CN102372647B - Free radical polymerization functional monomer and synthesis method thereof - Google Patents
Free radical polymerization functional monomer and synthesis method thereof Download PDFInfo
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- CN102372647B CN102372647B CN 201010263526 CN201010263526A CN102372647B CN 102372647 B CN102372647 B CN 102372647B CN 201010263526 CN201010263526 CN 201010263526 CN 201010263526 A CN201010263526 A CN 201010263526A CN 102372647 B CN102372647 B CN 102372647B
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- 238000010526 radical polymerization reaction Methods 0.000 title claims abstract description 34
- 238000001308 synthesis method Methods 0.000 title claims description 9
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- 238000000034 method Methods 0.000 claims abstract description 18
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 5
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- 239000003960 organic solvent Substances 0.000 claims description 22
- 150000004985 diamines Chemical class 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 15
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Abstract
The invention discloses a free radical polymerization functional monomer, with a molecular structural formula shown as a formula (11), wherein n is 2 or 6, and R is C11-C24 saturated alkyl or unsaturated alkyl. The invention also discloses a method for synthesizing a long chain branch polymer used for oil displacement by utilizing the monomer and a structural formula of the long chain branch polymer used for the oil displacement as well as a method for preparing a binary complex oil displacement agent by utilizing the long chain branch polymer used for the oil displacement. Under the conditions of high hypersalinity and high temperature, viscosity of single polymer oil displacement agent is greatly improved, thus being beneficial to application in tertiary oil recovery.
Description
Technical Field
The invention relates to the field of tertiary oil recovery, in particular to the synthesis of free radical polymerization monomers and long-chain branched chain polymers, which can be applied to the fields of tertiary oil recovery binary composite oil displacement agents and the like.
Background
Radical polymerization refers to a reaction in which a vinyl monomer having a carbon-carbon double bond is polymerized by radical chain addition to form a polymer. As many monomers can be subjected to free radical polymerization, can be subjected to suspension and emulsion polymerization by using water as a medium, the polymerization process is simple and convenient to operate, and the reproducibility is good, the monomers become important technologies for industrially producing high molecular products since the last 50 th century.
The general free radical polymerization synthesis mainly includes synthesis methods such as a bulk method, an aqueous solution method, an emulsion method and a suspension method. According to whether other monomers are added or not, the method can be divided into homopolymerization and copolymerization, and the method has wide application in industries such as petroleum, mining, papermaking, water treatment, textile and the like, and the demand of the method is continuously increased.
Common free radical polymerization monomers are: styrene, vinyl chloride, vinyl acetate, acrylonitrile, acrylamide, acrylic acid and esters, functional monomers having various properties are often required to improve the properties of the polymer. Such as polymerized monomers having an emulsifying function.
Emulsifiers play an important role in emulsion polymerization: before polymerization, the monomer can be dispersed and solubilized to form stable monomer emulsion; providing a polymerization site for the monomer in polymerization, and influencing the polymerization behavior of the monomer, the size and distribution of latex particles and the properties of the latex particles; the latex particles are stabilized against agglomeration after polymerization. The traditional emulsifier is adsorbed on the surface of emulsion particles through physical action, and the emulsion stability can be changed or even emulsion breaking can be realized during freeze-thaw cycle, or shear force is applied, or electrolyte is added; during film forming, the emulsifier can migrate or be enriched on the interface between the film and the air to influence the gloss and other surface properties of the film, or be enriched on the interface between the film and a substrate to influence the adhesive property of the film; residual emulsifier also causes slow film formation rate and reduces the water resistance of the film. In some production applications, when components such as pigment and the like are added into the latex solution, the emulsifier and the pigment dispersant generate competitive adsorption on two interfaces of latex particles and water and pigment and water, so that the rheological property and stability of the latex solution are influenced; (2) when a solid product is prepared by a gel method, the emulsifier can remain in a water phase to cause environmental pollution; therefore, polymerizable groups are introduced into the traditional emulsifier to form a new surface active monomer, which is also called polymerizable emulsifier. The polymerizable emulsifier molecules are bonded on the surface of the emulsion particles in a covalent bond mode, and the strong bonding ensures that the emulsifier molecules are not desorbed when the emulsion is stored and used, thereby effectively solving the defects of the traditional emulsifier and greatly improving the mechanical property, the glossiness, the adhesion, the water resistance and the like of the film. The polymerizable emulsifiers studied so far are mainly of the allyl (oxy) type, (meth) acrylic type, acrylamide type, styrene type, maleic type, and the like.
The aqueous solution of polyacrylamide and partially hydrolyzed polyacrylamide has some defects in application, such as poor mechanical shear stability, and particularly when the aqueous solution is used for tertiary oil recovery oil displacement agents, viscosity loss can be caused by high shear speed; there is a viscosity loss in the brine; the product is easy to degrade after being placed for a long time or at a higher temperature; the carboxyl groups carried by the partially hydrolyzed polyacrylamide can react with divalent ions. These drawbacks have affected the widespread use of polyacrylamides. In order to further improve the viscosity of the polyacrylamide and improve the temperature resistance and salt resistance of the polyacrylamide, a copolymerization method with a novel functional monomer is an effective way.
Patent CN1470504A discloses a synthesis method for acrylamide derivative functional monomers.
The product which is industrially popularized and applied in the oilfield polymer flooding is mainly partially hydrolyzed polyacrylamide, the polyacrylamide with the molecular weight of more than 2300 ten thousand is applied to the class I oil reservoir of the oilfield, and is prepared and injected by clear water, and the clear water has a certain hydrodynamic volume under a certain concentration, so that the viscosity of the aqueous solution is improved, the permeability of the oil reservoir can be reduced, the water absorption thickness is increased, and the water absorption capacity is improved, thereby being beneficial to improving the crude oil recovery ratio. However, with the increase of the salt concentration in the solution, the molecular chain of the polymer gradually shrinks, the viscosity loss is large when the ionic strength is high, the swept volume of the polymer is reduced, and the oil displacement effect is influenced. Therefore, improving the thickening and salt resistance of polymer solutions has become an important issue in the field of polymer research.
At present, there are two main approaches for the research of salt-resistant polymers at home and abroad: firstly, the molecular weight of the polymer is improved as much as possible to increase the hydrodynamic size of a single polymer molecular chain, meanwhile, the rigidity of the molecular chain is increased to increase the hydrodynamic size of the polymer in a high-mineralization-degree aqueous solution, and the polyacrylamide with ultrahigh molecular weight is developed, and secondly, the interaction between the molecular chains is utilized, and the hydrodynamic size of the molecular chain bundle is increased by forming a supermolecular structure through association, so that the purpose of high-efficiency tackifying is achieved.
The hydrophobic association polymer is a hydrolytic polymer with hydrophobic groups on the hydrophilic macromolecular chain of the polymer, and the solution property of the hydrolytic polymer is greatly different from that of a general polymer. In aqueous solutions, the hydrophobic groups of such polymers aggregate due to hydrophobic interactions, resulting in intramolecular and intermolecular associations of the macromolecular chains. In dilute solution, the macromolecules mainly exist in an intramolecular association mode, so that macromolecular chains are curled, the hydrodynamic volume is reduced, and the viscosity is reduced. When the concentration of the polymer is higher than a certain critical concentration (critical association concentration C), macromolecular chains are aggregated through hydrophobic association to form a supermolecular structure-dynamic physical crosslinking network mainly based on meta-association, the hydrodynamic size is increased, and the solution viscosity is greatly increased. The addition of small molecule electrolytes increases the polarity of the solvent, enhancing the hydrophobic association, and thus producing significant salt resistance.
The purpose of increasing the molecular weight is to ensure that even under the high mineralization environment, although the viscosity of the polymer solution is lost, the absolute viscosity of the polymer is still higher due to the high molecular weight, so that the requirement of the working fluid on the tackifying capability of the polymer is met. This method, however, has some drawbacks, firstly the difficulty of synthesizing high molecular weight polymers, and secondly the greater the molecular weight of the polymer, the more pronounced the problem of dissolution is exposed. At present, the polymer at home and abroad can meet the requirements at a lower temperature under clear water. However, the water with high mineralization can not meet the requirement.
Some monomer units with higher thermal stability, monomer units with larger frameworks and groups with strong hydration capability are introduced into a polymer molecular chain, so that the thermal stability and the rigidity of the molecular chain of the polymer are enhanced, the hydration capability of the polymer is enhanced, polymer molecules can keep larger hydrodynamic size in a high-salinity aqueous solution, and the salt tolerance of the polymer is enhanced to a certain degree. Meanwhile, the introduction of the functional monomer limits the hydrolysis of the polymer under the condition of high-salinity water quality, and the phenomenon of precipitation of calcium and magnesium ions cannot occur, so that the aim of salt resistance is fulfilled.
Disclosure of Invention
The technical problems to be solved by the invention are as follows:
the invention aims to overcome the defects and provide a free radical polymerization functional monomer and a synthesis method thereof.
The product technical scheme of the free radical polymerization functional monomer is as follows:
a free radical polymerization functional monomer, the molecular structural formula of which is shown as (11):
(11) in the formula: n is 2 or 6, R is C11～C24Saturated or unsaturated alkyl groups. Preferably, R is an alkyl moiety (moiety without a terminal carboxyl group) of lauric acid, oleic acid or hard fatty acid.
The first synthesis method of the free radical polymerization functional monomer of the invention is as follows:
firstly, mixing diamine and fatty acid according to a molar ratio of 1: 1-1.2; wherein,
the diamine has the structural formula: NH (NH)2-(CH2)n-NH2N is 2 or 6;
the structural formula of the fatty acid is: R-COOH, R being C11～C24The saturated straight-chain alkane or the unsaturated straight-chain alkane of (1);
heating to 110-160 ℃, and reacting for 2-6 hours to obtain an intermediate M, wherein the structural formula of the intermediate M is (12):
secondly, adding an organic solvent and maleic anhydride into the obtained intermediate M, and carrying out reflux reaction for 4-8 hours at the reaction temperature of 80-110 ℃;
the organic solvent is one or a mixture of more than one of the following: ethanol, acetone, ethyl acetate, benzene, toluene, xylene, dichloromethane, and chloroform;
diamine and an organic solvent are 1: 20-30;
diamine and maleic anhydride are 1: 1-1.2 (molar ratio);
and thirdly, evaporating the product obtained in the last step out the organic solvent, and drying to obtain the free radical polymerization functional monomer product.
Preferably, the product is further recrystallized and purified.
The second synthesis method of the free radical polymerization functional monomer of the invention is as follows:
firstly, mixing diamine and fatty acid in an organic solvent, heating to 110-156 ℃, and reacting for 2-6 hours to obtain a solution of an intermediate M; the structural formulas of the diamine, the fatty acid and the intermediate M are as defined in the first synthesis method;
according to molar ratio: diamine and an organic solvent are 1: 20-30; diamine and fatty acid are 1: 1-1.2;
the organic solvent is one or a mixture of more than one of the following: ethanol, acetone, ethyl acetate, benzene, toluene, xylene, dichloromethane, and chloroform;
secondly, adding maleic anhydride into the obtained intermediate M solution according to a molar ratio of 1: 1-1.2, and carrying out reflux reaction at a reaction temperature of 80-110 ℃ for 4-8 hours;
and thirdly, evaporating the product obtained in the last step out the organic solvent, and drying to obtain the free radical polymerization functional monomer product.
Preferably, the product is further recrystallized and purified.
The free radical polymerization functional monomer product is used for preparing long-chain branched chain polymer for oil displacement. The long-chain branched polymer for oil displacement is prepared by the polymerization reaction of at least two monomers under the action of an initiator, and is shown as a reaction formula (21):
the preparation method of the long-chain branched polymer for oil displacement comprises the following steps:
firstly, weighing a monomer A and a monomer B to prepare an aqueous solution, and adjusting the pH value to 4-11 by using alkali; the preferred base is sodium hydroxide, or sodium carbonate.
The monomer A is at least one of the following free radical polymerization monomers:
acrylamide, acrylic acid, acrylates, styrene, 2-acrylamido-2-methylpropanesulfonic acid, and N-vinylpyrrolidone (NVP); the amount of the above-mentioned surfactant may be one kind alone or a mixture of two or more kinds.
The monomer B is a free radical polymerization functional monomer and is at least one compound shown as a general formula structure (11).
The total mass concentration of the monomer A and the monomer B in the aqueous solution is 10-40 percent, wherein the mass of the monomer B is 0.008-16 percent of that of the monomer A;
secondly, adding an initiator C at the temperature of 0-20 ℃ under the protection of nitrogen, and polymerizing for 1-8 hours;
the initiator C is any two of the following free radical polymerization initiator systems: azo initiator systems, peroxide initiator systems or redox initiator systems;
the azo initiator system is at least one of the following: dimethyl azobisisobutyrate (trade name AIBME, V601), azobisisobutyramidine hydrochloride (trade name AIBA, V50), azodicarbonamide (trade name ADC blowing agent), azobisisopropylimidazoline hydrochloride (trade name AIBI, VA044), azobisisobutyronitrile formamide (trade name CABN, V30), azobiscyclohexylcarbonitrile (trade name ACCN, V40), azobiscyanovaleric acid (trade name ACVA, V501), azobisdiisopropylimidazoline (trade name AIP, VA061), azobisisobutyronitrile (trade name AIBN, V60), azobisisovaleronitrile (trade name AMBN, V59) and azobisisoheptonitrile (trade name ABVN, V65);
the peroxide initiator system is at least one of the following: hydrogen peroxide, ammonium persulfate, sodium persulfate, potassium persulfate, benzoyl peroxide and benzoyl peroxide tert-butyl ester;
the redox initiator system is at least one of the following: sulfate-sulfite, persulfate-thiourea, persulfate-organic salts, and ammonium persulfate-fatty amine (preferably at least one of ammonium persulfate-N, N-tetramethylethylenediamine and ammonium persulfate-diethylamine).
The mass of the initiator C is 0.01-0.1% of the total mass of the monomers.
Thirdly, heating to 40-80 ℃, and continuing to polymerize for 1-4 hours;
and fourthly, taking out the obtained colloid, granulating, drying and crushing to obtain a white granular long-chain branched polymer product for oil displacement.
In the above method, a preferred embodiment is: the monomer A is acrylamide and 2-acrylamido-2-methylpropanesulfonic acid; adjusting the pH value by using a sodium hydroxide aqueous solution, wherein an initiator C is azodiisobutyramidine hydrochloride and ammonium persulfate, and obtaining the oil displacement long-chain branched polymer with the structural formula as (22):
(22) in the formula: n is 2 or 6; x is the polymerization degree of acrylamide, and x is 10 to 50 ten thousand; y is the polymerization degree of 2-acrylamido-2-methylpropanesulfonic acid, and y is 5 to 15 ten thousand; z is the polymerization degree of the free radical polymerization functional monomer B, and z is 1 ten thousand to 5 ten thousand; r is C11～C24Saturated straight-chain alkanes or C11～C24Unsaturated linear alkanes of (1).
The long-chain branched polymer for oil displacement is compounded with a surfactant to form a binary composite oil displacement agent so as to improve the temperature resistance and salt resistance of the oil displacement agent.
The technical scheme of the binary composite oil displacement agent is as follows:
the composition consists of the following components: the long-chain branched polymer for oil displacement, which has a structural formula shown as (22), a surfactant and a saline solution.
(22) In the formula: n is 2 or 6; x is the polymerization degree of acrylamide, and x is 10 to 50 ten thousand; y is the polymerization degree of 2-acrylamido-2-methylpropanesulfonic acid, and y is 5 to 15 ten thousand; z is the polymerization degree of the free radical polymerization functional monomer B, and z is 1 ten thousand to 5 ten thousand; r is C11～C24Saturated straight-chain alkanes or C11～C24Unsaturated straight-chain alkane of (1);
the surfactant is a mixture of one or more of the following compounds: alkylaryl sulfonates, arylalkyl sulfonates, polyoxyethylene ether sulfonates, succinate sulfonates, petroleum carboxylates, amido carboxylates, polyoxyethylene ether carboxylates, and polyoxyethylene phosphates;
the saline solution is a water solution containing calcium ions, magnesium ions and NaCl;
the mass ratio of the long-chain branch polymer for oil displacement in the total mass is 0.05-0.3%; the mass ratio of the surfactant in the total mass is 0.05-0.1%; the balance being brine solution.
In the saline solution, the mass of calcium ions is 0.004-0.05% of the total mass, the mass of magnesium ions is 0.004-0.05% of the total mass, and the mass of NaCl is 0.1-5% of the total mass.
The preparation method of the binary composite oil displacement agent comprises the following steps:
step one, weighing the long-chain branched polymer for oil displacement, adding a saline solution, and stirring for 1-2 hours to fully dissolve the long-chain branched polymer;
and secondly, weighing a surfactant, adding the surfactant into the solution, and stirring for 0.5-1 hour to fully dissolve the surfactant to obtain the binary composite oil-displacing agent.
The invention has the beneficial effects that:
the free radical polymerization functional monomer product can be used as a polymerization emulsifier and used for synthesizing a long-chain branched polymer for oil displacement, and the long-chain branched polymer for oil displacement is used as an oil displacement agent for tertiary oil recovery, so that the temperature resistance and salt tolerance of the oil displacement agent can be improved.
Drawings
FIG. 1 is a structural test chart of a radical polymerization functional monomer.
Detailed Description
Examples 1-6 [ Synthesis of free radical polymerization functional monomers ]
Example 1
According to the first synthesis technical scheme of the free radical polymerization functional monomer, 0.1mol of ethylenediamine and 0.1mol of lauric acid are mixed, heated to 130 ℃, and reacted for 2-6 hours to obtain an intermediate. Adding 150 ml of organic solvent methylene dichloride into the obtained intermediate, adding 0.1mol of maleic anhydride, performing reflux reaction for 4-8 hours at the temperature of 80-110 ℃, evaporating the solvent, and drying to obtain a functional monomer product polymerized from the monomer, wherein the functional monomer product is marked as a monomer 1.
The structural test is shown in figure 1, 2848.3cm-1、2916.8cm-1Symmetric and asymmetric stretching vibration absorption peaks of methyl and methylene, 1377.5cm-1、1406.0cm-1、1467.5cm-1The in-plane bending vibration peak of methyl and methylene; 1709.3cm-1A stretching vibration peak of C ═ O; 1642.5cm-1、1588.5cm-1Is the stretching vibration peak of C ═ C double bond; 3073.1cm-1Is the stretching vibration peak of C-H bond on C-H,these demonstrate the presence of double bonds. 3241.2cm-1Is the stretching vibration peak of the N-H bond, 1524.8cm-1It is the in-plane bending vibration of N-H. These characteristic absorption peaks demonstrate that the resulting product is a free radical polymerizable functional monomer of formula (11).
Example 2
According to the first synthesis technical scheme of the free radical polymerization functional monomer, 0.1mol of hexamethylene diamine and 0.1mol of lauric acid are mixed and heated to 130 ℃ to react for 2-6 hours, and an intermediate is obtained. Adding 150 ml of organic solvent methylene dichloride into the obtained intermediate, adding 0.1mol of maleic anhydride, performing reflux reaction for 4-8 hours at the temperature of 80-110 ℃, evaporating the solvent, and drying to obtain a functional monomer product polymerized from the monomer group, wherein the functional monomer product is marked as a monomer 2.
Example 3
According to the second synthesis technical scheme of the free radical polymerization functional monomer, 150 ml of p-xylene is measured, 0.1mol of ethylenediamine and 0.1mol of oleic acid are added and mixed, the mixture is heated to 130-150 ℃ and reacts for 2-6 hours, the solvent is evaporated, 150 ml of organic solvent dichloromethane is added, 0.1mol of maleic anhydride is added, the mixture is refluxed and reacts for 4-8 hours at 80-110 ℃, the solvent is evaporated and dried, and the product obtained from the free radical polymerization functional monomer is marked as a monomer 3.
Example 4
According to the second synthesis technical scheme of the free radical polymerization functional monomer, 150 ml of p-xylene is measured, 0.1mol of hexamethylenediamine and 0.1mol of oleic acid are added and mixed, the mixture is heated to 130-150 ℃ and reacts for 2-6 hours, the solvent is evaporated, 150 ml of organic solvent methylene dichloride is added, 0.1mol of maleic anhydride is added, the reflux reaction is carried out for 4-8 hours at 80-110 ℃, the solvent is evaporated and dried, and the product obtained from the free radical polymerization functional monomer is marked as a monomer 4
Example 5
According to the first synthesis technical scheme of the free radical polymerization functional monomer, 0.1mol of ethylenediamine and 0.1mol of stearic acid are mixed, heated to 130 ℃, and reacted for 2-6 hours to obtain an intermediate. Adding 150 ml of organic solvent methylene dichloride into the obtained intermediate, adding 0.1mol of maleic anhydride, performing reflux reaction for 4-8 hours at the temperature of 80-110 ℃, evaporating the solvent, and drying to obtain a functional monomer product polymerized from the monomer, namely monomer 5.
Example 6
According to the first synthesis technical scheme of the free radical polymerization functional monomer, 0.1mol of hexamethylene diamine and 0.1mol of stearic acid are mixed and heated to 130 ℃ to react for 2-6 hours to obtain an intermediate. Adding 150 ml of organic solvent methylene dichloride into the obtained intermediate, adding 0.1mol of maleic anhydride, performing reflux reaction for 4-8 hours at the temperature of 80-110 ℃, evaporating the solvent, and drying to obtain a functional monomer product polymerized from the monomer group, wherein the functional monomer product is marked as a monomer 6.
Examples 7 to 12 [ Synthesis of Long chain branched Polymer for flooding ]
Example 7
Weighing 7.23 g of acrylamide and 2.27 g of 2-acrylamide-2-methylpropanesulfonic acid to prepare an aqueous solution, adjusting the pH value to be alkaline (pH is more than 9) by using an aqueous solution of sodium hydroxide, adding 0.15 g of monomer 1, adding 3.0 mg of azobisisobutyramidine hydrochloride (AIBA), adding 6.0 mg of ammonium persulfate under the protection of nitrogen, polymerizing at the temperature of 20 ℃ for 8 hours, then heating to 50 ℃, continuing to polymerize for 4 hours, taking out the obtained colloid, granulating, drying and crushing to obtain a white powder acrylamide water-soluble polymer product, marking as polymer 1, testing the molecular weight of the polymer to be 1200 ten thousand, and testing the apparent viscosity at the mineralization degree of 32868mg/L and the temperature of 85 ℃ to be 18.1mPa & s.
Example 8
Weighing 7.23 g of acrylamide and 2.27 g of 2-acrylamide-2-methylpropanesulfonic acid to prepare an aqueous solution, adjusting the pH value to be alkaline (pH is more than 9) by using an aqueous solution of sodium hydroxide, adding 0.15 g of monomer 2, adding 3.0 mg of azobisisobutyramidine hydrochloride (AIBA), adding 6.0 mg of ammonium persulfate under the protection of nitrogen, polymerizing at the temperature of 20 ℃ for 8 hours, then heating to 50 ℃, continuing to polymerize for 4 hours, taking out the obtained colloid, granulating, drying and crushing to obtain a white powder acrylamide water-soluble polymer product, marking as a polymer 2, testing the molecular weight of the polymer to be 1500 ten thousand, and testing the apparent viscosity at the mineralization degree of 32868mg/L and the temperature of 85 ℃ to be 20.7mPa & s.
Example 9
Weighing 7.23 g of acrylamide and 2.27 g of 2-acrylamide-2-methylpropanesulfonic acid to prepare an aqueous solution, adjusting the pH value to alkalinity (pH is more than 9) by using an aqueous sodium hydroxide solution, adding 0.15 g of monomer 3, adding 3.0 mg of azobisisobutyramidine hydrochloride (AIBA), adding 6.0 mg of ammonium persulfate under the protection of nitrogen, selecting the temperature to be 20 ℃, polymerizing for 8 hours, then heating to 50 ℃, continuing to polymerize for 4 hours, taking out the obtained colloid, granulating, drying and crushing to obtain a white powder acrylamide water-soluble polymer product, marking as polymer 3, testing the molecular weight of the polymer to be 1800 ten thousand, and testing the apparent viscosity to be 26.5 mPas at the mineralization degree of 32868mg/L and the temperature of 85 ℃.
Example 10
Weighing 7.23 g of acrylamide and 2.27 g of 2-acrylamide-2-methylpropanesulfonic acid to prepare an aqueous solution, adjusting the pH value to be alkaline (pH is more than 9) by using an aqueous solution of sodium hydroxide, adding 0.15 g of monomer 4, adding 3.0 mg of azobisisobutyramidine hydrochloride (AIBA), adding 6.0 mg of ammonium persulfate under the protection of nitrogen, selecting the temperature to be 20 ℃, polymerizing for 8 hours, then heating to 50 ℃, continuing to polymerize for 4 hours, taking out the obtained colloid, granulating, drying and crushing to obtain a white powder acrylamide water-soluble polymer product, marking as polymer 4, testing the molecular weight of the polymer to be 2000 ten thousand, and testing the apparent viscosity to be 28.4 mPas at the mineralization degree of 32868mg/L and the temperature of 85 ℃.
Example 11
Weighing 7.23 g of acrylamide and 2.27 g of 2-acrylamide-2-methylpropanesulfonic acid to prepare an aqueous solution, adjusting the pH value to alkalinity (pH is more than 9) by using an aqueous sodium hydroxide solution, adding 0.15 g of monomer 5, adding 3.0 mg of azobisisobutyramidine hydrochloride (AIBA), adding 6.0 mg of ammonium persulfate under the protection of nitrogen, selecting the temperature to be 20 ℃, polymerizing for 8 hours, then heating to 50 ℃, continuing to polymerize for 4 hours, taking out the obtained colloid, granulating, drying and crushing to obtain a white powder acrylamide water-soluble polymer product, marking as polymer 5, testing the molecular weight of the polymer to be 2500 ten thousand, and testing the apparent viscosity to be 32.6 mPas at the mineralization degree of 32868mg/L and the temperature of 85 ℃.
Example 12
Weighing 7.23 g of acrylamide and 2.27 g of 2-acrylamide-2-methylpropanesulfonic acid to prepare an aqueous solution, adjusting the pH value to be alkaline (pH is more than 9) by using an aqueous solution of sodium hydroxide, adding 0.15 g of monomer 6, adding 3.0 mg of azobisisobutyramidine hydrochloride (AIBA), adding 6.0 mg of ammonium persulfate under the protection of nitrogen, selecting the temperature to be 20 ℃, polymerizing for 8 hours, then heating to 50 ℃, continuing to polymerize for 4 hours, taking out the obtained colloid, granulating, drying and crushing to obtain a white powder acrylamide water-soluble polymer product, marking as polymer 6, testing the molecular weight of the polymer to be 2800 ten thousand, and testing the apparent viscosity at the mineralization degree of 32868mg/L and the temperature of 85 ℃ to be 38.2mPa & s.
Examples 13-18 [ preparation of binary Compound oil-displacing agent ]
Example 13
0.3g of long-chain branched polymer 1 for oil displacement is weighed and added into 200g of saline solution containing 0.04% of calcium ions, 0.0377% of magnesium ions and 2.9% of NaCl, stirred for 1.5 hours under a magnetic stirrer, then 0.1g of alkyl aryl sulfonate is added, and stirred for 0.5 hour to be fully dissolved, so that the binary composite oil-displacing agent 1 is obtained.
Example 14
0.3g of long-chain branched polymer 2 for oil displacement is weighed and added into 200g of saline solution containing 0.04% of calcium ions, 0.0377% of magnesium ions and 2.9% of NaCl, stirred for 1.5 hours under a magnetic stirrer, then 0.1g of aryl alkyl sulfonate is added, and stirred for 0.5 hour to be fully dissolved, so that the binary composite oil-displacing agent 2 is obtained.
Example 15
0.3g of long-chain branched polymer 3 for oil displacement is weighed and added into 200g of saline solution containing 0.04% of calcium ions, 0.0377% of magnesium ions and 2.9% of NaCl, stirred for 1.5 hours under a magnetic stirrer, then 0.1g of polyoxyethylene ether sulfonate is added, and stirred for 0.5 hour to be fully dissolved, so that the binary composite oil-displacing agent 3 is obtained.
Example 16
0.3g of long-chain branched polymer 4 for oil displacement is weighed and added into 200g of saline solution containing 0.04% of calcium ions, 0.0377% of magnesium ions and 2.9% of NaCl, stirred for 1.5 hours under a magnetic stirrer, then 0.1g of petroleum sulfonate is added, and stirred for 0.5 hour to be fully dissolved, so that the binary composite oil-displacing agent 4 is obtained.
Example 17
0.3g of long-chain branched polymer 5 for oil displacement is weighed and added into 200g of saline solution containing 0.04% of calcium ions, 0.0377% of magnesium ions and 2.9% of NaCl, stirred for 1.5 hours under a magnetic stirrer, then 0.1g of petroleum carboxylate is added, and stirred for 0.5 hour to be fully dissolved, so that the binary composite oil-displacing agent 5 is obtained.
Example 18
0.3g of long-chain branched polymer 6 for oil displacement is weighed and added into 200g of saline solution containing 0.04% of calcium ions, 0.0377% of magnesium ions and 2.9% of NaCl, stirred for 1.5 hours under a magnetic stirrer, then 0.1g of polyoxyethylene phosphate is added, and stirred for 0.5 hour to be fully dissolved, so that the binary composite oil-displacing agent 6 is obtained.
To further illustrate the effectiveness of the present invention, the apparent viscosities of the long chain branched polymer oil-displacing agent and the binary composite oil-displacing agent were tested and compared, see table 31.
Watch 31
Viscosity Using BROOKFIELD DV-IIIThe rotation speed of the instrument is 7.34S-1The apparent viscosity of the aqueous polymer solution was measured at 85 ℃ under test conditions: 7.34s-185 ℃, polymer concentration: 1500mg/L, and the total mineralization of the solution is 32868 mg/L.
According to the analysis of the results, the viscosity of the binary composite oil displacement agent is greatly improved under the conditions of high salinity (32868mg/L) and high temperature (85 ℃), and the binary composite oil displacement agent is favorable for application in tertiary oil recovery.
Claims (10)
1. A free radical polymerization functional monomer, the molecular structural formula of which is shown as (11):
(11) in the formula: n is 2 or 6, R is C11～C24Straight chain alkyl or C11～C24The unsaturated linear hydrocarbon group of (1).
2. The free radical polymerizable functional monomer of claim 1, (11) wherein R is a hydrocarbyl moiety of lauric acid, oleic acid, or stearic acid.
3. Use of the free-radically polymerizable functional monomer according to claim 1 or 2 for the preparation of long-chain branched polymers for flooding.
4. The method of synthesizing a free radical polymerizable functional monomer of claim 1:
firstly, mixing diamine and fatty acid according to a molar ratio of 1: 1-1.2; wherein,
the diamine has the structural formula: NH (NH)2-(CH2)n-NH2N is 2 or 6;
the structural formula of the fatty acid is: R-COOH, R being C11～C24Straight chain alkyl or C11～C24The unsaturated straight-chain hydrocarbon group of (1);
heating to 110-160 ℃, and reacting for 2-6 hours to obtain an intermediate M, wherein the structural formula of the intermediate M is (12):
secondly, adding an organic solvent and maleic anhydride into the obtained intermediate M, and carrying out reflux reaction for 4-8 hours at the reaction temperature of 80-110 ℃;
diamine and an organic solvent are 1: 20-30;
diamine and maleic anhydride are in a molar ratio of 1: 1-1.2;
and thirdly, evaporating the product obtained in the last step out the organic solvent, and drying to obtain the free radical polymerization functional monomer.
5. The method of claim 4, wherein the organic solvent in the second step is one or more of the following: ethanol, acetone, ethyl acetate, benzene, toluene, xylene, dichloromethane, and chloroform.
6. The synthesis process according to claim 4 or 5, wherein the product is purified by recrystallization after the third step.
7. The method of synthesizing a free radical polymerizable functional monomer of claim 1:
firstly, mixing diamine and fatty acid in an organic solvent, heating to 110-156 ℃, and reacting for 2-6 hours to obtain a solution of an intermediate M; the structural formulae of the diamine, the fatty acid and the intermediate M are as defined in claim 5;
according to molar ratio: diamine and an organic solvent are 1: 20-30; diamine and fatty acid are 1: 1-1.2;
secondly, adding maleic anhydride into the obtained intermediate M solution according to a molar ratio of 1: 1-1.2, and carrying out reflux reaction at a reaction temperature of 80-110 ℃ for 4-8 hours;
and thirdly, evaporating the product obtained in the last step out the organic solvent, and drying to obtain the free radical polymerization functional monomer.
8. The synthesis method according to claim 7, wherein the organic solvent in the first step is one or more of the following: ethanol, acetone, ethyl acetate, benzene, toluene, xylene, dichloromethane, and chloroform.
9. The synthesis process according to claim 7 or 8, wherein the product is purified by recrystallization after the third step.
10. The method of claim 5 or 8, wherein said free radical polymerizable functional monomer (11) is a hydrocarbyl moiety of lauric acid, oleic acid, or stearic acid.
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