrial in producing but seldom.
Summary of the invention
The objective of the invention is the deficiency to prior art, the no-solvent synthesis process of a kind of simple to operate, environmental protection, octadecyl methyl dihydroxy ethyl brometo de amonio that transformation efficiency is high is provided.
The no-solvent synthesis process of a kind of octadecyl methyl dihydroxy ethyl brometo de amonio provided by the invention is with N methyldiethanol amine and the synthetic title product of bromo-octadecane stirring reaction under heating condition.
Preferably; The range of temperature of heating condition is 80 ℃～100 ℃; The reaction times variation range is 120 min～180min, is 9:10 ~ 11:10 as the N methyldiethanol amine of raw material and the mol ratio variation range of bromo-octadecane, and stirring velocity is 200r/min.
Preferred plan of the present invention is: temperature of reaction is 100 ℃, and the reaction times is 180min, and the mol ratio of N methyldiethanol amine and bromo-octadecane is 1:1.
Synthetic product under condition of no solvent is carried out recrystallization to be handled.
The present invention also adopts the method for amplifying step by step to carry out amplification test under the preferred plan condition; In order to solve the problem that occurs in the amplification test process; Made following improvement: when reactant total mass during greater than 1000g; Take following measure: keep stirring in the reaction process, reactant concn and temperature are evenly distributed in reaction system; Change the adding mode of N methyldiethanol amine into adding in batches by disposable adding; Elder generation adds 1/2 N methyldiethanol amine during i.e. reaction beginning; Add 1/4 N methyldiethanol amine behind the reaction 30min, react 30min again and add remaining 1/4 N methyldiethanol amine.
Compared with prior art, the present invention has following beneficial effect: 1) transformation efficiency is high, can reach more than 87%; 2) product purity is high, can reach more than 98%; 3) solvent-freely synthetic make synthetic simplyr, save energy, and prevented generation of waste, avoided harm and toxicity; 4) through amplification test experimental program is improved, make this method can be applied to commercial scale prodn.
In order to verify beneficial effect of the present invention, the present invention has also adopted following means that this compound method is assessed:
The measuring method of transformation efficiency and product purity is to the transformation efficiency of synthetic product and the measuring method of product purity with reference to publication number in the patented claim of 101898971A.
Description of drawings
Fig. 1: temperature is to the influence of transformation efficiency;
Fig. 2: the mol ratio of reactant is to the influence of transformation efficiency;
Fig. 3: the time is to the influence of transformation efficiency;
Fig. 4: the infrared absorption spectrum of synthetic product;
Fig. 5: synthetic product
1H NMR spectrogram.
Embodiment
Used material and reagent are in following examples: N methyldiethanol amine, CR, the many and petrochemical industry ltd in Maoming, Guangdong; Bromo-octadecane, CR, Guangzhou section joins equipment ltd; Absolute ethyl alcohol, AR, Tianjin Da Mao chemical reagent factory; Acetone, AR, Tianjin Da Mao chemical reagent factory; Tetrabromophenol sulfonphthalein, AR, new fine chemistry industry development centre, sky, Tianjin; Concentrated hydrochloric acid, AR, Dafeng City's clever gram send out chemical reagent factory extraordinary.
Used instrument and equipment is in following examples: heat collecting type thermostatically heating magnetic agitation, and DF-101S, the Ying Yu of Gongyi City gives magnificent instrument plant; Fourier infrared spectrograph, TENSOR27, French BRUKER company; Vacuum drying oven, DZG-6050SA, the gloomy reliable Instr Ltd. that tests in Shanghai; NMR, DRX400, German Bruker company; Electronic analytical balance, AL204, Shanghai people and scientific instrument ltd; Reaction kettle (2L), GY-2, the Ying Yu of Gongyi City gives magnificent instrument plant.
The mol ratio (11.92gN-methyldiethanolamine and 33.33g bromo-octadecane) of raw material with 1:1 joined in the round-bottomed flask; The magnetic agitation speed setting is 200r/min; Under 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃ temperature, react 120min respectively, measure the transformation efficiency of N methyldiethanol amine.Result such as Fig. 1.Can draw from Fig. 1, temperature of reaction guarantees that considerable yield is all being arranged more than 90 ℃, though improved temperature of reaction afterwards; Transformation efficiency also can correspondingly improve; But increasing degree is gradually little, based on the consideration of production energy consumption, the range of temperature of optimizing is set at 80～100 ℃ simultaneously.
Raw material N methyldiethanol amine (MDEA) and bromo-octadecane (C with different mol ratio
18H
37Br) join respectively in the round-bottomed flask, the magnetic agitation speed setting is 200r/min, stirring reaction 120min under 90 ℃ temperature, the transformation efficiency of mensuration N methyldiethanol amine.Result such as Fig. 2.Wherein the numerical value of mol ratio is 0.9 corresponding 9:10 with the corresponding relation of ratio, 1.1 corresponding 11:10, by that analogy.Can be known that by Fig. 2 along with the increase of reactant molar ratio, transformation efficiency improves gradually, when reactant molar ratio was 1.2, transformation efficiency was 93.10%; The amplitude that continues to increase then transformation efficiency raising reduces.The theoretical molar of N methyldiethanol amine and bromo-octadecane is than being 1:1, and for improving yield, it is wherein a kind of excessive to make, but no matter which kind of is excessive, all can bring unnecessary by product, and product effective constituent is reduced.Therefore the mol ratio variation range of optimizing is set at 9:10 ~ 11:10.
Embodiment 3
The mol ratio (11.92gN-methyldiethanolamine and 33.33g bromo-octadecane) of raw material with 1:1 joined in the round-bottomed flask; 90 ℃ of constant temperature; React 30,60,90,120,150,180 under the magnetic agitation speed 200r/min respectively, 210min, measure the transformation efficiency of N methyldiethanol amine.Result such as Fig. 3.
Can know that by Fig. 3 the reaction times is too short, react very insufficient, so productive rate is lower; Along with the prolongation in reaction times, reaction is accelerated, and when the reaction times was 150min, productive rate had reached 93.36%.Though along with the prolongation in reaction times, yield also can correspondingly improve, increasing degree is gradually little, therefore the time variation range of optimizing is set at 120～180min.
Embodiment 4
According to single factor experiment, this research emphasis is considered temperature of reaction (A), the reaction times (B), and 3 factors of reactant molar ratio (C), 3 levels of each factor adopt three factors, three horizontal L9 (33) orthogonal tests, and factor and level set are seen table 1.
Table 1 orthogonal test factor-water-glass
Table 2 orthogonal test table
Range analysis by table 2 orthogonal experiments shows that each factor influences size order to transformation efficiency and is: A (temperature of reaction)>B (reaction times)>C (reactant molar ratio); Wherein temperature is the principal element that influences transformation efficiency; Reaction times and reactant molar ratio are for influencing the secondary cause of transformation efficiency; The final best experimental program of confirming is A3B3C3; Be that temperature of reaction is 100 ℃, the reaction times is 180min, and the mol ratio of bromo-octadecane and N methyldiethanol amine is 1:1.
Do one group again by above definite best experimental program and append confirmatory experiment, the supplementary test result shows that the peak rate of conversion of reaction is 94.50%.
Embodiment 5
Can confirm that through single factor experiment the reaction conditions that scale-up adopts is: 100 ℃ of temperature of reaction; Reaction times 180min; The mol ratio of bromo-octadecane and N methyldiethanol amine is 1.1; Adopt the method for amplifying step by step to carry out the amplification test of octadecyl methyl dihydroxy ethyl brometo de amonio (OMDAB), the result sees table 3.
The amplification test result of table 3 OMDAB
Annotate: in the above experiment, 1,2,3,4 all is in there-necked flask, to carry out, and 5,6,7 all is in the normal-pressure reaction kettle of 2L, to carry out, and the amount of reactant is shown in table, and reaction conditions is constant, has investigated the transformation efficiency that amplifies the afterreaction thing.
Can find out by table 3, when magnification hour, to the almost not influence of transformation efficiency of reactant, but when reacting multiple when being amplified to 25 times, 50 times, the transformation efficiency of reactant has reduced by 1.86% and 2.05% respectively.For the solvent-free compound experiment of OMDAB that in the reaction kettle of 2L, amplifies 50 times,, still be more satisfactory for such experimental result though transformation efficiency decreases.This explanation does not change reaction conditions, and the method that relies on the increase experimental size to improve output is feasible.
For the experiment of amplifying 25 times; Not only experimental result changes; And the phenomenon in the reaction process also there are differences, and its evident difference is: in the 2L reaction kettle, when temperature of reaction rises to design temperature and stablizes the 0.5h left and right sides; One rapid exothermic process is arranged, cause the temperature of reaction fast rise.This is that mass transfer, heat transfer rate change in the solution because amplification back strength of solution increases, and the heat that produces in the short period of time in the reaction process can't in time distribute in limited space, thereby makes system temperature moment rising, thereby influences reaction result.In addition, the rising of system temperature also can promote simultaneously the carrying out that react, and considers from this angle; Can form benign cycle, therefore, in the reaction process; System temperature raises a little to some extent; Can not influence the carrying out of reaction, but will avoid the rapid rising of temperature in the reaction process, so not only have the by product generation but also equipment is also caused certain pressure.
Amplify in 50 times the experiment reaction process, also there is certain difference in phenomenon, magnification hour, the viscosity of product is moderate, when magnification increased gradually, the product more and more thickness that becomes brought certain influence to the stirring of late phase reaction.
In order to solve the problem that occurs in the amplification test process, made following improvement:
1. in this reaction process,, good stirring must be arranged, make material concentration, temperature uniform distribution because the viscosity of product is bigger.
2. the adding mode of N methyldiethanol amine is changed in batches by disposable adding and adding, be i.e. add 1/2 N methyldiethanol amine during reaction beginning earlier, add 1/4 behind the reaction 30min, react 30min again and add remaining 1/4.Add the accumulation of a large amount of heats that N methyldiethanol amine avoided producing in the reaction process in batches, can concentration of reactants be remained on lower level, the generation of avoiding temperature sharply to raise as far as possible.Amplify 50 times experimental result also proved adding mode with N methyldiethanol amine change into add in batches after, the generation of having avoided temperature sharply to raise effectively.
Embodiment 6
In order to confirm that institute's synthetic compound is a title product octadecyl methyl dihydroxy ethyl brometo de amonio, the contriver has also adopted following means that institute's synthetic compound has been carried out structural analysis:
1. ultimate analysis
The results of elemental analyses of sintetics is seen table 4.
The results of elemental analyses of table 4 product
| ? | ω（C）/% | ω（H）/% | ω（N）/% |
| Theoretical value | 61.06 | 11.06 | 3.10 |
| Measured value | 61.05 | 11.09 | 3.10 |
Can be drawn by table 4, the measured value of experiment and the theoretical value difference of C, H, N element massfraction are little, show recrystallization after product gas purity higher.
2. infrared absorption spectrum
With infrared absorption spectrometer the product (using the KBr compressing tablet) behind the recrystallization 5 times is done infrared absorption spectrum, the infrared absorpting light spectra of sintetics is seen Fig. 4.
Can know 3350 cm by Fig. 4
-1A near absorption peak that strong and wide absorption peak is the O-H stretching vibration that occurs, 2925 cm
-1With 2853 cm
-1Be the stretching vibration absorption peak of methyl and methylene radical, 1392 cm
-1Near be the vibration absorption peak of quaternary ammonium group, 1058 cm
-1Neighbouring is C-O formation vibration absorption peak, 723 cm
-1Near is the scissoring vibration absorption peak of methyl and methylene radical, and the C-Br key in the raw material do not show in collection of illustrative plates, but preliminary evaluation is an octadecyl methyl dihydroxy ethyl brometo de amonio through no-solvent process synthetic product thus.
3. proton nmr spectra
Make solvent with acetone, TMS does kernel, does the proton nmr spectra of product, and Fig. 5 is proton nmr spectra (1HNMR) figure of no-solvent process sintetics.
Draw by Fig. 5 that H chemical shift δ is on each group :-CH
3(δ (0.89～0.92), 3H);-(CH
2)
15-(δ (1.32～1.45), 30H);-N-C-CH
2-(δ (1.93～1.97), 2H);-N-CH
3(δ 3.42,6H);-N-CH
2-C (δ (3.72～3.88), 6H); C-CH
2(δ 4.10,4H) for-O; OH
*(δ 5.10,2H); δ 2.80 is absorption peaks that the micro-moisture of absorption produces.This collection of illustrative plates meets the chemical structure of title product OMDAB.
Claims (10)
1. the no-solvent synthesis process of an octadecyl methyl dihydroxy ethyl brometo de amonio is characterized in that N methyldiethanol amine and bromo-octadecane stirred under heating condition and carries out building-up reactions.
2. the no-solvent synthesis process of octadecyl methyl dihydroxy ethyl brometo de amonio according to claim 1, the range of temperature that it is characterized in that said heating condition are 80 ℃～100 ℃.
3. the no-solvent synthesis process of octadecyl methyl dihydroxy ethyl brometo de amonio according to claim 2, the temperature that it is characterized in that said heating condition is 100 ℃.
4. the no-solvent synthesis process of octadecyl methyl dihydroxy ethyl brometo de amonio according to claim 1 is characterized in that the reaction times variation range is 120 min～180min.
5. the no-solvent synthesis process of octadecyl methyl dihydroxy ethyl brometo de amonio according to claim 4 is characterized in that the reaction times is 180min.
6. the no-solvent synthesis process of octadecyl methyl dihydroxy ethyl brometo de amonio according to claim 1 is characterized in that as the bromo-octadecane of raw material and the mol ratio variation range of N methyldiethanol amine be 9:10 ~ 11:10.
7. the no-solvent synthesis process of octadecyl methyl dihydroxy ethyl brometo de amonio according to claim 6 is characterized in that as the bromo-octadecane of raw material and the mol ratio of N methyldiethanol amine be 1:1.
8. the no-solvent synthesis process of octadecyl methyl dihydroxy ethyl brometo de amonio according to claim 1 is characterized in that stirring velocity is 200r/min.
9. the no-solvent synthesis process of octadecyl methyl dihydroxy ethyl brometo de amonio according to claim 1; It is characterized in that when reactant total mass during greater than 1000g; Take following measure: keep stirring in the reaction process, reactant concn and temperature are evenly distributed in reaction system; Change the adding mode of N methyldiethanol amine into adding in batches by disposable adding; Elder generation adds 1/2 N methyldiethanol amine during i.e. reaction beginning; Add 1/4 N methyldiethanol amine behind the reaction 30min, react 30min again and add remaining 1/4 N methyldiethanol amine.
10. according to the no-solvent synthesis process of each described octadecyl methyl dihydroxy ethyl brometo de amonio of claim 1 ~ 9, it is characterized in that the product after the building-up reactions also carries out the recrystallization processing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011102566636A CN102381987A (en) | 2011-09-01 | 2011-09-01 | Solvent-free synthesis method for octodecyl methyl dihydroxy ethyl ammonium bromide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011102566636A CN102381987A (en) | 2011-09-01 | 2011-09-01 | Solvent-free synthesis method for octodecyl methyl dihydroxy ethyl ammonium bromide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102381987A true CN102381987A (en) | 2012-03-21 |
Family
ID=45821883
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011102566636A Pending CN102381987A (en) | 2011-09-01 | 2011-09-01 | Solvent-free synthesis method for octodecyl methyl dihydroxy ethyl ammonium bromide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102381987A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0428970A1 (en) * | 1989-11-21 | 1991-05-29 | BASF Aktiengesellschaft | Process for preparing aqueous solutions or suspensions of quaternization products of tertiary aminoalkylesters or tertiary aminoalkylamides of acrylic or methacrylic acid, for instance of dimethylaminoethyl-acrylate-methochloride |
| CN101381318A (en) * | 2008-10-22 | 2009-03-11 | 广州大学 | Microwave synthetic method of dodecyl methyl biethoxyl ammonium bromide |
| CN101898971A (en) * | 2010-05-21 | 2010-12-01 | 广州科技贸易职业学院 | Method for synthesizing octadecyl methyl dihydroxyethyl ammonium bromide by using microwave |
-
2011
- 2011-09-01 CN CN2011102566636A patent/CN102381987A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0428970A1 (en) * | 1989-11-21 | 1991-05-29 | BASF Aktiengesellschaft | Process for preparing aqueous solutions or suspensions of quaternization products of tertiary aminoalkylesters or tertiary aminoalkylamides of acrylic or methacrylic acid, for instance of dimethylaminoethyl-acrylate-methochloride |
| CN101381318A (en) * | 2008-10-22 | 2009-03-11 | 广州大学 | Microwave synthetic method of dodecyl methyl biethoxyl ammonium bromide |
| CN101898971A (en) * | 2010-05-21 | 2010-12-01 | 广州科技贸易职业学院 | Method for synthesizing octadecyl methyl dihydroxyethyl ammonium bromide by using microwave |
Non-Patent Citations (4)
| Title |
|---|
| WEI TONG 等: "Critical Micellar Concentrations of Quaternary Ammonium Surfactants with Hydroxyethyl Substituents on Headgroups Determined by Isothermal Titration Calorimetry", 《J.CHEM.ENG.DATA》 * |
| WYNNE, JAMES H. 等: "Synthesis and Development of a Multifunctional Self-Decontaminating Polyurethane Coating", 《ACS APPLIED MATERIALS & INTERFACES》 * |
| 张学同: "N-甲基二乙醇胺三个季铵盐衍生物的合成与表征", 《合成化学》 * |
| 毛桃嫣: "新型阳离子表面活性剂十二烷基甲基二羟乙基溴化胺的合成与性能研究", 《中国优秀硕士论文全文数据库 工程科技Ⅰ辑》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105272851B (en) | A kind of preparation method of (methyl) hydroxy-ethyl acrylate | |
| CN101337870B (en) | Method for synthesizing 4-(4'-n-alkyl cyclohexyl)cyclohexanone | |
| CN102795973B (en) | Synthetic method of ethylene glycol monoallyl ether | |
| CN105771990A (en) | Iron oxide catalyst, preparation method therefor and application of iron oxide catalyst | |
| CN101962424A (en) | Preparation method of acrylamide/methyl methacrylate grafted bagasse xylan copolymer | |
| CN105503784B (en) | A kind of method and device for industrializing ultrasonic response production tetrahydrofurfuryl alcohol ether | |
| CN102381987A (en) | Solvent-free synthesis method for octodecyl methyl dihydroxy ethyl ammonium bromide | |
| CN110627754B (en) | Method for preparing 2-oxo-2-furyl acetic acid by using continuous flow microchannel reactor | |
| Zou et al. | Microfluidic continuous flow synthesis of 1, 5-ditosyl-1, 5-diazocane-3, 7-dione using response surface methodology | |
| CN110028518B (en) | Method for preparing medical intermediate pyrano [2, 3-d ] pyrimidone derivative through catalysis | |
| CN107382961B (en) | Method for preparing 2-thiocarbonyl-2H-thiopyran derivative by chitosan catalysis one-pot method | |
| CN113999247B (en) | Preparation method of fluorone reagent | |
| CN107162970B (en) | Method for synthesizing 2-aryl-2, 3-dihydro-4 (1H) -quinolinone derivative under catalysis of high-acidity ionic liquid | |
| CN106238098B (en) | A kind of preparation method and its catalyst for preparing of 1,2,4,5- tetra- substituted ramification of imidazole | |
| CN104326893A (en) | Side-chain-type difluoro monomer and synthesis method thereof | |
| CN105669413B (en) | A kind of method that microwave radiation prepares 2- methyl-1,4-naphthaquinone | |
| CN103224481A (en) | Preparation method of dehydrogenated equol | |
| CN103086903A (en) | Preparation method of mixed crystal of glycine and ammonium chloride | |
| CN112321525B (en) | Method for synthesizing 3, 4-bis (4 '-aminofurazan-3' -yl) furoxan by one-step method | |
| CN105061255A (en) | Series of asymmetric double-Schiff base mononuclear copper complexes, and preparation method and application thereof | |
| CN111087367A (en) | Synthesis method of N- (4 cyano-3- (trifluoromethyl) phenyl) -2-methyl epoxy propylene-2-amide | |
| CN114315683B (en) | Preparation method of N-phenylmaleimide | |
| CN113845475A (en) | Method for preparing hydroxychloroquine sulfate by using microchannel reaction device | |
| CN103408481A (en) | Method for synthesizing substituted pyrrole-3-formate compound by virtue of microwave radiation in one step | |
| CN105152871B (en) | A kind of method of the different octyl ether of synthesizing glycol and its polyol ethers |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| ASS | Succession or assignment of patent right |
Owner name: GUANGZHOU UNIVERSITY Free format text: FORMER OWNER: GUANGZHOU VOCATIONAL COLLEGE OF TECHNOLOGY + BUSINESS Effective date: 20130327 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| COR | Change of bibliographic data |
Free format text: CORRECT: ADDRESS; FROM: 511442 GUANGZHOU, GUANGDONG PROVINCE TO: 510006 GUANGZHOU, GUANGDONG PROVINCE |
|
| TA01 | Transfer of patent application right |
Effective date of registration: 20130327 Address after: 510006 Guangdong City, Guangzhou Province University, West Ring Road, No. 230 Applicant after: Guangzhou University Address before: 511442, Guangzhou, Panyu District, Guangdong Province South Town Industrial Road, Guangzhou science and technology trade, Career Academy Applicant before: Guangzhou Vocational College of Technology & Business |
|
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20120321 |