CN102531971A - Preparation method of alpha-N,N-dialkyl oxyamino fatty acid surfactant - Google Patents
Preparation method of alpha-N,N-dialkyl oxyamino fatty acid surfactant Download PDFInfo
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- CN102531971A CN102531971A CN2011104457506A CN201110445750A CN102531971A CN 102531971 A CN102531971 A CN 102531971A CN 2011104457506 A CN2011104457506 A CN 2011104457506A CN 201110445750 A CN201110445750 A CN 201110445750A CN 102531971 A CN102531971 A CN 102531971A
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Abstract
The invention discloses a preparation method of an alpha-N,N-dialkyl oxyamino fatty acid surfactant. The method comprises the following steps: allowing alpha-halogenated fatty acid and lower secondary amine to carry out an aminolysis at ambient pressure or in an autoclave to obtain alpha-N,N-dialkyl amino fatty acid; and oxidating by hydrogen peroxide to prepare the alpha-N,N-dialky oxyamino fatty acid surfactant. The oxyamino surfactants are widely used in industries such as tableware detergent, personal care, cosmetic, textile and the like, due to the excellent surface activity, the excellent foaming and foam stabilizing properties, the emulsifying property, the good biodegradation property and low-toxicity and low irritation to human body of the oxyamino surfactants. In the method of the invention, the main raw material is derived from fatty acid which is cheap and easily accessible, and thus the situation that the use amount of the oxyamino surfactants is limited in formula products due to the expensive price will be greatly improved.
Description
Technical field
The present invention relates to a kind of is raw material with alpha-halogen lipid acid, and earlier with rudimentary secondary amine generation aminolysis reaction, through the synthetic α-N of hydrogen peroxide oxidation, N-dialkyl group oxidation amido lipid acid method belongs to the organic cpds synthesis technical field again.
Background technology
The tensio-active agent that contains the amine oxide group is used owing to the irreplaceable premium properties of other type list surface-active agent has widely.
The synthetic tensio-active agent usual method that contains the amine oxide group is to prepare fat tertiary amine by the fatty alcohol catalyzing amination, makes long-chain alkyl amine oxide through the hydrogen peroxide oxidation again.Because the fatty alcohol catalyzing amination prepares the catalyzer that the synthesis technique of fat tertiary amine requires high temperature, highly selective, high reactivity and high stability; Make that the synthetic cost of fat tertiary amine is higher; Thereby make the price of amine oxide surfactant far above other type list surface-active agent, the consumption in formulation product is restricted.
Summary of the invention
The purpose of this invention is to provide a kind of is that raw material obtains α-N, the preparation method of N-dialkyl group oxidation amido lipid acid tensio-active agent through two step simple reactions by alpha-halogen lipid acid.
Technical scheme of the present invention: with alpha-halogen lipid acid is raw material; In normal pressure reactor or pressure thermal response still, carry out aminolysis reaction with excessive rudimentary secondary amine; Decompression removes the rudimentary secondary amine of unreacted behind the reaction certain hour; To proper pH value, in solution, separate out highly purified intermediate product α-N with hydrochloric acid conditioning solution, N-dialkyl amino lipid acid.With intermediate product α-N; N-dialkyl amino lipid acid mixes with EDTA disodium salt and Hydrocerol A; Add hydrogen peroxide and carry out oxidizing reaction; Reaction finishes the back and adds the hydrogen peroxide that an amount of S-WAT is removed remnants, makes α-N of 20 ~ 40%, N-dialkyl group oxidation amido lipid acid surfactant soln.
Concrete building-up process is following:
Alpha-halogen lipid acid and rudimentary secondary amine feed intake by the mol ratio of 1:2 ~ 8 in normal pressure reactor or pressure thermal response still; 40-120 ℃ of following constant temperature stirred 2-12 hour; Decompression removes the rudimentary secondary amine of unreacted; With hydrochloric acid conditioning solution pH to slightly acidic, intermediate product α-N, N-dialkyl amino lipid acid is by separating out in the solution.
In the reactor drum that has constant temperature, stirring and constant pressure arrangement; With α-N; N-dialkyl amino lipid acid, EDTA disodium salt and Hydrocerol A feed intake by 100:0.05:0.05 ~ 100:4:4 mass ratio; Keep-uping pressure under the constant temperature in the 20-60 ℃ of scope dropwise adds hydrogen peroxide, is heated to 60-90 ℃ of constant temperature stirring reaction 4-10 hour.Solution is cooled to room temperature, adds an amount of S-WAT and removes remaining hydrogen peroxide.Make α-N of 20 ~ 40%, N-dialkyl group oxidation amido lipid acid surfactant soln.
R is C in the reaction formula
1~ C
30Saturated or unsaturated, straight or branched, single carbon or mix the alkyl of carbon; X is Cl, Br or I; R
1, R
2For alkyl or alcohol saturated or unsaturated, straight or branched, promptly has general formula C
nH
2n ± 1O
mFatty Alcohol(C12-C14 and C12-C18), n=1 wherein, 2 or 3, m=0,1,2, or 3.
Beneficial effect of the present invention:
(1) to adopt alpha-halogen lipid acid be raw material in the present invention, with rudimentary secondary amine reaction, again through the synthetic α-N of oxidation two-step reaction, N-dialkyl group oxidation amido lipid acid.The technology for preparing amine oxide surfactant with the expensive long chain tertiary amine oxidation of common employing is compared, and reduces the production cost of the tensio-active agent that has the oxidation amido significantly, and reaction conditions is gentle, and technical process is simple.
(2) α-N of the present invention's exploitation; N-dialkyl group oxidation amido lipid acid tensio-active agent contains carboxyl and two kinds of polar groups of amine oxide; Make such surfactivity not only have the high surface of amine oxide type tensio-active agent; And having more excellent foaming and foam stability ability, emulsifying property significantly strengthens.
Embodiment
Embodiment 1 α-N, N-dimethyl-oxidation amido propionic acid synthetic
The alpha-chloro propionic acid and the n n dimetylaniline (30% aqueous solution) that contains 0.20mol that in the normal pressure reactor that has TM and magnetic agitation, add 0.10mol; Oil bath constant temperature to 40 ℃, stirring reaction 2h is after reaction finishes; PH=12 with 2mol/L NaOH regulator solution; Reduction vaporization is removed the unreacted n n dimetylaniline, and with hydrochloric acid conditioning solution pH to 5.0, synthetic intermediate is separated out from solution.Through suction filtration, washing, drying, obtain solid α-N, TMSDMA N dimethylamine base propionic acid, yield 63.2%.
In the four-hole boiling flask that TM, constant pressure funnel, stirring, reflux are housed, add 500 g α-N, TMSDMA N dimethylamine base propionic acid 0.250 g EDTA disodium salt, 0.250 g Hydrocerol A; 20 ℃ dripped 6.610g 30% hydrogen peroxide solution in following 30 minutes, and after dropwising, elevated temperature to 60 ℃ continues reaction 6h; The pH=5.5 of regulator solution; Obtain 38% α-N, the sad aqueous solution of N-dimethyl-oxidation amido, productive rate 63.2%.
Synthesizing of embodiment 2 α-N-methyl-N-hydroxyethyl oxidation amido capric acid
In the normal pressure reactor that has TM and magnetic agitation, add the alpha-chloro capric acid of 0.10mol and the methyl monoethanolamine aqueous solution of 0.80mol, stir 12h, after reaction finishes in 90 ℃ of waters bath with thermostatic control; With pH=11 ~ 12 of sodium hydrate regulator solution, reduction vaporization is removed unreacted methyl monoethanolamine, with hydrochloric acid conditioning solution pH to 5.4; Synthetic intermediate is separated out from solution, through suction filtration, washing, drying, obtain solid α-; N-methyl-N-hydroxyethyl capric acid, yield 65.8%.
In the four-hole boiling flask that TM, constant pressure funnel, stirring, reflux are housed; Add 0.04 mol α-N-methyl-N-hydroxyethyl capric acid, 0.502 g EDTA disodium salt, 0.750 g Hydrocerol A, control bath temperature to 40 ~ 45 ℃ drip 6.812g 30% hydrogen peroxide solution down, after dropwising in 30 minutes; Elevated temperature to 90 ℃ continuation reaction 10h; Reaction is cooled to room temperature, the pH=5.5 of regulator solution after finishing; Obtain 40% α-N-methyl-N-hydroxyethyl oxidation amido capric acid aqueous solution, productive rate 85.7%.
Embodiment 3 α-N, N-dimethyl-oxidation amido laurostearic acid synthetic
In having the pressure thermal reactor of heating, temperature control, stirring, add the alpha-chloro laurostearic acid of 0.15mol and contain the n n dimetylaniline (30% aqueous solution) of 0.75mol, tighten kettle cover rapidly, 90 ℃ of constant temperature stirring reaction 10h; After reaction finished, with pH=11 ~ 12 of 2mol/L NaOH regulator solution, reduction vaporization was removed the unreacted n n dimetylaniline; With hydrochloric acid conditioning solution pH to 5.7, midbody is separated out from solution, through suction filtration, washing, drying; Obtain solid α-N, TMSDMA N dimethylamine base laurostearic acid, yield 86.7%.With 80% ethanolic soln recrystallization, vacuum-drying obtains the α-N of purifying, N-dimethyl amido capric acid solid.
In the four-hole boiling flask that TM, constant pressure funnel, stirring, reflux are housed, add 12.5g α-N, TMSDMA N dimethylamine base laurostearic acid, 0.501g EDTA disodium salt, 0.498 g Hydrocerol A; With the pH=8.0 of sodium hydroxide solution regulator solution, control bath temperature to 60 ℃ drips 8.801g 30% hydrogen peroxide solution down, drips 8.610g 30% hydrogen peroxide solution in 30 minutes; After dropwising, elevated temperature to 75 ℃ continuation reaction 7h is after reaction finishes; Be cooled to room temperature, the pH=5.6 of regulator solution obtains 30% a-N; The N-dimethyl-oxidation amido laurostearic acid aqueous solution, productive rate 82.4%.From solution, extract α-N with chloroform, N-dimethyl-oxidation amido is sad, and vacuum rotary steam reclaims chloroform; The solid that obtains is used the acetone soln recrystallization; In vacuum-drying, deposit a small amount of Vanadium Pentoxide in FLAKES and carry out vacuum-drying, obtain the α-N of purifying, N-dimethyl-oxidation amido laurostearic acid solid.
Embodiment 4 α-N, N-dipropyl oxidation amido palmitic acid synthetic
In the potheater that heating, stirring, temperature control system are housed, add the alpha-brominated palmitic acid and the dipropylamine that contains 0.50mol of 0.10mol, tighten kettle cover rapidly, 100 ℃ of constant temperature stirring reaction 8h; After reaction finished, with pH=11 ~ 12 of 2mol/L NaOH regulator solution, reduction vaporization was removed the unreacted n n dimetylaniline; With hydrochloric acid conditioning solution pH to 5.4, midbody is separated out from solution, through suction filtration, washing, drying; Obtain solid α-N, N-dipropyl amido laurostearic acid, yield 81.7%.Purification step is with embodiment 3.
In the four-hole boiling flask that TM, constant pressure funnel, stirring, reflux are housed, add 0.05 mol α-N, N-dipropyl amido palmitic acid, 1.500g EDTA disodium salt, 0.501 g Hydrocerol A; After reaction finished, with the pH=8.2 of sodium hydroxide solution regulator solution, control bath temperature to 55 ~ 60 are dropping 8.801g 30% hydrogen peroxide solution ℃ down; Dripped 8.610g 30% hydrogen peroxide solution in 30 minutes, after dropwising, elevated temperature to 70 ℃ continuation reaction 12h; Reaction is cooled to room temperature, the pH=5.6 of regulator solution after finishing; Obtain 30% a-N, the N-dipropyl oxidation amido palmitic acid aqueous solution, productive rate 90.5%.Purification step is with embodiment 3.
Embodiment 5 α-N, N-dimethyl-oxidation amido mixed fatty acid synthetic
In the potheater that heating, stirring, temperature control system are housed, add the alpha-brominated coconut oil and the n n dimetylaniline (30% aqueous solution) that contains 0.60mol of 0.10mol, tighten kettle cover rapidly; 105 ℃ of constant temperature stirring reaction 10h are after reaction finishes, with pH=11 ~ 12 of 2mol/L NaOH regulator solution; Reduction vaporization is removed the unreacted n n dimetylaniline, and with hydrochloric acid conditioning solution pH to 6.0, midbody is separated out from solution; Through suction filtration, washing, drying; Obtain solid α-N, TMSDMA N dimethylamine base coconut oil, yield 89.3%.Purification step is with embodiment 3.
In the four-hole boiling flask that TM, constant pressure funnel, stirring, reflux are housed, add 0.04 mol α-N, TMSDMA N dimethylamine base coconut oil, 1.502g EDTA disodium salt, 0.803 g Hydrocerol A; After reaction finished, with the pH=8.5 of sodium hydroxide solution regulator solution, control bath temperature to 55 ~ 60 are dropping 8.801g 30% hydrogen peroxide solution ℃ down; Dripped 8.610g 30% hydrogen peroxide solution in 30 minutes, after dropwising, elevated temperature to 70 ℃ continuation reaction 12h; Reaction is cooled to room temperature, the pH=6.0 of regulator solution after finishing; Obtain 32% a-N, the N-dimethyl-oxidation amido palmitic acid aqueous solution, productive rate 90.7%.Purification step is with embodiment 3.
Embodiment 6 α-N, N-dimethyl-oxidation amido myricyl acid synthetic
In the potheater that heating, stirring, temperature control system are housed, the alpha-iodine that adds 0.10mol contains the n n dimetylaniline (30% aqueous solution) of 0.80mol for myricyl acid (alpha-iodine is for triacontanoic acid); 0.10mol particulate state sodium hydroxide, tighten kettle cover rapidly, 120 ℃ of constant temperature stirring reaction 12h; After reaction finished, with pH=11 ~ 12 of 2mol/L NaOH regulator solution, reduction vaporization was removed the unreacted n n dimetylaniline; With hydrochloric acid conditioning solution pH to 6.5, midbody is separated out from solution, through suction filtration, washing, drying; Obtain solid α-N, TMSDMA N dimethylamine base myricyl acid, yield 80.7%.
In the four-hole boiling flask that TM, constant pressure funnel, stirring, reflux are housed, add 0.05 mol α-N, TMSDMA N dimethylamine base myricyl acid, 10.800g EDTA disodium salt, 15.030 g Hydrocerol As; After reaction finished, with the pH=8.8 of sodium hydroxide solution regulator solution, control bath temperature to 55 ~ 60 are dropping 8.801g 30% hydrogen peroxide solution ℃ down; Dripped 9.065g 30% hydrogen peroxide solution in 30 minutes, after dropwising, elevated temperature to 70 ℃ continuation reaction 12h; Reaction is cooled to room temperature, the pH=5.6 of regulator solution after finishing; Obtain 30% a-N, the N-dimethyl-oxidation amido myricyl acid aqueous solution, productive rate 86.2%.
Claims (4)
1. α-N; The preparation method of N-dialkyl group oxidation amido lipid acid tensio-active agent; It is characterized in that with alpha-halogen lipid acid being that raw material prepares α-N through aminolysis, oxidation two step simple reactions, N-dialkyl group oxidation amido lipid acid tensio-active agent, synthetic route is following:
Alpha-halogen lipid acid and rudimentary secondary amine feed intake by the mol ratio of 1:2 ~ 8 in normal pressure reactor or pressure thermal response still; 40-120 ℃ of following constant temperature stirred 2-12 hour; Decompression removes the rudimentary secondary amine of unreacted; With hydrochloric acid conditioning solution pH to slightly acidic, intermediate product α-N, N-dialkyl amino lipid acid is by separating out in the solution;
In the reactor drum that has constant temperature, stirring and constant pressure arrangement; With α-N; N-dialkyl amino lipid acid, EDTA disodium salt and Hydrocerol A feed intake by 100:0.05:0.05 ~ 100:4:4 mass ratio; Constant temperature dropwise adds hydrogen peroxide in the 20-60 ℃ of scope, is heated to 60-90 ℃ of constant temperature stirring reaction 4-10 hour; Solution is cooled to room temperature, adds S-WAT and removes remaining hydrogen peroxide; Make α-N of 20 ~ 40%, N-dialkyl group oxidation amido lipid acid surfactant soln.
2. α-N according to claim 1, the preparation method of N-dialkyl group oxidation amido lipid acid tensio-active agent is characterized in that described synthetic surfactant has following structure:
R is C in the formula
1~ C
30Saturated or unsaturated, straight or branched, single carbon or mix the alkyl of carbon; R
1, R
2Be alkyl or alcohol saturated or unsaturated, straight or branched.
3. α-N according to claim 1, the preparation method of N-dialkyl group oxidation amido lipid acid tensio-active agent is characterized in that described halogenated aliphatic acid representes with following general formula:
R is C in the formula
1~ C
30Saturated or unsaturated, straight or branched, single carbon or mix the alkyl of carbon; X is Cl, Br or I.
4. α-N according to claim 1, the preparation method of N-dialkyl group oxidation amido lipid acid tensio-active agent is characterized in that described rudimentary secondary amine representes with following general formula:
In the formula, R
1, R
2For alkyl or alcohol saturated or unsaturated, straight or branched, promptly has general formula C
nH
2n ± 1O
mFatty Alcohol(C12-C14 and C12-C18), n=1 wherein, 2 or 3, m=0,1,2 or 3.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103086927A (en) * | 2012-12-06 | 2013-05-08 | 广西民族大学 | Tertiary amine oxide with rosinyl three-membered phenanthrene ring structure and preparation method of tertiary amine oxide |
| CN108210354A (en) * | 2016-12-22 | 2018-06-29 | 江南大学 | A kind of disposable nourishing pack of moisturizing |
| CN109721511A (en) * | 2019-01-21 | 2019-05-07 | 北京工商大学 | A kind of preparation method of the Shuangzi amine oxide of the ethyl of ester group containing alkyl |
| CN113122196A (en) * | 2019-12-30 | 2021-07-16 | 中石化石油工程技术服务有限公司 | High-temperature-resistant pH response type wetting agent and preparation and application methods thereof |
| CN113122191A (en) * | 2019-12-30 | 2021-07-16 | 中石化石油工程技术服务有限公司 | pH response type wetting agent and preparation and application methods thereof |
| CN114276272A (en) * | 2021-12-03 | 2022-04-05 | 江南大学 | Method for producing fullerene water-soluble derivative and recovering triethanolamine oxide |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2159967A (en) * | 1938-04-15 | 1939-05-30 | Du Pont | Oxides of amino acids |
| US4397776A (en) * | 1981-03-17 | 1983-08-09 | The Procter & Gamble Company | Liquid detergent compositions containing alpha-amine oxide surfactants |
| CN1803269A (en) * | 2005-12-01 | 2006-07-19 | 江南大学 | Preparation method of alpha-alkyl betaine amphoteric surfactant |
| CN101108814A (en) * | 2007-07-24 | 2008-01-23 | 王伟松 | Method of synthesizing axungia alkyl dimethyl group amine oxide |
-
2011
- 2011-12-28 CN CN201110445750.6A patent/CN102531971B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2159967A (en) * | 1938-04-15 | 1939-05-30 | Du Pont | Oxides of amino acids |
| US4397776A (en) * | 1981-03-17 | 1983-08-09 | The Procter & Gamble Company | Liquid detergent compositions containing alpha-amine oxide surfactants |
| CN1803269A (en) * | 2005-12-01 | 2006-07-19 | 江南大学 | Preparation method of alpha-alkyl betaine amphoteric surfactant |
| CN101108814A (en) * | 2007-07-24 | 2008-01-23 | 王伟松 | Method of synthesizing axungia alkyl dimethyl group amine oxide |
Non-Patent Citations (2)
| Title |
|---|
| 倪沛洲等: "《有机化学》", 31 August 2003, 人民卫生出版社 * |
| 刘书秀: "氧化胺的制备、性质及应用", 《河北化工》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103086927A (en) * | 2012-12-06 | 2013-05-08 | 广西民族大学 | Tertiary amine oxide with rosinyl three-membered phenanthrene ring structure and preparation method of tertiary amine oxide |
| CN103086927B (en) * | 2012-12-06 | 2014-11-26 | 广西民族大学 | Tertiary amine oxide with rosinyl three-membered phenanthrene ring structure and preparation method of tertiary amine oxide |
| CN108210354A (en) * | 2016-12-22 | 2018-06-29 | 江南大学 | A kind of disposable nourishing pack of moisturizing |
| CN109721511A (en) * | 2019-01-21 | 2019-05-07 | 北京工商大学 | A kind of preparation method of the Shuangzi amine oxide of the ethyl of ester group containing alkyl |
| CN113122196A (en) * | 2019-12-30 | 2021-07-16 | 中石化石油工程技术服务有限公司 | High-temperature-resistant pH response type wetting agent and preparation and application methods thereof |
| CN113122191A (en) * | 2019-12-30 | 2021-07-16 | 中石化石油工程技术服务有限公司 | pH response type wetting agent and preparation and application methods thereof |
| CN113122191B (en) * | 2019-12-30 | 2022-10-25 | 中石化石油工程技术服务有限公司 | Application method of pH response type wetting agent |
| CN113122196B (en) * | 2019-12-30 | 2022-10-25 | 中石化石油工程技术服务有限公司 | High-temperature-resistant pH-responsive wetting agent and preparation and application methods thereof |
| CN114276272A (en) * | 2021-12-03 | 2022-04-05 | 江南大学 | Method for producing fullerene water-soluble derivative and recovering triethanolamine oxide |
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