CN106749889B - Weak cross-linked copolymer and preparation method thereof and application and water-base drilling fluid and its application as sealing agent - Google Patents
Weak cross-linked copolymer and preparation method thereof and application and water-base drilling fluid and its application as sealing agent Download PDFInfo
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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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- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
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- 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
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- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/42—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells
- C09K8/426—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells for plugging
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Abstract
The present invention relates to the drilling applications of petroleum industry, in particular it relates to a kind of weak cross-linked copolymer and preparation method thereof and the application as sealing agent and water-base drilling fluid and its application.The weak cross-linked copolymer contains the construction unit shown in formula (1), the construction unit shown in formula (2) and the construction unit shown in formula (3), and the content that minor structure is crosslinked in the weak cross-linked copolymer is 0.1 1 weight %.Weak cross-linked copolymer provided by the invention can be used in water-base drilling fluid as sealing agent, and formed microgranular, so as to adjust itself particulate form by water absorption and swelling in drilling process, to be suitable to the closure in Different Strata crack or pore-size, drilling fluid filtration can be effectively reduced.
Description
Technical field
The present invention relates to the drilling applications of petroleum industry, in particular it relates to a kind of weak cross-linked copolymer and preparation method thereof
With the application as sealing agent and water-base drilling fluid and its application.
Background technology
Leakage generally existing in drilling process, and circulation problems are an important factor for restricting safe, smooth, efficient drilling well.
Drilling process can cause huge economic losses because the complicated leakage such as Fractured, hole, inductivity occurs often.According to foreign countries
Count, in economic loss caused by challenge is met in current drilling well underground, more than 58.5% is just accounted for caused by circulation problems.Often
The blocking method of rule is mainly by the way of stopping boring leak stopping, blocked up and bore again, although this mode can handle some, to only have several big
The stratum in crack, but be invalid in face of the stratum that crack is a lot, position is uncertain, is missed once boring and meeting.It is and every
It is secondary stop bore leak stopping will spend more time and manpower and materials, cause drilling cost persistently to rise, or even cause not boring up to mesh
Layer, the accident for scrapping full well.
With bore leak-proof leak-stopping technology be exactly introduced in drilling fluid it is certain density by size is suitable, intensity is higher particle
Shape material presses the sealing agent that rational gradation composition is formed, and when crack growth is to when causing leakage degree, closure particle enters with drilling fluid leakage
Enter in crack, big closure particle stuck bridge formation in some position in crack, it is remaining empty in the less particles filled crack of closure
Between, crack is finally blocked, is realized i.e. stifled.
The drill-feeding plugging agent developed at present mainly has pitch, fibrous material, intumescent material and other rigid materials etc..
Although the use of these materials can solve the problems, such as partial loss, but a series of problems be present, it is mainly shown as：When these
When plugging while drilling material mismatches with formation fracture or pore-size, plugging effect is then very poor.
The content of the invention
It is an object of the invention to be difficult to and good of formation fracture or pore-size for existing plugging while drilling material
Match somebody with somebody and the defects of plugging effect difference, there is provided one kind can spontaneously change in drilling course according to formation fracture or pore-size
Become its own shape and effectively realize weak cross-linked copolymer of closure and preparation method thereof and the application as sealing agent and water base brill
Well liquid and its application.
To achieve these goals, the present invention provides a kind of weak cross-linked copolymer, and the weak cross-linked copolymer contains formula (1) institute
Construction unit shown in the construction unit that shows, formula (2) and the construction unit shown in formula (3), and handed in the weak cross-linked copolymer
The content for joining minor structure is 0.1-1 weight %, wherein：
Formula (1)Formula (2)
Formula (3)
Wherein, R1、R1'、R2、R2'、R6And R6'It is each independently selected from H and C1-C6 alkyl；R3Alkylene selected from C0-C6
Base；R4Selected from-COOM ,-SO3M or-CO-NH-R5-SO3M, R5Alkylidene selected from C0-C6, M are selected from H or alkali metal；R7
Alkyl selected from H or C1-C20.
Present invention also offers a kind of preparation method of weak cross-linked copolymer, this method includes：In aqueous solvent, in oxygen
In the presence of change-reduction initiating system, crosslinking agent and emulsifying agent, by formula (1') shown compound, formula (2') shown compound
(3') shown compound carries out emulsion polymerization with formula, wherein, the dosage of the crosslinking agent causes the weak cross-linked copolymer of gained
The content of middle crosslinking minor structure is 0.1-1 weight %,
Formula is (1')Formula is (2')
Formula is (3')
Wherein, R1、R1'、R2、R2'、R6And R6'It is each independently selected from H and C1-C6 alkyl；R3Alkylene selected from C0-C6
Base；R4Selected from-COOM ,-SO3M or-CO-NH-R5-SO3M, R5Alkylidene selected from C0-C6, M are selected from H or alkali metal；R7
Alkyl selected from H or C1-C20.
Present invention also offers the weak cross-linked copolymer as made from the above method.
The present invention also provides above-mentioned weak cross-linked copolymer or the weak cross-linked copolymer as made from the above method in drilling fluid
Application as sealing agent.
Present invention also offers a kind of water-base drilling fluid for containing above-mentioned weak cross-linked copolymer as sealing agent.
Present invention also offers application of the above-mentioned water-base drilling fluid in oil/gas drilling.
Weak cross-linked copolymer provided by the invention can water-base drilling fluid as sealing agent use, and formed it is microgranular, from
And itself particulate form is adjusted by water absorption and swelling in drilling process, to be suitable to the envelope in Different Strata crack or pore-size
It is stifled, drilling fluid filtration can be effectively reduced.
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 weak cross-linked copolymer, and the weak cross-linked copolymer contains construction unit shown in formula (1), formula
(2) construction unit shown in construction unit and formula (3) shown in, and the content that minor structure is crosslinked in the weak cross-linked copolymer is
0.1-1 weight %, wherein：
Formula (1)Formula (2)
Formula (3)
Wherein, R1、R1'、R2、R2'、R6And R6'It is each independently selected from H and C1-C6 alkyl；R3Alkylene selected from C0-C6
Base；R4Selected from-COOM ,-SO3M or-CO-NH-R5-SO3M, R5Alkylidene selected from C0-C6, M are selected from H or alkali metal；R7
Alkyl selected from H or C1-C20.
According to the present invention, the weak cross-linked copolymer is the copolymerzation with cross-linking that the content of crosslinking minor structure is 0.1-1 weight %
Thing, in the case of such crosslinking, the construction unit shown in formula (1) in the copolymer, the construction unit shown in formula (2) and formula
(3) construction unit shown in can in drilling process, into borehole wall gap by water suction, construction unit shown in formula (1) and
Construction unit shown in formula (2) adjusts the size of weak cross-linked copolymer particulate, the construction unit shown in formula (3) by hydration swelling
Make to form dynamic bridging structure between polymer particles by heat resistance and salt tolerance, adjusting the weak cross-linked copolymer with this exists
Structure between the particle size and particulate that are formed in water-base drilling fluid, and then formation fracture or pore-size are meshed well into,
Closure is completed, prevents leakage.
According to the present invention, wherein, above-mentioned C1-C6 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 etc..
The alkylidene that above-mentioned C0-C6 alkylidene can for example be formed by C0 alkylidene, above-mentioned C1-C6 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.
Above-mentioned C1-C20 alkyl for example can be methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, Zhong Ding
Base, the tert-butyl group, n-pentyl, isopentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, n-undecane base, positive 12
Alkyl, n-tridecane base, n-tetradecane base, n-pentadecane base or n-hexadecyl, n-heptadecane base, n-octadecane base, positive ten
Nine alkyl, n-eicosane base etc..
In order to preferably play effect of the copolymer as sealing agent, under preferable case, R1、R1'、R2、R2'、
R6And R6'It is each independently selected from H and C1-C4 alkyl；R3Alkylidene selected from C0-C4；R4Selected from-COOM ,-SO3M or-CO-
NH-R5-SO3M, R5Alkylidene selected from C1-C6, M are selected from H, Na or K；R7Alkyl selected from C2-C16.
It is highly preferred that R1、R1'、R2、R2'、R6And R6'It is each independently selected from H, methyl, ethyl and n-propyl；R3Selected from C0
Alkylidene ,-CH2-、-CH2-CH2-、-CH2-CH2-CH2-、-CH(CH3)-CH2-、-CH2-CH(CH3)-or-CH2-(CH2)2-
CH2-；R4Selected from-COOH ,-SO3M or-CO-NH-R5-SO3M, R5Selected 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- or-CH2-C
(CH3)2-, M is selected from H, Na or K；R7Selected from ethyl, n-propyl, normal-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, positive nonyl
Base, positive decyl, n-undecane base, dodecyl, n-tridecane base, n-tetradecane base, n-pentadecane base or n-hexadecyl.
In the case of, according to the invention it is preferred to, the weight average molecular weight of the weak cross-linked copolymer is 3 × 106-10×106g/
Mol, preferably 3.5 × 106-7×106G/mol, more preferably 4 × 106-5.5×106g/mol.When the weak cross-linked copolymer
Weight average molecular weight within the above range when, the weak cross-linked copolymer of gained can be well used as sealing agent, and with more preferable
Temperature resistance, also can spontaneously be matched in the ground environment of higher temperature borehole wall gap complete closure.The weak friendship
The molecular weight distribution index of polymers of allying the communists for example can be 2-4.
According to the present invention, although shown in construction unit, formula (2) shown in the formula (1) that the weak cross-linked copolymer contains
The amount of construction unit shown in construction unit and formula (3) can change in wider scope, but be in order at the weak of optimization gained
Thickening, salt resistance and the heat-resisting property of cross-linked copolymer consider, under preferable case, shown in the construction unit, formula (2) shown in formula (1)
Construction unit and formula (3) shown in the mol ratio of construction unit be 10-50：3-20：1, preferably 12-40：5-15：1, more enter
One step is preferably 12-30：5-10：1.
According to the present invention, in order to obtain the sealing agent stronger with the ground spontaneous matching capacity of layer gap, it is preferable that the weak friendship
It is 0.3-0.6 weight %, more preferably 0.35-0.45 weight % to ally the communists and the content of minor structure is crosslinked in polymers.It should be understood that
It is that copolymer of the invention is a kind of cross-linked copolymer, in addition to above-mentioned construction unit, should also has and cross-bond is provided
Crosslinking, although there is no particular limitation by the present invention, the present invention by using crosslinking agent forms cross-bond, so as to
It is sub (it is appreciated that forming structure for what is formed by crosslinking agent) that crosslinking is formed in weak cross-linked copolymer.Preferably, the weak crosslinking
Crosslinking minor structure in copolymer is provided as the one or more in the crosslinking agent shown in following formula (4)：
Formula (4)N is selected from 1-6 integer.
The instantiation of crosslinking agent shown in above-mentioned formula (4) is：
In formula (4-1), n is 1 (also referred to as N, N- methylene-bisacrylamide)；
In formula (4-2), n is 2 (also referred to as N, N- ethylenebisacrylamides)；
In formula (4-3), n is 3 (also referred to as N, N- propylidene bisacrylamides).
In that case, it is believed that the content of the crosslinking minor structure of the weak cross-linked copolymer is above-mentioned crosslinking agent
The weight of the structure of offer accounts for the percentage by weight of whole weak cross-linked copolymer.Wherein, containing for above-mentioned crosslinking minor structure is being met
In the case of amount, in the weak cross-linked copolymer, using the expansion multiple of the weak cross-linked copolymer of laser particle size analyzer measurement
Preferably 30-50, more preferably 35-45.
Present invention also offers a kind of preparation method of weak cross-linked copolymer, this method includes：In aqueous solvent, in oxygen
In the presence of change-reduction initiating system, crosslinking agent and emulsifying agent, by formula (1') shown compound, formula (2') shown compound
(3') shown compound carries out emulsion polymerization with formula, wherein, the dosage of the crosslinking agent causes the weak cross-linked copolymer of gained
The content of middle crosslinking minor structure be 0.1-1 weight %,
Formula is (1')Formula is (2')
Formula is (3')
Wherein, R1、R1'、R2、R2'、R6And R6'It is each independently selected from H and C1-C6 alkyl；R3Alkylene selected from C0-C6
Base；R4Selected from-COOM ,-SO3M or-CO-NH-R5-SO3M, R5Alkylidene selected from C0-C6, M are selected from H or alkali metal；R7
Alkyl selected from H or C1-C20.
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)：R2And R2'For H, R3For C0 alkylidene, R4Selected from-COOH (also referred to as acrylic acid)；
In formula (2'-2)：R2For methyl, R2'For H, R3For C0 alkylidene, R4Selected from-COOH (also referred to as metering systems
Acid)；
In formula (2'-3)：R2And R2'For H, R3For-CH2-, R4Selected from-SO3H (also referred to as propane sulfonic acid)；
In formula (2'-4)：R2For methyl, R2'For H, R3For-CH2-, R4Selected from-SO3H (also referred to as methyl propane sulfonic acid)；
In formula (2'-5)：R2And R2'For H, R3For C0 alkylidene, R4Selected from-CO-NH-C (CH3)2-CH2-SO3M is (also referred to as
Make 2- acrylamide-2-methyl propane sulfonics).
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)：R6For methyl, R6'For H, R7Selected from normal-butyl (the also referred to as Arrcostab of methacrylic acid ten)；
In formula (3'-2)：R6And R6'For H, R7Selected from normal-butyl (the also referred to as Arrcostab of acrylic acid ten)；
In formula (3'-3)：R6For methyl, R6'For H, R7Selected from n-pentyl (also referred to as methacrylic acid hendecane base ester)；
In formula (3'-4)：R6And R6'For H, R7Selected from n-pentyl (also referred to as acrylic acid hendecane base ester)；
In formula (3'-5)：R6For methyl, R6'For H, R7Selected from n-hexyl (also referred to as lauryl methacrylate)；
In formula (3'-6)：R6And R6'For H, R7Selected from n-hexyl (also referred to as dodecylacrylate)；
In formula (3'-7)：R6For methyl, R6'For H, R7Selected from n-heptyl (also referred to as Tridecyl methacrylate base ester)；
In formula (3'-8)：R6And R6'For H, R7Selected from n-heptyl (also referred to as tridecyl acrylate)；
In formula (3'-9)：R6For methyl, R6'For H, R7Selected from n-octyl (also referred to as methacrylic acid tetradecane base ester)；
In formula (3'-10)：R6And R6'For H, R7Selected from n-octyl (also referred to as acrylic acid tetradecane base ester)；
In formula (3'-11)：R6For methyl, R6'For H, R7Selected from n-nonyl (also referred to as methacrylic acid pentadecane base ester)；
In formula (3'-12)：R6And R6'For H, R7Selected from n-nonyl (also referred to as acrylic acid pentadecane base ester)；
In formula (3'-13)：R6For methyl, R6'For H, R7Selected from positive decyl (also referred to as methacrylic acid cetyl ester)；
In formula (3'-14)：R6And R6'For H, R7Selected from positive decyl (also referred to as aliphatic acrylate)；
In formula (3'-15)：R6For methyl, R6'For H, R7Selected from n-undecane base (also referred to as methacrylic acid heptadecyl
Ester)；
In formula (3'-16)：R6And R6'For H, R7Selected from n-undecane base (also referred to as acrylic acid heptadecane base ester)；
In formula (3'-17)：R6For methyl, R6'For H, R7Selected from dodecyl (also referred to as methacrylic acid octadecyl
Ester)；
In formula (3'-18)：R6And R6'For H, R7Selected from dodecyl (also referred to as octadecyl acrylate).
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 10-50：3-20：1, preferably 12-40：5-15：1, it is still more preferably 12-30：5-10：1.In order to suitable for
The progress of the emulsion polymerization, and the molecular weight of copolymer of gained is reasonably controlled, under preferable case, relative to 100g institute
State aqueous solvent, formula (1') shown compound, formula (2') shown compound and formula (3') shown compound it is mole total
Measure as 0.1-5mol, preferably 0.2-2mol, more preferably 0.5-1mol.Wherein, the aqueous solvent can be single water,
Can also be miscible solvent (for example, methanol, ethanol, ethylene glycol, propyl alcohol, the isopropanol for having some reactions for not influenceing the present invention
One or more in) water mixture, preferably water certainly.
According to the present invention, the introducing of the crosslinking agent can cause formula (1') shown compound, formula (2') shown change
(3') shown compound carries out a certain degree of crosslinking in emulsion polymerization process for compound and formula, and the dosage of the crosslinking agent makes
The content for obtaining crosslinking minor structure in the weak cross-linked copolymer of gained is 0.1-1 weight %, so as to form the required weak friendship of the present invention
The structure of connection, it is preferable that the dosage of the crosslinking agent cause gained weak cross-linked copolymer in be crosslinked minor structure content be
0.3-0.6 weight %, more preferably 0.35-0.45 weight %.Meeting in this case, it is preferable that with formula (1') shown change
Compound, formula (2') shown compound, formula (3') on the basis of shown compound and the gross weight of crosslinking agent, the crosslinking agent
Dosage is, for example, 0.1-1 weight %, preferably 0.3-0.6 weight %, more preferably 0.35-0.45 weight %.The crosslinking agent
Selection it is as described above, will not be repeated here.
According to the present invention, the oxidation-reduction trigger system can be the conventional various redox initiator bodies in this area
System, as long as polymerization can be triggered to obtain the weak cross-linked copolymer of the present invention, it is preferable that the oxidation-reduction trigger system
In one or more of the oxidant in sodium peroxydisulfate, potassium peroxydisulfate, ammonium persulfate and hydrogen peroxide.Preferably, it is described
Reducing agent in oxidation-reduction trigger system is selected from ferrous sulfate, frerrous chloride, sodium sulfite, sodium hydrogensulfite, potassium sulfite
With the one or more in sodium thiosulfate.In order to preferably play oxidant in the oxidation-reduction trigger system and go back
Mating reaction between former agent, it is preferable that the mol ratio 1 of the Oxidizing and Reducing Agents：0.2-1, preferably 1：0.3-0.8,
More preferably 1：0.4-0.6.Although the Oxidizing and Reducing Agents can be incorporated into reaction system in solid form, can also
Introduce in form of an aqueous solutions, the aqueous solution for example with concentration for the 0.12-0.22mol/L oxidant, for example with
Concentration is the aqueous solution of the 0.05-0.2mol/L reducing agent.
According to the present invention, the oxidation-reduction trigger system can be carried out suitably according to required weak cross-linked copolymer
Adjustment, it is preferable that relative to 1mol formula (1') shown compound, formula (2') shown compound and formula (3') shown change
Mole total amount of compound, the dosage of the oxidation-reduction trigger system is 1-10mmol, preferably 2-5mmol, more preferably 2-
3mmol。
According to the present invention, the emulsifying agent can use this area routinely to use various emulsifying agents, as long as can pass through institute
State emulsion polymerization and obtain the weak cross-linked copolymer of the present invention, under preferable case, the emulsifying agent is Sorbitan alcohol ester
Fat acid esters (such as SPAN-60, SPAN-80, SPAN-85 etc.), APES, polyoxyethylene sorbitan fat
One or more in acid esters (such as TWEEN40, TWEEN60, TWEEN80 etc.) and polyglyceryl fatty acid ester.The emulsifying agent
Dosage can also correspondingly be adjusted according to required weak cross-linked copolymer, under preferable case, the aqueous solvent and institute
The weight ratio for stating the dosage of emulsifying agent is 100：10-20, preferably 100：12-14.
According to the present invention, in order to form the system of emulsion polymerization, this method is carried out in the presence of being preferably included in oils reagent,
For example, the oils reagent is liquefied petrolatum.Preferably, the weight ratio of the dosage of the emulsifying agent and oils reagent is 100：
500-2000, preferably 100：800-1500.
In the case of, according to the invention it is preferred to, the condition of the emulsion polymerization includes：It (is preferably 35- that temperature, which is 30-60 DEG C,
50 DEG C), the time is 5-10h (being preferably 7-9h).
According to the present invention, in order to keep the activity of initiator etc., this method can also include：So that the emulsion is gathered
Conjunction 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 are replaced
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 emulsion polymerization, it is preferable that this method includes：
PH is (pH is 7 or so) under 6-8, first by formula (1') shown compound, formula (2') shown compound, formula (3') shown change
Compound, the aqueous solvent, the oxidant in the oxidation-reduction trigger system and the crosslinking agent are mixed the (mixing
Condition can for example include：30-60min is mixed under 200-250rpm mixing speed, at 10-40 DEG C) (it is highly preferred that first
By formula, (1') (2') (3') shown compound, the aqueous solvent mix for shown compound, formula for shown compound, formula,
And it is 6-8 to adjust pH, is then re-introduced into, the oxidant in the oxidation-reduction trigger system and the crosslinking agent are mixed
Close), then introduce the emulsifying agent and oils reagent and emulsified that (emulsification can for example carry out emulsification 1- on emulsification instrument
5min), then under an inert atmosphere, the reducing agent that is introduced into the oxidation-reduction trigger system simultaneously carries out the emulsion polymerization.
By above-mentioned emulsion polymerize made from emulsion just containing the present invention weak cross-linked copolymer described above, it is such
Weak cross-linked copolymer can extract, and for the sake of certainly convenient, such emulsion can uses directly as sealing agent.
Present invention also offers the weak cross-linked copolymer as made from the above method.Although there is no particular limitation by the present invention,
But the weak cross-linked copolymer may be considered above described in weak cross-linked copolymer in one kind, or a variety of weak crosslinkings
The mixture of copolymer.However, it is to be understood that the weak cross-linked copolymer prepared by the above method typically refers to the above method
Without the direct product of purification, the product of even now is probably the mixture of a variety of weak cross-linked copolymers, but of the invention
Also such situation is included within the scope of the invention.
The present invention also provides above-mentioned weak cross-linked copolymer or the weak cross-linked copolymer as made from the above method in drilling fluid
Application as sealing agent.
Present invention also offers a kind of water-base drilling fluid for containing above-mentioned weak cross-linked copolymer as sealing agent.
Weak cross-linked copolymer provided by the invention, it can be used in being used as sealing agent in water-base drilling fluid, so as in drilling well
Cheng Zhong, it is distributed in formation fracture or hole, and by water absorption and swelling, spontaneously adjusts its own shape to mesh well into stratum
Crack or pore-size, closure is completed, prevents leakage.The present invention has no special limit to the content of the weak cross-linked copolymer
It is fixed, can suitably it be adjusted according to strata condition, it is preferable that relative to the water in the water-base drilling fluid of 100 parts by weight, institute
The content for stating weak cross-linked copolymer is 1-3 parts by weight.
According to the present invention, in addition to water and above-mentioned copolymer, the water-base drilling fluid can also contain as water base
Other additives of drilling fluid, for example, the drilling fluid of the present invention contains bentonite, salt resistant filter loss reduction agent, temperature resistance fluid loss additive, anti-
One or more in agent, inhibitor, heavy weight additive, the pH adjusting agent etc. of collapsing.
Wherein, the bentonite refers to the clay using montmorillonite as main mineral constituent, and it has imparting drilling fluid is viscous to cut
The effect of power and leak-off wave making machine, such as can be sodium bentonite and/or calcium-base bentonite, preferably sodium bentonite.More
Preferably, relative to the water in the water-base drilling fluid of 100 parts by weight, the bentonitic content is 2-2.5 parts by weight.
Wherein, the salt resistant filter loss reduction agent has the function that to improve drilling fluid saline-alkaline tolerance and reduces drilling fluid filtration,
Such as can be the one or more in cellulose ether derivatives (PAC), modified starch and carboxymethyl cellulose etc..Relative to
Water in the drilling fluid of 100 parts by weight, it is highly preferred that the content of the salt resistant filter loss reduction agent is 1-1.5 parts by weight.
Wherein, the temperature resistance fluid loss additive has the function that to improve drilling fluids at high temperature stability and reduces filter loss, such as
Can be the one or more in modified sodium humate condensation polymer (KJAN), sulfonated lignite resin and phenolic resin etc..Relatively
Water in the drilling fluid of 100 parts by weight, it is highly preferred that the content of the temperature resistance fluid loss additive is 3-4 parts by weight.
Wherein, the anti-sloughing agent, which has, suppresses shale hydration expansion and scattered, the effect of stabilizing borehole, such as can be
One or more in modified higher fatty alcohol (DWFT-1), emulsified asphalt (YK-H) and sulfonated gilsonite (FT-1) etc..Phase
For the water in the drilling fluid of 100 parts by weight, it is highly preferred that the content of the anti-sloughing agent is 4-8 parts by weight, more preferably
5-7 parts by weight.
Wherein, the inhibitor has the function that to suppress shale infiltration aquation, reduces drilling fluid filtrate activity, such as can be with
For the one or more in inorganic salts material (such as KCl), polynary amine and quaternary ammonium salt.Relative to the institute of 100 parts by weight
The water in drilling fluid is stated, it is highly preferred that the content of the inhibitor is 5-7 parts by weight.
Wherein, the heavy weight additive can adjust the density of drilling fluid and reach required density, such as can be barite, organic
One or more in salt (weigh-1, weigh-2 (active component is potassium formate), weigh-3, Organic Sodium Salt GD-WT) etc..
Relative to the water in the drilling fluid of 100 parts by weight, it is highly preferred that the content of the heavy weight additive is 50-55 parts by weight.
Wherein, pH adjusting agent can adjust the pH of drilling fluid to more suitable scope, such as can be sodium carbonate, hydrogen-oxygen
Change the one or more in sodium etc..Relative to the water in the drilling fluid of 100 parts by weight, it is highly preferred that the pH adjusting agent
Content be 0.15-0.2 parts by 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 water-base drilling fluid in oil/gas drilling.
Weak cross-linked copolymer provided by the invention can water-base drilling fluid as sealing agent use, and formed it is microgranular, from
And itself particulate form is adjusted by water absorption and swelling in drilling process, to be suitable to the envelope in Different Strata crack or pore-size
It is stifled, drilling fluid filtration can be effectively reduced, particularly also there is higher heat-resisting property, it is higher this area can be applied to
The closure on warm stratum.
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.
Expansion multiple refers to the ratio with loose volume before expansion after the expansion of weak cross-linked copolymer, and it passes through laser particle size point
Analyzer test expansion before and after median particle size ratio and obtain.
Crosslinking minor structure content refers to that the amount for the crosslinking minor structure that crosslinking agent provides accounts for the percentage of total weak cross-linked copolymer
Weight.
Embodiment 1
The present embodiment is used to illustrate weak cross-linked copolymer of the present invention and preparation method thereof and sealing agent.
By 0.615mol total amounts (about 74g) Methacrylamide, 2- acrylamide-2-methyl propane sulfonics and metering system
Sour cetyl ester (mol ratio 30：10：1) it is added in 100g water, regulation pH is 7；Add 1.75mmol persulfuric acid
Crosslinking agent N, the N- methylene-bisacrylamide of potassium and 0.3g, and it is stirred 40min at 200rpm, 25 DEG C；Then add
120g atoleine (PARAFFIN for being purchased from An Naiji companies), 8g sorbitan fatty ester (is purchased from An Naiji
The SPAN-80 of company) and 5g the polyoxyethylene sorbitan fatty acid ester TWEEN60 of An Naiji companies (be purchased from), and will
Gained mixture emulsifies 1min on emulsification instrument；Nitrogen 15min is subsequently passed with deoxygenation；Then it is added dropwise to 0.7mmol sulfurous
Sour hydrogen sodium (in the form of the aqueous solution by concentration for 0.07mol/L) (about 10min drops finish), and react 8h at 50 DEG C；Gained emulsion
As sealing agent A1, wherein the content of weak cross-linked copolymer is 23.3 weight %, the weight average molecular weight of the weak cross-linked copolymer is 5
×106G/mol, molecular weight distribution index 3, through infrared, proton nmr spectra and carbon spectrum analysis detection, the knot shown in formula (1)
Structure unit (R1For methyl, R1'For H), the construction unit (R shown in formula (2)2And R2'For H, R3For C0 alkylidene, R4Selected from-CO-
NH-C(CH3)2-CH2-SO3) and the construction unit (R shown in formula (3) M6For methyl, R6'For H, R7Selected from positive decyl) mol ratio
For 29.4：9.2：1, crosslinking minor structure content is 0.4 weight %, expansion multiple 40.
Embodiment 2
The present embodiment is used to illustrate weak cross-linked copolymer of the present invention and preparation method thereof and sealing agent.
By 0.572mol total amounts (about 76.5g) acrylamide, 2- acrylamide-2-methyl propane sulfonics and methacrylic acid
Stearyl (mol ratio 15：10：1) it is added in 100g water, regulation pH is 7；Add 1.9mmol ammonium persulfate and
0.34g crosslinking agent N, N- ethylenebisacrylamide, and it is stirred 50min at 220rpm, 25 DEG C；Then add 120g
The atoleine PARAFFIN of An Naiji companies (be purchased from), 7g sorbitan fatty ester (be purchased from An Naiji companies
SPAN-60) and 7g the polyoxyethylene sorbitan fatty acid ester TWEEN80 of An Naiji companies (be purchased from), and by gained
Mixture emulsifies 2min on emulsification instrument；Nitrogen 15min is subsequently passed with deoxygenation；Then it is added dropwise to 0.95mmol thiosulfuric acid
Sodium (in the form of the aqueous solution by concentration for 0.095mol/L) (about 12min drops finish), and react 9h at 35 DEG C；Gained emulsion is
Sealing agent A2, wherein the content of weak cross-linked copolymer is 23.9 weight %, the weight average molecular weight of the weak cross-linked copolymer for 4 ×
106G/mol, molecular weight distribution index 2, through infrared, proton nmr spectra and carbon spectrum analysis detection, the structure shown in formula (1)
Unit (R1And R1'For H), the construction unit (R shown in formula (2)2And R2'For H, R3For C0 alkylidene, R4Selected from-CO-NH-C
(CH3)2-CH2-SO3) and the construction unit (R shown in formula (3) M6For methyl, R6'For H, R7Selected from dodecyl) mol ratio
For 14.2：9.1：1, crosslinking minor structure content is 0.44 weight %, expansion multiple 35.
Embodiment 3
The present embodiment is used to illustrate weak cross-linked copolymer of the present invention and preparation method thereof and sealing agent.
By 0.8mol total amounts (about 64.4g) acrylamide, acrylic acid and lauryl methacrylate, (mol ratio is
13：6：1) it is added in 100g water, regulation pH is 7；Add 1.5mmol potassium peroxydisulfate and 0.23g crosslinking agent N, N- Asia
Bisacrylamide, and it is stirred 60min at 210rpm, 20 DEG C；The atoleine for then adding 120g is (resistance to purchased from pacifying
The PARAFFIN of Ji companies), 7g sorbitan fatty ester (SPAN-80 for being purchased from An Naiji companies) and 5g polyoxy
Ethene sorbitan fatty acid ester (TWEEN60 for being purchased from An Naiji companies), and gained mixture is emulsified on emulsification instrument
1min；Nitrogen 20min is subsequently passed with deoxygenation；Then 0.9mmol sodium hydrogensulfite is added dropwise to (using concentration as 0.09mol/L
Aqueous solution form) (about 10min drops finish), and react 7h at 45 DEG C；Gained emulsion is sealing agent A3, wherein weak crosslinking is altogether
The content of polymers is 21 weight %, and the weight average molecular weight of the weak cross-linked copolymer is 5.5 × 106G/mol, molecular weight distribution index
For 4, through infrared, proton nmr spectra and carbon spectrum analysis detection, the construction unit (R shown in formula (1)1And R1'For H), formula (2) institute
Construction unit (the R shown2And R2'For H, R3For C0 alkylidene, R4Selected from-COOH) and formula (3) shown in construction unit (R6For first
Base, R6'For H, R7Selected from n-hexyl) mol ratio be 12.1：5.4：1, crosslinking minor structure content is 0.36 weight %, expansion times
Number is 45.
Embodiment 4
According to the method described in embodiment 1, unlike, the dosage of potassium peroxydisulfate is 2.4mmol, the use of sodium hydrogensulfite
Measure as 0.96mmol, so as to which final gained emulsion is sealing agent A4, wherein the content of weak cross-linked copolymer is 23.3 weight %,
The weight average molecular weight of the weak cross-linked copolymer is 3.6 × 106G/mol, molecular weight distribution index 2.8, through infrared, nuclear magnetic resonance
Hydrogen is composed and carbon spectrum analysis detection, the construction unit (R shown in formula (1)1For methyl, R1'For H), the construction unit (R shown in formula (2)2
And R2'For H, R3For C0 alkylidene, R4Selected from-CO-NH-C (CH3)2-CH2-SO3) and the construction unit (R shown in formula (3) M6For
Methyl, R6'For H, R7Selected from positive decyl) mol ratio be 29.1：9.3：1, crosslinking minor structure content is 0.4 weight %, expansion times
Number is 38.
Embodiment 5
According to the method described in embodiment 1, unlike, the dosage of potassium peroxydisulfate is 1mmol, the dosage of sodium hydrogensulfite
For 0.34mmol, so as to which final gained emulsion is sealing agent A5, wherein the content of weak cross-linked copolymer is 23.3 weight %, it is somebody's turn to do
The weight average molecular weight of weak cross-linked copolymer is 6.5 × 106G/mol, molecular weight distribution index 3.1, through infrared, hydrogen nuclear magnetic resonance
Spectrum and carbon spectrum analysis detection, the construction unit (R shown in formula (1)1For methyl, R1'For H), the construction unit (R shown in formula (2)2With
R2'For H, R3For C0 alkylidene, R4Selected from-CO-NH-C (CH3)2-CH2-SO3) and the construction unit (R shown in formula (3) M6For first
Base, R6'For H, R7Selected from positive decyl) mol ratio be 29：9.4：1, crosslinking minor structure content is 0.4 weight %, and expansion multiple is
41。
Comparative example 1
According to the method described in embodiment 1, the difference is that, n-BMA replaces methacrylic acid octadecyl
Ester, so as to which final gained emulsion is sealing agent DA1, wherein the content of weak cross-linked copolymer is 22.8 weight %, the weak crosslinking
The weight average molecular weight of copolymer is 4.7 × 106G/mol, molecular weight distribution index 3.2, through infrared, proton nmr spectra and carbon
Spectrum analysis detection, the construction unit (R shown in formula (1)1For methyl, R1'For H), the construction unit (R shown in formula (2)2And R2'For H,
R3For C0 alkylidene, R4Selected from-CO-NH-C (CH3)2-CH2-SO3M) and octadecyl methacrylate provide structure list
The mol ratio of member is 29.1：9：1, crosslinking minor structure content is 0.4 weight %, expansion multiple 39.
Comparative example 2
According to the method described in embodiment 1, the difference is that, 2- acrylamide-2-methyl propane sulfonics are not used, but are used
Mol ratio is 30：1 Methacrylamide and methacrylic acid cetyl ester is as monomer, so as to which final gained emulsion is
Sealing agent DA2, wherein the content of weak cross-linked copolymer is 19 weight %, the weight average molecular weight of the weak cross-linked copolymer for 4.4 ×
106G/mol, molecular weight distribution index 2.7, through infrared, proton nmr spectra and carbon spectrum analysis detection, the knot shown in formula (1)
Structure unit (R1For methyl, R1'For H) and octadecyl methacrylate provide construction unit mol ratio be 28.6：1, hand over
Connection minor structure content is 0.4 weight %, expansion multiple 44.
Comparative example 3
According to the method described in embodiment 1, the difference is that, the dosage of crosslinking agent N, N- methylene-bisacrylamide is
0.05g, so as to which final gained emulsion is sealing agent DA3, wherein the content of weak cross-linked copolymer is 23.3 weight %, the weak friendship
Ally the communists polymers weight average molecular weight be 5.05 × 106G/mol, molecular weight distribution index 2.86, through infrared, proton nmr spectra
Analysis detection, the construction unit (R shown in formula (1) are composed with carbon1For methyl, R1'For H), the construction unit (R shown in formula (2)2And R2'
For H, R3For C0 alkylidene, R4Selected from-CO-NH-C (CH3)2-CH2-SO3) and the construction unit (R shown in formula (3) M6For first
Base, R6'For H, R7Selected from positive decyl) mol ratio be 29：9：1, crosslinking minor structure content is 0.068 weight %, and expansion multiple is
28。
Comparative example 4
According to the method described in embodiment 1, the difference is that, the dosage of crosslinking agent N, N- methylene-bisacrylamide is 1g,
So as to which final gained emulsion is sealing agent DA4, wherein the content of weak cross-linked copolymer is 23.3 weight %, the weak copolymerzation with cross-linking
The weight average molecular weight of thing is 4.72 × 106G/mol, molecular weight distribution index 3.2, composed through infrared, proton nmr spectra and carbon
Analysis detection, the construction unit (R shown in formula (1)1For methyl, R1'For H), the construction unit (R shown in formula (2)2And R2'For H, R3
For C0 alkylidene, R4Selected from-CO-NH-C (CH3)2-CH2-SO3) and the construction unit (R shown in formula (3) M6For methyl, R6'For
H, R7Selected from positive decyl) mol ratio be 29.3：9：1, crosslinking minor structure content is 1.4 weight %, expansion multiple 53.
Drilling fluid embodiment 1
The present embodiment is used for the water-base drilling fluid for illustrating the present invention.
Drilling fluid composition：The water of 100 parts by weight, (parts by weight are with the copolymer in sealing agent by the sealing agent A1 of 1 parts by weight
Dry weight meter), the sodium bentonite (purchased from Weifang China dimension bentonite Technical Research Center) of 2.5 parts by weight, 0.15 parts by weight
Na2CO3, the salt resistant filter loss reduction agent (being purchased from the Henan marine chemical industry Co., Ltd PAC trades mark) of 1 parts by weight, the temperature resistance drop of 3 parts by weight
Fluid loss agents (are purchased from Shijiazhuang Hualai Dingsheng Technology Co., Ltd.'s KJAN trades mark), and the anti-sloughing agent of 3 parts by weight (is purchased from Henan ocean
The work Co., Ltd DWFT-I trades mark), the anti-sloughing agent emulsified asphalt powder of 1.5 parts by weight (is purchased from Renqiu City Ren Yuan chemical plant YK-H boards
Number), the sulfonated gilsonite powder (being purchased from the Henan marine chemical industry Co., Ltd FT-1 trades mark) of 2 parts by weight, the KCl of 5 parts by weight, 10 weight
The heavy weight additive (being purchased from Shijiazhuang Hualai Dingsheng Technology Co., Ltd.'s Weigh2 trades mark) of part, the barite of 45 parts by weight (is purchased from stone
The village prosperous Science and Technology Ltd. of Lay of China of family)；So as to obtain drilling fluid Y1.
Drilling fluid embodiment 2-5
The present embodiment is used for the water-base drilling fluid for illustrating the present invention.
According to drilling fluid embodiment 1, the difference is that, sealing agent A2-A5 is respectively adopted and replaces above-mentioned A1, so as to respectively obtain
Drilling fluid Y2-Y5.
Drilling fluid comparative example 1-4
According to drilling fluid embodiment 1, the difference is that, sealing agent DA1-DA4 is respectively adopted and replaces above-mentioned A1, so as to obtain respectively
To drilling fluid DY1-DY4.
Drilling fluid comparative example 5
The present embodiment is used for the water-base drilling fluid for illustrating the present invention.
According to drilling fluid embodiment 1, the difference is that, sealing agent A1 is not used, so as to obtain drilling fluid DY5.
Test case 1
The rheological characteristic and filtration property of above-mentioned drilling fluid are measured respectively, specifically by the drilling fluid of gained before ageing
And apparent viscosity (AV), plastic viscosity (PV), yield value (YP), first egress are measured after the near room temperatures of aging 6h at 120 DEG C
(G10 "/10 ') and middle filter pressing loss (API)
Apparent viscosity (AV) is to use six fast viscosimeter of normal form side according to specified in standard GB/T/T29170-2012
What method measured, unit mPas,
Plastic viscosity (PV) is to use six fast viscosimeter of normal form side according to specified in standard GB/T/T29170-2012
What method measured, unit mPas, PV=θ600-θ300。
Yield value (YP) is to use six fast viscosimeter of normal form method according to specified in standard GB/T/T29170-2012
Measure, YP=0.511 × (2 × φ 300- φ 600), unit Pa.
First egress (G10 "/10 ') is to be provided according to six fast viscosimeter of normal form according in standard GB/T/T29170-2012
Method measure, unit Pa/Pa.
API refers to middle filter pressing loss, is that the method that press filtration is committed a breach of etiquette in SY/T 5621-93 standards in using is surveyed
Amount, unit mL.
Table 1
Can be seen that by the data of table 1 after adding sealing agent in drilling fluid system, the change of the rheological characteristic of system compared with
Small, it is good with drilling fluid compatibility to illustrate；Filter loss substantially reduces, and illustrates that sealing agent has good sealing characteristics.
Test case 2
The sealing characteristics of above-mentioned drilling fluid is measured respectively, that is, the above-mentioned system drilling liquid of 400mL is taken, at 120 DEG C
Aging 16h respectively, using HTHP casting bed leakage instrument measure plugging effect, measurement result is shown in Table 2.
HTHP casting bed misses instrument assay method：Taking the quartz sand 200g of corresponding mesh number, (specific mesh number is shown in Table 2 institutes
Show) leakage instrument lower floor is filled in, load drilling fluid thereto to graduation mark；Booster is loaded into connection valve rod upper end, by back pressure
Device loads lower connection valve rod lower end, and both ends will insert positioning finger setting, connect source of the gas；Adjustment increases, back pressure device handle makes its instruction
0.7MPa pressure values；Open overhead-valve and keep 0.7MPa pressure, booster is adjusted to 4.2MPa, beaten by temperature up to 120 DEG C, then rapidly
Drive bottom valve and clock；Timing is missed 30 minutes, record leakage drilling fluid volume.
Table 2
The DY5 phases of sealing agent are can be seen that with instance Y 1-Y5, comparative example DY 1-DY4 and not added by the data of table 2
Than example 1-3 has fabulous plugging effect, all has preferably closure to various sizes of leakage situation.
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 (32)
1. a kind of weak cross-linked copolymer, it is characterised in that the weak cross-linked copolymer is as the construction unit shown in formula (1), formula (2) institute
Construction unit and crosslinking minor structure composition shown in the construction unit that shows, formula (3), and son knot is crosslinked in the weak cross-linked copolymer
The content of structure is 0.1-1 weight %, wherein：Shown in construction unit shown in construction unit, formula (2) and formula (3) shown in formula (1)
The mol ratio of construction unit be 10-50：3-20：1；The weight average molecular weight of the weak cross-linked copolymer is 4 × 106-5.5×
106g/mol；
Wherein, R1、R1'、R2、R2'、R6And R6'It is each independently selected from H and C1-C6 alkyl；R3Alkylidene selected from C0-C6；R4
Selected from-COOM ,-SO3M or-CO-NH-R5-SO3M, R5Alkylidene selected from C0-C6, M are selected from H or alkali metal；R7Selected from H
Or C1-C20 alkyl；C0 alkylidene refers to connecting key, and the group at the group both ends will be joined directly together；
Wherein, the crosslinking minor structure in the weak cross-linked copolymer is carried as the one or more in the crosslinking agent shown in following formula (4)
For：
N is selected from 1-6 integer.
2. weak cross-linked copolymer according to claim 1, wherein, R1、R1'、R2、R2'、R6And R6'It is each independently selected from H
With C1-C4 alkyl；R3Alkylidene selected from C0-C4；R4Selected from-COOM ,-SO3M or-CO-NH-R5-SO3M, R5Selected from C1-C6
Alkylidene, M is selected from H, Na or K；R7Alkyl selected from C2-C16.
3. weak cross-linked copolymer according to claim 2, wherein, R1、R1'、R2、R2'、R6And R6'Be each independently selected from H,
Methyl, ethyl and n-propyl；R3Alkylidene ,-CH selected from C02-、-CH2-CH2-、-CH2-CH2-CH2-、-CH(CH3)-CH2-、-
CH2-CH(CH3)-or-CH2-(CH2)2-CH2-；R4Selected from-COOH ,-SO3M or-CO-NH-R5-SO3M, R5Selected 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- or-CH2-C(CH3)2-, M is selected from H, Na or K；R7Selected from ethyl, n-propyl, normal-butyl, n-pentyl,
N-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, n-undecane base, dodecyl, n-tridecane base, n-tetradecane
Base, n-pentadecane base or n-hexadecyl.
4. the weak cross-linked copolymer according to any one in claim 1-3, wherein, construction unit, formula shown in formula (1)
(2) mol ratio of the construction unit shown in construction unit and formula (3) shown in is 12-40：5-15：1.
5. weak cross-linked copolymer according to claim 4, wherein, the knot shown in construction unit, formula (2) shown in formula (1)
The mol ratio of construction unit shown in structure unit and formula (3) is 12-30：5-10：1.
6. weak cross-linked copolymer according to claim 4, wherein, the content of crosslinking minor structure in the weak cross-linked copolymer
For 0.3-0.6 weight %.
7. a kind of preparation method of weak cross-linked copolymer, it is characterised in that this method includes：In aqueous solvent, aoxidizing-going back
In the presence of former initiation system, crosslinking agent and emulsifying agent, by formula (1') shown compound, formula (2') shown compound and formula
(3') shown compound carries out emulsion polymerization, wherein, the dosage of the crosslinking agent to hand in the weak cross-linked copolymer of gained
The content of connection minor structure is 0.1-1 weight %, and (1') (2') shown compound and formula are (3') shown for shown compound, formula for formula
The mole dosage ratio of compound be 10-50：3-20：1；This method make it that the weight average molecular weight of the weak cross-linked copolymer of gained is
4×106-5.5×106g/mol；
Wherein, R1、R1'、R2、R2'、R6And R6'It is each independently selected from H and C1-C6 alkyl；R3Alkylidene selected from C0-C6；R4
Selected from-COOM ,-SO3M or-CO-NH-R5-SO3M, R5Alkylidene selected from C0-C6, M are selected from H or alkali metal；R7Selected from H
Or C1-C20 alkyl；C0 alkylidene refers to connecting key, and the group at the group both ends will be joined directly together；
The crosslinking agent is selected from the one or more in the crosslinking agent shown in following formula (4)：
N is selected from 1-6 integer.
8. the method according to claim 11, wherein, R1、R1'、R2、R2'、R6And R6'It is each independently selected from H's and C1-C4
Alkyl；R3Alkylidene selected from C0-C4；R4Selected from-COOM ,-SO3M or-CO-NH-R5-SO3M, R5Alkylidene selected from C1-C6,
M is selected from H, Na or K；R7Alkyl selected from C2-C16.
9. the method according to claim 11, wherein, R1、R1'、R2、R2'、R6And R6'It is each independently selected from H, methyl, second
Base and n-propyl；R3Alkylidene ,-CH selected from C02-、-CH2-CH2-、-CH2-CH2-CH2-、-CH(CH3)-CH2-、-CH2-CH
(CH3)-or-CH2-(CH2)2-CH2-；R4Selected from-COOH ,-SO3M or-CO-NH-R5-SO3M, R5Selected 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- or-CH2-C(CH3)2-, M is selected from H, Na or K；R7Selected from ethyl, n-propyl, normal-butyl, n-pentyl,
N-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, n-undecane base, dodecyl, n-tridecane base, n-tetradecane
Base, n-pentadecane base or n-hexadecyl.
10. according to the method described in any one in claim 7-9, wherein, (1') shown compound, formula are (2') shown for formula
Compound and the mole dosage ratio of formula (3') shown compound be 12-40：5-15：1.
11. according to the method for claim 10, wherein, formula (1') shown compound, formula (2') shown compound and
The mole dosage ratio of formula (3') shown compound is 12-30：5-10：1.
12. according to the method for claim 10, wherein, the dosage of the crosslinking agent causes in the weak cross-linked copolymer of gained
The content for being crosslinked minor structure is 0.3-0.6 weight %.
13. according to the method for claim 10, wherein, relative to the 100g aqueous solvent, formula (1') shown change
Mole total amount of compound, formula (2') shown compound and formula (3') shown compound is 0.1-5mol.
14. according to the method for claim 13, wherein, relative to the 100g aqueous solvent, formula (1') shown change
Mole total amount of compound, formula (2') shown compound and formula (3') shown compound is 0.2-2mol.
15. according to the method for claim 14, wherein, relative to the 100g aqueous solvent, formula (1') shown change
Mole total amount of compound, formula (2') shown compound and formula (3') shown compound is 0.5-1mol.
16. according to the method described in any one in claim 7-9, wherein, the oxidation in the oxidation-reduction trigger system
One or more of the agent in sodium peroxydisulfate, potassium peroxydisulfate, ammonium persulfate and hydrogen peroxide, the redox initiator body
Reducing agent in system is in ferrous sulfate, frerrous chloride, sodium sulfite, sodium hydrogensulfite, potassium sulfite and sodium thiosulfate
One or more.
17. according to the method for claim 16, wherein, the mol ratio of the Oxidizing and Reducing Agents is 1：0.2-1.
18. according to the method for claim 17, wherein, the mol ratio of the Oxidizing and Reducing Agents is 1：0.3-0.8.
19. 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 oxidation-reduction trigger system is 1-
10mmol。
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 oxidation-reduction trigger system is 2-
5mmol。
21. according to the method for claim 20, 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 oxidation-reduction trigger system is 2-
3mmol。
22. according to the method described in any one in claim 7-9 and 17-21, wherein, the emulsifying agent is Sorbitan
One in alcohol fatty acid ester, APES, polyoxyethylene sorbitan fatty acid ester and polyglyceryl fatty acid ester
Kind is a variety of.
23. according to the method for claim 22, wherein, the aqueous solvent and the weight ratio of the dosage of the emulsifying agent are
100：10-20.
24. according to the method for claim 23, wherein, the aqueous solvent and the weight ratio of the dosage of the emulsifying agent are
100：12-14.
25. according to the method for claim 22, wherein, this method is carried out in the presence of being included in oils reagent, the oils
Reagent is liquefied petrolatum；The weight ratio of the dosage of the emulsifying agent and oils reagent is 100：500-2000.
26. according to the method described in any one in claim 7-9,17-21 and 23-25, wherein, the bar of the emulsion polymerization
Part includes：Temperature is 30-60 DEG C, time 5-10h.
27. according to the method described in any one in claim 7-9,17-21 and 23-25, wherein, this method includes：In pH
For under 6-8, first by formula (1') shown compound, formula (2') shown compound, formula (3') shown compound, described aqueous
Solvent, the oxidant in the oxidation-reduction trigger system and the crosslinking agent are mixed, then introduce the emulsifying agent and
Oils reagent is simultaneously emulsified, then under an inert atmosphere, and the reducing agent being introduced into the oxidation-reduction trigger system simultaneously carries out institute
State emulsion polymerization.
28. the weak cross-linked copolymer as made from the method described in any one in claim 7-27.
29. application of the weak cross-linked copolymer in drilling fluid as sealing agent in claim 1-6 and 28 described in any one.
A kind of 30. water base brill of weak cross-linked copolymer contained in claim 1-6 and 28 described in any one as sealing agent
Well liquid.
31. water-base drilling fluid according to claim 30, wherein, relative to the water in the water-base drilling fluid of 100 parts by weight,
The content of the weak cross-linked copolymer is 1-3 parts by weight.
32. application of the water-base drilling fluid described in claim 30 or 31 in oil/gas drilling.
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