CN101475691A - Acrylic amide modified polymer micro-crosslinking gel and preparation thereof - Google Patents
Acrylic amide modified polymer micro-crosslinking gel and preparation thereof Download PDFInfo
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- 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
- C09K8/588—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 polymers
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- 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
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F216/00—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 an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F216/12—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 an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
- C08F216/14—Monomers containing only one unsaturated aliphatic radical
- C08F216/1416—Monomers containing oxygen in addition to the ether oxygen, e.g. allyl glycidyl ether
- C08F216/1425—Monomers containing side chains of polyether groups
- C08F216/1433—Monomers containing side chains of polyethylene oxide groups
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- 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
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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- 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
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
- C08F220/285—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety
- C08F220/286—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety and containing polyethylene oxide in the alcohol moiety, e.g. methoxy polyethylene glycol (meth)acrylate
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- C08F226/00—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 single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F226/02—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 single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a single or double bond to nitrogen
- C08F226/04—Diallylamine
Abstract
The invention discloses acrylamide modified polymer micro-crosslinking gel and a preparation method thereof. The preparation method is characterized in that the method comprises the following steps that: acrylamide modified polymer PAE containing functional macro monomer is prepared into an aqueous solution with the concentration between 0.1 and 4g/L, the concentration of crosslinking agent between 0.01 and 1.0g/L, the concentration of surface active agent between 0.01 and 8mmol/L and the concentration of heat stabilizer sodium sulfite between 0.005 and 1.0g/L; the aqueous solution is added in a mixing container with a stirring device and is stirred evenly at room temperature; the pH value of the solution is adjusted between 4 and 11 to prepare a polymer solution system of the acrylamide modified polymer micro-crosslinking gel used for tertiary oil recovery and displacement, oil displacement modification, profile modification or water plugging; and the polymer solution system undergoes micro crosslinking during flowing inside an oil layer to form the gel. The acrylamide modified polymer micro-crosslinking gel has ideal elasticity, difficult dehydration, stable performance and excellent performances on tackifying, temperature resistance, salt resistance, shearing resistance and ageing resistance.
Description
One, technical field
The present invention relates to a kind of acrylic amide modified polymer micro-crosslinking gel and preparation method thereof, belong to macromolecular material and oilfield chemistry field.
Two, technical background
The flowable weak gel displacement of reservoir oil, weak gel profile drive profile control and strong gel water-plugging technique is the important technology that improves oil recovery, and the on-the-spot gelling system that uses in oil field mainly is partially hydrolyzed polyacrylamide (HPAM) gel at present, but there is following deficiency in the HPAM gelling system: temperature tolerance relatively poor (being lower than 80 ℃), salt tolerance relatively poor (being lower than 10000mg/L), easily dehydration, system elasticity is lower, long-term anti-aging less stable, validity period is short, therefore, the application of HPAM gelling system in high temperature, high salinity oil reservoir is restricted.In addition, polymkeric substance HPAM is a ultra-high molecular weight, and the molecular chain size is big, and macromolecular shear degradation easily takes place in dissolving, injection process.Therefore, development can be applicable to high temperature (being higher than 80 ℃), high salt, resistance to deterioration stable polymer gelling system, reduces cost for oil production, is the important research target that improves oil recovery.In order to improve the temperature resistant antisalt performance of HPAM gelling system, the HPAM as gel host has been carried out modification, in the polyacrylamide molecular chain, introduce the synthetic temperature resistant antisalt multipolymer of big side group or rigid radical; Introduce the synthetizing hydrophobic associated multipolymer of hydrophobic grouping.These polyacrylamide modified gel systems respectively have its outstanding advantage, but heatproof, anti-salt and other performance are still waiting raising, and polymer loading is higher.Lv Xin etc., polymer material science and engineering, 2006,22 (3): organoaluminum and the weak gelling system of the crosslinked HPAM of phenolic aldehyde have been compared in research, find because the existence of crosslinking structure, the polymkeric substance rigidity strengthens, the conformational change difficulty increases, the weak gelling system of HPAM has higher soltion viscosity under high temperature, high salinity, but temperature is only limited to (75-90 ℃), be higher than 90 ℃ after, weak gel is because of excessive crosslinked the dehydration, also there is thermal destruction in polymkeric substance under the hot conditions simultaneously, and these factors all cause weak gel unstable under the hot conditions.Guo Yongjun etc., oilfield chemistry, 2007,24 (4): 343-346, having studied polymkeric substance and dosage of crosslinking agent influences hydrophobic associated polymer AP-P4 weak gel profile and drives the gel-forming property of agent, and institute is 1.5～1.8g/L with polymer concentration, but the salinity that becomes glue to use is not high, have only 9.34g/L, temperature also is only limited to 84 ℃.Liu Qingwang etc., journal of Zhejiang university (version of science), 2005,32 (3): 295-299, studied the cationic-type polyacrylamide weak gel profile and driven the composition and performance of agent, found that, mass concentration is that to become the highest gel viscosity behind the glue be 50000mPa.s to the polymkeric substance of 5g/L, this shows, become the consumption of the used polymkeric substance of glue higher.
Three, summary of the invention
The objective of the invention is at the not enough and higher polymer loading on the gelling system performance that is used for the displacement of reservoir oil, transfer drive, profile control and water-plugging technique at present, according to heatproof, anti-salt pair gelatin polymer molecular structure and performance demands, a kind of acrylic amide modified polymer micro-crosslinking gel and preparation method thereof is provided, be characterized in wide material sources, price is low, polymerization activity is high acrylamide (AM) as main hydrophilic monomer, with a spot of anionic monomer or/and cationic monomer is the solubilising hydrophilic monomer, with 4-vinyl benzyl alkylphenol polyoxyethylene (CH
2=CH-C
6H
4-CH
2(OCH
2CH
2) n-O-C
6H
4-C
mH
2m+1, n=1～60, m=1～20), 4-vinyl benzyl alkyl polyoxyethylene ether (CH
2=CH-C
6H
4-CH
2(OCH
2CH
2) n-O-C
mH
2m+1, n=1～60, m=1～20), allyl group alkylphenol polyoxyethylene (CH
2=CH-CH
2(OCH
2CH
2) n-O-C
6H
4-C
mH
2m+1, n=1～60, m=1～20), allyl group alkyl polyoxyethylene ether (CH
2=CH-CH
2(OCH
2CH
2) n-O-C
mH
2m+1, n=1～60, m=1～20), alkylphenol polyoxyethylene acrylate (CH
2=CH-CO (OCH
2CH
2) n-O-C
6H
4-C
mH
2m+1, n=1～60, m=1～20), alkylphenol polyoxyethylene methacrylic ester (CH
2=C (CH
3)-CO (OCH
2CH
2) n-O-C
6H
4-C
mH
2m+1, n=1～60, m=1～20), alkyl polyoxyethylene ether acrylate (CH
2=CH-CO (OCH
2CH
2) n-O-C
mH
2m+1, n=1～60, m=1～20) or/and alkyl polyoxyethylene ether methacrylic ester (CH
2=C (CH
3)-CO (OCH
2CH
2) n-O-C
mH
2m+1N=1～60, m=1～20) the big monomer of at least a function in is a comonomer, adopt the aqueous free radical process for copolymerization to synthesize comb copolymer PAE, in copolymer p AE solution, add linking agent aluminum chloride then, chromium chloride, potassium bichromate/S-WAT, chromic formate, Chromic lactate, chromium acetate, chromium propionate, chromium butyrate, chromium+oxalic acid, propanedioic acid chromium, Tiorco 677, oligomeric resol, formaldehyde, oxalic dialdehyde, glutaraldehyde, terpolycyantoamino-formaldehyde resin, phenol, pyrocatechol, Resorcinol, Resorcinol, or/and at least a in the vulkacit H, add tensio-active agent and thermo-stabilizer S-WAT again, obtain a kind of polymer solution system that forms the acrylic amide modified polymer gel, this polymer solution system takes place little crosslinked in oil reservoir in the flow process, difference according to polymer concentration, the apparent viscosity of gelling system obviously or sharply increases, gelling system is as the displacement of reservoir oil, transfer drive, profile control or water blockoff, thus oil recovery improved.
The present inventor finds that the big monomer concentration of various factors such as function, copolymer concentration, crosslinker concentration, formation temperature, stratum salinity, surfactant concentration and thermo-stabilizer concentration have a significant impact the structure and the performance of gained gelling system in the crosslinking reaction of copolymer p AE and linking agent.When contain the big monomeric comb copolymer PAE of an amount of function take place little crosslinked after, the molecular weight of multipolymer increases, the rigid structure that itself just contains the multipolymer of long side chain further obviously strengthens.Different copolymer concentrations can guarantee the superperformance of the gelling system of different purposes.Add proper amount of cross-linking agent in cross-linking system, salt resistance and ageing resistance significantly improve.Formation temperature can obviously influence the time of crosslinking reaction, and therefore, different cross-linking systems are applicable to the oil reservoir of differing temps.
Purpose of the present invention is realized that by following technical measures wherein said raw material umber is parts by weight except that specified otherwise.
1. the preparation of acrylic amide modified polymer PAE
With 20 parts of acrylamides, anionic monomer is or/and 1～10 part of cationic monomer, 0.5～15 part of the big monomer of function, deionized water adds in the three neck reaction flasks regulator solution pH=4～9 for 30～1000 parts, behind the logical N230min, add 0.002～0.5 part of initiator persulphate down for 30～70 ℃ in temperature, reacted 12～36 hours, make PAE, dilute with water obtains the PAE strong solution again.
Wherein anionic monomer is vinylformic acid, methacrylic acid, 3-acrylimide base-3 Methylbutanoic acid, 2-acrylamido-2-C
1-18Alkyl C
2-18Alkylsulphonic acid, methylene-succinic acid are or/and at least a in the vinylbenzenesulfonic acid; Cationic monomer is dimethyl diallyl ammonium chloride, Jia Jibingxisuanyizhi base trimethyl ammonium chloride, ethyl propenoate base trimethyl ammonium chloride or/and at least a in 2-acrylamido-2-trimethoxysilyl propyl methacrylate ammonium chloride; The big monomer of function is 4-vinyl benzyl alkylphenol polyoxyethylene (CH
2=CH-C
6H
4-CH
2(OCH
2CH
2) n-O-C
6H
4-C
mH
2m+1, n=1～60, m=1～20), 4-vinyl benzyl alkyl polyoxyethylene ether (CH
2=CH-C
6H
4-CH
2(OCH
2CH
2) n-O-C
mH
2m+1, n=1～60, m=1～20), allyl group alkylphenol polyoxyethylene (CH
2=CH-CH
2(OCH
2CH
2) n-O-C
6H
4-C
mH
2m+1, n=1～60, m=1～20), allyl group alkyl polyoxyethylene ether (CH
2=CH-CH
2(OCH
2CH
2) n-O-C
mH
2m+1, n=1～60, m=1～20), alkylphenol polyoxyethylene acrylate (CH
2=CH-CO (OCH
2CH
2) n-O-C
6H
4-C
mH
2m+1, n=1～60, m=1～20), alkylphenol polyoxyethylene methacrylic ester (CH
2=C (CH
3)-CO (OCH
2CH
2) n-O-C
6H
4-C
mH
2m+1, n=1～60, m=1～20), alkyl polyoxyethylene ether acrylate (CH
2=CH-CO (OCH
2CH
2) n-O-C
mH
2m+1, n=1～60, m=1～20) or/and alkyl polyoxyethylene ether methacrylic ester (CH
2=C (CH
3)-CO (OCH
2CH
2) n-O-C
mH
2m+1, n=1～60, m=1～20) at least a.
Acrylic amide modified polymer micro-crosslinking gel preparation
It is 0.1～4.0g/L that copolymer p AE is made into concentration, crosslinker concentration is 0.01～1.0g/L, surfactant concentration is 0.01～8mmol/L, the thermo-stabilizer concentration of sodium sulfite is the aqueous solution of 0.005～1.0g/L, add and have in the mixing tank of whipping appts, at room temperature stir, regulator solution pH=4～11, obtain the polymer solution system as the acrylic amide modified polymer micro-crosslinking gel of the displacement of reservoir oil, transfer drive, profile control or water blockoff, little gel that is cross-linked to form takes place in this polymer solution system in the flow process in oil reservoir.
Wherein tensio-active agent contains: anion surfactant C
8-16Sodium alkyl benzene sulfonate, C
8-16Sodium alkyl sulfate; Cats product is C
8-16Alkyl trimethyl bromine (chlorine) is changed ammonium or/and C
8-16A kind of in the alkyl polyoxyethylene ether.Linking agent be aluminum chloride, chromium chloride, potassium bichromate/S-WAT, chromic formate, Chromic lactate, chromium acetate, chromium propionate, chromium butyrate, chromium+oxalic acid, propanedioic acid chromium, Tiorco 677, oligomeric resol, formaldehyde, oxalic dialdehyde, glutaraldehyde, terpolycyantoamino-formaldehyde resin, phenol, pyrocatechol, Resorcinol, Resorcinol be or/and at least a in the vulkacit H.
3. the performance of acrylic amide modified polymer micro-crosslinking gel
(1) polymers soln that contains 0.45g/L PAE, 0.15g/L (phenol+glutaraldehyde), 0.03g/L S-WAT, 0.855mol/L NaCl is little crosslinked and aging down 85 ℃ and 110 ℃ respectively, and solution apparent viscosity and time relation are as shown in Table 1 and Table 2.The result show the PAE of lower concentration in salt brine solution, take place little crosslinked after, the apparent viscosity and the ageing resistance of solution obviously improve.
(2) by copolymer p AE and the mass ratio of oligomeric resol be the polymers soln of 3:1,0.03g/L S-WAT in the 0.855mol/L of different polymer concentrations NaCl salt brine solution in 90 ℃ down behind little crosslinked 48h, the apparent viscosity of weak gel and the relation of polymer concentration are as shown in table 3.The result shows that the thickening property of PAE gelling system is good, still has high apparent viscosity under high salt.
(3) in 110 ℃ down behind little crosslinked 48h, the relation of the apparent viscosity of weak gel and NaCl concentration is as shown in table 4 in the salt brine solution of different N aCl concentration for the polymer oil-displacing agent that contains the oligomeric resol of 0.45g/L PAE, 0.10g/L, 0.03g/L S-WAT.The result shows that the weak gel of PAE has excellent anti-salt property.
(4) polymers soln that contains 0.5g/L PAE, 0.15g/L chromium butyrate, 0.855mol/L NaCl is behind little crosslinked 24h under 70 ℃, and shearing action is as shown in table 5 to the influence of polymer solution viscosity.As seen from the figure, in the process of eliminating shearing action, the apparent viscosity of weak gel is recovered again gradually, illustrates that weak gel has high elasticity, and shear degradation does not take place.
(5) contain the polymers soln of 0.45g/L PAE, 0.25g/L terpolycyantoamino-formaldehyde resin, 0.05g/L S-WAT, 0.855mol/LNaCl and 0.6mmol/L Sodium dodecylbenzene sulfonate behind little crosslinked 72h under 90 ℃, the apparent viscosity of weak gel is 470mPa.s, the result shows, do not compare with adding tensio-active agent, the solution apparent viscosity sharply rises.Compare with the result of study (＜350mPas is under the same test condition) of reported in literature, the tackifying of polymer weak gel of the present invention obviously improves.
4. the purposes of acrylic amide modified polymer micro-crosslinking gel
Different according to the apparent viscosity of gel and intensity, acrylic amide modified polymer micro-crosslinking gel can be used as used for tertiary oil recovery oil-displacing agent, adjusting driving agnet, amendment or plugging agent.
It is 0.1～1.0g/L that copolymer p AE is made into concentration, crosslinker concentration is 0.01～1.0g/L, surfactant concentration is 0.01～6mmol/L, the thermo-stabilizer concentration of sodium sulfite is the aqueous solution of 0.005～1.0g/L, add and have in the mixing tank of whipping appts, at room temperature stir, regulator solution pH=4～11, obtain the polymer solution system as the acrylic amide modified polymer micro-crosslinking gel of polymer flooding, little weak gel that is cross-linked to form takes place in this polymer solution system in the flow process in oil reservoir.
It is 0.8～2.5g/L that copolymer p AE is made into concentration, crosslinker concentration is 0.01～1.0g/L, surfactant concentration is 0.01～7mmol/L, the thermo-stabilizer concentration of sodium sulfite is the aqueous solution of 0.005～1.0g/L, add and have in the mixing tank of whipping appts, at room temperature stir, regulator solution pH=4～11, obtain the polymer solution system as the acrylic amide modified polymer micro-crosslinking gel of adjusting driving agnet or amendment, little weak gel that is cross-linked to form takes place in this polymer solution system in the flow process in oil reservoir.
It is 2.0～5.0g/L that copolymer p AE is made into concentration, crosslinker concentration is 0.01～1.0g/L, surfactant concentration is 0.01～8mmol/L, the thermo-stabilizer concentration of sodium sulfite is the aqueous solution of 0.005～1.0g/L, add and have in the mixing tank of whipping appts, at room temperature stir, regulator solution pH=4～11, obtain the polymer solution system as the acrylic amide modified polymer micro-crosslinking gel of plugging agent, little strong gel that is cross-linked to form takes place in this polymer solution system in the flow process in oil reservoir.
When the above acrylic amide modified polymer micro-crosslinking gel of preparation, wherein tensio-active agent contains: anion surfactant C
8-16Sodium alkyl benzene sulfonate, C
8-16Sodium alkyl sulfate; Cats product is C
8-16Alkyl trimethyl bromine (chlorine) is changed ammonium or/and C
8-16A kind of in the alkyl polyoxyethylene ether.Linking agent be aluminum chloride, chromium chloride, potassium bichromate/S-WAT, chromic formate, Chromic lactate, chromium acetate, chromium propionate, chromium butyrate, chromium+oxalic acid, propanedioic acid chromium, Tiorco 677, oligomeric resol, formaldehyde, oxalic dialdehyde, glutaraldehyde, terpolycyantoamino-formaldehyde resin, phenol, pyrocatechol, Resorcinol, Resorcinol be or/and at least a in the vulkacit H.
5. the advantage of acrylic amide modified polymer micro-crosslinking gel of the present invention
The present invention is a basic structural unit with the acrylamide, and introducing the big monomer of function in polymer molecule is 4-vinyl benzyl alkylphenol polyoxyethylene (CH
2=CH-C
6H
4-CH
2(OCH
2CH
2) n-O-C
6H
4-C
mH
2m+1, n=1～60, m=1～20), 4-vinyl benzyl alkyl polyoxyethylene ether (CH
2=CH-C
6H
4-CH
2(OCH
2CH
2) n-O-C
mH
2m+1, n=1～60, m=1～20), allyl group alkylphenol polyoxyethylene (CH
2=CH-CH
2(OCH
2CH
2) n-O-C
6H
4-C
mH
2m+1, n=1～60, m=1～20), allyl group alkyl polyoxyethylene ether (CH
2=CH-CH
2(OCH
2CH
2) n-O-C
mH
2m+1, n=1～60, m=1～20), alkylphenol polyoxyethylene acrylate (CH
2=CH-CO (OCH
2CH
2) n-O-C
6H
4-C
mH
2m+1, n=1～60, m=1～20), alkylphenol polyoxyethylene methacrylic ester (CH
2=C (CH
3)-CO (OCH
2CH
2) n-O-C
6H
4-C
mH
2m+1, n=1～60, m=1～20), alkyl polyoxyethylene ether acrylate (CH
2=CH-CO (OCH
2CH
2) n-O-C
mH
2m+1, n=1～60, m=1～20) or/and alkyl polyoxyethylene ether methacrylic ester (CH
2=C (CH
3)-CO (OCH
2CH
2) n-O-C
mH
2m+1, n=1～60, m=1～20) at least a, in multipolymer, also introduce negatively charged ion or/and positively charged ion solubilising monomer to increase the solvability and the tackifying of polymkeric substance, has at first synthesized acrylic amide modified polymer PAE.The big monomeric introducing of function that contains the long shoot chain makes that the structure of PAE molecular chain is the rigid structure of comb type, be difficult to take place intramolecularly and curl in salt brine solution, and the oxyethyl group of molecular chain is to Ca
2+, Mg
2+Divalent cation has complexing action, and therefore, PAE has the ability of good anti-one, divalent cation salt.In addition, the alkyl of molecular side chain end (benzene) can form the supramolecule aggregation structure by Intermolecular Forces, and compares with line style ultra-high molecular weight HPAM, and the molecular weight of PAE is not high.Therefore, the polymer P AE with above special molecular structure take place little crosslinked after, the molecular weight of polymkeric substance increases, and molecule chain rigidity and the effect of molecule interchain hydrophobic association obviously strengthen, and the gelling system of formation has excellent tackify, heatproof, anti-salt, anti-shearing and aging-resistant performance.Have the effect of physics reversible hydrophobic association owing to PAE is intermolecular, therefore, the consumption of linking agent and polymer P AE is not high, and the molecular weight of PAH is not high, and the good springiness of gel is not easy dehydration like this.In cross-linking system, add an amount of tensio-active agent, can strengthen intermolecular hydrophobic association effect, make the apparent viscosity of gelling system further obviously rise by the bridging action of hydrophobic grouping in the tensio-active agent.
Four, embodiment
Below by embodiment the present invention is carried out concrete description; be necessary to be pointed out that at this present embodiment only is used for the present invention is further specified; can not be interpreted as limiting the scope of the invention, the researchist in this field can make some nonessential improvement and adjustment to the present invention according to the content of the invention described above.
Embodiment 1
Acrylamide 20.000 grams, vinylformic acid 8.042 grams, 4-vinyl benzyl polyoxyethylene octylphenol ether (the affixture EO of Soxylat A 25-7 is 40) 1.800 grams are dissolved in 380mL distilled water, add in three mouthfuls of reaction flasks, with NaOH regulator solution pH=8,65 ℃ of temperature of reaction, logical N
230min adds 0.05mol/L Potassium Persulphate initiator solution 6.50mL, reaction 32h, and the polymkeric substance dilute with water makes the PAE strong solution.Get a certain amount of polymer P AE preparation oil-displacing agent aqueous sample, sample is the water white transparency shape.Is polymer concentration 0.5g/L, Tiorco 677 concentration is 0.15g/L, Sodium dodecylbenzene sulfonate concentration is 0.3mmol/L, concentration of sodium sulfite is the aqueous solution of 0.03g/L, add and have in the mixing vessel of whipping appts, at room temperature stir, regulator solution pH=5～10 obtain the acrylic amide modified polymer oil-displacing agent.This polymer oil-displacing agent takes place crosslinked in 30～110 ℃ of oil reservoirs in the flow process, soltion viscosity obviously increases.
Embodiment 2
Acrylamide 20.000 grams, 2-acrylamido-2-methyl propane sulfonic acid, 6.300 grams, 4-vinyl benzyl polyoxyethylene octylphenol ether (the affixture EO of Soxylat A 25-7 is 20) 9.500 grams are dissolved in 120mL distilled water, add in three mouthfuls of reaction flasks, with NaOH regulator solution pH=7,60 ℃ of temperature of reaction, logical N
230min adds 0.05mol/L Potassium Persulphate initiator solution 5.20mL, reaction 32h, and the polymkeric substance dilute with water makes the PAE strong solution.Get a certain amount of polymer P AE preparation oil-displacing agent aqueous sample, sample is the water white transparency shape.Is polymer concentration 2.2g/L, oligomeric resol concentration is 0.75g/L, Sodium dodecylbenzene sulfonate concentration is 0.2mmol/L, concentration of sodium sulfite is the aqueous solution of 0.05g/L, add and have in the mixing vessel of whipping appts, at room temperature stir, regulator solution pH=5～10 obtain the little crosslinked profile control system of acrylic amide modified polymer.This polymers soln takes place little crosslinked in 50～120 ℃ of oil reservoirs in the flow process, form weak gel.
Embodiment 3
Acrylamide 20.000 grams, 3-acrylimide base-3 Methylbutanoic acid 5.100 grams, allyl group polyoxyethylene octylphenol ether (the affixture EO of Soxylat A 25-7 is 12) 7.000 grams are dissolved in 630mL distilled water, add in three mouthfuls of reaction flasks, with NaOH regulator solution pH=5,60 ℃ of temperature of reaction, logical N
230min adds 0.05mol/L Potassium Persulphate initiator solution 12.0mL, reaction 24h, and the polymkeric substance dilute with water makes the PAE strong solution.Get a certain amount of polymer P AE preparation oil-displacing agent aqueous sample, sample is the water white transparency shape.Is polymer concentration 1.2g/L, the total concn of phenol and glutaraldehyde is 0.25g/L, Sodium dodecylbenzene sulfonate concentration is 0.2mmol/L, concentration of sodium sulfite is the aqueous solution of 0.03g/L, add and have in the mixing vessel of whipping appts, at room temperature stir, regulator solution pH=5～10 obtain the little crosslinked transfer drive system of acrylic amide modified polymer.This polymers soln takes place little crosslinked in 50～95 ℃ of oil reservoirs in the flow process, form weak gel.
Embodiment 4
Acrylamide 20.000 grams, vinylbenzenesulfonic acid 6.450 grams, ceteth acrylate (the affixture EO of Soxylat A 25-7 is 10) 2.600 grams are dissolved in 750mL distilled water, add in three mouthfuls of reaction flasks, with NaOH regulator solution pH=5,60 ℃ of temperature of reaction, logical N
230min adds 0.05mol/L Potassium Persulphate initiator solution 9.0mL, reaction 36h, and the polymkeric substance dilute with water makes the PAE strong solution.Get a certain amount of polymer P AE preparation oil-displacing agent aqueous sample, sample is the water white transparency shape.Is polymer concentration 3.0g/L, terpolycyantoamino-formaldehyde resin concentration is 0.800g/L, Sodium dodecylbenzene sulfonate concentration is 0.2mmol/L, concentration of sodium sulfite is the aqueous solution of 0.05g/L, add and have in the mixing vessel of whipping appts, at room temperature stir, regulator solution pH=5～10 obtain the little crosslinked water blockoff system of acrylic amide modified polymer.This polymers soln takes place little crosslinked in 50～120 ℃ of oil reservoirs in the flow process, form strong gel.
Embodiment 5
Acrylamide 20.000 grams, dimethyl diallyl ammonium chloride 2.500 grams, dodecyl Soxylat A 25-7 acrylate (the affixture EO of Soxylat A 25-7 is 50) 12.000 grams are dissolved in 430mL distilled water, add in three mouthfuls of reaction flasks, with NaOH regulator solution pH=5,70 ℃ of temperature of reaction, logical N
230min adds 0.05mol/L Potassium Persulphate initiator solution 16.0mL, reaction 36h, and the polymkeric substance dilute with water makes the PAE strong solution.Get a certain amount of polymer P AE preparation oil-displacing agent aqueous sample, sample is the water white transparency shape.Is polymer concentration 0.7g/L, terpolycyantoamino-formaldehyde resin concentration is 0.800g/L, Sodium dodecylbenzene sulfonate concentration is 0.2mmol/L, concentration of sodium sulfite is the aqueous solution of 0.05g/L, add and have in the mixing vessel of whipping appts, at room temperature stir, regulator solution pH=5～10 obtain the acrylic amide modified polymer oil-displacing agent.This polymer oil-displacing agent takes place little crosslinked in 30～95 ℃ of oil reservoirs in the flow process, form weak gel.
Five, subordinate list explanation
Table 1 salt brine solution apparent viscosity is with variation (crosslinking temperature: 85 ℃) crosslinked, digestion time
Annotate: multipolymer 0.45g/L, NaCl 0.855mol/L, (phenol+glutaraldehyde) 0.15g/L, S-WAT 0.03g/L.
Table 2 salt brine solution apparent viscosity is with variation (crosslinking temperature: 110 ℃) crosslinked, digestion time
Annotate: multipolymer 0.45g/L, NaCl 0.855mol/L, (phenol+glutaraldehyde) 0.15g/L, S-WAT 0.03g/L.
Table 3 polymer concentration is to the influence (crosslinking temperature: 90 ℃) of solution apparent viscosity
Annotate: multipolymer: oligomeric resol=3:1 (mass ratio), NaCl 0.855mol/L, S-WAT 0.03g/L.
Table 4 NaCl concentration is to the influence (crosslinking temperature: 110 ℃) of solution apparent viscosity
Annotate: multipolymer 0.45g/L, oligomeric resol 0.10g/L, S-WAT 0.03g/L.
Table 5 shearing rate is to the influence (crosslinking temperature: 70 ℃) of solution apparent viscosity
Annotate: multipolymer 0.5g/L, NaCl0.855mol/L, chromium butyrate 0.15g/L.
More than the apparent viscosity in the table is except that specifying, test condition is 45 ℃, 7.34s
-1
Claims (2)
1. the preparation of acrylic amide modified polymer PAE
A kind of acrylic amide modified polymer micro-crosslinking gel and preparation method thereof is characterized in that:
With 20 parts of acrylamides, anionic monomer is or/and 1～10 part of cationic monomer, 0.5～15 part of the big monomer of function, and deionized water adds in the three neck reaction flasks for 30～1000 parts, regulator solution pH=4～9, logical N
2Behind the 30min, add 0.002～0.5 part of initiator persulphate down for 30～70 ℃, reacted 12～36 hours, make polymer P AE in temperature.
Wherein anionic monomer is vinylformic acid, methacrylic acid, 3-acrylimide base-3 Methylbutanoic acid, 2-acrylamido-2-C
1-18Alkyl C
2-18Alkylsulphonic acid, methylene-succinic acid are or/and at least a in the vinylbenzenesulfonic acid; Cationic monomer is dimethyl diallyl ammonium chloride, Jia Jibingxisuanyizhi base trimethyl ammonium chloride, ethyl propenoate base trimethyl ammonium chloride or/and at least a in 2-acrylamido-2-trimethoxysilyl propyl methacrylate ammonium chloride; The big monomer of function is 4-vinyl benzyl alkylphenol polyoxyethylene (CH
2=CH-C
6H
4-CH
2(OCH
2CH
2)
n-O-C
6H
4-C
mH
2m+1, n=1～60, m=1～20), 4-vinyl benzyl alkyl polyoxyethylene ether (CH
2=CH-C
6H
4CH
2(OCH
2CH
2)
n-O-C
mH
2m+1, n=1～60, m=1～20), allyl group alkylphenol polyoxyethylene (CH
2=CH-CH
2(OCH
2CH
2)
n-O-C
6H
4-C
mH
2m+1, n=1～60, m=1～20), allyl group alkyl polyoxyethylene ether (CH
2=CH-CH
2(OCH
2CH
2)
n-O-C
mH
2m+1, n=1～60, m=1～20), alkylphenol polyoxyethylene acrylate (CH
2=CH-CO (OCH
2CH
2)
n-O-C
6H
4-C
mH
2m+1, n=1～60, m=1～20), alkylphenol polyoxyethylene methacrylic ester (CH
2=C (CH
3)-CO (OCH
2CH
2)
n-O-C
6H
4-C
mH
2m+1, n=1～60, m=1～20), alkyl polyoxyethylene ether acrylate (CH
2=CH-CO (OCH
2CH
2)
n-O-C
mH
2m+1, n=1～60, m=1～20) or/and alkyl polyoxyethylene ether methacrylic ester (CH
2=C (CH
3)-CO (OCH
2CH
2)
n-O-C
mH
2m+1, n=1～60, m=1～20) at least a.
2. according to claim 1, a kind of acrylic amide modified polymer micro-crosslinking gel and preparation method thereof is characterized in that:
It is 0.1～4.0g/L that copolymer p AE is made into concentration, crosslinker concentration is 0.01～1.0g/L, surfactant concentration is 0.01～8mmol/L, the thermo-stabilizer concentration of sodium sulfite is the aqueous solution of 0.005～1.0g/L, add and have in the mixing tank of whipping appts, at room temperature stir, regulator solution pH=4～11, obtain the polymer solution system as the acrylic amide modified polymer micro-crosslinking gel of the displacement of reservoir oil, transfer drive, profile control or water blockoff, little gel that is cross-linked to form takes place in this polymer solution system in the flow process in oil reservoir.
Wherein tensio-active agent contains: anion surfactant C
8-16Sodium alkyl benzene sulfonate, C
8-16Sodium alkyl sulfate; Cats product is C
8-16Alkyl trimethyl bromine (chlorine) is changed ammonium or/and C
8-16A kind of in the alkyl polyoxyethylene ether.Linking agent be aluminum chloride, chromium chloride, potassium bichromate/S-WAT, chromic formate, Chromic lactate, chromium acetate, chromium propionate, chromium butyrate, chromium+oxalic acid, propanedioic acid chromium, Tiorco 677, oligomeric resol, formaldehyde, oxalic dialdehyde, glutaraldehyde, terpolycyantoamino-formaldehyde resin, phenol, pyrocatechol, Resorcinol, Resorcinol be or/and at least a in the six industry methyl tetramines.
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