CN108440712A - The dissaving polymer complex microsphere of nucleocapsid, preparation method and application - Google Patents
The dissaving polymer complex microsphere of nucleocapsid, preparation method and application Download PDFInfo
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- CN108440712A CN108440712A CN201810271358.6A CN201810271358A CN108440712A CN 108440712 A CN108440712 A CN 108440712A CN 201810271358 A CN201810271358 A CN 201810271358A CN 108440712 A CN108440712 A CN 108440712A
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
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- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
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- C09K8/588—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific polymers
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- C09K8/62—Compositions for forming crevices or fractures
- C09K8/72—Eroding chemicals, e.g. acids
- C09K8/74—Eroding chemicals, e.g. acids combined with additives added for specific purposes
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Abstract
The present invention relates to a kind of dissaving polymer complex microspheres of nucleocapsid, which is characterized in that the dissaving polymer microballoon is the composite construction of kernel and shell, and the kernel is dissaving polymer, and the shell is polystyrene vinylacetate.The invention also includes the preparation method and application of the dissaving polymer complex microsphere lotion of nucleocapsid.The complex microsphere of the present invention is during actual production use, and after the polystyrene vinyl acetate ester hydrolysis of shell sections, surface generates a large amount of hydroxyl, has hydrophily, therefore be conducive to disperse in water.When formation temperature is less than 80 DEG C, polystyrene vinylacetate Shell Materials can keep not decomposing for a long time；When temperature is 120 DEG C, polystyrene vinylacetate shell material can be crushed at 2~3 months, and the dissaving polymer for keeping it internal is released, with dissaving polymer water swelling and decomposition, the polymer with viscosity is gradually generated, viscosity can be kept 2~3 months.
Description
Technical field
The present invention relates to a kind of preparation methods of the functional composite microsphere of nucleocapsid, belong to the preparation of functional polymer microballoon
Technical field, and in particular to it is a kind of using dissaving polymer as the microballoon of kernel, preparation method and application, belong to petroleum works
Oil recovery field is improved, for the deep profile controlling control water of oil reservoir or the acid solution diversion agent of acidification de-plugging.
Background technology
During oil exploitation, waterflooding extraction and tertiary oil recovery are to improve the most important technology of oil recovery.Due to oil
The displacing fluid of the anisotropism of Tibetan, water drive and chemical flooding can be flowed along high permeability zone, reduce swept volume, seriously affect stone
The production efficiency of oil.Therefore the swept volume of improving ecology and chemical flooding is exactly cost-effectively to improve oil production rate, this is also
The research topic that oil worker payes attention to for a long time.
Currently, the technology for improving heterogeneous reservoir water drive and chemical flooding swept volume mainly uses high molecular weight (2000
~3,600 ten thousand) polyacrylamide solution and its crosslinked mobility gel improve sweep efficiency.Since oil reservoir is complicated and changeable, gather
The problems such as conjunction object is sheared by machinery and stratum, the biodegradable and resistance to temperature difference, has by mobility ratio come the target for improving sweep efficiency
When can not achieve.Therefore, petroleum science and technology worker has developed pre-crosslinking swell particle, but since its grain diameter is larger, can only
Suitable for macropore, the profile control of the high water-cut reservoir of hypertonic band.Polymer microballoon transfer drive profile control technique is one developed in recent years
The novel deep profile correction profile control technique of kind blocks formation pore throat using nanometer or the realization of micron-sized polymerizing microballoons, reaches deep step by step
The purpose of portion's profile control.In addition, the chemical displacing fluid formed using nanoscale or submicron polymer microballoon and oil displacement agent, is adapted to
In higher temperature oil reservoir, the purpose for improving oil recovery is realized.
Chinese patent CN1903974A discloses a kind of nano-water soluble microgel oil displacing material and preparation method thereof, by adopting
Synthesize terpolymer nano-scale microgel oil displacing material, Third monomer with acrylamide/anionic monomer/Third monomer
(M3) acrylamide derivative, acrylate, methacrylate, N- vinylpyridines salt, n-vinyl pyrrolidone are selected from
In one or more kinds of mixtures etc..Chinese patent CN102399345A discloses a kind of " micro- containing nucleocapsid gel
The preparation method and emulsion deep profile control agent of the emulsion deep profile control agent of ball " makes water-soluble monomer (including acrylamide, ion
Monomer I, ion monomer II, Third monomer) it is reacted with crosslinking agent and prepares the nucleocapsid containing nanometer to micron size range
The emulsion deep profile control agent of gel micro-ball, kernel are acrylamide, base acrylyl oxy-ethyl-trimethyl salmiac and N- methyl-props
The reaction of acrylamide copolymerzation with cross-linking is made, and shell is made of acrylamide, sodium acrylate and N methacrylamide copolymerzation with cross-linking,
Nucleocapsid ingredient is sufficiently close to.Chinese patent CN101735413A discloses a kind of " system of the functional composite microsphere of multi-layer core-shell structure
Preparation Method and its application " is copolymerized by the single aggregation group nucleation portion of styrene by acrylamide, cationic monomer and crosslinking agent
The cationic shell parts of composition；Anion shell parts are formed by the copolymerization of acrylamide, anionic monomer and crosslinking agent.The nucleocapsid
Microballoon is that core is hard material, and shell is cross-linked polymer.Chinese patent CN104829784A disclose " inverse suspension polymerization preparation can divide
Depolymerize object microballoon in-depth profile control ", it is by acrylamide monomer, heat-resistant salt-resistant monomer, decomposable asymmetric choice net cross-linking monomer is copolymerized,
Decomposable asymmetric choice net cross-linking monomer is polyethyleneglycol diacrylate class monomer, such cross-linking monomer has temperature dependency, can pass through tune
Its dosage control decomposition temperature and time are saved, to adapt to different reservoir temperatures.
Various polymer microballoons or gel micro-ball disclosed in the prior art, although largely improving swept volume,
But heatproof is not high enough (may be only available for 80 DEG C or less), and becomes very crisp after water swelling, is easily sheared by stratum.
Invention content
Present invention is generally directed to the resistance to temperature difference of polymerizing microballoons existing in the prior art, and intensity is low after water swelling, and not
The deficiencies of polymer of viscosity higher can be decomposited, provides a kind of dissaving polymer complex microsphere of nucleocapsid, makes this hair
Bright polymer microballoon has high temperature resistant, high intensity, extends the dissaving polymer viscosity retention time, adapts in higher temperature
Oil reservoir is exploited, and oil recovery is improved.
In order to solve the above problem of the prior art, it is compound micro- that the present invention provides a kind of dissaving polymer of nucleocapsid
Ball, the dissaving polymer microballoon are the composite construction of kernel and shell, and the kernel is dissaving polymer, the shell
For polystyrene-vinylacetate.
According to a preferred embodiment of the present invention, the kernel is copolymerized by acrylamide, functional monomer and branching agent
The dissaving polymer of formation；The functional monomer is hydroxymethyl acrylamide, N,N-DMAA, dimethylamino
At least one of propylacrylamide and hydroxyethyl methacrylate.
According to a preferred embodiment of the present invention, the branching agent is polypropylene-base acrylamide, and molecular structural formula is such as
Under：
Wherein：X is H, CH3, CH2CH3；Y is H, CH3；n≥3.
According to a preferred embodiment of the present invention, it is polymer monomers that the shell, which is by styrene, vinylacetate, with
Divinylbenzene is polystyrene-vinylacetate that crosslinking agent obtains.
According to a preferred embodiment of the present invention, the mass ratio of the kernel and shell is 1:0.1~0.3.
The invention also includes a kind of dissaving polymer complex microsphere lotions of nucleocapsid, are implemented by any of the above-described kind
The dissaving polymer complex microsphere for the nucleocapsid that example is defined, is dispersed in the oil medium containing emulsifier and is formed.
The invention also includes the preparation method of the dissaving polymer complex microsphere lotion of the nucleocapsid, method packets
It includes：
Prepare aqueous phase solution A：Based on mass fraction, each component monomer for being used to form kernel for amounting to 15~50 parts is molten
Water phase is formed in 20~70 parts of water；
Prepare oil-phase solution B：Based on mass fraction, will amount to 1~10 part of each component monomer for being used to form shell and 5~
25 parts of being dissolved in 20~70 parts of oil mediums for emulsifier form oil phase；
Aqueous phase solution A is added drop-wise in oil-phase solution B, reversed-phase emulsion or Reverse Microemulsion System are formed, initiator is added
Initiated polymerization forms the dissaving polymer complex microsphere lotion of nucleocapsid.
According to a preferred embodiment of the present invention, the method comprises the following steps：
Prepare aqueous phase solution A：By mass, by 10~50 parts of acrylamides, 0.2~5 part of function monomer and 0.05~2 part
Polypropylene-base acrylamide branching agent is dissolved in 20~70 parts of deionized waters, forms homogeneous aqueous phase；The polypropylene-base acryloyl
The structural formula of amine branching agent is：
Wherein：X is H, CH3, CH2CH3；Y is H, CH3；n≥3.
Prepare oil-phase solution B：By mass, by 5~25 parts of emulsifiers, 1~8 part of styrene, 0.2~5 part of vinyl acetate
Ester and 0.1~3 part of divinylbenzene are that crosslinking agent is dissolved in 20~70 parts of oil mediums, form uniform oil phase；
Heating polymerization：Oil phase is heated to 30~50 DEG C, under constant stirring, aqueous phase solution A is added drop-wise to oil-phase solution B
In it is transparent or translucent or initiator is added into reaction system under anaerobic or anaerobic environment for milky to oil-phase solution B
Initiated polymerization, reaction time are 2~10h, obtain the dissaving polymer complex microsphere lotion of nucleocapsid.
Preferably, the initiator is also known as radical initiator, refer to it is a kind of be easy to be thermally decomposed into free radical (i.e. it is primary oneself
By base) compound, can be used for cause alkenes, double vinyl monomers free radical polymerization and copolymerization.The initiator is
A kind of organic peroxide evocating agent, inorganic peroxide initiator, azo-initiator or redox initiator, preferably
A kind of redox initiator.
Preferably, the initiator be ammonium persulfate/sodium hydrogensulfite, potassium peroxydisulfate/sodium hydrogensulfite, hydrogen peroxide/
Tartaric acid, hydrogen peroxide/sodium formaldehyde sulfoxylate, ammonium persulfate/ferrous sulfate, hydrogen peroxide/sulfuric acid ferrous iron, benzoyl peroxide //N, N-
Diethylaniline, benzoyl peroxide/ferrous pyrophosphate, potassium peroxydisulfate/silver nitrate, persulfate/mercaptan, isopropylbenzene peroxidating
Aziridine of hydrogen/frerrous chloride, potassium peroxydisulfate/frerrous chloride, hydrogen peroxide/frerrous chloride, isopropyl benzene hydroperoxide/tetra- etc..
Wherein ammonium persulfate/sodium hydrogensulfite reaction speed is most appropriate.
Preferably, the emulsifier is by fatty alcohol polyoxyethylene ether (3), fatty alcohol polyoxyethylene ether (4), poly alkyl alcohol
Ethylene oxide ether (5), fatty alcohol polyoxyethylene ether (9), fatty alcohol polyoxyethylene ether (15), in fatty alcohol polyoxyethylene ether (20)
At least two combination.【The digital representation degree of polymerization】
Preferably, the anaerobic or anaerobic environment are realized by nitrogen displacement method, i.e., are polymerize in addition initiator
Before reaction, nitrogen is passed through into reaction system, with 0.3~1h of nitrogen displaced air.Oxygen, which enters reaction system, has inhibition to make
With N2For protecting reaction system, it in high temperature is to be aoxidized to prevent substance (such as double bond).It will be in logical nitrogen tube intercalation reaction liquid
It is taken out after the 0.3~1h of displaced air of face.
The invention also includes the applications of the dissaving polymer complex microsphere lotion of the nucleocapsid, that is, use it for
Two, the deep profile controlling control water of three classes oil reservoir；It is either combined with oil displacement agent for combined chemical flooding or as acidification de-plugging
Acid solution diversion agent.
The invention also includes the preparation methods of the dissaving polymer complex microsphere of the nucleocapsid, including：
Prepare aqueous phase solution A：By mass, by 10~50 parts of acrylamides, 0.2~5 part of function monomer and 0.05~2 part
Polypropylene-base acrylamide branching agent is dissolved in 20~70 parts of deionized waters, forms homogeneous aqueous phase；
Prepare oil-phase solution B：By mass, by 1~8 part of styrene, 0.2~5 part of vinylacetate and 0.1~3 part two
Vinyl benzene is that crosslinking agent is dissolved in 20~70 parts of finishes, forms uniform oil phase；
Heating polymerization：Oil phase is heated to 30~50 DEG C, under constant stirring, aqueous phase solution A is added drop-wise to oil-phase solution B
In it is transparent or translucent or initiator is added into reaction system under anaerobic or anaerobic environment for milky to oil-phase solution B
Initiated polymerization, reaction time are 2~10h, obtain the suspension of the dissaving polymer complex microsphere of nucleocapsid；
Detach the dissaving polymer complex microsphere of the nucleocapsid.
In all of above scheme, the oil-phase medium in the group that aliphatic hydrocarbon, solvent naphtha and aromatic hydrocarbons are formed at least
It is a kind of；Wherein, the aliphatic hydrocarbon is preferably selected from least one of the group that octane, decane and hexamethylene are formed；It is described molten
Agent oil is preferably selected from least one of the group that atoleine, kerosene, white oil, diesel oil, gasoline and naphtha are formed；It is described
Aromatic hydrocarbons is preferably selected from least one of the group that benzene, toluene and dimethylbenzene are formed.
In all of above scheme, oil medium is preferably white oil.White oil alias paraffin oil, white oil, mineral oil, are by stone
The mixture of oily gained refining liquid hydrocarbon, the cycloalkane and alkane mixture being predominantly saturated, crude oil is through normal pressure and decompression point
Evaporate, solvent extraction and dewaxing, hydrofinishing and obtain.
The beneficial effects of the invention are as follows：
(1) the dissaving polymer complex microsphere of nucleocapsid of the present invention, using dissaving polymer as the kernel of microballoon
Material, using polystyrene-vinylacetate as Shell Materials.Inner nuclear material dissaving polymer is that one kind is highly branched, has three
The polymer of reticular structure is tieed up, there is the features such as high temperature resistant, anti-shearing, long-term holding is sticky, can reach the deep profile controlling displacement of reservoir oil
Purpose；The Shell Materials have heatproof, acid and alkali-resistance, are not easy water swelling, high-strength characteristic, can preferably protect inside
Dissaving polymer is not destroyed during injecting stratum, it can be achieved that long-time, the purpose of temperature resistance and resistant to shearing.The kernel with
Both shells act synergistically, and common play has good deep profile controlling Oil Displacing Capacity.
(2) during actual production use, after polystyrene-vinyl acetate ester hydrolysis of shell sections, surface production
Raw a large amount of hydroxyl, has hydrophily, therefore be conducive to disperse in water.When formation temperature is less than 80 DEG C, polystyrene-vinegar
Vinyl acetate Shell Materials can keep not decomposing for a long time；When temperature is 120 DEG C, polystyrene-vinylacetate shell material
Material can be crushed at 2~3 months, and the dissaving polymer for keeping it internal is released, as dissaving polymer absorbs water
Expansion and decomposition, gradually generate the polymer with viscosity, and viscosity can be kept 2~3 months.Therefore it by the Shell Materials, carries
The heat resistance of high dissaving polymer complex microsphere forms delay and slow releasing function to dissaving polymer.
(3) existing polymer microballoon temperature tolerance is increased to 120 DEG C, kernel portion by technology through the invention by 80 DEG C
Dissaving polymer viscosity can keep 2~3 months.The dissaving polymer complex microsphere lotion of the nucleocapsid of the present invention can
Increase in oil control water operation for the two, deep profile controlling of three classes oil reservoir and transfer drive etc., it is also possible to make the acid solution diversion agent of acidification de-plugging,
Or combined with oil displacement agent and be used as chemical combined flooding oil systems, improve oil recovery.
Description of the drawings
Fig. 1 is the preparation method flow chart of the dissaving polymer complex microsphere lotion of nucleocapsid.
Specific implementation mode
In order to preferably explain the present invention, in order to understand, below by specific implementation mode, present invention work is retouched in detail
It states.
Embodiment 1
In four mouthfuls of reaction bulbs equipped with reflux condensing tube, thermometer, blender and nitrogen replaceable equipment, it is added 40 parts in vain
Oil and 10 parts of fatty alcohol polyoxyethylene ether (3) and 3.5 parts of fatty alcohol polyoxyethylene ether (15), heating are heated to 45 DEG C, and dissolving is equal
After even, it is separately added into 5.4 parts of styrene, 2.3 parts of vinylacetates and 0.30 part of divinylbenzene, 40 DEG C of constant temperature is gone at 55 parts
0.95 part of branching agent polypropylene-base Methacrylamide is added in ionized water and is separately added into 38 after 45 DEG C are sufficiently stirred dissolving
Part acrylamide, 3.6 parts of dimethylamino-propyl acrylamides obtain water phase after being uniformly dissolved.Oil phase is 400r/ with mixing speed
Min is added dropwise water phase and obtains translucent lotion.With nitrogen displaced air 0.5h, 2% ammonium persulfate aqueous solution 2mL is instilled, 2% is sub-
Niter cake 3mL obtains the dissaving polymer microballoon lotion of nucleocapsid in 40 DEG C of isothermal reaction 6h.
Embodiment 2
In four mouthfuls of reactors equipped with reflux condensing tube, thermometer, blender and nitrogen replaceable equipment, it is added 40 parts in vain
Oil and 12 parts of fatty alcohol polyoxyethylene ether (3) and 4 parts of fatty alcohol polyoxyethylene ether (15), heating are heated to 45 DEG C, are uniformly dissolved
Afterwards, 6 parts of styrene, 3.5 parts of vinylacetates and 0.30 part of divinylbenzene, 40 DEG C of constant temperature are separately added into.In 40 parts of deionizations
1.5 parts of branching agent polypropylene-base (N- methyl) Methacrylamides are added in water to be separately added into after 45 DEG C are sufficiently stirred dissolving
30 parts of acrylamides, 2.5 parts of hydroxymethyl acrylamide obtain water phase after being uniformly dissolved.Oil phase is 400r/min with mixing speed, drop
Water phase is added to obtain transparency emulsion.With nitrogen displaced air 0.5h, 2% ammonium persulfate aqueous solution 2mL, 2% sodium hydrogensulfite are instilled
3mL obtains the dissaving polymer microballoon lotion of nucleocapsid in 40 DEG C of isothermal reaction 4h.
Embodiment 3
In four mouthfuls of reactors equipped with reflux condensing tube, thermometer, blender and nitrogen replaceable equipment, it is added 55 parts in vain
Oil and 7 parts of fatty alcohol polyoxyethylene ether (3), 3 parts of fatty alcohol polyoxyethylene ether (5) and 3.5 parts of fatty alcohol polyoxyethylene ether (9),
Heating is heated to 45 DEG C, after being uniformly dissolved, and is separately added into 3.5 parts of styrene, 3.0 parts of vinylacetates and 0.25 part of divinyl
Benzene, 40 DEG C of constant temperature.0.80 part of branching agent polypropylene-base acrylamide is added in 35 parts of deionized waters, is sufficiently stirred at 45 DEG C molten
Xie Hou, is separately added into 26 parts of acrylamides, and 3 parts of hydroxyethyl methacrylates obtain water phase after being uniformly dissolved.Oil phase is with mixing speed
For 400r/min, water phase is added dropwise and obtains transparency emulsion.With nitrogen displaced air 0.5h, 2% ammonium persulfate aqueous solution 2mL is instilled,
2% sodium hydrogensulfite 2mL obtains the dissaving polymer microballoon lotion of nucleocapsid in 40 DEG C of isothermal reaction 7h.
Embodiment 4
In four mouthfuls of reactors equipped with reflux condensing tube, thermometer, blender and nitrogen replaceable equipment, it is added 35 parts in vain
Oil and 8 parts of fatty alcohol polyoxyethylene ether (3) and 7 parts of fatty alcohol polyoxyethylene ether (7), heating are heated to 45 DEG C, after being uniformly dissolved,
It is separately added into 4.8 parts of styrene, 2.2 parts of vinylacetates and 0.25 part of divinylbenzene, 40 DEG C of constant temperature.In 65 parts of deionized waters
2.10 parts of branching agent polypropylene-base (N- ethyls) acrylamides of middle addition are separately added into 35 parts after 40 DEG C are sufficiently stirred dissolving
Acrylamide, 4.0 parts of N,N-DMAAs obtain water phase after being uniformly dissolved.Oil phase is 500r/min with mixing speed, drop
Water phase is added to obtain milky emulsion.With nitrogen displaced air 0.5h, 2% ammonium persulfate aqueous solution 3mL, 2% bisulfite are instilled
Sodium 3mL obtains the dissaving polymer microballoon lotion of nucleocapsid in 40 DEG C of isothermal reaction 4.5h.
Embodiment 5
In four mouthfuls of reactors equipped with reflux condensing tube, thermometer, blender and nitrogen replaceable equipment, it is added 40 parts in vain
Oil and 8 parts of fatty alcohol polyoxyethylene ether (4) and 6 parts of fatty alcohol polyoxyethylene ether (7), heating are heated to 45 DEG C, after being uniformly dissolved,
It is separately added into 4.0 parts of styrene, 1.8 parts of vinylacetates and 0.30 part of divinylbenzene, 40 DEG C of constant temperature.In 60 parts of deionized waters
1.0 parts of branching agent polypropylene-base acrylamides of middle addition are separately added into 40 parts of acrylamides after 40 DEG C are sufficiently stirred dissolving,
2.0 parts of hydroxymethyl acrylamide obtain water phase after being uniformly dissolved.Oil phase is 450r/min with mixing speed, and water phase is added dropwise and obtains breast
White emulsion.With nitrogen displaced air 0.5h, 2% ammonium persulfate aqueous solution 3mL, 2% sodium hydrogensulfite 3mL, at 40 DEG C is instilled
Isothermal reaction 6h obtains the dissaving polymer microballoon lotion of nucleocapsid.
Embodiment 6
In four mouthfuls of reactors equipped with reflux condensing tube, thermometer, blender and nitrogen replaceable equipment, it is added 40 parts in vain
Oil and 9 parts of fatty alcohol polyoxyethylene ether (3), 2 parts of fatty alcohol polyoxyethylene ether (4) and 4 parts of fatty alcohol polyoxyethylene ether (20) rise
Temperature is heated to 45 DEG C, after being uniformly dissolved, and is separately added into 5.0 parts of styrene, 2.0 parts of vinylacetates and 0.40 part of divinyl
Benzene, 40 DEG C of constant temperature.0.55 part of branching agent polypropylene-base Methacrylamide is added in 70 parts of deionized waters, is fully stirred at 40 DEG C
After mixing dissolving, 40 parts of acrylamides are separately added into, 3.0 parts of hydroxymethyl acrylamide obtain water phase after being uniformly dissolved.Oil phase is to stir
Speed is 400r/min, and water phase is added dropwise and obtains milky emulsion.With nitrogen displaced air 0.5h, it is water-soluble to instill 2% ammonium persulfate
Liquid 2.5mL, 2% sodium hydrogensulfite 3mL obtain the dissaving polymer microballoon lotion of nucleocapsid in 40 DEG C of isothermal reaction 4h.
Embodiment 7
In four mouthfuls of reactors equipped with reflux condensing tube, thermometer, blender and nitrogen replaceable equipment, it is added 45 parts in vain
Oil and 10 parts of fatty alcohol polyoxyethylene ether (3), 5 parts of fatty alcohol polyoxyethylene ether (4) and 6 parts of fatty alcohol polyoxyethylene ether (15),
Heating is heated to 45 DEG C, after being uniformly dissolved, and is separately added into 4.6 parts of styrene, 2.5 parts of vinylacetates and 0.65 part of divinyl
Benzene, 40 DEG C of constant temperature.1.20 parts of branching agent polypropylene-base (N- methyl) acrylamides are added in 55 parts of deionized waters, are filled at 40 DEG C
After dividing stirring and dissolving, 36 parts of acrylamides are separately added into, 3.5 parts of dimethylamino-propyl acrylamides obtain water phase after being uniformly dissolved.
Oil phase is 400r/min with mixing speed, and water phase is added dropwise and obtains transparency emulsion.With nitrogen displaced air 0.5h, 2% over cure is instilled
Sour aqueous ammonium 2mL, 2% sodium hydrogensulfite 3mL obtain the dissaving polymer of nucleocapsid in 40 DEG C of isothermal reaction 5.5h
Microballoon lotion.
Comparative example 1
In four mouthfuls of reactors equipped with reflux condensing tube, thermometer, blender and nitrogen replaceable equipment, it is added 40 parts in vain
Oil and 14 parts of fatty alcohol polyoxyethylene ether (3) and 6 parts of fatty alcohol polyoxyethylene ether (15), heating are heated to 45 DEG C, are uniformly dissolved
Afterwards, 4.0 parts of styrene, 2.0 parts of vinylacetates and 0.45 part of divinylbenzene, 40 DEG C of constant temperature are separately added into.Gone at 55 parts from
0.60 part of N is added in sub- water, N- methylene-bisacrylamides are separately added into 38 parts of acryloyls after 40 DEG C are sufficiently stirred dissolving
Amine, 3.0 parts of hydroxyethyl methacrylates obtain water phase after being uniformly dissolved.Oil phase is 400r/min with mixing speed, and water phase is added dropwise and obtains
To transparency emulsion.With nitrogen displaced air 0.5h, 2% ammonium persulfate aqueous solution 2mL, 2% sodium hydrogensulfite 3mL, 40 is instilled
DEG C isothermal reaction 5h, obtains the polymer microballoon lotion of nucleocapsid.
Comparative example 2
In four mouthfuls of reactors equipped with reflux condensing tube, thermometer, blender and nitrogen replaceable equipment, it is added 55 parts in vain
Oil and 7 parts of fatty alcohol polyoxyethylene ether (3), 3 parts of fatty alcohol polyoxyethylene ether (5) and 3.5 parts of fatty alcohol polyoxyethylene ether (9),
Heating is heated to 45 DEG C, after being uniformly dissolved, and is separately added into 3.5 parts of styrene, 2.5 parts of vinylacetates and 0.30 part of divinyl
Benzene, 40 DEG C of constant temperature.1.80 parts of polyethylene glycol (200) double methacrylates are added in 65 parts of deionized waters, are sufficiently stirred at 40 DEG C
After dissolving, 35 parts of acrylamides are separately added into, 3.0 parts of hydroxyethyl methacrylates obtain water phase after being uniformly dissolved.Oil phase is to stir
Speed is 500r/min, and water phase is added dropwise and obtains transparent milk Virgin's milk liquid.With nitrogen displaced air 0.5h, 2% ammonium persulfate water is instilled
Solution 3mL, 2% sodium hydrogensulfite 3mL obtain the polymer microballoon lotion of nucleocapsid in 40 DEG C of isothermal reaction 5h.
Comparative example 3
In four mouthfuls of reactors equipped with reflux condensing tube, thermometer, blender and nitrogen replaceable equipment, it is added 40 parts in vain
Oil and 14 parts of fatty alcohol polyoxyethylene ether (3) and 6 parts of fatty alcohol polyoxyethylene ether (15), heating are heated to 45 DEG C, are uniformly dissolved
After obtain oil phase.0.60 part of N is added in 55 parts of deionized waters, N- methylene-bisacrylamides are sufficiently stirred dissolving at 40 DEG C
Afterwards, 38 parts of acrylamides are separately added into, 3.5 parts of dimethylamino-propyl acrylamides obtain water phase after being uniformly dissolved.Oil phase is to stir
Speed is 400r/min, and water phase is added dropwise and obtains transparency emulsion.With nitrogen displaced air 0.5h, 2% ammonium persulfate aqueous solution is instilled
2mL, 2% sodium hydrogensulfite 3mL obtain the polymer microballoon lotion of no nucleocapsid in 40 DEG C of isothermal reaction 4h.
Bottom water is simulated according to SY/T 5862-2008 standard preparations, it is anhydrous to dissolve 1.143g for 980.536g deionized waters
Calcium chloride, 0.863g magnesium chloride hexahydrates and 17.458g sodium chloride, acquired solution total salinity are 19334mg/L.Polymer microballoon
Median grain diameter is measured with 3690 potentiometers of Malvern Zen, and viscosity is surveyed with silent your the HAAKE MAR40 rotational rheometers of winged generation of match
It is fixed, the frequency-conversion high-speed blender GJS-B12K that resistant to shearing Qingdao Jiaonan Analytical Instruments Plant produces, with 10000r/min, stirring
0.5h, sealing ratiod measure the multifunctional chemical driving device HBQT-90 produced with jewel oil Instrument Ltd. of Yangzhou China.According to
The assay method of Shengli Oilfiedld Subsidiary Company Of China Petrochemical Corporation's company standard " polymer microballoon deep profile correction technical conditions ", evaluation
The performance of 1~3 polymer microballoon of Examples 1 to 7 and comparative example, evaluation results are shown in Table 1 shown in shown and table 2.
1 polymer microballoon heat resistance of table and viscosity change
2 polymer microballoon of table is anti-shearing and blocks efficiency
Claims (12)
1. a kind of dissaving polymer complex microsphere of nucleocapsid, which is characterized in that the dissaving polymer microballoon is interior
The composite construction of core and shell, the kernel are dissaving polymer, and the shell is polystyrene-vinylacetate.
2. the dissaving polymer complex microsphere of nucleocapsid according to claim 1, which is characterized in that the kernel is
The dissaving polymer formed is copolymerized by acrylamide, functional monomer and branching agent；The functional monomer is methylol third
Acrylamide, N,N-DMAA, at least one of dimethylamino-propyl acrylamide and hydroxyethyl methacrylate.
3. the dissaving polymer complex microsphere of nucleocapsid according to claim 2, which is characterized in that the branching agent
For polypropylene-base acrylamide, molecular structural formula is as follows：
Wherein：X is H, CH3, CH2CH3；Y is H, CH3；n≥3.
4. the dissaving polymer complex microsphere of nucleocapsid according to claim 1, which is characterized in that the shell is
It is polymer monomers, the polystyrene-vinyl acetate obtained as crosslinking agent using divinylbenzene by styrene, vinylacetate
Ester.
5. according to the dissaving polymer complex microsphere of claim 1-4 any one of them nucleocapsids, which is characterized in that institute
The mass ratio for stating kernel and shell is 1:0.1~0.3.
6. the dissaving polymer complex microsphere lotion of a kind of nucleocapsid, by claim 1-5 any one of them nucleocapsids
The dissaving polymer complex microsphere of structure, is dispersed in the oil medium containing emulsifier and is formed.
7. a kind of preparation method of the dissaving polymer complex microsphere lotion of nucleocapsid, which is characterized in that the method packet
It includes：
Prepare aqueous phase solution A：Based on mass fraction, each component monomer for being used to form kernel for amounting to 15~50 parts is dissolved in 20
Water phase is formed in~70 parts of water；
Prepare oil-phase solution B：Based on mass fraction, 1~10 part of each component monomer for being used to form shell and 5~25 parts will be amounted to
Being dissolved in 20~70 parts of oil mediums for emulsifier forms oil phase；
Aqueous phase solution A is added drop-wise in oil-phase solution B, reversed-phase emulsion or Reverse Microemulsion System are formed, initiator is added and causes
Polymerisation forms the dissaving polymer complex microsphere lotion of nucleocapsid.
8. preparation method according to claim 7, which is characterized in that the method comprises the following steps：
Prepare aqueous phase solution A：By mass, by 10~50 parts of acrylamides, 0.2~5 part of function monomer and 0.05~2 part poly- third
Alkenyl acrylamide branching agent is dissolved in 20~70 parts of deionized waters, forms homogeneous aqueous phase；The polypropylene-base acrylamide branch
The structural formula of agent is as follows：
Wherein：X is H, CH3, CH2CH3；Y is H, CH3；n≥3；
Prepare oil-phase solution B：By mass, by 5~25 parts of emulsifiers, 1~8 part of styrene, 0.2~5 part of vinylacetate and
0.1~3 part of divinylbenzene is that crosslinking agent is dissolved in 20~70 parts of oil mediums, forms uniform oil phase；
Heating polymerization：Oil phase is heated to 30~50 DEG C, under constant stirring, aqueous phase solution A is added drop-wise in oil-phase solution B extremely
Oil-phase solution B is transparent or translucent or initiator initiation is added into reaction system under anaerobic or anaerobic environment for milky
Polymerisation, reaction time are 2~10h, obtain the dissaving polymer complex microsphere lotion of nucleocapsid.
9. preparation method according to claim 8, which is characterized in that the initiator is redox initiator, choosing
From ammonium persulfate/sodium hydrogensulfite, potassium peroxydisulfate/sodium hydrogensulfite, hydrogen peroxide/tartaric acid, hydrogen peroxide/sodium formaldehyde sulfoxylate, mistake
Ammonium sulfate/ferrous sulfate, hydrogen peroxide/sulfuric acid ferrous iron, benzoyl peroxide //N, N- diethylanilines, benzoyl peroxide/
Ferrous pyrophosphate, potassium peroxydisulfate/silver nitrate, persulfate/mercaptan, isopropyl benzene hydroperoxide/frerrous chloride, potassium peroxydisulfate/chlorine
Change one or more of ferrous iron, the aziridine of hydrogen peroxide/frerrous chloride, isopropyl benzene hydroperoxide/tetra-.
10. preparation method according to claim 8, which is characterized in that the emulsifier is by fatty alcohol polyoxyethylene ether
(3), fatty alcohol polyoxyethylene ether (4), fatty alcohol polyoxyethylene ether (5), fatty alcohol polyoxyethylene ether (9), fatty alcohol polyoxy second
Alkene ether (15), at least two combination in fatty alcohol polyoxyethylene ether (20).
11. according to claim 6 described in the dissaving polymer complex microsphere lotion of nucleocapsid or claim 7-10
The application of the dissaving polymer complex microsphere lotion of nucleocapsid made from preparation method, the application include being used for two, three
The deep profile controlling control water of class oil reservoir；It is either combined with oil displacement agent for chemical combined flooding or the acid solution as acidification de-plugging turns
To agent.
12. a kind of preparation method of the dissaving polymer complex microsphere of nucleocapsid, including：
Prepare aqueous phase solution A：By mass, by 10~50 parts of acrylamides, 0.2~5 part of function monomer and 0.05~2 part poly- third
Alkenyl acrylamide branching agent is dissolved in 20~70 parts of deionized waters, forms homogeneous aqueous phase；
Prepare oil-phase solution B：By mass, by 1~8 part of styrene, 0.2~5 part of vinylacetate and 0.1~3 part of divinyl
Base benzene is that crosslinking agent is dissolved in 20~70 parts of oil mediums, forms uniform oil phase；
Heating polymerization：Oil phase is heated to 30~50 DEG C, under constant stirring, aqueous phase solution A is added drop-wise in oil-phase solution B extremely
Oil-phase solution B is transparent or translucent or initiator initiation is added into reaction system under anaerobic or anaerobic environment for milky
Polymerisation, reaction time are 2~10h, obtain the suspension of the dissaving polymer complex microsphere of nucleocapsid；Described in removal
Oil medium detaches the dissaving polymer complex microsphere of the nucleocapsid.
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