CN104761687A - Preparation method of temperature-resistant fluorine-containing polymer surfactant - Google Patents
Preparation method of temperature-resistant fluorine-containing polymer surfactant Download PDFInfo
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Abstract
The invention discloses a preparation method of a temperature-resistant fluorine-containing polymer surfactant, which comprises the following steps: adding 10 parts of acrylamide, 1.5-20 parts of anionic monomer , 0.5-10 parts of surface macro monomer, 0.5-15 parts of sodium dodecyl sulfate and 50-500 parts of deionized water in a three-necked reaction flask, stirring for 30 minutes, adding 0.05-3 parts of fluorine-containing monomer, adjusting pH value of a solution to 5-9, introducing N2 for 60 minutes under stirring, adding 0.006-2.0 parts of initiator potassium peroxodisulfate or ammonium persulfate at temperature of 45-85 DEG C, and performing a polymerization reaction for 12-32 hours to prepare the temperature-resistant fluorine-containing polymer surfactant PAF with good interfacial activity. Addition of less fluorine-containing monomer can obviously increase the temperature-resistant and ageing resistance capabilities of the surfactant. PAF is prepared to an aqueous solution with mass concentration being 0.05-0.5g/L, a low-molecular-weight surfactant with concentration being 0.01-4mmol/L is added, so that an oil-displacing agent used for tertiary oil recovery is obtained. The surfactant solution with PAF mass concentration being 0.01-1.0g/L can be used as an emulsifier, a solubilizer and a wetting agent.
Description
Technical field
The present invention relates to a kind of preparation method of heatproof fluoro containing polymers tensio-active agent, this tensio-active agent can be used as the oil-displacing agent in tertiary oil recovery technology, also can be used as emulsifying agent, solubilizing agent and wetting agent, belong to organic chemistry, macromolecular material and raising oil recovery field.
Background technology
Improve in recovery efficiency technique at chemical flooding, recovery ratio is the product of sweep efficiency and oil displacement efficiency, in order to can sweep efficiency be improved, oil displacement efficiency can be improved again, thus increase substantially recovery ratio, usually polymkeric substance and tensio-active agent are carried out compound, wherein polymkeric substance mainly increases the sweep efficiency injecting water, tensio-active agent is for improving oil displacement efficiency, and be used for tensio-active agent mainly Small molecular surfactant hydrocarbon oil sulfonate and the compound system thereof of compound at present, but the micelle-forming concentration of sulfonated petro-leum is higher, saline-alkaline tolerance is limited, when multivalent ion concentration more than 500 mg/L or total mineralization higher than 3 × 10
4during mg/L, sulfonated petro-leum is understood Precipitation or is transferred to oil phase, loses activity, causes the loss in oil displacement process.In addition, in the binary combination flooding increasing glutinous polymkeric substance and Small molecular surfactant, easily there is chromatographic fractionation effect in the two.Polymeric surface active agent is compared with Small molecular surfactant, except there is table, interfacial activity, also there is good dispersion, thickening, the performance such as stable, and low toxicity or nontoxic, owing to sticking with increasing the similarity that polymkeric substance has molecular structure, chromatographic fractionation effect can improve.Current aggretion type polymeric surface active agent is primarily of the non-ionic surfactant polymeric monomer of amphiphilic and acrylamide, hydrophobic monomer is as (methyl) alkyl acrylate, vinylbenzene etc., and the copolymerization of ionic hydrophilic monomer obtains, surface active monomer is the unsaturated polymeric monomer such as esterification products and acrylamide analog derivative that generates of (methyl) vinylformic acid, toxilic acid etc. and alkyl (phenol) Soxylat A 25-7, aliphatic acid polyethenoxy Sorbitol Powder, polyvinyl alcohol etc. mainly.These polymeric monomer have good reactive behavior and table, interfacial activity, but higher than 70
oat the temperature of C and acid, facile hydrolysis in alkaline media, thus make polymeric surface active agent lose the function of table, interfacial activity, in addition, with the hydrophobic monomer of its copolymerization also mainly heatproof lower than 70
othe vinylbenzene that the alkyl acrylate of C, alkyl methacrylate, fluorine-containing propene acid alkyl ester or hydrophobicity are weak, therefore, current polymeric surface active agent is difficult to meet high temperature and high salt oil deposit (temperature>=85
oc, salinity>=30 000 mg/L) requirement to its performance, the temperature resistant antisalt performance improving high temperature and high salt oil deposit oil recovery tensio-active agent improves focus and the difficulties in recovery ratio field at present.Gui Zhangliang etc., polymer journal, 2008 (10): 955-959, with surface-active macromonomers polyoxyethylene octylphenol ether maleic mono-ester (OPMA) and acrylamide (AM) copolymerization of synthesis, obtain polymeric surface active agent poly-(AM/OPMA), this tensio-active agent is respectively 53.94 mN/m and 5.41 mN/m on the surface of 1.5 g/L aqueous copolymers solutions and oil water interfacial tension, has stronger thickening capabilities in addition.Zhang Jiehui etc., Speciality Petrochemicals, 1998,3 (3): 14-19, with alkylphenol polyoxyethylene and vinylformic acid Reactive Synthesis alkylphenol polyoxyethylene acrylate surface surface-active macromonomer (AE), synthesize acrylamide/vinylformic acid/alkylphenol polyoxyethylene acrylate (AM/AA/AE) terpolymer tensio-active agent, research shows, for this tensio-active agent, the surface tension of 1% copolymer solution can be down to 27 mN/m, and interfacial tension is 0.5 mN/m.Liu Guoqiang etc., polymer journal, 2011, (12): 1402-1410, with methoxypolyethylene glycol methacrylic ester (MPEGMA) for macromonomer, Hexafluorobutyl mathacrylate (HFMA), sodium p styrene sulfonate (NaSS) is comonomer, adopt macromonomer grafting copolymerization process, prepare the fluorine-containing amphipathic graft copolymer P (HFMA-co-NaSS) of a kind of anionic-g-PEG, result of study shows, tensammetric determination P (HFMA-co-NaSS)-g-PEG micelle-forming concentration in aqueous (CMC) is 0. 16 g/L, surface tension under this concentration is 42. 52 mN/m.The heatproof of above-mentioned three kinds of polymeric surface active agents is restricted, higher than 70
oat the temperature of C, the ester bond in surface-active macromonomers or hydrophobic minor comonomer molecule all can be hydrolyzed, and lipophilic group is lost, and tensio-active agent also just loses the function of table, interfacial activity and thickening; Concentration when these polymeric surface active agents make solution reach low table, interfacial tension is higher, makes its consumption high.
Summary of the invention
The object of the invention is present Research and the deficiency for improving displacement of reservoir oil polymer and organic low molecular tensio-active agent in oil recovery field at present, provide a kind of preparation method of polymeric surface active agent that can be used for high, medium and low infiltration oil reservoir oil displacement, heatproof, be characterized in acrylamide (AM) and anionic monomer for hydrophilic monomer, to have the polymeric monomer allyl alkylphenol ethoxylate CH of table, interfacial activity
2=CH-CH
2(OCH
2cH
2)
n-O-C
6h
4-C
mh
2m+1, n=4 ~ 60, at least one in m=1 ~ 18 is comonomer, with fluorochemical monomer 1,1,2,2-tetrahydrochysene perfluoroalkyl 4-vinyl benzyl ether CH
2=CH-C
6h
4-CH
2oCH
2cH
2c
mf
2m+1, at least one in m=4 ~ 18 is another comonomer, adopts free radical copolymerization method to synthesize polymeric surface active agent PAF.
Present inventor find various reaction conditions in polyreaction as anionic monomer concentration, surface-active macromonomers concentration, fluorochemical monomer concentration and temperature of reaction to obtain the table of polymeric surface active agent, interfacial activity has a significant impact.Add the wetting ability that appropriate anionic monomer can increase considerably tensio-active agent, and molecular chain is stretched; Appropriate surface-active macromonomers can make tensio-active agent have good table, interfacial activity, and significantly can also increase the saline-alkaline tolerance of tensio-active agent; Appropriate fluorochemical monomer can significantly improve the resistance to gentle resistance of aging of tensio-active agent, and can also improve the surfactivity of tensio-active agent further.Under suitable initiator concentration, total reaction monomer concentration, temperature of reaction and pH value in reaction, table can be obtained, interfacial activity is strong, the heatproof high molecule tensio-active agent PAF of anti-salt.
Object of the present invention is realized by following technical measures, and wherein said raw material number, except specified otherwise, is parts by weight.
1. the recipe ingredient of heatproof fluoro containing polymers tensio-active agent is:
Acrylamide 10 parts
Anionic monomer 1.5 ~ 20 parts
Surface-active macromonomers 0.5 ~ 10 part
Fluorochemical monomer 0.05 ~ 3 part
0.5 ~ 15 part, tensio-active agent
Deionized water 50 ~ 500 parts
Wherein anionic monomer is at least one in vinylformic acid, methacrylic acid, 2-acrylamide-2-methylpro panesulfonic acid and vinylbenzenesulfonic acid; Surface-active macromonomers is allyl alkylphenol ethoxylate CH
2=CH-CH
2(OCH
2cH
2)
n-O-C
6h
4-C
mh
2m+1, n=4 ~ 60, at least one in m=1 ~ 18; Fluorochemical monomer is 1,1,2,2-tetrahydrochysene perfluoroalkyl 4-vinyl benzyl ether CH
2=CH-C
6h
4-CH
2oCH
2cH
2c
mf
2m+1, at least one in m=4 ~ 18; Tensio-active agent is sodium lauryl sulphate.
2. the preparation of polymeric surface active agent PAF
By acrylamide 10 parts, anionic monomer 1.5 ~ 20 parts, surface-active macromonomers 0.5 ~ 10 part, Surfactant SDS 0.5 ~ 15 part, deionized water 50 ~ 500 parts adds in three mouthfuls of reaction flasks, stirs 30 minutes, then adds fluorochemical monomer 0.05 ~ 3 part, regulator solution pH=5 ~ 9, under agitation logical N
2after 60 minutes, at temperature 45 ~ 85 DEG C, add initiator potassium persulfate or ammonium persulphate 0.006 ~ 2.0 part, polyreaction 12 ~ 32 hours, obtained PAF, then use water dissolution, obtain PAF strong solution;
Wherein anionic monomer is at least one in vinylformic acid, methacrylic acid, 2-acrylamide-2-methylpro panesulfonic acid and vinylbenzenesulfonic acid; Surface-active macromonomers is allyl alkylphenol ethoxylate CH
2=CH-CH
2(OCH
2cH
2)
n-O-C
6h
4-C
mh
2m+1, n=4 ~ 60, at least one in m=1 ~ 18; Fluorochemical monomer is 1,1,2,2-tetrahydrochysene perfluoroalkyl 4-vinyl benzyl ether CH
2=CH-C
6h
4-CH
2oCH
2cH
2c
mf
2m+1, at least one in m=4 ~ 18.
3. the performance of polymeric surface active agent PAF
Except specified otherwise, in following PAF solution, all do not add low-molecular-weight surfactant.
(1) impact of PAF concentration on solution surface tension is as shown in table 1.Result shows, PAF has good surfactivity in pure water and salt solution.
(2) impact of PAF concentration on solution interface tension force is as shown in table 2.Result shows, the interfacial tension of PAF solution is low, has good interfacial activity.
(3) impact of sodium chloride concentration on 1.0 g/L PAF solution tables, interfacial tension is as shown in table 3.Result shows, PAF has strong saline-alkaline tolerance, and in wide salt concentration range, PAF solution all has the table lower than pure water solution, interfacial tension value, and PAF does not have Precipitation in haline water solution.
(4) relation of temperature and PAF solution table, interfacial tension is as shown in table 4.Result shows, PAF has good heat resistance, and PAF salt brine solution at high temperature still has low table, interfacial tension.
(5) ageing resistance of the PAF aqueous solution is as shown in table 5.Result shows, the introducing of fluorine-containing hydrophobic monomer can improve the ageing resistance of PAF solution effectively.
(6) interfacial activity of petroleum sodium sulfonate and PAF/ petroleum sodium sulfonate compound system as shown in tables 6 and 7.Result shows, PAF can with the hydrocarbon low-molecular-weight surfactant generation synergistic effect of trace, the oil water interfacial tension of solution can significantly be reduced to ultralow (10
-3the mN/m order of magnitude).
4. the purposes of polymeric surface active agent PAF
(1) polymeric surface active agent PAF is made into the aqueous solution that mass concentration is 0.05 ~ 0.5 g/L, add the low-molecular-weight surfactant that concentration is 0.01 ~ 4 mmol/L, stir in the mixing tank of band stirring under room temperature, namely obtain heatproof, anti-salt, there is the oil-displacing agent used for tertiary oil recovery of good table, interfacial activity;
Wherein tensio-active agent is petroleum sodium sulfonate, C
8-16sodium alkyl benzene sulfonate and C
8-16at least one in sodium alkyl sulfate.
(2) PAF being made into mass concentration is 0.01 ~ 1.0 g/L, obtains the polymeric surface active agent solution with good table, interfacial activity, can be used as emulsifying agent, solubilizing agent and wetting agent.
Polymeric surface active agent PAF of the present invention has following advantage:
The present invention is with polymeric monomer allyl alkylphenol ethoxylate CH
2=CH-CH
2(OCH
2cH
2)
n-O-C
6h
4-C
mh
2m+1, n=4 ~ 60, at least one in m=1 ~ 18 is comonomer, makes the table of tensio-active agent, interfacial activity significantly improves; With fluorochemical monomer 1,1,2,2-tetrahydrochysene perfluoroalkyl 4-vinyl benzyl ether CH
2=CH-C
6h
4-CH
2oCH
2cH
2c
mf
2m+1, at least one in m=4 ~ 18 is heatproof function monomer, adopts aqueous free radical process for copolymerization to synthesize heatproof, anti-aging, anti-salt, table, polymeric surface active agent PAF that interfacial tension is low.Because the carbon fluorin radical of same carbon chain length is compared with hydrocarbon group, surface energy is lower, and hydrophobicity is stronger, more can reduce the surface tension of water; Because the fluorochemical monomer containing phenyl ring and C-F key has excellent thermotolerance, after this monomer is introduced in tensio-active agent, significantly can suppress whole high molecular oxidative degradation, significantly improve high molecular resistance to gentle ageing resistance.Therefore, compared with acrylamide/polymeric monomer/anionic monomer ternary polymeric surface active agent, PAF has better heatproof, ageing resistance and lower surface tension.When alkali-free, in PAF solution, add the hydrocarbon low-molecular-weight surfactant of trace, the oil water interfacial tension of solution can be made significantly to be reduced to ultralow (10
-3the mN/m order of magnitude), oil displacement efficiency in tertiary oil recovery is significantly improved.
Embodiment
Below by embodiment, the present invention is specifically described; what be necessary to herein means out is that the present embodiment is only used to further illustrate the present invention; can not be interpreted as limiting the scope of the invention, the researchist in this field can make some nonessential improvement and adjustment according to the content of the invention described above to the present invention.
Embodiment 1
By acrylamide 10.000 grams, vinylbenzenesulfonic acid 2.417 grams, allyl group polyoxyethylene octylphenol ether (the affixture EO of Soxylat A 25-7 is 8) 1.260 grams, sodium lauryl sulphate 2.580 grams, deionized water 95 mL adds in three mouthfuls of reaction flasks, stir 30 minutes, then add 1,1,2,0.230 gram, 2-tetrahydrochysene perfluoro capryl 4-vinyl benzyl ether is 5 by NaOH regulator solution pH value, under agitation logical N
2after 60 minutes, add 0.05 mol/L potassium persulfate solution 3.5 mL, polyreaction 24 hours under temperature 60 C, products in water dissolves, obtained PAF strong solution.
Embodiment 2
By acrylamide 10.000 grams, 2-acrylamide-2-methylpro panesulfonic acid 17.850 grams, allyl group polyoxyethylene octylphenol ether (the affixture EO of Soxylat A 25-7 is 60) 8.766 grams, sodium lauryl sulphate 12.453 grams, deionized water 420 mL adds in three mouthfuls of reaction flasks, stir 30 minutes, then add 1,1,2,2.840 grams, 2-tetrahydrochysene perfluor octadecyl 4-vinyl benzyl ether is 7 by NaOH regulator solution pH value, under agitation logical N
2after 60 minutes, add 0.05 mol/L potassium persulfate solution 8.96 mL, polyreaction 32 hours at temperature 80 DEG C, products in water dissolves, obtained PAF strong solution.
Embodiment 3
By acrylamide 10.000 grams, 1.640 grams, vinylformic acid, allyl group polyoxyethylene octylphenol ether (the affixture EO of Soxylat A 25-7 is 30) 3.152 grams, sodium lauryl sulphate 2.205 grams, deionized water 63 mL adds in three mouthfuls of reaction flasks, stir 30 minutes, then add 1,1,2,1.137 grams, 2-tetrahydrochysene perfluorododecyl 4-vinyl benzyl ether is 6 by NaOH regulator solution pH value, under agitation logical N
2after 60 minutes, add 0.05 mol/L potassium persulfate solution 1.94 mL, polyreaction 24 hours under temperature 70 C, products in water dissolves, obtained PAF strong solution.
Embodiment 4
By acrylamide 10.000 grams, methacrylic acid 8.025 grams, allyl group polyoxyethylene octylphenol ether (the affixture EO of Soxylat A 25-7 is 40) 6.308 grams, sodium lauryl sulphate 7.430 grams, deionized water 147 mL adds in three mouthfuls of reaction flasks, stir 30 minutes, then add 1,1,2,1.726 grams, 2-tetrahydrochysene perfluor hexadecyl 4-vinyl benzyl ether is 8 by NaOH regulator solution pH value, under agitation logical N
2after 60 minutes, add 0.05 mol/L ammonium persulfate solution 4.06 mL, polyreaction 16 hours at temperature 55 DEG C, products in water dissolves, obtained PAF strong solution.
Embodiment 5
By acrylamide 10.000 grams, 2-acrylamide-2-methylpro panesulfonic acid 11.645 grams, allyl group polyoxyethylene octylphenol ether (the affixture EO of Soxylat A 25-7 is 18) 4.710 grams, sodium lauryl sulphate 3.640 grams, deionized water 86 mL adds in three mouthfuls of reaction flasks, stir 30 minutes, then add 1,1,2,2.361 grams, 2-tetrahydrochysene perfluor tetradecyl 4-vinyl benzyl ether is 6 by NaOH regulator solution pH value, under agitation logical N
2after 60 minutes, add 0.05 mol/L potassium persulfate solution 3.62 mL, polyreaction 12 hours under temperature 50 C, products in water dissolves, obtained PAF strong solution.
Application example 1
Polymeric surface active agent PAF is made into the aqueous solution that mass concentration is 0.2 g/L, adds Sodium dodecylbenzene sulfonate 0.4 mmol/L, stir in the mixing tank of band stirring under room temperature, obtain the chemical oil displacement agent being used for tertiary oil recovery.
Application example 2
Polymeric surface active agent PAF is made into the aqueous solution that mass concentration is 0.1 g/L, adds petroleum sodium sulfonate 0.3 g/L, stir in the mixing tank of band stirring under room temperature, obtain the chemical oil displacement agent being used for tertiary oil recovery.
Application example 3
Polymeric surface active agent PAF is made into the aqueous solution that mass concentration is 0.3 g/L, adds sodium lauryl sulphate 1 mmol/L, stir in the mixing tank of band stirring under room temperature, obtain the chemical oil displacement agent being used for tertiary oil recovery.
Application example 4
Polymeric surface active agent PAF is made into the aqueous solution that mass concentration is 0.3 g/L, obtains the emulsifying agent with excellent surface activity.
Application example 5
Polymeric surface active agent PAF is made into the aqueous solution that mass concentration is 0.5 g/L, obtains the wetting agent with excellent surface activity.
Subordinate list explanation
Table 1
the relation of PAF concentration and solution surface tension
。
Table 2
the relation of PAF concentration and oil water interfacial tension
。
Table 3 NaCl concentration is on the impact of PAF solution table, interfacial tension
Note: PAF concentration: 1.0 g/L.
Table 4 temperature is on the impact of PAF solution table, interfacial tension
Note: PAF concentration: 1.0 g/L.
Table 5 digestion time is on the impact of PAF solution table, interfacial tension
Note: PAF concentration: 1.0 g/L, aging temperature: 90 DEG C.
Table 6
the relation of mahogany acid na concn and oil water interfacial tension
Note: NaCl concentration: 5 g/L.
Table 7
the relation of PAF concentration and PAF/ petroleum sodium sulfonate compound system table, interfacial tension
Note: NaCl concentration: 5 g/L.
More than in table, oil used is kerosene, and unless otherwise indicated, test condition is 25 DEG C.
Claims (1)
1. the preparation method of heatproof fluoro containing polymers tensio-active agent, is characterized in that:
Each composition by weight, by acrylamide 10 parts, anionic monomer 1.5 ~ 20 parts, surface-active macromonomers 0.5 ~ 10 part, Surfactant SDS 0.5 ~ 15 part, deionized water 50 ~ 500 parts adds in three mouthfuls of reaction flasks, stir 30 minutes, then fluorochemical monomer 0.05 ~ 3 part is added, regulator solution pH=5 ~ 9, under agitation logical N
2after 60 minutes, at temperature 45 ~ 85 DEG C, add initiator potassium persulfate or ammonium persulphate 0.006 ~ 2.0 part, polyreaction 12 ~ 32 hours, obtained heatproof high molecule tensio-active agent;
Wherein anionic monomer is at least one in vinylformic acid, methacrylic acid, 2-acrylamide-2-methylpro panesulfonic acid and vinylbenzenesulfonic acid; Surface-active macromonomers is allyl alkylphenol ethoxylate CH
2=CH-CH
2(OCH
2cH
2)
n-O-C
6h
4-C
mh
2m+1, n=4 ~ 60, at least one in m=1 ~ 18; Fluorochemical monomer is 1,1,2,2-tetrahydrochysene perfluoroalkyl 4-vinyl benzyl ether CH
2=CH-C
6h
4-CH
2oCH
2cH
2c
mf
2m+1, at least one in m=4 ~ 18.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105622839A (en) * | 2016-01-04 | 2016-06-01 | 中国石油天然气股份有限公司 | Environment-friendly nanometer emulsion fracturing fluid and preparation method thereof |
| CN111825811A (en) * | 2020-07-31 | 2020-10-27 | 贵州石博士科技有限公司 | High-water-retention polycarboxylate superplasticizer and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070225176A1 (en) * | 2006-03-27 | 2007-09-27 | Pope Gary A | Use of fluorocarbon surfactants to improve the productivity of gas and gas condensate wells |
| WO2008089391A1 (en) * | 2007-01-19 | 2008-07-24 | 3M Innovative Properties Company | Fluorinated surfactants and methods of using the same |
| CN101274974A (en) * | 2008-04-29 | 2008-10-01 | 成都理工大学 | Temperature-resistant water-soluble copolymer, preparation and use thereof |
| CN101463116A (en) * | 2009-01-12 | 2009-06-24 | 成都理工大学 | Non-linear associating water-soluble quadripolymer, and preparation and use thereof |
| CN101543748A (en) * | 2009-03-31 | 2009-09-30 | 成都理工大学 | Method for preparing 4-vinyl benzyl surface-active macromonomer |
| CN102365340A (en) * | 2009-03-25 | 2012-02-29 | 大金工业株式会社 | Surfactant comprising fluorine-containing polymer |
-
2015
- 2015-03-20 CN CN201510124420.5A patent/CN104761687B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070225176A1 (en) * | 2006-03-27 | 2007-09-27 | Pope Gary A | Use of fluorocarbon surfactants to improve the productivity of gas and gas condensate wells |
| WO2008089391A1 (en) * | 2007-01-19 | 2008-07-24 | 3M Innovative Properties Company | Fluorinated surfactants and methods of using the same |
| CN101274974A (en) * | 2008-04-29 | 2008-10-01 | 成都理工大学 | Temperature-resistant water-soluble copolymer, preparation and use thereof |
| CN101463116A (en) * | 2009-01-12 | 2009-06-24 | 成都理工大学 | Non-linear associating water-soluble quadripolymer, and preparation and use thereof |
| CN102365340A (en) * | 2009-03-25 | 2012-02-29 | 大金工业株式会社 | Surfactant comprising fluorine-containing polymer |
| CN101543748A (en) * | 2009-03-31 | 2009-09-30 | 成都理工大学 | Method for preparing 4-vinyl benzyl surface-active macromonomer |
Non-Patent Citations (2)
| Title |
|---|
| CHUANRONG ZHONG等: "Synthesis and Solution Properties of an Associative Polymer with Excellent Salt-Thickening", 《JOURNAL OF APPLIED POLYMER SCIENCE》 * |
| 史鸿鑫等: "氟表面活性剂在油田领域的应用", 《精细化工》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105622839A (en) * | 2016-01-04 | 2016-06-01 | 中国石油天然气股份有限公司 | Environment-friendly nanometer emulsion fracturing fluid and preparation method thereof |
| CN111825811A (en) * | 2020-07-31 | 2020-10-27 | 贵州石博士科技有限公司 | High-water-retention polycarboxylate superplasticizer and preparation method thereof |
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