CN1370788A - Copolymer latex for reinforcing oil well and its prepn - Google Patents
Copolymer latex for reinforcing oil well and its prepn Download PDFInfo
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- CN1370788A CN1370788A CN 01108322 CN01108322A CN1370788A CN 1370788 A CN1370788 A CN 1370788A CN 01108322 CN01108322 CN 01108322 CN 01108322 A CN01108322 A CN 01108322A CN 1370788 A CN1370788 A CN 1370788A
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Abstract
The present invention relates to a copolymer latex with excellent performance for well cementation and its production process. The disperse phase of the latex is polymer particle in core-shell structure comprising core copolymer region and shell copolymer region. The monomers for copolymer in the core copolymer region include mono vinyl aromatic compound, unsaturated carboxylic acid and sulfonate; and those for copolymer in the shell copolymer region include conjugated diene, monovinyl aromatic compound, unsaturated carboxylic acid and sulfonate.
Description
The present invention relates to copolymer latex for reinforcing oil well and preparation method thereof.This latex has excellent chemical stability and mechanical stability in cementing concrete, can significantly improve cementing quality, separates out, improves the ultimate compression strength of cement stone etc. as the fluid loss that reduces grout, the free-water that reduces grout.
Along with the progress of petroleum exploration and development, formation condition is complicated day by day, adopts the neat slurry well cementation can't adapt to and handle complicated well cementation condition.Therefore, the researcher in this field has done a large amount of work, reaches the performance of improving cementing concrete, the purpose that prolongs the oil well life-span by the mode of adding admixture or extra material in cement.
Adopting polymkeric substance is very general in oil exploration and development fields as the additive of cementing concrete.For example, be seen in the polymkeric substance of the additive that can be used as cementing concrete of document and have: polyvinyl acetate (PVA), Natvosol, acrylamide polymer, styrene-butadiene latex etc.Yet, owing to these polymkeric substance have respectively processing temperature require too harsh, as to make grout plastic viscosity rise excessive, be easy to hydrolysis, self coagulate defective such as wadding its application is very restricted.
According to the record of document, overcome one of the method for the defective of latex, be in the latex cement composite formula, to add one or more latex stabilizers or tensio-active agent.For example, United States Patent (USP) 4,537,918 have introduced a kind of latex cement composition.This latex cement composition contains styrene-butadiene latex, and (weight ratio of vinylbenzene and divinyl is 70-30%: 30-70%), also contain a kind of specific anionic polyelectrolyte type stablizer (as melamino-formaldehyde resin of sulfonic acid or sulfurous acid modification etc.).The document points out that adding stablizer is the key that realizes the goal of the invention of this invention.United States Patent (USP) 5,258,072 and 5,401,786 have introduced several latex cement composite formulas.This latex cement composition contains styrene-butadiene latex (weight ratio of vinylbenzene and divinyl is 2: 1), also contain a kind of alkylphenol polyoxyethylene ethers nonionic surface active agent, keep the stability of styrene-butadiene latex in cement with another nonionic surface active agent (four senses ethylene oxide/propylene oxide-quadrol segmented copolymer, or acrylate homopolymer).Yet, add stablizer and specific tensio-active agent and make execute-in-place complicated, and strengthened cost.This is a significant deficiency of improving this method of latex cement composition properties with the mode of adding specific stablizer and tensio-active agent.
Based on this background, the present invention is devoted to a kind of improved well cementation copolymer emulsion and its production and use.This latex just can have excellent mechanical stability and chemical stability without stablizer in cement, and can significantly improve cementing quality.
The present invention also is devoted to provide a kind of latex cement paste composition superperformance, that can not contain stablizer that has.
The present invention relates to a kind of improved well cementation copolymer emulsion.Disperse phase-the polymer particle of this latex has nuclear-shell structure, and this structure contains nuclear multipolymer district and shell multipolymer district, wherein:
(1) comonomer in nuclear multipolymer district comprises:
(a) single-ethenyl aromatic compound,
(b) unsaturated carboxylic acid and
(c) sulfonate;
(2) comonomer in shell multipolymer district comprises:
(a) conjugated diene and
(b) single-ethenyl aromatic compound.The comonomer in shell multipolymer district can also comprise:
(c) unsaturated carboxylic acid and
(d) sulfonate.
Secondly, the invention still further relates to the preparation method of this improved well cementation with copolymer emulsion.
The invention still further relates to a kind of cement slurry composition that contains above-mentioned copolymer emulsion.Said composition contains:
The well cementation cement of (1) 100 parts by weight,
(2) copolymer emulsion of the present invention of 10-20 parts by weight and
(3) water of 30-40 parts by weight.
Copolymer emulsion of the present invention has excellent mechanical stability and chemical stability in cement, its latex cement paste composition is compared with latex-cement slurry with existing well cementation, need not add latex stabilizer and just can obtain excellent well cementation performance in cement.
The polymer particle of copolymer emulsion of the present invention has nucleocapsid structure, and its composition is the nuclear multipolymer district of small portion, most shell multipolymer district.
Nuclear multipolymer district is the important component part of latex, accounts for the 10-30% of polymer particle weight.The monomer that constitutes the nuclear multipolymer comprises single-ethenyl aromatic compound and water-soluble monomer, as unsaturated carboxylic acid and sulfonate.Single-ethenyl aromatic compound is a hard monomer, can be vinylbenzene, neighbour,, two kinds or multiple monomeric mixture in contraposition vinyl toluene etc. or these monomers, be preferably vinylbenzene.In nuclear multipolymer district, the consumption of single-ethenyl aromatic compound is the 5-25% of polymer particle gross weight.Unsaturated carboxylic acid can be two kinds or a multiple monomeric mixture in vinylformic acid, methacrylic acid, methylene-succinic acid, fumaric acid, toxilic acid etc. or these monomers.In nuclear multipolymer district, the usage quantity of unsaturated carboxylic acid is the 0.1-5% of polymer particle gross weight.Sulfonate can be two kinds or multiple monomeric mixture in styryl sulfonate, 2-acrylamide-2-methyl propane sulfonic acid salt etc. or these monomers, and wherein said salt can be sylvite and/or sodium salt, is preferably sodium salt.In nuclear multipolymer district, the consumption of sulfonate is the 0.1-5% of polymer particle gross weight.
The multipolymer that constitutes nuclear is " firmly " multipolymer, and its second-order transition temperature is higher than 90 ℃.The median size in nuclear multipolymer district should be preferably between the 50-200nm in 50-250nm (nanometer).
The kind of water-soluble monomer and consumption play important effect to the stability of nucleation, nuclear and the particle diameter of nuclear.The consumption of water-soluble monomer is as the criterion with the least possible formation water-soluble polymers, because water-soluble polymers can make system viscosity raise, thereby influences polymerization.
Shell accounts for the 70-90% of polymer particle weight.The monomer that constitutes shell multipolymer district comprises aliphatics conjugated diene and single-ethenyl aromatic compound.The monomer that constitutes shell multipolymer district can also comprise water-soluble monomer, as unsaturated carboxylic acid and sulfonate etc.The shell part can be by different forming.In order enough to wrap up harder nuclear multipolymer district, shell can also have different thickness.
In the monomer that constitutes shell multipolymer district, the aliphatics conjugated diene is a soft monomer.Can make latex in cement, have required cohesiveness and intensity by regulating monomeric consumption of soft or hard and ratio.In shell multipolymer district, the aliphatics conjugated diene can be a 1,3-butadiene, and isoprene etc. or their mixture are preferably 1,3-butadiene.In shell multipolymer district, the content of aliphatics conjugated diene is the 20-70% of polymer particle gross weight.In shell multipolymer district, the hard monomer single-ethenyl aromatic compound can be a vinylbenzene, adjacent,, two kinds or multiple monomeric mixture in contraposition vinyl toluene or these monomers, be preferably vinylbenzene.In shell multipolymer district, the content of single-ethenyl aromatic compound is the 20-70% of polymer particle gross weight.Unsaturated carboxylic acid can be two kinds or a multiple monomeric mixture in vinylformic acid, methacrylic acid, methylene-succinic acid, fumaric acid, toxilic acid etc. or these monomers; In shell multipolymer district, its content is the 0-5% of polymer particle gross weight.Sulfonate can be two kinds or multiple monomeric mixture in styryl sulfonate, 2-acrylamide-2-methyl propane sulfonic acid salt or these monomers, and wherein said salt can be sylvite and/or sodium salt, is preferably sodium salt.In shell multipolymer district, the content of sulfonate is the 0-5% of polymer particle gross weight.
Latex of the present invention can adopt the preparation of segmentation emulsion polymerization as medium with water.Specifically, in first section polymerization, at first prepare the nuclear multipolymer exactly.Termination reaction not after nuclear multipolymer district generates, but add second section polymerization that shell monomers generates shell continuously.When adding shell monomers, can add molecular weight regulator.
Being used for the radical initiator with styrene-butadiene latex of nucleocapsid structure polymer particle of the present invention can be water-soluble peroxide, as (but being not limited to) hydrogen peroxide, ammonium persulphate, Potassium Persulphate, Sodium Persulfate etc.The consumption of initiator will reach is enough to take place polymerization.The consumption of initiator is per 100 parts of monomers (weight) 0.1-1.0 part, is preferably 0.3-0.6 part.
Polymerization process of the present invention is carried out at no soap or below the emulsifying agent consumption subcritical micellar concentration (CMC).The emulsifying agent that uses in the process of the preparation latex with nucleocapsid structure polymer particle of the present invention is anionic emulsifier and/or nonionic emulsifying agent.Generally can use one or more composite emulsifiers.Anionic emulsifier includes, but is not limited to sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, dodecyl biphenyl ether sodium disulfonate, dialkyl succinate sodium sulfonate etc.Nonionic emulsifying agent includes, but is not limited to fatty alcohol-polyoxyethylene ether etc.
Can make latex reach stable fully and obtain desired latex particle size by changing the emulsifying agent consumption.
In polymerization process of the present invention, at first prepare the nuclear multipolymer at first section.In this stage, single-ethenyl aromatic compound, unsaturated carboxylic acid and the sulfonate aqueous solution etc. are examined in polymer monomers and the initiator adding reactor, under polymerizing condition, carry out letex polymerization.Reaction should be carried out under the condition that has emulsifying agent to exist, and its consumption is per 100 parts of monomers (weight) 0.01-2 part, preferably 0.1-0.8 part.
As required, can also in reaction system, add auxiliary agents such as ionogen, sequestrant, buffer reagent, PH conditioning agent.
The polymerization temperature of fs more than 55 ℃, is preferably between 65-76 ℃ usually.Polymerization temperature is too low or too high, all can have a negative impact to polymerization.
Termination reaction not after nuclear multipolymer district generates, but in reaction vessel, drip second section polymerization that the shell monomers that contains molecular weight regulator generates shell continuously.Molecular weight regulator can be sulfur alcohol compound (as uncle's lauryl mercaptan), tetracol phenixin, and the known compound that generally uses as molecular weight regulator.The consumption of molecular weight regulator is generally per 100 parts of monomers (weight) 0.1-1.0 part, is preferably 0.3-0.6 part.The initiator of first section polymerization use still works in second section polymerization, adds a small amount of initiator when carrying out second section polymerization but be preferably in, and general additional amount is not more than 1.0 parts of per 100 parts of monomers (weight).
In the polymerization process of subordinate phase, outside nuclear multipolymer district, generate the shell in this multipolymer district of parcel.Conjugated diene and single-ethenyl aromatic compound, and can select shell polymer monomers such as the unsaturated carboxylic acid that adds and sulfonate after the polymerization of nuclear polymer monomers is finished, to begin to add, also can adding before the polymerization of nuclear polymer monomers is thoroughly finished as yet.Monomeric add-on and time can be regulated.The polymerization temperature of subordinate phase is preferably between 79-85 ℃ between 76-95 ℃.
In order to reach purpose of the present invention, the mean diameter of gained latex particle can be between 100-500nm, and between 100-300nm, to be advisable.The solid content of latex is 45-60%, is advisable with 50-55%.
Copolymer emulsion with nucleocapsid structure of the present invention is specially adapted to the cementing concrete composition.When preparation contains the cement slurry composition of copolymer emulsion of the present invention, can use the cement of any usefulness that is suitable for cementing the well, as API G class g cement.The cement of per 100 parts by weight can add the 10-20 parts by weight, is preferably the copolymer emulsion of the present invention and the 30-40 parts by weight of 15 parts by weight, is preferably the water of 35 parts by weight.
Copolymer emulsion of the present invention shows very excellent mechanical stability and chemical stability in cementing concrete.Copolymer emulsion of the present invention has overcome the existing defective of existing latex, thereby does not add stablizer specified in the prior art document or tensio-active agent and just can make the cementing concrete composition have good performance (listed table-2 and table-3 vide infra).
The cementing concrete composition that contains copolymer emulsion of the present invention can also contain retardant, and as (but being not limited to) tartrate, glucoheptonic acid and salt thereof etc., its consumption is per 100 parts by weight of cement (dry weight) 0-3 part; The drag reduction dispersion agent, as (but being not limited to) sulfonated lignin and derivative thereof etc., its consumption is per 100 parts by weight of cement (dry weight) 0-3 part; Defoamer, as (but being not limited to) organic silicone oil, tributyl phosphate etc., its consumption is per 100 parts by weight of cement (dry weight) 0-3 part; The PH conditioning agent, as (but being not limited to) ammoniacal liquor, sodium hydroxide etc., its consumption is per 100 parts by weight of cement (dry weight) 0-3 part.
Followingly explain the present invention, but the present invention has more than and is confined to these embodiment with reference to the embodiment comparative example.Umber in embodiment and the comparative example is unless other specified otherwise is meant parts by weight or weight percent.
The preparation of example one multipolymer latex
Follow these steps to, prepare copolymer emulsion of the present invention with two sections emulsion polymerizations.When first section preparation nuclear multipolymer, at first with 80phm (phm :) deionized water, 0.05phm disodium edta with respect to the consumption umber of 100 parts of monomer weights, 0.1phm sodium lauryl sulphate, 0.2phm ammonium persulphate, and the monomer that is used to form nuclear in the table-1 adds, and stirring is warming up to 76 ℃ in the reactor, constant temperature 1.5 hours obtains examining copolymer emulsion.
Then, carry out second section shell polymerization.At first be warming up to 80 ℃, the water-insoluble monomer mixture and the water-soluble monomer aqueous solution that will contain uncle's 0.5phm lauryl mercaptan molecular weight regulator were added drop-wise in the reactor in 5 hours continuously.After monomer dropping is intact, is warmed up to 85 ℃ and continues reaction 2.0 hours.With ammoniacal liquor the pH value of latex is adjusted to 7.0 then, obtains solid content and be 52% copolymer emulsion product.Measure the median size of latex by dynamic light scattering.
Comparative example a does not use sulfonate monomer when polymerization; Comparative example b does not use unsaturated carboxylic acid monomer when first section nuclear polymerization; Comparative example c does not use the carboxylic acid monomer when polymerization; Comparative example d is the copolymer emulsion of single stage method synthetic homogeneous phase particle structure.
Table-1
Polymerization formula
Embodiment comparative example monomer composition 123456 a b c d nuclear forms (part): styrene 17.5 10 25 7.5 13 11 18 10 15 methacrylic acids 33 acrylic acid 23 itaconic acids 1.5 1.5 2 fumaric acid maleic acid SSSs 221 22-acrylamide-2-1 212 methyl propane sulfonic acid soda-lime glass temperature 93 100 100 91 100 100 100 100 100 (℃) average grain diameter (nm) 120 98 140 81 91 88 107 88 99 shells compositions (part): butadiene 44 42 40 50 40 40 40 36 42 45 styrene 34 42 30 37 43 44 38 50 40 50 methacrylic acids 12 acrylic acid 2213 itaconic acid fumaric acid maleic acid SSSs 11 12-acrylamide-2-1 2 methyl propane sulfonic acid sodium nucleocapsids are than 20,/80 15,/85 29,/71 11,/89 16,/84 15,/85 21,/79 12/88 17/83-
The preparation of example two latex-cement slurries
Chemical stability and the mechanical stability detection in cement of the preparation of latex-cement slurry and copolymer emulsion is to carry out on Chandler engineer Model-708 constant speed stirrer.At first copolymer emulsion and water are poured in the jar, under 1000 rev/mins of conditions, mixed, pour the cement that sieved with 450 μ (micron) (20 order) square hole sieve in 15 seconds into, observe latex and in cement, have or not demulsifying phenomenon.If do not have breakdown of emulsion to take place, illustrate that the chemical stability of latex in cement is good.Stirring velocity is brought up to 12000 rev/mins then, stirred 35 seconds, observe latex-cement slurry and have or not the shear thickening phenomenon.If there is not the shear thickening phenomenon, the good mechanical stability of latex in cement is described.Latex-cement slurry can carry out next step well cementation Performance Detection.The Detection of Stability of all styrene-butadiene latexes in cement the results are shown in Table-2 in latex cement slurry formula and the table-1.
Table-2
Prescription
Embodiment comparative example raw material consumption 123456 a b c dAPI G class g cements (
*) the better good carefully thickening carefully of breakdown of emulsion breakdown of emulsion breakdown of emulsion good mechanical stability carefully of 100 copolymer emulsions, 15 water, 35 chemical stabilities---annotate: (
*) AIP G class g cement is good magnificent cement mill, Sichuan product.
Example three well cementation performance tests
According to API standard 10, the grout with No. 1 copolymer emulsion preparation of embodiment has been carried out following well cementation performance test, the results are shown in Table-3.
Fluid loss property:
The fluid loss property of latex-cement slurry is to carry out on the dynamic filter press of Chandler engineer Model-7120 High Temperature High Pressure, and experiment condition is 75 ℃, 6.9MPa (MPa)/30 minute.
Free-water:
The fresh latex grout for preparing is poured in 250 milliliters of graduated cylinders, left standstill the amount of separating out that detects water after 2 hours at ambient temperature and be the free water yield.
Thickening time:
Time when the High Temperature High Pressure multiviscosisty instrument gluing whey livering time reaches 100Bc (BEIERDUN) for stirring, noting initial consistency and denseness under 75 ℃, 52MPa.
Ultimate compression strength:
Adopt the automatic constant stress loading of ZYS-300 type intensity experiment machine, experiment condition is maintenance 24 hours under 110 ℃, 21MPa.
Table-3 test item experiment condition technical indicator assay API fluid losses, 75 ℃ of milliliters, 6.9MPa/30 divide≤50 32 free water yields, milliliter static 2 hours≤1.5 1.5 thickening times of normal pressure, divide 75 ℃, 52MPa 〉=60 130 initial consistencies, 75 ℃ of Bc, 52MPa≤15 11 ultimate compression strength, 75 ℃ of MPa, 21MPa maintenance 24 hours 〉=14 18
Copolymer emulsion of the present invention and the grout that contains copolymer emulsion of the present invention also can be used for industry and covil construction except that can be used for reinforcing oil well.
Claims (16)
1. a copolymer latex for reinforcing oil well is characterized in that the disperse phase-polymer particle of this copolymer emulsion has nuclear-shell structure, and this structure contains nuclear multipolymer district and shell multipolymer district, wherein:
(1) comonomer in nuclear multipolymer district comprises:
(a) single-ethenyl aromatic compound,
(b) unsaturated carboxylic acid and
(c) sulfonate;
(2) comonomer in shell multipolymer district comprises:
(a) conjugated diene and
(b) single-ethenyl aromatic compound.
2. the described copolymer latex for reinforcing oil well of claim 1 is characterized in that the nuclear multipolymer district of polymer particle accounts for the 10-30% of polymer particle weight, and shell multipolymer district accounts for the 70-90% of polymer particle weight.
3. the described copolymer latex for reinforcing oil well of claim 2, it is characterized in that by the polymer particle gross weight, the single-ethenyl aromatic compound of 5-25% (weight), the water-soluble unsaturated carboxylic acid of 0.1-5% (weight) and the sulfonate of 0.1-5% (weight) are contained in nuclear multipolymer district, and the single-ethenyl aromatic compound of 20-70% (weight) and the aliphatics conjugated diene of 20-70% (weight) are contained in shell multipolymer district.
4. the described copolymer latex for reinforcing oil well of claim 3 is characterized in that the water-soluble unsaturated carboxylic acid of 0-5% (weight) and the sulfonate of 0-5% (weight) are also contained in the shell multipolymer district of polymer particle.
5. claim 3 or 4 described copolymer latex for reinforcing oil well is characterized in that the aliphatics conjugated diene can be a 1,3-butadiene, isoprene or these monomeric mixtures; Single-ethenyl aromatic compound can be a vinylbenzene, adjacent,, two kinds or multiple monomeric mixture in contraposition vinyl toluene or these monomers; Water-soluble unsaturated carboxylic acid can be a methacrylic acid, vinylformic acid, methylene-succinic acid, fumaric acid, two kinds or multiple monomeric mixture in toxilic acid or these monomers; Water-soluble sulfonate can be a styryl sulfonate, two kinds or multiple monomeric mixture in 2-acrylamide-2-methyl propane sulfonic acid salt or these monomers.
6. the described copolymer latex for reinforcing oil well of claim 5, it is characterized in that the aliphatics conjugated diene is 1,3-divinyl, single-ethenyl aromatic compound are vinylbenzene, and water-soluble sulfonate is styryl sodium sulfonate, 2-acrylamide-2-methyl propane sulfonic acid sodium.
7. claim 3 or 4 described copolymer latex for reinforcing oil well, the particle diameter that it is characterized in that polymer particle is between 100-300nm.
8. the preparation method of a copolymer latex for reinforcing oil well is characterized in that preparing this latex with the segmentation emulsion polymerization, and wherein disperse phase-the polymer particle of copolymer emulsion has nuclear-shell structure, in the method
At first prepare the nuclear multipolymer at first section; In this stage, will examine polymer monomers and initiator and add in the reactor, under polymerizing condition, carry out letex polymerization, with product nucleus multipolymer district;
The monomer of its center multipolymer comprises:
(a) single-ethenyl aromatic compound,
(b) unsaturated carboxylic acid and
(c) sulfonate;
Termination reaction not after nuclear multipolymer district generates, but in reaction vessel, drip second section polymerization that shell monomers generates shell continuously, outside nuclear multipolymer district, generate the shell in this multipolymer district of parcel;
The monomer of its mesochite multipolymer comprises:
(a) conjugated diene and
(b) single-ethenyl aromatic compound.
9. the preparation method of the described copolymer latex for reinforcing oil well of claim 8 is characterized in that the monomer that constitutes shell multipolymer district also comprises unsaturated carboxylic acid and/or sulfonate.
10. the preparation method of the described copolymer latex for reinforcing oil well of claim 9 is characterized in that conjugated diene can be a 1,3-butadiene, isoprene or these monomeric mixtures; Single-ethenyl aromatic compound can be a vinylbenzene, adjacent,, two kinds or multiple monomeric mixture in contraposition vinyl toluene or these monomers; Water-soluble unsaturated carboxylic acid can be a methacrylic acid, vinylformic acid, methylene-succinic acid, fumaric acid, two kinds or multiple monomeric mixture in toxilic acid or these monomers; Water-soluble sulfonate can be a styryl sulfonate, two kinds or multiple monomeric mixture in 2-acrylamide-2-methyl propane sulfonic acid salt or these monomers.
11. the preparation method of the described copolymer latex for reinforcing oil well of claim 10, it is characterized in that conjugated diene is 1,3-divinyl, single-ethenyl aromatic compound are vinylbenzene, and water-soluble sulfonate is styryl sodium sulfonate and/or 2-acrylamide-2-methyl propane sulfonic acid sodium.
12. the preparation method of the described copolymer latex for reinforcing oil well of claim 8 is characterized in that letex polymerization carries out at no soap or below the emulsifying agent consumption subcritical micellar concentration (CMC).
13. the preparation method of the described copolymer latex for reinforcing oil well of claim 8, the second-order transition temperature that it is characterized in that examining the multipolymer district is greater than 90 ℃, and median size is between 50-250nm.
14. the preparation method of claim 10,11 described copolymer latex for reinforcing oil well, the particle diameter that it is characterized in that polymer particle is between 100-300nm.
15. the described copolymer latex for reinforcing oil well of claim 1 is used to produce the application of well cementation latex-cement slurry.
16. contain the well cementation latex-cement slurry of the described copolymer latex for reinforcing oil well of claim 1.
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| CNB011083220A CN1155630C (en) | 2001-02-27 | 2001-02-27 | Copolymer latex for reinforcing oil well and its prepn |
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| CN101328401A (en) * | 2007-06-20 | 2008-12-24 | 中国石油天然气集团公司 | High temperature toughcementing carboxyl butadiene-styrene latex additive |
| CN100500794C (en) * | 2006-04-24 | 2009-06-17 | 淄博永麒化工技术开发有限公司 | Gas channeling preventing cement slurry for cementing oil field |
| CN100513430C (en) * | 2007-03-28 | 2009-07-15 | 北京化工大学 | Preparation method of core-shell type emulsion particle emulsion for enhancing rubber |
| CN104193914A (en) * | 2014-08-18 | 2014-12-10 | 清华大学 | Polymer latex for oil-gas field casing cement paste and preparation method thereof |
| CN106367048A (en) * | 2015-07-22 | 2017-02-01 | 中国石油化工股份有限公司 | Cementing cement slurry plasticizer and preparation method thereof, and cement slurry prepared from cementing cement slurry plasticizer |
| CN107778403A (en) * | 2016-08-30 | 2018-03-09 | 中国石油天然气股份有限公司 | A kind of styrene-acrylic latex and its preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100500794C (en) * | 2006-04-24 | 2009-06-17 | 淄博永麒化工技术开发有限公司 | Gas channeling preventing cement slurry for cementing oil field |
| CN100513430C (en) * | 2007-03-28 | 2009-07-15 | 北京化工大学 | Preparation method of core-shell type emulsion particle emulsion for enhancing rubber |
| CN101328401A (en) * | 2007-06-20 | 2008-12-24 | 中国石油天然气集团公司 | High temperature toughcementing carboxyl butadiene-styrene latex additive |
| CN101328401B (en) * | 2007-06-20 | 2014-04-02 | 中国石油天然气集团公司 | High temperature toughcementing carboxyl butadiene-styrene latex additive |
| CN104193914A (en) * | 2014-08-18 | 2014-12-10 | 清华大学 | Polymer latex for oil-gas field casing cement paste and preparation method thereof |
| CN106367048A (en) * | 2015-07-22 | 2017-02-01 | 中国石油化工股份有限公司 | Cementing cement slurry plasticizer and preparation method thereof, and cement slurry prepared from cementing cement slurry plasticizer |
| CN106367048B (en) * | 2015-07-22 | 2018-09-18 | 中国石油化工股份有限公司 | Cementing slurry plasticizer and preparation method thereof and cement mortar prepared therefrom |
| CN107778403A (en) * | 2016-08-30 | 2018-03-09 | 中国石油天然气股份有限公司 | A kind of styrene-acrylic latex and its preparation method and application |
| CN107778403B (en) * | 2016-08-30 | 2020-02-14 | 中国石油天然气股份有限公司 | Styrene-acrylic latex and preparation method and application thereof |
| CN114181352A (en) * | 2021-11-10 | 2022-03-15 | 中国石油天然气集团有限公司 | Polymer material, preparation method thereof and well cementation cement slurry system |
| CN114181352B (en) * | 2021-11-10 | 2023-07-14 | 中国石油天然气集团有限公司 | Polymer material, preparation method thereof and well cementation cement slurry system |
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