CN104262602A - Aryl alkyl carboxylic acid polyoxypropylene polyoxyethylene block copolymer, and preparation method and application thereof - Google Patents
Aryl alkyl carboxylic acid polyoxypropylene polyoxyethylene block copolymer, and preparation method and application thereof Download PDFInfo
- Publication number
- CN104262602A CN104262602A CN201410466418.1A CN201410466418A CN104262602A CN 104262602 A CN104262602 A CN 104262602A CN 201410466418 A CN201410466418 A CN 201410466418A CN 104262602 A CN104262602 A CN 104262602A
- Authority
- CN
- China
- Prior art keywords
- acid
- carboxylic acids
- carboxylic acid
- preparation
- aryl alkyl
- 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
- Polyethers (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses an aryl alkyl carboxylic acid polyoxypropylene polyoxyethylene block copolymer, which comprises a structure represented by the general formula I. A preparation method comprises the following steps of: alkylating alkenyl carboxylic acid with aromatic hydrocarbon to obtain aryl alkyl carboxylic acid, carrying out ring-opening reaction on aryl alkyl carboxylic acid and epoxypropane to obtain aryl alkyl carboxylic acid polyoxypropylene ester, and carrying out ethoxylation reaction on aryl alkyl carboxylic acid polyoxypropylene ester and ethylene oxide to obtain the aryl alkyl carboxylic acid polyoxypropylene polyoxyethylene block copolymer. The aryl alkyl carboxylic acid polyoxypropylene polyoxyethylene block copolymer disclosed by the invention can be used in the fields, such as emulsion of residual oil, viscosity reduction of thickened oil, pour point depression of heavy oil, preparation of nano-emulsion, tertiary oil recovery, daily-use chemical industry and the like.
Description
Technical field
The present invention relates to a kind of arylalkyl carboxylic acids's polyoxyethylene polyoxypropylene segmented copolymer and its preparation method and application.
Background technology
Fatty acid polyglycol oxypropylene polyoxyethylene block copolymer is the novel nonionogenic tenside of a class, owing to have employed polyoxyethylene polyoxypropylene block copolymeric structure, makes it use as emulsifying agent and have unique application performance in fields such as oil productions.
The direct-connected alkyl structure of fatty acid polyglycol oxypropylene polyoxyethylene block copolymer with there is alkane, aromatic hydrocarbons, colloid differ comparatively large with the performance of crude oils of bituminous matter component, therefore, some performance index is often unsatisfactory.
The chemical composition of usual crude oil is alkane, aromatic hydrocarbon, resin and asphalt.List the fractions consisting of Daqing crude oil and some crude oil of China below, in table 1 and table 2.
Table 1 Daqing oil field crude oil forms
Some crude oil fractions consistings of table 2 China
There is the carboxylic acid polyoxyethylene polyoxypropylene segmented copolymer of arylalkyl structure, in the emulsification, viscosity reduction, pour point depression etc. of crude oil, viscous crude, residual oil, performance can be more outstanding, is also with a wide range of applications in fields such as tertiary oil recovery, low permeability oil field exploitations simultaneously.
Summary of the invention
Object of the present invention aims to provide a kind of arylalkyl carboxylic acids's polyoxyethylene polyoxypropylene segmented copolymer, has formula I structure:
Wherein: m+n is 0,1,2 ... 28,29,30 positive integers;
P is 1,2 ... 4998,4999,5000 positive integers;
Q is 0,1,2 ... 4998,4999,5000 positive integers;
R is phenyl, tolyl, m-xylene base, p-Xylol base, o-Xylol base, ethylbenzene, n-propyl phenyl, isopropyl phenyl, n-butylphenyl, isobutyl phenenyl, tert-butyl-phenyl, naphthyl, methyl naphthyl, dimethyl naphthyl, ethyl naphthyl, propyl group naphthyl, butyl naphthyl, xenyl, the one in phenylol.
Further, in technique scheme, m+n is preferably the positive integer of 8,15,19, is more preferably 15,
Further, in technique scheme, p is preferably 5,6 ... 49,50 positive integers,
Further, in technique scheme, q is preferably 5,6 ... 49,50 positive integers,
Further, in technique scheme, R is preferably m-xylene.
Another object of the present invention is to provide the preparation method of above-mentioned arylalkyl carboxylic acids's polyoxyethylene polyoxypropylene segmented copolymer, and technical scheme is:
Under an acidic catalyst effect, by alkene-carboxylic acid and aromatic hydrocarbon alkylation, obtain arylalkyl carboxylic acids;
Again arylalkyl carboxylic acids and propylene oxide are carried out ring-opening reaction under acidity or basic catalyst effect, obtain arylalkyl carboxylic acids's polyoxypropylene ester, arylalkyl carboxylic acids's polyoxypropylene ester carries out ethoxylation with oxyethane again under acidity or basic catalyst effect, obtains arylalkyl carboxylic acids's polyoxyethylene polyoxypropylene segmented copolymer;
Further, in technique scheme, the an acidic catalyst that preparation arylalkyl carboxylic acids of the present invention is used, for any one or a few mixture in the trifluoromethanesulfonic acid root of sulfuric acid, hydrofluoric acid, methylsulphonic acid, trifluoromethanesulfonic acid, metal salts of trifluoromethane sulphonic acid or load, heteropolyacid, solid super-strong acid, acid zeolite, perfluorinated resin, ionic liquid, the trifluoromethanesulfonic acid root of preferable methyl sulfonic acid, metal salts of trifluoromethane sulphonic acid or load, more preferably methylsulphonic acid.
Further, in technique scheme, ring-opening reaction or ethylation reaction an acidic catalyst used are selected from BF
3, SbCI
5, SnCI
4, solid acid, heteropolyacid, one in carried molecular sieve catalyst, basic catalyst used is selected from the one in potassium hydroxide, sodium hydroxide, sodium methylate, sodium ethylate, Mg/AI composite oxides (MAO), the oxide compound of barium and the mixture of oxyhydroxide, aluminum alkoxide sulfonate, rare metal alcoxyl vitriol, alkaline earth metal oxide and phosphoric acid, preferred potassium hydroxide, sodium methylate, Mg/AI composite oxides (MAO).
Further, in technique scheme, alkene-carboxylic acid of the present invention is undecylenic acid: CH
2=CH (CH
2)
8cOOH, oleic acid: CH
3(CH
2)
7cH=CH (CH
2)
7cOOH, erucic acid: cis-13-docosenoic acid, preferred oleic acid.
Further, in technique scheme, aromatic hydrocarbon of the present invention is benzene, toluene, m-xylene, p-Xylol, o-Xylol, ethylbenzene, n-propylbenzene, isopropyl benzene, n-butylbenzene, isobutyl-benzene, tert.-butylbenzene, naphthalene, methylnaphthalene, dimethylnaphthalene, ethyl naphthalene, propyl group naphthalene, dibutyl naphthalene, biphenyl, the one in phenol, preferred m-xylene.
Further, in technique scheme, methylsulphonic acid is as catalyzer, the mol ratio of alkene-carboxylic acid and aromatic hydrocarbon is 1:1.5-3.5, temperature of reaction 100-135 DEG C, drips alkene-carboxylic acid, then react 5 hours, be washed to pH value neutrality, short-path distillation removes unreacted raw material and saturated acid wherein, obtains arylalkyl carboxylic acids.The mol ratio of described alkene-carboxylic acid and methylsulphonic acid is 1:1.15-2.0.
Further, in technique scheme, the ring-opening reaction that arylalkyl carboxylic acids of the present invention and propylene oxide carry out, preferred aryl groups alkyl carboxylic acid and propylene oxide mol ratio are the reaction of 1:5 ~ 50.
Further, the ethoxylation that arylalkyl carboxylic acids's polyoxypropylene ester of the present invention and oxyethane carry out, preferred aryl groups alkyl carboxylic acid polyoxypropylene ester and molar are than the reaction for 1:5 ~ 50.
Beneficial outcomes of the present invention is:
1. arylalkyl carboxylic acids's group of the present invention and oxypropylene block are oil soluble, have very strong can with mixing of crude oil, viscous crude, residual oil etc., by controlling the size of access ethylene oxide block, the oleophylic hydrophilic balance of arylalkyl carboxylic acids's polyoxyethylene polyoxypropylene block can be controlled, be widely used in the fields such as residual oil emulsification, reducing thick oil viscosity, emulsification of crude oil;
2. arylalkyl carboxylic acids's polyoxyethylene polyoxypropylene segmented copolymer of the present invention, for the nonionic surface active agent that molecular weight is larger, there is the effect of thickening under finite concentration, can be used for improving oil recovery factor, especially use under weak base and alkali-free system, there is thickening, solubilising, emulsification, the effect such as wetting;
3. arylalkyl carboxylic acids's polyoxyethylene polyoxypropylene segmented copolymer preparation method transformation efficiency of the present invention is high, is applicable to industrialization and produces.
Accompanying drawing explanation
Accompanying drawing 3 width of the present invention,
Fig. 1 is the infrared spectrogram of the m-xylene base octadecane carboxylic acid that embodiment 1 prepares;
Fig. 2 is m-xylene base octadecane carboxylic acid polyoxypropylene (15) the ester flight time mass spectrum figure that embodiment 1 prepares;
Fig. 3 is m-xylene base octadecane carboxylic acid polyoxypropylene (15) polyoxyethylene (15) the segmented copolymer flight time mass spectrum figure that embodiment 1 prepares.
Embodiment
The present invention is further illustrated below in conjunction with embodiment, but not as a limitation of the invention.
Embodiment 1:
Friedel-Crafts alkylation:
In the 1000ml reaction flask that agitator, thermometer, constant voltage dropper, condenser are housed, drop into 248 grams of m-xylenes (AR), 112 grams of methylsulphonic acids (AR), be warming up to 125 ~ 130 DEG C, drip high-purity oleic acid (oleic acid content >=75%) 220 grams, time for adding is 5 hours, continues reaction 2 hours.Cooling, be washed to pH value neutrality, Rotary Evaporators removes excessive m-xylene, and molecular distillation decolours, and obtains m-xylene base octadecane carboxylic acid.Liquid-phase chromatographic analysis oleic acid conversion >=90%.
M-xylene base octadecane carboxylic acid infrared spectrogram is shown in Fig. 1.
1412cm in FIG
-1(carboxylic acid O-H flexural vibration), 1710cm
-1(carboxylic acid C=O stretching vibration); 725cm
-1(a disubstituted C-H out-of-plane deformation vibration), 1047cm
-1(aromatic hydrocarbons C-H in-plane bending vibration), 1459cm
-1(aromatic hydrocarbons C=C stretching vibration); 2853cm
-1(CH2 alkane symmetrical stretching vibration), 2925cm
-1(antisymmetric stretching vibration of CH2 alkane).
Ring-opening reaction:
Take 116 grams of m-xylene base octadecane carboxylic acids and 1.5 grams of Mg/AI composite oxides (MAO) are dropped in 1 liter of synthesis reactor, synthesis reactor is sealed, with nitrogen replacement 3 times.Start and stir, be warming up to 140 DEG C, start vacuum pump evacuation, stop vacuumizing when being warming up to 170 DEG C.Open feed valve, be pressed into gradually in reactor by 261.36 grams of propylene oxide in storage tank with nitrogen, control temperature of reaction at 140 DEG C ~ 180 DEG C, pressure≤0.15MPa, reacts 5 hours.Cooling, discharging, filters, and removing catalyzer, obtains m-xylene base octadecane carboxylic acid polyoxypropylene (15) ester.
M-xylene base octadecane carboxylic acid polyoxypropylene (15) ester flight time mass spectrum figure is shown in Fig. 2.
Be the normal distribution of polyoxypropylene structure distribution in fig. 2, because this experiment used catalyst is Mg/AI composite oxides (MAO), embodied the feature of narrow ditribution.
Ethylation reaction:
Take 252 grams of m-xylene base octadecane carboxylic acid polyoxypropylene (15) esters and 1.5 grams of sodium methylates drop in 1 liter of synthesis reactor, synthesis reactor is sealed, with nitrogen replacement 3 times.Start and stir, be warming up to 130 DEG C, start vacuum pump evacuation, stop vacuumizing when being warming up to 160 DEG C.Open feed valve, be pressed into gradually in reactor by 133 grams of oxyethane in storage tank with nitrogen, control temperature of reaction at 130 DEG C ~ 170 DEG C, pressure≤0.15MPa, reacts 6 hours.Cooling, discharging, obtains m-xylene base octadecane carboxylic acid polyoxypropylene (15) polyoxyethylene (15) segmented copolymer.
M-xylene base octadecane carboxylic acid polyoxypropylene (15) polyoxyethylene (15) segmented copolymer flight time mass spectrum figure is shown in Fig. 3.
At Fig. 3, we see on the basis of m-xylene base octadecane carboxylic acid polyoxypropylene (15) ester, add oxyethane (15EO), obtain very complicated flight time mass spectrum figure, this is because in the polyoxypropylene structure in normal distribution state, each structure all may add the oxyethane of normal distribution, result in very complicated structure distribution form.
Application examples 1
The application of arylalkyl carboxylic acids's polyoxyethylene polyoxypropylene segmented copolymer of the present invention in tertiary oil recovery:
Composition components and content:
Erucicamide propyl group carboxybetaine (from synthesis) 0.20%
M-xylene base octadecane carboxylic acid polyoxypropylene (15) polyoxyethylene (15) ester 0.15%
All the other are water.
Erucicamide propyl group carboxybetaine is wherein that 100 DEG C of methyl alcohol make solvent, and carry out quaternary ammonium reaction 8 hours, separating methanol obtains product with erucicamide propyl group tertiary amine and sodium chloroacetate proportioning for 1:1.1 (mol ratio).
Adopt grand celebration to recover the oil ten factory's crude oil and Simulated Water, the interfacial tension of test system is 5.63x10
-3mN/m, system viscosity is 18.6mPa.s.
M-xylene base octadecane carboxylic acid polyoxypropylene (15) polyoxyethylene (15) ester solubilising erucicamide propyl group carboxybetaine, interfacial tension reaches ultralow; Thickening binary system, has certain viscosity under not polyaddition principle condition; And play emulsifying effect.
Natural core oil displacement experiment carries out according to People's Republic of China (PRC) oil and gas industry standard SY/T6424-2000.Experiment oil is grand celebration ten factory simulated oil, and experimental water is grand celebration ten factory Simulated Water.When water drive to moisture 100% time inject the formula system of the above-mentioned composition of 0.7 times of volume of voids (PV), then carry out water drive to moisture 100% time terminate.
Natural core parameter is as shown in table 3:
The natural core parameter of table 3. composite formula system
Composite formula system is utilized to carry out natural core oil displacement experiment result as shown in table 4:
The oil displacement experiment result of table 4. composite formula system
Conclusion: the interfacial tension of erucicamide propyl group carboxybetaine and profit reaches ultralow, but only with the uncontrollable mobility of tensio-active agent itself, simultaneously bad due to macromolecular beet alkali surface activator solvability, its effect is also difficult to play.M-xylene base octadecyl carboxylic acid polyoxyethylene polyoxypropylene segmented copolymer, can solubilising beet alkali surface activator, can have the aqueous phase of trimethyl-glycine promoting agent by thickening again, play the object controlling mobility, reach the object improving oil recovery factor.
Application examples 2
The application of arylalkyl carboxylic acids's polyoxyethylene polyoxypropylene segmented copolymer of the present invention in microemulsion preparation:
Oil-sand is a kind of sand shape mineral reserve containing crude oil, and main component is pitch, water, clay and gravel, and its stock number is huge, accounts for 30% of world oil reserves.
Be used in by microemulsion in oil-sand washing oil and will have very important application prospect, microemulsion directly acts on oil-sand, normal temperature, does not need more heat energy, can reduce cost of winning.
Hexadecyl hydroxypropyl sultaine is wherein that 125 DEG C of methyl alcohol make solvent, and carry out quaternary ammonium reaction 8 hours, separating methanol obtains product with 16 tertiary amines and 3-chlorine-2-hydroxyl propanesulfonate proportioning for 1:1.1 (mol ratio).
Form middle microemulsion phase when profit volume ratio is 1, displacement efficiency can reach 89.6%.
Claims (9)
1. arylalkyl carboxylic acids's polyoxyethylene polyoxypropylene segmented copolymer, is characterized in that having formula I structure:
Wherein, m+n is 0-30 positive integer;
P is 1-5000 positive integer;
Q is 0 or 1-5000 positive integer;
R is phenyl, tolyl, m-xylene base, p-Xylol base, o-Xylol base, ethylbenzene, n-propyl phenyl, isopropyl phenyl, n-butylphenyl, isobutyl phenenyl, tert-butyl-phenyl, naphthyl, methyl naphthyl, dimethyl naphthyl, ethyl naphthyl, propyl group naphthyl, butyl naphthyl, xenyl, the one in phenylol.
2. arylalkyl carboxylic acids's polyoxyethylene polyoxypropylene segmented copolymer according to claim 1, is characterized in that: described m+n is 15, p is 5,6 ... 49,50 positive integers, q is 5,6 ... 49,50 positive integers, R is m-xylene.
3. the preparation method of a kind of arylalkyl carboxylic acids's polyoxyethylene polyoxypropylene segmented copolymer as claimed in claim 1, is characterized in that, comprise the following steps:
1.. the alkylated reaction that alkene-carboxylic acid and aromatic hydrocarbon carry out under an acidic catalyst effect, obtains arylalkyl carboxylic acids;
2.. arylalkyl carboxylic acids step 1. obtained again and propylene oxide carry out ring-opening reaction under acidity or basic catalyst effect, under acidity or basic catalyst effect, carry out ethoxylation with oxyethane again, obtain arylalkyl carboxylic acids's polyoxyethylene polyoxypropylene segmented copolymer.
4. preparation method according to claim 3, is characterized in that: described step 1. in an acidic catalyst be any one or a few in sulfuric acid, hydrofluoric acid, methylsulphonic acid, trifluoromethanesulfonic acid, the trifluoromethanesulfonic acid root of metal salts of trifluoromethane sulphonic acid or load, heteropolyacid, solid super-strong acid, acid zeolite, perfluorinated resin, ionic liquid.
5. preparation method according to claim 3, is characterized in that, described step 2. in an acidic catalyst of ring-opening reaction or ethylation reaction be selected from BF
3, SbCI
5, SnCI
4, solid acid, heteropolyacid, one in carried molecular sieve catalyst; Basic catalyst is selected from the one in potassium hydroxide, sodium hydroxide, sodium methylate, sodium ethylate, Mg/AI composite oxides, the oxide compound of barium and the mixture of oxyhydroxide, aluminum alkoxide sulfonate, rare metal alcoxyl vitriol, alkaline earth metal oxide and phosphoric acid.
6. preparation method according to claim 3, is characterized in that: described step 1. in alkene-carboxylic acid be one or more in undecylenic acid, oleic acid, erucic acid.
7. preparation method according to claim 3, is characterized in that: described step 2. in arylalkyl carboxylic acids and the propylene oxide ring-opening reaction of carrying out, arylalkyl carboxylic acids and propylene oxide mol ratio are the reaction of 1:5 ~ 50.
8. preparation method according to claim 3, is characterized in that: described step 2. in the ethoxylation that carries out of arylalkyl carboxylic acids's polyoxypropylene ester and oxyethane, arylalkyl carboxylic acids's polyoxypropylene ester and molar are than being 1:5 ~ 50.
9. the application of arylalkyl carboxylic acids's polyoxyethylene polyoxypropylene segmented copolymer in residual oil emulsification, reducing thick oil viscosity, heavy oil pour point depression, nanoemulsions preparation, tertiary oil recovery, daily-use chemical industry as claimed in claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410466418.1A CN104262602B (en) | 2014-09-12 | 2014-09-12 | A kind of arylalkyl carboxylic acids's polyoxyethylene polyoxypropylene block copolymer and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410466418.1A CN104262602B (en) | 2014-09-12 | 2014-09-12 | A kind of arylalkyl carboxylic acids's polyoxyethylene polyoxypropylene block copolymer and its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104262602A true CN104262602A (en) | 2015-01-07 |
| CN104262602B CN104262602B (en) | 2016-08-17 |
Family
ID=52154204
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410466418.1A Expired - Fee Related CN104262602B (en) | 2014-09-12 | 2014-09-12 | A kind of arylalkyl carboxylic acids's polyoxyethylene polyoxypropylene block copolymer and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104262602B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107235529A (en) * | 2017-06-27 | 2017-10-10 | 中国石油化工股份有限公司 | A kind of degreaser handled for oil-contaminated water of oil field and preparation method thereof |
| CN108084982A (en) * | 2016-11-21 | 2018-05-29 | 中国科学院化学研究所 | Nano-viscosity reduction pour-point depressant stable emulsion and its preparation method and application |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108117639B (en) * | 2016-11-30 | 2021-04-30 | 中国石油天然气股份有限公司 | Unsaturated fatty alcohol polyoxypropylene polyoxyethylene block copolymer, and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000038443A (en) * | 1998-07-23 | 2000-02-08 | Mitsui Chemicals Inc | Production of polyoxyalkylenepolyol |
| CN103320110A (en) * | 2013-06-26 | 2013-09-25 | 工合聚能(天津)石油精化科技发展有限公司 | Nano composite high-temperature-resistant extraction aid for thickened oil and super-thickened oil recovery and preparation method thereof |
| CN103641750A (en) * | 2013-11-28 | 2014-03-19 | 中国石油天然气股份有限公司 | Surfactant containing aralkyl hydrophobic chain and amido bond linking group |
| CN103865053A (en) * | 2012-12-10 | 2014-06-18 | 辽宁奥克化学股份有限公司 | Terminal alkenyl unsaturated acid/ester polyoxyalkyl ether, and preparation method and use thereof |
-
2014
- 2014-09-12 CN CN201410466418.1A patent/CN104262602B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000038443A (en) * | 1998-07-23 | 2000-02-08 | Mitsui Chemicals Inc | Production of polyoxyalkylenepolyol |
| CN103865053A (en) * | 2012-12-10 | 2014-06-18 | 辽宁奥克化学股份有限公司 | Terminal alkenyl unsaturated acid/ester polyoxyalkyl ether, and preparation method and use thereof |
| CN103320110A (en) * | 2013-06-26 | 2013-09-25 | 工合聚能(天津)石油精化科技发展有限公司 | Nano composite high-temperature-resistant extraction aid for thickened oil and super-thickened oil recovery and preparation method thereof |
| CN103641750A (en) * | 2013-11-28 | 2014-03-19 | 中国石油天然气股份有限公司 | Surfactant containing aralkyl hydrophobic chain and amido bond linking group |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108084982A (en) * | 2016-11-21 | 2018-05-29 | 中国科学院化学研究所 | Nano-viscosity reduction pour-point depressant stable emulsion and its preparation method and application |
| CN107235529A (en) * | 2017-06-27 | 2017-10-10 | 中国石油化工股份有限公司 | A kind of degreaser handled for oil-contaminated water of oil field and preparation method thereof |
| CN107235529B (en) * | 2017-06-27 | 2020-07-03 | 中国石油化工股份有限公司 | Oil removal agent for oil-containing sewage treatment of oil field and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104262602B (en) | 2016-08-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104231257B (en) | A kind of aryl alkyl alcohol polyoxyethylene polyoxypropylene block copolymer and its preparation method and application | |
| CN101418230B (en) | Crude de-emulsifier and its preparing process | |
| CA2795104C (en) | Process for producing mineral oil using surfactants based on a mixture of c32 guerbet-, c34 guerbet-, c36 guerbet-containing alkyl alkoxylates | |
| CN104399406B (en) | Arylalkyl Soxylat A 25-7 amine oxide surfactant and method for making and application | |
| CN102807478B (en) | Aralkyl alcohol polyoxyethylene ether compound and preparation method and application thereof | |
| CN102432888B (en) | Comb-shaped polysiloxane crude-oil demulsifying agent and preparation method thereof | |
| CN104399405B (en) | Arylalkyl Soxylat A 25-7 sultaine tensio-active agent and method for making and application | |
| CN104262602A (en) | Aryl alkyl carboxylic acid polyoxypropylene polyoxyethylene block copolymer, and preparation method and application thereof | |
| CN110229654B (en) | High-molecular surfactant type thick oil viscosity reducer and preparation method thereof | |
| CN104946298A (en) | Crude oil demulsifier and production technology thereof | |
| CN108117639B (en) | Unsaturated fatty alcohol polyoxypropylene polyoxyethylene block copolymer, and preparation method and application thereof | |
| CN104326905B (en) | A kind of aryl alkyl carboxylic acid polyoxyethylene ester and its preparation method and application | |
| CN104403654A (en) | Aryl alkyl polyoxyethylene ether carboxyl betaine surfactant and preparation method and application thereof | |
| CN102876309A (en) | Viscous oil viscosity reducer | |
| CN104673359A (en) | Method for preparing novel phenolic amine resin demulsifier | |
| CN104326906A (en) | Aryl alkyl carboxylic monoester and preparation method and application thereof | |
| CN115558096A (en) | Comb-type cardanol polyether demulsifier, and preparation method and application thereof | |
| CN102504228B (en) | Method for preparing non-ionic hyperbranched linear polymer emulsifier | |
| CN107400230A (en) | A kind of high efficient cryogenic petroleum demulsifier and preparation method | |
| CN111087606A (en) | Double-long-chain alkyl polyoxyethylene-polyoxypropylene ether sulfate surfactant for oil displacement and preparation method thereof | |
| CN111592910A (en) | Compound polyether demulsifier and preparation method thereof | |
| CN115160508B (en) | Polycarboxylate viscosity reducing agent containing polyether chain segments, and preparation method and application thereof | |
| CN104774645B (en) | The preparation method of low temperature polyether type thick oil demulsifying agent | |
| CN102041039A (en) | Composite crude oil demulsifying agent | |
| CN108485630A (en) | A kind of fluoride silicon surfactant and oil-based foam oil displacement agent containing single perfluoro capryl |
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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160817 Termination date: 20210912 |