CN102372820B - Long branched chain polymer used for tertiary oil recovery and synthesis method thereof - Google Patents

Long branched chain polymer used for tertiary oil recovery and synthesis method thereof Download PDF

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CN102372820B
CN102372820B CN 201010263536 CN201010263536A CN102372820B CN 102372820 B CN102372820 B CN 102372820B CN 201010263536 CN201010263536 CN 201010263536 CN 201010263536 A CN201010263536 A CN 201010263536A CN 102372820 B CN102372820 B CN 102372820B
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oil recovery
monomer
tertiary oil
long chain
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CN102372820A (en
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赵方园
李勇
林蔚然
计文希
刘希
伊卓
杜凯
刘晓光
魏小林
祝纶宇
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Abstract

The invention provides a polymerizable functional monomer shown in a formula (11) and a synthesis method thereof. The prepared polymerizable functional monomer can be used for synthesizing a long branched chain polymer used for tertiary oil recovery, thus finally preparing a binary composite oil displacement agent for tertiary oil recovery. The binary composite oil displacement agent for tertiary oil recovery obtained in the invention can be used for greatly improving the viscosity of a single polymer oil displacement agent under the conditions of high salinity and high temperature, thereby being beneficial to the application in tertiary oil recovery.

Description

A kind of used for tertiary oil recovery long chain branched polymers and synthetic method thereof
Technical field
The present invention relates to the tertiary oil recovery field, relate in particular to synthetic, long chain branched polymers synthetic of polymerizable functional monomer, can be applicable to fields such as tertiary oil recovery binary combination flooding finish.
Background technology
Radical polymerization is one of effective means of preparation vinyl polymer.Obtain by radical polymerization more than 70% in the vinyl polymer that uses at present.Radical polymerization has many advantages, and is many as suitable monomers, polymerizing condition is gentle, polymerization technique is simple etc.Because many monomers can carry out radical polymerization, can water be that medium suspends and letex polymerization, polymerization technique is easy and simple to handle, its favorable reproducibility, thereby since the fifties in last century, become the important technology of industrial production macromolecule product.
General free radical polymerisation process mainly contains synthetic methods such as substance law, aqua-solution method, emulsion method and suspension method.Whether add other monomers according to polymerization, can be divided into two kinds of homopolymerization and copolymerization again, of many uses in industries such as oil, mining, papermaking, water treatment, weaving, its demand is also in continuous increase.
What free yl polymerizating monomer was commonly used has: vinylbenzene, and vinylchlorid, vinyl acetate between to for plastic, vinyl cyanide, acrylamide, vinylformic acid and ester class for improving polymer properties, often need have the functional monomer of various performances.As has a polymerization single polymerization monomer of emulsification function.
Polymerization single polymerization monomer with emulsification function, claim polymerisable emulsifier again, in its molecular structure except the emulsifying agent group that contains hydrophilic and oleophilic, also contain the functional group that to participate in Raolical polymerizable, can be bonded in the latex particle surface in the mode of chemical bond, become the part of polymkeric substance, therefore the emulsifying agent molecule desorb can not occur again, thereby make polymer particle in agglomeration process, be subjected to electrostatic repulsion and bigger steric restriction effect, make the be improved kind of polymerisable emulsifier of the stability of latex a lot, it is moderate that Malaysia acids polymerisable emulsifier has reactive behavior, be difficult for distinct advantages such as homopolymerization.
The product that obtains industrial application at oilfield polymer flooding mainly is partially hydrolyzed polyacrylamide, but has also found some problems in the practice process that uses POLYACRYLAMIDE FLOODING.The degraded of polyacrylamide is one of more serious problem, comprises shear degradation, thermal destruction and oxidative degradation.Sampling analysis before and after the injection pump of partially hydrolyzed polyacrylamide can be found its viscosity degradation 10~30% in order to solve this shear degradation problem, and can adopt increases implantation concentration, adds linking agent or underground method such as synthetic.Present developing direction is by process for copolymerization, introduces branched chain link in the polyacrylamide amine molecule, improves its rigidity, thereby improves its anti-shear ability.When polyacrylamide surpasses 93 ℃ in temperature, serious thermal destruction can take place, therefore be not suitable for using polyacrylamide at high-temperature stratum.Also can in the polyacrylamide amine molecule, introduce ring texture and sulfonic group by the method for copolymerization, improve its thermostability.Oxygenizement also can cause the degraded of partially hydrolyzed polyacrylamide.
Introduce the monomeric unit of some high thermal stability monomeric units, big skeleton and the group of strong hydratability at polymer molecular chain, thereby strengthen polymer thermostable and molecule chain rigidity, strengthen the polymer hydration ability, make polymer molecule can keep bigger ydrodynamics size in the high salinity aqueous solution, this has strengthened the polymkeric substance salt resistance ability to a certain extent.Simultaneously, the introducing of function monomer is restricted polymkeric substance hydrolysis under high salinity water quality condition, the phenomenon of precipitation can not occur taking place with calcium ions and magnesium ions, thereby reaches the purpose of anti-salt.
Summary of the invention
The technical problem to be solved in the present invention:
The objective of the invention is at above-mentioned weak point, a kind of polymerizable functional monomer and synthetic method thereof are provided, prepared polymerizable functional monomer, can be used as polymeric emulsifiers, and synthesizing for the used for tertiary oil recovery long chain branched polymers, to improve displacement of reservoir oil polymer properties, can be used as tertiary oil recovery binary combination flooding finish.
The product technology scheme of polymerizable functional monomer of the present invention is:
A kind of polymerizable functional monomer, its molecular structural formula are as (11) formula:
(11) in the formula: n be 2 or 6, m be 4,6 or 8.
First kind of synthetic method technical scheme of polymerizable functional monomer of the present invention is:
The first step is mixed diamines with binary lipid acid, diamines structural formula NH 2-(CH 2) n-NH 2, binary fatty acid structure formula HOOC-(CH 2) m-COOH, n be 2 or 6, m be 4,6 or 8, be heated to 110 ℃~160 ℃, reacted 2~6 hours, obtain intermediate M, the structural formula of intermediate M is (12) formula:
In molar ratio, diamines: binary lipid acid=1: 1~1.2;
Second step in gained intermediate M, added organic solvent, added cis-butenedioic anhydride again, under 80 ℃~110 ℃ of temperature of reaction, and back flow reaction 4~8 hours;
Described organic solvent is one or more the mixture in following: ethanol, acetone, ethyl acetate, benzene,toluene,xylene, methylene dichloride and trichloromethane; In molar ratio,
Diamines: organic solvent=1: 20~30;
Diamines: cis-butenedioic anhydride=1: 1~1.2;
The 3rd step, will go up the step product and steam organic solvent, drying obtains polymerizable functional monomer product;
Can further carry out recrystallization to product purifies.
Second kind of synthetic method technical scheme of polymerizable functional monomer of the present invention is:
The first step in organic solvent, is mixed diamines with binary lipid acid, be heated to 110 ℃~156 ℃, reacts 2~6 hours, obtains the solution of intermediate M; The structural formula of intermediate M is (12) formula:
Described organic solvent is one or more the mixture in following: ethanol, acetone, ethyl acetate, benzene,toluene,xylene, methylene dichloride and trichloromethane;
In molar ratio, diamines: organic solvent=1: 20~30;
Diamines: lipid acid=1: 1~1.2;
Second step in gained intermediate M solution, added cis-butenedioic anhydride again, under 80 ℃~110 ℃ of temperature of reaction, and back flow reaction 4~8 hours,
In molar ratio, diamines: cis-butenedioic anhydride=1: 1~1.2;
The 3rd step, will go up the step product and steam organic solvent, drying obtains polymerizable functional monomer product;
Can further carry out recrystallization to product purifies.
Polymerizable functional monomer product of the present invention is for the preparation of the used for tertiary oil recovery long chain branched polymers.Used for tertiary oil recovery long chain branched polymers of the present invention is under action of evocating, finishes by the polyreaction of at least two kinds of monomers, shown in reaction formula (21):
Used for tertiary oil recovery long chain branched polymers of the present invention prepares by the following method:
The first step takes by weighing monomer A, monomers B (polymerizable functional monomer) is made into the aqueous solution, and regulating the pH value with alkali is 4~11; Preferred bases is sodium hydroxide, or yellow soda ash.
Described monomer A is at least a in the following free yl polymerizating monomer:
Acrylamide, vinylformic acid, esters of acrylic acid, vinylbenzene, 2-acrylamido-2-methyl propane sulfonic acid and N-vinyl pyrrolidone (NVP); Can be wherein a kind of separately, also can be multiple mixture.
Described polymerizable functional monomer B is that at least a formula is the compound shown in (11).
Above-mentioned monomer A and the monomers B total mass concentration in the aqueous solution is 10%~40%, and wherein the quality of polymerizable functional monomer B is 0.008%~16% of monomer A;
In second step, under 0 ℃~20 ℃ temperature, under nitrogen protection, add initiator C, polymerization 1 to 8 hour;
Described initiator C is any two kinds in the following radical polymerization initiator system: azo initiator system, peroxide initiator system or redox initiation system;
Described azo initiator system is at least a in following: azo-bis-iso-dimethyl (trade(brand)name AIBME, V601), azo-bis-isobutyrate hydrochloride (trade(brand)name AIBA, V50), Cellmic C 121 (trade(brand)name ADC whipping agent), azo di-isopropyl imidazoline salt hydrochlorate (trade(brand)name AIBI, VA044), azo isobutyl cyano group methane amide (trade(brand)name CABN, V30), azo dicyclohexyl formonitrile HCN (trade(brand)name ACCN, V40), azo dicyano valeric acid (trade(brand)name ACVA, V501), azo di-isopropyl tetrahydroglyoxaline (trade(brand)name AIP, VA061), Diisopropyl azodicarboxylate (trade(brand)name AIBN, V60), 2,2'-Azobis(2,4-dimethylvaleronitrile) (trade(brand)name AMBN, V59) and 2,2'-Azobis(2,4-dimethylvaleronitrile) (trade(brand)name ABVN, V65);
Described peroxide initiator system is at least a in following: hydrogen peroxide, ammonium persulphate, Sodium Persulfate, Potassium Persulphate, benzoyl peroxide and the benzoyl peroxide tert-butyl ester;
Described redox initiation system is at least a in following: vitriol-sulphite, persulphate-thiocarbamide, persulphate-organic salt and ammonium persulphate-aliphatic amide;
Preferred described ammonium persulphate-aliphatic amide is at least a in following: ammonium persulphate-N, N-Tetramethyl Ethylene Diamine and ammonium persulphate-diethylamine.
The quality of initiator C is 0.01%~0.1% of monomer total mass;
The 3rd step was warmed up to 40 ℃~80 ℃, continued polymerization 1~4 hour;
The 4th step, the gained colloid is taken out, granulation, drying is pulverized, and obtains the used for tertiary oil recovery long chain branched polymers product of white granular.
In the above method, by a preferred scheme, the used for tertiary oil recovery long chain branched polymers that obtains, its structural formula are as (22) formula:
(22) in the formula; N is 2 or 6; M is 6,8 or 10; X is the polymerization degree of acrylamide (monomer A), x=10 ten thousand~500,000; Y is the polymerization degree of 2-acrylamido-2-methyl propane sulfonic acid (monomer A), y=5 ten thousand~150,000; Z is the polymerization degree of polymerizable functional monomer B, z=1 ten thousand~50,000.
With used for tertiary oil recovery long chain branched polymers of the present invention and surfactant compound, form the binary combination flooding finish, to improve the temperature resistant antisalt performance of oil-displacing agent.
Tertiary oil recovery binary combination flooding finish of the present invention is made up of following component: structural formula fully obtains the binary combination flooding finish after the stirring and dissolving as used for tertiary oil recovery long chain branched polymers, tensio-active agent, the salt brine solution of (22).
Described tensio-active agent is one or more mixture of following compound: alkylaryl sulphonate, alkylaryl sulfonate, polyethenoxy ether sulphonate, sulphosuccinates, sulfonated petro-leum, petroleum carboxylate, amido-carboxylic acid salt, polyethenoxy ether carboxylate and polyoxyethylene phosphoric acid salt;
Described salt brine solution is the aqueous solution that contains calcium ion, magnesium ion and NaCl;
The mass ratio of described used for tertiary oil recovery long chain branched polymers in total mass is 0.05%~0.3%; The mass ratio of described tensio-active agent quality in total mass is 0.05%~0.1%; Surplus is salt solution.
In the described salt brine solution, the calcium ion quality is 0.004%~0.05% of total mass, and the magnesium ion quality is 0.004%~0.05% of total mass, and the NaCl quality is 0.1%~5% of total mass;
Preparation method's technical scheme of binary combination flooding finish of the present invention is:
The first step takes by weighing described used for tertiary oil recovery long chain branched polymers, adds salt brine solution, stirs 1~2 hour, and it is fully dissolved; Described used for tertiary oil recovery long chain branched polymers is a kind of polymkeric substance in the structural formula (22);
Second step took by weighing tensio-active agent, joined in the above-mentioned solution, stirred 0.5~1 hour, and it is fully dissolved, and obtained the binary combination flooding finish.
The invention has the beneficial effects as follows:
Polymerizable functional monomer product of the present invention can be used as polymeric emulsifiers, and is used for the synthetic of used for tertiary oil recovery long chain branched polymers, improves the used for tertiary oil recovery polymer properties, as the oil-displacing agent of tertiary oil recovery, can improve heatproof, the salt resistant character of oil-displacing agent.
Description of drawings
Fig. 1 is the structured testing figure of radical polymerization functional monomer.
Embodiment
Synthesizing of embodiment 1-6[polymerizable functional monomer]
Embodiment 1
Press first kind of synthetic technology scheme of polymerizable functional monomer, the quadrol of getting 0.1mol mixes with the 0.1mol sebacic acid, is heated to 130 ℃, reacts 2~6 hours, obtains intermediate.In the gained intermediate, add 150 milliliters of organic solvent dichloromethane, add the cis-butenedioic anhydride of 0.1mol, under 80 ℃~110 ℃, back flow reaction steamed solvent after 4~8 hours, and drying gets polymerizable functional monomer product, is designated as monomer 1.
Fig. 1 is seen in structured testing, 2848.3cm -1, 2916.8cm -1Be symmetry and the asymmetric stretching vibration absorption peak of methyl, methylene radical, 1377.5cm -1, 1406.0cm -1, 1467.5cm -1In-plane bending vibration peak for methyl, methylene radical; 1709.3cm -1Stretching vibration peak for C=O; 1642.5cm -1, 1588.5cm -1Stretching vibration peak for the two keys of C=C; 3073.1cm -1Be the stretching vibration peak of the last c h bond of C=C-H, these have proved the existence of two keys.3241.2cm -1Be the stretching vibration peak of N-H key, 1524.8cm -1It then is the in-plane bending vibration of N-H.These charateristic avsorption bands have proved that the product that obtains is the radical polymerization functional monomer of structural formula (11).
Embodiment 2
Press first kind of synthetic technology scheme of polymerizable functional monomer, the hexanediamine of getting 0.1mol mixes with the 0.1mol sebacic acid, is heated to 130 ℃, reacts 2~6 hours, obtains intermediate.In the gained intermediate, add 150 milliliters of organic solvent dichloromethane, add the cis-butenedioic anhydride of 0.1mol, under 80 ℃~110 ℃, back flow reaction steamed solvent after 4~8 hours, and drying gets polymerizable functional monomer product, is designated as monomer 2.
Embodiment 3
Press second kind of synthetic technology scheme of polymerizable functional monomer, measure 150 milliliters of p-Xylol, the quadrol that adds 0.1mol mixes with the 0.1mol suberic acid, be heated to 130 ℃~150 ℃, reacted 2~6 hours, steam solvent, add 150 milliliters of organic solvent dichloromethane, the cis-butenedioic anhydride that adds 0.1mol again, under 80 ℃~110 ℃, back flow reaction is after 4~8 hours, steam solvent, drying gets polymerizable functional monomer product, is designated as monomer 3.
Embodiment 4
Press second kind of synthetic technology scheme of polymerizable functional monomer, measure 150 milliliters of p-Xylol, the hexanediamine that adds 0.1mol mixes with the 0.1mol suberic acid, be heated to 130 ℃~150 ℃, reacted 2~6 hours, steam solvent, add 150 milliliters of organic solvent dichloromethane, the cis-butenedioic anhydride that adds 0.1mol again, under 80 ℃~110 ℃, back flow reaction is after 4~8 hours, steam solvent, drying gets polymerizable functional monomer product, is designated as monomer 4
Embodiment 5
Press first kind of synthetic technology scheme of polymerizable functional monomer, quadrol and 0, the 1mol hexanodioic acid of getting 0.1mol mix, and are heated to 130 ℃, react 2~6 hours, obtain intermediate.In the gained intermediate, add 150 milliliters of organic solvent dichloromethane, add the cis-butenedioic anhydride of 0.1mol, under 80 ℃~110 ℃, back flow reaction steamed solvent after 4~8 hours, and drying gets polymerizable functional monomer product, is designated as monomer 5.
Embodiment 6
Press first kind of synthetic technology scheme of polymerizable functional monomer, the hexanediamine of getting 0.1mol mixes with the 0.1mol hexanodioic acid, is heated to 130 ℃, reacts 2~6 hours, obtains intermediate.In the gained intermediate, add 150 milliliters of organic solvent dichloromethane, add the cis-butenedioic anhydride of 0.1mol, under 80 ℃~110 ℃, back flow reaction steamed solvent after 4~8 hours, and drying gets polymerizable functional monomer product, is designated as monomer 6.
Synthesizing of embodiment 7-12[used for tertiary oil recovery long chain branched polymers]
Embodiment 7 synthetic used for tertiary oil recovery long chain branched polymers
Take by weighing acrylamide 7.23 grams; 2.27 gram 2-acrylamide-2-methyl propane sulfonic acid is made into the aqueous solution; regulate the pH value to alkalescence (pH>8) with aqueous sodium hydroxide solution, add 0.15 gram monomer, 1 back and add azo-bis-isobutyrate hydrochloride (AIBA) 1.0 milligrams, under nitrogen protection; add 2.0 milligrams of Ammonium Persulfate 98.5s; select 20 ℃ of temperature earlier, polymerization is warming up to 50 ℃ after 8 hours again; continue polymerization 4 hours; the gained colloid is taken out granulation, drying; pulverize; obtain white granular used for tertiary oil recovery long chain branched polymers product, be designated as polymkeric substance 1, the test polymer molecular weight is 2,800 ten thousand; at salinity 32868mg/L, the apparent viscosity under 85 ℃ of the temperature is 35.5mPas.
Embodiment 8 synthetic used for tertiary oil recovery long chain branched polymers
Take by weighing acrylamide 7.23 grams; 2.27 gram 2-acrylamide-2-methyl propane sulfonic acid is made into the aqueous solution; regulate the pH value to alkalescence (pH>8) with aqueous sodium hydroxide solution, add 0.15 gram monomer, 2 backs and add azo-bis-isobutyrate hydrochloride (AIBA) 1.0 milligrams, under nitrogen protection; add 2.0 milligrams of Ammonium Persulfate 98.5s; select 20 ℃ of temperature earlier, polymerization is warming up to 50 ℃ after 8 hours again; continue polymerization 4 hours; the gained colloid is taken out granulation, drying; pulverize; obtain white granular used for tertiary oil recovery long chain branched polymers product, be designated as polymkeric substance 2, the test polymer molecular weight is 2,600 ten thousand; at salinity 32868mg/L, the apparent viscosity under 85 ℃ of the temperature is 33.8mPas.
Embodiment 9 synthetic used for tertiary oil recovery long chain branched polymers
Take by weighing acrylamide 7.23 grams; 2.27 gram 2-acrylamide-2-methyl propane sulfonic acid is made into the aqueous solution; regulate the pH value to alkalescence (pH>8) with aqueous sodium hydroxide solution, add 0.15 gram monomer, 3 backs and add azo-bis-isobutyrate hydrochloride (AIBA) 1.0 milligrams, under nitrogen protection; add 2.0 milligrams of Ammonium Persulfate 98.5s; select 20 ℃ of temperature earlier, polymerization is warming up to 50 ℃ after 8 hours again; continue polymerization 4 hours; the gained colloid is taken out granulation, drying; pulverize; obtain white granular used for tertiary oil recovery long chain branched polymers product, be designated as polymkeric substance 3, the test polymer molecular weight is 2,500 ten thousand; at salinity 32868mg/L, the apparent viscosity under 85 ℃ of the temperature is 30.2mPas.
Embodiment 10 synthetic used for tertiary oil recovery long chain branched polymers
Take by weighing acrylamide 7.23 grams; 2.27 gram 2-acrylamide-2-methyl propane sulfonic acid is made into the aqueous solution; regulate the pH value to alkalescence (pH>8) with aqueous sodium hydroxide solution, add 0.15 gram monomer, 4 backs and add azo-bis-isobutyrate hydrochloride (AIBA) 1.0 milligrams, under nitrogen protection; add 2.0 milligrams of Ammonium Persulfate 98.5s; select 20 ℃ of temperature earlier, polymerization is warming up to 50 ℃ after 8 hours again; continue polymerization 4 hours; the gained colloid is taken out granulation, drying; pulverize; obtain white granular used for tertiary oil recovery long chain branched polymers product, be designated as polymkeric substance 4, the test polymer molecular weight is 2,400 ten thousand; at salinity 32868mg/L, the apparent viscosity under 85 ℃ of the temperature is 29.4mPas.
Embodiment 11 synthetic used for tertiary oil recovery long chain branched polymers
Take by weighing acrylamide 7.23 grams; 2.27 gram 2-acrylamide-2-methyl propane sulfonic acid is made into the aqueous solution; regulate the pH value to alkalescence (pH>8) with aqueous sodium hydroxide solution, add 0.15 gram monomer, 5 backs and add azo-bis-isobutyrate hydrochloride (AIBA) 1.0 milligrams, under nitrogen protection; add 2.0 milligrams of Ammonium Persulfate 98.5s; select 20 ℃ of temperature earlier, polymerization is warming up to 50 ℃ after 8 hours again; continue polymerization 4 hours; the gained colloid is taken out granulation, drying; pulverize; obtain white granular used for tertiary oil recovery long chain branched polymers product, be designated as polymkeric substance 5, the test polymer molecular weight is 2,000 ten thousand; at salinity 32868mg/L, the apparent viscosity under 85 ℃ of the temperature is 20.6mPas.
Embodiment 12 synthetic used for tertiary oil recovery long chain branched polymers
Take by weighing acrylamide 7.23 grams; 2.27 gram 2-acrylamide-2-methyl propane sulfonic acid is made into the aqueous solution; regulate the pH value to alkalescence (pH>8) with aqueous sodium hydroxide solution, add 0.15 gram monomer, 6 backs and add azo-bis-isobutyrate hydrochloride (AIBA) 3.0 milligrams, under nitrogen protection; add 6.0 milligrams of Ammonium Persulfate 98.5s; select 20 ℃ of temperature earlier, polymerization is warming up to 50 ℃ after 8 hours again; continue polymerization 4 hours; the gained colloid is taken out granulation, drying; pulverize; obtain white granular used for tertiary oil recovery long chain branched polymers product, be designated as polymkeric substance 6, the test polymer molecular weight is 1,900 ten thousand; at salinity 32868mg/L, the apparent viscosity under 85 ℃ of the temperature is 18.2mPas.
The preparation of embodiment 13-18[tertiary oil recovery binary combination flooding finish]
Embodiment 13 preparation tertiary oil recovery binary combination flooding finishes
Taking by weighing 0.3 gram used for tertiary oil recovery long chain branched polymers 1 joins in the 200 gram salt brine solutions of calcium ions 0.04%, magnesium ion 0.0377%, NaCl content 2.9%, under magnetic stirring apparatus, stir after 1.5 hours, add 0.1 gram alkylaryl sulphonate again, stir and it was fully dissolved in 0.5 hour, obtain tertiary oil recovery binary combination flooding finish 1.
Embodiment 14 preparation tertiary oil recovery binary combination flooding finishes
Taking by weighing 0.3 gram used for tertiary oil recovery long chain branched polymers 2 joins in the 200 gram salt brine solutions of calcium ions 0.04%, magnesium ion 0.0377%, NaCl content 2.9%, under magnetic stirring apparatus, stir after 1.5 hours, add 0.1 gram alkylaryl sulfonate again, stir and it was fully dissolved in 0.5 hour, obtain tertiary oil recovery binary combination flooding finish 2.
Embodiment 15 preparation tertiary oil recovery binary combination flooding finishes
Taking by weighing 0.3 gram used for tertiary oil recovery long chain branched polymers 3 joins in the 200 gram salt brine solutions of calcium ions 0.04%, magnesium ion 0.0377%, NaCl content 2.9%, under magnetic stirring apparatus, stir after 1.5 hours, add 0.1 gram polyethenoxy ether sulphonate again, stir and it was fully dissolved in 0.5 hour, obtain tertiary oil recovery binary combination flooding finish 3.
Embodiment 16 preparation tertiary oil recovery binary combination flooding finishes
Taking by weighing 0.3 gram used for tertiary oil recovery long chain branched polymers 4 joins in the 200 gram salt brine solutions of calcium ions 0.04%, magnesium ion 0.0377%, NaCl content 2.9%, under magnetic stirring apparatus, stir after 1.5 hours, add 0.1 gram sulfonated petro-leum again, stir and it was fully dissolved in 0.5 hour, obtain tertiary oil recovery binary combination flooding finish 4.
Embodiment 17 preparation tertiary oil recovery binary combination flooding finishes
Taking by weighing 0.3 gram used for tertiary oil recovery long chain branched polymers 5 joins in the 200 gram salt brine solutions of calcium ions 0.04%, magnesium ion 0.0377%, NaCl content 2.9%, under magnetic stirring apparatus, stir after 1.5 hours, add 0.1 gram petroleum carboxylate again, stir and it was fully dissolved in 0.5 hour, obtain tertiary oil recovery binary combination flooding finish 5.
Embodiment 18 preparation tertiary oil recovery binary combination flooding finishes
Taking by weighing 0.3 gram used for tertiary oil recovery long chain branched polymers 6 joins in the 200 gram salt brine solutions of calcium ions 0.04%, magnesium ion 0.0377%, NaCl content 2.9%, under magnetic stirring apparatus, stir after 1.5 hours, add 0.1 gram polyoxyethylene phosphoric acid salt again, stir and it was fully dissolved in 0.5 hour, obtain tertiary oil recovery binary combination flooding finish 6.
In order to further specify effect of the present invention, the apparent viscosity of long chain branched polymers oil-displacing agent and tertiary oil recovery binary combination flooding finish is tested and comparison, see Table 31
Table 31
Use BROOKFIELD DV-III viscosity apparatus at rotating speed to be: 7.34S -1, the apparent viscosity of mensuration aqueous solutions of polymers under 85 ℃ the condition, test condition: 7.34s -1, 85 ℃, polymer concentration: 1500mg/L, the solution total mineralization is 32868mg/L.
By above interpretation of result, gained tertiary oil recovery binary combination flooding finish of the present invention has improved the viscosity of single polymers oil-displacing agent greatly under high salinity (32868mg/L) and high temperature (85 ℃), be conducive to the application in tertiary oil recovery.

Claims (8)

1. used for tertiary oil recovery long chain branched polymers, its structural formula are as (22) formula:
(22) in the formula: n is 2 or 6; M is 6,8 or 10; X=10 ten thousand~500,000; Y=5 ten thousand~150,000; Z=1 ten thousand~50,000.
2. a used for tertiary oil recovery long chain branched polymers, preparation by the following method:
The first step takes by weighing monomer A, polymerizable functional monomer B is made into the aqueous solution, and regulating the pH value with alkali is 4~11;
Described monomer A is one or more the arbitrary proportion mixture in the following free yl polymerizating monomer: acrylamide, vinylformic acid, 2-acrylamido-2-methyl propane sulfonic acid and N-vinyl pyrrolidone;
Described polymerizable functional monomer B is that at least a formula is the compound shown in (11), and n is 2 or 6 in (11) formula, and m is 4,6 or 8:
Above-mentioned monomer A and the total mass concentration of polymerizable functional monomer B in the aqueous solution are 10%~40%, and wherein the quality of polymerizable functional monomer B is 0.008%~16% of monomer A;
In second step, under 0 ℃~20 ℃ temperature, under nitrogen protection, add initiator C, polymerization 1 to 8 hour;
Described initiator C is any two kinds in the following radical polymerization initiator system: azo initiator system, peroxide initiator system or redox initiation system; The quality of initiator C is 0.01%~0.1% of monomer total mass;
The 3rd step was warmed up to 40 ℃~80 ℃, continued polymerization 1~4 hour;
The 4th step, the gained colloid is taken out, granulation, drying is pulverized, and obtains the used for tertiary oil recovery long chain branched polymers product of white granular.
3. used for tertiary oil recovery long chain branched polymers according to claim 2 adopts sodium hydroxide or yellow soda ash to regulate the pH value in preparation method's the first step.
4. according to claim 2 or 3 described used for tertiary oil recovery long chain branched polymers, in the preparation method in second step,
Described azo initiator system is at least a in following: azo-bis-iso-dimethyl, azo-bis-isobutyrate hydrochloride, Cellmic C 121, azo di-isopropyl imidazoline salt hydrochlorate, azo isobutyl cyano group methane amide, azo dicyclohexyl formonitrile HCN, azo dicyano valeric acid, azo di-isopropyl tetrahydroglyoxaline, Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile) and 2,2'-Azobis(2,4-dimethylvaleronitrile);
Described peroxide initiator system is at least a in following: hydrogen peroxide, ammonium persulphate, Sodium Persulfate, Potassium Persulphate, benzoyl peroxide and the benzoyl peroxide tert-butyl ester;
Described redox initiation system is at least a in following: vitriol-sulphite, persulphate-thiocarbamide, persulphate-organic salt and ammonium persulphate-aliphatic amide.
5. used for tertiary oil recovery long chain branched polymers according to claim 4, in the preparation method in second step, described ammonium persulphate-aliphatic amide is at least a in following: ammonium persulphate-N, N, N', N'-Tetramethyl Ethylene Diamine and ammonium persulphate-diethylamine.
6. the preparation method of a used for tertiary oil recovery long chain branched polymers comprises the steps:
The first step takes by weighing monomer A, polymerizable functional monomer B is made into the aqueous solution, and regulating the pH value with alkali is 4~11;
Described monomer A is one or more the arbitrary proportion mixture in the following free yl polymerizating monomer: acrylamide, vinylformic acid, 2-acrylamido-2-methyl propane sulfonic acid and N-vinyl pyrrolidone;
Described polymerizable functional monomer B is that at least a formula is the compound shown in (11), and n is 2 or 6 in (11) formula, and m is 4,6 or 8:
Above-mentioned monomer A and the total mass concentration of polymerizable functional monomer B in the aqueous solution are 10%~40%, and wherein the quality of polymerizable functional monomer B is 0.008%~16% of monomer A;
In second step, under 0 ℃~20 ℃ temperature, under nitrogen protection, add initiator C, polymerization 1 to 8 hour;
Described initiator C is any two kinds in the following radical polymerization initiator system: azo initiator system, peroxide initiator system or redox initiation system; The quality of initiator C is 0.01%~0.1% of monomer total mass;
Described azo initiator system is at least a in following: azo-bis-iso-dimethyl, azo-bis-isobutyrate hydrochloride, Cellmic C 121, azo di-isopropyl imidazoline salt hydrochlorate, azo isobutyl cyano group methane amide, azo dicyclohexyl formonitrile HCN, azo dicyano valeric acid, azo di-isopropyl tetrahydroglyoxaline, Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile) and 2,2'-Azobis(2,4-dimethylvaleronitrile);
Described peroxide initiator system is at least a in following: hydrogen peroxide, ammonium persulphate, Sodium Persulfate, Potassium Persulphate, benzoyl peroxide and the benzoyl peroxide tert-butyl ester;
Described redox initiation system is at least a in following: vitriol-sulphite, persulphate-thiocarbamide, persulphate-organic salt and ammonium persulphate-aliphatic amide;
The 3rd step was warmed up to 40 ℃~80 ℃, continued polymerization 1~4 hour;
The 4th step, the gained colloid is taken out, granulation, drying is pulverized, and obtains the used for tertiary oil recovery long chain branched polymers product of white granular.
7. the preparation method of used for tertiary oil recovery long chain branched polymers according to claim 6 adopts sodium hydroxide or yellow soda ash to regulate the pH value in the first step.
8. according to the preparation method of claim 6 or 7 described used for tertiary oil recovery long chain branched polymers, be at least a in following at the ammonium persulphate-aliphatic amide described in second step: ammonium persulphate-N, N, N', N'-Tetramethyl Ethylene Diamine and ammonium persulphate-diethylamine.
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