CN114644732A - Thermoplastic elastic material for oil well cement and preparation method thereof - Google Patents
Thermoplastic elastic material for oil well cement and preparation method thereof Download PDFInfo
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- 239000004568 cement Substances 0.000 title claims abstract description 85
- 239000013013 elastic material Substances 0.000 title claims abstract description 64
- 229920001169 thermoplastic Polymers 0.000 title claims abstract description 60
- 239000004416 thermosoftening plastic Substances 0.000 title claims abstract description 60
- 239000003129 oil well Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000003999 initiator Substances 0.000 claims abstract description 30
- 239000002904 solvent Substances 0.000 claims abstract description 23
- 239000000178 monomer Substances 0.000 claims abstract description 22
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 10
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims abstract description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 10
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims abstract description 10
- DZSVIVLGBJKQAP-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylcyclohex-2-en-1-yl)propan-1-one Chemical compound CCC(=O)C1CC(C(C)C)CC=C1C DZSVIVLGBJKQAP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 7
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims abstract description 6
- YFICSDVNKFLZRQ-UHFFFAOYSA-N 3-trimethylsilylpropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC[Si](C)(C)C YFICSDVNKFLZRQ-UHFFFAOYSA-N 0.000 claims abstract description 6
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims abstract description 6
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229920002725 thermoplastic elastomer Polymers 0.000 claims description 34
- 238000003756 stirring Methods 0.000 claims description 30
- 239000000463 material Substances 0.000 claims description 29
- 238000002156 mixing Methods 0.000 claims description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 18
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 13
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical group N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 11
- 239000007795 chemical reaction product Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 7
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 6
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 6
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 6
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 5
- 238000005469 granulation Methods 0.000 claims description 3
- 230000003179 granulation Effects 0.000 claims description 3
- 239000003002 pH adjusting agent Substances 0.000 claims description 3
- 229920000728 polyester Polymers 0.000 claims description 3
- 229920002635 polyurethane Polymers 0.000 claims description 3
- 239000004814 polyurethane Substances 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000004575 stone Substances 0.000 abstract description 17
- 238000006116 polymerization reaction Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 39
- 239000000843 powder Substances 0.000 description 18
- 230000004048 modification Effects 0.000 description 12
- 238000012986 modification Methods 0.000 description 12
- 238000005303 weighing Methods 0.000 description 12
- 239000000203 mixture Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- 230000005465 channeling Effects 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000007789 sealing Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- 239000005060 rubber Substances 0.000 description 4
- 239000012745 toughening agent Substances 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical class C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000011246 composite particle Substances 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 239000013005 self healing agent Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/02—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polycarbonates or saturated polyesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/544—Silicon-containing compounds containing nitrogen
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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
- C09K8/50—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
- C09K8/504—Compositions based on water or polar solvents
- C09K8/506—Compositions based on water or polar solvents containing organic compounds
- C09K8/508—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
- C09K8/5083—Compositions based on water or polar solvents containing organic compounds macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
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Abstract
The invention provides a thermoplastic elastic material for oil well cement, which comprises the following raw materials in parts by weight: 100 parts of thermoplastic elastic material; 100-200 parts of a reactive solvent; 10-50 parts of a water-soluble monomer; 20-100 parts of water; 1-44 parts of a pH regulator; 0.1-1 part of oil-soluble initiator; 0.1-1 part of water-soluble initiator; the reactive solvent is one or more of aminopropyltriethoxysilane, 3-methacryloxypropyltrimethylsilane, vinyltrimethoxysilane or vinyltriethoxysilane; the water-soluble monomer is one or more of acrylic acid, itaconic acid and 2-acrylamide-2-methylpropanesulfonic acid. The invention mixes the thermoplastic elastic material with the reactive solvent, and carries out polymerization reaction with the water-soluble monomer solution, so that the surface of the thermoplastic elastic material has hydrophilic groups, thereby having better temperature resistance and improving the hard brittleness and the elastic toughness of the cement stone.
Description
Technical Field
The invention relates to the technical field of materials, in particular to a thermoplastic elastic material for oil well cement and a preparation method thereof.
Background
The well cementation operation is one of the most important links in the oil and gas well drilling engineering, and the main purpose of the well cementation operation is to use cement rings to seal oil layers, gas layers and water layers in the well bore, protect oil and gas well casings, prolong the service life of the oil and gas well and improve the oil and gas yield. Cement stone is a hard and brittle material, and later-stage operation such as casing pressure test, perforation, later-stage fracturing yield increase, stress change caused by temperature field fluctuation, stratum compaction slippage and the like can cause cracks inside a cement ring, a micro annular gap is generated on a cementing surface, the sealing integrity of the cement ring is damaged, and therefore underground oil and gas water channeling and casing annular pressure are caused, further a wellhead is unsafe, the service life of an oil and gas well is reduced, and the like. Therefore, the problems that the whole sealing performance of the cement sheath is improved and the annular gas channeling is prevented are needed to be solved in the well cementation engineering.
At present, research and application of foreign annular sealing resin provide a brand-new solution for difficult problems of gas channeling, annular pressure and the like after well cementation, but the resin is mainly used for operations such as well repair, wellhead gas channeling treatment, well sealing and the like of an annular pressure problem gas well on site, cannot play a role in preventing fundamentally, is expensive and contains biological harmful components; the research on the domestic elastic and tough admixture mainly comprises an oil well cement self-healing agent, an oil well cement plasticizer, a high-temperature oil well cement stone elastic material, an oil well cement elastoplastic agent, an oil well cement toughening agent, a water-oil-encountering double-absorption resin, a gas channeling preventing agent, an inorganic organic interpenetrating network oil well cement channeling preventing agent and the like, and the oil well cement toughening agent mainly comprises high polymers, rigid material composite particles, modified materials or a mixture formed by physically mixing multiple materials.
Thermoplastic elastomer (TPE) is an important new composite material which is being widely researched and applied in polymer alloy and is also called third-generation rubber, the performance of the Thermoplastic elastomer is between that of rubber and plastic, the Thermoplastic elastomer has high elasticity of rubber at normal temperature, deformability of soft plastic at high temperature and certain thermal expansibility, and is an ideal material for improving the elastic toughness of cement stones.
In 201610937961.4, a high temperature oil well cement stone elastic material and a preparation method thereof in the prior art, a nano metal oxide and a surfactant are coated on a hydrogenated styrene-butadiene block copolymer to form the elastic material, but the used mode is physical coating, the elastic material is a multi-material blend, and the application temperature is 100 ℃. 201910464441.X, an elastic agent for oil well cement, consists of thermoplastic rubber, temperature-resistant rubber and an adhesion promoter, is obtained by using a mode of optimizing particle size, physically mixing, stirring, adhering and drying, is a multi-material blend, the addition amount is 2 percent, and the elastic modulus of a set cement is reduced to 5.68GPa at the lowest.
Therefore, the thermoplastic elastic material for oil well cement is developed, can be adsorbed or uniformly dispersed among cement particles, still exists among cement stones after being cured, increases the elasticity of the cement stones at a lower temperature and the deformability of the cement stones at a higher temperature, improves the radial and axial deformation capacity of the cement stones, improves the elastic toughness of the cement stones, enables the cement stones and a casing to synchronously deform without breaking in the environment of formation confining pressure, can effectively avoid the occurrence of micro cracks and micro annular gaps, and is very necessary for realizing the long-term sealing of a cement sheath.
In order to solve the above technical problems, it is necessary to develop a novel thermoplastic elastic material having better elasticity, compressive strength and flexural strength.
Disclosure of Invention
In view of this, the technical problem to be solved by the present invention is to provide a thermoplastic elastic material for oil well cement, which has good elasticity, compressive strength and flexural strength.
The invention provides a thermoplastic elastic material for oil well cement, which comprises the following raw materials in parts by weight:
100 parts of thermoplastic elastic material; 100-200 parts of a reactive solvent; 10-50 parts of a water-soluble monomer; 20-100 parts of water; 1-44 parts of a pH regulator; 0.1-1 part of oil-soluble initiator; 0.1-1 part of water-soluble initiator;
the reactive solvent is one or more of aminopropyltriethoxysilane, 3-methacryloxypropyltrimethylsilane, vinyltrimethoxysilane or vinyltriethoxysilane;
the water-soluble monomer is one or more of acrylic acid, itaconic acid and 2-acrylamide-2-methylpropanesulfonic acid.
Preferably, the thermoplastic elastomer is one or more of polyester (TPEE) and polyurethane (TPU) thermoplastic elastomers.
Preferably, the pH regulator is sodium hydroxide or potassium hydroxide.
Preferably, the water-soluble initiator is ammonium persulfate or potassium persulfate.
Preferably, the oil-soluble initiator is azobisisobutyronitrile or benzoyl peroxide.
The invention provides a preparation method of the thermoplastic elastic material for the oil well cement, which comprises the following steps:
A) mixing a thermoplastic elastic material, a reactive solvent and an oil-soluble initiator, and heating and stirring to obtain a first solution;
mixing a water-soluble monomer, water, a pH regulator and a water-soluble initiator to obtain a second solution;
B) mixing the first solution and the second solution, heating and stirring to obtain a reaction product; and granulating the reaction product to obtain the thermoplastic elastic material for the oil well cement.
Preferably, the temperature of the heating and stirring in the step A) is 80-120 ℃; the stirring time is 20-40 min.
Preferably, the pH regulator is used for regulating the pH of the second solution to 6-9.
Preferably, the heating temperature in the step B) is 70-90 min; the stirring time is 20-40 min.
Preferably, the particle size of the thermoplastic elastomer material for oil well cement obtained after granulation is 74 to 125 μm.
Compared with the prior art, the invention provides a thermoplastic elastic material for oil well cement, which comprises the following raw materials in parts by weight: 100 parts of thermoplastic elastic material; 100-200 parts of a reactive solvent; 10-50 parts of a water-soluble monomer; 20-100 parts of water; 1-44 parts of a pH regulator; 0.1-1 part of oil-soluble initiator; 0.1-1 part of water-soluble initiator; the reactive solvent is one or more of aminopropyltriethoxysilane, 3-methacryloxypropyltrimethylsilane, vinyltrimethoxysilane or vinyltriethoxysilane; the water-soluble monomer is one or more of acrylic acid, itaconic acid and 2-acrylamide-2-methylpropanesulfonic acid. According to the invention, the thermoplastic elastic material and the reactive solvent are mixed and dissolved at a certain temperature, and the mixture is subjected to polymerization reaction with the water-soluble monomer solution, so that the surface of the thermoplastic elastic material has hydrophilic groups, and the thermoplastic elastic material has better temperature resistance than toughening agents such as thermoplastic rubber and the like and elastic agents modified in an adsorption mode, and can be used at higher temperature, such as 130 ℃ in example 9. Meanwhile, the cement can be uniformly dispersed in cement paste, the hardness and brittleness of the cement stone are improved, the elasticity and toughness of the cement stone are enhanced, the requirements of later-stage exploitation and staged fracturing on the mechanical properties of the cement stone are met, and the long-term stable development of an oil-gas well is ensured.
Drawings
FIG. 1 is a comparison of the dispersion state of a thermoplastic elastomer material in set cement before modification;
FIG. 2 is a cement paste with the addition of the modified thermoplastic elastomer of example 4;
FIG. 3 is a contact angle of a thermoplastic elastomer material before modification;
FIG. 4 is a contact angle of the modified thermoplastic elastomer of example 4.
Detailed Description
The invention provides a thermoplastic elastic material for oil well cement and a preparation method thereof, and a person skilled in the art can use the contents to reference the text and appropriately improve the process parameters to realize the thermoplastic elastic material. It is expressly intended that all such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the scope of the invention. While the methods and applications of this invention have been described in terms of preferred embodiments, it will be apparent to those of ordinary skill in the art that variations and modifications in the methods and applications described herein, as well as other suitable variations and combinations, may be made to implement and use the techniques of this invention without departing from the spirit and scope of the invention.
The invention provides a thermoplastic elastic material for oil well cement, which comprises the following raw materials in parts by weight:
100 parts of thermoplastic elastic material; 100-200 parts of a reactive solvent; 10-50 parts of a water-soluble monomer; 20-100 parts of water; 1-44 parts of a pH regulator; 0.1-1 part of oil-soluble initiator; 0.1-1 part of water-soluble initiator;
the invention provides a thermoplastic elastic material for oil well cement, which comprises 100 parts by weight of thermoplastic elastic material.
The thermoplastic elastic material is one or more of polyester (TPEE) thermoplastic elastic materials and polyurethane (TPU) thermoplastic elastic materials. The present invention is not limited to the source, and may be commercially available.
The invention provides a thermoplastic elastic material for oil well cement, which comprises 100-200 parts by weight of a reactive solvent; preferably 120 to 180 parts by weight.
The reactive solvent is one or more of aminopropyltriethoxysilane, 3-methacryloxypropyltrimethylsilane, vinyltrimethoxysilane or vinyltriethoxysilane; the present invention is not limited in its source, and may be commercially available.
The invention provides a thermoplastic elastic material for oil well cement, which comprises 10-50 parts by weight of water-soluble monomers; preferably 10 parts by weight, 20 parts by weight, 30 parts by weight, 40 parts by weight or 50 parts by weight, and also a point value between any two of the above values.
The water-soluble monomer is one or more of acrylic acid, itaconic acid and 2-acrylamide-2-methylpropanesulfonic acid. The present invention is not limited in its source, and may be commercially available.
The invention provides a thermoplastic elastic material for oil well cement, which comprises 20-100 parts by weight of water as a raw material.
The invention provides a thermoplastic elastic material for oil well cement, which comprises 1-44 parts by weight of pH regulator; preferably 10 to 40 parts by weight.
The pH value regulator is sodium hydroxide or potassium hydroxide. The present invention is not limited in its source, and may be commercially available.
The invention provides a thermoplastic elastic material for oil well cement, which comprises 0.1-1 part by weight of oil-soluble initiator; preferably 0.2 to 1 part by weight; more preferably 0.3 to 0.9 parts by weight.
The oil-soluble initiator is azobisisobutyronitrile or benzoyl peroxide. The present invention is not limited in its source, and may be commercially available.
The invention provides a thermoplastic elastic material for oil well cement, which comprises 0.1-1 part by weight of water-soluble initiator; specifically, it may be 0.1 part by weight, 0.2 part by weight, 0.3 part by weight, 0.4 part by weight, 0.5 part by weight, 0.6 part by weight, 0.7 part by weight, 0.8 part by weight, 0.9 part by weight or 1 part by weight; or a point value between any of the above.
The water-soluble initiator is ammonium persulfate or potassium persulfate. The present invention is not limited to the source, and may be commercially available.
The thermoplastic elastic material formed by the invention has good compatibility with cement paste, and is uniformly dispersed and floating-free in the curing process; the formed thermoplastic elastic material can obviously reduce the elastic modulus of the set cement and increase the deformation capability of the set cement.
The invention provides a preparation method of the thermoplastic elastic material for the oil well cement, which comprises the following steps:
A) mixing a thermoplastic elastic material, a reactive solvent and an oil-soluble initiator, and heating and stirring to obtain a first solution;
mixing a water-soluble monomer, water, a pH regulator and a water-soluble initiator to obtain a second solution;
B) mixing the first solution and the second solution, heating and stirring to obtain a reaction product; and granulating the reaction product to obtain the thermoplastic elastic material for the oil well cement.
The components and the proportion of the components are clearly described in the invention, and the description is omitted.
The invention mixes the thermoplastic elastic material, the reactive solvent and the oil-soluble initiator, heats up and stirs to obtain the first solution.
In the present invention, the thermoplastic elastomer and the reactive solvent are first mixed, and more preferably, the thermoplastic elastomer and the reactive solvent are placed in a four-neck flask equipped with a mechanical stirrer, a thermometer and a condenser, and are heated and stirred to be dissolved to form a uniform solution, which is referred to as a solution A.
The temperature of the heating and stirring is preferably 80-120 ℃; the stirring time is preferably 20-40 min; more preferably 25-35 min; most preferably 30 min.
The water-soluble monomer, water, pH adjuster, and water-soluble initiator are mixed to obtain a second solution. Preferably, the water-soluble monomer, water, pH adjuster are first mixed; namely, the water-soluble monomer and water are placed in an open container to be fully dissolved to form a uniform aqueous solution, and the pH value is adjusted to 6-9 by using a pH regulator to obtain a solution B.
Adding an oil-soluble initiator into the solution A and uniformly mixing to obtain a first solution; and adding a water-soluble initiator into the solution B, and uniformly mixing to obtain a second solution.
And mixing the first solution and the second solution, heating and stirring to obtain a reaction product.
Namely, the first solution is added into the mixed second solution, and the mixture is heated and stirred to obtain a blocky product. The heating temperature is 70-90 min; the stirring time is preferably 20-40 min; more preferably 25-35 min; most preferably 30 min.
And granulating the reaction product to obtain the thermoplastic elastic material for the oil well cement. And granulating the reaction product to obtain the thermoplastic elastic material for the oil well cement, wherein the particle size of the thermoplastic elastic material is 74-125 mu m.
The present invention is not limited to the specific manner of the granulation, and those skilled in the art will be familiar with the present invention.
The invention provides a thermoplastic elastic material for oil well cement, which comprises the following raw materials in parts by weight: 100 parts of thermoplastic elastic material; 100-200 parts of a reactive solvent; 10-50 parts of a water-soluble monomer; 20-100 parts of water; 1-44 parts of a pH regulator; 0.1-1 part of oil-soluble initiator; 0.1-1 part of water-soluble initiator; the reactive solvent is one or more of aminopropyltriethoxysilane, 3-methacryloxypropyltrimethylsilane, vinyltrimethoxysilane or vinyltriethoxysilane; the water-soluble monomer is one or more of acrylic acid, itaconic acid and 2-acrylamide-2-methylpropanesulfonic acid. According to the invention, the thermoplastic elastic material and the reactive solvent are mixed and dissolved at a certain temperature, and the mixture is subjected to polymerization reaction with the water-soluble monomer solution, so that the surface of the thermoplastic elastic material has hydrophilic groups, and the thermoplastic elastic material has better temperature resistance than toughening agents such as thermoplastic rubber and the like modified in an adsorption mode and elastic agents, can be used at higher temperature, can be uniformly dispersed in cement paste, improves the hardness and brittleness of the cement stone, enhances the elastic toughness of the cement stone, meets the requirements of later-stage exploitation and staged fracturing on the mechanical properties of the cement stone, and ensures the long-term stable development of oil and gas wells.
In order to further illustrate the present invention, the following will describe in detail a thermoplastic elastomer material for oil well cement and a method for preparing the same, which are provided by the present invention, with reference to examples.
Comparative example 1
In patent 201810594403.1, 100 parts by weight of thermoplastic rubber is weighed, 5 parts by weight of a silane coupling agent is weighed and fully dissolved in a solvent (at least one of water, acetone and ethanol), thermoplastic rubber particles are added into a solution of the silane coupling agent and stirred at a rotation speed of 300 +/-30 r/min for 5min until the mixture is uniformly stirred, and finally, a thermoplastic rubber dispersion is placed in a dry environment until the particle surface is completely dried, so that the flexibilizer for oil well cement is obtained.
Example 1
Weighing 200 parts of A171 and 100 parts of TPU powder, placing the powder into a four-neck flask with a mechanical stirrer, a thermometer and a condenser, heating to 120 ℃, and stirring for about 30min to completely dissolve the powder to form a uniform solution; weighing 10 parts of acrylic acid and 20 parts of water, fully dissolving in an open container to obtain a uniform aqueous solution, and using 8.5 parts of potassium hydroxide; respectively adding 1.0 part of benzoyl peroxide and 0.1 part of potassium persulfate, and uniformly mixing; and uniformly mixing the two solutions, maintaining the temperature at 90 ℃, continuously stirring for 30min to obtain a blocky product, and crushing and granulating to obtain the thermoplastic elastic material with the particle size of 74-125 mu m.
Example 2
Weighing 150 parts of KH570 and 100 parts of TPU powder, placing the powder into a four-neck flask with a mechanical stirrer, a thermometer and a condenser, heating to 120 ℃, and stirring for about 30min to completely dissolve the powder to obtain a uniform solution; weighing 20 parts of itaconic acid and 40 parts of water, placing the itaconic acid and the water in an open container to be fully dissolved to form a uniform aqueous solution, and using 12 parts of sodium hydroxide; respectively adding 0.75 part of azobisisobutyronitrile and 0.2 part of ammonium persulfate, and uniformly mixing; and uniformly mixing the two solutions, maintaining the temperature at 90 ℃, continuously stirring for 30min to obtain a blocky product, and crushing and granulating to obtain the thermoplastic elastic material with the particle size of 74-125 mu m.
Example 3
Weighing 200 parts of A172 and 100 parts of TPEE powder, placing the powder in a four-neck flask with a mechanical stirrer, a thermometer and a condenser, heating to 80 ℃, and stirring for about 30min to completely dissolve the powder to obtain a uniform solution; weighing 50 parts of acrylic acid and 100 parts of water, fully dissolving in an open container to obtain a uniform aqueous solution, and using 32 parts of sodium hydroxide; respectively adding 1.0 part of benzoyl peroxide and 1.0 part of ammonium persulfate and uniformly mixing; and uniformly mixing the two solutions, maintaining the temperature at 70 ℃, continuously stirring for 30min to obtain a blocky product, and crushing and granulating to obtain the thermoplastic elastic material with the particle size of 74-125 mu m.
Example 4
Weighing 100 parts of KH570 and 100 parts of TPEE powder, placing the powder into a four-neck flask with a mechanical stirrer, a thermometer and a condenser, heating to 100 ℃, and stirring for about 30min to completely dissolve the powder to obtain a uniform solution; weighing 30 parts of 2-acrylamide-2-methylpropanesulfonic acid and 60 parts of water, fully dissolving the materials in an open container to obtain a uniform aqueous solution, and using 8 parts of potassium hydroxide; respectively adding 0.5 part of azodiisobutyronitrile and 0.6 part of potassium persulfate, and uniformly mixing; and uniformly mixing the two solutions, maintaining the temperature at 80 ℃, continuously stirring for 30min to obtain a blocky product, and crushing and granulating to obtain the thermoplastic elastic material with the particle size of 74-125 mu m.
Example 5
Weighing 100 parts of KH570 and 100 parts of TPEE powder, placing the powder in a four-neck flask with a mechanical stirrer, a thermometer and a condenser, heating to 100 ℃, and stirring for about 30min to completely dissolve the powder to obtain a uniform solution; weighing 30 parts of acrylic acid and 100 parts of water, placing the acrylic acid and the water in an open container to be fully dissolved to form a uniform water solution, and using 19 parts of sodium hydroxide; respectively adding 0.5 part of azobisisobutyronitrile and 0.6 part of ammonium persulfate, and uniformly mixing; and uniformly mixing the two solutions, maintaining the temperature at 90 ℃, continuously stirring for 30min to obtain a blocky product, and crushing and granulating to obtain the thermoplastic elastic material with the particle size of 74-125 mu m.
Example 6
Weighing 150 parts of KH550 and 100 parts of TPEE powder, placing the powder in a four-neck flask with a mechanical stirrer, a thermometer and a condenser, heating to 100 ℃, and stirring for about 30min to completely dissolve the powder to obtain a uniform solution; weighing 40 parts of itaconic acid and 80 parts of water, placing the itaconic acid and the water in an open container to be fully dissolved to form a uniform aqueous solution, and using 25 parts of sodium hydroxide; respectively adding 0.75 part of benzoyl peroxide and 0.8 part of ammonium persulfate, and uniformly mixing; and uniformly mixing the two solutions, maintaining the temperature at 80 ℃, continuously stirring for 30min to obtain a blocky product, and crushing and granulating to obtain the thermoplastic elastic material with the particle size of 74-125 mu m.
Comparative example 2
For comparison, 100 parts of cement (Jiahua grade G) and 44 parts of water are adopted to prepare conventional cement paste with the density of 1.9G/cm3And curing at 100 ℃ under 21MPa for 48h, and measuring the elastic modulus to be 8.4GPa, the Poisson ratio to be 0.17, the compressive strength to be 35.7MPa and the breaking strength to be 9.3 MPa.
Comparative example 3
For comparison, 100 parts of cement (Jiahua grade G) and 44 parts of water are adopted to prepare conventional cement paste with the density of 1.9G/cm3Curing at 130 ℃ under 21MPa for 48h, and measuring the elastic modulus to be 9.2GPa, the Poisson ratio to be 0.17, the compressive strength to be 40.1MPa and the breaking strength to be 10.1 MPa.
Example 7
A cement slurry with a density of 1.9G/cm was prepared from 85 parts of cement (Jiahua grade G), 5 parts of the thermoplastic elastomer material described in example 3, and 42 parts of water3And curing at 100 ℃ under 21MPa for 48h, and measuring the elastic modulus to be 5.1GPa, the Poisson ratio to be 0.20, the compressive strength to be 25.3MPa and the breaking strength to be 6.4 MPa.
Example 8
A cement slurry with a density of 1.9G/cm was prepared from 85 parts of cement (Jiahua grade G), 15 parts of the thermoplastic elastomer material described in example 4, and 39 parts of water3And curing at 100 ℃ under 21MPa for 48h, and measuring the elastic modulus to be 2.7GPa, the Poisson ratio to be 0.25, the compressive strength to be 14.4MPa and the breaking strength to be 3.5 MPa.
FIG. 1 is a comparison of the dispersion state of a thermoplastic elastomer material in set cement before modification. FIG. 2 is a cement set with the addition of the modified thermoplastic elastomer of example 4. FIG. 3 is a contact angle of a thermoplastic elastomer material before modification; FIG. 4 is a contact angle of the modified thermoplastic elastomer of example 4. As can be seen from fig. 1 and 2, the thermoplastic elastomer material after modification is uniformly dispersed in the set cement, and as can be seen from fig. 3 and 4, the contact angle of the thermoplastic elastomer material after modification is reduced from 118 ℃ to 33 ℃ before modification, which indicates that the hydrophilic property of the thermoplastic elastomer material after modification is greatly increased.
Example 9
A cement paste with a density of 1.9G/cm was prepared from 85 parts of cement (Jiahua grade G), 10 parts of the thermoplastic elastomer material described in example 5 and 41 parts of water3And curing at 130 ℃ under 21MPa for 48h, and measuring the elastic modulus to be 2.9GPa, the Poisson ratio to be 0.22, the compressive strength to be 15.5MPa and the breaking strength to be 3.7 MPa.
From examples 7 to 9, compared with comparative examples 1 and 2, the elastic modulus of the set cement added with the thermoplastic elastic material is obviously reduced, the compressive strength is higher, and the deformation capability of the set cement is enhanced.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The thermoplastic elastic material for oil well cement is characterized by comprising the following raw materials in parts by weight:
100 parts of thermoplastic elastic material; 100-200 parts of a reactive solvent; 10-50 parts of a water-soluble monomer; 20-100 parts of water; 1-44 parts of a pH regulator; 0.1-1 part of oil-soluble initiator; 0.1-1 part of water-soluble initiator;
the reactive solvent is one or more of aminopropyltriethoxysilane, 3-methacryloxypropyltrimethylsilane, vinyltrimethoxysilane or vinyltriethoxysilane;
the water-soluble monomer is one or more of acrylic acid, itaconic acid and 2-acrylamide-2-methylpropanesulfonic acid.
2. The material according to claim 1, characterized in that said thermoplastic elastomer material is one or more of polyester (TPEE), polyurethane (TPU) thermoplastic elastomer materials.
3. The material of claim 1, wherein the pH modifier is sodium hydroxide or potassium hydroxide.
4. The material of claim 1, wherein the water-soluble initiator is ammonium persulfate or potassium persulfate.
5. The material of claim 1, wherein the oil soluble initiator is azobisisobutyronitrile or benzoyl peroxide.
6. A method for producing a thermoplastic elastomer material for oil well cement according to any one of claims 1 to 5, comprising:
A) mixing a thermoplastic elastic material, a reactive solvent and an oil-soluble initiator, and heating and stirring to obtain a first solution;
mixing a water-soluble monomer, water, a pH regulator and a water-soluble initiator to obtain a second solution;
B) mixing the first solution and the second solution, heating and stirring to obtain a reaction product; and granulating the reaction product to obtain the thermoplastic elastic material for the oil well cement.
7. The preparation method according to claim 6, wherein the temperature of the temperature raising and stirring in the step A) is 80-120 ℃; the stirring time is 20-40 min.
8. The method according to claim 6, wherein the pH regulator is used for regulating the pH of the second solution to 6-9.
9. The method according to claim 6, wherein the heating temperature in step B) is 70 to 90 min; the stirring time is 20-40 min.
10. The method according to claim 6, wherein the particle size of the thermoplastic elastomer material for oil well cement obtained after granulation is 74 to 125 μm.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070151484A1 (en) * | 2005-12-29 | 2007-07-05 | Reddy B R | Cement compositions comprising particulate carboxylated elastomers and associated methods |
| CN108659803A (en) * | 2018-06-11 | 2018-10-16 | 长江大学 | A kind of oil-well cement toughener and its application |
| CN109609107A (en) * | 2019-01-16 | 2019-04-12 | 中国石油集团长城钻探工程有限公司 | A kind of toughness material resistant to high temperatures and preparation method thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070151484A1 (en) * | 2005-12-29 | 2007-07-05 | Reddy B R | Cement compositions comprising particulate carboxylated elastomers and associated methods |
| CN108659803A (en) * | 2018-06-11 | 2018-10-16 | 长江大学 | A kind of oil-well cement toughener and its application |
| CN109609107A (en) * | 2019-01-16 | 2019-04-12 | 中国石油集团长城钻探工程有限公司 | A kind of toughness material resistant to high temperatures and preparation method thereof |
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