CN115850566A - Elastomer polymer, preparation method and application thereof, and water-based drilling fluid - Google Patents
Elastomer polymer, preparation method and application thereof, and water-based drilling fluid Download PDFInfo
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- CN115850566A CN115850566A CN202211702070.2A CN202211702070A CN115850566A CN 115850566 A CN115850566 A CN 115850566A CN 202211702070 A CN202211702070 A CN 202211702070A CN 115850566 A CN115850566 A CN 115850566A
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- JHUFGBSGINLPOW-UHFFFAOYSA-N 3-chloro-4-(trifluoromethoxy)benzoyl cyanide Chemical compound FC(F)(F)OC1=CC=C(C(=O)C#N)C=C1Cl JHUFGBSGINLPOW-UHFFFAOYSA-N 0.000 description 1
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- IOMDIVZAGXCCAC-UHFFFAOYSA-M diethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](CC)(CC)CC=C IOMDIVZAGXCCAC-UHFFFAOYSA-M 0.000 description 1
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Abstract
The invention relates to the field of oil drilling plugging, in particular to an elastomer polymer, a preparation method and application thereof and a water-based drilling fluid, wherein the elastomer polymer comprises a structural unit A, a structural unit B, a structural unit C and a structural unit D, the structural unit A is shown as a formula (1), the structural unit B is shown as a formula (2), and the structural unit C is shown as a formula (2)The structural unit D is shown as a formula (4) in the formula (3). The elastomer polymer provided by the invention is non-toxic and harmless, has excellent environmental protection performance, can ensure that the water-based drilling fluid has good plugging performance when being used in the water-based drilling fluid, and also has good high temperature resistance, and has the advantages of simple preparation process, low cost, easily-controlled parameters and wide industrial application prospect.
Description
Technical Field
The invention relates to the field of petroleum drilling plugging, in particular to an elastomer polymer, a preparation method and application thereof and a water-based drilling fluid.
Background
The lost circulation is a technical problem frequently encountered in the drilling process, and particularly, the high-temperature lost circulation can cause a great amount of drilling fluid to be lost, so that the drilling cost is increased, the bottom hole pressure is changed, complex accidents such as instability of a well wall, collapse, kick, blowout and the like are induced, and the improvement of the drilling speed is severely restricted.
At present, a large amount of research work is carried out on drilling fluid plugging materials at home and abroad, however, no matter the drilling stopping plugging materials or the drilling plugging materials, the problems of insufficient toughness and the like of the plugging wall bridge plug generally exist, and then plugging failure is caused, especially, when the drilling tool meets a complex stratum, the plugging slug with insufficient toughness is damaged or the plugging effect is reduced due to pressure fluctuation in the well, and then the drilling fluid breaks the slug and flows to the deep part of the stratum.
To improve the plugging performance of lost circulation materials in water-based drilling fluids, many researchers have developed crosslinked polymeric lost circulation materials in which a crosslinked polymer agent is squeezed into induced fractures and fracture inducing pressure is increased, which helps fracture healing and prevents fluid loss. However, the existing cross-linked polymer plugging material usually has high toxicity, has high potential safety hazard to users and the environment, and is not environment-friendly.
CN113045699A discloses a plugging gel polymer for self-repairing of drilling fluid, a preparation method and application thereof, and a drilling fluid containing the gel polymer, wherein the gel polymer has excellent mechanical properties and good self-repairing properties, and when the gel polymer is used as a plugging agent of a water-based drilling fluid, the gel polymer has good plugging properties and higher plugging layer repairing efficiency, and simultaneously has better high temperature resistance. However, the gel polymer has better plugging performance only below 150 ℃, the downhole temperature with the well depth of more than 5000m is usually higher than 150 ℃, and for the condition that the downhole temperature is higher than 150 ℃, the gel polymer has obvious insufficient plugging performance, and the defects of short plugging effective period, poor plugging efficiency and the like can occur, and the defects directly influence the drilling development process of high-temperature wells and geothermal wells.
Therefore, the development of the environment-friendly plugging material which has good plugging performance and high temperature resistance and is used in the drilling field has important practical significance.
Disclosure of Invention
The invention aims to overcome the defects that the plugging material for the water-based drilling fluid in the prior art cannot have environmental protection, high temperature resistance and good plugging performance.
In order to achieve the above object, the present invention provides an elastomeric polymer, wherein the elastomeric polymer comprises a structural unit a, a structural unit B, a structural unit C and a structural unit D, the structural unit a is represented by formula (1), the structural unit B is represented by formula (2), the structural unit C is represented by formula (3), the structural unit D is represented by formula (4), and the number average molecular weight of the elastomeric polymer is 0.5-50 ten thousand,
wherein, in the formula (1), R 1 Is H or-CH 3 ，R 2 Is selected from C 1 -C 6 One of alkyl groups of (a);
in the formula (2), R 3 Is H or-CH 3 ，R 4 Is C 1 -C 6 One of alkylene groups of (a);
in the formula (3), R 5 Is H or-CH 3 ，R 6 is-OM, M is selected from one of H, na and K;
in the formula (4), R 7 Is H or-CH 3 ，R 8 Is selected from C 1 -C 6 One of the alkyl groups of (1).
In a second aspect, the present invention provides a process for preparing the elastomeric polymer provided in the first aspect, comprising the steps of:
polymerizing each component of the composition to be polymerized in the presence of an alkaline substance and an initiator under a protective atmosphere to obtain the elastomer polymer,
the composition to be polymerized contains a monomer A ', a monomer B', a monomer C 'and a monomer D', wherein the monomer A 'is selected from at least one of the monomers shown in the formula (I), the monomer B' is selected from at least one of the monomers shown in the formula (I), the monomer C 'is selected from at least one of the monomers shown in the formula (III), and the monomer D' is selected from at least one of the monomers shown in the formula (IV),
the monomer A ', the monomer B', the monomer C 'and the monomer D' respectively enable the elastomer polymer to contain a structural unit A, a structural unit B, a structural unit C and a structural unit D, the structural unit A is shown as a formula (1), the structural unit B is shown as a formula (2), the structural unit C is shown as a formula (3), and the structural unit D is shown as a formula (4);
wherein R is 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 Is correspondingly the same as defined in the first aspect.
In a third aspect, the invention provides the use of the elastomeric polymer provided in the first aspect in the field of well plugging.
In a fourth aspect, the present invention provides a water-based drilling fluid comprising an aqueous solvent and an elastomeric polymer, wherein the elastomeric polymer is present in an amount of 3 to 6 parts by weight per 100 parts by weight of the aqueous solvent.
The elastomer polymer provided by the invention is non-toxic and harmless, has excellent environmental protection performance, and can be used in water-based drilling fluid, so that the water-based drilling fluid has good plugging performance and better high temperature resistance.
The method for preparing the elastomer polymer has the advantages of simple preparation process, low cost, easily controlled parameters, wide industrial application prospect and the like.
Drawings
FIG. 1 is a sample plot of a preferred elastomeric polymer M1 of the present invention dispersed in water;
FIG. 2 is a tensile strength curve for a preferred elastomeric polymer M1 of the present invention;
FIG. 3 is a microstructure diagram of a preferred elastomeric polymer M1 of the present invention, wherein FIG. 3 (a) is a scanning electron microscope spectrum of elastomeric polymer M1 at an enlargement to 200 μ M, and FIG. 3 (b) is a scanning electron microscope spectrum of elastomeric polymer M1 at an enlargement to 100 μ M;
FIG. 4 is a particle size distribution diagram of preferred elastomeric polymers M1, M2 and M3 of the present invention, wherein FIG. 4 (a) is a particle size distribution diagram of elastomeric polymer M1, FIG. 4 (b) is a particle size distribution diagram of elastomeric polymer M2, and FIG. 4 (c) is a particle size distribution diagram of elastomeric polymer M3;
FIG. 5 is a graph of the plugging loss evaluation of a preferred water-based drilling fluid L1 and a preferred water-based drilling fluid DL3 of the present invention;
fig. 6 is a diagram comparing the sand table apertures of a preferred water-based drilling fluid L1 and a water-based drilling fluid DL0 of the present invention, wherein fig. 6 (a) is a diagram of the sand table apertures of the water-based drilling fluid DL0 and fig. 6 (b) is a diagram of the sand table apertures of the water-based drilling fluid L1.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In the present invention, said C 1 -C 6 The alkylene group of (2) means an alkylene group having 1 to 6 carbon atoms, illustratively, C in the present invention 1 -C 6 Alkylene groups of (a) include, but are not limited to: methylene, ethylene, n-propylene, isopropylene.
As described above, the first aspect of the present invention provides an elastomeric polymer, which contains a structural unit A, a structural unit B, a structural unit C and a structural unit D, wherein the structural unit A is represented by formula (1), the structural unit B is represented by formula (2), the structural unit C is represented by formula (3), the structural unit D is represented by formula (4), the number average molecular weight of the elastomeric polymer is 0.5-50 ten thousand,
wherein, in the formula (1), R 1 Is H or-CH 3 ，R 2 Is selected from C 1 -C 6 One of the alkyl groups of (a);
in the formula (2), R 3 Is H or-CH 3 ，R 4 Is C 1 -C 6 One of alkylene groups of (a);
in the formula (3), the reaction mixture is,R 5 is H or-CH 3 ，R 6 is-OM, M is selected from one of H, na and K;
in the formula (4), R 7 Is H or-CH 3 ，R 8 Is selected from C 1 -C 6 One of the alkyl groups of (1).
The inventor of the invention finds that the elastomer polymer provided by the invention is a material which can recover after external force is removed, and has great advantages when being used as a plugging material, after the elastomer is used as a plugging agent and enters a stratum, the elastomer polymer enters pores under the action of the temperature and the pressure of the stratum, and each elastomer polymer microsphere generates detention, accumulation, bridging and filling and fully exerts respective synergistic effect, so that the cementing capacity and the plugging pressure-bearing capacity of a leaking stratum are integrally improved, and the aim of plugging a leaking layer is further fulfilled.
Preferably, the average particle size of the elastomer polymer is 40-370 μm, the sizes of formation pore fractures are different under different formation conditions, and in practical application, the matched elastomer polymer is selected according to the formation pore fractures with different sizes, so that the plugging effect is better.
Preferably, in the elastomeric polymer, the content molar ratio of the structural unit A, the structural unit B, the structural unit C and the structural unit D is 1 (0.05-0.5): 0.05-0.3.
According to a particularly preferred embodiment, the elastomeric polymer contains the structural units A, B, C and D in a molar ratio of 1 (0.08-0.2) to (0.08-0.2), in which case the elastomeric polymer of the invention has greater leak stopping properties and superior mechanical properties.
According to a preferred embodiment, in formula (1), R 2 Is selected from-CH 3 、-CH 2 -CH 3 and-CH 2 -CH 2 -CH 3 One of (1);
in the formula (2), R 4 is-CH 2 -or-CH 2 -CH 2 -；
In the formula (1)3) In, R 6 One selected from-OH, -ONa and-OK;
in the formula (4), R 8 is-CH 3 or-CH 2 -CH 3 。
According to a particularly preferred embodiment, the structural unit A is at least one member selected from the group consisting of structural units represented by the formula (1-1), the formula (1-2), the formula (1-3), the formula (1-4), the formula (1-5) and the formula (1-6);
the structural unit B is at least one selected from a structure shown in a formula (2-1), a structure shown in a formula (2-2), a structure shown in a formula (2-3) and a structural unit shown in a formula (2-4);
the structural unit C is at least one of a structure shown by a formula (3-1), a structure shown by a formula (3-2), a structure shown by a formula (3-3), a structure shown by a formula (3-4), a structure shown by a formula (3-5) and a structural unit shown by a formula (3-6);
the structural unit D is at least one of a structure shown by a formula (4-1), a structure shown by a formula (4-2), a structure shown by a formula (4-3) and a structural unit shown by a formula (4-4);
formula (1-1): r 1 Is H, R 2 is-CH 3 ；
Formula (1-2): r 1 Is H, R 2 is-CH 2 -CH 3 ；
Formula (1-3): r 1 Is H, R 2 is-CH 2 -CH 2 -CH 3 ；
Formula (1-4): r is 1 is-CH 3 ，R 2 is-CH 3 ；
Formula (1-5): r 1 is-CH 3 ，R 2 is-CH 2 -CH 3 ；
Formula (1-6): r is 1 is-CH 3 ，R 2 is-CH 2 -CH 2 -CH 3 ；
Formula (2-1): r 3 Is H, R 4 is-CH 2 -；
Formula (2-2): r is 3 Is H, R 4 is-CH 2 -CH 2 -；
Formula (2-3): r 3 is-CH 3 ，R 4 is-CH 2 -；
Formula (2-4): r 3 is-CH 3 ，R 4 is-CH 2 -CH 2 -；
Formula (3-1): r is 5 Is H, R 6 is-OH;
formula (3-2): r 5 Is H, R 6 is-ONa;
formula (3-3): r 5 Is H, R 6 is-OK;
formula (3-4): r 5 is-CH 3 ，R 6 is-OH;
formula (3-5): r 5 is-CH 3 ，R 6 is-ONa;
formula (3-6): r 5 is-CH 3 ，R 6 is-OK;
formula (4-1): r 7 Is H, R 8 is-CH 3 ；
Formula (4-2): r 7 Is H, R 8 is-CH 2 -CH 3 ；
Formula (4-3): r is 7 is-CH 3 ，R 8 is-CH 3 ；
Formula (4-4): r 7 is-CH 3 ，R 8 is-CH 2 -CH 3 。
As previously mentioned, a second aspect of the present invention provides a process for preparing the elastomeric polymer provided in the first aspect, comprising the steps of:
polymerizing each component of the composition to be polymerized in the presence of an alkaline substance and an initiator under a protective atmosphere to obtain the elastomer polymer,
the composition to be polymerized contains a monomer A ', a monomer B', a monomer C 'and a monomer D', wherein the monomer A 'is selected from at least one of the monomers shown in the formula (I), the monomer B' is selected from at least one of the monomers shown in the formula (II), the monomer C 'is selected from at least one of the monomers shown in the formula (IV), and the monomer D' is selected from at least one of the monomers shown in the formula (IV),
the monomer A ', the monomer B', the monomer C 'and the monomer D' respectively enable the elastomer polymer to contain a structural unit A, a structural unit B, a structural unit C and a structural unit D, wherein the structural unit A is shown as a formula (1), the structural unit B is shown as a formula (2), the structural unit C is shown as a formula (3), and the structural unit D is shown as a formula (4);
wherein R is 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 Corresponds to the same definitions as described in the elastomeric polymer provided in the first aspect.
In the method according to the second aspect of the present invention, the definitions and material types of the substituents in the monomer having the structure shown in formula (i), the monomer having the structure shown in formula (ii), and the monomer having the structure shown in formula (iv) are the same as those of the substituents described above, and the present invention is not described herein again, and those skilled in the art should not be construed as limiting the technical solution of the present invention.
It is to be understood that the elastomeric polymers prepared by the above process are generally referred to as the direct products of the above process without purification, and that the present invention includes such cases within the scope of the present invention, although such products may be mixtures of a plurality of elastomeric polymers.
In the present invention, the monomer a ', the monomer B', the monomer C 'and the monomer D' may be obtained commercially, or may be synthesized according to the structural formula provided by the present invention in combination with a known method in the field of organic synthesis.
Preferably, the polymerization reaction is carried out under stirring conditions, and the inventor of the invention finds that the elastomer polymers with different particle sizes can be obtained by adjusting the stirring rate during the polymerization reaction, and exemplarily, the average particle size of the prepared elastomer polymers is 40-370 μm when the stirring rate is 300-800 rpm, so that the method is suitable for formation pores with different fracture sizes under different formation conditions and has better plugging effect.
Preferably, before the polymerization reaction is carried out, a mixture containing the monomer a ', the monomer B', the monomer C 'and the monomer D' is subjected to emulsification shear treatment, and the conditions of the emulsification shear treatment at least satisfy: the shearing rate is 1000rpm-5000rpm, the treatment temperature is 20-50 ℃, and the treatment time is 1min-3min.
The inventor of the present invention finds that before the polymerization reaction, the mixture containing the monomer a ', the monomer B', the monomer C 'and the monomer D' is subjected to emulsification and shearing treatment, and various parameters such as shearing rate of the emulsification and shearing treatment are adjusted, so that polymer elastomers with different particle sizes can be obtained to match formation pores with different fracture sizes under different formation conditions.
Preferably, the emulsification shearing treatment is carried out in the presence of an emulsifier, the emulsifier is used in an amount of 0.01mol to 0.1mol, and the emulsifier is selected from at least one of tween 20, tween 40, tween 60, tween 80, a non-ionic paraffin microemulsion NMP, an anionic paraffin emulsifier AMP, OP-10, OP-15, and more preferably tween 80, based on the total molar amount of the monomer a ', the monomer B', the monomer C ', and the monomer D' being 1 mol.
Preferably, the conditions of the polymerization reaction are at least: the pH value is 7-9, the temperature is 30-90 ℃, and the time is 6-12 h. More preferably, the conditions of the polymerization reaction are at least: the pH value is 7-9, the temperature is 60-80 ℃, and the time is 7-9h. Wherein, the pH value of 7-9 means that the polymerization reaction is carried out under the condition.
Preferably, the amount of the initiator is 1mmol to 10mmol based on 1mol of the total molar amount of the monomer A ', the monomer B', the monomer C 'and the monomer D'; preferably 1 to 5mmol; more preferably from 2mmol to 4mmol. The inventor of the invention finds that when the total molar quantity of the monomer A ', the monomer B', the monomer C 'and the monomer D' is 1mol and the dosage of the initiator is 2mmol-4mmol, the prepared elastomer polymer has higher high temperature resistance and better plugging performance when used as a plugging agent for a water-based drilling fluid.
Preferably, the initiator is selected from at least one of azo-type initiators, peroxide-type initiators, and redox-type initiators. Further preferably, the azo initiator is at least one selected from azobisisobutyramidine hydrochloride, azobisisopropylimidazoline hydrochloride, azobiscyanovaleric acid, and azobisisopropylimidazoline; the peroxide initiator is at least one selected from hydrogen peroxide, ammonium persulfate, sodium persulfate and potassium persulfate; the redox initiator is at least one selected from persulfate-sulfite, persulfate-thiourea and persulfate-organic salt.
Preferably, the monomer A ', the monomer B', the monomer C 'and the monomer D' are used in such amounts that the elastomeric polymer is produced such that the molar ratio of the structural unit A, the structural unit B, the structural unit C and the structural unit D is 1 (0.05-0.5): 0.05-0.3.
According to some particularly preferred embodiments, the monomers A ', the monomers B', the monomers C 'and the monomers D' are used in such amounts that the elastomeric polymer is produced with a molar ratio of the structural units A, the structural units B, the structural units C and the structural units D of 1 (0.08-0.2): 0.08-0.2.
In the present invention, it should be noted that the monomer is converted into the corresponding structural unit contained in the polymer approximately completely, and the amount of the monomer used may be the same as the content of the corresponding structural unit contained in the polymer.
In the present invention, the protective atmosphere may be exemplarily selected from at least one of, but not limited to, nitrogen, helium, neon, and argon.
Preferably, the alkaline substance is at least one selected from the group consisting of sodium hydroxide, potassium carbonate, sodium carbonate, and sodium bicarbonate.
In the present invention, according to another preferred embodiment, the process for the preparation of the elastomeric polymer comprises the following steps:
(1) Under the condition of stirring at 0-5 ℃, carrying out first mixing treatment on the monomer B ', the monomer C ' and the monomer D ', and adjusting the pH value to 7-9 to obtain a first mixture, wherein the mixing time is 10-20 min;
(2) Carrying out second mixing treatment on the monomer A' and the first mixture at the temperature of 10-50 ℃ to obtain a second mixture, wherein the mixing time is 10-20 min;
(3) And adding an initiator into the second mixture under a protective atmosphere, carrying out polymerization reaction on the second mixture and the initiator at the temperature of 60-80 ℃, obtaining an aqueous solution containing the elastomer polymer after reaction for 7-9h, and transferring the aqueous solution to a centrifuge for separation to obtain the elastomer polymer.
As previously mentioned, a third aspect of the invention provides the use of the elastomeric lost circulation polymer of the first aspect described above in the field of well plugging.
Illustratively, the elastomeric lost circulation polymers are capable of acting as lost circulation agents in drilling fluids. Furthermore, the elastomer plugging polymer is used as a plugging agent in water-based drilling fluid, has the advantages of no toxicity, no harm, environmental protection and safety, and also has excellent plugging performance and better high temperature resistance.
In the invention, when the elastomer polymer is applied to the drilling fluid as a plugging agent, the obtained drilling fluid can still keep lower filtration loss in a high-temperature environment and well maintain the stability of a well wall, so the method is particularly suitable for developing ultra-deep layer oil and gas resources in the high-temperature environment.
In accordance with a fourth aspect of the present invention, there is provided a water-based drilling fluid comprising an aqueous solvent and an elastomeric polymer, wherein the elastomeric polymer is present in an amount of from 3 to 6 parts by weight per 100 parts by weight of the aqueous solvent; the elastomeric polymer is the elastomeric polymer provided in the first aspect of the invention.
The water-based drilling fluid provided by the invention is non-toxic and harmless, is environment-friendly and safe, and has excellent plugging performance and high temperature resistance.
It will be appreciated that in the present invention, the elastomeric polymer may be one elastomeric polymer as provided in the first aspect above, or may be a mixture of a plurality of elastomeric polymers as provided in the first aspect above.
Preferably, the water-based drilling fluid system further comprises additives, wherein the additives comprise at least one of bentonite, a tackifier, an anti-collapse agent, an inhibitor and sodium carbonate.
Preferably, the additive comprises a combination of bentonite, a tackifier, an anti-collapse agent, an inhibitor and sodium carbonate, wherein the content of the bentonite is 2-4 parts by weight, the content of the tackifier is 0.1-2 parts by weight, the content of the anti-collapse agent is 2-4 parts by weight, the content of the inhibitor is 6-8 parts by weight and the content of the sodium carbonate is 0.2-0.3 part by weight relative to 100 parts by weight of the aqueous solvent in the water-based drilling fluid.
Further preferably, in the water-based drilling fluid, the content of the bentonite is 3-4 parts by weight, the content of the tackifier is 0.5-1 part by weight, the content of the anti-collapse agent is 3-4 parts by weight, the content of the inhibitor is 7-8 parts by weight, and the content of the sodium carbonate is 0.2-0.3 part by weight, relative to 100 parts by weight of the aqueous solvent.
In the present invention, the aqueous solvent is water, and illustratively, deionized water is used.
In the present invention, the bentonite refers to clay with montmorillonite as a main mineral component, which mainly plays a role of a slurrying wall protection in a water-based drilling fluid, and is illustratively sodium bentonite and/or calcium bentonite, and is preferably sodium bentonite.
In the present invention, the tackifier refers to a substance capable of improving the viscous shear force of the drilling fluid, and is at least one of polyanionic cellulose (for example PAC), polyacrylamide potassium salt (for example KPAM), and acrylamide-sodium acrylate copolymer (for example 80a 51), and is preferably polyanionic cellulose (for example PAC).
In the present invention, the anti-collapse agent is a substance capable of preventing the collapse of the well wall and improving the stability of the well wall, and is at least one of sulfonated asphalt (for example, FT-1A), potassium humate (KHM), and silicone (for example, GF-1), preferably white asphalt.
In the present invention, the inhibitor is a substance having an ability to inhibit hydration swelling of clay, and is illustratively at least one of potassium chloride, sodium humate, and inorganic positive electrolyte gel (MMH), and preferably potassium chloride.
In the present invention, there is no particular limitation on the preparation method of the water-based drilling fluid, and the preparation method known to those skilled in the art can be adopted, and the present invention is not described herein again, and the present invention is described in detail in the following, and those skilled in the art should not be construed as limiting the present invention.
In the present invention, the amount of said polymers, when referred to the amount, is not specifically indicated, based on the dry elastomeric polymer.
The present invention will be described in detail below by way of examples. In the following examples, all the raw materials used are commercially available ones unless otherwise specified.
A monomer A': propyl acrylate, available from Beijing Bailingwei science and technology Co., ltd under the brand name B60489;
a monomer B': sodium allylsulfonate, available from Shanghai Aladdin Biochemical technology, inc. under the designation S121961;
a monomer C': acrylic acid, available from fine chemicals, inc. of Yili, beijing under the brand name yh 023;
monomer D' in example 1: dimethyldiallylammonium chloride, available from Shanghai Allantin Biotechnology GmbH under the designation D110133;
monomer D' in example 2: dimethyl diallyl ammonium chloride with the purity of 99.9 percent, a product is prepared, and the product is prepared according to the reference document of the preparation method: liuli Hua et al, copolymerization reactivity ratio of ammonium diethyldiallylammonium chloride with acrylamide and acrylic acid, applied chemistry, vol.24, no. 2, month 2007.
Example 1
(1) Adding 0.1mol of the monomer B ', 0.1mol of the monomer C' and 0.1mol of the monomer D 'into a beaker, stirring until the monomers are uniformly mixed, adjusting the pH value to 7, wherein the monomer B' is a structure shown in a formula (II), and R is 3 Is H, R 4 is-CH 2 -; the monomer C 'is a structure shown in a formula (III), and R in the monomer C' is 5 Is H, R 6 is-OH; the monomer D 'is a structure shown in a formula (IV), and R in the monomer D' is 7 Is H, R 8 is-CH 3 。
(2) Adding 1mol of monomer A 'into the solution obtained in the step (1), and stirring until the monomers are uniformly mixed, wherein the monomer A' has a structure shown in a formula (I), and R 1 Is H, R 2 is-CH 2 -CH 2 -CH 3 。
(3) And (3) transferring the mixture obtained in the step (2) into a three-neck flask, sealing the three-neck flask, adding a nitrogen introducing device to introduce nitrogen into the three-neck flask, adding an initiator, fully removing air in the flask, heating to 70 ℃, carrying out constant-temperature polymerization reaction for 8 hours, setting the stirring speed to be 500rpm, cooling to room temperature after the reaction is finished, obtaining a solution containing the elastomer polymer, and centrifuging to obtain the elastomer polymer M1.
In the preparation process of the elastomer polymer M1, based on 1mol of the monomer A', the using amount of the initiator is 3mmol, and the initiator is potassium persulfate.
Example 2
This example was carried out in a similar manner to example 1, except that R in the monomer D' was 8 is-CH 2 -CH 3 And the stirring speed was set to 300rpm at the time of polymerization in this example to obtain an elastomeric polymer M2.
Example 3
This example was conducted in a similar manner to example 1 except that the stirring speed at the time of polymerization in this example was set to 800rpm, to obtain an elastomeric polymer M3.
Comparative example 1
This comparative example was carried out in a similar manner to example 1, except that the amount of monomer A' used in this comparative example was 0.01mol, giving elastomeric polymer DM1.
Comparative example 2
This comparative example was carried out in a similar manner to example 1, except that the amount of monomer D' used in this comparative example was 0.5mol, giving elastomeric polymer DM2.
Comparative example 3
Gel polymer DM3 prepared according to the technical solution described in CN 113045699A.
And (3) testing tensile strength: the polymers prepared in the above examples 1 to 3 and comparative examples 1 to 3 were subjected to tensile strength tests, the results of which are shown in the following table 1:
TABLE 1
| Average particle diameter | Elongation at break | Tensile strength | Number average molecular weight | Whether or not it is an elastomer | |
| M1 | 200μm | 1289％ | 0.18MPa | 120000 | Is that |
| M2 | 500μm | 1256％ | 0.17MPa | 500000 | Is that |
| M3 | 52μm | 1203％ | 0.17MPa | 15000 | Is that |
| DM1 | 177μm | 884％ | 0.12MPa | 85000 | Is that |
| DM2 | 166μm | 986％ | 0.14MPa | 80000 | Is that |
| DM3 | / | 337.2％ | 0.08MPa | / | Whether or not |
The polymers prepared in the examples and comparative examples were formulated into a water-based drilling fluid L having the following formulation: the water-based drilling fluid L series formula comprises: 100 parts by weight of a water-based drilling fluid base slurry +4 parts by weight of a polymer;
the preparation process of the water-based drilling fluid base slurry comprises the following steps: sequentially adding 4 parts by weight of bentonite and 0.25 part by weight of sodium carbonate into 100 parts by weight of water, stirring for 10min by using a high-speed stirrer after each raw material is added until the raw materials are uniformly dispersed, wherein the stirring speed is 10000rpm, and stirring for 24h after the raw materials are added to obtain the base slurry of the water-based drilling fluid.
The water-based drilling fluid prepared according to the formula comprises the following components in percentage by weight: l1 (addition of M1), L2 (addition of M2), L3 (addition of M3), DL0 (no addition of polymer), DL1 (addition of DM 1), DL2 (addition of DM 2), DL3 (addition of DM 3).
And (3) testing the plugging performance of the water-based drilling fluid at 90 ℃, wherein V0 represents instantaneous leakage, V1 represents 60min accumulated leakage, the smaller the numerical value is, the better the plugging effect is, and the specific result is shown in Table 2.
TABLE 2
And testing the high temperature resistance of the water-based drilling fluid, wherein V0 represents instantaneous leakage loss, V1 represents 60min accumulated leakage loss, the smaller the numerical value is, the better the plugging effect is, and the specific result is shown in Table 3.
TABLE 3
The polymers prepared in the examples and comparative examples are prepared into a water-based drilling fluid T, and the formula of the water-based drilling fluid T is as follows: the water-based drilling fluid L series formula comprises: 100 parts by weight of water-based drilling fluid base slurry, 4 parts by weight of polymer, 0.8 part by weight of PAC (tackifier), 3 parts by weight of white asphalt (anti-collapse agent) and 7 parts by weight of sodium chloride;
the preparation process of the water-based drilling fluid base slurry comprises the following steps: sequentially adding 4 parts by weight of bentonite and 0.25 part by weight of sodium carbonate into 100 parts by weight of water, stirring for 10min by using a high-speed stirrer after each addition of one raw material until the raw materials are uniformly dispersed, wherein the stirring speed is 10000rpm, and stirring for 24h after the addition of the raw materials is finished to obtain the base slurry of the water-based drilling fluid.
The water-based drilling fluid prepared according to the formula comprises the following components in percentage by weight: t1 (addition of M1), T2 (addition of M2), T3 (addition of M3), DL0 (no addition of polymer).
And (3) testing the plugging performance of the water-based drilling fluid at 90 ℃, wherein V0 represents instantaneous leakage, V1 represents accumulated leakage, the smaller the numerical value is, the better the plugging effect is, and the specific result is shown in Table 4.
TABLE 4
The results show that the elastomer polymer provided by the invention has excellent mechanical property and plugging property, and has good plugging effect and better high-temperature resistance when being used for water-based drilling fluid.
Exemplarily, the following steps are carried out: FIG. 1 is a sample diagram of the dispersion of elastomeric polymer M1 in water, illustrating that the elastomeric polymer prepared by the present invention can be uniformly dispersed in water and is suitable for use in water-based drilling fluids;
FIG. 2 is a tensile strength curve of elastomeric polymer M1, from FIG. 2 it can be seen that the elastomer has an elongation at break of 1289% and a tensile strength of 0.18MPa, indicating that the elastomeric polymer prepared by the present invention has excellent mechanical properties;
FIG. 3 is a microstructure diagram of the elastomer polymer M1, wherein FIG. 3 (a) is a scanning electron microscope spectrum of the elastomer polymer M1 at an enlargement to 200 μ M, and FIG. 3 (b) is a scanning electron microscope spectrum of the elastomer polymer M1 at an enlargement to 200 μ M. The accumulation of elastomer particles is clearly observed in FIG. 3 (a), and the extrusion and adhesion between the large and small elastomer particles is clearly observed in FIG. 3 (b);
FIG. 4 is a particle size distribution diagram of the elastomeric polymers M1, M2 and M3, wherein FIG. 4 (a) is a particle size distribution diagram of the elastomeric polymer M1, FIG. 4 (b) is a particle size distribution diagram of the elastomeric polymer M2, FIG. 4 (c) is a particle size distribution diagram of the elastomeric polymer M3, it can be seen from FIG. 4 that the stirring rate is different during the polymerization reaction, the particle sizes of the prepared elastomeric polymers have certain difference, and in practical application, the elastomeric polymers with different sizes can be selected according to the difference of the leakage stratum to achieve a better plugging effect;
fig. 5 is a graph of the plugging evaluation of the water-based drilling fluid L1 and the water-based drilling fluid DL3 prepared from the elastomer polymer M1 and the gel polymer DM3 at different temperatures, and it can be seen that the plugging capability and the high temperature resistance of the elastomer polymer M1 are significantly improved compared with the gel polymer DM3. (ii) a
Fig. 6 is a diagram comparing sand table apertures of water-based drilling fluid L1 and water-based drilling fluid DL0, where fig. 6 (a) is a diagram of sand table apertures of water-based drilling fluid DL0, and fig. 6 (b) is a diagram of sand table apertures of water-based drilling fluid L1, and it can be seen from fig. 6 (b) that particles of elastomeric polymer M1 are uniformly distributed on the surface of filter cake, and a phenomenon that particles of elastomeric polymer M1 are piled up with each other can be observed in holes where the filter cake is broken, which shows that elastomeric polymer M1 can enter into pores and bridge and pile up, and has good applicability to formations whose underground fracture sizes are difficult to predict and cannot be predicted.
In conclusion, the elastomer polymer provided by the invention has good mechanical properties, when the elastomer polymer is used as a plugging agent in drilling fluid, the drilling fluid can have a good plugging effect through the synergistic effect of all structural units, and meanwhile, the elastomer polymer has good high-temperature resistance, and is simple in preparation method and low in cost.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. An elastomer polymer is characterized by comprising a structural unit A, a structural unit B, a structural unit C and a structural unit D, wherein the structural unit A is shown as a formula (1), the structural unit B is shown as a formula (2), the structural unit C is shown as a formula (3), the structural unit D is shown as a formula (4), the number average molecular weight of the elastomer polymer is 0.5-50 ten thousand,
wherein, in the formula (1), R 1 Is H or-CH 3 ，R 2 Is selected from C 1 -C 6 One of the alkyl groups of (a);
in the formula (2), R 3 Is H or-CH 3 ，R 4 Is C 1 -C 6 One of alkylene groups of (a);
in the formula (3), R 5 Is H or-CH 3 ，R 6 is-OM, M is selected from one of H, na and K;
in the formula (4), R 7 Is H or-CH 3 ，R 8 Is selected from C 1 -C 6 One of the alkyl groups of (1).
2. The elastomeric polymer of claim 1, wherein the elastomeric polymer has an average particle size of 40 μ ι η to 370 μ ι η;
and/or, in the elastomer polymer, the content molar ratio of the structural unit A, the structural unit B, the structural unit C and the structural unit D is 1 (0.05-0.5): 0.05-0.3;
preferably, in the elastomeric polymer, the content molar ratio of the structural unit A, the structural unit B, the structural unit C and the structural unit D is 1 (0.08-0.2): (0.08-0.2).
3. Elastomeric polymer according to claim 1 or 2, characterized in that in formula (1), R 2 Is selected from-CH 3 、-CH 2 -CH 3 and-CH 2 -CH 2 -CH 3 One of (1);
in the formula (2), R 4 is-CH 2 -or-CH 2 -CH 2 -；
In the formula (3), R 6 One selected from-OH, -ONa and-OK;
in the formula (4), R 8 is-CH 3 or-CH 2 -CH 3 。
4. A process for preparing an elastomeric polymer according to any one of claims 1 to 3, comprising the steps of:
polymerizing each component of the composition to be polymerized in the presence of an alkaline substance and an initiator under a protective atmosphere to obtain the elastomer polymer,
the composition to be polymerized contains a monomer A ', a monomer B', a monomer C 'and a monomer D', wherein the monomer A 'is selected from at least one of the monomers shown in the formula (I), the monomer B' is selected from at least one of the monomers shown in the formula (II), the monomer C 'is selected from at least one of the monomers shown in the formula (IV), and the monomer D' is selected from at least one of the monomers shown in the formula (IV),
the monomer A ', the monomer B', the monomer C 'and the monomer D' respectively enable the elastomer polymer to contain a structural unit A, a structural unit B, a structural unit C and a structural unit D, wherein the structural unit A is shown as a formula (1), the structural unit B is shown as a formula (2), the structural unit C is shown as a formula (3), and the structural unit D is shown as a formula (4);
wherein R is 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 Is correspondingly the same as defined in any of claims 1-3.
5. The process of claim 4, wherein the polymerization is carried out under stirring conditions at a rate of from 300rpm to 800rpm;
and/or, the method further comprises: before the polymerization reaction, the mixture containing the monomer A ', the monomer B', the monomer C 'and the monomer D' is subjected to emulsification and shearing treatment, wherein the conditions of the emulsification and shearing treatment at least meet the following conditions: the shearing rate is 1000rpm-5000rpm, the processing temperature is 20-50 ℃, and the processing time is 1min-3min;
preferably, the emulsifying shear treatment is carried out in the presence of an emulsifier, the amount of the emulsifier used is 0.01mol to 0.1mol, based on 1mol of the total molar amount of the monomer A ', the monomer B', the monomer C 'and the monomer D';
more preferably, the emulsifier is at least one selected from Tween 20, tween 40, tween 60, tween 80, non-ionic paraffin microemulsion NMP, and anionic paraffin emulsifiers AMP, OP-10, and OP-15.
6. The process according to claim 4 or 5, characterized in that the polymerization conditions are at least such that: the pH value is 7-9, the temperature is 30-90 ℃, and the time is 6-12 h;
preferably, the amount of the initiator is 1mmol to 10mmol based on the total molar amount of the monomer A ', the monomer B', the monomer C 'and the monomer D'.
7. Use of an elastomeric polymer according to any one of claims 1 to 3 in the field of well plugging.
8. A water-based drilling fluid comprising an aqueous solvent and an elastomeric polymer, wherein the elastomeric polymer is present in an amount of 3 to 6 parts by weight per 100 parts by weight of the aqueous solvent;
the elastomeric polymer is an elastomeric polymer according to any one of claims 1 to 3.
9. The water-based drilling fluid of claim 8, wherein the water-based drilling fluid further comprises at least one of bentonite, a tackifier, an anti-sloughing agent, an inhibitor and sodium carbonate;
preferably, in the water-based drilling fluid, relative to 100 parts by weight of the aqueous solvent, the content of the bentonite is 2-4 parts by weight, the content of the tackifier is 0.1-2 parts by weight, the content of the anti-collapse agent is 2-4 parts by weight, the content of the inhibitor is 6-8 parts by weight, and the content of the sodium carbonate is 0.2-0.3 part by weight.
10. The water-based drilling fluid of claim 8 or 9, wherein the aqueous solvent is water;
the bentonite is sodium bentonite and/or calcium bentonite;
the tackifier is selected from at least one of polyanionic cellulose, polyacrylamide potassium salt and acrylamide-sodium acrylate copolymer;
the anti-collapse agent is selected from at least one of white asphalt, sulfonated asphalt, potassium humate and organic silicon;
the inhibitor is at least one selected from potassium chloride, sodium humate and inorganic positive electricity glue.
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