CN106634926A - Polymer surfactant with efficient carbon dioxide responsiveness and preparation method - Google Patents

Polymer surfactant with efficient carbon dioxide responsiveness and preparation method Download PDF

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Publication number
CN106634926A
CN106634926A CN201611098363.9A CN201611098363A CN106634926A CN 106634926 A CN106634926 A CN 106634926A CN 201611098363 A CN201611098363 A CN 201611098363A CN 106634926 A CN106634926 A CN 106634926A
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solvent
mixed solvent
preparation
surfactant
high molecular
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CN106634926B (en
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贾胜见
徐盛明
徐政和
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Tsinghua University
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Tsinghua University
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
    • C09K8/584—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific surfactants
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F228/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a bond to sulfur or by a heterocyclic ring containing sulfur
    • C08F228/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a bond to sulfur or by a heterocyclic ring containing sulfur by a bond to sulfur

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The invention provides a polymer surfactant with efficient carbon dioxide responsiveness and a preparation method, and belongs to the field of preparation of surfactants. The preparation method comprises the steps as follows: DMAEMA (2-(dimethylamino)ethyl methacrylate) and sodium ethanesulfonate are mixed in water, APS (ammonium persulphate) is added, the mixture reacts for 4 hours at 80 DEG C, a reaction solution is extracted, subjected to impurity removal and vacuum solvent removal and dried at 50 DEG C, and the polymer surfactant with efficient carbon dioxide responsiveness is obtained. The polymer surfactant and the preparation method have the advantages that the preparation method is simple, the cost is low, a material has good stability, the prepared polymer surfactant has excellent carbon dioxide responsiveness, and the polymer surfactant can be applied to development of low-quality petroleum resources such as heavy oil and the like.

Description

High molecular surfactant with effective carbon-dioxide response and preparation method
Technical field
One class of present invention design has the high molecular surfactant and its synthetic method of effective carbon-dioxide response.
Background technology
Oil field enter high water-cut stage after, remaining oil with discontinuous oil film by trap in the hole of reservoir rockses, make Two main power on oil droplet are viscaps, if from suitable surfactant system, reducing profit Between interfacial tension, make the interfacial tension between oil reservoirs profit be down to relatively low or ultralow value (10 from 20-30mN/m3～104mN/ M), just can reduce oil droplet when moving remaining oil and deform brought resistance, so as to greatly improve oil displacement efficiency.
Now surfactant is used as solubilising, and hydrophobic organic compound is easy to be dissolved in surfactant solution, but But become extremely difficult when both are separated, this prevents surfactant from reusing, need in actual application big The surfactant of amount, causes environment remediation and commercial Application high cost, is very restricted in actual application.
The content of the invention
It is an object of the invention to prepare a kind of high molecular surfactant with effective carbon-dioxide response.The height Molecular surface active agent preparation process is simple, and it is cheap.High molecular surfactant obtained by preparation has to carbon dioxide There is excellent response；Can be used for the exploitation of the low product petroleum resources such as viscous crude, oil-sand.
A kind of high molecular surfactant with effective carbon-dioxide response, it is characterised in that structural formula is:
Wherein x:Y=1:1；N=12～20, and n is natural number.
Further, it is poly- with ammonium persulfate with vinyl sulfonic acid sodium and diethylaminoethyl methacrylate as polymerized monomer Close initiator.
Further, the method is carried out according to the following steps：
First, using vinyl sulfonic acid sodium and diethylaminoethyl methacrylate, (DMAEMA is as polymerized monomer according to mol ratio For (3-0.5):Solvent I mixing is added after 1 mixing, is added and is slightly produced after reacting 6 hours at 80 DEG C after ammonium persulfate (APS) Thing；Wherein ammonium sulfate addition is the 1wt% of polymerized monomer gross mass；
2nd, unreacted diethylaminoethyl methacrylate list in the crude product for being obtained using solvent II extraction step one Body, aqueous solution revolving obtains lotion.
Further, the solvent I in step one is deionized water.
Further, the volume ratio of the quality sum of vinyl sulfonic acid sodium and diethylaminoethyl methacrylate and deionized water For 1g:(1～100) mL.
Further, the solvent II in step 2 is one or more mixtures in ester, ketone and ether.
Further, the solvent II in step 2 mixes molten with petroleum ether mixed solvent, ethyl acetate for acetone with petroleum ether Agent, ethanol and petroleum ether mixed solvent, acetone and hexamethylene mixed solvent, acetone and dichloromethane mixed solvent, isopropanol with Ether mixed solvent, chloroform and pentane mixed solvent or for acetonitrile and n-hexane mixed solvent.
Vinyl sulfonic acid sodium and diethylaminoethyl methacrylate (DMAEMA) are added to (second in deionized water by the present invention The ratio of alkene sodium sulfonate and diethylaminoethyl methacrylate is respectively 3:1,2:1,1:1,0.5:1), being stirred continuously fills it Divide mixing, 1wt% ratios to add after reacting 6 hours at 80 DEG C after ammonium persulfate (APS), crude product is obtained, using solvent II Unreacted diethylaminoethyl methacrylate (DMAEMA) monomer in the crude product that extraction step one is obtained, aqueous solution revolving is obtained Obtain thick lotion.
Described high molecular surfactant, it is characterised in that with commercially available vinyl sulfonic acid sodium and methacrylic acid two Ethylamino ethyl ester is the polymerized monomer of surfactant.Wherein vinyl sulfonic acid sodium has strong hydrophilicity group, methacrylic acid diethyl Amino ethyl ester has tertiary amine group, there is excellent response characteristic to carbon dioxide.
Described high molecular surfactant, it is characterised in that water is solvent, water is a kind of cheap solvent, reduces reaction Cost.
Described high molecular surfactant, it is characterised in that prepare in the method for emulsifier-free emulsion polymerization and extraction desolventizing High molecular surfactant, preparation technology flow process is simple, and energy consumption is low, low cost.
Described high molecular surfactant has excellent response to carbon dioxide, is because that vinyl sulfonic acid sodium itself has There is strongly hydrophilic, diethylaminoethyl methacrylate has certain lipophile, the product that both are polymerized has surfactant Property, when carbon dioxide is passed through, tertiary amine is hydrophilic into salt, and surface-active is lost.By rising the method for being gently passed through nitrogen Destroy can quaternary ammonium salt, always surfactant recovery.
Description of the drawings
Fig. 1 is the table of the aqueous solution of the high molecular surfactant of the effective carbon-dioxide response of the embodiment of the present invention 1～4 Situation of change of the face tension force under effect of carbon dioxide.
Fig. 2. for the photosynthesis-carbon dioxide response of the high molecular surfactant of the effective carbon-dioxide response of the embodiment of the present invention 3 Cyclic curve figure.
Fig. 3 is the IR collection of illustrative plates of the high molecular surfactant of the effective carbon-dioxide response of the embodiment of the present invention 3.
Fig. 4 is the high molecular surfactant of the effective carbon-dioxide response of the embodiment of the present invention 31HNMR collection of illustrative plates.
Fig. 5 is the gpc chromatogram of the high molecular surfactant of the effective carbon-dioxide response of the embodiment of the present invention 3.
Fig. 6 is the CMC collection of illustrative plates of the high molecular surfactant of the effective carbon-dioxide response of the embodiment of the present invention 3.
Specific embodiment
Using vinyl sulfonic acid sodium and diethylaminoethyl methacrylate, (DMAEMA is according to mol ratio as polymerized monomer (3-0.5):Deionized water mixing is added after 1 mixing, is added after reacting 6 hours at 80 DEG C after ammonium persulfate (APS), wherein sulphur Sour ammonium addition is the 1wt% of polymerized monomer quality, obtains crude product yield for 60～85%
Using unreacted methacrylic acid two in the crude product that the mixed extractant solvent step one of acetone and petroleum ether is obtained Ethylamino ethyl ester (DMAEMA) monomer, aqueous solution revolving obtains lotion；Both mixed solvent using acetone and petroleum ether volumes Than for 1:300
The quality sum of vinyl sulfonic acid sodium and diethylaminoethyl methacrylate (DMAEMA) and the volume of deionized water Than for 1g:100mL.
The capillary contrast test of reduction is done to different proportion high molecular surfactant.Change monomer consumption, obtain The ratio of vinyl sulfonic acid sodium and diethylaminoethyl methacrylate is respectively 3:1,2:1,1:1,0.5:1 macromolecule surface is lived Property agent, respectively embodiment 1, embodiment 2, embodiment 3, embodiment 4.
Fig. 1 is to obtain high molecular surfactant under different proportion to change situation to the surface tension of water.Can be with from figure Find out, when identical addition, the surfactant and response of example 3 is best.This is due to when 3:In 1 example 1, parent Oily monomer is significantly larger than hydrophilic monomer, and the surface tension of the aqueous solution reduces minimum, and initial emulsification is poor, in the same manner in example 4 by Too high in hydrophilic monomer ratio, the surface tension of the aqueous solution reduces also very little, and initial emulsification is poor.Example 2 and example 3 all have Having preferably reduce capillary performance, and restorative good, but the capillary change model of the aqueous solution in example 3 Enclose bigger, with higher constant interval.
Fig. 2 schemes for the photosynthesis-carbon dioxide response circulation of example 3.Surfactant solution is passed through the increase of carbon dioxide electrical conductivity, Nitrogen is passed through while intensification, electrical conductivity of solution is determined again and is found to revert to original state, so circulation four times, illustrate surface Activating agent has excellent response.
Fig. 3 for example 3 IR collection of illustrative plates. as can be seen from the figure 2968cm-1For the 2-CH replaced on N2CH3Stretching vibration Absworption peak, 1728cm-1For the stretching vibration absworption peak of C=O in ester group, 1148cm-1For the absworption peak of tertiary amine C-N, 1385cm-1 And 1148cm-1For sulfonate ion R-SO2Asymmetric and symmetrical stretching vibration absworption peak, 587cm in-O--1Flexible for S-O shakes Dynamic absworption peak.Prove that synthetic is the binary polymer containing sulfonic group and tertiary amino.
Fig. 4 is the embodiment of the present invention 31HNMR collection of illustrative plates.1HNMR (400MHz, C3D6O),0.9-1.0(m,9H,-CH3), 1.8-2.1(m,9H,-CH3), 2.55 (dd, H, CH2), 2.75 (t, H, CH2), 4.00 (t, H, CH2)
Example 3 is in C3D6In O1HNMR
Gel permeation chromatograph
INSTRUMENT MODEL：The multi-angle laser light scattering apparatus of DAWN HELEOS II 18 (Wyatt companies of the U.S.)
Chromatographic condition：Chromatographic column：Shodex OHpak SB-804HQ, SB-806HQ；Mobile phase：0.1mol/L sodium nitrate Solution：Flow velocity：1ml/min；Column temperature：25℃.
Fig. 5 is the gpc chromatogram of the embodiment of the present invention 3, and molecular weight distribution is in 3500～4500, n=12～20, molecular weight point Cloth is narrower.
Fig. 6 is water-oil interface tension force collection of illustrative plates under the variable concentrations of the embodiment of the present invention 3, and the sample of example 3 is drawn after fitting CMC concentration is 0.02%, illustrates that such surfactant can form micella in low concentration, has the advantages that low consumption.

Claims (7)

1. a kind of high molecular surfactant with effective carbon-dioxide response, it is characterised in that structural formula is:
Wherein x:Y=1:1；N=12～20, and n is natural number.
2. the method for preparing surfactant as claimed in claim 1, it is characterised in that with vinyl sulfonic acid sodium and methacrylic acid Lignocaine ethyl ester is polymerized monomer, with ammonium persulfate as polymerization initiator.
3. method according to claim 2, it is characterised in that the method is carried out according to the following steps：
First, it is (3-0.5) according to mol ratio as polymerized monomer using vinyl sulfonic acid sodium and diethylaminoethyl methacrylate:1 Solvent I mixing is added after mixing, to be added and obtain crude product after reacting 6 hours at 80 DEG C after ammonium persulfate；Wherein ammonium sulfate adds Enter the 1wt% that amount is polymerized monomer gross mass；
2nd, unreacted diethylaminoethyl methacrylate monomer in the crude product for being obtained using solvent II extraction step one, water Solution revolving obtains lotion.
4. method according to claim 3, it is characterised in that the solvent I in step one is deionized water.
5. method according to claim 4, it is characterised in that vinyl sulfonic acid sodium and diethylaminoethyl methacrylate Quality sum is 1g with the volume ratio of deionized water:(1～100) mL.
6. the preparation side of a kind of high molecular surfactant with effective carbon-dioxide response according to claim 3 Method, it is characterised in that the solvent II in step 2 is one or more mixtures in ester, ketone and ether.
7. the preparation side of a kind of high molecular surfactant with effective carbon-dioxide response according to claim 3 Method, it is characterised in that the solvent II in step 2 be acetone and petroleum ether mixed solvent, ethyl acetate and petroleum ether mixed solvent, Ethanol and petroleum ether mixed solvent, acetone and hexamethylene mixed solvent, acetone and dichloromethane mixed solvent, isopropanol and ether Mixed solvent, chloroform and pentane mixed solvent or for acetonitrile and n-hexane mixed solvent.
CN201611098363.9A 2016-12-03 2016-12-03 High molecular surfactant and preparation method with photosynthesis-carbon dioxide response Active CN106634926B (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107353886A (en) * 2017-08-03 2017-11-17 西南石油大学 A kind of anti-CO of compact oil reservoir2Nano composite material of has channeling and preparation method thereof
CN109181707A (en) * 2018-09-21 2019-01-11 佛山市禅城区诺高环保科技有限公司 A kind of water-loss reducer of soil and preparation method thereof
CN115850569A (en) * 2022-12-08 2023-03-28 西南石油大学 For micro-crack of cement stoneRepaired CO 2 Preparation method of responsive gel material

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103304730A (en) * 2013-06-13 2013-09-18 西南石油大学 CO2/N2 type switch-type stiffening water-soluble polymer and synthetic method thereof
CN103936947A (en) * 2014-03-10 2014-07-23 同济大学 Preparation method for double carbon dioxide responsive block copolymer
CN105384863A (en) * 2015-12-07 2016-03-09 江南大学 Responsiveness-based copolymer modified polypropylene (PP) micro-filtration membrane

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103304730A (en) * 2013-06-13 2013-09-18 西南石油大学 CO2/N2 type switch-type stiffening water-soluble polymer and synthetic method thereof
CN103936947A (en) * 2014-03-10 2014-07-23 同济大学 Preparation method for double carbon dioxide responsive block copolymer
CN105384863A (en) * 2015-12-07 2016-03-09 江南大学 Responsiveness-based copolymer modified polypropylene (PP) micro-filtration membrane

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107353886A (en) * 2017-08-03 2017-11-17 西南石油大学 A kind of anti-CO of compact oil reservoir2Nano composite material of has channeling and preparation method thereof
CN109181707A (en) * 2018-09-21 2019-01-11 佛山市禅城区诺高环保科技有限公司 A kind of water-loss reducer of soil and preparation method thereof
CN115850569A (en) * 2022-12-08 2023-03-28 西南石油大学 For micro-crack of cement stoneRepaired CO 2 Preparation method of responsive gel material

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