CN106565126A - Polymer latex solidification adjustive agent used for oil absorption expansion of cement base material - Google Patents
Polymer latex solidification adjustive agent used for oil absorption expansion of cement base material Download PDFInfo
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- CN106565126A CN106565126A CN201510651400.3A CN201510651400A CN106565126A CN 106565126 A CN106565126 A CN 106565126A CN 201510651400 A CN201510651400 A CN 201510651400A CN 106565126 A CN106565126 A CN 106565126A
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Abstract
The invention discloses a polymer latex solidification adjustive agent used for oil absorption expansion of a cement base material, and the polymer latex solidification adjustive agent includes 46-76 parts by weight of a hydroxy carboxylic acid component and 10-24 parts by weight of an organic alcohol amine component. The polymer latex solidification adjustive agent can effectively solve the problem of serious influence on rheological properties and thickening performance of cement slurry due to gelation and strong delayed coagulation phenomenon of polymer latex cement slurry caused by polymer latex effect at high temperature. The present invention also provides a combination additive used for the oil absorption expansion of the cement base material and cement base material slurry used for the oil absorption expansion of the cement base material and a preparation method and application thereof.
Description
Technical field
The present invention relates to petroleum exploration field, and in particular to a kind of polymerization for cement-based material oil suction expansion
Thing latex adjustable solidification agent, and for the combined additive of cement-based material oil suction expansion, further relate to for cement base
The cement-based material slurries and its compound method of material oil suction expansion.
Background technology
With domestic oil-gas exploration work deepen continuously, cement sheath Inter-zonal packing failure and cement sheath damage to
The long-term Efficient Development of safety of Oil/gas Well brings greatly challenge.The annular space problem energy with pressure that oil gas channelling is caused
Shorten the life-span of Oil/gas Well, need high cost of remedying, and need longer make-up time, and success rate
It is low.By adding a kind of special aqueous high molecular oil suction expanded polymer latex in cement, necessarily to mix
Amount is added in oil well cement paste, is played raising petrifying water mudstone toughness, is reduced cracking risk, improves Behavior of Hardened Cement Paste
Impermeability and durability effect；Simultaneously when cement eyelet thimble cracking causes hydrocarbon seepage, mixed with the polymerization
There is larger oil suction expansion in the Behavior of Hardened Cement Paste of thing latex, in the case where cement sheath is subject to the constraintss such as the borehole wall, make crack
Healing, plays a part of to block petro-gas permeation.
But the polymer emulsion of oil suction expansion is a kind of dispersed metastable state system in the solution of emulsified particles,
Being disturbed by polar ion, violent mechanical agitation or during larger temperature change, will breaking stable
Structure and breakdown of emulsion, emulsion particle is mutually assembled, and causes flocculation.In emulsion cement mortar, cement belongs in itself height
Scattered dry powder-shaped material, there is extremely strong water imbibition, when emulsion plus fashionable, can quickly absorb the moisture in emulsion,
Emulsion is promoted to solidify, the Ca in cement mortar2+And Al3+Deng in polyvalent cation and other cement additives
Polar functional group, can to the chemical stability of emulsion rise destruction.Simultaneously because the polymer of oil suction expansion
Latex is mostly the emulsion being polymerized with styrene monomer by copolymerization long-chain acrylic acid, acrylic ester monomer,
When higher using temperature, the esters of acrylic acid in polymer emulsion will be decomposed in the basic conditions, be led
Cause cement mortar that gelling and strong retardation phenomenon occur, have a strong impact on the rheological property and thickening performance of cement mortar.Water
The livering time is an important parameter for controlling cementing job, is related to the quality of construction quality, is to make
The key of industry success or failure.Polymer latex systems are made to have preferably scene value, it is necessary to emulsion is adapted to not
Same working condition requirement.But the condensation effect that at present adjustable solidification agent based on suction-operated is starched stage polymer latex cement
Fruit improves unobvious.Need a kind of suitable adjustable solidification agent badly, come regulation system thickening time and rheological behavior with
Meet indoor and site operation to require, realize the well cementation effect that oil suction expands.
The content of the invention
For solve prior art in can oil suction expansion stage polymer latex cement slurry be gelled in higher temperature
With the problem of strong slow setting, the construction requirement under different condition is met, the invention provides a kind of swollen for oil suction
The polymer emulsion adjustable solidification agent of swollen cement-based material, it can significantly avoid going out in stage polymer latex cement is starched
Existing gelling retardation phenomenon.
Present invention also offers a kind of combined additive for cement-based material oil suction expansion.
Further, present invention also offers a kind of cement-based material slurries for cement-based material oil suction expansion
And its compound method.
According to the present invention, there is provided a kind of polymer emulsion adjustable solidification agent for cement-based material oil suction expansion, bag
Include the hydroxycarboxylic acid component of 46-76 weight portions and the Organic Alcohol amine component of 10-24 weight portions.
In a preferred embodiment of the invention, the adjustable solidification agent includes the hydroxycarboxylic acid group of 51-69 weight portions
Divide the Organic Alcohol amine component with 11-19 weight portions.It is also preferred that the adjustable solidification agent includes 55-60 weight
The hydroxycarboxylic acid component of part and the Organic Alcohol amine component of 13-16 weight portions.
In some specific embodiments, the polymer emulsion adjustable solidification agent that the present invention is provided is including weight ratio
(1.9-13)：1 hydroxycarboxylic acid component and Organic Alcohol amine component.Preferably, the hydroxycarboxylic acid group
Divide and the weight ratio of Organic Alcohol amine component is (2.6-9.9)：1, more preferably (3.1-5.9)：1.
According to the present invention, hydroxycarboxylic acid component preferably include lactic acid, hydroxybutyric acid, salicylic acid, gluconic acid,
In one or more in tartaric acid, citric acid and its salt, preferably gluconic acid, tartaric acid and citric acid
One or more.
According to the present invention, Organic Alcohol amine component preferably includes triisopropanolamine, dimethylethanolamine, diethanol
One or more in amine and triethanolamine, further preferably including diethanol amine and/or triethanolamine.
According to the present invention, the cement-based material can be cement material commonly used in the art, for example, G levels oil
Well cement etc..
The invention provides a kind of combined additive for cement-based material oil suction expansion, including esters of acrylic acid
Polymer emulsion and the polymerization for being used for cement-based material oil suction expansion as above provided according to the present invention
Thing latex adjustable solidification agent.
Preferably, the polymer emulsion and the weight ratio of adjustable solidification agent are 100：(1-9), also preferably 100：(2-8),
More preferably 100：(2-5).
It is not particularly limited suitable for the acrylic polymer latex of the present invention, existing or city can be selected from
Any one the acrylic polymer latex sold, or the esters of acrylic acid prepared by existing method
Polymer emulsion.
In a preferred embodiment of the invention, the polymerized monomer of the acrylic polymer latex includes third
Alkene acrylic monomer, acrylic ester monomer and styrene monomer.Preferably, the acrylic polymer glue
The mol ratio of acrylic monomer units, methacrylate-based monomer unit and styrenic monomer units in breast
For (1-12):(31-120):115, preferably (5-8):(58-98):115.
The acrylic monomer is selected from methacrylic acid, ethylacrylic acid, propylacrylate, butyl third
Olefin(e) acid and acrylic acid etc..
The acrylic ester monomer is selected from butyl methacrylate, methacrylic acid cetyl ester, first
Base Hexyl 2-propenoate and hydroxyethyl methacrylate etc..
Acrylic polymer latex used in the present invention can be by such as patent application CN104177555A
Disclosed polymer emulsion preparation method is preparing；The entire disclosure of which is incorporated by reference into herein
In.Acrylic polymer latex used in the present invention can also be by other known suitable acrylic acid
Preparing, preferred polymeric monomer includes acrylic monomer, esters of acrylic acid to esters polymer latex preparation method
Monomer and styrene monomer.
Preferably, the combined additive is included acrylic polymer latex and adjustable solidification agent are using front
It is separate, i.e., mutually do not premix；When in use, it is respectively added in cement-based material.
Without being bound by theoryly, it is believed that mainly led to according to the hydroxycarboxylic acid component in the adjustable solidification agent that the present invention is provided
Cross and be engaged with acrylate component, improve tricalcium silicate (3CaOSiO in water2, C3S) and high dispersive system
Kinetic stability, starched stage polymer latex cement the effect of preferable High Temperature Disperse；While hydroxycarboxylic acid polarity
It is solidifying that molecule promotes the nucleation coagulation of aluminium glue to promote tricalcium aluminate, and esters of acrylic acid is in alkalescence when effectively inhibiting high temperature
Under the conditions of decomposed and caused cement mortar occur gelling and strong slow setting problem.Organic alcohol amine can promote aluminium
The aquation of sour DFP (C3A), improves the early strength of stage polymer latex cement, further cooperates with hydroxycarboxylic acid
Component, and increase later stage gel strength rapidly.
On the other hand, the invention provides it is a kind of for cement-based material oil suction expansion cement-based material slurries,
The slurries are comprising cement-based material, acrylic polymer latex, according to the as described above of present invention offer
Adjustable solidification agent and water, or comprising cement-based material, according to the present invention provide additive combined as described above and
Water.
Preferably, in the slurries, the cement-based material, acrylic polymer latex and adjustable solidification agent
Weight ratio be 100：(2-10)：(0.05-4.5), preferably 100：(3.0-5.5)：(0.1-2.4).
In other preferred embodiment, the hydroxycarboxylic acid constituent content of the adjustable solidification agent is based on cement matrix
Material is calculated as 0.05-3.5wt%, preferably 0.07-2.1wt%.The scope is i.e. equivalent to the hydroxycarboxylic acid component
Volume in cement-based material.
Preferably, the content of the Organic Alcohol amine component is calculated as 0.05-1.45wt% based on cement-based material content,
Preferably 0.1-0.9wt%, further preferably 0.1-0.5wt%.The scope exists equivalent to the Organic Alcohol amine component
Volume in cement-based material.
Another further aspect, present invention also offers a kind of compound method of slurries as described above, is included in cement matrix
Addition acrylic polymer latex, the adjustable solidification agent as described above provided according to the present invention and water in material, or
Person is included in cement-based material the additive combined as described above and water for adding the present invention to provide.
In a specific embodiment, methods described includes：The polymer emulsion and adjustable solidification agent are added into water
Middle mixing, then adds the cement-based material and continues to mix.
Preferably, the acrylic polymer latex can by acrylic monomer, acrylic ester monomer and
The mol ratio of styrene monomer is (1-12):(31-120):115, preferably (5-8):(58-98):115
Polymerized monomer prepare.
In addition, the present invention still further provides adjustable solidification agent as described above, the combination addition provided according to the present invention
The application of agent or cement-based material slurries in oil exploration cementing operation.
The use temperature of the cement-based material includes 70 DEG C of -130 DEG C of stages, preferably includes 75 DEG C of -120 DEG C of stages,
It is more excellent including 85-100 DEG C of stage, such as 90 DEG C stages.
It is therefore preferable that the temperature of above-mentioned application is 70 DEG C -130 DEG C, further preferably 75 DEG C -120 DEG C.It is i.e. described to adjust solidifying
The application temperature of agent, combined additive or cement-based material slurries is 70 DEG C -130 DEG C, further preferably
75℃-120℃。
The technique effect of technical solution of the present invention includes：
The adjustable solidification agent that the present invention is provided can solve the cement mortar thickening that polymer emulsion occurs in high temperature and strong
The problem of slow setting, by the composition and dosage that control adjustable solidification agent, not only can adjust cement and deposit in emulsion components
Hydration process under, makes the high temperature thickening time adjustable, and can unexpectedly improve stage polymer latex cement slurry
Decentralization and dynamic stability, improve high temperature rheology, suppress acrylate component high temperature or alkaline decomposition
The cement cementitious slow setting defect brought；Behavior of Hardened Cement Paste early strength can also be improved simultaneously, solve latex-cement slurry glue
Solidifying strength development morning, later strength develops slow problem.The combined additive product that the present invention is provided can be by just
Promptly using realizing the effect above.Additionally, the cement-based material slurries provided using the present invention can be solved effectively
Certainly can the stage polymer latex cement of oil suction expansion starch the problem that gelling and strong slow setting occur in higher temperature, it is full
Construction requirement under sufficient different condition.
Description of the drawings
Accompanying drawing provided by the present invention is that but the scope of the present invention is not in order to be illustrated more clearly that the thought of the present invention
It is limited.
Fig. 1 is the stage polymer latex cement slurry thickening curve synoptic diagram that comparative example 1 is not added with adjustable solidification agent of the present invention.
Fig. 2 is the stage polymer latex cement slurry that comparative example 2 only adds hydroxycarboxylic acid component in adjustable solidification agent of the present invention
Thickening curve synoptic diagram.
Fig. 3 is the stage polymer latex cement slurry thickening that the adjustable solidification agent provided according to the present invention is with the addition of in embodiment 3
Curve synoptic diagram.
Specific embodiment
With reference to embodiment, invention is described in further detail.It is not intended that above-mentioned master of the invention
The scope of topic is only limitted to following examples, and all technologies realized based on present invention belong to the model of the present invention
Enclose.
The unaccounted preparation process of institute and condition are according to API oil-well cements and MAT'L specification or existing in the present invention
There is technology to be implemented.
Embodiment 1
64g acrylic polymer latex (its polymerized monomer methacrylic acid, first are added in 286g water
Base butyl acrylate, methacrylic acid cetyl ester and cinnamic mol ratio are 6:48:12:115)、2.4g
Citric acid, diethanol amine 0.8g, stir, and G level oil-well cement 800g are added thereto, and at the uniform velocity stir
Uniformly, stage polymer latex cement slurry is obtained.
Embodiment 2
Its polymerized monomer (its polymerized monomer propylene of addition 80g acrylic polymers latex in 270g water
Acid, hexyl methacrylate and cinnamic mol ratio are 5:92:115), 4g tartaric acid, triethanolamine 1.2g,
Stir, G level oil-well cement 800g are added thereto, at the uniform velocity stir, obtain stage polymer latex cement
Slurry.
Embodiment 3
80g acrylic polymer latex (its polymerized monomer methacrylic acid, first are added in 270g water
Base butyl acrylate, methacrylic acid cetyl ester and cinnamic mol ratio are 6:67:19:115)、4.8g
Gluconic acid, triethanolamine 1.6g, stir, and G level oil-well cement 800g are added thereto, and at the uniform velocity stir
Mix uniform, obtain stage polymer latex cement slurry.
Embodiment 4
44g acrylic polymer latex (its polymerized monomer acrylic acid, methyl-prop are added in 270g water
Olefin(e) acid butyl ester, cinnamic mol ratio are 8:48:115), 16.4g gluconic acids, triethanolamine 2.8g, stirring
Uniformly, G level oil-well cement 800g are added thereto, are at the uniform velocity stirred, obtain stage polymer latex cement slurry.
Embodiment 5
32g acrylic polymer latex (its methacrylic acid, methacrylic acid are added in 270g water
Butyl ester, methacrylic acid cetyl ester and cinnamic mol ratio are 5:58:20:115), 8.1g gluconic acids,
Triethanolamine 1.9g, stirs, and G level oil-well cement 800g are added thereto, and at the uniform velocity stirs, and obtains
Stage polymer latex cement is starched.
Embodiment 6
24g acrylic polymer latex (its methacrylic acid, methacrylic acid are added in 270g water
Butyl ester and cinnamic mol ratio are 7:92:115), 0.6g lactic acid, dimethylethanolamine 0.2g, stir,
G level oil-well cement 800g are added thereto, are at the uniform velocity stirred, obtain stage polymer latex cement slurry.
Comparative example 1
G level oil-well cements 800g is added in 270g water and stirs and evenly mixs to obtain cement mortar；By 80g acrylate
Birds of the same feather flock together compound latex (its methacrylic acid, butyl methacrylate, methacrylic acid cetyl ester and benzene second
The mol ratio of alkene is 6:67:19:115) at the uniform velocity add in cement mortar, at the uniform velocity stir, obtain polymer latex whey
Mud.
Comparative example 2
Add stirring and dissolving in 270g water uniform G level oil-well cements 800g；It is subsequently adding 80g acrylic acid
Esters polymer latex (its methacrylic acid, butyl methacrylate, methacrylic acid cetyl ester and benzene
The mol ratio of ethene is 6:67:19:115), uniform stirring, at the same time at the uniform velocity adds water by 4.8g gluconic acids
In mud, at the uniform velocity stir, obtain stage polymer latex cement slurry.
Stage polymer latex cement slurry rheology, thickening performance test
Comparative example 1,2 and embodiment 1-3 are prepared into resulting polymers latex-cement slurry, using six fast rotary viscosities
Meter carries out rheological characteristic detection.
Testing conditions：By obtained cement mortar respectively in normal pressure multiviscosity meter carrying out under 90 DEG C of temperature conditionss
20min is conserved, then with six fast its 600rpm/min (being expressed as Ф 600) of rotary viscosity measuring,
Reading under 300rpm/min, 200rpm/min, 100rpm/min, 6rpm/min, 3rpm/min.As a result such as
Shown in table 1.
The stage polymer latex cement of table 1 starches rheological property
As it can be seen from table 1 the stage polymer latex cement of comparative example 1 slurry is not plus before adjustable solidification agent, 90 DEG C of slurry is supported
After shield 20min, cement mortar retrogradation, the both greater than full amount of six fast rotation viscometer Ф 600, Ф 300, the readings of Ф 200
The reading of journey 300, cement mortar fluidity of slurry is poor, and 24h Behavior of Hardened Cement Paste is not hard, and state of cure is low, without intensity.
The stage polymer latex cement of comparative example 2 is starched, and after adding hydroxycarboxylic acid component, stage polymer latex cement starches six fast readings
Number decreases, and cement paste rheological makes moderate progress, but 24h does not have intensity.By contrast, add according to this
Ф 600, the Ф 300 and Ф 200 of the stage polymer latex cement of the embodiment 1,2 and 3 after the adjustable solidification agent that invention is provided
Reading is greatly reduced, and 24h Behavior of Hardened Cement Paste hardening, completion of cure, intensity is more than 14MPa.And addition different component
The stage polymer latex cement slurry that the adjustable solidification agent of ratio and dosage is obtained, when producing different rheological behaviors and thickening
Between.
Thickening test (ginseng is carried out to comparative example 1, comparative example 2 and the resulting polymers latex-cement slurry of embodiment 3
According to GB1939-2012 oil-well cement test methods), as a result distinguish thickening curve as shown in Figure 1, Figure 2 and Figure 3
It is shown.△, and ◇ respectively illustrate denseness, the pressure and temperature of stage polymer latex cement slurry with thickening in figure
The change curve of time.
Being thickened curve and can be seen that from Fig. 1 does not add the stage polymer latex cement slurry denseness fluctuation of adjustable solidification agent larger,
And over time, temperature increase, consistency change becomes apparent from, and cement mortar is in persistently gelatinized, is not possessed
Pumpability, it is impossible in being applied to cementing operation.
In the stage polymer latex cement of Fig. 2, after adding hydroxycarboxylic acid component, thickening curve fluctuation improves, but
Thickening setting time is long, and transit time is long from 20BC to 50BC for curve, more than 30min, 240min rear thicks
Degree is just significantly increased but fluctuates substantially, and denseness increases to be tended towards stability after 24BC to 265min, until connecing
Just there is obvious flex point at nearly 300min.
From Fig. 3 be thickened curve can be seen that add the present invention provide adjustable solidification agent after, cement mortar 103 DEG C,
There is good mobility within 144min, after reaching 150min, denseness increases sharply, from 20BC to 50BC
Transit time short only 5min, flex point projects rectangular.Demonstrate by adding adjustable solidification agent of the present invention, Ke Yiyou
Effect improves the decentralization and dynamic stability of stage polymer latex cement slurry, improves high temperature rheology, suppresses propylene
The cement cementitious slow setting defect that esters of gallic acid component high temperature or alkaline decomposition bring.
Finally it should be noted that：The preferred embodiments of the present invention are the foregoing is only, this is not limited to
Invention, although being described in detail to the present invention with reference to the foregoing embodiments, for the ordinary skill of this area
For personnel, it still can modify to the technical scheme described in foregoing embodiments, or to wherein
Some technical characteristics carry out equivalent.All any modifications within the spirit and principles in the present invention, made,
Equivalent, improvement etc., should be included within the scope of the present invention.
Claims (11)
1. a kind of polymer emulsion adjustable solidification agent for cement-based material oil suction expansion, including 46-76 weight portions
The Organic Alcohol amine component of hydroxycarboxylic acid component and 10-24 weight portions.
2. adjustable solidification agent according to claim 1, it is characterised in that the hydroxycarboxylic acid in the adjustable solidification agent
Component is (2.6-9.9) with the weight ratio of Organic Alcohol amine component：1, preferably (3.1-5.9)：1.
3. adjustable solidification agent according to claim 1 and 2, it is characterised in that the hydroxycarboxylic acid component bag
One or more in lactic acid, hydroxybutyric acid, salicylic acid, gluconic acid, tartaric acid, citric acid and its salt is included,
One or more preferably in gluconic acid, tartaric acid and citric acid；And/or
The Organic Alcohol amine component includes triisopropanolamine, dimethylethanolamine, diethanol amine and triethanolamine
In one or more, preferably diethanol amine and/or triethanolamine.
4. a kind of combined additive for expanding cement-based material oil suction, including acrylic polymer glue
Breast and the adjustable solidification agent as any one of claim 1-3；Preferably, the polymer emulsion and adjustable solidification agent
Weight ratio be 100：(1-9), preferably 100：(2-8), also preferably 100：(2-5).
5. combined additive according to claim 4, it is characterised in that the acrylic polymer
The polymerized monomer of latex includes acrylic monomer, acrylic ester monomer and styrene monomer；Preferably, institute
State acrylic monomer units in acrylic polymer latex, acrylic ester monomer unit and styrene
The mol ratio of monomeric unit is (1-12):(31-120):115, preferably (5-8):(58-98):115.
6. it is a kind of for cement-based material oil suction expansion cement-based material slurries, the slurries include cement matrix
Material, acrylic polymer latex, the adjustable solidification agent as any one of claim 1-3 and water, or
Person includes cement-based material, the combined additive as described in claim 4 or 5 and water.
7. slurries according to claim 6, it is characterised in that in the slurries, the cement matrix
The weight ratio of material, acrylic polymer latex and adjustable solidification agent is 100：(2-10)：(0.05-4.5),
It is preferred that 100：(3.0-5.5)：(0.1-2.4).
8. slurries according to claim 6, it is characterised in that in the slurries, the adjustable solidification agent
Hydroxycarboxylic acid constituent content 0.05-3.5wt%, preferably 0.07-2.1wt% are calculated as based on cement-based material；
And/or
The content of the Organic Alcohol amine component is calculated as 0.05-1.45wt% based on cement-based material content, preferably
0.1-0.9wt%, further preferably 0.1-0.5wt%.
9. slurries according to any one of claim 6-8, it is characterised in that include in the slurries
The polymerized monomer of acrylic polymer latex includes acrylic monomer, acrylic ester monomer and styrene
Monomer；Preferably, the mol ratio of the acrylic monomer, acrylic ester monomer and the styrene monomer that are used
For (1-12):(31-120):115, preferably (5-8):(58-98):115.
10. a kind of compound method of the slurries according to any one of claim 6-9, methods described includes
Acrylic polymer latex, the tune as any one of claim 1-3 are added in cement-based material
Solidifying agent and water, or the combined additive added as described in claim 4 or 5 is included in cement-based material
And water；Preferably, first the polymer emulsion and adjustable solidification agent be added to the water into mixing, then add the cement
Sill continues to mix.
11. adjustable solidification agents according to any one of claim 1-3 or according to claim 4 or 5
Combined additive or the cement-based material slurries according to any one of claim 6-9 in oil exploration
Application in cementing operation；It is preferred that the temperature applied is 70 DEG C -130 DEG C, further preferably 75 DEG C -120 DEG C.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102031097A (en) * | 2009-09-29 | 2011-04-27 | 中国石油集团西部钻探工程有限公司克拉玛依钻井工艺研究院 | Method for enhancing oil well cement slurry |
| CN104177555A (en) * | 2014-08-18 | 2014-12-03 | 清华大学 | Polymer latex for cement-base material oil absorption and expansion and preparation method thereof |
| CN104261749A (en) * | 2014-08-27 | 2015-01-07 | 清华大学 | Cement based material with strong expanding performance and applications thereof |
| CN104418965A (en) * | 2013-08-27 | 2015-03-18 | 中国石油化工股份有限公司 | Preparation method of self-healing agent for oil well cement, well cementation self-healing cement slurry and application |
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2015
- 2015-10-10 CN CN201510651400.3A patent/CN106565126B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102031097A (en) * | 2009-09-29 | 2011-04-27 | 中国石油集团西部钻探工程有限公司克拉玛依钻井工艺研究院 | Method for enhancing oil well cement slurry |
| CN104418965A (en) * | 2013-08-27 | 2015-03-18 | 中国石油化工股份有限公司 | Preparation method of self-healing agent for oil well cement, well cementation self-healing cement slurry and application |
| CN104177555A (en) * | 2014-08-18 | 2014-12-03 | 清华大学 | Polymer latex for cement-base material oil absorption and expansion and preparation method thereof |
| CN104261749A (en) * | 2014-08-27 | 2015-01-07 | 清华大学 | Cement based material with strong expanding performance and applications thereof |
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