CN106565892A - Styrene-acrylic latex used for oil field well cementation, and preparation and applications thereof - Google Patents
Styrene-acrylic latex used for oil field well cementation, and preparation and applications thereof Download PDFInfo
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Abstract
The invention relates to styrene-acrylic latex used for oil field well cementation and a preparing method thereof. The styrene-acrylic latex is prepared by subjecting styrene, an acrylate compound, another functional water-soluble monomer and an optional water soluble monomer having a sulfonic acid functional group to emulsion polymerization under functions of an emulsifier, an initiator and an optional chain transfer and/or a crosslinking agent. The invention also relates to application of the styrene-acrylic latex in oil field well cementation. Through adding the styrene-acrylic latex into a cement paste system used for well cementation, the filter loss of the cement paste can be effectively reduced, API water loss at high temperatures is controlled to be 50 mL or below, compactness of oil well cement is enhanced, set cement permeability is reduced, oil, gas and water channeling in well sealing and cementation segments is effectively prevented, physical performance of set cement is improved and oil cementation quality of oil gas wells is improved.
Description
Technical field
The invention belongs to reinforcing oil well technical field, and in particular to a kind of reinforcing oil well styrene-acrylic latex and its preparation
With application.
Background technology
As the investigation and prospecting of China's petroleum resources is constantly extended to deep layer complex geological structure band area, deep-well,
Ultradeep well well cementation is faced with a High Temperature High Pressure anti-gas channeling difficult problem.And the latex-cement slurry of latex additive is added with anti-
The characteristics of high temperature, grease proofing air water are altered, drop dehydration reservoir protec-tion, can effectively improve deep-well and ultradeep well
Cementing quality, is the excellent mortar architecture of the anti-channeling performance generally acknowledged both at home and abroad at present.
It is styrene-butadiene latex mortar architecture currently used for the latex-cement slurry major part of reinforcing oil well operation, and applies
Styrene-acrylic latex cement mortar yet there are no report.It is multiple to there is synthesis condition in existing styrene-butadiene latex mortar architecture
Miscellaneous, wayward, sensitivity is strong, scene adjusts the difficult problem such as extremely difficult.
Therefore, the problem that presently, there are is that a kind of synthesis condition of urgent need research and development is simple, easily controllable, scene
Adjustment reinforcing oil well latex cement slurry system easy to use.
The content of the invention
The technical problem to be solved is for above-mentioned the deficiencies in the prior art, there is provided a kind of reinforcing oil well
With styrene-acrylic latex and preparation method thereof.By the related additive system of styrene-acrylic latex compounding, a kind of suitable oil is formed
The latex cement slurry system that air water is altered, can improve the cementing strength of the first and second cement planes of well cementation, reduce water
The permeability of mudstone, reduces the generation of oil gas water breakthrough phenomenon；And the malleable of Behavior of Hardened Cement Paste can be increased, water is reduced
Mudstone improves cementing quality in the level of breakage of the well cementation subsequent job such as perforation, pressure break.
For this purpose, first aspect present invention provides a kind of reinforcing oil well styrene-acrylic latex, which is by styrene, propylene
Acid esters compound, other functions water-soluble monomer and the optional water-soluble monomer with sulfonic acid functional group
Pass through emulsion polymerization system in the presence of emulsifying agent, initiator and optional chain-transferring agent and/or cross-linking agent
.
According to the present invention, the styrene-acrylic latex passes through emulsion polymerization system by the following components based on quality meter
：
In some embodiments of the invention, the other functions water-soluble monomer includes acrylic acid, methyl-prop
At least one in olefin(e) acid, acrylamide and N, N- DMAA.
In other embodiments of the present invention, the water-soluble monomer with sulfonic acid functional group includes 2- propylene
Amide -2- methyl propane sulfonic acids (AMPS), sodium allylsulfonate (SAS), methylpropene sodium sulfonate (SMS)
With at least one in vinylbenzenesulfonic acid sodium.
According to the present invention, the acrylic ester compound includes acrylate and/or alkyl methacrylate；
The acrylate includes one or more in acrylic acid methyl ester., ethyl acrylate and butyl acrylate；It is described
Alkyl methacrylate includes methyl methacrylate and/or butyl methacrylate.
According to the present invention, the emulsifying agent is anion and nonionic compound emulsifier；The anion emulsifier
Including sodium lauryl sulphate, dodecylbenzene sodium sulfonate, dodecyl sodium sulfate, tetradecylphenol polyether sulphur
At least one in base succinic acid monoester sodium salt and dodecylphenol ether ammonium sulfate salt；The nonionic emulsifier is
Alkylphenol-polyethenoxy (10) ether.
In some embodiments of the invention, the cross-linking agent include divinylbenzene, glycidyl acrylate,
Glycidyl methacrylate, TEGDMA, n-methylolacrylamide, metering system
One or more in amide, 1,6-HD acrylate and neopentyl glycol acrylate.
In other embodiments of the present invention, the chain-transferring agent includes C2-C12Alkyl hydrosulfide, sulfydryl third
One or more in acid, TGA, mercaptoethanol and hydrosulphonyl silane.
In other embodiments of the invention, the initiator includes that azo-initiator, peroxide cause
At least one in agent and redox initiator.
Second aspect present invention provides a kind of preparation method of styrene-acrylic latex as described in the first aspect of the invention,
Including：
Step A, by least one in component a, b, d, g and h and optional component c, e and f with
Water mixes, and Jing emulsifyings are obtained monomer pre-emulsion；
Step B, initiator is mixed with water, prepares initiator solution；
Step C, by the monomer pre-emulsion of 5%-10% (quality) and the initiator solution of 5%-10% (quality)
Reacted, emulsion seed is obtained；
Step D, in emulsion seed, the remaining monomer pre-emulsion of Deca and remaining initiator solution are reacted,
Prepared reactant mixture；
Step E, the Deca redox initiator in reactant mixture, after completion of dropping, adds pH
Regulator, obtains final product 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 present invention, in step D, the time of the Deca is 2-6h.It is preferred that institute
The time for stating Deca is 2-4h.
According to the present invention, in step E, in the styrene-acrylic latex, the mean diameter of emulsion particle is 180nm；Institute
The time for stating Deca is 2h.
Third aspect present invention provides a kind of cement paste for well cementation system, and which contains following components by weight：
Wherein, the styrene-acrylic latex is styrene-acrylic latex as described in the first aspect of the invention or such as second party of the present invention
Styrene-acrylic latex prepared by face methods described.
Fourth aspect present invention provides a kind of styrene-acrylic latex as described in the first aspect of the invention, the such as present invention the
Styrene-acrylic latex or the cement paste for well cementation system as described in third aspect present invention prepared by two aspect methods describeds
Application in reinforcing oil well.
Specific embodiment
To make the present invention easier to understand, the present invention is described in detail below in conjunction with embodiment, these enforcements
Example only plays illustrative effect, it is not limited to the range of application of the present invention.
As it was previously stated, existing styrene-butadiene latex mortar architecture to there is synthesis condition complicated, wayward, sensitive
Property the difficult problem such as strong, scene adjustment is extremely difficult, and yet there are no report using styrene-acrylic latex cement mortar.This
It is bright by way of introducing some other feature water-soluble monomers and the water-soluble monomer with sulfonic acid functional group
Carry out emulsion polymerization and prepare a kind of reinforcing oil well styrene-acrylic latex.The latex is used to make cement paste for well cementation body
System, synthesis condition are simple, easily controllable, and scene adjustment is easy to use.
Therefore, first aspect present invention is related to a kind of reinforcing oil well styrene-acrylic latex, and which is by styrene, acrylic acid
Ester type compound, other functions water-soluble monomer and the optional water-soluble monomer with sulfonic acid functional group exist
Pass through emulsion polymerization system in the presence of emulsifying agent, initiator and optional chain-transferring agent and/or cross-linking agent
.
According to the present invention, the styrene-acrylic latex passes through emulsion polymerization system by the following components based on quality meter
：
In some embodiments of the invention, the other functions water-soluble monomer includes acrylic acid, methyl-prop
At least one in olefin(e) acid, acrylamide and N, N- DMAA.
It is optional in the present invention to add the water-soluble monomer with sulfonic acid functional group.In other realities of the present invention
Apply in example, the water-soluble monomer with sulfonic acid functional group includes 2- acrylamide-2-methyl propane sulfonics
(AMPS), sodium allylsulfonate (SAS), methylpropene sodium sulfonate (SMS) and vinylbenzenesulfonic acid sodium
In at least one.
Due to adding in copolymerization containing sulfonic monomer or other functions water-soluble monomer in the present invention, because
This latex has the good compatibility with oil-well cement.
According to the present invention, the acrylic ester compound includes acrylate and/or alkyl methacrylate；
The acrylate includes one or more in acrylic acid methyl ester., ethyl acrylate and butyl acrylate；It is described
Alkyl methacrylate includes methyl methacrylate and/or butyl methacrylate.
Esters soft monomer in the present invention, can effectively reduce the vitrification point of polymer, synthesized phenylpropyl alcohol
Latex has efficient drop dehydration function.
In the present invention, all comonomers are liquid monomer, and manufacturing parameter is easily controlled, the styrene-acrylic latex of synthesis
Solid content compares other well cementation styrene-butadiene latexes height, and latex-cement slurry can be more reached so under conditions of dosage is equal
Performance requirement.
According to the present invention, the emulsifying agent is anion and nonionic compound emulsifier.The anion emulsifier
Including sodium lauryl sulphate, dodecylbenzene sodium sulfonate, dodecyl sodium sulfate, tetradecylphenol polyether sulphur
At least one in base succinic acid monoester sodium salt and dodecylphenol ether ammonium sulfate salt；The nonionic emulsifier is
Alkylphenol-polyethenoxy (10) ether.
Optional addition cross-linking agent in the present invention.In some embodiments of the invention, the cross-linking agent includes
Divinylbenzene, glycidyl acrylate, glycidyl methacrylate, triethylene glycol dimethyl allene
Acid esters, n-methylolacrylamide, Methacrylamide, 1,6-HD acrylate and neopentyl glycol acrylic acid
One or more in ester.
Term " optional " of the present invention refers to and can add, it is also possible to be added without.
Optional addition chain-transferring agent in the present invention.The chain-transferring agent includes C2-C12Alkyl hydrosulfide, mercapto
One or more in base propanoic acid, TGA, mercaptoethanol and hydrosulphonyl silane.
According to the present invention, the initiator includes azo-initiator, peroxide type initiators and oxidoreduction
At least one in initiator.The azo-initiator includes azodiisobutyronitrile and/or 2,2'-Azobis(2,4-dimethylvaleronitrile).
The peroxide type initiators are inorganic peroxygen species initiator, including potassium peroxydisulfate, sodium peroxydisulfate and mistake
One or more in ammonium sulfate.The redox initiator is tert-butyl hydroperoxide-sodium thiosulfate.
The inventors found that the hydroxy-acid group in styrene-acrylic latex so that emulsion is served in oil-well cement
Dispersion and the effect for lubricating, are easier to the construction pumping at scene added with the oil well cement paste of styrene-acrylic latex.
The component of scope is limited in the present invention with "≤", the component of optional or selective addition is referred to.
For example, " component c, water-soluble monomer≤30% with sulfonic acid functional group " represents that component c carries sulfonic acid sense
The water-soluble monomer of group is to be optionally added component, and its consumption is 0≤component c water-soluble with sulfonic acid functional group
Property monomer≤30%.Again for example, " component e, cross-linking agent≤5% " represents component e cross-linking agent to be optionally added group
Point, and its consumption is 0≤component e cross-linking agent≤5%.Again for example, " component f, chain-transferring agent≤5% " is represented
Component f chain-transferring agent is to be optionally added component, and its consumption is 0≤component f chain-transferring agent≤5%.
Second aspect present invention is related to a kind of preparation method of styrene-acrylic latex as described in the first aspect of the invention, bag
Include：
Step A, by least one in component a, b, d, g and h and optional component c, e and f with
Water mixes, then carries out the prepared monomer pre-emulsion of emulsifying by emulsification pretreatment pump；
Step B, initiator is mixed with water, prepares initiator solution；
Step C, by the monomer pre-emulsion of 5%-10% (quality) and the initiator solution of 5%-10% (quality)
Reacted, emulsion seed is obtained；
Step D, in emulsion seed, the remaining monomer pre-emulsion of Deca and remaining initiator solution are reacted,
Prepared reactant mixture；
Step E, the Deca redox initiator in reactant mixture, after completion of dropping, adds pH
Regulator, obtains final product styrene-acrylic latex.
In the present invention, " water " word used, in the case where not specifying, refers to deionized water.
Actually to prepare the prepolymerization of emulsion seed, the temperature of the reaction can be above-mentioned steps C
80-90℃.The time of the reaction is usually 30min.
The styrene-acrylic latex of the present invention is prepared using the method for seeded emulsion polymerization.Concrete grammar is as follows：First will
A certain amount of emulsifier solution, or seed emulsion are added in reaction vessel, after being heated to reaction temperature, is added
A small amount of monomer [such as 5%-10% (quality)] and a small amount of initiator [such as 5%-10% (quality)] carry out prepolymerization 30min.
Then, by pre-emulsification monomer and initiator in 2-6 hour, preferably continuously it is added drop-wise in 2-4 hour anti-
In answering container, after completion of dropping, then in 2 hours Deca redox initiator react a period of time again with
Afterwards, so that residual monomer quantity is preferably minimized, finally obtain the styrene-acrylic latex for oil-well cement of cementing the well.
In some specific embodiments of the present invention, seeded emulsion polymerization method includes：
1. emulsion seed is prepared
Each component is weighed by the composition and usage ratio of above-mentioned monomer, is added in the reactor with stirring, then plus
Enter emulsifying agent and water, disperse 40-50min using emulsification pretreatment pump high-speed circulating, i.e., fully sheared scattered
Monomer pre-emulsion.First by the monomer pre-emulsion of 5%-10%, be added to equipped with thermometer, heater, agitator,
In the reactor of charge pipe, be slowly ramped to temperature for 80-90 DEG C when, add initiator, after a few minutes, breast
There is faint blue light in liquid, is stirred for 5-10min, that is, form emulsion seed.
2. styrene-acrylic latex is prepared
Monomer pre-emulsion and initiator are continuously added drop-wise in reactor in 2-4 hours, are reacted with latex seed,
Reaction temperature is maintained at 85-90 DEG C, after completion of the reaction, after insulation 1 hour, then the Deca oxidation in 2 hours
Reduction initiator, after completion of dropping, after being incubated 1 hour, cools to less than 50 DEG C, adds sodium hydroxide water-soluble
Liquid, the pH value of regulation system is 7-8, that is, the styrene-acrylic latex required for obtaining.
According to the present invention, the pH adjusting agent includes the carbonate of alkali metal, alkaline-earth metal or amine, bicarbonate
At least one in salt, phosphate and disulfate, such as sodium bicarbonate, sodium carbonate, potassium sulfate, potassium acid sulfate
Deng.0.2%-1% (quality) of the consumption of pH adjusting agent for monomer total amount.
According to the present invention, in step E, in the styrene-acrylic latex, the mean diameter of emulsion particle is 180nm.
Third aspect present invention is related to a kind of cement paste for well cementation system, including oil-well cement, quartz sand, drop are lost
Water preparation, retarder, dispersant and styrene-acrylic latex, which contains following components by weight：
Wherein, the styrene-acrylic latex is styrene-acrylic latex as described in the first aspect of the invention or such as second party of the present invention
Styrene-acrylic latex prepared by face methods described.Typically count by 100 parts by weight of oil-well cement content, by 5-15 parts
Styrene-acrylic latex of the present invention is mixed with oil-well cement, quartz sand, fluid loss agent, retarder and dispersant component
Close uniform i.e. prepared 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 China G level oil-well cements；The fluid loss agent, dispersant and
The additive that retarder is commonly used in can adopting cementing system.
According to the present invention, silica flour can be also added in well cementing mortar architecture, which is commonly use in cementing system outer
Spike.Above extra material, additive can be by commercially available and obtain.
Fourth aspect present invention is related to a kind of styrene-acrylic latex as described in the first aspect of the invention, the such as present invention second
Styrene-acrylic latex or the cement paste for well cementation system as described in third aspect present invention prepared by aspect methods described exists
Application in reinforcing oil well.
Characterization test method of the present invention is as follows：
(1) API dehydrations：The High Temperature High Pressure dehydration produced using Institute for Applied Technology of Shenyang Aerospace University
Instrument OWC-9710 is determined.
(2) thickening time：Determined using 8040 multiviscosity meter of HT/HP types that Chandler companies of the U.S. produce.
(3) resistance to compression, tensile strength and elastic modelling quantity：Surveyed using German Tony Mechanical Behavior of Hardened Cement Paste analyzer
It is fixed.
(4) permeability：Pressure hole is covered using the intelligence of the big scientific and technological group company's production of Shandong stone and oozes combined measuring instrument measure.
Through lot of experiments research, the present inventor has found that styrene-acrylic latex of the present invention belongs to specific function
Additive agent for anti gassing-out class, the styrene-acrylic latex of the present invention is added in the mortar architecture of well cementation, effectively can be dropped
The percentage of water loss of low cement mortar, it is to avoid the generation of gas channeling phenomenon, reduces the permeability of Behavior of Hardened Cement Paste, while improving cement
The mechanical property of slurry, improves oil well cementing quality.Its mechanism is：
(1) present invention in oil-well cement styrene-acrylic latex in latex granule mean diameter in 180nm or so,
Less than cement granules particle diameter (being typically 20-50 μm) is more, and micelle has good elasticity, micelle
Block, be filled between cement granules, make filter cake permeability reduction, two kinds of synergistic results serve drop
Low dehydration effect.
(2) styrene-acrylic emulsion particle is assembled under differential pressure, is formed with the latex film of some strength, prevents gas from invading
Enter in cement mortar；Reduce the surface tension of cement mortar so that alter into minimum gas be dispersed into microvesicle, this
Steep slightly in bond, will not gather and alter to form gas passage；After the static gel strength of cement mortar is formed, emulsion
It is particle-filled in the space of cement granules to reduce the microfissure that hydrated cementitious are caused, reduce permeability,
Effectively prevent the has channeling of well cementation section from occurring, improve oil gas well cementing operation quality.
(3) traditional performance of styrene-acrylic latex cement mortar has obvious rapid hardening, early strong, low dehydration, right angle thick
The features such as change, the bonding capacity between cement sheath and sleeve pipe, stratum can be improved, reduce cement sheath and sleeve pipe,
Annular space between stratum, is prevented effectively from the generation of gas channeling phenomenon.
(4) as the polymeric film generated by styrene-acrylic latex has preferable toughness, so significantly improve
The shock resistance of cementing concrete ring.Latex-cement slurry can give cement sheath with toughness in addition, and benzene is introduced in cement
Mechanical property after third latex has clear improvement, and elastic modelling quantity improves (drop to 7.7GPa by 15.5GPa),
Rupture strength increases (being improved to 0.27MPa by 0.14MPa), makes the dynamic mechanical of Behavior of Hardened Cement Paste obtain bright
It is aobvious to improve, the anti-perforation of cement sheath (pressure break etc.) dynamic impulsion ability is improve, perforation and drilling process is reduced
The destruction probability of middle cement sheath.
(5) styrene-acrylic latex cement has compactness and hypotonicity, with stronger resistance to corrosion, favorably
In the life-span for extending producing well.
The oil-well cement styrene-acrylic latex of the present invention is added in the mortar architecture of well cementation, water can be effectively reduced
The filter loss of mud, in 140 DEG C of Applicable temperature, the fully controllable system of API dehydrations is in below 50mL, nanoscale
Latex particle fills up the gap of Behavior of Hardened Cement Paste after hydrated cementitious, increases the compactness of oil-well cement, reduces Behavior of Hardened Cement Paste and oozes
Rate, effectively prevents the oil gas water breakthrough of well cementation interval isolation from occurring thoroughly, while improve the mechanical property of Behavior of Hardened Cement Paste, so as to
Improve oil gas well cementing operation quality.
Embodiment
Embodiment 1
In the inner addition 900kg deionized waters of reactor (head tank) of band stirring, 20kg alkylphenol-polyethenoxies
(10) ether, 500kg styrene, 800kg butyl acrylate, 12kg divinylbenzene, 60kg acrylamides,
50kg AMPS (2- acrylamide-2-methyl propane sulfonics), pre-emulsification half an hour is stand-by.It is simultaneously former at another
Sodium peroxydisulfate 11kg, deionized water 1100kg are added in material dropping tank, as initiator Deca component.
Deionized water 700kg is put in reactor, 90 DEG C are warmed up to, the above-mentioned pre-emulsion of addition 5%, 10%
Above-mentioned initiator solution, after reaction 20 to 30 minutes, start the simultaneously remaining pre-emulsion of Deca and initiator
Solution, Deca process continue 4 hours.30 minutes are incubated after dripping off, temperature 85 DEG C is dropped to, while Deca
The solution A of 4.2kg tert-butyl hydroperoxide and 200kg water composition, 2.5kg sodium thiosulfate and 120kg go from
The solution B of sub- water composition, time for adding is after 2 hours, then is incubated half an hour, is cooled to less than 50 DEG C, Deca
20% NaOH solution, is transferred to pH value between 7.5-8, that is, obtain stable milky styrene-acrylic latex
1#。
Embodiment 2
In the inner addition 900kg deionized waters of reactor (head tank) of band stirring, 30kg tetradecylphenols gather
Ether sulfosuccinic acid monoester sodium salt, 20kg alkylphenol-polyethenoxies (10) ether, 700kg styrene, 600kg propylene
Acid butyl ester, 60kg acrylamides, pre-emulsification half an hour are stand-by.Sodium peroxydisulfate is added in raw material dropping tank simultaneously
11kg, deionized water 1100kg, as initiator Deca component.
Deionized water 700kg is put in reactor, 90 DEG C are warmed up to, the above-mentioned pre-emulsion of addition 5%, 10%
Above-mentioned initiator solution, after reaction 20 to 30 minutes, start the simultaneously remaining pre-emulsion of Deca and initiator
Solution, Deca process continue 4 hours.30 minutes are incubated after dripping off, temperature 85 DEG C is dropped to, while Deca
The solution A of 4.2kg tert-butyl hydroperoxide and 200kg water composition, 2.5kg sodium thiosulfate and 120kg go from
The solution B of sub- water composition, time for adding is after 2 hours, then is incubated half an hour, is cooled to less than 50 DEG C, Deca
20% NaOH solution, is transferred to pH value between 7.5-8, that is, obtain stable milky styrene-acrylic latex
2#。
Embodiment 3
In the inner addition 900kg deionized waters of reactor (head tank) of band stirring, 30kg dodecyl 2, 2-Oxydiphenol sulfur
Acid ammonium salt, 20kg alkylphenol-polyethenoxies (10) ether, 1000kg styrene, 300kg acrylic acid-2-ethyl caproites,
300kg dodecylacrylates, 35kg AMPS (2- acrylamide-2-methyl propane sulfonics), 60kg propylene
Amide, it is stand-by using emulsification pretreatment pump pre-emulsification 40-50 minute.Add in another raw material dropping tank simultaneously
Ammonium persulfate. 11kg, deionized water 1100kg, as initiator Deca component.
Deionized water 700kg is put in reactor, 85 DEG C are warmed up to, the above-mentioned pre-emulsion of addition 5%, 10%
Above-mentioned initiator solution, after reaction 20 to 30 minutes, start the simultaneously remaining pre-emulsion of Deca and initiator
Solution, Deca process continue 4 hours.30 minutes are incubated after dripping off, temperature 85 DEG C is dropped to, while Deca
The solution A of 4.2kg tert-butyl hydroperoxide and 200kg water composition, 2.5kg sodium thiosulfate and 120kg go from
The solution B of sub- water composition, time for adding is after 2 hours, then is incubated half an hour, is cooled to less than 50 DEG C, Deca
20% NaOH solution, is transferred to pH value between 7.5-8, that is, obtain stable milky styrene-acrylic latex
3#。
Embodiment 4
In the inner addition 900kg deionized waters of reactor (head tank) of band stirring, 20kg alkylphenol-polyethenoxies
(10) ether, 800kg styrene, 500kg butyl acrylate, 12kg divinylbenzene, 60kg acrylamides,
50kg AMPS (2- acrylamide-2-methyl propane sulfonics), 30g lauryl mercaptans, pre-emulsification half an hour are treated
With.Sodium peroxydisulfate 11kg, deionized water 1100kg are added in another raw material dropping tank simultaneously, as drawing
Send out agent Deca component.
Deionized water 700kg is put in reactor, 90 DEG C are warmed up to, the above-mentioned pre-emulsion of addition 5%, 10%
Above-mentioned initiator solution, after reaction 20 to 30 minutes, start the simultaneously remaining pre-emulsion of Deca and initiator
Solution, Deca process continue 4 hours.30 minutes are incubated after dripping off, temperature 85 DEG C is dropped to, while Deca
The solution A of 4.2kg tert-butyl hydroperoxide and 200kg water composition, 2.5kg sodium thiosulfate and 120kg go from
The solution B of sub- water composition, time for adding is after 2 hours, then is incubated half an hour, is cooled to less than 50 DEG C, Deca
20% NaOH solution, is transferred to pH value between 7.5-8, that is, obtain stable milky styrene-acrylic latex
4#。
Embodiment 5
Cementing slurry：Good China's G levels oil-well cement is 100 parts of weight, and 35 parts of quartz sand, 5 parts of drop lose
Water preparation, 2 parts of dispersant, 1.5 parts of retarder, 12 parts of styrene-acrylic latex 1#、2#、3#、4#With 20 parts
Water.
Rheological property is surveyed after cement mortar added with styrene-acrylic latex is put into 93 DEG C of maintenances, and presses API standard and determine high
Warm high pressure dehydration performance.Result of the test is shown in Table 1.
1 styrene-acrylic latex cement mortar key property of table
Embodiment 6
Cementing slurry：Good China's G levels oil-well cement is 100 parts of weight, and 35 parts of quartz sand, 5 parts of drop lose
Water preparation, 2 parts of dispersant, 1.5 parts of retarder, 15 parts of styrene-acrylic latex 1#、2#、3#、4#Same matches somebody with somebody
Side determines cement slurry thickening time at 140 DEG C under the conditions of 70MPa, calculate the SPN anti-gas channelings of mortar architecture
The coefficient of performance.Result of the test is shown in Table 2.
The anti-channeling performance table of 2 styrene-acrylic latex cement mortar of table
Embodiment 7
Cementing slurry：Good China's G levels oil-well cement is 100 parts of weight, and 35 parts of quartz sand, 5 parts of drop are filtered
Lose agent, 2 parts of dispersant, 1.5 parts of retarder, 20 parts of styrene-acrylic latex 1#、2#、3#、4#。
Conserve 48 hours under 140 DEG C, 21MPa, contrast is not added with the comprcssive strength that styrene-acrylic latex tests Behavior of Hardened Cement Paste
With tensile strength and elastic modelling quantity, and the permeability of Behavior of Hardened Cement Paste is tested.Result of the test is shown in Table 3.
3 styrene-acrylic latex cement properties table of table
By table 1, table 2, table 3 as can be seen that addition styrene-acrylic latex slurry flowing performance-changing well, is being suitable for
During 140 DEG C of temperature, the fully controllable system of API dehydrations is in below 50mL, anti-gas channeling performance index SPN values less than 3,
Belong to anti-channeling performance good.The addition of styrene-acrylic latex can be obviously improved the mechanical property of Behavior of Hardened Cement Paste, effectively reduce bullet
Property modulus, improve tensile strength, and the addition of styrene-acrylic latex causes the particles filled Behavior of Hardened Cement Paste hole of some nanoemulsions
Gap, hence it is evident that reduce the permeability of Behavior of Hardened Cement Paste, this also effectively improves the anti-channeling performance and anti-corrosion capability of cement mortar.
Embodiment 8
By the styrene-acrylic latex 1 in the embodiment of the present invention 1#Scene has been carried out in the well cementation of three mouthfuls of wells with reference to cement mortar
Test application, application effect are 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 is only used for explaining the present invention, do not constitute to the present invention's
Any restriction.By referring to exemplary embodiments, invention has been described, it should be appreciated that wherein used
Word is descriptive and explanatory vocabulary, rather than limited vocabulary.Can be by regulation in the claims in the present invention
In the range of the present invention is modified, and the present invention is carried out in without departing substantially from scope and spirit of the present invention
Revision.Although the present invention described in which is related to specific method, material and embodiment, it is not intended that
The present invention is limited to wherein disclosed particular case, conversely, the present invention to can be extended to other all with identical function
Methods and applications.
Claims (11)
1. a kind of reinforcing oil well styrene-acrylic latex, which is by styrene, acrylic ester compound, other functions
Water-soluble monomer and the optional water-soluble monomer with sulfonic acid functional group are in emulsifying agent, initiator and optionally
Chain-transferring agent and/or cross-linking agent in the presence of by emulsion polymerization be obtained.
2. styrene-acrylic latex according to claim 1, it is characterised in that the styrene-acrylic latex is by based on quality
The following components of meter is obtained by emulsion polymerization：
3. styrene-acrylic latex according to claim 1 and 2, it is characterised in that the other functions are water-soluble
Property monomer includes acrylic acid, methacrylic acid, acrylamide and N, at least one in N- DMAAs.
4. the styrene-acrylic latex according to any one in claim 1-3, it is characterised in that described with sulphur
The water-soluble monomer of acid functional group includes 2- acrylamide-2-methyl propane sulfonics, sodium allylsulfonate, metering system sulphur
At least one in sour sodium and vinylbenzenesulfonic acid sodium.
5. the styrene-acrylic latex according to any one in claim 1-4, it is characterised in that the acrylic acid
Ester type compound includes acrylate and/or alkyl methacrylate；The acrylate includes acrylic acid first
One or more in ester, ethyl acrylate and butyl acrylate；The alkyl methacrylate includes methyl
Acrylic acid methyl ester. and/or butyl methacrylate；
The emulsifying agent is anion and nonionic compound emulsifier；The anion emulsifier includes dodecyl
Sodium sulfate, dodecylbenzene sodium sulfonate, dodecyl sodium sulfate, tetradecylphenol polyethers sulfosuccinic acid monoesters
At least one in sodium salt and dodecylphenol ether ammonium sulfate salt；The nonionic emulsifier is alkyl phenol polyoxy second
Alkene (10) ether；
The cross-linking agent include divinylbenzene, glycidyl acrylate, glycidyl methacrylate,
TEGDMA, n-methylolacrylamide, Methacrylamide, 1,6-HD acrylic acid
One or more in ester and neopentyl glycol acrylate；
The chain-transferring agent includes C2-C12Alkyl hydrosulfide, mercaptopropionic acid, TGA, mercaptoethanol and mercapto
One or more in base silane；
The initiator is included in azo-initiator, peroxide type initiators and redox initiator extremely
Few one kind.
6. a kind of preparation method of the styrene-acrylic latex as described in any one in claim 1-5, including：
Step A, by least one in component a, b, d, g and h and optional component c, e and f with
Water mixes, and Jing emulsifyings are obtained monomer pre-emulsion；
Step B, initiator is mixed with water, prepares initiator solution；
Step C, by the monomer pre-emulsion of 5%-10% (quality) and the initiator solution of 5%-10% (quality)
Reacted, emulsion seed is obtained；
Step D, in emulsion seed, the remaining monomer pre-emulsion of Deca and remaining initiator solution are reacted,
Prepared reactant mixture；
Step E, the Deca redox initiator in reactant mixture, after completion of dropping, adds pH
Regulator, obtains final product styrene-acrylic latex.
7. preparation method according to claim 6, it is characterised in that in step C, the reaction
Temperature is 80-90 DEG C.
8. the preparation method according to claim 6 or 7, it is characterised in that in step D, described
The time of Deca is 2-6h；It is preferred that the time of the Deca is 2-4h.
9. the preparation method according to any one in claim 6-8, it is characterised in that in step E,
In the styrene-acrylic latex, the mean diameter of emulsion particle is 180nm.
10. a kind of cement paste for well cementation system, which contains following components by weight：
Wherein, the styrene-acrylic latex is styrene-acrylic latex as described in any one in claim 1-5 or such as right
Require the styrene-acrylic latex of any one methods described preparation in 6-9.
Any one in 11. styrene-acrylic latexes as described in any one in claim 1-5, such as claim 6-9
The styrene-acrylic latex or cement paste for well cementation system as claimed in claim 10 of methods described preparation is in reinforcing oil well
In application.
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| CN109485800A (en) * | 2017-09-12 | 2019-03-19 | 中国石油化工股份有限公司 | A kind of integration styrene-acrylic latex, preparation method and application |
| CN113416277A (en) * | 2021-08-24 | 2021-09-21 | 中国石油大学(华东) | Non-foaming oil well cement latex fluid loss agent, preparation method and application |
| 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 |
| CN115725017A (en) * | 2021-08-31 | 2023-03-03 | 中国石油天然气集团有限公司 | High-temperature gas channeling prevention polymer and preparation method and application thereof |
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