CN106084125A - Copolymer being applicable to extracting and cutting agent and its preparation method and application and saturated salt-water drilling fluid and application thereof - Google Patents
Copolymer being applicable to extracting and cutting agent and its preparation method and application and saturated salt-water drilling fluid and application thereof Download PDFInfo
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- CN106084125A CN106084125A CN201610585181.8A CN201610585181A CN106084125A CN 106084125 A CN106084125 A CN 106084125A CN 201610585181 A CN201610585181 A CN 201610585181A CN 106084125 A CN106084125 A CN 106084125A
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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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
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- 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
- C09K8/02—Well-drilling compositions
- C09K8/03—Specific additives for general use in well-drilling compositions
- C09K8/035—Organic additives
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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
- C09K8/02—Well-drilling compositions
- C09K8/04—Aqueous well-drilling compositions
- C09K8/06—Clay-free compositions
- C09K8/12—Clay-free compositions containing synthetic organic macromolecular compounds or their precursors
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Abstract
The present invention relates to the drilling applications of petroleum industry, disclose a kind of copolymer being applicable to extracting and cutting agent and its preparation method and application and saturated salt-water drilling fluid and application thereof.The copolymer being applicable to extracting and cutting agent contains the construction unit shown in the construction unit shown in formula (1), formula (2) and the construction unit shown in formula (3).The copolymer that the present invention provides, can be used in saturated salt-water drilling fluid as extracting and cutting agent, it can keep higher stability in saline, even if at a higher temperature, it also is able to that there is preferable Efficient Adhesive Promotion, effectively promotes the apparent viscosity of saturated salt-water drilling fluid system, yield value and gel strength.
Description
Technical field
The present invention relates to the drilling applications of petroleum industry, in particular it relates to a kind of copolymer being applicable to extracting and cutting agent and
Preparation method and application and saturated salt-water drilling fluid and application thereof.
Background technology
Saturated salt-water drilling fluid is a kind of Solid Free, cleaning, the drilling fluid system of high drilling speed.This system does not contains swelling
The solid phases such as soil, barite, are only made up of heavy weight additives such as polymerization species thickening extracting and cutting agent, fluid loss additive and inorganic salt KCl, NaCl.
The polymerization species thickening extracting and cutting agent kind being currently used for saturated salt-water drilling fluid system is less, predominantly partial hydrolysis polyacrylamide
Amine and the natural polymer such as xanthan gum, carboxymethyl cellulose, but all there is certain drawback in these thickening extracting and cutting agent: part water
Solve polyacrylamide to be affected by cation in lacking bentonitic highly concentrated saltwater environment, cause strand to be curled, from
And lose activity, further result in the viscosity of drilling fluid system, shear force declines to a great extent, lose suspending power；Natural polymer subclass
The temperature resistance of extracting and cutting agent is poor, and residue rate is big, has injury for reservoirs such as shallow gas.
Summary of the invention
The purpose of the present invention is for poor the lacking of the extracting and cutting agent salt-resistance in existing saturated salt-water drilling fluid and temperature resistance
Fall into, it is provided that a kind of copolymer being applicable to extracting and cutting agent having preferable salt-resistance and temperature resistance concurrently and its preparation method and application with
And saturated salt-water drilling fluid and application thereof.
To achieve these goals, the present invention provides a kind of copolymer being applicable to extracting and cutting agent, and this copolymer contains formula (1)
Construction unit shown in shown construction unit, formula (2) and the construction unit shown in formula (3), wherein:
Wherein, R1、R1'、R2、R2'、R5、R5'、R4With each R7It is each independently selected from the alkyl of H and C1-C8；R3、R6And R8
It is each independently selected from the alkylidene of C0-C8；X is selected from-NH-or-O-；N is the integer of 1-4.
Present invention also offers the preparation method of a kind of copolymer being applicable to extracting and cutting agent, the method includes: containing water-soluble
In agent, in the presence of radical initiator and chain-transferring agent, by formula (1') shown in compound, formula (2') shown in compound and
Formula (3') shown in compound carry out Raolical polymerizable, wherein,
Wherein, R1、R1'、R2、R2'、R5、R5'、R4With each R7It is each independently selected from the alkyl of H and C1-C8；R3、R6And R8
It is each independently selected from the alkylidene of C0-C8；X is selected from-NH-or-O-；N is the integer of 1-4.
Present invention also offers the copolymer being applicable to extracting and cutting agent prepared by said method.
Present invention also offers the application as extracting and cutting agent in drilling fluid of above-mentioned copolymer.
Present invention also offers a kind of containing above-mentioned copolymer as the saturated salt-water drilling fluid of extracting and cutting agent.
Present invention also offers the application in oil/gas drilling of the above-mentioned drilling fluid.
The copolymer that the present invention provides, it is possible to as extracting and cutting agent in saturated salt-water drilling fluid, it can be in saline
Keep higher stability, even if at a higher temperature, it is also possible to there is preferable Efficient Adhesive Promotion, effectively promote saturated
The apparent viscosity of DWSW liquid system, yield value and gel strength.
Other features and advantages of the present invention will be described in detail in detailed description of the invention part subsequently.
Detailed description of the invention
Hereinafter the detailed description of the invention of the present invention is described in detail.It should be appreciated that described herein specifically
Embodiment is merely to illustrate and explains the present invention, is not limited to the present invention.
The end points of scope disclosed in this article and any value are not limited to this accurate scope or value, these scopes or
Value should be understood to the value comprised close to these scopes or value.For numerical range, between the endpoint value of each scope, respectively
Between endpoint value and the single point value of individual scope, and can obtain one or more between single point value with combination with one another
New numerical range, these numerical rangies should be considered the most specifically to disclose.
The present invention provides a kind of copolymer being applicable to extracting and cutting agent, and this copolymer contains the construction unit shown in formula (1), formula
(2) construction unit shown in and the construction unit shown in formula (3), wherein:
Wherein, R1、R1'、R2、R2'、R5、R5'、R4With each R7It is each independently selected from the alkyl of H and C1-C8；R3、R6And R8
It is each independently selected from the alkylidene of C0-C8；X is selected from-NH-or-O-；N is the integer (for example, 1,2,3 or 4) of 1-4.
According to the present invention, described copolymer can be sufficiently spread out strand in saline, and is mutually wound high intensity
Space grid structure, thus in saturated salt-water drilling fluid system, show good thickening carry and cut performance.Even if higher
At a temperature of, the Efficient Adhesive Promotion that this copolymer provides also be able to effectively to promote saturated salt-water drilling fluid system apparent viscosity,
Yield value and gel strength.
According to the present invention, wherein, the alkyl of above-mentioned C1-C8 can be such as methyl, ethyl, n-pro-pyl, isopropyl, positive fourth
Base, isobutyl group, sec-butyl, the tert-butyl group, n-pentyl, isopentyl, n-hexyl, n-heptyl, n-nonyl etc..
The alkylidene that the alkylidene of above-mentioned C0-C8 such as can be formed by the alkyl of the alkylidene of C0, above-mentioned C1-C8.
Wherein, the alkylidene of C0 is it is believed that be only connecting key or do not exist, and the group at these group two ends will be joined directly together.
In order to preferably play the effect as extracting and cutting agent of the described copolymer, under preferable case, R1、R1'、R2、R2'、
R5、R5'、R4With each R7It is each independently selected from the alkyl of H and C1-C6；R3、R6And R8It is each independently selected from the alkylene of C0-C6
Base；N is the integer of 1-3.
It is highly preferred that R1、R1'、R2、R2'、R5、R5'And R4It is each independently selected from the alkyl of H and C1-C4；Each R7Each
Alkyl independently selected from C1-C6；R3Alkylidene selected from C0-C4；R6And R8It is each independently selected from the alkylidene of C1-C6.
It is further preferred that R1、R1'、R2、R2'、R5、R5'And R4Be each independently selected from H, methyl, ethyl, n-pro-pyl,
Isopropyl and normal-butyl；Each R7It is each independently selected from methyl, ethyl, n-pro-pyl, isopropyl and normal-butyl；R3Selected from C0's
Alkylidene ,-CH2-、-CH2-CH2-、-CH2-CH2-CH2-、-CH(CH3)-CH2-、-CH2-CH(CH3)-or-CH2-(CH2)2-
CH2-；R6And R8It is each independently selected from-CH2-、-CH2-CH2-、-CH2-CH2-CH2-、-CH(CH3)-CH2-、-CH2-CH
(CH3)-、-CH2-(CH2)2-CH2-、-CH2-CH(CH3)-CH2-、-C(CH3)2-CH2-、-CH2-C(CH3)2-、-CH2-(CH2)3-
CH2-and-CH2-(CH2)4-CH2-。
In the case of according to the invention it is preferred to, the weight average molecular weight of described copolymer is 1,000,000-6,000,000g/
Mol, more preferably 2,000,000-5,500,000g/mol, the most preferably 2,500,000-5,000,000g/mol,
More preferably 3,000,000-4,500,000g/mol, for example, 3,000,000-4,000,000g/mol.When this copolymer
Weight average molecular weight within the above range time, particularly 3,000,000-4, during 500,000g/mol scope, the polymer of gained
Extracting and cutting agent can be well used as, it is possible in saturated salt-water drilling fluid, keep preferable anti-salt and heat-resisting property.Described copolymerization
The molecular weight distribution index of thing can be such as 1.2-4, preferably 1.5-3.
According to the present invention, although the structure list shown in the construction unit shown in the formula that described copolymer contains (1), formula (2)
The amount of unit and the construction unit shown in formula (3) can change in wider scope, but be in order at the copolymer of optimization gained
Thickening, anti-salt and heat-resisting property consider, under preferable case, the construction unit shown in the construction unit shown in formula (1), formula (2) and
The mol ratio of the construction unit shown in formula (3) is 10-40:1-10:1, more preferably 15-30:2-5:1, is further preferably
18-25:3-4:1.
According to the present invention, described copolymer is understood as a kind of linear copolymer, can be random, block
, alternately, but be generally understood as a kind of linear random copolymer.Although described copolymer can also include
Do not affect its other construction units as extracting and cutting agent performance it should be appreciated that, for the sake of convenience, described copolymer is by formula
(1) construction unit shown in the construction unit shown in, formula (2) and the construction unit shown in formula (3) are constituted, but end group is also
It is not particularly limited, but is hydrogen under normal circumstances.
Present invention also offers the preparation method of a kind of copolymer being applicable to extracting and cutting agent, the method includes: containing water-soluble
In agent, in the presence of radical initiator and chain-transferring agent, by formula (1') shown in compound, formula (2') shown in compound and
Formula (3') shown in compound carry out Raolical polymerizable, wherein,
Wherein, R1、R1'、R2、R2'、R5、R5'、R4With each R7It is each independently selected from the alkyl of H and C1-C8；R3、R6And R8
It is each independently selected from the alkylidene of C0-C8；X is selected from-NH-or-O-；N is the integer of 1-4.
Wherein, each substituent group that the monomer in said method relates to is as described above, does not repeats them here.Formula
Shown in compound, formula (2') shown in compound and formula (3') shown in compound can also be according to described above
The concrete construction unit kind of copolymer properly select.
Wherein, the instantiation of the compound that formula is (1') shown such as can be for the one in the compound shown in following formula
Or multiple:
In formula (1'-1): R1And R1'For H (also referred to as acrylamide)；
In formula (1'-2): R1For methyl, R1'For H (also referred to as Methacrylamide)；
In formula (1'-3): R1For ethyl, R1'For H (also referred to as ethyl acrylamide)；
In formula (1'-4): R1For H, R1'For methyl (also referred to as 2-butylene amide).
Wherein, the instantiation of the compound that formula is (2') shown such as can be for the one in the compound shown in following formula
Or multiple:
In formula (2'-1): R4、R2And R2'For H, R3Selected from the alkylidene of C0, n=2 (also referred to as NVP)；
In formula (2'-2): R4、R2And R2'For H, R3Selected from the alkylidene of C0, n=1；
In formula (2'-3): R4、R2And R2'For H, R3Selected from the alkylidene of C0, n=3；
In formula (2'-4): R4、R2And R2'For H, R3Selected from-CH2-, n=2；
In formula (2'-5): R4、R2And R2'For H, R3Selected from-CH2-, n=1；
In formula (2'-6): R4、R2And R2'For H, R3Selected from-CH2-, n=3.
Wherein, the instantiation of the compound that formula is (3') shown such as can be for the one in the compound shown in following formula
Or multiple:
In formula (3'-1): R5For methyl, R5'For H, X selected from-O-, R6Selected from-CH2-CH2-, R7It is methyl, R8Selected from-
CH2-CH2-CH2-(also referred to as 3-[N, N-dimethyl-[2-(methacryloxy) ethyl] ammonium] propyl group-1-sulfonate)；
In formula (3'-2): R5For methyl, R5'For H, X selected from-O-, R6Selected from-CH2-CH2-, R7It is methyl, R8Selected from-
CH2-CH(CH3)-CH2-(also referred to as 3-[N, N-dimethyl-[2-(methacryloxy) ethyl] ammonium] isobutyl group-1-sulfonic acid
Salt)；
In formula (3'-3): R5And R5'For H, X selected from-NH-, R6Selected from-CH2-CH2-CH2-, R7It is methyl, R8Selected from-
CH2-CH2-CH2-(also referred to as [3-(methacrylamido) propyl group] dimethyl (3-sulfopropyl) ammonium hydroxide)；
In formula (3'-4): R5And R5'For H, X selected from-NH-, R6Selected from-CH2-CH2-CH2-, R7It is methyl, R8Selected from-
CH2-(CH2)2-CH2-(also referred to as [3-(methacrylamido) propyl group] dimethyl (3-thiobutyl) ammonium hydroxide)；
In formula (3'-5): R5For methyl, R5'For H, X selected from-O-, R6Selected from-CH2-CH2-, R7It is methyl, R8Selected from-CH
(CH3)2-CH2-(also referred to as 3-[N, N-dimethyl-[2-(methacryloxy) ethyl] ammonium] tert-butyl group-1-sulfonate).
According to the present invention, the consumption of above-mentioned monomer can be according to the accounting of the construction unit of required copolymer and molecular weight
Select, under preferable case, formula (1') shown in compound, formula (2') shown in compound and formula (3') shown in compound
Mol ratio be 10-40:1-10:1, more preferably 15-30:2-5:1, the most preferably 18-25:3-4:1, for example,
20-25:3-4:1.In order to be suitable to the carrying out of described Raolical polymerizable, and reasonably control the copolymer molecule of gained
Amount, under preferable case, the formula relative to 1mol (1') shown in compound, formula (2') shown in compound and formula (3') shown in
Mole total amount of compound, the consumption of described aqueous solvent is 400-1000mL, preferably 400-600mL.Wherein, described aqueous
Solvent can be single water, it is also possible to be miscible solute (for example, sodium chloride, the chlorine having some reactions not affecting the present invention
Change one or more in potassium, sodium bromide, potassium bromide etc.) the mixture of water, the most preferably water.
According to the present invention, described Raolical polymerizable can use the multiple radical initiator that this area routine uses
Causing, it is contemplated that the reactivity between above-mentioned monomer, under preferable case, described radical initiator is 4,4'-
Azo (4-cyanopentanoic acid), azo diisobutyl amidine hydrochlorate, azo diisopropyl imidazoline hydrochloride and azo diisobutyl
One or more in imidazoline hydrochloride.The consumption of described radical initiator can change in relative broad range, it is preferable that
Formula relative to 1mol (1') shown in compound, formula (2') shown in compound and formula (3') shown in compound mole total
Amount, the consumption of described radical initiator is 0.1-0.2mmol, preferably 0.11-0.14mmol.
According to the present invention, described chain-transferring agent can use the multiple chain-transferring agent that this area routine uses, it is contemplated that
To obtaining the copolymer of more particularly suitable molecular weight, under preferable case, described chain-transferring agent selected from sodium formate, sodium acetate,
One or more in ammonium hydroxide and carbamide, more preferably sodium formate and/or sodium acetate.The consumption of described chain-transferring agent is permissible
In relative broad range change, it is preferable that the formula relative to 1mol (1') shown in compound, formula (2') shown in compound and formula
(3') mole total amount of the compound shown in, the consumption of described chain-transferring agent is 0.1-0.2mmol, preferably 0.13-
0.15mmol。
In the case of according to the invention it is preferred to, the condition of described Raolical polymerizable includes: temperature is 40-80 DEG C, the time
For 6-12h.It is highly preferred that the condition of described Raolical polymerizable includes: temperature is 50-70 DEG C, the time is 7-10h.
According to the present invention, in order to the metal ingredient that some in the system of going out are possible, it is preferable that above-mentioned copolymer
In preparation method, described Raolical polymerizable is also carried out in the presence of chelating agen.In this case, by the work of chelating agen
With, just can be smoothly through chelation and suppress the metal ion that some are possible.Described chelating agen such as can be selected from ethylenediamine
Tetraacethyl and salt (such as sodium ethylene diamine tetracetate), nitrilotriacetic acid and salt (sodium ammonium triacetate), hexa metaphosphoric acid and salt (six thereof
Polymeric sodium metaphosphate .) and diethylenetriamine penta in one or more.Preferably, the formula relative to 1mol is (1') shown
Compound, formula (2') shown in compound and formula (3') shown in mole total amount of compound, the consumption of described chelating agen is
0.01-0.05mmol, more preferably 0.01-0.02mmol.
According to the present invention, in order to keep the activity of initiator etc., the method can also include: makes described free radical
Polyreaction is carried out in an inert atmosphere, such as can be passed through in system nitrogen, helium, neon, argon etc. one or more
And replace atmosphere therein (this process such as can carry out 5-300min, mainly deoxygenation).
According to the present invention, in order to better control over the carrying out of above-mentioned Raolical polymerizable, it is preferable that the method bag
Include: first by formula (1') shown in compound, formula (2') shown in compound, formula (3') shown in compound and aqueous solvent carry out
Mixing (this mixing condition such as can be included under the mixing speed of 100-300rpm, 10-40 DEG C at mix 10-40min), then
Introduce described radical initiator, chain-transferring agent and optional chelating agen to mix, and (this inert atmosphere under an inert atmosphere
Formed described in above) carry out as described in Raolical polymerizable.
According to the present invention, in order to will extract in described copolymer product from the reactions above, the method is all right
Including: the product of described Raolical polymerizable is dried at 70-100 DEG C 2-5h.
Present invention also offers the copolymer being applicable to extracting and cutting agent prepared by said method.Although the present invention is the most especially
Restriction, but this copolymer may be considered above described in copolymer in one, or multiple copolymer is mixed
Compound.However, it is to be understood that the copolymer prepared by said method typically refer to said method without purify direct
Product (or merely through the above dried), the product of even now is probably the mixture of multiple polymers, but
Such situation is also included within the scope of the invention by the present invention.
Present invention also offers above-mentioned copolymer or carried by the conduct in drilling fluid of the copolymer prepared by said method
Cut the application of agent.
Present invention also offers a kind of containing above-mentioned copolymer as the saturated salt-water drilling fluid of extracting and cutting agent.
The copolymer that the present invention provides, it is possible to as extracting and cutting agent in saturated salt-water drilling fluid, it can be in saline
Keep higher stability, even if at a higher temperature, it is also possible to there is preferable Efficient Adhesive Promotion, effectively promote saturated
The apparent viscosity of DWSW liquid system, yield value and gel strength.There is no particular limitation to the content of this copolymer for the present invention,
The consumption of the extracting and cutting agent of routine can be used, naturally it is also possible to suitably adjust according to the situation of different wells, it is preferable that
The content of described copolymer is 1-2 weight % (on the basis of the gross weight of described saturated salt-water drilling fluid).
According to the present invention, described saturated salt-water drilling fluid can be the various saturated salt-water drilling fluids that this area is conventional, example
As can be salt content be the salt-containing drilling liquid of 5-40 weight % (preferably 20-35 weight %).Wherein, described saturated salt water drilling
Salt in well liquid can be such as one or more in NaCl, KCl, NaBr and KBr.
According to the present invention, described saturated salt-water drilling fluid except can be above-mentioned salt and extracting and cutting agent in addition to, it is also possible to contain
The various additives in saturated salt-water drilling fluid that this area is conventional, such as fluid loss additive.
Wherein, one or more in fluid loss additive such as starch, PAC-LV, albino bitumen and sulfonated gilsonite, its content example
As being 1.5-3 weight %.
The various materials that above-mentioned additive is can be commercially available product, it is also possible to prepares according to the method that this area is conventional, this
In repeat no more.
Present invention also offers the application in oil/gas drilling of the above-mentioned drilling fluid.
When the drilling fluid of the present invention is applied in oil/gas drilling, it is possible to remain in that higher at a higher temperature
Apparent viscosity, yield value and gel strength, it is adaptable to higher layer environment.
Hereinafter will be described the present invention by embodiment.
In following example and comparative example, weight average molecular weight and molecular weight distributing index are to use (the experiment of GPC gel chromatography
Instrument is the gel permeation chrommatograph of waters company of the U.S., and model is E2695) measure.
Embodiment 1
The present embodiment is for copolymer that the present invention is described and preparation method thereof and extracting and cutting agent.
By the acrylamide of 1mol total amount, NVP and 3-[N, N-dimethyl-[2-(methacryloxypropyl
Base) ethyl] ammonium] propyl group-1-sulfonate (mol ratio is 25:4:1) joins in the water of 500mL, stirs at 150rpm, at 30 DEG C
Mixing 30min；And backward this mixture adds the 4,4'-azo of the disodiumedetate of 0.01mmol, 0.12mmol
(4-cyanopentanoic acid) and the sodium acetate of 0.14mmol, and it is passed through nitrogen 15min with deoxygenation；At 60 DEG C, then carry out polyreaction
8h；Polymerizate is dried at 90 DEG C 2.5h, pulverizes and obtain copolymer, be extracting and cutting agent A1.The Weight-average molecular of this polymer
Amount is 4,000,000g/mol, and molecular weight distribution index is 1.5, detects through infrared, proton nmr spectra and carbon analysis of spectrum, formula
(1) construction unit (R shown in1And R1'For H), the construction unit (R shown in formula (2)4、R2And R2'For H, R3Alkylene selected from C0
Base, n=2) and formula (3) shown in construction unit (R5For methyl, R5'For H, X selected from-O-, R6Selected from-CH2-CH2-, R7It is first
Base, R8Selected from-CH2-CH2-CH2-) mol ratio be 25:3.75:1.
Embodiment 2
The present embodiment is for copolymer that the present invention is described and preparation method thereof and extracting and cutting agent.
By the Methacrylamide of 1mol total amount, NVP and [3-(methacrylamido) propyl group] two
Methyl (3-sulfopropyl) ammonium hydroxide (mol ratio is 20:4:1) joins in the water of 500mL, at 200rpm, stirs at 30 DEG C
Mixing 30min；And backward this mixture adds azo two isobutyl of the disodiumedetate of 0.01mmol, 0.14mmol
Amidine hydrochlorate and the sodium formate of 0.15mmol, and it is passed through nitrogen 20min with deoxygenation；At 50 DEG C, then carry out polyreaction 10h；
Polymerizate is dried at 80 DEG C 3h, pulverizes and obtain copolymer, be extracting and cutting agent A2.The weight average molecular weight of this polymer is 3,
200,000g/mol, molecular weight distribution index is 2.2, detects through infrared, proton nmr spectra and carbon analysis of spectrum, shown in formula (1)
Construction unit (R1For methyl, R1'For H), the construction unit (R shown in formula (2)4、R2And R2'For H, R3Selected from the alkylidene of C0, n
=2) and the construction unit (R shown in formula (3)5And R5'For H, X selected from-NH-, R6Selected from-CH2-CH2-CH2-, R7It is methyl, R8
Selected from-CH2-CH2-CH2-) mol ratio be 18:3.2:1.
Embodiment 3
The present embodiment is for copolymer that the present invention is described and preparation method thereof and extracting and cutting agent.
By the acrylamide of 1mol total amount, NVP and 3-[N, N-dimethyl-[2-(methacryloxypropyl
Base) ethyl] ammonium] propyl group-1-sulfonate (mol ratio is 25:4:1) joins in the water of 400mL, stirs at 200rpm, at 40 DEG C
Mixing 20min；And backward this mixture adds the 4,4'-azo of the disodiumedetate of 0.02mmol, 0.12mmol
(4-cyanopentanoic acid) and the sodium acetate of 0.14mmol, and it is passed through nitrogen 10min with deoxygenation；At 70 DEG C, then carry out polyreaction
7h；Polymerizate is dried at 90 DEG C 5h, pulverizes and obtain copolymer, be extracting and cutting agent A3.The weight average molecular weight of this polymer
Being 3,000,000g/mol, molecular weight distribution index is 2.8, detects through infrared, proton nmr spectra and carbon analysis of spectrum, formula (1)
Shown construction unit (R1And R1'For H), the construction unit (R shown in formula (2)4、R2And R2'For H, R3Selected from the alkylidene of C0, n
=2) and the construction unit (R shown in formula (3)5For methyl, R5'For H, X selected from-O-, R6Selected from-CH2-CH2-, R7It is methyl, R8
Selected from-CH2-CH2-CH2-) mol ratio be 22:3.5:1.
Embodiment 4
According to the method described in embodiment 1, except for the difference that, the consumption as the water of the solvent of reaction system is 1000mL,
Thus finally pulverize and obtain copolymer, it is extracting and cutting agent A4.The weight average molecular weight of this polymer is 2,400,000g/mol, molecule
Amount breadth coefficient is 1.7, detects through infrared, proton nmr spectra and carbon analysis of spectrum, the construction unit (R shown in formula (1)1And R1'
For H), the construction unit (R shown in formula (2)4、R2And R2'For H, R3Selected from the alkylidene of C0, n=2) and formula (3) shown in structure
Unit (R5For methyl, R5'For H, X selected from-O-, R6Selected from-CH2-CH2-, R7It is methyl, R8Selected from-CH2-CH2-CH2-) rub
That ratio is 25:3.75:1.
Embodiment 5
According to the method described in embodiment 1, except for the difference that, the temperature of the polyreaction carried out after logical nitrogen deoxygenation is 30
DEG C, thus finally pulverize and obtain copolymer, it is extracting and cutting agent A5.The weight average molecular weight of this polymer is 5,100,000g/mol,
Molecular weight distribution index is 2.0, detects through infrared, proton nmr spectra and carbon analysis of spectrum, the construction unit (R shown in formula (1)1
And R1'For H), the construction unit (R shown in formula (2)4、R2And R2'For H, R3Selected from the alkylidene of C0, n=2) and formula (3) shown in
Construction unit (R5For methyl, R5'For H, X selected from-O-, R6Selected from-CH2-CH2-, R7It is methyl, R8Selected from-CH2-CH2-CH2-)
Mol ratio be 25:3.9:1.
Comparative example 1
According to the method described in embodiment 1, except for the difference that, 3-[N, N-dimethyl-[2-(methacryloxypropyl is not used
Base) ethyl] ammonium] propyl group-1-sulfonate, but the acrylamide and the NVP conduct that use mol ratio to be 6:1
Monomer, and total consumption of monomer is 1mol, thus prepare copolymer, it is extracting and cutting agent DA1.The weight average molecular weight of this polymer is
4,400,000g/mol, molecular weight distribution index is 1.6.
Comparative example 2
According to the method described in embodiment 1, except for the difference that, do not use NVP, but use mol ratio
Acrylamide and 3-[N, N-dimethyl-[2-(methacryloxy) ethyl] ammonium] propyl group-1-sulfonate conduct for 25:1
Monomer, and total consumption of monomer is 1mol, thus prepare copolymer, it is extracting and cutting agent DA2.The weight average molecular weight of this polymer is
3,200,000g/mol, molecular weight distribution index is 2.4.
Test case 1
Preparation: saline Y1 is the NaCl aqueous solution of 10 weight %；
Saline Y2 is the NaCl aqueous solution of 30 weight %；
(concrete carrying of test selection is cut to be separately added into the one in the extracting and cutting agent obtained by above-mentioned example in above-mentioned saline
Agent is shown in Table 1), obtain the saline solution containing 2 weight % extracting and cutting agent and be not added with the saline of extracting and cutting agent as blank right
According to, and by high-speed stirred 20min under the conditions of blender 3000r/min, under room temperature (25 ± 5 DEG C), measure drilling wells with six speed viscometers
Apparent viscosity, yield value, gel initial and the 10-minute gel strength of liquid-based slurry measure, and the results are shown in Table shown in 1；
Apparent viscosity (AV) is calculated as follows: AV=0.5 × φ 600, and unit is mPa s.‘’
Yield value (YP) is calculated as follows: YP=0.511 × (2 × φ 300-φ 600), unit is Pa.
Gel initial calculates by the following method: stir 10s under the speed of 600r/min, reads the maximum of φ 3 after standing 10s
Reading, then obtains gel initial by full-scale reading divided by 2, and unit is Pa.
10-minute gel strength calculates by the following method: stir 10s under the speed of 600r/min, stands and reads φ 3 after 10min
Big reading, then obtains 10-minute gel strength by full-scale reading divided by 2, and unit is Pa.
Table 1
By table 1 it can be seen that the extracting and cutting agent of the present invention shows in 10 weight % or 30 weight %NaCl saline
Significantly thickening carries and cuts effect, and yield value, gel initial and 10-minute gel strength are all obviously improved, and the extracting and cutting agent of the present invention has bright simultaneously
Aobvious Efficient Adhesive Promotion, is effectively improved the apparent viscosity of saline.Compared to the copolymer of comparative example, use as extracting and cutting agent of the present invention
The salt tolerance of copolymer significantly higher, can use in high concentration saline.
Test case 2
The starch of drilling well liquid-based slurry Y3:2 weight %, the KCl of 35 weight %, surplus is water.
Above-mentioned drilling well liquid-based slurry is separately added into the extracting and cutting agent obtained by above-mentioned example, and (extracting and cutting agent that concrete test is selected is shown in
Shown in table 2) obtain the drilling fluid containing the extracting and cutting agent obtained by the 1.5 above-mentioned examples of weight % and to be not added with above-mentioned example made
The drilling well liquid-based of the extracting and cutting agent obtained is starched as blank, before ageing and incites somebody to action after 90 DEG C of aging 16h, after 120 DEG C of aging 16h
High-speed stirred 20min under the conditions of using blender 3000r/min to room temperature (25 ± 5 DEG C), measures drilling well liquid-based with six speed viscometers
Apparent viscosity, yield value, gel initial, 10-minute gel strength and the middle filter pressing vector (API) of slurry, the results are shown in Table shown in 2；
Apparent viscosity, yield value, gel initial and 10-minute gel strength use the method in test case 1 to measure, and API refers to middle pressure
Filter loss, is that in using, filter pressing is committed a breach of etiquette and measured according to the method in SY/T 5621-93 standard, and unit is mL.
Table 2
During by table 2 it can be seen that the copolymer of the present invention is used for during saturated salt-water drilling fluid has as extracting and cutting agent, it is possible to
Keep good rheological characteristic, certain yield value, gel initial, 10-minute gel strength can be kept under relatively low viscosity, the most common with starch
Use and also have part filtrate reducing effect；The rheological characteristic of saturated salt-water drilling fluid of the present invention, filter loss change after 90 DEG C of heat rollings
The least, after 120 DEG C of heat rollings, rheological characteristic, filter loss also can meet normal use, and the extracting and cutting agent of this explanation present invention has preferably
Heat-resisting property.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited in above-mentioned embodiment
Detail, in the technology concept of the present invention, technical scheme can be carried out multiple simple variant, this
A little simple variant belong to protection scope of the present invention.
It is further to note that each the concrete technical characteristic described in above-mentioned detailed description of the invention, at not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to various can
The compound mode of energy illustrates the most separately.
Additionally, combination in any can also be carried out between the various different embodiment of the present invention, as long as it is without prejudice to this
The thought of invention, it should be considered as content disclosed in this invention equally.
Claims (17)
1. the copolymer being applicable to extracting and cutting agent, it is characterised in that this copolymer contains the construction unit shown in formula (1), formula
(2) construction unit shown in and the construction unit shown in formula (3), wherein:
Formula (1)Formula (2)
Formula (3)
Wherein, R1、R1'、R2、R2'、R5、R5'、R4With each R7It is each independently selected from the alkyl of H and C1-C8；R3、R6And R8Each
Alkylidene independently selected from C0-C8；X is selected from-NH-or-O-；N is the integer of 1-4.
Copolymer the most according to claim 1, wherein, R1、R1'、R2、R2'、R5、R5'、R4With each R7Select independently of one another
From the alkyl of H and C1-C6；R3、R6And R8It is each independently selected from the alkylidene of C0-C6；N is the integer of 1-3；
Preferably, R1、R1'、R2、R2'、R5、R5'And R4It is each independently selected from the alkyl of H and C1-C4；Each R7Independently of one another
Alkyl selected from C1-C6；R3Alkylidene selected from C0-C4；R6And R8It is each independently selected from the alkylidene of C1-C6；
It is highly preferred that R1、R1'、R2、R2'、R5、R5'And R4It is each independently selected from H, methyl, ethyl, n-pro-pyl, isopropyl and just
Butyl；Each R7It is each independently selected from methyl, ethyl, n-pro-pyl, isopropyl and normal-butyl；R3Selected from C0 alkylidene ,-
CH2-、-CH2-CH2-、-CH2-CH2-CH2-、-CH(CH3)-CH2-、-CH2-CH(CH3)-or-CH2-(CH2)2-CH2-；R6And R8
It is each independently selected from-CH2-、-CH2-CH2-、-CH2-CH2-CH2-、-CH(CH3)-CH2-、-CH2-CH(CH3)-、-CH2-
(CH2)2-CH2-、-CH2-CH(CH3)-CH2-、-C(CH3)2-CH2-、-CH2-C(CH3)2-、-CH2-(CH2)3-CH2-and-CH2-
(CH2)4-CH2-。
Copolymer the most according to claim 1 and 2, wherein, the structure list shown in the construction unit shown in formula (1), formula (2)
The mol ratio of unit and the construction unit shown in formula (3) is 10-40:1-10:1, preferably 15-30:2-5:1.
4. according to the copolymer described in any one in claim 1-3, wherein, the weight average molecular weight of described copolymer is 1,
000,000-6,000,000g/mol, preferably 2,000,000-5,500,000g/mol, more preferably 2,500,000-5,
000,000g/mol, the most preferably 3,000,000-4,500,000g/mol.
5. the preparation method of the copolymer being applicable to extracting and cutting agent, it is characterised in that the method includes: in aqueous solvent,
In the presence of radical initiator and chain-transferring agent, by formula (1') shown in compound, formula (2') shown in compound and formula
(3') the compound shown in carries out Raolical polymerizable, wherein,
Formula is (1')Formula is (2')
Formula is (3')
Wherein, R1、R1'、R2、R2'、R5、R5'、R4With each R7It is each independently selected from the alkyl of H and C1-C8；R3、R6And R8Each
Alkylidene independently selected from C0-C8；X is selected from-NH-or-O-；N is the integer of 1-4.
Method the most according to claim 5, wherein, R1、R1'、R2、R2'、R5、R5'、R4With each R7It is each independently selected from H
Alkyl with C1-C6；R3、R6And R8It is each independently selected from the alkylidene of C0-C6；N is the integer of 1-3；
Preferably, R1、R1'、R2、R2'、R5、R5'And R4It is each independently selected from the alkyl of H and C1-C4；Each R7Independently of one another
Alkyl selected from C1-C6；R3Alkylidene selected from C0-C4；R6And R8It is each independently selected from the alkylidene of C1-C6；
It is highly preferred that R1、R1'、R2、R2'、R5、R5'And R4It is each independently selected from H, methyl, ethyl, n-pro-pyl, isopropyl and just
Butyl；Each R7It is each independently selected from methyl, ethyl, n-pro-pyl, isopropyl and normal-butyl；R3Selected from C0 alkylidene ,-
CH2-、-CH2-CH2-、-CH2-CH2-CH2-、-CH(CH3)-CH2-、-CH2-CH(CH3)-or-CH2-(CH2)2-CH2-；R6And R8
It is each independently selected from-CH2-、-CH2-CH2-、-CH2-CH2-CH2-、-CH(CH3)-CH2-、-CH2-CH(CH3)-、-CH2-
(CH2)2-CH2-、-CH2-CH(CH3)-CH2-、-C(CH3)2-CH2-、-CH2-C(CH3)2-、-CH2-(CH2)3-CH2-and-CH2-
(CH2)4-CH2-。
7. according to the method described in claim 5 or 6, wherein, formula (1') shown in compound, formula (2') shown in compound and
Formula (3') shown in the mole dosage ratio of compound for 10-40:1-10:1, preferably 15-30:2-5:1；
Preferably, the formula relative to 1mol (1') shown in compound, formula (2') shown in compound and formula (3') shown in change
Mole total amount of compound, the consumption of described aqueous solvent is 400-1000mL, preferably 400-600mL.
Method the most according to claim 5, wherein, described radical initiator is 4,4'-azo (4-cyanopentanoic acid), idol
One in nitrogen diisobutyl amidine hydrochlorate, azo diisopropyl imidazoline hydrochloride and azo diisobutyl imidazoline hydrochloride
Or it is multiple；
Preferably, the formula relative to 1mol (1') shown in compound, formula (2') shown in compound and formula (3') shown in change
Mole total amount of compound, the consumption of described radical initiator is 0.1-0.2mmol, preferably 0.11-0.14mmol.
Method the most according to claim 5, wherein, described chain-transferring agent is selected from sodium formate, sodium acetate, ammonium hydroxide and urine
One or more in element；
Preferably, the formula relative to 1mol (1') shown in compound, formula (2') shown in compound and formula (3') shown in change
Mole total amount of compound, the consumption of described chain-transferring agent is 0.1-0.2mmol, preferably 0.13-0.15mmol.
Method the most according to claim 5, wherein, the condition of described Raolical polymerizable includes: temperature is 40-80
DEG C, the time is 6-12h；
Preferably, the condition of described Raolical polymerizable includes: temperature is 50-70 DEG C, and the time is 7-10h.
11. according to the method described in any one in claim 5-10, and wherein, described Raolical polymerizable is also at chelating agen
In the presence of carry out, described chelating agen be selected from ethylenediaminetetraacetic acid and salt, nitrilotriacetic acid and salt thereof, hexa metaphosphoric acid and salt thereof and two
One or more in ethylene triamine pentamethylene phosphonic acids；
Preferably, the formula relative to 1mol (1') shown in compound, formula (2') shown in compound and formula (3') shown in change
Mole total amount of compound, the consumption of described chelating agen is 0.01-0.05mmol, preferably 0.01-0.02mmol.
12. methods according to claim 11, wherein, the method includes: first by compound (1') shown for formula, formula (2')
Shown compound, formula (3') shown in compound and aqueous solvent mix, be re-introduced into described radical initiator, chain turns
Move agent and optional chelating agen, and carry out described Raolical polymerizable under an inert atmosphere.
13. copolymers being applicable to extracting and cutting agent prepared by the method described in any one in claim 5-12.
In 14. claim 1-4 and 13 copolymer described in any one in drilling fluid as the application of extracting and cutting agent.
15. 1 kinds containing copolymer described in any one in claim 1-4 and 13 as the saturated brine drilling well of extracting and cutting agent
Liquid.
16. drilling fluids according to claim 15, wherein, the content of described copolymer is 1-2 weight %.
The application in oil/gas drilling of the drilling fluid described in 17. claim 15 or 16.
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| CN110016325A (en) * | 2018-01-10 | 2019-07-16 | 中国石油化工股份有限公司 | A kind of water-base drilling fluid extracting and cutting agent and preparation method thereof |
| CN110396152A (en) * | 2019-06-26 | 2019-11-01 | 中国石油集团川庆钻探工程有限公司钻井液技术服务公司 | The hydrophobically modified polyacrylamide polymer for being suitable for supermolecule extracting and cutting agent and the application in water-base drilling fluid |
| CN115960310A (en) * | 2021-10-09 | 2023-04-14 | 中国石油化工股份有限公司 | Polymer cutting agent, well slurry gas stagnation and preparation method thereof |
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| CN110016325A (en) * | 2018-01-10 | 2019-07-16 | 中国石油化工股份有限公司 | A kind of water-base drilling fluid extracting and cutting agent and preparation method thereof |
| CN110396152A (en) * | 2019-06-26 | 2019-11-01 | 中国石油集团川庆钻探工程有限公司钻井液技术服务公司 | The hydrophobically modified polyacrylamide polymer for being suitable for supermolecule extracting and cutting agent and the application in water-base drilling fluid |
| CN110396152B (en) * | 2019-06-26 | 2021-08-06 | 中国石油集团川庆钻探工程有限公司钻井液技术服务公司 | Hydrophobically modified polyacrylamide polymer suitable for use as supramolecular shear promoter and use in water-based drilling fluids |
| CN115960310A (en) * | 2021-10-09 | 2023-04-14 | 中国石油化工股份有限公司 | Polymer cutting agent, well slurry gas stagnation and preparation method thereof |
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