CN106084125B - Copolymer suitable for extracting and cutting agent and its preparation method and application and saturated salt-water drilling fluid and its application - Google Patents
Copolymer suitable for extracting and cutting agent and its preparation method and application and saturated salt-water drilling fluid and its application Download PDFInfo
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- CN106084125B CN106084125B CN201610585181.8A CN201610585181A CN106084125B CN 106084125 B CN106084125 B CN 106084125B CN 201610585181 A CN201610585181 A CN 201610585181A CN 106084125 B CN106084125 B CN 106084125B
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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 suitable for copolymer of extracting and cutting agent and its preparation method and application and saturated salt-water drilling fluid and its application.Contain the construction unit shown in formula (1), the construction unit shown in formula (2) and the construction unit shown in formula (3) suitable for the copolymer of extracting and cutting agent.Copolymer provided by the invention, it can be used in being used as extracting and cutting agent in saturated salt-water drilling fluid, it can keep higher stability in salt solution, even at a higher temperature, also there can be preferable Efficient Adhesive Promotion, effectively lift apparent viscosity, yield value and the gel strength of saturated salt-water drilling fluid system.
Description
Technical field
The present invention relates to the drilling applications of petroleum industry, in particular it relates to a kind of copolymer suitable for extracting and cutting agent and its
Preparation method and application and saturated salt-water drilling fluid and its application.
Background technology
Saturated salt-water drilling fluid is a kind of Solid Free, cleaning, the drilling fluid system of high drilling speed.The system does not contain swelling
The solid phases such as soil, barite, only viscosify the heavy weight additive such as extracting and cutting agent, fluid loss additive and inorganic salts KCl, NaCl by polymerization species and form.
Polymerization species thickening extracting and cutting agent species currently used for saturated salt-water drilling fluid system is less, predominantly partial hydrolysis polyacrylamide
The natural polymer such as amine and xanthans, carboxymethyl cellulose, but the drawbacks of certain be present in these thickening extracting and cutting agents：Part water
Solution polyacrylamide can be influenceed in bentonitic highly concentrated saltwater environment is lacked by cation, 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, forfeiture 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.
The content of the invention
The purpose of the present invention lacks for the extracting and cutting agent salt-resistance in existing saturated salt-water drilling fluid and temperature resistance are poor
Fall into, there is provided it is a kind of have concurrently preferable salt-resistance and temperature resistance suitable for copolymer of extracting and cutting agent and its preparation method and application with
And saturated salt-water drilling fluid and its application.
To achieve these goals, the present invention provides a kind of copolymer suitable for extracting and cutting agent, and the 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 H and C1-C8 alkyl；R3、R6And R8
It is each independently selected from C0-C8 alkylidene；X is selected from-NH- or-O-；N is 1-4 integer.
Present invention also offers a kind of preparation method of the copolymer suitable for extracting and cutting agent, this method includes：Containing water-soluble
In agent, in the presence of radical initiator and chain-transferring agent, by formula (1') shown compound, formula (2') shown compound and
(3') shown compound carries out Raolical polymerizable to formula, wherein,
Wherein, R1、R1'、R2、R2'、R5、R5'、R4With each R7It is each independently selected from H and C1-C8 alkyl；R3、R6And R8
It is each independently selected from C0-C8 alkylidene；X is selected from-NH- or-O-；N is 1-4 integer.
Present invention also offers the copolymer for being applied to extracting and cutting agent as made from the above method.
Present invention also offers application of the above-mentioned copolymer in drilling fluid as extracting and cutting agent.
Present invention also offers a kind of saturated salt-water drilling fluid for containing above-mentioned copolymer as extracting and cutting agent.
Present invention also offers application of the above-mentioned drilling fluid in oil/gas drilling.
Copolymer provided by the invention, it can be used in being used as extracting and cutting agent in saturated salt-water drilling fluid, it can be in salt solution
Higher stability is kept, even at a higher temperature, can also have preferable Efficient Adhesive Promotion, effectively lift saturation
Apparent viscosity, yield value and the gel strength of DWSW liquid system.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The end points of disclosed scope and any value are not limited to the accurate scope or value herein, these scopes or
Value should be understood to comprising the value close to these scopes or value.For number range, between the endpoint value of each scope, respectively
It can be combined with each other between the endpoint value of individual scope and single point value, and individually between point value and obtain one or more
New number range, these number ranges should be considered as specific open herein.
The present invention provides a kind of copolymer suitable for extracting and cutting agent, and the copolymer contains construction unit shown in formula (1), formula
(2) construction unit shown in construction unit and formula (3) shown in, wherein：
Wherein, R1、R1'、R2、R2'、R5、R5'、R4With each R7It is each independently selected from H and C1-C8 alkyl；R3、R6And R8
It is each independently selected from C0-C8 alkylidene；X is selected from-NH- or-O-；The integer (being, for example, 1,2,3 or 4) that n is 1-4.
According to the present invention, the copolymer can be sufficiently spread out strand in salt solution, and mutually be wound high intensity
Space grid structure, performance is cut so as to show good thickening in saturated salt-water drilling fluid system and carry.Even higher
At a temperature of, the copolymer provide Efficient Adhesive Promotion also can effectively be lifted saturated salt-water drilling fluid system apparent viscosity,
Yield value and gel strength.
According to the present invention, wherein, above-mentioned C1-C8 alkyl for example can be methyl, ethyl, n-propyl, 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 above-mentioned C0-C8 alkylidene can for example be formed by C0 alkylidene, above-mentioned C1-C8 alkyl.
Wherein, C0 alkylidene, which can consider, is only connecting key or is not present, and the group at the group both ends will be joined directly together.
In order to preferably play effect of the copolymer as extracting and cutting agent, under preferable case, R1、R1'、R2、R2'、
R5、R5'、R4With each R7It is each independently selected from H and C1-C6 alkyl；R3、R6And R8It is each independently selected from C0-C6 alkylene
Base；N is 1-3 integer.
It is highly preferred that R1、R1'、R2、R2'、R5、R5'And R4It is each independently selected from H and C1-C4 alkyl；Each R7Each
Independently selected from C1-C6 alkyl；R3Alkylidene selected from C0-C4；R6And R8It is each independently selected from C1-C6 alkylidene.
It is further preferred that R1、R1'、R2、R2'、R5、R5'And R4Be each independently selected from H, methyl, ethyl, n-propyl,
Isopropyl and normal-butyl；Each R7It is each independently selected from methyl, ethyl, n-propyl, 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 the copolymer is 1,000,000-6,000,000g/
Mol, more preferably 2,000,000-5,500,000g/mol, it is still more 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 the copolymer
Weight average molecular weight within the above range when, particularly at 3,000,000-4,500,000g/mol scope, the polymer of gained
Extracting and cutting agent can be well used as, preferable salt resistance and heat-resisting property can be kept in saturated salt-water drilling fluid.The copolymerization
The molecular weight distribution index of thing for example can be 1.2-4, preferably 1.5-3.
According to the present invention, although the structure list shown in construction unit, formula (2) shown in the formula (1) that the copolymer contains
The amount of construction unit shown in member and formula (3) can change in wider scope, but be in order at the copolymer of optimization gained
Thickening, salt resistance and heat-resisting property consider, under preferable case, construction unit shown in construction unit, formula (2) shown in formula (1) and
The mol ratio of construction unit shown in formula (3) is 10-40：1-10：1, more preferably 15-30：2-5：1, still more preferably for
18-25：3-4：1.
According to the present invention, the copolymer is understood as a kind of linear copolymer, can be random, block
, it is alternate, but be generally understood as a kind of linear random copolymer.Although the copolymer can also include
Its other structures unit as extracting and cutting agent performance is not influenceed it should be appreciated that for the sake of convenient, the copolymer is by formula
(1) construction unit shown in construction unit, formula (2) shown in and the construction unit shown in formula (3) are formed, but end group is simultaneously
It is not particularly limited, but is under normal circumstances hydrogen.
Present invention also offers a kind of preparation method of the copolymer suitable for extracting and cutting agent, this method includes：Containing water-soluble
In agent, in the presence of radical initiator and chain-transferring agent, by formula (1') shown compound, formula (2') shown compound and
(3') shown compound carries out Raolical polymerizable to formula, wherein,
Wherein, R1、R1'、R2、R2'、R5、R5'、R4With each R7It is each independently selected from H and C1-C8 alkyl；R3、R6And R8
It is each independently selected from C0-C8 alkylidene；X is selected from-NH- or-O-；N is 1-4 integer.
Wherein, each substituent that the monomer in the above method is related to is as described above, will not be repeated here.Formula
(1') (2') (3') shown compound can also be according to described above for shown compound and formula for shown compound, formula
The specific construction unit species of copolymer properly selected.
Wherein, the instantiation of formula (1') shown compound for example can be one kind in the compound shown in following formula
It is or a variety of：
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- crotonamides).
Wherein, the instantiation of formula (2') shown compound for example can be one kind in the compound shown in following formula
It is or a variety of：
In formula (2'-1)：R4、R2And R2'For H, R3Alkylidene selected from C0, n=2 (also referred to as NVP)；
In formula (2'-2)：R4、R2And R2'For H, R3Alkylidene selected from C0, n=1；
In formula (2'-3)：R4、R2And R2'For H, R3Alkylidene selected from 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 formula (3') shown compound for example can be one kind in the compound shown in following formula
It is or a variety of：
In formula (3'-1)：R5For methyl, R5'- O-, R are selected from for H, X6Selected 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'- O-, R are selected from for H, X6Selected 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'- NH-, R are selected from for H, X6Selected from-CH2-CH2-CH2-, R7It is methyl, R8Selected from-
CH2-CH2-CH2- (also referred to as [3- (methacrylamido) propyl group] dimethyl (3- sulfopropyls) ammonium hydroxide)；
In formula (3'-4)：R5And R5'- NH-, R are selected from for H, X6Selected from-CH2-CH2-CH2-, R7It is methyl, R8Selected from-
CH2-(CH2)2-CH2- (also referred to as [3- (methacrylamido) propyl group] dimethyl (3- thiobutyls) ammonium hydroxide)；
In formula (3'-5)：R5For methyl, R5'- O-, R are selected from for H, X6Selected 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 dosage of above-mentioned monomer can be according to the accounting and molecular weight of the construction unit of required copolymer
Selected, under preferable case, formula (1') shown compound, formula (2') shown compound and formula (3') shown compound
Mol ratio be 10-40：1-10：1, more preferably 15-30：2-5：1, it is still more preferably 18-25：3-4：1, be, for example,
20-25：3-4：1.For the progress suitable for the Raolical polymerizable, and the reasonably copolymer molecule of control gained
Amount, under preferable case, relative to 1mol formula, (1') (2') shown compound and formula are (3') shown for shown compound, formula
Mole total amount of compound, the dosage of the aqueous solvent is 400-1000mL, preferably 400-600mL.Wherein, it is described aqueous
Solvent can be single water or miscible solute (for example, sodium chloride, the chlorine for having some reactions for not influenceing the present invention
Change the one or more in potassium, sodium bromide, KBr etc.) water mixture, preferably water certainly.
According to the present invention, the Raolical polymerizable can use a variety of radical initiators that this area routinely uses
To be triggered, it is contemplated that the reactivity between above-mentioned monomer, under preferable case, the radical initiator is 4,4'-
Azo (4- cyanopentanoic acids), azo diisobutyl amidine hydrochloride, azo dicyclohexyl formonitrile HCN hydrochloride and azo diisobutyl
One or more in imidazoline hydrochloride.The dosage of the radical initiator can change in relative broad range, it is preferable that
Relative to 1mol formula (1') shown compound, formula (2') shown compound and formula (3') shown compound it is mole total
Amount, the dosage of the radical initiator is 0.1-0.2mmol, preferably 0.11-0.14mmol.
According to the present invention, the chain-transferring agent can use a variety of chain-transferring agents that this area routinely uses, it is contemplated that
To the copolymer that can obtain more particularly suitable molecular weight, under preferable case, the chain-transferring agent be selected from sodium formate, sodium acetate,
One or more in ammonium hydroxide and urea, more preferably sodium formate and/or sodium acetate.The dosage of the chain-transferring agent can be with
Changed in relative broad range, it is preferable that relative to 1mol formula (1') shown compound, formula (2') shown compound and formula
(3') mole total amount of shown compound, the dosage of the 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 the Raolical polymerizable includes：Temperature is 40-80 DEG C, the time
For 6-12h.It is highly preferred that the condition of the Raolical polymerizable includes：Temperature is 50-70 DEG C, time 7-10h.
According to the present invention, in order to some possible metal ingredients in the system of going out, it is preferable that above-mentioned copolymer
In preparation method, the Raolical polymerizable is carried out also in the presence of chelating agent.In this case, the work of chelating agent is passed through
With can be smoothly through chelation and suppress some possible metal ions.The chelating agent can for example be selected from ethylenediamine
Tetraacethyl and its salt (such as sodium ethylene diamine tetracetate), nitrilotriacetic acid and its salt (sodium ammonium triacetate), hexa metaphosphoric acid and its salt (six
Sodium metaphosphate) and diethylenetriamine penta in one or more.Preferably, it is (1') shown relative to 1mol formula
Compound, mole total amount of formula (2') shown compound and formula (3') shown compound, the dosage of the chelating agent 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., this method can also include：So that the free radical
Polymerisation is carried out in an inert atmosphere, such as the one or more such as nitrogen, helium, neon, argon gas can be passed through into system
And replace atmosphere therein (process can for example carry out 5-300min, mainly deoxygenation).
According to the present invention, in order to better control over the progress of above-mentioned Raolical polymerizable, it is preferable that this method bag
Include：First by formula, (1') (2') (3') shown compound and aqueous solvent is carried out for shown compound, formula for shown compound, formula
Mix (mixing condition can for example be included under 100-300rpm mixing speed, mix 10-40min at 10-40 DEG C), then
The radical initiator, chain-transferring agent and optional chelating agent is introduced to be mixed, and (inert atmosphere under an inert atmosphere
Formation as described in above) the carry out Raolical polymerizable.
According to the present invention, in order to be extracted in the copolymer from the reactions above product, this method can be with
Including：The product of the Raolical polymerizable is dried into 2-5h at 70-100 DEG C.
Present invention also offers the copolymer for being applied to extracting and cutting agent as made from the above method.Although the present invention is not special
Restriction, but the copolymer may be considered above described in copolymer in one kind, or a variety of copolymers is mixed
Compound.However, it is to be understood that the copolymer prepared by the above method typically refers to the above method without the direct of purification
Product (or merely through the above drying after), the product of even now is probably the mixture of multiple polymers, still
Such situation is also included within the scope of the invention by the present invention.
In drilling fluid it is used as present invention also offers above-mentioned copolymer or as the copolymer prepared by the above method and is carried
Cut the application of agent.
Present invention also offers a kind of saturated salt-water drilling fluid for containing above-mentioned copolymer as extracting and cutting agent.
Copolymer provided by the invention, it can be used in being used as extracting and cutting agent in saturated salt-water drilling fluid, it can be in salt solution
Higher stability is kept, even at a higher temperature, can also have preferable Efficient Adhesive Promotion, effectively lift saturation
Apparent viscosity, yield value and the gel strength of DWSW liquid system.There is no particular limitation for content of the present invention to the copolymer,
The dosage of conventional extracting and cutting agent can be used, naturally it is also possible to suitably adjusted according to the situation of different wells, it is preferable that
The content of the copolymer is 1-2 weight % (on the basis of the gross weight of the saturated salt-water drilling fluid).
According to the present invention, the saturated salt-water drilling fluid can be the conventional various saturated salt-water drilling fluids in this area, example
Such as can be salt-containing drilling liquid of the salt content for 5-40 weight % (being preferably 20-35 weight %).Wherein, the saturated salt water drilling
Salt in well liquid for example can be the one or more in NaCl, KCl, NaBr and KBr.
According to the present invention, the saturated salt-water drilling fluid can also contain in addition to can be with above-mentioned salt and extracting and cutting agent
The conventional various additives being used in saturated salt-water drilling fluid in this area, such as fluid loss additive.
Wherein, the one or more in fluid loss additive such as starch, PAC-LV, albino bitumen and sulfonated gilsonite, its content example
Such as can be 1.5-3 weight %.
The various materials that above-mentioned additive is can be commercially available product, can also be made according to the conventional method in this area, this
In repeat no more.
Present invention also offers application of the above-mentioned drilling fluid in oil/gas drilling.
When the drilling fluid of the present invention is applied in oil/gas drilling, can remain in that at a higher temperature higher
Apparent viscosity, yield value and gel strength, suitable for higher layer environment.
The present invention will be described in detail by way of examples below.
In following examples and comparative example, weight average molecular weight and molecular weight distributing index are using (the experiment of GPC gel chromatographies
Instrument be waters companies of the U.S. gel permeation chrommatograph, model E2695) measure.
Embodiment 1
The present embodiment is used to illustrate copolymer of the present invention and preparation method thereof and extracting and cutting agent.
By acrylamide, NVP and 3- [N, the N- dimethyl-[2- (methacryloxypropyls of 1mol total amounts
Base) ethyl] ammonium] propyl group -1- sulfonate (mol ratios 25：4：1) it is added in 500mL water, is stirred at 150rpm, 30 DEG C
Mix 30min；And 0.01mmol disodium ethylene diamine tetraacetate, 0.12mmol 4,4'- azos are added in the backward mixture
The sodium acetate of (4- cyanopentanoic acids) and 0.14mmol, and nitrogen 15min is passed through with deoxygenation；Polymerisation is then carried out at 60 DEG C
8h；Polymerizate is dried into 2.5h at 90 DEG C, crushing obtains copolymer, as extracting and cutting agent A1.The Weight-average molecular of the polymer
Measure as 4,000,000g/mol, molecular weight distribution index 1.5, through infrared, proton nmr spectra and carbon spectrum analysis detection, 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'- O-, R are selected from for H, X6Selected 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 used to illustrate copolymer of the present invention and preparation method thereof and extracting and cutting agent.
By the Methacrylamide of 1mol total amounts, NVP and [3- (methacrylamido) propyl group] two
Methyl (3- sulfopropyls) ammonium hydroxide (mol ratio 20：4：1) it is added in 500mL water, is stirred at 200rpm, 30 DEG C
Mix 30min；And 0.01mmol disodium ethylene diamine tetraacetate, the 0.14mmol isobutyl of azo two are added in the backward mixture
The sodium formate of amidine hydrochloride and 0.15mmol, and nitrogen 20min is passed through with deoxygenation；Polymerisation 10h is then carried out at 50 DEG C；
Polymerizate is dried into 3h at 80 DEG C, crushing obtains copolymer, as extracting and cutting agent A2.The weight average molecular weight of the polymer is 3,
200,000g/mol, molecular weight distribution index 2.2 is shown through infrared, proton nmr spectra and carbon spectrum analysis detection, formula (1)
Construction unit (R1For methyl, R1'For H), the construction unit (R shown in formula (2)4、R2And R2'For H, R3Alkylidene selected from C0, n
=2) and the construction unit (R shown in formula (3)5And R5'- NH-, R are selected from for H, X6Selected 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 used to illustrate copolymer of the present invention and preparation method thereof and extracting and cutting agent.
By acrylamide, NVP and 3- [N, the N- dimethyl-[2- (methacryloxypropyls of 1mol total amounts
Base) ethyl] ammonium] propyl group -1- sulfonate (mol ratios 25：4：1) it is added in 400mL water, is stirred at 200rpm, 40 DEG C
Mix 20min；And 0.02mmol disodium ethylene diamine tetraacetate, 0.12mmol 4,4'- azos are added in the backward mixture
The sodium acetate of (4- cyanopentanoic acids) and 0.14mmol, and nitrogen 10min is passed through with deoxygenation；Polymerisation is then carried out at 70 DEG C
7h；Polymerizate is dried into 5h at 90 DEG C, crushing obtains copolymer, as extracting and cutting agent A3.The weight average molecular weight of the polymer
For 3,000,000g/mol, molecular weight distribution index 2.8, through infrared, proton nmr spectra and carbon spectrum analysis detection, formula (1)
Shown construction unit (R1And R1'For H), the construction unit (R shown in formula (2)4、R2And R2'For H, R3Alkylidene selected from C0, n
=2) and the construction unit (R shown in formula (3)5For methyl, R5'- O-, R are selected from for H, X6Selected 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, the difference is that, the dosage as the water of the solvent of reaction system is 1000mL,
Copolymer, as extracting and cutting agent A4 are obtained so as to finally crush.The weight average molecular weight of the polymer is 2,400,000g/mol, molecule
It is 1.7 to measure breadth coefficient, through infrared, proton nmr spectra and carbon spectrum analysis detection, 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, R3Alkylidene selected from C0, n=2) and formula (3) shown in structure
Unit (R5For methyl, R5'- O-, R are selected from for H, X6Selected from-CH2-CH2-, R7It is methyl, R8Selected from-CH2-CH2-CH2-) rub
You are than being 25：3.75：1.
Embodiment 5
According to the method described in embodiment 1, the difference is that, the temperature of the polymerisation carried out after logical nitrogen deoxygenation is 30
DEG C, obtain copolymer, as extracting and cutting agent A5 so as to finally crush.The weight average molecular weight of the polymer is 5,100,000g/mol,
Molecular weight distribution index is 2.0, through infrared, proton nmr spectra and carbon spectrum analysis detection, 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, R3Alkylidene selected from C0, n=2) and formula (3) shown in
Construction unit (R5For methyl, R5'- O-, R are selected from for H, X6Selected 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, the difference is that, 3- [N, N- dimethyl-[2- (methacryloxypropyls is not used
Base) ethyl] ammonium] propyl group -1- sulfonate, but mol ratio is used as 6：1 acrylamide and NVP conduct
Monomer, and total dosage of monomer is 1mol, so as to which copolymer, as extracting and cutting agent DA1 be made.The weight average molecular weight of the polymer is
4,400,000g/mol, molecular weight distribution index 1.6.
Comparative example 2
According to the method described in embodiment 1, the difference is that, NVP is not used, but use mol ratio
For 25：1 acrylamide and 3- [N, N- dimethyl-[2- (methacryloxy) ethyl] ammonium] propyl group -1- sulfonate conducts
Monomer, and total dosage of monomer is 1mol, so as to which copolymer, as extracting and cutting agent DA2 be made.The weight average molecular weight of the polymer is
3,200,000g/mol, molecular weight distribution index 2.4.
Test case 1
Prepare：Salt solution Y1 is the 10 weight % NaCl aqueous solution；
Salt solution Y2 is the 30 weight % NaCl aqueous solution；
The one kind being separately added into above-mentioned salt solution in the extracting and cutting agent obtained by above-mentioned example (cut by specific carrying for test selection
Agent is shown in Table 1), the saline solution that obtains containing 2 weight % extracting and cutting agents and the salt solution of extracting and cutting agent is not added with as blank pair
According to, and with high-speed stirred 20min under the conditions of mixer 3000r/min, drilling wells are determined with six fast viscosimeters under room temperature (25 ± 5 DEG C)
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, unit mPas.‘’
Yield value (YP) is calculated as follows：YP=0.511 × (2 × φ 300- φ 600), unit Pa.
Gel initial calculates by the following method：10s is stirred under 600r/min speed, stands the maximum of reading φ 3 after 10s
Reading, full-scale reading divided by 2 are then obtained into gel initial, unit Pa.
10-minute gel strength calculates by the following method：10s is stirred under 600r/min speed, φ 3 is read most after standing 10min
Big reading, full-scale reading divided by 2 are then obtained into 10-minute gel strength, unit Pa.
Table 1
It can be seen from Table 1 that extracting and cutting agent of the invention is shown in 10 weight % or 30 weight %NaCl salt solution
Obvious thickening, which carries, cuts effect, and yield value, gel initial and 10-minute gel strength are obviously improved, at the same the extracting and cutting agent of the present invention have it is bright
Aobvious Efficient Adhesive Promotion, effectively improve the apparent viscosity of salt solution.Compared to the copolymer of comparative example, used as extracting and cutting agent of the present invention
Copolymer salt tolerance it is significantly higher, can be used in high concentration salt solution.
Test case 2
Drilling well liquid-based starches Y3：2 weight % starch, 35 weight % KCl, surplus is water.
Above-mentioned drilling well liquid-based is starched to the extracting and cutting agent being separately added into obtained by above-mentioned example (specifically to test the extracting and cutting agent selected to see
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 slurry of the extracting and cutting agent obtained is used as blank control, before ageing and will after 90 DEG C of aging 16h, after 120 DEG C of aging 16h
High-speed stirred 20min under the conditions of using mixer 3000r/min to (25 ± 5 DEG C) of room temperature, drilling well liquid-baseds are determined with six fast viscosimeters
Apparent viscosity, yield value, gel initial, 10-minute gel strength and the middle filter pressing loss (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, it is that the method that press filtration is committed a breach of etiquette in SY/T 5621-93 standards in using measures, unit mL.
Table 2
It can be seen from Table 2 that when copolymer of the invention is used in saturated salt-water drilling fluid tool as extracting and cutting agent, can
Good rheological characteristic is kept, can be while common with starch compared with keeping certain yield value, gel initial, 10-minute gel strength under low viscosity
Using also there is part filtrate reducing effect；The rheological characteristic of saturated salt-water drilling fluid of the invention, filter loss change after 90 DEG C of heat rollings
Very little, rheological characteristic, filter loss can also meet normal use after 120 DEG C of heat rollings, and the extracting and cutting agent of this explanation present invention is with preferable
Heat-resisting property.
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (34)
1. a kind of copolymer suitable for extracting and cutting agent, it is characterised in that the copolymer is as the construction unit shown in formula (1), formula (2)
Construction unit composition shown in shown construction unit and formula (3), the weight average molecular weight of the copolymer is 2,500,000-5,
000,000g/mol, wherein：
Wherein, R1、R1'、R2、R2'、R5、R5'、R4With each R7It is each independently selected from H and C1-C8 alkyl；R3、R6And R8Each
Independently selected from C0-C8 alkylidene；X is selected from-NH- or-O-；N is 1-4 integer；C0 alkylidene simply mean to connecting key or
It is not present, the group at the group both ends will be joined directly together.
2. copolymer according to claim 1, wherein, R1、R1'、R2、R2'、R5、R5'、R4With each R7Select independently of one another
From H and C1-C6 alkyl；R3、R6And R8It is each independently selected from C0-C6 alkylidene；N is 1-3 integer.
3. copolymer according to claim 2, wherein, R1、R1'、R2、R2'、R5、R5'And R4It is each independently selected from H and C1-
C4 alkyl；Each R7It is each independently selected from C1-C6 alkyl；R3Alkylidene selected from C0-C4；R6And R8Independently of one another
Alkylidene selected from C1-C6.
4. copolymer according to claim 3, wherein, R1、R1'、R2、R2'、R5、R5'And R4It is each independently selected from H, first
Base, ethyl, n-propyl, isopropyl and normal-butyl；Each R7It is each independently selected from methyl, ethyl, n-propyl, isopropyl and just
Butyl；R3Alkylidene ,-CH selected from C02-、-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-。
5. according to the copolymer described in any one in claim 1-4, wherein, construction unit, formula (2) institute shown in formula (1)
The mol ratio of the construction unit shown in construction unit and formula (3) shown is 10-40：1-10：1.
6. copolymer according to claim 5, wherein, the construction unit shown in construction unit, formula (2) shown in formula (1)
Mol ratio with the construction unit shown in formula (3) is 15-30：2-5：1.
7. copolymer according to claim 1, wherein, the weight average molecular weight of the copolymer is 3,000,000-4,500,
000g/mol。
8. copolymer according to claim 7, wherein, the weight average molecular weight of the copolymer is 3,000,000-4,000,
000g/mol。
9. the preparation method of a kind of copolymer suitable for extracting and cutting agent, it is characterised in that this method includes：In aqueous solvent,
In the presence of radical initiator and chain-transferring agent, by formula (1') shown compound, formula (2') shown compound and formula
(3') shown compound carries out Raolical polymerizable, wherein, this method make it that the weight average molecular weight of the copolymer of gained is
2,500,000-5,000,000g/mol；
Wherein, R1、R1'、R2、R2'、R5、R5'、R4With each R7It is each independently selected from H and C1-C8 alkyl；R3、R6And R8Each
Independently selected from C0-C8 alkylidene；X is selected from-NH- or-O-；N is 1-4 integer；C0 alkylidene simply mean to connecting key or
It is not present, the group at the group both ends will be joined directly together.
10. according to the method for claim 8, wherein, this method make it that the weight average molecular weight of the copolymer of gained is 3,
000,000-4,500,000g/mol。
11. the method according to claim 11, wherein, R1、R1'、R2、R2'、R5、R5'、R4With each R7It is each independently selected from
H and C1-C6 alkyl；R3、R6And R8It is each independently selected from C0-C6 alkylidene；N is 1-3 integer.
12. the method according to claim 11, wherein, R1、R1'、R2、R2'、R5、R5'And R4It is each independently selected from H and C1-
C4 alkyl；Each R7It is each independently selected from C1-C6 alkyl；R3Alkylidene selected from C0-C4；R6And R8Independently of one another
Alkylidene selected from C1-C6.
13. the method according to claim 11, wherein, R1、R1'、R2、R2'、R5、R5'And R4It is each independently selected from H, first
Base, ethyl, n-propyl, isopropyl and normal-butyl；Each R7It is each independently selected from methyl, ethyl, n-propyl, isopropyl and just
Butyl；R3Alkylidene ,-CH selected from C02-、-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-。
14. according to the method described in any one in claim 9-13, wherein, formula (1') shown compound, formula (2') institute
The mole dosage ratio of the compound and formula shown (3') shown compound is 10-40：1-10：1.
15. according to the method for claim 14, wherein, formula (1') shown compound, formula (2') shown compound and
The mole dosage ratio of formula (3') shown compound is 15-30：2-5：1.
16. according to the method for claim 14, wherein, relative to 1mol formula (1') shown compound, formula (2') institute
Mole total amount of the compound and formula shown (3') shown compound, the dosage of the aqueous solvent is 400-1000mL.
17. according to the method for claim 16, wherein, relative to 1mol formula (1') shown compound, formula (2') institute
Mole total amount of the compound and formula shown (3') shown compound, the dosage of the aqueous solvent is 400-600mL.
18. according to the method for claim 9, wherein, the radical initiator be 4,4'- azos (4- cyanopentanoic acids),
One in azo diisobutyl amidine hydrochloride, azo dicyclohexyl formonitrile HCN hydrochloride and azo diisobutyl imidazoline hydrochloride
Kind is a variety of.
19. according to the method for claim 18, wherein, relative to 1mol formula (1') shown compound, formula (2') institute
Mole total amount of the compound and formula shown (3') shown compound, the dosage of the radical initiator is 0.1-0.2mmol.
20. according to the method for claim 19, wherein, relative to 1mol formula (1') shown compound, formula (2') institute
Mole total amount of the compound and formula shown (3') shown compound, the dosage of the radical initiator is 0.11-
0.14mmol。
21. according to the method for claim 9, wherein, the chain-transferring agent be selected from sodium formate, sodium acetate, ammonium hydroxide and
One or more in urea.
22. according to the method for claim 21, wherein, relative to 1mol formula (1') shown compound, formula (2') institute
Mole total amount of the compound and formula shown (3') shown compound, the dosage of the chain-transferring agent is 0.1-0.2mmol.
23. according to the method for claim 22, wherein, relative to 1mol formula (1') shown compound, formula (2') institute
Mole total amount of the compound and formula shown (3') shown compound, the dosage of the chain-transferring agent is 0.13-0.15mmol.
24. according to the method for claim 9, wherein, the condition of the Raolical polymerizable includes：Temperature is 40-80
DEG C, time 6-12h.
25. according to the method for claim 24, wherein, the condition of the Raolical polymerizable includes：Temperature is 50-70
DEG C, time 7-10h.
26. according to the method described in any one in claim 9-13 and 15-25, wherein, the Raolical polymerizable is also
Carried out in the presence of chelating agent, the chelating agent be selected from ethylenediamine tetra-acetic acid and its salt, nitrilotriacetic acid and its salt, hexa metaphosphoric acid and
One or more in its salt and diethylenetriamine penta.
27. according to the method for claim 26, wherein, relative to 1mol formula (1') shown compound, formula (2') institute
Mole total amount of the compound and formula shown (3') shown compound, the dosage of the chelating agent is 0.01-0.05mmol.
28. according to the method for claim 27, wherein, relative to 1mol formula (1') shown compound, formula (2') institute
Mole total amount of the compound and formula shown (3') shown compound, the dosage of the chelating agent is 0.01-0.02mmol.
29. according to the method for claim 26, wherein, this method includes：First by formula, (1') shown compound, formula be (2')
(3') shown compound and aqueous solvent is mixed for shown compound, formula, is re-introduced into the radical initiator, chain turns
Agent and optional chelating agent are moved, and carries out the Raolical polymerizable under an inert atmosphere.
30. it is applied to the copolymer of extracting and cutting agent as made from the method described in any one in claim 9-29.
31. application of the copolymer in claim 1-8 and 30 described in any one in drilling fluid as extracting and cutting agent.
A kind of 32. saturated brine drilling well of copolymer contained in claim 1-8 and 30 described in any one as extracting and cutting agent
Liquid.
33. drilling fluid according to claim 32, wherein, the content of the copolymer is 1-2 weight %.
34. application of the drilling fluid described in claim 32 or 33 in oil/gas drilling.
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