CN101239927A - Method for preparing monomer of temperature-sensitive polyisopropylacrylamide - Google Patents
Method for preparing monomer of temperature-sensitive polyisopropylacrylamide Download PDFInfo
- Publication number
- CN101239927A CN101239927A CNA2007100031531A CN200710003153A CN101239927A CN 101239927 A CN101239927 A CN 101239927A CN A2007100031531 A CNA2007100031531 A CN A2007100031531A CN 200710003153 A CN200710003153 A CN 200710003153A CN 101239927 A CN101239927 A CN 101239927A
- Authority
- CN
- China
- Prior art keywords
- temperature
- isopropylamine
- ethyl acetate
- monomer
- sensitive
- 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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the chemical synthesis technology field, particularly relates to a temperature-sensitive poly(N-isopropylacrylamide) monomer preparing method. The method comprises steps of: (1) respectively adding isopropyl amine and acryloyl chloride into ethyl acetate solvent; (2) adding sollution of acryloyl chloride and ethyl acetate into sollution of isopropyl amine and ethyl acetate to perform synthesis reaction; (3) after the synthesis reaction, filtering to obtain isopropyl amine hydrochloride solution; (4) adding inhibitors; (5) rotating and vaporizing the sollution to remove ethyl acetate solvent, obataining crude products of N-isopropylacrylamide; (6) adding the extraction agent n-hexane, cooling to obtain white crystal N-isopropylacrylamide monomer; (7) vacuum-drying to obain N-isopropylacrylamide monomer products. The invention is free of strong acid, the feeding sequence is simple, the reaction temperature is easy to control, the subsequent separation and purification operation is simple. The invention also has the advantages of small by-products, good selectivety, simple process, high yield and low cost.
Description
Technical field
The invention belongs to technical field of chemical synthesis, be specifically related to a kind of method for preparing monomer of temperature-sensitive polyisopropylacrylamide.
Background technology
High-molecular gel is a kind of soft and wet material that has both liquid, both character of solid, be by polymer three-dimensional cross-linked network and the multicomponent system that is fixed in small molecules solvent composition wherein, be that a class can not be dissolved, can not fusion, and have certain elastic cross-linked polymer swelling body.This material can be made soft reaction such as stimulations such as pH value, temperature, light intensity, electric field, magnetic field and chemical substance etc. to the variation of environment.In recent years, the research work of intelligent polymer gel is carried out, and it is quite paid close attention in fields such as medical science, pharmacy, life science, biotechnology, electronics and mechanical organs.And thermo-sensitive gel is a kind of intelligent macromolecule, and reversible expansion-contraction, the critical temperature that has volume to change can take place with the variation of envrionment temperature.Poly-N one N-isopropylacrylamide (PNIPA) hydrogel has temperature sensitive property feature, when temperature is lower than LCST (lower critical solution temperature, LCST, lower critical solution temperature), in water, form good hydrated state, be contraction schedule when temperature reaches LCST., its LCST is with a wide range of applications in fields such as temperature sensitive film, feed separation, induction pieces, bionical and medical science about 32 ℃.Particularly aspect separating, have very high industrial application value concentrating of material. therefore study the synthetic very important of monomer N-isopropylacrylamide (NIPA).
Monomer N-isopropylacrylamide synthetic route has multiple, as the N alkylated reaction of the reaction of amine and unsaturated acyl chlorides, ethylenic unsaturation nitrile or enamine, Beckmann rearrangement etc.Wherein report such as Chen Wenming { is seen Chen Wenming, Yu Zhenning, Yan Lifeng: the acid catalysis of N-N-isopropylacrylamide and N-isopropyl methyl acrylamide is synthetic to be improved, [J]. fine chemistry industry, 1998, (6) } synthetic method of vinyl cyanide and Virahol NIPA in the presence of the vitriol oil, this method all has requirement to the temperature and the pH value of sulfuric acid consumption, order of addition(of ingredients), step of reaction, later separation is extracted complicated, is unsuitable for batch process.The Beckmann rearrangement synthetic method is directly amine substance and acrylate chloride (ACC) reaction to be obtained NIPA, reaction is violent, heat release severity, and NIPA easy polymerization when synthetic, yield is lower, and can produce multiple N substituted amide by product, poor selectivity, the Isopropylamine (IPA) of report is complicated with synthetic its technology of NIPA of acrylate chloride (ACC), the cost height.Introduce method in French Patent FR2498182 and the U.S. Pat 4835312 with acrylamide and the synthetic NIPA of bromo propane reaction, productive rate has only 65%, because the impurity effect that is mixed with in product can cause monomer variable color in the process of life-time service, thereby influence quality.
Summary of the invention
Technical problem to be solved by this invention is at existing deficiency in the above-mentioned prior art, provide a kind of energy to be fit to low laboratory condition, impurity in products content is that by product is few less, the method for preparing monomer of yield height, temperature-sensitive polyisopropylacrylamide that production cost is low.
The method for preparing monomer that solves technical scheme that the technology of the present invention problem adopted and be this temperature-sensitive polyisopropylacrylamide is to use Isopropylamine (IPA) and acrylate chloride (ACC) to carry out chemosynthesis and produces:
The amount of the Isopropylamine (IPA) that adds amount relative and that the acrylate chloride building-up reactions is required is excessive, makes medium be neutrality or weakly alkaline.
Preferably the usage ratio of Isopropylamine (IPA) and acrylate chloride (ACC) is (1.5-2.6) in molar ratio: 1;
Further preferably the usage ratio of Isopropylamine (IPA) and acrylate chloride (ACC) is 2.1: 1 in molar ratio;
Preferably Isopropylamine (IPA) is to carry out in the organic acid acetic solvent with the acrylate chloride building-up reactions;
Further preferably described organic acid acetic solvent is an ethyl acetate;
Preferably the method for preparing monomer of temperature-sensitive polyisopropylacrylamide of the present invention may further comprise the steps:
(1) add Isopropylamine IPA and acrylate chloride ACC in the solvent ethyl acetate respectively;
(2) again the solution of acrylate chloride ACC and ethyl acetate is joined in the solution of Isopropylamine IPA and ethyl acetate and carry out building-up reactions; Temperature of reaction is 0-10 ℃, reaction times: 4-16 hour;
(3), building-up reactions finishes, filter isopropylamine hydrochloride solution.
Further, the method for preparing monomer of PNIPAM is further comprising the steps of:
(4), add stopper: can be when beginning mixing raw material in step (1), to add stopper, stopper be 4-methoxyl group phenol or 1,4 Resorcinol, preferred 4-methoxyl group phenol; 4-methoxyl group phenol is as the amount ranges of stopper, by can be 0.2-0.4% with Isopropylamine IPA quality-mass ratio in the system of Isopropylamine IPA/ ethyl acetate; Building-up reactions in step (3) finishes, filter isopropylamine hydrochloride solution, before rotary evaporation, add stopper once more according to the ratio that can be 0.1-0.3% with the acrylate chloride that feeds intake (ACC) quality-mass ratio.
(5), solution rotating evaporation removes solvent ethyl acetate, obtains the N-isopropylacrylamide crude product, in bath temperature 70-80 ℃;
(6), add extraction agent while hot, used extraction agent is a normal hexane, cool off white crystals thing N-isopropylacrylamide monomer, used extraction agent normal hexane amount ranges is: to add the 150-350ml normal hexane by every 1L liquid in the N-isopropylacrylamide crude product thick liquid that obtains after step (5) distillation.Do not dissolve the NIPA monomer owing to a normal hexane dissolved impurity, and the normal hexane volatility is more intense, removes easily, so make extraction agent with normal hexane.
(7), vacuum-drying gets the N-isopropylacrylamide monomer product.
The main points of the inventive method mainly contain following some:
1, the ratio of Isopropylamine (IPA) and acrylate chloride (ACC) is that mol ratio 2.1: 1 is comparatively suitable.Adding excessive Isopropylamine (IPA) makes medium be neutrality or weakly alkaline; to improve acidylate speed and acidylate productive rate; the synthetic route that adopts acrylate chloride (ACC) and Isopropylamine (IPA) to react, the hydrochloric acid of generation can form salt with Isopropylamine (IPA), has reduced N one acidylate speed.
2, temperature of reaction be controlled at 10 ℃ with interior help the reaction carry out because this reaction is thermopositive reaction.
3, solvent adopts ethyl acetate.Aspect choice of Solvent; benzene, ethyl acetate all can be used as reaction medium; the productive rate of gained NIPAAm (Am represents amine) all reaches more than 80%; but because the specific inductivity (￡ 1) of ethyl acetate is greater than the specific inductivity (￡ 1) of benzene; the acidylate that helps acyl chlorides is can shorten in reaction times of solvent with ethyl acetate.From productive rate with reduce to react toxicity and consider that reaction solvent adopts ethyl acetate.
Reaction 8-12h was more abundant when 4, solvent was for ethyl acetate.Under the reaction conditions of 1,2,3 inventive points, further investigate the influence of reaction times to the NIPA productive rate, solvent during for ethyl acetate reaction 8-12h more abundant, continue to prolong the basic no change of reaction times productive rate;
5, reactant concn (acrylate chloride and Isopropylamine and ethyl acetate volume ratio) is controlled at 0.1-0.5, preferred 0.25.Experimental observation is to the increase along with concentration, and reaction becomes gradually acutely, is difficult to control, and productive rate descends after concentration reaches certain value.Analyzing its reason is because reactant concn is crossed conference aggravation side reaction, influences monomeric generation, so reactant concn (acrylate chloride and Isopropylamine and ethyl acetate volume ratio) is controlled at about 0.25 better.
6, adopt the monomeric stopper of 4-methoxyl group phenol as acrylate chloride (ACC) and product N-isopropylacrylamide.Can remedy adopt 1,4 Resorcinol as stopper after because the oxidation of 1,4 Resorcinol causes the deficiency of monomer generation color change.
7, adopt normal hexane as extraction agent.Can purify Isopropylamine (IPA) and the reacted crude product of acrylate chloride (ACC).
The present invention obtains the N-isopropylacrylamide monomer with acrylate chloride and Isopropylamine reaction, (need to use vacuum pump in the existing technology to equipment requirements is lower with condition of high vacuum degree, it costs an arm and a leg, and use is also cumbersome, and is very high to the seal request of pipeline and whole reaction system.And only need common vacuum pump to get final product among the present invention), there is not the use of strong acid, order of addition(of ingredients) is simple, the easy control of temperature of step of reaction, the operation that later separation is purified is fairly simple, impurity in products content is that by product is few less, and the monomer of acquisition is purer, and selectivity is good, whole technology is simple, the yield height, production cost low (with adopt additive method, compare as using the method for being introduced in French Patent FR2498182 and the U.S. Pat 4835312, with the method for acrylamide and the synthetic NIPA of bromo propane reaction, productive rate has only 65%, because the impurity effect that is mixed with in product can cause monomer variable color in the process of life-time service, thereby influence quality, in the resulting monomer of the inventive method, can variable color owing to the influence of impurity, improved the quality of product, and productive rate reaches 80%).Use the solvent of ethyl acetate among the present invention, added 4-methoxyl group phenol then as stopper, thereby improved yield as Isopropylamine IPA and acrylate chloride ACC; The inventive method building-up reactions is relatively gentle, makes that the polymeric possibility reduces greatly when synthesizing owing to added stopper.
Embodiment
Below be non-limiting examples of the present invention, content of the present invention is described in further detail.
Embodiment 1:
The four-necked bottle of equipment: 2000ml (reactor), rotatory evaporator, electric heater, water-bath, glass-stem thermometer, porose plug, vacuum drier, separating funnel, Erlenmeyer flask;
Raw material: ethyl acetate, Isopropylamine, acrylate chloride, 4-methoxyl group phenol, normal hexane
Step:
1) four-necked bottle of 2000ml after the adding 950ml ethyl acetate, adds the 160g Isopropylamine again, and adds stopper 4-methoxyl group phenol, and amount is that 0.5 gram is cooled to below 5 ℃ with frozen water.
2) drip the 117g acrylate chloride that dilutes with the 300ml ethyl acetate, keep reaction below 5 ℃.
3) drip off after, reacted 12 hours, keeping reaction below 5 ℃ is that ice-water bath stirs 12h.
4) reaction finishes, and filters, and the elimination throw out gets the about 1200ml of isopropylamine hydrochloride solution, and solution adds 0.3g stopper 4-methoxyl group phenol.
5) ethyl acetate is removed in solution rotating evaporation, in bath temperature 70-80 ℃, and must about 180g liquid.
6) add while hot normal hexane 50ml cool off white crystals thing N-isopropylacrylamide monomer.
7) vacuum-drying gets product 120g, and productive rate is 82.1% in acrylate chloride.
Embodiment 2:
The four-necked bottle of equipment raw material: 2L (reactor), rotatory evaporator, electric heater, water-bath, glass-stem thermometer, porose plug, vacuum drier, separating funnel, Erlenmeyer flask;
Raw material: ethyl acetate, Isopropylamine, acrylate chloride, 4-methoxyl group phenol, normal hexane
Step:
1) four-necked bottle of 2L after the adding 1000ml ethyl acetate, adds the 80g Isopropylamine again, and adds stopper 4-methoxyl group phenol, and amount is 0.2 gram, is cooled to below 5 ℃ with frozen water.
2) drip the 57.5g acrylate chloride that dilutes with the 300ml ethyl acetate, keep reaction below 5 ℃.
3) drip off after, reacted 12 hours, keep reaction below 5 ℃.
4) reaction finishes, filter the about 1350ml of isopropylamine hydrochloride solution, solution adding 0.1g stopper 4-methoxyl group phenol.
5) ethyl acetate is removed in solution rotating evaporation, in bath temperature 70-80 ℃, and must about 90g liquid.
6) add while hot normal hexane 25ml cool off white crystals thing N-isopropylacrylamide monomer.
7) vacuum-drying gets the about 60g of product, and productive rate is 83.5% in acrylate chloride.
Embodiment 3:
The four-necked bottle of equipment: 2L (reactor), rotatory evaporator, electric heater, water-bath, glass-stem thermometer, porose plug, vacuum drier, separating funnel, Erlenmeyer flask;
Raw material: ethyl acetate, Isopropylamine, acrylate chloride, 4-methoxyl group phenol, normal hexane
Step:
1) four-necked bottle of 2L after the adding 1000ml ethyl acetate, adds the 240g Isopropylamine again, and adds stopper 4-methoxyl group phenol, and amount is 1.0 grams, is cooled to below 5 ℃ with frozen water.
2) drip the 175g acrylate chloride that dilutes with the 500ml ethyl acetate, keep reaction below 5 ℃.
3) drip off after, reacted 12 hours, keep reaction below 5 ℃.
4) reaction finishes, filter the about 1000ml of isopropylamine hydrochloride solution, solution adding 0.5g stopper 4-methoxyl group phenol.
5) ethyl acetate is removed in solution rotating evaporation, in bath temperature 70-80 ℃, and must about 260g liquid.
6) add while hot normal hexane 90ml cool off white crystals thing N-isopropylacrylamide monomer.
7) vacuum-drying gets product 175g, and productive rate is 80.0% in acrylate chloride.
Illustrate: the method for calculation of productive rate or yield: we generally are that the molar ratio according to acrylate chloride and product (N-isopropylacrylamide monomer) calculates.80% productive rate or yield are meant that 1 mol propylene acyl chlorides is synthetic and produce 0.8 mole of N-isopropylacrylamide monomer.
Claims (13)
1. the method for preparing monomer of a temperature-sensitive polyisopropylacrylamide is characterized in that using Isopropylamine and acrylate chloride to carry out chemosynthesis reaction and produces:
The amount of the Isopropylamine that adds amount relative and that the acrylate chloride building-up reactions is required is excessive, makes medium be neutrality or weakly alkaline.
2. the method for preparing monomer of temperature-sensitive polyisopropylacrylamide according to claim 1 is characterized in that the usage ratio of Isopropylamine and acrylate chloride is (1.5-2.6) in molar ratio: 1.
3. monomer N-isopropylacrylamide according to claim 2 is synthetic, and the usage ratio that it is characterized in that Isopropylamine and acrylate chloride is 2.1: 1 in molar ratio.
4. according to the method for preparing monomer of one of claim 1-3 described temperature-sensitive polyisopropylacrylamide, it is characterized in that Isopropylamine and acrylate chloride building-up reactions are to carry out in the organic acid acetic solvent.
5. the method for preparing monomer of temperature-sensitive polyisopropylacrylamide according to claim 4 is characterized in that described organic acid acetic solvent is an ethyl acetate.
6. the method for preparing monomer of temperature-sensitive polyisopropylacrylamide according to claim 5 is characterized in that reactant concn is that acrylate chloride and Isopropylamine and ethyl acetate volume ratio are 0.1-0.5.
7. the method for preparing monomer of temperature-sensitive polyisopropylacrylamide according to claim 6 is characterized in that reactant concn is that acrylate chloride and Isopropylamine and ethyl acetate volume ratio are 0.25.
8. the method for preparing monomer of temperature-sensitive polyisopropylacrylamide according to claim 6 may further comprise the steps:
(1), add Isopropylamine and acrylate chloride in the solvent ethyl acetate respectively;
(2), again the solution of acrylate chloride and ethyl acetate is joined in the solution of Isopropylamine and ethyl acetate and carry out building-up reactions; Temperature of reaction is 0-10 ℃, reaction times: 4-16 hour.
(3), building-up reactions finishes, filter isopropylamine hydrochloride solution.
9. the method for preparing monomer of PNIPAM according to claim 8, further comprising the steps of:
(4), add stopper: can be when in step (1), beginning mixing raw material, to add stopper; Building-up reactions in step (3) finishes, filter isopropylamine hydrochloride solution, before rotary evaporation, add stopper once more;
(5), solution rotating evaporation removes solvent ethyl acetate, obtains the N-isopropylacrylamide crude product, in bath temperature 60-87 ℃;
(6), while hot add extraction agent, cool off white crystals thing N-isopropylacrylamide monomer;
(7), vacuum-drying gets the N-isopropylacrylamide monomer product.
10. the method for preparing monomer of temperature-sensitive polyisopropylacrylamide according to claim 9 is characterized in that in the step (2), temperature of reaction is 0-5 ℃, reaction times: 8-12 hour.
11. the method for preparing monomer of temperature-sensitive polyisopropylacrylamide according to claim 9, it is characterized in that the stopper that adds in the step (4) is a 4-methoxyl group phenol, 4-methoxyl group phenol is as the amount ranges of stopper, in step (1) in beginning during mixing raw material: can be 0.2-0.4% with Isopropylamine IPA quality-mass ratio in by the system of Isopropylamine IPA/ ethyl acetate, building-up reactions in step (3) finishes, filter isopropylamine hydrochloride solution before rotary evaporation, add stopper once more according to the ratio that can be 0.1-0.3% with the acrylate chloride that feeds intake (ACC) quality-mass ratio.
12. the method for preparing monomer of temperature-sensitive polyisopropylacrylamide according to claim 9 is characterized in that in the step (5), bath temperature is in 70-80 ℃.
13. the method for preparing monomer of temperature-sensitive polyisopropylacrylamide according to claim 9, it is characterized in that used extraction agent is a normal hexane in the step (6), used extraction agent normal hexane amount ranges is: to add the 150-350ml normal hexane by every 1L liquid in the N-isopropylacrylamide crude product thick liquid that obtains after step (5) distillation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007100031531A CN101239927B (en) | 2007-02-07 | 2007-02-07 | Method for preparing monomer of temperature-sensitive polyisopropylacrylamide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007100031531A CN101239927B (en) | 2007-02-07 | 2007-02-07 | Method for preparing monomer of temperature-sensitive polyisopropylacrylamide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101239927A true CN101239927A (en) | 2008-08-13 |
| CN101239927B CN101239927B (en) | 2012-03-21 |
Family
ID=39931814
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2007100031531A Active CN101239927B (en) | 2007-02-07 | 2007-02-07 | Method for preparing monomer of temperature-sensitive polyisopropylacrylamide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101239927B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE112009000374T5 (en) | 2008-02-21 | 2011-01-20 | Chongqing Haifu (Hifu) Technology Co., Ltd. | Intelligent Tissue Imitating Ultrasonic Phantom and Procedures for its Manufacture |
| CN109665971A (en) * | 2017-10-17 | 2019-04-23 | 无锡海特圣大光电材料科技有限公司 | A kind of method for preparing monomer of temperature sensitive type monomer n-isopropyl acrylamide |
| CN112521300A (en) * | 2020-12-06 | 2021-03-19 | 苏州双格新材料科技有限公司 | Method for preparing N-isopropylacrylamide based on 3-halogen-N-isopropylamide |
| CN113061477A (en) * | 2021-03-30 | 2021-07-02 | 扬州工业职业技术学院 | Additive of water-based lubricant and preparation method thereof |
| CN113308226A (en) * | 2021-06-07 | 2021-08-27 | 绍兴徐越环境服务有限公司 | Pavement humectant and preparation method thereof |
-
2007
- 2007-02-07 CN CN2007100031531A patent/CN101239927B/en active Active
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE112009000374T5 (en) | 2008-02-21 | 2011-01-20 | Chongqing Haifu (Hifu) Technology Co., Ltd. | Intelligent Tissue Imitating Ultrasonic Phantom and Procedures for its Manufacture |
| CN109665971A (en) * | 2017-10-17 | 2019-04-23 | 无锡海特圣大光电材料科技有限公司 | A kind of method for preparing monomer of temperature sensitive type monomer n-isopropyl acrylamide |
| CN112521300A (en) * | 2020-12-06 | 2021-03-19 | 苏州双格新材料科技有限公司 | Method for preparing N-isopropylacrylamide based on 3-halogen-N-isopropylamide |
| CN113061477A (en) * | 2021-03-30 | 2021-07-02 | 扬州工业职业技术学院 | Additive of water-based lubricant and preparation method thereof |
| CN113061477B (en) * | 2021-03-30 | 2022-08-02 | 扬州工业职业技术学院 | Additive of water-based lubricant and preparation method thereof |
| CN113308226A (en) * | 2021-06-07 | 2021-08-27 | 绍兴徐越环境服务有限公司 | Pavement humectant and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101239927B (en) | 2012-03-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101239927B (en) | Method for preparing monomer of temperature-sensitive polyisopropylacrylamide | |
| TW201038515A (en) | N-(1-hydroxyethyl)carboxamide compound and process for producing same | |
| US10385147B2 (en) | Method for producing polyvinylamine crosslinked polymer particles | |
| CN101284805A (en) | Production method for 2-acryloylamino-2-methylpropane sulfonic acid | |
| CN109608361B (en) | Synthesis method of dichloroacetonitrile | |
| CN102388017A (en) | A method of synthesising an amino acid derivative of azelaic acid | |
| TW200934750A (en) | Process for amidating nitriles in the presence of sulphuric acid | |
| RU2501786C2 (en) | Method of producing n-alkyl (alkyl) acrylamides | |
| CN110803996A (en) | Synthesis method of hydroxybenzylamine | |
| CN106699595B (en) | A kind of scheme for lacosamide preparation method | |
| CA2724716C (en) | Process for preparation of .alpha.-hydroxycarboxylic acid amides | |
| CN103951590B (en) | The preparation method of N, O-dimethyl-N '-nitro isourea | |
| JP2004203837A (en) | Method for producing diamine dicarboxylic acid salt | |
| CN102008978B (en) | Chiral catalyst and preparation method and application thereof | |
| CN112521308A (en) | Synthesis method of dichloroacetonitrile | |
| CN103910654B (en) | The synthetic method of 1-methyl isophthalic acid-methoxyl group-3-phenylurea | |
| CN102050754A (en) | Method for preparing alpha-amino-dialkyl substituted acetamide | |
| JP5295622B2 (en) | Method for producing target compound using bacterial cell catalyst | |
| CN1224710A (en) | Synthesis of hydrochloride of betaine | |
| CN101603063A (en) | The fixation of microbial cell enzyme process prepares the method for the amino lipid acid of L-2- | |
| CN112358442B (en) | Preparation method of 2-fluoro-5-formyl chloropyridine | |
| CN107445856A (en) | A kind of synthesis technique of N N-isopropylacrylamides | |
| CN107501200B (en) | Organic small molecule with recognition effect on ammonia water, methylamine and aniline and recognition method thereof | |
| CN1944371A (en) | Process for preparing DL-ortho-chloro mandelic acid | |
| CN101676269A (en) | Functionalized united imidazole derivative and synthesizing method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C53 | Correction of patent for invention or patent application | ||
| CB03 | Change of inventor or designer information |
Inventor after: Tian Yunbo Inventor after: Fang Liaoqiong Inventor after: Wang Zhibiao Inventor after: Ye Fangwei Inventor before: Tian Yunbo Inventor before: Wang Zhibiao Inventor before: Ye Fangwei |
|
| COR | Change of bibliographic data |
Free format text: CORRECT: INVENTOR; FROM: TIAN YUNBO WANG ZHIBIAO YE FANGWEI TO: TIAN YUNBO FANG LIAOQIONG WANG ZHIBIAO YE FANGWEI |