CN102372647A - 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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- CN102372647A CN102372647A CN2010102635260A CN201010263526A CN102372647A CN 102372647 A CN102372647 A CN 102372647A CN 2010102635260 A CN2010102635260 A CN 2010102635260A CN 201010263526 A CN201010263526 A CN 201010263526A CN 102372647 A CN102372647 A CN 102372647A
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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 present invention relates to the TOR field, relate in particular to synthetic, long chain branched polymers synthetic of free yl polymerizating monomer, can be applicable to fields such as TOR binary combination flooding finish.
Background technology
Radical polymerization is meant the vinyl monomer that contains carbon-carbon double bond, forms the reaction of polymkeric substance through the addition polymerization of radical chain type.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 radical polymerization is synthetic, mainly contains compound 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, acrylic amide, 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.
Emulsifying agent plays an important role in letex polymerization: can disperse before the polymerization and the solubilising monomer, form stable monomer emulsion; For monomer provides the polymerization place, and influence the character of monomeric polymerization behavior, latex particle size and distribution, emulsion particle in the polymerization; Stablizing latex particle after the polymerization makes it not take place to condense.Traditional emulsifying agent is to be adsorbed in the emulsion particle surface through physical action, at freeze-thaw cycle, perhaps imposes shearing force, and when perhaps adding ionogen, stability of emulsion can change and even breakdown of emulsion; During film forming, emulsifying agent can move, or is enriched in the interface between film and air, influences the gloss and other surface properties of film, or is enriched in the interface of film and matrix, influences the adhesiveproperties of film; Residual emulsifying agent also can cause rate of film build slow, reduces the water tolerance of film.In some production application, when adding component such as pigment in (1) latax, emulsifying agent can with the pigment dispersing agent absorption of competing at two interfaces of emulsion particle and water, pigment and water, thereby influence the rheological property and the stability of latax; (2) when producing solid phase prod through gel method, emulsifying agent can remain in water, causes environmental pollution; Therefore people introduce polymerisable group in conventional emulsifier, constitute new surface active monomer, claim polymerisable emulsifier again.The polymerisable emulsifier molecule is bonded in the surface of emulsion particle through the mode of covalent linkage; This intensive bonding makes the emulsifying agent molecule that desorb not take place when latax is deposited and use; Effectively solve the shortcoming of conventional emulsifier, the mechanical property, glossiness of film, cementability, water tolerance etc. all are greatly improved.The polymerisable emulsifier of being studied at present mainly contains allyl (oxygen) fundamental mode, (methyl) acrylic type, acid/acrylic amide type, styrene type, Malaysia acids etc.
Also there are some defectives in the SEPIGEL 305 and the partially hydrolyzed polyacrylamide aqueous solution when using, poor like the mechanical shearing stability, during in particular for the TOR oil-displacing agent, high velocity of shear can cause viscosity loss; Viscosity loss is arranged in salt solution; The long-time placement or the easy degraded of comparatively high temps held; The carboxyl that SEPIGEL 305 is with of partly hydrolysed can react with divalent ion.These defective effects the widespread use of SEPIGEL 305.In order further to improve the viscosity of SEPIGEL 305, improve its temperature resistant antisalt property, through with the novel functional monomer copolymerization process be a valid approach.
Patent CN1470504A discloses a kind of compound method that is used for acrylic amide analog derivative function monomer.
The product that obtains the industrialization promotion application at oilfield polymer flooding mainly is a partially hydrolyzed polyacrylamide, and molecular weight 2,300 ten thousand is used at the I in oil field class oil reservoir with interior SEPIGEL 305, injects with the clear water configuration; It has a certain amount of ydrodynamics volume under finite concentration; Viscosity in aqueous solution is improved, can reduce the rate of permeation of oil reservoir, increase water sucting thickness; Improve water-retaining capacity, be beneficial to improve oil recovery factor.Yet along with the increase of salt concn in the solution, polymer molecular chain can shrink gradually, and viscosity loss is very big when ionic strength is higher, has reduced the polymkeric substance swept volume, influences oil displacement efficiency.Therefore, improve the tackifying of polymers soln and the important topic that salt tolerance has become the polymkeric substance research field.
At present; The research salt-resistant polymer has two main paties both at home and abroad: the one, improve the hydromeehanics size that polymericular weight increases single polymer molecular chain as far as possible; Consider that simultaneously increasing the molecular chain rigidity increases the hydromeehanics size of polymkeric substance in the high salinity aqueous solution, the development super high molecular weight polyacrylamide, the 2nd, utilize the interaction between the molecular chain; Form the hydromeehanics size that supramolecular structure increases the molecule chain bundle through associating, reach the purpose of high-effective viscosity.
Hydrophobic associated polymer is meant the water-disintegrable polymkeric substance that on polymkeric substance wetting ability macromolecular chain, has hydrophobic grouping, and its SOLUTION PROPERTIES and general polymerization thing differ greatly.In the aqueous solution, the hydrophobic grouping of this base polymer makes macromolecular chain produce intramolecularly and intermolecular association owing to hydrophobic interaction is assembled.Macromole mainly exists with the associating form of intramolecularly in dilute solution, makes macromolecular chain take place to curl, and hydrodynamic volume reduces, and viscosity reduces.After polymer concentration is higher than a certain threshold concentration (critical association concentration C); Macromolecular chain is assembled through the hydrophobic association effect; Formation is supramolecular structure-dynamic physical cross-linked network of master to associate between having divided, and the hydromeehanics size increases, and soltion viscosity raises significantly.The electrolytical adding of small molecules can increase polarity of solvent, the hydrophobic association effect is strengthened, thereby produce tangible salt resistance.
Even increase the purpose of molecular weight is to guarantee under the high salinity environment, although polymer solution viscosity can lose, because polymericular weight is high, corresponding its absolute viscosity will be than higher, thereby satisfy the requirement of working fluid to the polymer viscosified ability.Yet there are some defectives in this method, at first is the synthetic difficulty of high-molecular weight polymer, and secondly polymericular weight is high more, and it is outstanding more that problems of dissolution exposes.At present, this base polymer both domestic and external can satisfy above-mentioned requirements under clear water and lesser temps.But then do not reach above-mentioned requirements in the high salinity water quality.
On polymer molecular chain, introduce the monomeric unit of some high thermal stability monomeric units, big skeleton and the group of strong hydratability; Thereby strengthen polymer thermostable property and molecule chain rigidity; Strengthen the polymer hydration ability; Make polymer molecule in the high salinity aqueous solution, can keep bigger ydrodynamics size, 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, can not occur with calcium ions and magnesium ions sedimentary phenomenon taking place, thereby reach the purpose of anti-salt.
Summary of the invention
The technical problem that the present invention will solve:
The objective of the invention is to above-mentioned weak point; A kind of radical polymerization functional monomer and compound method thereof are provided; Prepared radical polymerization functional monomer can be used as polymeric emulsifiers, and is used for the displacement of reservoir oil synthesizing with long chain branched polymers; The synthetic displacement of reservoir oil can be used for the oil-displacing agent of TOR with long chain branched polymers, improves the performance of oil-displacing agent.
The product technology scheme of radical polymerization functional monomer of the present invention is:
A kind of radical polymerization functional monomer, its molecular structural formula are like (11) formula:
(11) in the formula: n is 2 or 6, and R is C
11～C
24Saturated alkyl or unsaturated alkyl.Preferred version is that R is the moieties (part that does not have terminal carboxyl(group)) of LAURIC ACID 99 MIN, oleic acid or hard fatty acids.
First kind of compound method of radical polymerization functional monomer of the present invention is:
The first step is mixed diamines with lipid acid, in molar ratio, and diamines: lipid acid=1: 1～1.2; Wherein,
The structural formula of diamines is: NH
2-(CH
2)
n-NH
2, n is 2 or 6;
The structural formula of lipid acid is: R-COOH, R are C
11～C
24Saturated straight chain alkane or unsaturated straight-chain paraffin;
Be heated to 110 ℃～160 ℃, reacted 2～6 hours, obtain midbody M, the structural formula of midbody M is (12) formula:
Second step in gained midbody 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, ETHYLE ACETATE, benzene,toluene,xylene, methylene dichloride and trichloromethane;
Diamines: organic solvent=1: 20～30;
Diamines: cis-butenedioic anhydride=1: 1～1.2 (all being mol ratios);
The 3rd step, will go up the step product and steam organic solvent, drying obtains radical polymerization functional monomer product.
Preferred version is further product to be carried out recrystallization and purify.
Second kind of compound method of radical polymerization functional monomer of the present invention is:
The first step in organic solvent, is mixed diamines with lipid acid, be heated to 110 ℃～156 ℃, reacts 2～6 hours, obtains the solution of midbody M; The structural formula of diamines, lipid acid and midbody M is with the definition in first kind of compound method;
In molar ratio: diamines: organic solvent=1: 20～30; Diamines: lipid acid=1: 1～1.2;
Described organic solvent is one or more the mixture in following: ethanol, acetone, ETHYLE ACETATE, benzene,toluene,xylene, methylene dichloride and trichloromethane;
Second step in gained midbody M solution, added cis-butenedioic anhydride again, in molar ratio, diamines: cis-butenedioic anhydride=1: 1～1.2, under 80 ℃～110 ℃ of temperature of reaction, back flow reaction 4～8 hours;
The 3rd step, will go up the step product and steam organic solvent, drying obtains radical polymerization functional monomer product.
Preferred version is further product to be carried out recrystallization and purify.
Radical polymerization functional monomer product of the present invention is used to prepare the displacement of reservoir oil and uses long chain branched polymers.Long chain branched polymers is used in the displacement of reservoir oil of the present invention, is under action of evocating, accomplish through at least two kinds of monomeric polyreactions, shown in reaction formula (21):
The displacement of reservoir oil of the present invention with the preparation method of long chain branched polymers is:
The first step takes by weighing monomer A, monomers B is made into the aqueous solution, and using alkali to regulate the pH value is 4～11; Preferred alkali is sodium hydroxide, or yellow soda ash.
Described monomer A is at least a in the following free yl polymerizating monomer:
Acrylic amide, 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 monomers B is the radical polymerization functional monomer, 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 monomers B is 0.008%～16% of a 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 initiator 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 cyanic acid 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), AMBN (trade(brand)name AMBN, V59) and ABVN (trade(brand)name ABVN, V65);
Described peroxide initiator system is at least a in following: hydrogen peroxide, ammonium persulphate, Sodium Persulfate, Potassium Persulphate, the Lucidol and the Lucidol tert-butyl ester;
Described redox initiator system is at least a in following: vitriol-sulphite, persulphate-thiocarbamide, persulphate-organic salt and ammonium persulphate-aliphatic amide (during described ammonium persulphate-aliphatic amide is preferably following at least a: ammonium persulphate-N, N-Tetramethyl Ethylene Diamine and ammonium persulphate-diethylamine).
The quality of initiator C is 0.01%～0.1% of a 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 the long chain branched polymers product is used in the displacement of reservoir oil that obtains white granular.
In the above method, a preferred scheme is: described monomer A is acrylic amide and 2-acrylamido-2-methyl propane sulfonic acid; Regulate the pH value with aqueous sodium hydroxide solution, initiator C is azo-bis-isobutyrate hydrochloride and Ammonium Persulfate 98.5, obtains structural formula and uses long chain branched polymers like the displacement of reservoir oil of (22) formula:
(22) in the formula: n is 2 or 6; X is the polymerization degree of acrylic amide, x=10 ten thousand～500,000; Y is the polymerization degree of 2-acrylamido-2-methyl propane sulfonic acid, y=5 ten thousand～150,000; Z is the polymerization degree of radical polymerization functional monomer B, z=1 ten thousand～50,000; R is C
11～C
24Saturated straight chain alkane or C
11～C
24Unsaturated straight-chain paraffin.
The displacement of reservoir oil of the present invention with long chain branched polymers and surfactant compound, is formed the binary combination flooding finish, to improve the temperature resistant antisalt performance of oil-displacing agent.
The product technology scheme of binary combination flooding finish of the present invention is:
Form by following component: structural formula like the displacement of reservoir oil of (22) with long chain branched polymers, tensio-active agent and salt brine solution.
(22) in the formula: n is 2 or 6; X is the polymerization degree of acrylic amide, x=10 ten thousand～500,000; Y is the polymerization degree of 2-acrylamido-2-methyl propane sulfonic acid, y=5 ten thousand～150,000; Z is the polymerization degree of radical polymerization functional monomer B, z=1 ten thousand～50,000; R is C
11～C
24Saturated straight chain alkane or C
11～C
24Unsaturated straight-chain paraffin;
Described tensio-active agent is one or more a 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 T 46155 phosphoric acid salt;
Described salt brine solution is the aqueous solution that contains calcium ion, mg ion and NaCl;
It is 0.05%～0.3% that the mass ratio of long chain branched polymers in total mass used in the described displacement of reservoir oil; The mass ratio of described tensio-active agent in total mass is 0.05%～0.1%; Surplus is a salt brine solution.
In the described salt brine solution, the calcium ion quality is 0.004%～0.05% of a total mass, and the mg ion quality is 0.004%～0.05% of a total mass, and the NaCl quality is 0.1%～5% of a total mass.
The preparation method of binary combination flooding finish of the present invention is:
The first step takes by weighing the described displacement of reservoir oil and uses long chain branched polymers, adds salt brine solution, stirs 1～2 hour, and it is fully dissolved;
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:
Radical polymerization functional monomer product of the present invention can be used as polymeric emulsifiers, and is used for the displacement of reservoir oil synthetic with long chain branched polymers, and the displacement of reservoir oil is used for the oil-displacing agent of TOR with long chain branched polymers, 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
Embodiment 1-6 [synthesizing of radical polymerization functional monomer]
Embodiment 1
By first kind of synthetic technology scheme of radical polymerization functional monomer, the quadrol of getting 0.1mol mixes with the 0.1mol LAURIC ACID 99 MIN, is heated to 130 ℃, reacts 2～6 hours, obtains midbody.In the gained midbody, 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 radical polymerizable functional property monomer product, is designated as monomer 1.
Fig. 1 is seen in structured testing, 2848.3cm
-1, 2916.8cm
-1Be the 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
By first kind of synthetic technology scheme of radical polymerization functional monomer, the hexanediamine of getting 0.1mol mixes with the 0.1mol LAURIC ACID 99 MIN, is heated to 130 ℃, reacts 2～6 hours, obtains midbody.In the gained midbody, 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 radical polymerizable functional property monomer product, is designated as monomer 2.
Embodiment 3
By second kind of synthetic technology scheme of radical polymerization functional monomer, measure 150 milliliters of p-Xylol, the quadrol that adds 0.1mol mixes with 0.1mol oleic acid, is heated to 130 ℃～150 ℃; Reacted 2～6 hours, and steamed solvent, add 150 milliliters of organic solvent dichloromethane, add the cis-butenedioic anhydride of 0.1mol again; Under 80 ℃～110 ℃, back flow reaction steamed solvent after 4～8 hours; Drying gets radical polymerizable functional property monomer product, is designated as monomer 3.
Embodiment 4
By second kind of synthetic technology scheme of radical polymerization functional monomer, measure 150 milliliters of p-Xylol, the hexanediamine that adds 0.1mol mixes with 0.1mol oleic acid, is heated to 130 ℃～150 ℃; Reacted 2～6 hours, and steamed solvent, add 150 milliliters of organic solvent dichloromethane, add the cis-butenedioic anhydride of 0.1mol again; Under 80 ℃～110 ℃, back flow reaction steamed solvent after 4～8 hours; Drying gets radical polymerizable functional property monomer product, is designated as monomer 4
Embodiment 5
By first kind of synthetic technology scheme of radical polymerization functional monomer, the quadrol of getting 0.1mol mixes with the 0.1mol hard fatty acids, is heated to 130 ℃, reacts 2～6 hours, obtains midbody.In the gained midbody, 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 radical polymerizable functional property monomer product, is designated as monomer 5.
Embodiment 6
By first kind of synthetic technology scheme of radical polymerization functional monomer, the hexanediamine of getting 0.1mol mixes with the 0.1mol hard fatty acids, is heated to 130 ℃, reacts 2～6 hours, obtains midbody.In the gained midbody, 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 radical polymerizable functional property monomer product, is designated as monomer 6.
Embodiment 7-12 [long chain branched polymers is used in the synthetic displacement of reservoir oil]
Embodiment 7
Take by weighing acrylic amide 7.23 grams, 2.27 gram 2-acrylic amide-2-methyl propane sulfonic acids are made into the aqueous solution, regulate the pH value to alkalescence (pH＞9) with aqueous sodium hydroxide solution, 0.15 gram monomer 1; Add azo-bis-isobutyrate hydrochloride (AIBA) 3.0 milligrams, under nitrogen protection, add 6.0 milligrams of Ammonium Persulfate 98.5s, 20 ℃ of polymerizations of temperature are after 8 hours; Be warming up to 50 ℃ again, continue polymerization 4 hours, the gained colloid is taken out granulation; Drying is pulverized, and obtains white powder acrylic amide water-soluble polymers product, is designated as polymkeric substance 1; The test polymer molecular weight is 1,200 ten thousand, and at salinity 32868mg/L, the AV under 85 ℃ of the temperature is 18.1mPas.
Embodiment 8
Take by weighing acrylic amide 7.23 grams, 2.27 gram 2-acrylic amide-2-methyl propane sulfonic acids are made into the aqueous solution, regulate the pH value to alkalescence (pH＞9) with aqueous sodium hydroxide solution, 0.15 gram monomer 2; Add azo-bis-isobutyrate hydrochloride (AIBA) 3.0 milligrams, under nitrogen protection, add 6.0 milligrams of Ammonium Persulfate 98.5s, 20 ℃ of polymerizations of temperature are after 8 hours; Be warming up to 50 ℃ again, continue polymerization 4 hours, the gained colloid is taken out granulation; Drying is pulverized, and obtains white powder acrylic amide water-soluble polymers product, is designated as polymkeric substance 2; The test polymer molecular weight is 1,500 ten thousand, and at salinity 32868mg/L, the AV under 85 ℃ of the temperature is 20.7mPas.
Embodiment 9
Take by weighing acrylic amide 7.23 grams, 2.27 gram 2-acrylic amide-2-methyl propane sulfonic acids are made into the aqueous solution, regulate the pH value to alkalescence (pH＞9) with aqueous sodium hydroxide solution, 0.15 gram monomer 3; 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; After the polymerization 8 hours, be warming up to 50 ℃ again, continue polymerization 4 hours, the gained colloid is taken out; Granulation, drying is pulverized, and obtains white powder acrylic amide water-soluble polymers product; Be designated as polymkeric substance 3, the test polymer molecular weight is 1,800 ten thousand, and at salinity 32868mg/L, the AV under 85 ℃ of the temperature is 26.5mPas.
Embodiment 10
Take by weighing acrylic amide 7.23 grams, 2.27 gram 2-acrylic amide-2-methyl propane sulfonic acids are made into the aqueous solution, regulate the pH value to alkalescence (pH＞9) with aqueous sodium hydroxide solution, 0.15 gram monomer 4; 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; After the polymerization 8 hours, be warming up to 50 ℃ again, continue polymerization 4 hours, the gained colloid is taken out; Granulation, drying is pulverized, and obtains white powder acrylic amide water-soluble polymers product; Be designated as polymkeric substance 4, the test polymer molecular weight is 2,000 ten thousand, and at salinity 32868mg/L, the AV under 85 ℃ of the temperature is 28.4mPas.
Embodiment 11
Take by weighing acrylic amide 7.23 grams, 2.27 gram 2-acrylic amide-2-methyl propane sulfonic acids are made into the aqueous solution, regulate the pH value to alkalescence (pH＞9) with aqueous sodium hydroxide solution, 0.15 gram monomer 5; 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; After the polymerization 8 hours, be warming up to 50 ℃ again, continue polymerization 4 hours, the gained colloid is taken out; Granulation, drying is pulverized, and obtains white powder acrylic amide water-soluble polymers product; Be designated as polymkeric substance 5, the test polymer molecular weight is 2,500 ten thousand, and at salinity 32868mg/L, the AV under 85 ℃ of the temperature is 32.6mPas.
Embodiment 12
Take by weighing acrylic amide 7.23 grams, 2.27 gram 2-acrylic amide-2-methyl propane sulfonic acids are made into the aqueous solution, regulate the pH value to alkalescence (pH＞9) with aqueous sodium hydroxide solution, 0.15 gram monomer 6; 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; After the polymerization 8 hours, be warming up to 50 ℃ again, continue polymerization 4 hours, the gained colloid is taken out; Granulation, drying is pulverized, and obtains white powder acrylic amide water-soluble polymers product; Be designated as polymkeric substance 6, the test polymer molecular weight is 2,800 ten thousand, and at salinity 32868mg/L, the AV under 85 ℃ of the temperature is 38.2mPas.
Embodiment 13-18 [preparation binary combination flooding finish]
Embodiment 13
Taking by weighing the 0.3g displacement of reservoir oil joins in the 200g salt brine solution of calcium ions 0.04%, mg ion 0.0377%, NaCl content 2.9% with long chain branched polymers 1; Under magnetic stirring apparatus, stir after 1.5 hours; Add the 0.1g alkylaryl sulphonate again; Stir and it was fully dissolved in 0.5 hour, obtain binary combination flooding finish 1.
Embodiment 14
Taking by weighing the 0.3g displacement of reservoir oil joins in the 200g salt brine solution of calcium ions 0.04%, mg ion 0.0377%, NaCl content 2.9% with long chain branched polymers 2; Under magnetic stirring apparatus, stir after 1.5 hours; Add the 0.1g alkylaryl sulfonate again; Stir and it was fully dissolved in 0.5 hour, obtain binary combination flooding finish 2.
Embodiment 15
Taking by weighing the 0.3g displacement of reservoir oil joins in the 200g salt brine solution of calcium ions 0.04%, mg ion 0.0377%, NaCl content 2.9% with long chain branched polymers 3; Under magnetic stirring apparatus, stir after 1.5 hours; Add the 0.1g polyethenoxy ether sulphonate again; Stir and it was fully dissolved in 0.5 hour, obtain binary combination flooding finish 3.
Embodiment 16
Taking by weighing the 0.3g displacement of reservoir oil joins in the 200g salt brine solution of calcium ions 0.04%, mg ion 0.0377%, NaCl content 2.9% with long chain branched polymers 4; Under magnetic stirring apparatus, stir after 1.5 hours; Add the 0.1g sulfonated petro-leum again; Stir and it was fully dissolved in 0.5 hour, obtain binary combination flooding finish 4.
Embodiment 17
Taking by weighing the 0.3g displacement of reservoir oil joins in the 200g salt brine solution of calcium ions 0.04%, mg ion 0.0377%, NaCl content 2.9% with long chain branched polymers 5; Under magnetic stirring apparatus, stir after 1.5 hours; Add the 0.1g petroleum carboxylate again; Stir and it was fully dissolved in 0.5 hour, obtain binary combination flooding finish 5.
Embodiment 18
Taking by weighing the 0.3g displacement of reservoir oil joins in the 200g salt brine solution of calcium ions 0.04%, mg ion 0.0377%, NaCl content 2.9% with long chain branched polymers 6; Under magnetic stirring apparatus, stir after 1.5 hours; Add 0.1g T 46155 phosphoric acid salt again; Stir and it was fully dissolved in 0.5 hour, obtain binary combination flooding finish 6.
In order to further specify effect of the present invention, the AV of long chain branched polymers oil-displacing agent and binary combination flooding finish is tested and comparison, see table 31.
Table 31
Use BROOKFIELD DV-III viscosity apparatus to be 7.34S at rotating speed
-1, the AV 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 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 ℃), help the application in TOR.
Claims (18)
1. radical polymerization functional monomer, its molecular structural formula are like (11) formula:
(11) in the formula: n is 2 or 6, and R is C
11～C
24Straight chain saturated alkyl or unsaturated straight chained alkyl.
2. radical polymerization functional monomer according to claim 1, R is the moieties of LAURIC ACID 99 MIN, oleic acid or hard fatty acids in (11) formula.
3. claim 1 or 2 described radical polymerization functional monomers are preparing the displacement of reservoir oil with the application in the long chain branched polymers.
4. the compound method of the described radical polymerization functional monomer of claim 1:
The first step is mixed diamines with lipid acid, in molar ratio, and diamines: lipid acid=1: 1～1.2; Wherein,
The structural formula of diamines is: NH
2-(CH
2)
n-NH
2, n is 2 or 6;
The structural formula of lipid acid is: R-COOH, R are C
11～C
24Saturated straight chain alkane or unsaturated straight-chain paraffin;
Be heated to 110 ℃～160 ℃, reacted 2～6 hours, obtain midbody M, the structural formula of midbody M is (12) formula:
Second step in gained midbody M, added organic solvent, added cis-butenedioic anhydride again, under 80 ℃～110 ℃ of temperature of reaction, and back flow reaction 4～8 hours;
Diamines: organic solvent=1: 20～30;
Diamines: cis-butenedioic anhydride=1: 1～1.2 all are mol ratios;
The 3rd step, will go up the step product and steam organic solvent, drying obtains the radical polymerization functional monomer.
5. compound method according to claim 4, the organic solvent described in second step are one or more the mixtures in following: ethanol, acetone, ETHYLE ACETATE, benzene,toluene,xylene, methylene dichloride and trichloromethane.
6. according to claim 5 or 4 described compound methods, in the 3rd step back product is carried out recrystallization and purify.
7. the compound method of the described radical polymerization functional monomer of claim 1:
The first step in organic solvent, is mixed diamines with lipid acid, be heated to 110 ℃～156 ℃, reacts 2～6 hours, obtains the solution of midbody M; The structural formula of diamines, lipid acid and midbody M is with the definition in the claim 5;
In molar ratio: diamines: organic solvent=1: 20～30; Diamines: lipid acid=1: 1～1.2;
Second step in gained midbody M solution, added cis-butenedioic anhydride again, in molar ratio, diamines: cis-butenedioic anhydride=1: 1～1.2, under 80 ℃～110 ℃ of temperature of reaction, back flow reaction 4～8 hours;
The 3rd step, will go up the step product and steam organic solvent, drying obtains the radical polymerization functional monomer.
8. compound method according to claim 7, the organic solvent described in the first step are one or more the mixtures in following: ethanol, acetone, ETHYLE ACETATE, benzene,toluene,xylene, methylene dichloride and trichloromethane.
9. according to Claim 8 or 7 described compound methods, in the 3rd step back product being carried out recrystallization purifies.
10. according to Claim 8 or 5 described compound methods, R is the moieties of LAURIC ACID 99 MIN, oleic acid or hard fatty acids in described radical polymerization functional monomer (11) formula.
11. radical polymerization functional monomer:
Said radical polymerization functional monomer prepares through following steps:
The first step is mixed diamines with lipid acid, in molar ratio, and diamines: lipid acid=1: 1～1.2; Wherein,
The structural formula of diamines is: NH
2-(CH
2)
n-NH
2, n is 2 or 6;
The structural formula of lipid acid is: R-COOH, R are C
11～C
24Saturated straight chain alkane or unsaturated straight-chain paraffin;
Be heated to 110 ℃～160 ℃, reacted 2～6 hours, obtain midbody M, the structural formula of midbody M is (12) formula:
Second step in gained midbody M, added organic solvent, added cis-butenedioic anhydride again, under 80 ℃～110 ℃ of temperature of reaction, and back flow reaction 4～8 hours;
Diamines: organic solvent=1: 20～30;
Diamines: cis-butenedioic anhydride=1: 1～1.2 all are mol ratios;
The 3rd step, will go up the step product and steam organic solvent, drying obtains the radical polymerization functional monomer.
12. radical polymerization functional monomer according to claim 11, R is the moieties of LAURIC ACID 99 MIN, oleic acid or hard fatty acids in (11) formula.
13. radical polymerization functional monomer according to claim 11, the organic solvent described in second step are one or more the mixtures in following: ethanol, acetone, ETHYLE ACETATE, benzene,toluene,xylene, methylene dichloride and trichloromethane.
14. radical polymerization functional monomer according to claim 11 carries out recrystallization in the 3rd step back to product and purifies.
15. radical polymerization functional monomer:
Said radical polymerization functional monomer prepares through following steps:
The first step in organic solvent, is mixed diamines with lipid acid, be heated to 110 ℃～156 ℃, reacts 2～6 hours, obtains the solution of midbody M; The structural formula of diamines, lipid acid and midbody M is with the definition in the claim 5;
In molar ratio: diamines: organic solvent=1: 20～30; Diamines: lipid acid=1: 1～1.2;
Second step in gained midbody M solution, added cis-butenedioic anhydride again, in molar ratio, diamines: cis-butenedioic anhydride=1: 1～1.2, under 80 ℃～110 ℃ of temperature of reaction, back flow reaction 4～8 hours;
The 3rd step, will go up the step product and steam organic solvent, drying obtains the radical polymerization functional monomer.
16. radical polymerization functional monomer according to claim 15, the organic solvent described in the first step are one or more the mixtures in following: ethanol, acetone, ETHYLE ACETATE, benzene,toluene,xylene, methylene dichloride and trichloromethane.
17. radical polymerization functional monomer according to claim 15 carries out recrystallization in the 3rd step back to product and purifies.
18. radical polymerization functional monomer according to claim 15, R is the moieties of LAURIC ACID 99 MIN, oleic acid or hard fatty acids in described radical polymerization functional monomer (11) formula.
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| CN103483216A (en) * | 2012-06-12 | 2014-01-01 | 中国石油化工股份有限公司 | Polymerizable monomer, and preparation method and application thereof |
| CN104059620A (en) * | 2014-07-09 | 2014-09-24 | 哈尔滨工业大学 | Water-in-oil type polyamide emulsifier for drilling fluid and synthetizing method thereof |
| CN105504104A (en) * | 2014-09-24 | 2016-04-20 | 中国石油化工股份有限公司 | Photo-initiator composition, polyacrylamide oil displacement polymer, preparation method and application thereof |
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| CN103483216A (en) * | 2012-06-12 | 2014-01-01 | 中国石油化工股份有限公司 | Polymerizable monomer, and preparation method and application thereof |
| CN103483216B (en) * | 2012-06-12 | 2015-02-11 | 中国石油化工股份有限公司 | Polymerizable monomer, and preparation method and application thereof |
| CN104059620A (en) * | 2014-07-09 | 2014-09-24 | 哈尔滨工业大学 | Water-in-oil type polyamide emulsifier for drilling fluid and synthetizing method thereof |
| CN105504104A (en) * | 2014-09-24 | 2016-04-20 | 中国石油化工股份有限公司 | Photo-initiator composition, polyacrylamide oil displacement polymer, preparation method and application thereof |
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