CN106947443B - Polymer dispersion powder composition and the stabilizer for preventing polymer dispersion powder to be demulsified - Google Patents
Polymer dispersion powder composition and the stabilizer for preventing polymer dispersion powder to be demulsified Download PDFInfo
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- CN106947443B CN106947443B CN201710157334.3A CN201710157334A CN106947443B CN 106947443 B CN106947443 B CN 106947443B CN 201710157334 A CN201710157334 A CN 201710157334A CN 106947443 B CN106947443 B CN 106947443B
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- amphoteric surfactant
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- 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
- C09K8/46—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells containing inorganic binders, e.g. Portland cement
- C09K8/467—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells containing inorganic binders, e.g. Portland cement containing additives for specific purposes
Abstract
This application discloses a kind of polymer dispersion powder composition and a kind of stabilizers and application thereof, the polymer dispersion powder composition includes polymer dispersion powder and stabilizer, and the additive amount of the stabilizer is 0.9~1.8% of the weight based on the polymer dispersion powder.The stabilizer includes the amphoteric surfactant and polyethers nonionic surfactant that weight ratio is 1:4~4:1；The stabilizer is for preventing polymer dispersion powder to be demulsified in cement slurry.The phenomenon that " is demulsified " will not occur in cement slurry for the polymer dispersion powder composition of the application, and have good adaptability in rubber powder Behavior of Hardened Cement Paste system.
Description
Technical field
This application involves but be not limited to reinforcing oil well technical field, being more particularly without limitation, to one kind can be used for reinforcing oil well
Polymer dispersion powder composition and prevent polymer dispersion powder be demulsified stabilizer.
Background technique
Well cementation is the important operation in drilling process.Well cementation is also referred to as cementing, i.e., usually additional by portland cement, cement
Agent and water prepare cement slurry, and the annular space that injection stratum and casing are constituted plays stratum Inter-zonal packing and stablizes the work such as casing
With.Cement slurry property is to influence one of cementing quality key factor.
It was verified that adding the latex cement slurry system that latex is constituted in cement slurry, there is anti-channeling, anti-corrosion and increasing water
The effects of mudstone toughness.Therefore, latex cement slurry system is in some complex hole conditions and the well cementing operation required with property
In be widely applied.Currently, the latex of latex cement slurry system mainly in liquid form is host agent, but in some constructions
Under operating condition, the additive of powder has the advantages that protrusion: powder body material can reduce transport of materials, packaging and storage at
This, can effectively be avoided the leakage of fluent material, the antifreezing measures etc. when without considering using liquid additive.In recent years, can divide
The latex for dissipating latex powder (hereinafter referred to as: rubber powder) substitution liquid form, is rarely reported in terms of constructing latex cement slurry system:
The A.Chougnet et al. of Eliokem company has studied the glue that styrene-acrylic latex (is copolymerized) preparation by styrene and acrylate monomer
Application (SPE102173,2006) of the powder in reinforcing oil well；Schlumberger company discloses in patent US8020618
Rubber powder as well cementation solid agent for anti gassing-out application, used in rubber powder be vinyl acetate esters (by vinyl acetate monomer with
Fluoride monomers) or butylbenzene class (being copolymerized by styrene butadiene monomer).
But it finds in practical applications, the prior art is showed themselves in that there are still insufficient and area for improvement in rubber powder
Selection and its anti-" demulsification " technical aspect, it is to be improved.Currently, industrialized rubber powder has vinyl acetate esters, versatic acid
Esters, esters of acrylic acid and butylbenzene class, these rubber powders are perhaps easy to happen " demulsification " in cement slurry or contain ester group in turn
It is easy to happen hydrolysis.Stabilizer can be added to prevent from " being demulsified ", related latex prevents that the report of " demulsification " has: United States Patent (USP)
US4537918, which discloses lignosulfonates, melamine sulfonate and naphthalene sulfonic salt, can be used as latex stabilizer；United States Patent (USP)
US7404855, which discloses alcohol ether sulphates (salt), can be used as latex stabilizer；United States Patent (USP) US7576042 discloses alkyl phenol
The latex stabilizer that polyether non-ionic surface active agent and alkyl phenol polyether sulfuric ester (salt) are constituted；United States Patent (USP)
US20150252243 discloses maleic acid and the copolymer of lipophilicity monomer can be used as latex stabilizer.But existing institute's public affairs
The stabilizer for latex opened stable rubber powder, rubber powder " demulsification " existing when applying in reinforcing oil well can not ask well
Topic is not resolved yet so far.
Summary of the invention
It is the general introduction to the theme being described in detail herein below.This general introduction is not the protection model in order to limit claim
It encloses.
This application provides one kind not to occur when applying in reinforcing oil well " to be demulsified " the polymer dispersion powder combination of phenomenon
Object and one kind can prevent the stabilizer of existing polymer dispersion powder generation " demulsification " phenomenon.
Specifically, this application provides a kind of polymer dispersion powder compositions.
Polymer dispersion powder composition provided herein, including polymer dispersion powder and stabilizer, the stabilizer
Additive amount be weight (the By Weight Of Re-dispersible latex based on the polymer dispersion powder
Powder, BWOR) 10~60%.
In presently filed embodiment, the polymer dispersion powder can be butylbenzene class polymer dispersion powder, for example, beautiful
The AXILATTM PSB150 of HEXION company, state.
In presently filed embodiment, the stabilizer can for amphoteric surfactant or amphoteric surfactant with
The combination of polyethers nonionic surfactant.
Optionally, the weight ratio of amphoteric surfactant and polyethers nonionic surfactant is 1:4~4:1.
Optionally, the weight ratio of amphoteric surfactant and polyethers nonionic surfactant is 3:1~2:1.
In presently filed embodiment, the amphoteric surfactant can be betaines amphoteric surfactant.
In presently filed embodiment, the betaines amphoteric surfactant can be selected from by dimethyl
Base glycine betaine, lauroylamidopropyl betaine, Cocoamidopropyl betaine, cocamidopropyl propyl amide hydroxyl sulphur glycine betaine, lauroyl
Amine propyl hydroxyl sulphur glycine betaine, oleamide propyl betaine, C11~C16 alkyl dimethylamine hydroxypropyl sulfobetaines composition
Group.
Optionally, the betaines amphoteric surfactant is dodecyl (C11) dimethylamine hydroxypropyl sulfobetaines
Alkali or myristyl (C14) dimethylamine hydroxypropyl sulfobetaines.
In presently filed embodiment, the polyethers nonionic surfactant can be selected from by the serial (octyl of OP
Phenol polyethenoxy ethers nonionic surfactant), NP (nonylphenol polyoxyethylene ether class nonionic surfactant) series, it is non-
The isomerous tridecanol class nonionic surfactant group of APEO (non-alkyl phenol polyoxyethylene ether class nonionic surfactant) class
At group.
In presently filed embodiment, the polyoxyethylene segment repetitive unit of the polyethers nonionic surfactant
Number can be 10~18.
Optionally, the polyoxyethylene segment number of repeat unit of the polyethers nonionic surfactant is 15~18.
In presently filed embodiment, the polymer dispersion powder composition can also include anti-aging agent, described anti-old
The additive amount of agent is 0.25~1% of the weight (BWOR) based on the polymer dispersion powder.
In presently filed embodiment, the anti-aging agent can be Hinered phenols anti-aging agent.
In presently filed embodiment, the anti-aging agent can be formed selected from single phenol anti-aging agent, Polyphenols anti-aging agent
Group.
In presently filed embodiment, the anti-aging agent can be the combination of single phenol anti-aging agent and Polyphenols anti-aging agent,
The weight ratio of single phenol anti-aging agent and Polyphenols anti-aging agent can be 1:4~4:1.
Optionally, the weight ratio of single phenol anti-aging agent and Polyphenols anti-aging agent is 1:1.
In presently filed embodiment, the anti-aging agent can be the anti-aging agent of emulsification form, such as Tiarco chemistry
The Octolite AO-50 of company.
Present invention also provides the stabilizers that one kind prevents polymer dispersion powder " demulsification ".
Stabilizer provided herein, including weight ratio be 1:4~4:1 amphoteric surfactant and polyethers it is non-from
Sub- surfactant.
Optionally, the weight ratio of the amphoteric surfactant and polyethers nonionic surfactant is 3:1~2:1.
In presently filed embodiment, the amphoteric surfactant is betaines amphoteric surfactant.
In presently filed embodiment, the betaines amphoteric surfactant can be selected from by dimethyl
Base glycine betaine, lauroylamidopropyl betaine, Cocoamidopropyl betaine, cocamidopropyl propyl amide hydroxyl sulphur glycine betaine, lauroyl
Amine propyl hydroxyl sulphur glycine betaine, oleamide propyl betaine, C11~C16 alkyl dimethylamine hydroxypropyl sulfobetaines composition
Group.
Optionally, the betaines amphoteric surfactant is dodecyl (C11) dimethylamine hydroxypropyl sulfobetaines
Alkali or myristyl (C14) dimethylamine hydroxypropyl sulfobetaines.
In presently filed embodiment, the polyethers nonionic surfactant can be selected from by the serial (octyl of OP
Phenol polyethenoxy ethers nonionic surfactant), NP (nonylphenol polyoxyethylene ether class nonionic surfactant) series, it is non-
The isomerous tridecanol class nonionic surfactant group of APEO (non-alkyl phenol polyoxyethylene ether class nonionic surfactant) class
At group.
In presently filed embodiment, the polyoxyethylene segment repetitive unit of the polyethers nonionic surfactant
Number can be 10~18.
Optionally, the polyoxyethylene segment number of repeat unit of the polyethers nonionic surfactant is 15~18.
Present invention also provides amphoteric surfactant or amphoteric surfactantes and polyethers nonionic surfactant
Purposes of the combination for preventing polymer dispersion powder to be demulsified in cement slurry.
In presently filed embodiment, the weight of the amphoteric surfactant and polyethers nonionic surfactant
Than that can be 1:4~4:1.
Optionally, the weight ratio of the amphoteric surfactant and polyethers nonionic surfactant is 3:1~2:1.
In presently filed embodiment, the amphoteric surfactant can be betaines amphoteric surfactant.
In presently filed embodiment, the betaines amphoteric surfactant can be selected from by dimethyl
Base glycine betaine, lauroylamidopropyl betaine, Cocoamidopropyl betaine, cocamidopropyl propyl amide hydroxyl sulphur glycine betaine, lauroyl
Amine propyl hydroxyl sulphur glycine betaine, oleamide propyl betaine, C11~C16 alkyl dimethylamine hydroxypropyl sulfobetaines composition
Group.
Optionally, the betaines amphoteric surfactant is dodecyl (C11) dimethylamine hydroxypropyl sulfobetaines
Alkali or myristyl (C14) dimethylamine hydroxypropyl sulfobetaines.
In presently filed embodiment, the polyethers nonionic surfactant can be selected from by the serial (octyl of OP
Phenol polyethenoxy ethers nonionic surfactant), NP (nonylphenol polyoxyethylene ether class nonionic surfactant) series, it is non-
The isomerous tridecanol class nonionic surfactant group of APEO (non-alkyl phenol polyoxyethylene ether class nonionic surfactant) class
At group.
In presently filed embodiment, the polyoxyethylene segment repetitive unit of the polyethers nonionic surfactant
Number can be 10~18.
Optionally, the polyoxyethylene segment number of repeat unit of the polyethers nonionic surfactant is 15~18.
In use, by the polymer dispersion powder composition of the application and oil-well cement, extra material, additive and fresh water (or
Seawater) slurry is carried out, the rubber powder mortar architecture for adapting to different well's conditions and performance requirement can be constructed.
In presently filed embodiment, additive amount of the polymer dispersion powder composition in rubber powder mortar architecture
It can be based on cement quality (By Weight Of Cement, BWOC) or to be based on blended cement quality (By Weight Of
Blend, BWOB) 1~10%.
The polymer dispersion powder composition of the application avoids and occurs in cement slurry by adding suitable stabilizer
" demulsification " phenomenon, and the stabilizer of the application selection is adaptable in rubber powder Behavior of Hardened Cement Paste system.In addition, in the prior art
In, seldom consider the long durability of latex or rubber powder modified Behavior of Hardened Cement Paste, and the polymer dispersion powder composition of the application passes through
Suitable anti-aging agent is added, Behavior of Hardened Cement Paste gradually aging in long-term maintenance processes can be prevented, make the dispersible latex of the application
Compound powder is more suitable for the subsurface environment of high temperature, high salinity, high corrosion.
Other features and advantage will illustrate in the following description, also, partly become from specification
It obtains it is clear that being understood and implementing the application.The purpose of the application and other advantages can be by specifications, right
Specifically noted structure is achieved and obtained in claim and attached drawing.
Detailed description of the invention
Attached drawing is used to provide to further understand technical scheme, and constitutes part of specification, with this
The embodiment of application is used to explain the technical solution of the application together, does not constitute the limitation to technical scheme.
Fig. 1 a is that thickening curve of the cement slurry for being 4 at 90 DEG C is numbered in table 2.
Fig. 1 b is that the cement slurry that number is 4 in table 2 tests the slurry condition of page in slurry cup in thickening.
Fig. 2 a is that thickening curve of the cement slurry for being 7 at 140 DEG C is numbered in table 2.
Fig. 2 b is that the cement slurry that number is 7 in table 2 tests the slurry condition of page in slurry cup in thickening.
Fig. 3 a is that thickening curve of the cement slurry for being 18 at 140 DEG C is numbered in table 2.
Fig. 3 b is that the cement slurry that number is 18 in table 2 tests the slurry condition of page in slurry cup in thickening.
Specific embodiment
For the purposes, technical schemes and advantages of the application are more clearly understood, below in conjunction with attached drawing to the application
Embodiment be described in detail.It should be noted that in the absence of conflict, in the embodiment and embodiment in the application
Feature can mutual any combination.
Manufacturer and the product type of used part material and reagent in embodiment, see table 1, other raw materials and
Reagent is unless otherwise instructed ordinary commercial products.
Table 1
Remarks: the effective concentration of some materials is the adjustment to commercial product concentration in table, hereby give notice that.
Embodiment 1
According to API specification, cement slurry is prepared according to the additional amount in table 2.Respectively at 90 DEG C and 140 DEG C of high temperature of low temperature,
Investigate the thickening situation of the mortar architecture constructed by different polymer dispersion powder compositions.As a result see table 2.
Wherein: the basic recipe of cement slurry at 90 DEG C are as follows: 100.0%API G+x%PSB150+4.0%G80L+1.0%
F45L+1.0%X60L+0.5%H21L+40.0% water, BWOC；
The basic recipe of cement slurry at 140 DEG C are as follows: 65.0%API G+35.0%B80S+x%PSB150+4.0%G80L+
1.5%F45L+1.0%X60L+1.5%H40L+39.0% water, BWOB.
Table 2
In thickening experiment, if when thickening curve, temperature control and normal pressure curve, it may be said that jelly powder stability is good,
There is no " demulsification " phenomenons.In general, thickening curve has following three types:
Such as the cement slurry that number is 4, thickening curve at 90 DEG C is shown in Fig. 1 a.This curve is characterized in very typical
" demulsification " phenomenon, show themselves in that slurry consistency is big, cement slurry loses flowability before cement is unhydrated.Cause this phenomenon
The reason of be that latex ion stability is poor, mutually assemble, occur " demulsification ", and make cement slurry consistency increase.It is tested taking out
On slurry page in slurry cup, it is seen that uncured cement slurry loses flowability completely, sees Fig. 1 b.Rubber powder particle occurs " broken
Cream ", cement slurry loses pumpability, is unable to satisfy needs of cementing operations.The feature of this thickening curve uses "×" table in table 1
Show.
Such as the cement slurry that number is 7, thickening curve at 140 DEG C is shown in Fig. 2 a.This curve is characterized in very typical
" cored " phenomenon.Specific manifestation are as follows: though consistency curve there may come a time when that normally, apparent waveform occurs in temperature control curve
Shape.On taking out the slurry page in experiment slurry cup, it is seen that the cement slurry not being fully cured has " cored " phenomenon, sees Fig. 2 b." packet
Core " causes slurry heat transfer uneven, makes multiviscosity meter temperature control curve that wave-like be presented." cored " is also showing for a kind of rubber powder " demulsification "
As can also cement slurry be made to thicken, influence cement slurry and normally pump.The feature of this thickening curve is indicated in table 1 with " ∥ ".
Such as the cement slurry that number is 18, thickening curve at 140 DEG C is shown in Fig. 3 a.This curve be characterized in temperature control and
Pressure curve is normal, cement consistency is small, " short transient time " is presented in thickening curve.On taking out the slurry page in experiment slurry cup,
It can be seen that the cement slurry not being fully cured is homogeneous, Fig. 3 b is seen.This illustrates rubber powder particle, and there is no " demulsifications ".This thickening
The feature of curve is indicated in table 1 with " √ ".
From table 2 it can be seen that the polymer dispersion powder composition of the embodiment of the present application by select suitable stabilizer and
Its additive amount can be effectively prevented rubber powder particle and " demulsification " occur in a low temperature of such as 90 DEG C, or even at a high temperature of 140 DEG C
With, also there is no " demulsification " phenomenon, it is normal to be thickened curve in seawater prepared bentonite drilling fluid.And stabilizer described in the prior art, match in seawater
When under slurry or high temperature, it is thickened curve abnormality, this abnormal phenomenon is related to rubber powder particle " demulsification ".
As can be seen from Table 2, when using amphoteric surfactant, or by amphoteric surfactant and polyethers nonionic table
The combination of face activating agent is as stabilizer, and its effective additive amount (=additive amount × stabilizer effective concentration) is based on can
When 0.9-1.8% (BWOR) of the weight of dispersed latex powder, the generation for the phenomenon that can effectively prevent " being demulsified ".
Embodiment 2
In the mortar architecture by different polymer dispersion powder composition buildings, stabilizer is investigated in mortar architecture
In applicability.As a result see table 3.
Table 3
As can be seen from Table 3, in the mortar architecture by different polymer dispersion powder composition buildings, at 90 DEG C and
At 140 DEG C, thickening time and retarder show good linear dependence, and strength development is good for 24 hours, illustrate that the application is implemented
The stabilizer of example is adaptable in rubber powder Behavior of Hardened Cement Paste system.
Embodiment 3
With reference to GB/T23445 " polymer cement waterproof paint " standard, aging 7 days at 80 DEG C are investigated anti-by not adding
The ageing-resistant situation for the film that old agent and the polymer dispersion powder composition for being added to anti-aging agent are formed.As a result see table 4.
Class coating material forms substantially when test: 43%API G+22%B80S+20% water+5%PSB150.Wherein, number 1
Further include the stabilizer (LHSB+NP:20+10) of 30%BWOR in formula, further includes the stabilizer of 30%BWOR in the formula of number 2
(LHSB+NP:20+10) and the BHT of 0.5%BWOR.
Table 4
From table 4, it can be seen that formed by the class coating material for the polymer dispersion powder composition building for not adding anti-aging agent
Film is tried, after aging, tensile strength increases, but elongation at break is obviously reduced, and stretch modulus obviously increases, this illustrates to try film warp
Become fragile after aging；The examination film that the class coating material that polymer dispersion powder composition by being added to anti-aging agent constructs is formed, after aging,
Its elongation at break is not substantially reduced, and stretch modulus is not also significantly increased, and what this illustrated the application includes anti-aging agent
Polymer dispersion powder composition have the advantages that it is anti-aging.
Embodiment 4
Cement slurry is prepared according to API specification, and after being conserved 2 months at 90 DEG C, produces diameter and is 50mm, is highly
The cylindrical body of 100mm, with reference to ASTM C469 " concrete static modulus and Poisson's ratio measure standard ", investigation is divided by different
Dissipate the Mechanical Behavior of Hardened Cement Paste of the mortar architecture of latex compound powder building.As a result see table 5.
Wherein, the basic recipe of cement slurry are as follows: 100.0%API G+x%PSB150+4%G80L+1%F45L+1.0%
X60L+40.5% fresh water, BWOC；Stabilizer and anti-aging agent additional amount are shown in Table 5.
Table 5
As can be seen from Table 5, when the additive amount of polymer dispersion powder is identical, the polymer dispersion powder combination containing anti-aging agent
The Behavior of Hardened Cement Paste modulus of the mortar architecture of object building, the cement slurry constructed compared to the polymer dispersion powder composition without anti-aging agent
The Behavior of Hardened Cement Paste modulus of system wants low, and Poisson's ratio is big.The reason of causing this phenomenon is: anti-aging agent can prevent Behavior of Hardened Cement Paste in length
Gradually aging in phase maintenance processes, the Behavior of Hardened Cement Paste that the mortar architecture for constructing polymer dispersion powder composition is formed still are able to maintain
Malleable.
Although embodiment disclosed by the application is as above, the content only for ease of understanding the application and use
Embodiment is not limited to the application.Technical staff in any the application fields, is taken off not departing from the application
Under the premise of the spirit and scope of dew, any modification and variation, but the application can be carried out in the form and details of implementation
Scope of patent protection, still should be subject to the scope of the claims as defined in the appended claims.
Claims (11)
1. a kind of polymer dispersion powder composition, the polymer dispersion powder composition includes polymer dispersion powder and stabilizer,
The additive amount of the stabilizer is 0.9~1.8% of the weight based on the polymer dispersion powder, and the stabilizer is both sexes table
The combination of face activating agent or amphoteric surfactant and polyethers nonionic surfactant, the amphoteric surfactant are sweet tea
Dish bases amphoteric surfactant, the polyethers nonionic surfactant are selected from serial by OP, serial, the non-APEO class of NP
The group of isomerous tridecanol class nonionic surfactant composition.
2. polymer dispersion powder composition according to claim 1, wherein the amphoteric surfactant and polyethers are non-
The weight ratio of ionic surface active agent is 1:4~4:1.
3. polymer dispersion powder composition according to claim 2, wherein the amphoteric surfactant and polyethers are non-
The weight ratio of ionic surface active agent is 3:1~2:1.
4. polymer dispersion powder composition according to claim 1, wherein the betaines amphoteric surfactant choosing
Free dodecyldimethylammonium hydroxide inner salt, lauroylamidopropyl betaine, Cocoamidopropyl betaine, cocamidopropyl propyl amide hydroxyl
Sulphur glycine betaine, dodecanamide propyl hydroxyl sulphur glycine betaine, oleamide propyl betaine, C11~C16 alkyl dimethylamine hydroxypropyl
The group of sulfobetaines composition.
5. polymer dispersion powder composition according to claim 4, wherein the betaines amphoteric surfactant is
Domiphen hydroxypropyl sulfobetaines or myristyl hydroxyl sulphur glycine betaine.
6. polymer dispersion powder composition according to claim 1, wherein the polyethers nonionic surfactant
Polyoxyethylene segment number of repeat unit is 10~18.
7. polymer dispersion powder composition according to claim 6, wherein the polyethers nonionic surfactant
Polyoxyethylene segment number of repeat unit is 15~18.
8. polymer dispersion powder composition according to any one of claim 1-3, further includes anti-aging agent, the anti-aging agent
Additive amount be the weight based on the polymer dispersion powder 0.25~1%.
9. polymer dispersion powder composition according to claim 8, wherein the anti-aging agent is Hinered phenols anti-aging agent,
The anti-aging agent is the anti-aging agent of emulsification form.
10. the combination of amphoteric surfactant or amphoteric surfactant and polyethers nonionic surfactant is for prevent can
The purposes that dispersed latex powder is demulsified in cement slurry, the amphoteric surfactant are betaines amophoteric surface active
Agent, the polyethers nonionic surfactant are selected from by the isomerous tridecanol class nonionic of OP series, NP series, non-APEO class
The group of surfactant composition.
11. purposes according to claim 10, wherein the amphoteric surfactant and polyethers non-ionic surface active
The weight ratio of agent is 1:4~4:1.
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| CN102504788A (en) * | 2011-10-25 | 2012-06-20 | 中国石油天然气股份有限公司 | Foaming agent suitable for oil-field development |
| CN103694975A (en) * | 2013-12-31 | 2014-04-02 | 中国海洋石油总公司 | Cement paste stabilizer and preparation method thereof |
| CN103834374A (en) * | 2014-03-25 | 2014-06-04 | 天津宁赛科技有限公司 | Multiple-effect latex anti-gas migration agent for deep well cementing in oil field and preparation method thereof |
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