CN103450254A - Preparation method of ultralow interfacial tension surfactant used in field of oilfield chemistry - Google Patents
Preparation method of ultralow interfacial tension surfactant used in field of oilfield chemistry Download PDFInfo
- Publication number
- CN103450254A CN103450254A CN201310374583XA CN201310374583A CN103450254A CN 103450254 A CN103450254 A CN 103450254A CN 201310374583X A CN201310374583X A CN 201310374583XA CN 201310374583 A CN201310374583 A CN 201310374583A CN 103450254 A CN103450254 A CN 103450254A
- Authority
- CN
- China
- Prior art keywords
- synthetic
- phosphoric acid
- chloropropane
- acid ester
- reaction
- 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
Abstract
The invention discloses a preparation method of an ultralow interfacial tension surfactant used in the field of oilfield chemistry and in particular discloses a method for preparing a betaine phosphate surfactant. The method comprises the following steps: taking higher aliphatic alcohol, epichlorohydrin and dimethylamine as raw materials and sodium dihydrogen phosphate as a phosphate esterification agent, reacting aliphatic alcohol with epichlorohydrin under alkaline conditions by using a phase transfer catalysis method to obtain alkoxy glycidyl ether, and then reacting alkoxy glycidyl ether with dimethylamine to obtain a reaction intermediate tertiary amine; dropwise adding epichlorohydrin to a sodium dihydrogen phosphate water solution to obtain another intermediate 2-hydroxy-3-chloropropane sodium phosphate, adding a certain proportion of tertiary amine and 2-hydroxy-3-chloropropane sodium phosphate to 70% of ethanol solution, carrying out reflux at 80 DEG C for 8 hours, then filtering out solids while the solution is hot, and cooling the liquid, thus obtaining betaine phosphate. The raw materials used in the method are cheap and accessible, and the method is low in production cost, environment-friendly and high in yield.
Description
Technical field
This invention relates to a kind of preparation method who is applied to the tensio-active agent in oilfield chemistry field, is specifically related to a kind of preparation method of Phosphobetain Surfactants.
Background technology
Trimethyl-glycine is that the center of positive charge majority of amphoterics loads on quaternary ammonium N atom, center of negative charge loads on electronegative acidic-group, according to the type of its acidic-group, is divided into carboxylic acid type, sulfonic acid type, sulfuric acid ester type, sulfurous acid type, phosphate type, phosphite type, phosphonic acids type, phosphonous acid type.The phosphoric acid ester trimethyl-glycine is to have replaced the carboxyl in the carboxylic acid type trimethyl-glycine with phosphate, and the phosphoglyceride that its similar is found in cytolemma is that a kind of toxicity and pungency are low, easily degraded, the amphoterics of excellent property.Trimethyl-glycine is that the synthetic major part of tensio-active agent is that to take long-chain haloalkane or long-chain amine be raw material, but it is expensive, also price is high for derivative amphoterics thus, and this defect has seriously limited the development of the amphoterics of this performance brilliance.
Summary of the invention
The object of the invention is to solve above-mentioned prior art not enough, a kind of method of producing the tensio-active agent with good interface performance with the expensive reagent in the cheap existing method of raw material replacement is provided.
For achieving the above object, the present invention is by the following technical solutions:
A kind of method of the tensio-active agent of the ultra low interfacial tension for the preparation of the oilfield chemistry field comprises following concrete steps:
1) intermediate 2-hydroxyl-3-chloropropane phosphoric acid ester sodium is synthetic
2) the intermediate tertiary amine is synthetic
n=12,14,16
3) the phosphoric acid ester trimethyl-glycine is synthetic
n=12,14,16。
Above-mentioned reaction is carried out in there-necked flask.
Preferably, reaction raw materials is epoxy chloropropane, SODIUM PHOSPHATE, MONOBASIC, hexadecanol, tetradecyl alcohol, the dimethylamine agueous solution of volume fraction 33%.
Preferably, reaction medium is normal hexane, dehydrated alcohol.
Preferably, catalyzer and pH value conditioning agent are phosphoric acid, sodium hydroxide, Tetrabutyl amonium bromide.
The purified rear infrared spectrum characterization of using of products therefrom, prove and generate target product.
Further, described method comprises following concrete steps:
1), intermediate 2-hydroxyl-3-chloropropane phosphoric acid ester sodium is synthetic:
15 parts of SODIUM PHOSPHATE, MONOBASIC,
Epoxy chloropropane 10-15 part,
40 parts of deionized waters,
SODIUM PHOSPHATE, MONOBASIC is dissolved in deionized water, uses the phosphorus acid for adjusting pH value to 4 left and right.Be transferred in there-necked flask, be warmed up to 60-80 ℃ of left and right, epoxy chloropropane slowly is added drop-wise in there-necked flask, vigorous stirring 2h is to without stopped reaction after the oily drop, and underpressure distillation steams most of water, the cooling white crystal of separating out, filtering drying.
2) the intermediate tertiary amine is synthetic
(1) alkyl alcohol is dissolved in a certain amount of normal hexane, add a small amount of Tetrabutyl amonium bromide and a certain amount of strong caustic limit to be warming up to limit, 50-60 ℃ of left and right and slowly drip stopped reaction after epoxy chloropropane reflux 5~7h, underpressure distillation steams the solvent normal hexane, the dry Off-white solid alkyl glycidyl ether that obtains.
(2) add a certain amount of synthetic alkyl glycidyl ether, appropriate solvent dehydrated alcohol and dimethylamine agueous solution in there-necked flask.Be heated to stopped reaction after 65-75 ℃ of left and right stirring and refluxing 1~3h, product divides three layers.With separating funnel separate orlop after the stillness of night underpressure distillation steam solvent and unreacted dimethylamine, dry product tertiary amine.
3) end product phosphoric acid ester trimethyl-glycine is synthetic
To adding appropriate synthetic 2-hydroxyl-3-chloropropane phosphoric acid ester sodium and volume fraction in there-necked flask, be 60% ethanolic soln, dripping NaOH solution, to regulate the pH value be 8-9.Add tertiary amine, be heated to 85 ℃ of back flow reaction 8~10h, after completion of the reaction, filtered while hot goes out solid, and the cooling faint yellow solid of separating out of liquid portion, be final product.
Determine its structure by carrying out the infrared spectra molecule after the intermediate product purifying.Get appropriate product obtain solution, measure its surface tension and and Gudong crude oil between interfacial tension.
Described part is parts by weight.
Advantage of the present invention is: (1) prepared phosphoric acid ester trimethyl-glycine under very low concentration and between crude oil interfacial tension can reach ultralow scope; (2) use raw material cheap and easy to get, production cost is low; (3) prepared phosphoric acid ester trimethyl-glycine toxicity and pungency is low, and easily degraded, be a kind of amophoteric surface active of excellent property.
The accompanying drawing explanation
Fig. 1 is the infrared spectrum that 2-hydroxyl-3-leads propane phosphoric acid ester sodium.
1440cm
-1place is the flexural vibration absorption peak of methylene radical c h bond; 3000-3500cm
-1the stretching vibration absorption peak that broad absorption band is O-H; 1100cm
-1there is the stretching vibration absorption peak that absorption peak is the C-O key left and right; 1200cm
-1there is the stretching vibration absorption peak that absorption peak is phosplate P=O key left and right; 1030-1100cm
-1locating wide absorption peak is the stretching vibration absorption peak of phosplate P-O-C key.
The infrared spectrum that Fig. 2 is tertiary amine.
Be greater than 3000cm
-1place's absorption band is caused by the stretching vibration absorption of OH base; 2700~3000cm
-1place is the stretching vibration absorption peak of methyl methylene radical; 1381~1272cm
-1place is the stretching vibration absorption peak of C-N; 1466cm
-1place has absorption peak further to show to contain methyl and methylene radical; 725cm
-1near have absorption peak to show that methylene radical quantity is greater than 4.
The infrared spectrum that Fig. 3 is the synthetic phosphoric acid ester trimethyl-glycine.
Be greater than 3000cm
-1broad absorption band be the stretching vibration absorption peak of OH key; 2913cm
-1and 2845cm
-1place is the stretching vibration absorption peak 1220cm of CH3 and CH2
-1place is the stretching vibration absorption peak of P=O key; 1086cm
-1near be the stretching vibration absorption peak of C-O key; 1036cm
-1place is the stretching vibration absorption peak of P-O key.
The interfacial tension Dynamic Graph that Fig. 4 is different concns phosphoric acid ester trimethyl-glycine.
Fig. 5 is the dynamic interface tonogram of synthetic phosphoric acid ester trimethyl-glycine under different pH.
Fig. 6 is the dynamic interface tonogram of synthetic phosphoric acid ester trimethyl-glycine under different salinities.
Embodiment
Embodiment 1
(1) accurately take the 12.00g SODIUM PHOSPHATE, MONOBASIC and be dissolved in 40ml distilled water, with phosphoric acid, regulate pH=4, transfer in there-necked flask, be warming up to 30 ℃, slowly drip the 13.87g epoxy chloropropane under whipped state.Be warming up to 85 ℃ after dropwising, reaction 3h, all pour product in beaker and use frozen water cooling, separates out white crystal, filters the final vacuum drying, is intermediate I 2-hydroxyl-3-chloropropane phosphoric acid ester sodium.Weighing, yield is 50.4%.
(2) accurately take in 12.10g hexadecanol and 70ml normal hexane and there-necked flask, add again the 1.29g Tetrabutyl amonium bromide, drip the sodium hydroxide solution of 24g massfraction 50% under whipped state, be warming up to 65 ℃, slowly drip epoxy chloropropane 9.25g, after reaction 5h, underpressure distillation steams normal hexane.Product is the milk yellow solid, and with the hot ethanol washing of volume fraction 95%, the salt produced in the unreacted raw material of elimination and reaction, obtain the product cetyl glycidyl ether.Dry weighing, yield is 92.4%.
Accurately take in 14.90g cetyl glycidyl ether and there-necked flask, dimethylamine solution 12.27g simultaneously that add wherein massfraction 33%, add again dehydrated alcohol 35ml, be warming up to 78 ℃ of reaction 1h after stirring 30min under room temperature, underpressure distillation boils off solvent, obtains faint yellow solid and is intermediate II tertiary amine.Dry weighing, productive rate is 90.1%.
(3) accurately take the 6.86g tertiary amine, 5.52g2-hydroxyl-3-chloropropane phosphoric acid ester sodium, be dissolved in 60ml volume fraction 60% aqueous ethanolic solution, with sodium hydroxide solution, regulates pH=8-9, is warming up to 85 ℃ of back flow reaction 8h in there-necked flask.After completion of the reaction, filtered while hot goes out solid, and the cooling faint yellow solid of separating out of liquid portion with the hot ethanol solution washing several of volume fraction 95%, dries up after filtration after hot blast drying, and the faint yellow dope of gained is final product phosphoric acid ester trimethyl-glycine.Weighing, productive rate is 51.8%.
Embodiment 2
(1) accurately take the 12.00g SODIUM PHOSPHATE, MONOBASIC and be dissolved in 40ml distilled water, with phosphoric acid, regulate pH=4, transfer in there-necked flask, be warming up to 30 ℃, slowly drip the 16.65g epoxy chloropropane under whipped state.Be warming up to 85 ℃ after dropwising, reaction 2h, all pour product in beaker and use frozen water cooling, separates out white crystal, filters the final vacuum drying, is intermediate I 2-hydroxyl-3-chloropropane phosphoric acid ester sodium.Weighing, yield is 54.3%.
(2) accurately take in 12.10g cetyl alcohol and 70ml normal hexane and there-necked flask, add again the 1.29g Tetrabutyl amonium bromide, drip the sodium hydroxide solution of 24g massfraction 50% under whipped state, be warming up to 60 ℃, slowly drip epoxy chloropropane 9.25g, after reaction 6h, underpressure distillation steams normal hexane.Product is the milk yellow solid, and with the hot ethanol washing of volume fraction 95%, the salt produced in the unreacted raw material of elimination and reaction, obtain the product cetyl glycidyl ether.Dry weighing, yield is 95.4%.
Accurately take in 14.90g cetyl glycidyl ether and there-necked flask, dimethylamine solution 12.27g simultaneously that add wherein volume fraction 33%, add again dehydrated alcohol 35ml, be warming up to 7870 ℃ of reaction 1h2h after stirring 30min under room temperature, underpressure distillation boils off solvent, obtains faint yellow solid and is intermediate II tertiary amine.Dry weighing, productive rate is 89.5%.
(3) accurately take the 6.86g tertiary amine, 5.52g2-hydroxyl-3-chloropropane phosphoric acid ester sodium, be dissolved in 60ml volume fraction 60% aqueous ethanolic solution, with sodium hydroxide solution, regulates pH=8-9, is warming up to 80 ℃ of back flow reaction 9h in there-necked flask.After completion of the reaction, filtered while hot goes out solid, and the cooling faint yellow solid of separating out of liquid portion with the hot ethanol solution washing several of volume fraction 95%, dries up after filtration after hot blast drying, and the faint yellow dope of gained is final product phosphoric acid ester trimethyl-glycine.Weighing, productive rate is 51.1%.
(1) accurately take the 12.00g SODIUM PHOSPHATE, MONOBASIC and be dissolved in 40ml distilled water, with phosphoric acid, regulate pH=4, transfer in there-necked flask, be warming up to 30 ℃, slowly drip the 13.87g epoxy chloropropane under whipped state.Be warming up to 85 ℃ after dropwising, reaction 2h, all pour product in beaker and use frozen water cooling, separates out white crystal, filters the final vacuum drying, is intermediate I 2-hydroxyl-3-chloropropane phosphoric acid ester sodium.Weighing, yield is 50.4%.
(2) accurately take in 10.70g tetradecyl alcohol and 70ml normal hexane and there-necked flask, add again the 1.17g Tetrabutyl amonium bromide, drip the sodium hydroxide solution of 24g massfraction 50% under whipped state, be warming up to 65 ℃, slowly drip epoxy chloropropane 9.25g, after reaction 6h, underpressure distillation steams normal hexane.Product is the milk yellow solid, and with the hot ethanol washing of volume fraction 95%, the salt produced in the unreacted raw material of elimination and reaction, obtain the product cetyl glycidyl ether.Dry weighing, yield is 93.5%.
Accurately take in 13.50g tetradecyl glycidyl ether and there-necked flask, dimethylamine solution 12.27g simultaneously that add wherein volume fraction 33%, add again dehydrated alcohol 35ml, be warming up to 78 ℃ of reaction 1h after stirring 30min under room temperature, underpressure distillation boils off solvent, obtains faint yellow solid and is intermediate II tertiary amine.Dry weighing, productive rate is 89.7%.
(3) accurately take the 6.30g tertiary amine, 5.52g2-hydroxyl-3-chloropropane phosphoric acid ester sodium, be dissolved in 60ml volume fraction 60% aqueous ethanolic solution, with sodium hydroxide solution, regulates pH=8-9, is warming up to 85 ℃ of back flow reaction 8h in there-necked flask.After completion of the reaction, filtered while hot goes out solid, and the cooling faint yellow solid of separating out of liquid portion with the hot ethanol solution washing several of volume fraction 95%, dries up after filtration after hot blast drying, and the faint yellow dope of gained is final product phosphoric acid ester trimethyl-glycine.Weighing, productive rate is 54.3%.
Product phosphoric acid ester trimethyl-glycine is made into to the aqueous solution of different concns, measures its surface tension, and with the interfacial tension of Gudong crude oil under different condition.As seen from Figure 4, concentration is that interfacial tension between 0.05% this tensio-active agent and Gudong crude oil can reach ultralow scope its interfacial tension when concentration is between 0.075% and 0.1% and can reach 10 70 ℃ the time
-4the mN/m level; Fig. 5 can find out that the effect of this tensio-active agent under neutral meta-alkalescence condition better can reach 10
-4the mN/m level, Fig. 6 can find out that the solution salinity is when 1000ppm is following, between synthetic surfactant and shareholder's crude oil, interfacial tension can remain in ultralow scope.
Claims (5)
1. the method for the tensio-active agent of the ultra low interfacial tension for the preparation of the oilfield chemistry field comprises following concrete steps:
1) intermediate 2-hydroxyl-3-chloropropane phosphoric acid ester sodium is synthetic:
2) the intermediate tertiary amine is synthetic:
n=12,14,16;
3) the phosphoric acid ester trimethyl-glycine is synthetic:
n=12,14,16。
2. the dimethylamine agueous solution that the method for claim 1, wherein reaction raw materials is epoxy chloropropane, SODIUM PHOSPHATE, MONOBASIC, hexadecanol, tetradecyl alcohol and volume fraction 33%.
3. the method for claim 1, wherein reaction medium is normal hexane and/or dehydrated alcohol.
4. the method for claim 1, wherein catalyzer and pH value conditioning agent are phosphoric acid, sodium hydroxide and/or Tetrabutyl amonium bromide.
5. the method for claim 1, wherein described method comprises following concrete steps:
(1), intermediate 2-hydroxyl-3-chloropropane phosphoric acid ester sodium is synthetic:
15 parts of SODIUM PHOSPHATE, MONOBASIC,
Epoxy chloropropane 10-15 part,
40 parts of deionized waters,
SODIUM PHOSPHATE, MONOBASIC is dissolved in deionized water, with phosphorus acid for adjusting pH value to 4, be transferred in there-necked flask, be warmed up to 60-80 ℃, epoxy chloropropane slowly is added drop-wise in there-necked flask, and vigorous stirring 2h is to without stopped reaction after the oily drop, and underpressure distillation steams most of water, the cooling white crystal of separating out, filtering drying;
(2) the intermediate tertiary amine is synthetic
A. alkyl alcohol is dissolved in normal hexane, add Tetrabutyl amonium bromide and sodium hydroxide solution limit to be warming up to 50-60 ℃ of limit and slowly drip stopped reaction after epoxy chloropropane reflux 5~7h, underpressure distillation steams the solvent normal hexane, the dry Off-white solid alkyl glycidyl ether that obtains;
B. add synthetic alkyl glycidyl ether, solvent dehydrated alcohol and dimethylamine agueous solution in there-necked flask, be heated to stopped reaction after 65-75 ℃ of left and right stirring and refluxing 1~3h, product divides three layers, with separating funnel separate orlop after the stillness of night underpressure distillation steam solvent and unreacted dimethylamine, dry product tertiary amine;
C. end product phosphoric acid ester trimethyl-glycine is synthetic
To adding synthetic 2-hydroxyl-3-chloropropane phosphoric acid ester sodium and volume fraction in there-necked flask, it is 60% ethanolic soln, dripping NaOH solution adjusting pH value is 8-9, add tertiary amine, be heated to 85 ℃ of back flow reaction 8~10h, after completion of the reaction, filtered while hot goes out solid, the cooling faint yellow solid of separating out of liquid portion, be final product, described part is parts by weight.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201310374583XA CN103450254A (en) | 2013-08-23 | 2013-08-23 | Preparation method of ultralow interfacial tension surfactant used in field of oilfield chemistry |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201310374583XA CN103450254A (en) | 2013-08-23 | 2013-08-23 | Preparation method of ultralow interfacial tension surfactant used in field of oilfield chemistry |
Publications (1)
Publication Number | Publication Date |
---|---|
CN103450254A true CN103450254A (en) | 2013-12-18 |
Family
ID=49733134
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201310374583XA Pending CN103450254A (en) | 2013-08-23 | 2013-08-23 | Preparation method of ultralow interfacial tension surfactant used in field of oilfield chemistry |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN103450254A (en) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106957331A (en) * | 2017-04-17 | 2017-07-18 | 中国石油大学(华东) | A kind of phosphate betaine type polymer-containing sewage in oil field efficient germicide and preparation method thereof |
CN107456917A (en) * | 2017-07-28 | 2017-12-12 | 中国海洋石油总公司 | The preparation method of double cropping ammonium cation Gemini surface active and the surfactant solution for including it |
CN108299571A (en) * | 2017-01-11 | 2018-07-20 | 南京华狮新材料有限公司 | A kind of derivatives of hyaluronic acids and the preparation method and application thereof |
CN109438507A (en) * | 2018-12-10 | 2019-03-08 | 如皋市万利化工有限责任公司 | A kind of preparation process of the third sodium phosphate of 2- hydroxyl -3- chlorine |
CN112321445A (en) * | 2020-11-25 | 2021-02-05 | 华南理工大学 | Synthesis method of amide derivative |
CN114716338A (en) * | 2022-05-23 | 2022-07-08 | 西南石油大学 | Synthesis and preparation method of amphoteric betaine Gemini surface active agent type hydrophobic monomer |
-
2013
- 2013-08-23 CN CN201310374583XA patent/CN103450254A/en active Pending
Non-Patent Citations (2)
Title |
---|
LANPING NONG,ET AL.: "Physicochemical Properties of Novel Phosphobetaine Zwitterionic Surfactants and Mixed Systems with an Anionic Surfactant", 《J SURFACT DETERG》 * |
农兰平 等: "3-[N-(3-烷氧基-2-羟基丙基)-N,N-二甲基铵]-2-羟基丙基酸性磷酸酯甜菜碱的合成", 《化学世界》 * |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108299571A (en) * | 2017-01-11 | 2018-07-20 | 南京华狮新材料有限公司 | A kind of derivatives of hyaluronic acids and the preparation method and application thereof |
CN106957331A (en) * | 2017-04-17 | 2017-07-18 | 中国石油大学(华东) | A kind of phosphate betaine type polymer-containing sewage in oil field efficient germicide and preparation method thereof |
CN107456917A (en) * | 2017-07-28 | 2017-12-12 | 中国海洋石油总公司 | The preparation method of double cropping ammonium cation Gemini surface active and the surfactant solution for including it |
CN107456917B (en) * | 2017-07-28 | 2020-02-07 | 中国海洋石油集团有限公司 | Preparation method of double quaternary ammonium cation Gemini surfactant and surfactant solution containing same |
CN109438507A (en) * | 2018-12-10 | 2019-03-08 | 如皋市万利化工有限责任公司 | A kind of preparation process of the third sodium phosphate of 2- hydroxyl -3- chlorine |
CN112321445A (en) * | 2020-11-25 | 2021-02-05 | 华南理工大学 | Synthesis method of amide derivative |
CN114716338A (en) * | 2022-05-23 | 2022-07-08 | 西南石油大学 | Synthesis and preparation method of amphoteric betaine Gemini surface active agent type hydrophobic monomer |
CN114716338B (en) * | 2022-05-23 | 2023-09-22 | 西南石油大学 | Synthesis and preparation method of amphoteric betaine Gemini surfactant type hydrophobic monomer |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN103450254A (en) | Preparation method of ultralow interfacial tension surfactant used in field of oilfield chemistry | |
KR100958876B1 (en) | Ionic liquids miscible with various polar/non-polar solvents and method for preparing the same | |
CN102516093A (en) | Gemini type asphalt emulsifier and preparation method thereof | |
WO2021047588A1 (en) | Tall oil fatty acid imidazoline sulfonate surfactant and preparation method therefor | |
EP3186217A2 (en) | Polyethers, polyamines, polythioethers, and methods for making same | |
CN102120728A (en) | Sulfonic- functionalized caprolactam acidic ion liquid and preparation method thereof | |
CN102503863A (en) | Dialkyl ether disulfonate surfactant and preparation method thereof | |
CN110721634A (en) | Tall oil fatty acid imidazoline sulfonate surfactant and preparation method thereof | |
CN103880676B (en) | A kind of preparation method of dodecyl nipagin ester | |
CN110694546A (en) | Tall oil fatty acid imidazoline sulfonate surfactant and preparation method thereof | |
CN102531971A (en) | Preparation method of alpha-N,N-dialkyl oxyamino fatty acid surfactant | |
CN102516971B (en) | Block polyether zwitterionic heavy oil emulsified viscosity reducer and preparation method thereof | |
CN105085980A (en) | Synthesis of citric acid ether ester plasticizer | |
CN101796007A (en) | Processes for making dibutyl ethers from 2-butanol | |
CN105026356A (en) | Use of sulphonic acid for recovering glycerol from a triglyceride transesterification reaction | |
CN101780381B (en) | N-alkylasparagine surfactant and preparation method thereof | |
CN102351749B (en) | Benzenesulphonate anionic gemini surfactant and preparation method thereof | |
CN103319312A (en) | Joint production process of antioxidant 264 and 6-tertiary butyl m-cresol | |
CN102676143A (en) | Fatty alcohol-polyoxyethylene ether propionate surfactant and preparation method thereof and application thereof to tertiary recovery | |
CN113402549B (en) | Preparation method of glyphosate raw medicine | |
CN104610351A (en) | Nitrogen-phosphorus type natural gas drag reducer and synthesis method thereof | |
CN102807495A (en) | 3-chlorine-2-hydroxypropyl dimethyl dehydroabietic-base ammonium chloride and preparation method thereof | |
CN103122242A (en) | Preparation method and application of surfactant for oil recovery | |
CN103951702B (en) | 1,1 '-dialkyl group-3, the preparation method of salt compound in 3 '-(2-phosphate-1,3-propylidene) imidazoles | |
CN103012475B (en) | A kind of preparation method of glyphosate |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20131218 |