CN108503744A - Acrylic emulsion and its preparation method and application with nucleocapsid - Google Patents
Acrylic emulsion and its preparation method and application with nucleocapsid Download PDFInfo
- Publication number
- CN108503744A CN108503744A CN201810264317.4A CN201810264317A CN108503744A CN 108503744 A CN108503744 A CN 108503744A CN 201810264317 A CN201810264317 A CN 201810264317A CN 108503744 A CN108503744 A CN 108503744A
- Authority
- CN
- China
- Prior art keywords
- emulsion
- monomer
- water
- weight
- surfactant
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- 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
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
-
- C—CHEMISTRY; METALLURGY
- 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
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/02—Well-drilling compositions
- C09K8/03—Specific additives for general use in well-drilling compositions
- C09K8/032—Inorganic additives
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/42—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells
- C09K8/426—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells for plugging
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Polymerisation Methods In General (AREA)
- Cosmetics (AREA)
Abstract
The present invention relates to field of oilfield chemistry, disclose a kind of acrylic emulsion and its preparation method and application with nucleocapsid.The lotion is obtained by the polymerizable raw material comprising following components：Polymerized monomer, nano silicon dioxide, surfactant, polyvinyl alcohol, initiator and water；Wherein, the polymerized monomer forms the shell of emulsion particle, is made of hard monomer and hydrophilic monomer, hard monomer is two or more in styrene, methyl methacrylate and acrylonitrile；Hydrophilic monomer is selected from least one of acrylic acid, hydroxyethyl methacrylate and hydroxy-ethyl acrylate；The nano silicon dioxide forms the stratum nucleare of emulsion particle.The lotion of the present invention is added to the effective closure that can be realized in water-base drilling fluid under high-temperature and high-pressure conditions to rock core hole as sealing agent.
Description
Technical field
The present invention relates to field of oilfield chemistry, and in particular to a kind of acrylic emulsion and its system with nucleocapsid
Preparation Method and application.
Background technology
According to american energy office, China has maximum shale gas reserves in the world, but since complicated geology is former
The exploitation of cause, shale gas is faced with huge challenge.Shale gas is drilled, drilling engineering faces maximum technical problem and exists
In the borehole well instability of shale.Since shale water sensitivity is serious, formation cementation intensity is low, can occur after rock of borehole meets water tight
The hydration swelling of weight, leads to well slough, necking down or caliper expansion.Shale formation is usually very fine and close, porosity is very low.According to many
Document introduction, shale pore-size is within the scope of several nanometers to hundreds of nanometers, it might even be possible to reach 1 micron.
In drilling process, drilling fluid filtrate invaded formation can effectively be prevented to the closure of shale hole, to a certain degree
On can prevent borehole well instability accident.But shale hole is largely nanoscale, conventional drilling fluid sealing agent (such as ultra-fine carbonic acid
Calcium) due to size it is larger (generally micron order), nano level hole cannot be blocked, stabilizing borehole, institute can not be played the role of
Nano level hole is blocked to need nano level granular materials.Currently, there are two main classes for common shale nanometer sealing agent：
The inorganic nano material and polymer material flexible of rigidity.
The inorganic nano material of conventional rigidity, such as nano silicon dioxide, nanometer silica flour material, can be to a certain degree
On shale nanoaperture is blocked, but due to the combination force difference of these materials and pore wall, plugging strength is not high, is easy
It is broken up by high-velocity flow.In addition, these inorganic nano materials can not preferably disperse in drilling fluid, it is easy to reunite.Polymer nano
Rice sealing agent is generally flexible particle, and rubbery state is presented at a certain temperature, can deform to adapt to various sizes of hole,
Also relatively strong with the active force of pore wall rock surface, this becomes the research hotspot of shale nanometer sealing agent.
CN104927051B is disclosed piperazine, diethylenetriamine are dissolved with solvent after, in N2In the presence of divinyl is added
Polymerisation 12-24 hours under the conditions of 40-60 DEG C, then through precipitation, washing and drying, a kind of water-based drilling is made in base sulfone
Liquid nanometer polymer sealing agent.
CN104762071B discloses a kind of preparation method of water-base drilling fluid shale micro-nano granules sealing agent, packet
It includes：By acrylate or methacrylate monomers and vinyl monomer polymerisation 2- in the presence of cosolvent and initiator
4 hours, water-base drilling fluid shale micro-nano granules sealing agent is made.
CN103602323B discloses a kind of drilling fluid nanometer sealing agent, by by nano-particle, modified natural pitch
It is soluble in water with macromolecular fibre, it is reacted at 90 DEG C 1-8 hours, then product is dried and is made.
Although polymer nanocomposite sealing agent disclosed in document above has stronger binding force with the borehole wall or hole inner wall,
It is under high-temperature and high-pressure conditions, particle is in rubbery state, is easy to be broken through by high temperature and pressure liquid stream, can not thoroughly be blocked.
As it can be seen that in order to improve the sealing characteristics of nanometer sealing agent under high temperature and pressure, it is necessary to develop new drilling fluid nanometer
Sealing agent.
Invention content
The present invention mesh be to provide a kind of acrylic emulsion and its preparation method and application with nucleocapsid,
Sealing agent of the lotion as water-base drilling fluid has preferable sealing characteristics at high temperature under high pressure.
According to the first aspect of the invention, the present invention provides a kind of acrylic emulsions with nucleocapsid, should
Lotion is obtained by the polymerizable raw material comprising following components：Polymerized monomer, surfactant, polyvinyl alcohol, is drawn nano silicon dioxide
Send out agent and water；Wherein,
The polymerized monomer forms the shell of emulsion particle, is made of hard monomer and hydrophilic monomer, the hard monomer is selected from
It is two or more in styrene, methyl methacrylate and acrylonitrile；The hydrophilic monomer is selected from acrylic acid, methacrylic acid
At least one of；The mass ratio of the hard monomer and hydrophilic monomer is 1：0.05-0.25；
The nano silicon dioxide forms the stratum nucleare of emulsion particle, described to receive relative to the polymerized monomer of 100 parts by weight
Rice silica is 1-10 parts by weight.
According to a second aspect of the present invention, the present invention provides a kind of method preparing the acrylic emulsion, the party
Method includes：
1) polymerized monomer, nano silicon dioxide, surfactant and part water are mixed, forms pre-emulsion；
2) aqueous solution of the polyvinyl alcohol and part pre-emulsion under inert gas protection, are stirred into 10- at 60-75 DEG C
30 minutes；
3) at 80-90 DEG C, the aqueous solution of the initiator and remaining pre- breast are added dropwise into emulsification system obtained by step 2)
Liquid carries out polymerisation, and after being added dropwise, the reaction was continued 1-5 hours.
According to the third aspect of the invention we, the present invention provides the acrylic emulsions made from the method.
According to the fourth aspect of the invention, the present invention provides acrylic emulsions of the present invention as water base brill
The application of well liquid sealing agent.
The acrylic emulsions of the present invention can be used as nanometer sealing agent and use, the acrylate tree formed after lotion drying
Fat/silicon dioxide composite material has higher thermal stability, traces it to its cause and may is that, the nano silicon dioxide and propylene
Attraction (such as hydrogen bond) existing for acid resin interface causes restriction effect.The contact angle of the composite material and water is small, favorably
In dispersion of the sealing agent in water-base drilling fluid.The lotion of the present invention is added in water-base drilling fluid as sealing agent and can realize
To effective closure of rock core hole under high-temperature and high-pressure conditions.
Description of the drawings
Fig. 1 is the TGA figures of gained powder sample after lotion drying prepared by embodiment 1；
Fig. 2 be indicate bentonite base fluid (curve 2), the bentonite base fluid (curve 1) of lotion containing embodiment 1 seals rock core
The curve graph of stifled effect.
Specific implementation mode
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
According to the first aspect of the invention, the present invention provides a kind of acrylic emulsions with nucleocapsid, should
Lotion is obtained by the polymerizable raw material comprising following components：Polymerized monomer, surfactant, polyvinyl alcohol, is drawn nano silicon dioxide
Send out agent and water.
In the present invention, the polymerized monomer is polymerized to form the shell of emulsion particle.The polymerized monomer is specifically by hard single
Body and hydrophilic monomer composition.
The hard monomer is selected from two or more in styrene (St), methyl methacrylate (MMA) and acrylonitrile (AN).
The hydrophilic monomer is selected from acrylic acid (AA), hydroxyethyl methacrylate (HEMA) and hydroxy-ethyl acrylate (2-
At least one of HEA).
In the polymerized monomer, the mass ratio of the hard monomer and hydrophilic monomer is 1：0.05-0.25, preferably 1：
0.05-0.2。
In the present invention, the nano silicon dioxide forms the stratum nucleare of emulsion particle in polymerization process.The nanometer titanium dioxide
Silicon is specially lipophilic nano silica.The lipophilic nano silica can be commercially available, such as purchased from Nanjing
Xian Feng nano materials scientific ＆ technical corporation, the trade mark are the product of XFI05.
In the present invention, relative to the polymerized monomer of 100 parts by weight, the nano silicon dioxide is 1-10 weight
Part.
In the present invention, the surfactant can refer to prior art progress as emulsifier, type and dosage
Selection.Relative to the polymerized monomer of 100 parts by weight, the surfactant can be 0.5-4 parts by weight, preferably 0.5-
2 parts by weight.For the present invention, in the preferred case, the surfactant is by nonionic surface active agent and ionic table
The mass ratio of face activating agent composition, the nonionic surface active agent and ionic surfactant is 1：0.5-1.
It is highly preferred that the nonionic surface active agent be selected from alkyl phenol polyoxyethylene ether (such as OP-10, OP-6) and
At least one of polyoxyethylene sorbitan monooleate (such as Tween-80)；The ionic surfactant is selected from
At least one of neopelex (SDBS), lauryl sodium sulfate and dodecyl sodium sulfate.
In the present invention, the polyvinyl alcohol (PVA) can play thickening power, improve emulsion intercalation method, Ke Yishi
Common stabilizer in acrylic emulsion.Normally, relative to the polymerized monomer of 100 parts by weight, the polyethylene
Alcohol can be 0.1-2 parts by weight, preferably 0.1-1 parts by weight.
The initiator and its dosage is not particularly limited in the present invention, can be selected from conventional radical initiator, only
Want it that there is water solubility.From the angle for reducing cost, the initiator be preferably selected from potassium peroxydisulfate, ammonium persulfate,
At least one of sodium hydrogensulfite and benzoyl peroxide.Normally, relative to the polymerized monomer of 100 parts by weight, institute
It can be 0.05-0.5 parts by weight to state initiator.
In the present invention, dispersion of the water as lotion, specific dosage can be determined according to the solid content of lotion.It is preferred that feelings
Under condition, the dosage of water so that the solid content of the lotion is 40-55 weight %.
In the present invention, the equal grain sizes of the Z of the acrylic emulsion can be 40-100nm, preferably 70-100nm.
The polydispersity coefficient (PDI) of the acrylic emulsion can be 0.1-0.6, preferably 0.2-0.4.
According to the second aspect of the invention, the present invention provides a kind of methods preparing the acrylic emulsion, should
Method belongs to semi-continuous emulsion polymerization, specifically includes：
1) polymerized monomer, nano silicon dioxide, surfactant and part water are mixed, forms pre-emulsion；
2) aqueous solution of the polyvinyl alcohol and part pre-emulsion under inert gas protection, are stirred into 10- at 60-75 DEG C
30 minutes；
3) at 80-90 DEG C, the aqueous solution of the initiator and remaining pre- breast are added dropwise into emulsification system obtained by step 2)
Liquid carries out polymerisation, and after being added dropwise, the reaction was continued 1-5 hours, preferably continues to reaction 2-4 hours.
In step 1), in order to make the nano silicon dioxide can be uniformly dispersed in pre-emulsion, under preferable case, the step
Including：
1-1：By the nano silicon dioxide ultrasonic disperse 10-30 minutes in the polymerized monomer, mixed liquor is obtained；
1-2：The surfactant is dissolved in the water of part, simultaneously emulsification pretreatment 2- is then added in the mixed liquor
10 minutes.
In step 2), the inert gas can be nitrogen, and the speed of the stirring can be 100-300rpm.
Preferably, the dosage of the part pre-emulsion is the 20-30 volumes % of pre-emulsion total amount.
The concentration of the aqueous solution of the polyvinyl alcohol can be 0.5-3 weight %.
According to the method for the present invention, the high-temperature stirring of the emulsification pretreatment of step 1) and step 2) can further promote oleophylic
Silicon dioxide granule makes hydrophilic polymerized monomer relative to moving outside micella to moving inside micella, more conducively emulsion particle core
The formation of shell structure.
In step 3), it is preferable to use two dropping funels to be added dropwise respectively for the aqueous solution of the initiator and remaining pre-emulsion.
The speed of the dropwise addition, which is can be controlled in, makes dropwise addition terminate in 1-3 hours.
The concentration of the aqueous solution of the initiator can be 0.1-2 weight %.
In order to further ensure gained emulsion intercalation method, it is preferable that the method further includes：4) with lye by step 3)
The pH of gained lotion is adjusted to 6.5-8.The step can carry out after cooling down the lotion.The present invention is to the lye without spy
It does not limit, as long as foregoing purpose can be realized, the lye is, for example, ammonium hydroxide.
According to the third aspect of the invention we, the present invention provides acrylic emulsions made from the method.With use
Other emulsion polymerisation process (such as discontinuous emulsion polymerization) are compared, and second aspect of the present invention is prepared using semi-continuous emulsion polymerization
Acrylic emulsion have higher stability, the particle diameter distribution of lotion is evenly.Prepared microemulsion transmission electricity
Sem observation, it was demonstrated that synthesized the emulsion particle with nucleocapsid.According to one preferred embodiment, prepared by method of the invention
The equal grain sizes of Z of acrylic emulsion be 70-100nm, the PDI of lotion is 0.2-0.4.
According to the fourth aspect of the invention, the present invention provides the acrylic emulsions of the present invention as water-base drilling fluid
The application of sealing agent.
The acrylic emulsion of the present invention through the dry acrylate/silicon dioxide composite material formed have compared with
High thermal stability is suitable for high temperature bottom, strong as the acrylate in shell portion and the adhesion strength of the borehole wall, while as core
The silicon dioxide granule in portion can provide a supporting role, and further improve plugging strength.Normally, with the weight of water-base drilling fluid
On the basis of, the additive amount of the acrylic emulsion is 0.5-2 weight %.
The present invention will be described in detail by way of examples below.
In following embodiment and comparative example, nano silicon dioxide is purchased from Nanjing Xian Feng nano materials scientific ＆ technical corporation, and the trade mark is
XFI05。
Embodiment 1
The present embodiment is used to illustrate the acrylic emulsion and preparation method thereof of the present invention.
S1：In 250mL beakers, 32g styrene, 16g methacrylates, 3g acrylic acid, 2g methacrylic acids is added
Hydroxyl ethyl ester and 2.5g nano silicon dioxides, then ultrasonic oscillation 20min, obtains mixed liquor；
S2：After 0.5g OP-10 and 0.25g SDBS are dissolved in 20mL distilled water, it is added in above-mentioned mixed liquor and shears
5min is emulsified, pre-emulsion is formed；
S3：In the four round flask of 250mL, the aqueous solution and part pre-emulsion of 2 weight %PVA of 15mL concentration is added
(the 25 volume % for accounting for pre-emulsion total amount)；
S4：Round-bottomed flask is immersed in 71 DEG C of water-bath, 10min is stirred with 300r/min under nitrogen protection；
S5：By above-mentioned warming-in-water to 80 DEG C, by the ammonium persulfate aqueous solution of 1 weight % of remaining pre-emulsion and 15mL concentration
Be added drop-wise to respectively in round-bottomed flask using two dropping funels and carry out polymerisation, rate of addition control dripped off in 2h, it is subsequent
Continuous reaction 2h, is finally cooled to 40 DEG C, and the ammonium hydroxide that 25 weight % of concentration is added adjusts pH to 7, obtains acrylic emulsion.
Embodiment 2
The present embodiment is used to illustrate the acrylic emulsion and preparation method thereof of the present invention.
S1：In 250mL beakers, 25g styrene, 24g acrylonitrile, 3g hydroxyethyl methacrylates and 1g nanometers two is added
Silica, then ultrasonic oscillation 20min, obtains mixed liquor；
S2：After 0.2g OP-10 and 0.1g SDBS are dissolved in 30mL distilled water, it is added in above-mentioned mixed liquor and shears breast
Change 5min, forms pre-emulsion；
S3：In the four round flask of 250mL, the aqueous solution and part pre-emulsion of 2 weight %PVA of 12mL concentration is added
(the 20 volume % for accounting for pre-emulsion total amount)；
S4：Round-bottomed flask is immersed in 75 DEG C of water-bath, 15min is stirred with 200r/min under nitrogen protection；
S5：By above-mentioned warming-in-water to 85 DEG C, by the ammonium persulfate aqueous solution of 1 weight % of remaining pre-emulsion and 10mL concentration
It is added drop-wise to respectively in round-bottomed flask using two dropping funels and carries out polymerisation, rate of addition control is dripped off in 2.5h, then
The reaction was continued 2h is finally cooled to 40 DEG C, and the ammonium hydroxide that 25 weight % of concentration is added adjusts pH to 7, obtains acrylic emulsion.
Embodiment 3
The present embodiment is used to illustrate the acrylic emulsion and preparation method thereof of the present invention.
S1：In 250mL beakers, 32g methacrylates, 14g acrylonitrile, 8g hydroxy-ethyl acrylates and 5g nanometers are added
Silica, then ultrasonic oscillation 20min, obtains mixed liquor；
S2：After 0.3g OP-10 and 0.15g SDBS are dissolved in 30mL distilled water, it is added in above-mentioned mixed liquor and shears
5min is emulsified, pre-emulsion is formed；
S3：In the four round flask of 250mL, the aqueous solution and part pre-emulsion of 2 weight %PVA of 15mL concentration is added
(the 20 volume % for accounting for pre-emulsion total amount)；
S4：Round-bottomed flask is immersed in 70 DEG C of water-bath, 15min is stirred with 300r/min under nitrogen protection；
S5：By above-mentioned warming-in-water to 90 DEG C, by the ammonium persulfate aqueous solution of 1 weight % of remaining pre-emulsion and 10mL concentration
It is added drop-wise to respectively in round-bottomed flask using two dropping funels and carries out polymerisation, rate of addition control is dripped off in 1.5h, then
The reaction was continued 2h is finally cooled to 40 DEG C, and the ammonium hydroxide that 25 weight % of concentration is added adjusts pH to 7, obtains acrylic emulsion.
Comparative example 1
Acrylic emulsion is prepared according to the method for embodiment 1, the difference is that in step S1, is added without nanometer two
Silica directly stirs evenly polymerized monomer, to which acrylic emulsion be made.
Comparative example 2
Acrylic emulsion is prepared according to the method for embodiment 1, the difference is that in step S1, is added without acrylic acid
And hydroxyethyl methacrylate, to which acrylic emulsion be made.
Comparative example 3
Acrylic emulsion is prepared according to the method for embodiment 1, the difference is that in step S1, by the use of styrene
Amount is reduced to 5g, and the dosage of hydroxyethyl methacrylate is increased to 12g, to which acrylic emulsion be made.
The acrylic emulsion prepared below to embodiment and comparative example carries out characterization and sealing characteristics is tested.Wherein,
Thermogravimetric analysis (TGA) and contact angle determination are the powder samples obtained after lotion drying, specifically, by lotion at 102 DEG C
Drying crushes, obtains powder sample；Particles size and distribution and sealing characteristics measurement use lotion.
1, thermogravimetric analysis
Thermogravimetric analysis is carried out to powder sample using STA 409PC types synchronous solving (Germany is resistance to speed).Make in test
Use argon gas as protection gas, temperature range is 25-400 DEG C, and heating rate is 5 DEG C/min.Sample is calculated according to gained TGA curves
In 250 DEG C, 300 DEG C of rate of weight loss (disregarding 100 DEG C of weight loss caused by solvent volatilization), the results are shown in Table 1.Separately
Outside, the TGA curves of 1 powder sample of embodiment are as shown in Figure 1.
2, contact angle determination
10min is suppressed to powder sample under the conditions of 10MPa using forcing press, the thin slice that can measure contact angle is made, it is thin
Piece surface is polished smooth using the sand paper of 400 mesh.The water of sheet surface is measured using JC2000C1 type contact angle instruments
Connect feeler.In test process, 0.6 to 1 microlitre of deionized water is slowly dropped in into sheet surface using micro syringe, waits for water droplet
It after stabilization, is taken pictures using high-resolution camera, contact angle is finally calculated with liquid consistency profiles, the results are shown in Table 1.
3, particles size and distribution is tested
Samples of latex is diluted 200 times using distilled water, then ultrasonic wave disperses 2h.Utilize laser particle analyzer
The equal particles size and distributions of Z of Zetasizer Nano ZS90 (Malvern) determination sample, the results are shown in Table 1.
4, sealing characteristics is tested
Use shale stability comprehensive simulation evaluation system (model JHWD-1, the limited public affairs of Jing Zhou modern petroleum development in science and technology
Department) lotion is evaluated as nanometer sealing agent to the plugging effect of shale core.
It is handled by rock core vacuumizing before test and with saturated brine (20wt%NaCl).Rock core is placed on core holding unit
In, add the constant confining pressure of 15MPa.Rock core tail end is full of 20wt%NaCl solution, and pressure is set as 0MPa.Then using containing
The bentonite base of 1wt% nanometers of sealing agents starches (4 weight % bentonites, remaining as tap water) displacement rock core, displacement pressure setting
For constant 11MPa.The variation of software records rock core tail end pressure is carried with instrument, and records rock core tail end pressure after balance
Value, the results are shown in Table 1.In addition, Fig. 2 shows bentonite base slurries and the pressure that the bentonite base slurry for having 1 lotion of embodiment is added
Power change curve.
Table 1
As shown in Table 1, rate of weight loss of the powder sample at 250 DEG C, 300 DEG C after lotion of the present invention is dried is very
Small, it is very slow that this illustrates that nanometer sealing agent decomposes under 300 DEG C, has higher thermal stability；Solid powder thin slice and water
Contact angle is small, illustrates by the way that hydrophilic monomer is added so that the hydrophily of gained acrylic resin is improved, this is conducive to seal
Dispersion of the blocking agent in water-base drilling fluid；In addition, in conjunction with Fig. 2 it is found that the nanometer sealing agent rock core tail end of the present invention balances pressure
Value is significantly smaller than bentonite base slurry, this proves that a small amount of water has passed through rock core.In summary, lotion of the invention is at high temperature under high pressure
With higher sealing characteristics.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In the skill of the present invention
In art conception range, technical scheme of the present invention can be carried out a variety of simple variants, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, belongs to
Protection scope of the present invention.
Claims (10)
1. a kind of acrylic emulsion with nucleocapsid, which is characterized in that the lotion is by the raw material comprising following components
Polymerization obtains：Polymerized monomer, nano silicon dioxide, surfactant, polyvinyl alcohol, initiator and water；Wherein,
The polymerized monomer forms the shell of emulsion particle, is made of hard monomer and hydrophilic monomer, and the hard monomer is selected from benzene second
It is two or more in alkene, methyl methacrylate and acrylonitrile；The hydrophilic monomer is selected from acrylic acid, hydroxyethyl methacrylate second
At least one of ester and hydroxy-ethyl acrylate；The mass ratio of the hard monomer and hydrophilic monomer is 1：0.05-0.25；
The nano silicon dioxide forms the stratum nucleare of emulsion particle, relative to the polymerized monomer of 100 parts by weight, the nanometer two
Silica is 1-10 parts by weight.
2. acrylic emulsion according to claim 1, wherein relative to the polymerized monomer of 100 parts by weight, institute
It is 0.5-4 parts by weight to state surfactant, and the initiator is 0.05-0.5 parts by weight, and the polyvinyl alcohol is 0.1-2 weight
Part, the dosage of water so that the solid content of lotion is 40-55 weight %.
3. acrylic emulsion according to claim 2, wherein the surfactant is by non-ionic surfactant
The mass ratio of agent and ionic surfactant composition, the nonionic surface active agent and ionic surfactant is 1：
0.5-1；
Preferably, the nonionic surface active agent is selected from alkyl phenol polyoxyethylene ether and polyethenoxy sorbitan list oil
At least one of acid esters；The ionic surfactant is selected from neopelex, lauryl sodium sulfate and ten
At least one of dialkyl sulfonates.
4. acrylic emulsion according to claim 1, wherein the equal grain sizes of Z of the acrylic emulsion are 40-
100nm。
5. a kind of method preparing any one of claim 1-4 acrylic emulsions, this method include：
1) polymerized monomer, nano silicon dioxide, surfactant and part water are mixed, forms pre-emulsion；
2) under inert gas protection, the aqueous solution of the polyvinyl alcohol and part pre-emulsion are stirred to 10-30 points at 60-75 DEG C
Clock；
3) at 80-90 DEG C, be added dropwise into emulsification system obtained by step 2) initiator aqueous solution and remaining pre-emulsion into
Row polymerisation, after being added dropwise, the reaction was continued 1-5 hours.
6. according to the method described in claim 5, wherein, step 1) includes：
1-1：By the nano silicon dioxide ultrasonic disperse 10-30 minutes in the polymerized monomer, mixed liquor is obtained；
1-2：The surfactant is dissolved in the water of part, is then added in the mixed liquor and emulsification pretreatment 2-10 divides
Clock.
7. according to the method described in claim 5, wherein, in step 2), the dosage of the part pre-emulsion is pre-emulsion total amount
20-30 volumes %.
8. according to the method described in any one of claim 5-7, wherein this method further includes：4) with lye by step 3)
The pH of gained lotion is adjusted to 6.5-8.
9. the acrylic emulsion made from the method described in any one of claim 5-8.
10. acrylic emulsion the answering as water-base drilling fluid sealing agent described in any one of claim 1-4 and 9
With.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810264317.4A CN108503744B (en) | 2018-03-28 | 2018-03-28 | Acrylic emulsion and its preparation method and application with core-shell structure |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810264317.4A CN108503744B (en) | 2018-03-28 | 2018-03-28 | Acrylic emulsion and its preparation method and application with core-shell structure |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108503744A true CN108503744A (en) | 2018-09-07 |
| CN108503744B CN108503744B (en) | 2019-09-06 |
Family
ID=63378964
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810264317.4A Active CN108503744B (en) | 2018-03-28 | 2018-03-28 | Acrylic emulsion and its preparation method and application with core-shell structure |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108503744B (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109762542A (en) * | 2018-12-28 | 2019-05-17 | 青岛科凯达橡塑有限公司 | A kind of oil-soluble lotion sealing agent and preparation method thereof |
| CN111393557A (en) * | 2020-03-27 | 2020-07-10 | 中国石油天然气集团有限公司 | Organosilicon film-forming agent for high-temperature oil-based drilling fluid and preparation method and application thereof |
| CN111484833A (en) * | 2020-03-27 | 2020-08-04 | 中国石油天然气集团有限公司 | Low-friction film-forming plugging agent for high-temperature oil-based drilling fluid and preparation method and application thereof |
| CN112780219A (en) * | 2021-02-24 | 2021-05-11 | 西南石油大学 | Targeted release water shutoff agent |
| CN112940705A (en) * | 2021-03-22 | 2021-06-11 | 郑州市新郑梅久实业有限公司 | Nano-material composite clean fracturing fluid and preparation method thereof |
| CN113355073A (en) * | 2021-06-22 | 2021-09-07 | 西南石油大学 | Synthesis of self-adaptive external flexible and internal rigid type nano plugging agent and water-based drilling fluid |
| CN113861957A (en) * | 2021-11-04 | 2021-12-31 | 中国石油大学(北京) | Double-base nano viscosity reducer and application thereof in heavy oil recovery and recovery method |
| CN114426652A (en) * | 2020-10-29 | 2022-05-03 | 中国石油化工股份有限公司 | High-temperature-resistant nano-micron plugging agent for drilling fluid and preparation method thereof |
| CN114426815A (en) * | 2022-01-18 | 2022-05-03 | 中国石油化工股份有限公司 | Oil-based drilling fluid suitable for strong water-sensitive and easily-collapsed stratum and preparation method and application thereof |
| CN114507512A (en) * | 2021-12-31 | 2022-05-17 | 中国石油大学(华东) | Self-crosslinking soap-free nano latex plugging agent, preparation method thereof, water-based drilling fluid and application |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101531729A (en) * | 2009-04-10 | 2009-09-16 | 中国石油大学(华东) | Preparation method for monodisperse composite nanoparticle |
| CN102485830A (en) * | 2010-12-02 | 2012-06-06 | 北京化工大学 | Profile control oil-displacement agent for core-shell type inorganic/organic polymer composite microballoon |
| CN103013478A (en) * | 2012-11-29 | 2013-04-03 | 蒋官澄 | Plugging material used for oil base drilling fluid, and preparation method thereof |
| WO2014165777A1 (en) * | 2013-04-04 | 2014-10-09 | Rohm And Haas Company | Alkaline-swellable emulsion polymers |
| CN104448087A (en) * | 2013-09-18 | 2015-03-25 | 中国石油天然气集团公司 | Core-shell type polymer microspheres, preparation and applications thereof |
| CN104558375A (en) * | 2014-12-04 | 2015-04-29 | 中国石油大学(华东) | Core-shell structure oil-absorptive resin microsphere suitable for oil well cement as well as preparation method and application of core-shell structure oil-absorptive resin microsphere |
| CN105936819A (en) * | 2016-04-22 | 2016-09-14 | 中国石油集团川庆钻探工程有限公司 | Plugging agent for oil-based drilling fluid and preparation method thereof |
-
2018
- 2018-03-28 CN CN201810264317.4A patent/CN108503744B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101531729A (en) * | 2009-04-10 | 2009-09-16 | 中国石油大学(华东) | Preparation method for monodisperse composite nanoparticle |
| CN102485830A (en) * | 2010-12-02 | 2012-06-06 | 北京化工大学 | Profile control oil-displacement agent for core-shell type inorganic/organic polymer composite microballoon |
| CN103013478A (en) * | 2012-11-29 | 2013-04-03 | 蒋官澄 | Plugging material used for oil base drilling fluid, and preparation method thereof |
| WO2014165777A1 (en) * | 2013-04-04 | 2014-10-09 | Rohm And Haas Company | Alkaline-swellable emulsion polymers |
| CN104448087A (en) * | 2013-09-18 | 2015-03-25 | 中国石油天然气集团公司 | Core-shell type polymer microspheres, preparation and applications thereof |
| CN104558375A (en) * | 2014-12-04 | 2015-04-29 | 中国石油大学(华东) | Core-shell structure oil-absorptive resin microsphere suitable for oil well cement as well as preparation method and application of core-shell structure oil-absorptive resin microsphere |
| CN105936819A (en) * | 2016-04-22 | 2016-09-14 | 中国石油集团川庆钻探工程有限公司 | Plugging agent for oil-based drilling fluid and preparation method thereof |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109762542A (en) * | 2018-12-28 | 2019-05-17 | 青岛科凯达橡塑有限公司 | A kind of oil-soluble lotion sealing agent and preparation method thereof |
| CN111393557A (en) * | 2020-03-27 | 2020-07-10 | 中国石油天然气集团有限公司 | Organosilicon film-forming agent for high-temperature oil-based drilling fluid and preparation method and application thereof |
| CN111484833A (en) * | 2020-03-27 | 2020-08-04 | 中国石油天然气集团有限公司 | Low-friction film-forming plugging agent for high-temperature oil-based drilling fluid and preparation method and application thereof |
| CN111484833B (en) * | 2020-03-27 | 2022-08-12 | 中国石油天然气集团有限公司 | Low-friction film-forming plugging agent for high-temperature oil-based drilling fluid and preparation method and application thereof |
| CN111393557B (en) * | 2020-03-27 | 2022-03-18 | 中国石油天然气集团有限公司 | Organosilicon film-forming agent for high-temperature oil-based drilling fluid and preparation method and application thereof |
| CN114426652A (en) * | 2020-10-29 | 2022-05-03 | 中国石油化工股份有限公司 | High-temperature-resistant nano-micron plugging agent for drilling fluid and preparation method thereof |
| CN114426652B (en) * | 2020-10-29 | 2024-05-17 | 中国石油化工股份有限公司 | High-temperature-resistant nano-micron plugging agent for drilling fluid and preparation method thereof |
| CN112780219A (en) * | 2021-02-24 | 2021-05-11 | 西南石油大学 | Targeted release water shutoff agent |
| CN112940705A (en) * | 2021-03-22 | 2021-06-11 | 郑州市新郑梅久实业有限公司 | Nano-material composite clean fracturing fluid and preparation method thereof |
| CN113355073A (en) * | 2021-06-22 | 2021-09-07 | 西南石油大学 | Synthesis of self-adaptive external flexible and internal rigid type nano plugging agent and water-based drilling fluid |
| CN113861957A (en) * | 2021-11-04 | 2021-12-31 | 中国石油大学(北京) | Double-base nano viscosity reducer and application thereof in heavy oil recovery and recovery method |
| CN113861957B (en) * | 2021-11-04 | 2022-09-30 | 中国石油大学(北京) | Double-base nano viscosity reducer and application thereof in heavy oil recovery and recovery method |
| CN114507512A (en) * | 2021-12-31 | 2022-05-17 | 中国石油大学(华东) | Self-crosslinking soap-free nano latex plugging agent, preparation method thereof, water-based drilling fluid and application |
| CN114507512B (en) * | 2021-12-31 | 2023-04-28 | 中国石油大学(华东) | Self-crosslinking soap-free nano latex plugging agent, preparation method thereof, water-based drilling fluid and application |
| CN114426815A (en) * | 2022-01-18 | 2022-05-03 | 中国石油化工股份有限公司 | Oil-based drilling fluid suitable for strong water-sensitive and easily-collapsed stratum and preparation method and application thereof |
| CN114426815B (en) * | 2022-01-18 | 2023-01-17 | 中国石油化工股份有限公司 | Oil-based drilling fluid suitable for strong water-sensitive and easily-collapsed stratum and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108503744B (en) | 2019-09-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108503744B (en) | Acrylic emulsion and its preparation method and application with core-shell structure | |
| CN104762071B (en) | A kind of preparation method of water-base drilling fluid shale micro-nano granules sealing agent | |
| CN105884954B (en) | A kind of temperature resistance salt tolerant latex sealing agent and preparation method thereof | |
| US4694035A (en) | Process for preparing large-sized polymer particles | |
| JP2007291359A (en) | Hollow polymer particle, colored hollow polymer particle and method for producing the same | |
| CN105085778A (en) | Coating material composition aqueous latex for slowly releasing function components, preparation method and applications thereof | |
| CN104558393A (en) | N-tetradecanol phase change microcapsule and preparation method thereof | |
| Chern et al. | Particle nucleation loci in styrene miniemulsion polymerization using alkyl methacrylates as the reactive cosurfactant | |
| CN111171221A (en) | Method for preparing thermal expansion microspheres by using SPG emulsion membrane technology | |
| CN111763505A (en) | Oil reservoir profile control agent and preparation method thereof | |
| JP2012087283A (en) | Polymerization method for acrylic latex without emulisifier | |
| JP2005520937A (en) | Styrene / acrylate copolymer composition suitable for surface sizing | |
| CA2395914C (en) | Latex with high non-volatile matter content, low viscosity and having a bimodal distribution | |
| CA2153026A1 (en) | Methods of preparing hollow polymeric particles | |
| JPS61215603A (en) | Production of polymer particle | |
| CN115260373B (en) | High Wen Gaogai-resistant flexible plugging agent and preparation method and application thereof | |
| CN103585936B (en) | A kind of preparation method of plastic hollow bead and its product prepared and application | |
| CN111303346A (en) | Nano-scale film forming agent for oil-based drilling fluid and preparation method and application thereof | |
| CN111087553B (en) | Multilayer core-shell structure polymer microsphere, profile control agent, preparation method and application thereof | |
| CN103709540A (en) | Organic hollow microspheres, preparation method thereof, and drilling fluid | |
| CN102358766B (en) | Synthesis method of clay modified room-temperature self-crosslinking core-shell polyacrylate emulsion | |
| JP2002121230A (en) | Temperature-sensitive polymer material having low viscosity at high temperature and high viscosity at low temperature | |
| CN110330955A (en) | A kind of nano rubber latex microcrack sealing agent and preparation method thereof | |
| CN114426652B (en) | High-temperature-resistant nano-micron plugging agent for drilling fluid and preparation method thereof | |
| CN104592440A (en) | Preparation method for polymer nanoparticle with two-sided anisotropic structure |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20200212 Address after: 266580 Qingdao Changjiang Road, Huangdao District, Shandong, No. 66 Co-patentee after: China Petroleum Group Engineering and Technology Research Institute Co., Ltd. Patentee after: China University of Petroleum (East China) Address before: 266580 Qingdao Changjiang Road, Huangdao District, Shandong, No. 66 Patentee before: China University of Petroleum (East China) |
|
| EE01 | Entry into force of recordation of patent licensing contract | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20180907 Assignee: Shandong Rongjia Petrochemical Co., Ltd Assignor: China University of Petroleum (East China) Contract record no.: X2020980006211 Denomination of invention: Acrylate emulsion with core-shell structure and its preparation method and Application Granted publication date: 20190906 License type: Common License Record date: 20200918 |