CN106565892B - Reinforcing oil well styrene-acrylic latex and its preparation and application - Google Patents
Reinforcing oil well styrene-acrylic latex and its preparation and application Download PDFInfo
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Abstract
The present invention relates to a kind of oil well cementing styrene-acrylic latexes and preparation method thereof.The styrene-acrylic latex is made under the action of emulsifier, initiator and optional chain-transferring agent and/or crosslinking agent by emulsion polymerization by styrene, acrylic ester compound, other function water-soluble monomer and the optional water-soluble monomer with sulfonic acid functional group.The invention further relates to application of the styrene-acrylic latex in oil well cementing.Styrene-acrylic latex is added in the mortar architecture of well cementation, the filter loss of cement slurry can be effectively reduced, API controls dehydration in 50mL or less at high temperature, increase the compactness of oil-well cement, reduce Behavior of Hardened Cement Paste permeability, it effectively prevents the oil gas water breakthrough of well cementation interval isolation from occurring, while improving the mechanical property of Behavior of Hardened Cement Paste, improve oil gas well cementing operation quality.
Description
Technical field
The invention belongs to reinforcing oil well technical fields, and in particular to a kind of reinforcing oil well styrene-acrylic latex and its preparation and answer
With.
Background technique
As the investigation and prospecting of China's petroleum resources is constantly extended to deep layer complex geological structure band area, deep-well, ultra-deep
Well well cementation is faced with high temperature and pressure anti-gas channeling problem.And the latex-cement slurry that latex additive is added has resistant to high temperatures, anti-oil gas
The characteristics of water breakthrough, drop dehydration protection oil-gas Layer, the cementing quality of deep-well and ultradeep well can be effectively improved, is domestic and international at present
The excellent mortar architecture of generally acknowledged anti-channeling performance.
Latex-cement slurry currently used for reinforcing oil well operation is largely styrene-butadiene latex mortar architecture, and applies phenylpropyl alcohol
Latex-cement slurry yet there are no report.That there are synthesis conditions is complicated, not easy to control, quick for existing styrene-butadiene latex mortar architecture
Perceptual strong, scene adjusts the problems such as extremely difficult.
Therefore, presently, there are the problem of be to be badly in need of researching and developing a kind of synthesis condition simple, easily controllable, scene adjustment makes
With convenient reinforcing oil well latex cement slurry system.
Summary of the invention
The technical problem to be solved by the present invention is to solve the above shortcomings of the prior art and to provide a kind of reinforcing oil well benzene
Third latex and preparation method thereof.The styrene-acrylic latex is compounded into related additive system, forms a kind of latex of suitable oil gas water breakthrough
The cementing strength of the first and second cement planes of well cementation can be improved in mortar architecture, reduces the permeability of Behavior of Hardened Cement Paste, reduces oil gas
The generation of water breakthrough phenomenon；And the malleable of Behavior of Hardened Cement Paste can be increased, reduce Behavior of Hardened Cement Paste in the well cementation subsequent job such as perforation, pressure break
Level of breakage improves cementing quality.
For this purpose, first aspect present invention provides a kind of reinforcing oil well styrene-acrylic latex, by styrene, esters of acrylic acid
Compound, other function water-soluble monomer and the optional water-soluble monomer with sulfonic acid functional group are in emulsifier, initiation
It is made under the action of agent and optional chain-transferring agent and/or crosslinking agent by emulsion polymerization.
According to the present invention, the styrene-acrylic latex is made by the following components based on quality by emulsion polymerization:
In some embodiments of the invention, the other function water-soluble monomer include acrylic acid, methacrylic acid,
Acrylamide and N, at least one of N- dimethylacrylamide.
In other embodiments of the invention, the water-soluble monomer with sulfonic acid functional group includes 2- acryloyl
In amine -2- methyl propane sulfonic acid (AMPS), sodium allylsulfonate (SAS), methylpropene sodium sulfonate (SMS) and vinylbenzenesulfonic acid sodium
It is at least one.
According to the present invention, the acrylic ester compound includes acrylate and/or alkyl methacrylate；It is described
Acrylate includes one of methyl acrylate, ethyl acrylate and butyl acrylate or a variety of；The methacrylic acid alkane
Base ester includes methyl methacrylate and/or butyl methacrylate.
According to the present invention, the emulsifier is anion and nonionic compound emulsifier；The anion emulsifier includes
Lauryl sodium sulfate, neopelex, dodecyl sodium sulfate, tetradecylphenol polyethers sulfo group succinic acid monoester sodium
At least one of salt and dodecylphenol ether ammonium sulfate salt；The nonionic emulsifier is alkylphenol-polyethenoxy (10) ether.
In some embodiments of the invention, the crosslinking agent includes divinylbenzene, glycidyl acrylate, methyl
Glycidyl acrylate, triethylene glycol dimethacrylate, hydroxymethyl acrylamide, Methacrylamide, 1,6- oneself two
One of alcohol acrylate and neopentyl glycol acrylate are a variety of.
In other embodiments of the invention, the chain-transferring agent includes C2-C12Alkyl hydrosulfide, mercaptopropionic acid, mercapto
One of guanidine-acetic acid, mercaptoethanol and hydrosulphonyl silane are a variety of.
In other embodiments of the invention, the initiator include azo-initiator, peroxide type initiators and
At least one of redox initiator.
Second aspect of the present invention provides a kind of preparation method of styrene-acrylic latex as described in the first aspect of the invention, packet
It includes:
Step A mixes at least one of component a, b, d, g and h and optional component c, e and f with water, through emulsifying
It handles and monomer pre-emulsion is made；
Initiator is mixed with water, prepares initiator solution by step B；
Step C carries out the initiator solution of the monomer pre-emulsion of 5%-10% (quality) and 5%-10% (quality) anti-
It answers, lotion seed is made；
Step D, remaining monomer pre-emulsion is added dropwise into lotion seed and remaining initiator solution is reacted, and is made
Reaction mixture；
Step E, redox initiator is added dropwise into reaction mixture, after being added dropwise, adds pH adjusting agent, i.e.,
Obtain styrene-acrylic latex.
In some embodiments of the invention, in step C, the temperature of the reaction is 80-90 DEG C.
In other embodiments of the invention, in step D, the time of the dropwise addition is 2-6h.It is preferred that the dropwise addition
Time be 2-4h.
According to the present invention, in step E, the average grain diameter of emulsion particle is 180nm in the styrene-acrylic latex；The dropwise addition
Time is 2h.
Third aspect present invention provides a kind of cement paste for well cementation system, contains following components by weight:
Wherein, the styrene-acrylic latex is for styrene-acrylic latex as described in the first aspect of the invention or such as second aspect of the present invention institute
State the styrene-acrylic latex of method preparation.
Fourth aspect present invention provides a kind of styrene-acrylic latex as described in the first aspect of the invention, second party such as of the present invention
The styrene-acrylic latex of face the method preparation or cement paste for well cementation system as described in the third aspect of the present invention are in reinforcing oil well
Application.
Specific embodiment
To keep the present invention easier to understand, below in conjunction with embodiment, the present invention will be described in detail, these embodiments are only
Serve illustrative, it is not limited to application range of the invention.
As previously mentioned, existing styrene-butadiene latex mortar architecture that there are synthesis conditions is complicated, not easy to control, sensibility is strong,
Scene adjusts the problems such as extremely difficult, and yet there are no report using styrene-acrylic latex cement slurry.The present invention is by introducing
The mode of other function water-soluble monomer and the water-soluble monomer with sulfonic acid functional group carries out emulsion polymerization and prepares a kind of oil
Styrene-acrylic latex is used in field well cementation.The latex is used to be made cement paste for well cementation system, synthesis condition is simple, easily controllable, and existing
Field adjustment is easy to use.
Therefore, first aspect present invention is related to a kind of reinforcing oil well styrene-acrylic latex, by styrene, esters of acrylic acid
Object, other function water-soluble monomer and the optional water-soluble monomer with sulfonic acid functional group are closed in emulsifier, initiator
And it is made under the action of optional chain-transferring agent and/or crosslinking agent by emulsion polymerization.
According to the present invention, the styrene-acrylic latex is made by the following components based on quality by emulsion polymerization:
In some embodiments of the invention, the other function water-soluble monomer include acrylic acid, methacrylic acid,
Acrylamide and N, at least one of N- dimethylacrylamide.
It is optional in the present invention that the water-soluble monomer for having sulfonic acid functional group is added.In other embodiments of the invention
In, the water-soluble monomer with sulfonic acid functional group includes 2- acrylamide-2-methyl propane sulfonic (AMPS), sodium allylsulfonate
(SAS), at least one of methylpropene sodium sulfonate (SMS) and vinylbenzenesulfonic acid sodium.
Due to joined in copolymerization containing sulfonic monomer or other function water-soluble monomer, glue in the present invention
Cream has good compatibility with oil-well cement.
According to the present invention, the acrylic ester compound includes acrylate and/or alkyl methacrylate；It is described
Acrylate includes one of methyl acrylate, ethyl acrylate and butyl acrylate or a variety of；The methacrylic acid alkane
Base ester includes methyl methacrylate and/or butyl methacrylate.
The glass transition temperature of polymer, synthesized styrene-acrylic latex can be effectively reduced in esters soft monomer in the present invention
Have the function of efficiently to drop dehydration.
All comonomers are liquid monomer in the present invention, and manufacturing parameter is easy to control, and the styrene-acrylic latex of synthesis contains admittedly
Amount is high compared to other well cementation styrene-butadiene latexes, can more reach the performance requirement of latex-cement slurry under conditions of dosage is same in this way.
According to the present invention, the emulsifier is anion and nonionic compound emulsifier.The anion emulsifier includes
Lauryl sodium sulfate, neopelex, dodecyl sodium sulfate, tetradecylphenol polyethers sulfo group succinic acid monoester sodium
At least one of salt and dodecylphenol ether ammonium sulfate salt；The nonionic emulsifier is alkylphenol-polyethenoxy (10) ether.
Optional addition crosslinking agent in the present invention.In some embodiments of the invention, the crosslinking agent includes diethyl
Alkenyl benzene, glycidyl acrylate, glycidyl methacrylate, triethylene glycol dimethacrylate, methylol third
One of acrylamide, Methacrylamide, 1,6-HD acrylate and neopentyl glycol acrylate are a variety of.
Term " optionally " of the present invention refers to and can be added, and can also be added without.
Optional addition chain-transferring agent in the present invention.The chain-transferring agent includes C2-C12Alkyl hydrosulfide, sulfydryl third
One of acid, thioacetic acid, mercaptoethanol and hydrosulphonyl silane are a variety of.
According to the present invention, the initiator includes azo-initiator, peroxide type initiators and Redox Initiator
At least one of agent.The azo-initiator includes azodiisobutyronitrile and/or azobisisoheptonitrile.The peroxide
Class initiator is one of inorganic peroxygen species initiator, including potassium peroxydisulfate, sodium peroxydisulfate and ammonium persulfate or a variety of.
The redox initiator is tert-butyl hydroperoxide-sodium thiosulfate.
The inventors found that the carboxylic acid group in styrene-acrylic latex makes lotion play dispersion in oil-well cement
With the effect of lubrication, the pumping of construction on site is easier to added with the oil well cement paste of styrene-acrylic latex.
The component for limiting range in the present invention with "≤", refers to the component of optional or selective addition.For example,
" component c, the water-soluble monomer with sulfonic acid functional group≤30% " water-soluble monomer of the expression component c with sulfonic acid functional group are
It is optionally added component, and its dosage is water-soluble monomer≤30% that 0≤component c has sulfonic acid functional group.In another example " group
Point e, crosslinking agent≤5% " expression component e crosslinking agent be optionally added component, and its dosage be 0≤component e crosslinking agent≤
5%.For another example " component f, chain-transferring agent≤5% " expression component f chain-transferring agent are to be optionally added component, and its dosage is 0
≤ component f chain-transferring agent≤5%.
Second aspect of the present invention is related to a kind of preparation method of styrene-acrylic latex as described in the first aspect of the invention, comprising:
At least one of component a, b, d, g and h and optional component c, e and f are mixed with water, then passed through by step A
Emulsification pretreatment pump carries out emulsification treatment and monomer pre-emulsion is made；
Initiator is mixed with water, prepares initiator solution by step B；
Step C carries out the initiator solution of the monomer pre-emulsion of 5%-10% (quality) and 5%-10% (quality) anti-
It answers, lotion seed is made；
Step D, remaining monomer pre-emulsion is added dropwise into lotion seed and remaining initiator solution is reacted, and is made
Reaction mixture；
Step E, redox initiator is added dropwise into reaction mixture, after being added dropwise, adds pH adjusting agent, i.e.,
Obtain styrene-acrylic latex.
" water " word used in the present invention refers to deionized water in the case where not specifying.
Above-mentioned steps C is actually the prepolymerization for being preparation lotion seed, and the temperature of the reaction can be 80-90
℃.The time of the reaction is usually 30min.
Styrene-acrylic latex of the invention is prepared using the method for seeded emulsion polymerization.The specific method is as follows: first will reaction
A certain amount of emulsifier solution or seed emulsion are added in container, after being heated to reaction temperature, a small amount of monomer is added [such as
5%-10% (quality)] and a small amount of initiator [such as 5%-10% (quality)] progress prepolymerization 30min.Then by pre-emulsification monomer
It with initiator within 2-6 hour, is preferably continuously added drop-wise in reaction vessel within 2-4 hour, after being added dropwise, then 2
After dropwise addition redox initiator reacts a period of time again in a hour, so that residual monomer quantity is preferably minimized, finally
Obtain the styrene-acrylic latex for oil-well cement of cementing the well.
In some embodiments of the invention, seeded emulsion polymerization method includes:
1. preparing lotion seed
Each component is weighed by the composition and usage ratio of above-mentioned monomer, is added in the reaction kettle with stirring, adds cream
Agent and water, using emulsification pretreatment pump high-speed circulating dispersion 40-50min to get the monomer pre-emulsion for arriving sufficiently shearing dispersion.First
By the monomer pre-emulsion of 5%-10%, be added to equipped with thermometer, heater, blender, charge pipe reaction kettle in, slowly rise
When temperature to temperature is 80-90 DEG C, initiator is added, after a few minutes, faint blue light occurs in lotion, is stirred for 5-10min, i.e. shape
At lotion seed.
2. preparing styrene-acrylic latex
Monomer pre-emulsion and initiator are continuously added drop-wise in reaction kettle in 2-4 hours, reacted with latex seed, is reacted
Temperature is maintained at 85-90 DEG C, after completion of the reaction, after heat preservation 1 hour, then in 2 hours redox initiator is added dropwise, drips
Bi Hou after heat preservation 1 hour, cools to 50 DEG C hereinafter, sodium hydrate aqueous solution is added, and the pH value of regulation system is 7-8 to get arriving
Required styrene-acrylic latex.
According to the present invention, the pH adjusting agent includes the carbonate, bicarbonate, phosphoric acid of alkali metal, alkaline-earth metal or amine
At least one of salt and disulfate, such as sodium bicarbonate, sodium carbonate, potassium sulfate, potassium acid sulfate.The dosage of pH adjusting agent is
The 0.2%-1% (quality) of monomer total amount.
According to the present invention, in step E, the average grain diameter of emulsion particle is 180nm in the styrene-acrylic latex.
Third aspect present invention is related to a kind of cement paste for well cementation system, including oil-well cement, quartz sand, fluid loss agent,
Retarder, dispersing agent and styrene-acrylic latex, contain following components by weight:
Wherein, the styrene-acrylic latex is for styrene-acrylic latex as described in the first aspect of the invention or such as second aspect of the present invention institute
State the styrene-acrylic latex of method preparation.In terms of generally by oil-well cement content for 100 parts by weight, by 5-15 parts of benzene of the present invention
Third latex is uniformly mixed with dispersant component with oil-well cement, quartz sand, fluid loss agent, retarder and obtains cement paste for well cementation
System.
According to the present invention, the quartz sand particle size is preferably 60-80 μm.
According to the present invention, the oil-well cement is good G grades of oil-well cements of China；The fluid loss agent, dispersing agent and retarder
Common additive in cementing system can be used.
According to the present invention, silicon powder can also be added in well cementing mortar architecture, be common extra material in cementing system.
The above extra material, additive can be obtained by commercially available.
Fourth aspect present invention is related to a kind of styrene-acrylic latex as described in the first aspect of the invention, such as second aspect of the present invention
The styrene-acrylic latex of the method preparation or cement paste for well cementation system as described in the third aspect of the present invention are in reinforcing oil well
Using.
Characterization test method of the present invention is as follows:
(1) API dehydration: the high-temperature and high-pressure filter press OWC- produced using Institute for Applied Technology, Shenyang Aerospace University
9710 measurements.
(2) it the thickening time: is measured using 8040 multiviscosity meter of HT/HP type of Chandler company, U.S. production.
(3) it resistance to compression, tensile strength and elasticity modulus: is measured using Germany's Tony Mechanical Behavior of Hardened Cement Paste analyzer.
(4) permeability: pressure hole is covered using the intelligence of the big scientific and technological group company's production of Shandong stone and seeps combined measuring instrument measurement.
The present inventor pass through a large number of experiments the study found that styrene-acrylic latex of the present invention to belong to specific function additional
Styrene-acrylic latex of the invention is added in the mortar architecture of well cementation, can effectively reduce the mistake of cement slurry by agent agent for anti gassing-out class
Water rate avoids the generation of gas channeling phenomenon, reduces the permeability of Behavior of Hardened Cement Paste, while improving the mechanical property of cement slurry, improves oil
Well cementing quality.Its mechanism are as follows:
(1) average grain diameter of latex granule is in 180nm or so in the oil-well cement styrene-acrylic latex in the present invention, than cement
Grain partial size (being typically 20-50 μm) small more, and micelle has good elasticity, and micelle blocks, is filled in cement granules
Between, make the reduction of filter cake permeability, the result of two kinds of synergistic effects plays the role of reducing dehydration.
(2) styrene-acrylic emulsion particle is assembled under differential pressure, is formed with the latex film of some strength, prevents gas from invading cement
In slurry；Reduce the surface tension of cement slurry so that alter into minimum gas be dispersed into microvesicle, these microvesicles are bound, will not
It alters to form gas passage in accumulation；After the static gel strength of cement slurry is formed, emulsion particle is filled in the gap of cement granules,
Reduce microfissure caused by hydrated cementitious, reduce permeability, effectively prevents the has channeling of well cementation section from occurring, improve oil gas
Well cementing quality.
(3) traditional performance of styrene-acrylic latex cement slurry has the characteristics that apparent rapid hardening, early strong, low dehydration, short transient time,
The bonding capacity between cement sheath and casing, stratum can be improved, reduce the annular space between cement sheath and casing, stratum, effectively
Avoid the generation of gas channeling phenomenon.
(4) since styrene-acrylic latex polymer film generated has preferable toughness, so significantly improving well cementation water
The shock resistance of mud ring.In addition latex-cement slurry can assign cement sheath with toughness, and the mechanics after styrene-acrylic latex is introduced in cement
Performance has clear improvement, and elasticity modulus improves (dropping to 7.7GPa by 15.5GPa), and flexural strength increase (is improved by 0.14MPa
To 0.27MPa), make Behavior of Hardened Cement Paste dynamic mechanical be improved significantly, improve the anti-perforation of cement sheath (pressure break etc.) dynamic
Impact capacity reduces the destruction probability of cement sheath in perforation and drilling process.
(5) styrene-acrylic latex cement has compactness and low-permeability, has stronger resistance to corrosion, is conducive to extend life
Produce the service life of well.
Oil-well cement styrene-acrylic latex of the invention is added in the mortar architecture of well cementation, cement slurry can be effectively reduced
Filter loss, at 140 DEG C of Applicable temperature API dehydration it is fully controllable system in 50mL hereinafter, nanoscale latex particle fills up cement
The gap of Behavior of Hardened Cement Paste after aquation increases the compactness of oil-well cement, reduces Behavior of Hardened Cement Paste permeability, effectively prevents well cementation interval isolation
Oil gas water breakthrough occurs, while improving the mechanical property of Behavior of Hardened Cement Paste, to improve oil gas well cementing operation quality.
Embodiment
Embodiment 1
With stirring the inner addition 900kg deionized water of reaction kettle (head tank), 20kg alkylphenol-polyethenoxy (10) ether,
500kg styrene, 800kg butyl acrylate, 12kg divinylbenzene, 60kg acrylamide, 50kg AMPS (2- acrylamide-
2- methyl propane sulfonic acid), pre-emulsification half an hour is stand-by.Simultaneously in another raw material dropping tank be added sodium peroxydisulfate 11kg, go from
Component is added dropwise as initiator in sub- water 1100kg.
Put into deionized water 700kg in reaction kettle, be warming up to 90 DEG C, be added 5% above-mentioned pre-emulsion, 10% it is above-mentioned
Initiator solution starts while being added dropwise remaining pre-emulsion and initiator solution after reaction 20 to 30 minutes, and process is added dropwise and continues
4 hours.30 minutes are kept the temperature after dripping off, temperature is dropped to 85 DEG C, while 4.2kg tert-butyl hydroperoxide and 200kg water group is added dropwise
At solution A, the solution B of 2.5kg sodium thiosulfate and 120kg deionized water composition after time for adding 2 hours, then keeps the temperature half
Hour, 50 DEG C are cooled to hereinafter, 20% NaOH solution is added dropwise, and pH value is transferred between 7.5-8 to get to stable milky
Styrene-acrylic latex 1#。
Embodiment 2
In the inner addition 900kg deionized water of reaction kettle (head tank) with stirring, 30kg tetradecylphenol polyethers sulfo group amber
Amber acid monoester sodium salt, 20kg alkylphenol-polyethenoxy (10) ether, 700kg styrene, 600kg butyl acrylate, 60kg acryloyl
Amine, pre-emulsification half an hour are stand-by.Sodium peroxydisulfate 11kg, deionized water 1100kg is added in raw material dropping tank simultaneously, as drawing
It sends out agent and component is added dropwise.
Put into deionized water 700kg in reaction kettle, be warming up to 90 DEG C, be added 5% above-mentioned pre-emulsion, 10% it is above-mentioned
Initiator solution starts while being added dropwise remaining pre-emulsion and initiator solution after reaction 20 to 30 minutes, and process is added dropwise and continues
4 hours.30 minutes are kept the temperature after dripping off, temperature is dropped to 85 DEG C, while 4.2kg tert-butyl hydroperoxide and 200kg water group is added dropwise
At solution A, the solution B of 2.5kg sodium thiosulfate and 120kg deionized water composition after time for adding 2 hours, then keeps the temperature half
Hour, 50 DEG C are cooled to hereinafter, 20% NaOH solution is added dropwise, and pH value is transferred between 7.5-8 to get to stable milky
Styrene-acrylic latex 2#。
Embodiment 3
With stirring the inner addition 900kg deionized water of reaction kettle (head tank), 30kg dodecylphenol ether ammonium sulfate salt,
20kg alkylphenol-polyethenoxy (10) ether, 1000kg styrene, 300kg acrylic acid-2-ethyl caproite, 300kg acrylic acid 12
Arrcostab, 35kg AMPS (2- acrylamide-2-methyl propane sulfonic), 60kg acrylamide pump pre-emulsification using emulsification pretreatment
40-50 minutes stand-by.Ammonium persulfate 11kg, deionized water 1100kg is added in another raw material dropping tank simultaneously, as drawing
It sends out agent and component is added dropwise.
Put into deionized water 700kg in reaction kettle, be warming up to 85 DEG C, be added 5% above-mentioned pre-emulsion, 10% it is above-mentioned
Initiator solution starts while being added dropwise remaining pre-emulsion and initiator solution after reaction 20 to 30 minutes, and process is added dropwise and continues
4 hours.30 minutes are kept the temperature after dripping off, temperature is dropped to 85 DEG C, while 4.2kg tert-butyl hydroperoxide and 200kg water group is added dropwise
At solution A, the solution B of 2.5kg sodium thiosulfate and 120kg deionized water composition after time for adding 2 hours, then keeps the temperature half
Hour, 50 DEG C are cooled to hereinafter, 20% NaOH solution is added dropwise, and pH value is transferred between 7.5-8 to get to stable milky
Styrene-acrylic latex 3#。
Embodiment 4
With stirring the inner addition 900kg deionized water of reaction kettle (head tank), 20kg alkylphenol-polyethenoxy (10) ether,
800kg styrene, 500kg butyl acrylate, 12kg divinylbenzene, 60kg acrylamide, 50kg AMPS (2- acrylamide-
2- methyl propane sulfonic acid), 30g lauryl mercaptan, pre-emulsification half an hour is stand-by.It was added in another raw material dropping tank simultaneously
Component is added dropwise as initiator in sodium sulphate 11kg, deionized water 1100kg.
Put into deionized water 700kg in reaction kettle, be warming up to 90 DEG C, be added 5% above-mentioned pre-emulsion, 10% it is above-mentioned
Initiator solution starts while being added dropwise remaining pre-emulsion and initiator solution after reaction 20 to 30 minutes, and process is added dropwise and continues
4 hours.30 minutes are kept the temperature after dripping off, temperature is dropped to 85 DEG C, while 4.2kg tert-butyl hydroperoxide and 200kg water group is added dropwise
At solution A, the solution B of 2.5kg sodium thiosulfate and 120kg deionized water composition after time for adding 2 hours, then keeps the temperature half
Hour, 50 DEG C are cooled to hereinafter, 20% NaOH solution is added dropwise, and pH value is transferred between 7.5-8 to get to stable milky
Styrene-acrylic latex 4#。
Embodiment 5
Cementing slurry: good G grades of oil-well cements of China are 100 parts of weight, 35 parts of quartz sand, 5 parts of fluid loss agent, 2 parts
Dispersing agent, 1.5 parts of retarder, 12 parts of styrene-acrylic latex 1#、2#、3#、4#With 20 parts of water.
Rheological property is surveyed by being put into after 93 DEG C of maintenances added with the cement slurry of styrene-acrylic latex, and high by API standard measurement high temperature
Press dehydration performance.Test result is shown in Table 1.
1 styrene-acrylic latex cement slurry basic performance of table
Embodiment 6
Cementing slurry: good G grades of oil-well cements of China are 100 parts of weight, 35 parts of quartz sand, 5 parts of fluid loss agent, 2 parts
Dispersing agent, 1.5 parts of retarder, 15 parts of styrene-acrylic latex 1#、2#、3#、4#Same formula is at 140 DEG C, under the conditions of 70MPa
Cement slurry thickening time is measured, the SPN anti-gas channeling coefficient of performance of mortar architecture is calculated.Test result is shown in Table 2.
The anti-channeling performance table of 2 styrene-acrylic latex cement slurry of table
Embodiment 7
Cementing slurry: good G grades of oil-well cements of China are 100 parts of weight, 35 parts of quartz sand, 5 parts of fluid loss additive, 2 parts
Dispersing agent, 1.5 parts of retarder, 20 parts of styrene-acrylic latex 1#、2#、3#、4#。
It is conserved 48 hours at 140 DEG C, 21MPa, the compression strength and tension of styrene-acrylic latex test Behavior of Hardened Cement Paste is not added in comparison
Intensity and elasticity modulus, and test the permeability of Behavior of Hardened Cement Paste.Test result is shown in Table 3.
3 styrene-acrylic latex cement properties table of table
It is good that styrene-acrylic latex slurry flowing performance-changing is added it can be seen from table 1, table 2, table 3, at 140 DEG C of Applicable temperature
When API dehydration it is fully controllable system in 50mL hereinafter, it is good to belong to anti-channeling performance less than 3 for anti-gas channeling performance index SPN value.Phenylpropyl alcohol
The addition of latex can be obviously improved the mechanical property of Behavior of Hardened Cement Paste, and elasticity modulus is effectively reduced, and improve tensile strength, and styrene-acrylic latex
Addition so that the particles filled Behavior of Hardened Cement Paste hole of some nanoemulsions, hence it is evident that reduce the permeability of Behavior of Hardened Cement Paste, this is also effectively improved
The anti-channeling performance and anti-corrosion capability of cement slurry.
Embodiment 8
By the styrene-acrylic latex 1 in the embodiment of the present invention 1#Field test has been carried out in the well cementation of three mouthfuls of wells in conjunction with cement slurry
Using application effect is good.Concrete condition is shown in Table 4.
4 styrene-acrylic latex cement properties table of table
It should be noted that embodiment described above for explaining only the invention, is not constituted to of the invention any
Limitation.By referring to exemplary embodiments, invention has been described, it should be appreciated that word used in it is descriptive
With explanatory vocabulary, rather than limited vocabulary.The present invention can be made within the scope of the claims by regulation
Modification, and the present invention is revised in without departing substantially from scope and spirit of the present invention.Although the present invention described in it relates to
And specific method, material and embodiment, it is not intended that the present invention is limited to particular case disclosed in it, on the contrary, this hair
It is bright to can be extended to other all methods and applications with the same function.
Claims (8)
1. a kind of reinforcing oil well styrene-acrylic latex, water-soluble by styrene, acrylic ester compound and other function
Monomer is made under the action of emulsifier and initiator by emulsion polymerization；
Wherein, the acrylic ester compound be selected from one of methyl acrylate, ethyl acrylate and butyl acrylate or
It is a variety of；The other function water-soluble monomer is selected from acrylic acid, methacrylic acid, acrylamide and N, N- dimethyl allene acyl
At least one of amine；
The average grain diameter of emulsion particle is 180nm in the styrene-acrylic latex；
The initiator is selected from least one of azo-initiator, peroxide type initiators and redox initiator；
The styrene-acrylic latex is made by the following components based on quality by emulsion polymerization:
2. styrene-acrylic latex according to claim 1, which is characterized in that the emulsifier is selected from anion and nonionic is compound
Emulsifier；The anion emulsifier is selected from lauryl sodium sulfate, neopelex, dodecyl sodium sulfate, ten
At least one of tetraalkyl phenol polyethers sulfo group succinic acid monoester sodium salt and dodecylphenol ether ammonium sulfate salt；The nonionic Emulsion
Agent is alkyl phenol polyoxyethylene ether.
3. a kind of preparation method of styrene-acrylic latex as claimed in claim 1 or 2, comprising:
Component a, b, d and g are mixed with water, monomer pre-emulsion are made through emulsification treatment by step A；
Initiator is mixed with water, prepares initiator solution by step B；
Step C carries out the initiator solution of the monomer pre-emulsion of 5 mass %-10 mass % and 5 mass %-10 mass % anti-
It answers, lotion seed is made；
Step D, remaining monomer pre-emulsion is added dropwise into lotion seed and remaining initiator solution is reacted, and reaction is made
Mixture；
Step E, redox initiator is added dropwise into reaction mixture, after being added dropwise, adds pH adjusting agent to get benzene
Third latex.
4. preparation method according to claim 3, which is characterized in that in step C, the temperature of the reaction is 80-90
℃。
5. preparation method according to claim 3 or 4, which is characterized in that in step D, the time of the dropwise addition is 2-
6h。
6. preparation method according to claim 3 or 4, which is characterized in that in step D, the time of the dropwise addition is 2-
4h。
7. a kind of cement paste for well cementation system, contains following components by weight:
Wherein, the styrene-acrylic latex is styrene-acrylic latex as claimed in claim 1 or 2 or any one of such as claim 3-6
The styrene-acrylic latex of the method preparation.
8. the phenylpropyl alcohol of styrene-acrylic latex as claimed in claim 1 or 2, any one of such as claim 3-6 the method preparation
The application of latex or cement paste for well cementation system as claimed in claim 7 in reinforcing oil well.
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| CN113416277B (en) * | 2021-08-24 | 2021-11-12 | 中国石油大学(华东) | Non-foaming oil well cement latex fluid loss agent, preparation method and application |
| CN115725017B (en) * | 2021-08-31 | 2023-09-19 | 中国石油天然气集团有限公司 | High-temperature gas channeling-preventing polymer and preparation method and application thereof |
| CN115109179A (en) * | 2022-05-23 | 2022-09-27 | 陕西科技大学 | Based on amphipathic Janus SiO 2 Nano particle stable styrene-acrylic emulsion profile control agent and preparation method thereof |
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