CN106749889A - Weak cross-linked copolymer and preparation method thereof and the application as sealing agent and water-base drilling fluid and its application - Google Patents
Weak cross-linked copolymer and preparation method thereof and the application as sealing agent and water-base drilling fluid and its application Download PDFInfo
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- CN106749889A CN106749889A CN201611007046.1A CN201611007046A CN106749889A CN 106749889 A CN106749889 A CN 106749889A CN 201611007046 A CN201611007046 A CN 201611007046A CN 106749889 A CN106749889 A CN 106749889A
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- 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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- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
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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
- C09K8/14—Clay-containing compositions
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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
- C09K8/42—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 the construction unit shown in formula (1), the construction unit shown in formula (2) and formula (3), and it is 0.1 1 weight % that the content of minor structure is crosslinked in the weak cross-linked copolymer.The weak cross-linked copolymer that the present invention is provided can be used in water-base drilling fluid as sealing agent, and form 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 the key factors for restricting safe, smooth, efficient drilling well.
Drilling process can cause huge economic losses because there is the complicated leakage such as Fractured, hole, inductivity often.According to foreign countries
Statistics, current drilling well underground is met in the economic loss that challenge is caused, and 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, having blocked up and bore again, although this mode can process some, and only several are big
The stratum in crack, but be invalid in face of the stratum that crack is a lot, position uncertain, missed once boring and meeting.And it is 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 to bore up to mesh
Layer, the accident for scrapping full well.
It is exactly to introduce certain density by size is suitable, intensity is higher particle in drilling fluid with leak-proof leak-stopping technology is bored
Shape material presses the sealing agent of rational gradation composition formation, and when crack growth is to cause leakage degree, closure particle enters with drilling fluid leakage
In entering crack, the big closure particle stuck bridge formation in certain position in crack is remaining empty in the less particles filled crack of closure
Between, crack is finally blocked, realize i.e. stifled.
The drill-feeding plugging agent of development mainly has pitch, fibrous material, intumescent material and other rigid materials etc. at present.
Although the use of these materials can solve the problems, such as partial loss, but there is a series of problems, it is mainly shown as：When these
When plugging while drilling material is mismatched with formation fracture or pore-size, plugging effect is then very poor.
The content of the invention
It is difficult to and good of formation fracture or pore-size it is an object of the invention to be directed to existing plugging while drilling material
With and plugging effect difference defect, 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 the alkyl of H and C1-C6；R3Selected from the alkylene of C0-C6
Base；R4Selected from-COOM ,-SO3M or-CO-NH-R5-SO3M, R5Selected from the alkylidene of C0-C6, M is selected from H or alkali metal；R7
Selected from the alkyl of H or C1-C20.
Present invention also offers a kind of preparation method of weak cross-linked copolymer, the method includes：In aqueous solvent, in oxygen
In the presence of change-reduction initiating system, crosslinking agent and emulsifying agent, by the (2') shown compound of the (1') shown compound of formula, formula
Emulsion polymerization is carried out with the (3') shown compound of formula, wherein, the consumption 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 the alkyl of H and C1-C6；R3Selected from the alkylene of C0-C6
Base；R4Selected from-COOM ,-SO3M or-CO-NH-R5-SO3M, R5Selected from the alkylidene of C0-C6, M is selected from H or alkali metal；R7
Selected from the alkyl of H or C1-C20.
Present invention also offers the weak cross-linked copolymer as obtained in the above method.
The present invention also provide above-mentioned weak cross-linked copolymer or as obtained in the above method weak cross-linked copolymer in drilling fluid
As the application of sealing agent.
Present invention also offers it is a kind of containing above-mentioned weak cross-linked copolymer as sealing agent water-base drilling fluid.
Present invention also offers application of the above-mentioned water-base drilling fluid in oil/gas drilling.
The weak cross-linked copolymer that the present invention is provided can be used in water-base drilling fluid as sealing agent, and form microgranular, from
And adjust itself particulate form by water absorption and swelling in drilling process and 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.
Specific embodiment
Specific embodiment of the invention is described in detail below.It should be appreciated that described herein specific
Implementation method is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The end points and any value of disclosed scope 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
One or more can be obtained with combination with one another between the endpoint value of individual scope and single point value, and individually between point value
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, the formula shown in formula (1)
(2) construction unit shown in construction unit and formula (3) shown in, and the content of crosslinking minor structure is in the weak cross-linked copolymer
0.1-1 weight %, wherein：
Formula (1)Formula (2)
Formula (3)
Wherein, R1、R1'、R2、R2'、R6And R6'It is each independently selected from the alkyl of H and C1-C6；R3Selected from the alkylene of C0-C6
Base；R4Selected from-COOM ,-SO3M or-CO-NH-R5-SO3M, R5Selected from the alkylidene of C0-C6, M is selected from H or alkali metal；R7
Selected from the alkyl of H or C1-C20.
According to the present invention, the weak cross-linked copolymer is that the content of crosslinking minor structure is the copolymerzation with cross-linking of 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 from occurring.
According to the present invention, wherein, the alkyl of above-mentioned C1-C6 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 the alkylidene of above-mentioned C0-C6 can for example be formed by the alkyl of the alkylidene of C0, above-mentioned C1-C6.
Wherein, the alkylidene of C0 can consider only be connecting key or do not exist, and the group at the group two ends will be joined directly together.
The alkyl of above-mentioned C1-C20 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 the alkyl of H and C1-C4；R3Selected from the alkylidene of C0-C4；R4Selected from-COOM ,-SO3M or-CO-
NH-R5-SO3M, R5Selected from the alkylidene of C1-C6, M is selected from H, Na or K；R7Selected from the alkyl of 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.
, according to the invention it is preferred in the case of, 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 contains of the weak cross-linked copolymer
The amount of the construction unit shown in construction unit and formula (3) can change in scope wider, but be in order at weak obtained by optimization
The thickening of cross-linked copolymer, salt resistance and heat-resisting property consider, under preferable case, shown in the construction unit, formula (2) shown in formula (1)
Construction unit and formula (3) shown in construction unit mol ratio 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 spontaneous matching capacity of ground 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 son, although the present invention there is no particular limitation, the present invention by forming cross-bond using crosslinking agent so that
Crosslinking is formed in weak cross-linked copolymer (being appreciated that to be to constitute structure by what crosslinking agent was formed).Preferably, the weak crosslinking
One or more offer in the crosslinking agent of crosslinking minor structure in copolymer as shown in following formula (4)：
Formula (4)N is selected from the integer of 1-6.
The instantiation of the 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, the expansion multiple of the weak cross-linked copolymer measured using laser particle size analyzer
Preferably 30-50, more preferably 35-45.
Present invention also offers a kind of preparation method of weak cross-linked copolymer, the method includes：In aqueous solvent, in oxygen
In the presence of change-reduction initiating system, crosslinking agent and emulsifying agent, by the (2') shown compound of the (1') shown compound of formula, formula
Emulsion polymerization is carried out with the (3') shown compound of formula, wherein, the consumption of the crosslinking agent causes the weak cross-linked copolymer of gained
Middle crosslinking minor structure content 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 the alkyl of H and C1-C6；R3Selected from the alkylene of C0-C6
Base；R4Selected from-COOM ,-SO3M or-CO-NH-R5-SO3M, R5Selected from the alkylidene of C0-C6, M is selected from H or alkali metal；R7
Selected from the alkyl of H or C1-C20.
Wherein, each substitution base that the monomer in the above method is related to is as described above, will not be repeated here.Formula
(1') the (2') shown compound of shown compound, formula and the (3') shown compound of formula can also be according to described above
The specific construction unit species of copolymer properly selected.
Wherein, the instantiation of the (1') shown compound of formula for example can be the one kind in the compound shown in following formula
Or it is various：
In formula (1'-1)：R1And R1'It is H (also referred to as acrylamide)；
In formula (1'-2)：R1It is methyl, R1'It is H (also referred to as Methacrylamide)；
In formula (1'-3)：R1It is ethyl, R1'It is H (also referred to as ethyl acrylamide)；
In formula (1'-4)：R1It is H, R1'It is methyl (also referred to as 2- crotonamides).
Wherein, the instantiation of the (2') shown compound of formula for example can be the one kind in the compound shown in following formula
Or it is various：
In formula (2'-1)：R2And R2'It is H, R3It is the alkylidene of C0, R4Selected from-COOH (also referred to as acrylic acid)；
In formula (2'-2)：R2It is methyl, R2'It is H, R3It is the alkylidene of C0, R4Selected from-COOH (also referred to as metering systems
Acid)；
In formula (2'-3)：R2And R2'It is H, R3For-CH2-, R4Selected from-SO3H (also referred to as propane sulfonic acid)；
In formula (2'-4)：R2It is methyl, R2'It is H, R3For-CH2-, R4Selected from-SO3H (also referred to as methyl propane sulfonic acid)；
In formula (2'-5)：R2And R2'It is H, R3It is the alkylidene of C0, 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 the (3') shown compound of formula for example can be the one kind in the compound shown in following formula
Or it is various：
In formula (3'-1)：R6It is methyl, R6'It is H, R7Selected from normal-butyl (the also referred to as Arrcostab of methacrylic acid ten)；
In formula (3'-2)：R6And R6'It is H, R7Selected from normal-butyl (the also referred to as Arrcostab of acrylic acid ten)；
In formula (3'-3)：R6It is methyl, R6'It is H, R7Selected from n-pentyl (also referred to as methacrylic acid hendecane base ester)；
In formula (3'-4)：R6And R6'It is H, R7Selected from n-pentyl (also referred to as acrylic acid hendecane base ester)；
In formula (3'-5)：R6It is methyl, R6'It is H, R7Selected from n-hexyl (also referred to as lauryl methacrylate)；
In formula (3'-6)：R6And R6'It is H, R7Selected from n-hexyl (also referred to as dodecylacrylate)；
In formula (3'-7)：R6It is methyl, R6'It is H, R7Selected from n-heptyl (also referred to as Tridecyl methacrylate base ester)；
In formula (3'-8)：R6And R6'It is H, R7Selected from n-heptyl (also referred to as tridecyl acrylate)；
In formula (3'-9)：R6It is methyl, R6'It is H, R7Selected from n-octyl (also referred to as methacrylic acid tetradecane base ester)；
In formula (3'-10)：R6And R6'It is H, R7Selected from n-octyl (also referred to as acrylic acid tetradecane base ester)；
In formula (3'-11)：R6It is methyl, R6'It is H, R7Selected from n-nonyl (also referred to as methacrylic acid pentadecane base ester)；
In formula (3'-12)：R6And R6'It is H, R7Selected from n-nonyl (also referred to as acrylic acid pentadecane base ester)；
In formula (3'-13)：R6It is methyl, R6'It is H, R7Selected from positive decyl (also referred to as methacrylic acid cetyl ester)；
In formula (3'-14)：R6And R6'It is H, R7Selected from positive decyl (also referred to as aliphatic acrylate)；
In formula (3'-15)：R6It is methyl, R6'It is H, R7Selected from n-undecane base (also referred to as methacrylic acid heptadecyl
Ester)；
In formula (3'-16)：R6And R6'It is H, R7Selected from n-undecane base (also referred to as acrylic acid heptadecane base ester)；
In formula (3'-17)：R6It is methyl, R6'It is H, R7Selected from dodecyl (also referred to as methacrylic acid octadecyl
Ester)；
In formula (3'-18)：R6And R6'It is H, R7Selected from dodecyl (also referred to as octadecyl acrylate).
According to the present invention, the consumption of above-mentioned monomer can be according to the accounting of the construction unit of required copolymer and molecular weight
Selected, under preferable case, the (2') shown compound of the (1') shown compound of formula, formula and the (3') shown compound of formula
Mol ratio be 10-50：3-20：1, preferably 12-40：5-15：1, still more preferably it is 12-30：5-10：1.In order to be suitable to
The carrying out of the emulsion polymerization, and the reasonably molecular weight of copolymer obtained by control, under preferable case, the institute relative to 100g
State aqueous solvent, the (2') shown compound of the (1') shown compound of formula, formula and the (3') shown compound of formula it is mole total
It is 0.1-5mol to measure, preferably 0.2-2mol, more preferably 0.5-1mol.Wherein, the aqueous solvent can be single water,
Can also miscible there are some not influence the solvent of reaction of the invention (for example, methyl alcohol, ethanol, ethylene glycol, propyl alcohol, isopropanol
The mixture of the water one or more) in, certainly preferably water.
According to the present invention, the introducing of the crosslinking agent can cause the (2') shown change of the (1') shown compound of formula, formula
The (3') shown compound of compound and formula carries out a certain degree of crosslinking in emulsion polymerization process, and the consumption 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 that the weak friendship needed for forming the present invention
The structure of connection, it is preferable that the consumption 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 the (1') shown change of formula
On the basis of the gross weight of the (3') shown compound of the (2') shown compound of compound, formula, formula and crosslinking agent, the crosslinking agent
Consumption is, for example, 0.1-1 weight %, more preferably preferably 0.3-0.6 weight %, 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 weak cross-linked copolymer of the invention, it is preferable that the oxidation-reduction trigger system
In oxidant be selected from sodium peroxydisulfate, potassium peroxydisulfate, ammonium persulfate and hydrogen peroxide in one or more.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 one or more in sodium thiosulfate.In order to preferably play in the oxidation-reduction trigger system oxidant and also
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, it is also possible to
Introduce in form of an aqueous solutions, be the aqueous solution of the oxidant of 0.12-0.22mol/L for example with concentration, for example with
Concentration is the aqueous solution of the reducing agent of 0.05-0.2mol/L.
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 the (2') shown compound of formula relative to 1mol (1') shown compound, formula and the (3') shown change of formula
Mole total amount of compound, the consumption of the oxidation-reduction trigger system is 1-10mmol, more preferably preferably 2-5mmol, 2-
3mmol。
According to the present invention, the emulsifying agent can routinely use various emulsifying agents using this area, as long as can be by institute
State emulsion polymerization and obtain weak cross-linked copolymer of the 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
Consumption 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 consumption 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, the 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 consumption of the emulsifying agent and oils reagent is 100：
500-2000, preferably 100：800-1500.
, according to the invention it is preferred in the case of, the condition of the emulsion polymerization includes：Temperature is 30-60 DEG C of (preferably 35-
50 DEG C), the time is 5-10h (preferably 7-9h).
According to the present invention, in order to keep the activity of initiator etc., the method to include：So that the emulsion is poly-
Conjunction is carried out in an inert atmosphere, for example can be to being passed through one or more of nitrogen, helium, neon, argon gas etc. in 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 carrying out of above-mentioned emulsion polymerization, it is preferable that the method includes：
PH is under 6-8 (pH be 7 or so), first by change that the (1') shown compound of formula, formula (2') shown compound, formula are (3') shown
Oxidant and the crosslinking agent in compound, the aqueous solvent, the oxidation-reduction trigger system are mixed the (mixing
Condition can for example include：Mix 30-60min under the mixing speed of 200-250rpm, at 10-40 DEG C) (it is highly preferred that first
The (3') shown compound of the (1') shown compound of formula, formula (2') shown compound, formula, the aqueous solvent are mixed,
And pH is adjusted for 6-8, then it is 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.
It is polymerized in obtained emulsion by above-mentioned emulsion and just contains the present invention weak cross-linked copolymer mentioned above, it is such
Weak cross-linked copolymer can be extracted, and certainly for the sake of convenience, such emulsion can just be used directly as sealing agent.
Present invention also offers the weak cross-linked copolymer as obtained in the above method.Although there is no particular limitation for the present invention,
But the weak cross-linked copolymer may be considered above described in weak cross-linked copolymer in one kind, or various 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 various weak cross-linked copolymers, but of the invention
Also such situation is included within the scope of the invention.
The present invention also provide above-mentioned weak cross-linked copolymer or as obtained in the above method weak cross-linked copolymer in drilling fluid
As the application of sealing agent.
Present invention also offers it is a kind of containing above-mentioned weak cross-linked copolymer as sealing agent water-base drilling fluid.
The weak cross-linked copolymer that the present invention is provided, can be used in water-base drilling fluid as sealing agent, so as in drilling well
Cheng Zhong, 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, complete closure, prevent leakage from occurring.The present invention has no special limit to the content of the weak cross-linked copolymer
It is fixed, can suitably be adjusted according to strata condition, it is preferable that relative to the water in the water-base drilling fluid of 100 weight portions, institute
The content for stating weak cross-linked copolymer is 1-3 weight portions.
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, drilling fluid of the 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 with montmorillonite as main mineral constituent, and it has, and imparting drilling fluid is viscous to be cut
The effect of power and leak-off wave making machine, for example, 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 weight portions, the bentonitic content is 2-2.5 weight portions.
Wherein, the salt resistant filter loss reduction agent has the effect for improving drilling fluid saline-alkaline tolerance and reducing drilling fluid filtration,
For example can be one or more in cellulose ether derivatives (PAC), modified starch and carboxymethylcellulose calcium etc..Relative to
Water in the drilling fluid of 100 weight portions, it is highly preferred that the content of the salt resistant filter loss reduction agent is 1-1.5 weight portions.
Wherein, the temperature resistance fluid loss additive has the effect for improving drilling fluids at high temperature stability and reducing filter loss, for example
Can be 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 weight portions, it is highly preferred that the content of the temperature resistance fluid loss additive is 3-4 weight portions.
Wherein, the anti-sloughing agent has and suppresses shale hydration expansion and disperse, and the effect of stabilizing borehole for example 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 weight portions, it is highly preferred that the content of the anti-sloughing agent is 4-8 weight portions, more preferably
5-7 weight portions.
Wherein, the inhibitor has the effect for suppressing shale infiltration aquation, reducing drilling fluid filtrate activity, for example can be with
It is one or more in inorganic salts material (such as KCl), polynary amine and quaternary ammonium salt.Relative to the institute of 100 weight portions
The water in drilling fluid is stated, it is highly preferred that the content of the inhibitor is 5-7 weight portions.
Wherein, the heavy weight additive can adjust the density of drilling fluid and reach required density, for example, 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 weight portions, it is highly preferred that the content of the heavy weight additive is 50-55 weight portions.
Wherein, pH adjusting agent can adjust the pH of drilling fluid to more suitable scope, for example, can be sodium carbonate, hydrogen-oxygen
Change one or more in sodium etc..Relative to the water in the drilling fluid of 100 weight portions, it is highly preferred that the pH adjusting agent
Content be 0.15-0.2 weight portions.
The various materials that above-mentioned additive is can be commercially available product, it is also possible to be obtained 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.
The weak cross-linked copolymer that the present invention is provided can be used in water-base drilling fluid as sealing agent, and form microgranular, from
And adjust itself particulate form by water absorption and swelling in drilling process and 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 heat-resisting property higher, this area can be applied to higher
The closure on warm stratum.
Below will the present invention will be described in detail by embodiment.
In following examples and comparative example, weight average molecular weight and molecular weight distributing index are using (the experiment of GPC gel chromatographies
Instrument is the gel permeation chrommatograph of waters companies of the U.S., model E2695) measure.
Expansion multiple refers to the ratio with the preceding loose volume of expansion after weak cross-linked copolymer expands, and it passes through laser particle size point
Analyzer test expands the ratio of front and rear median particle size and obtains.
It is crosslinked the percentage that the amount that minor structure content refers to the crosslinking minor structure that crosslinking agent is provided accounts for total weak cross-linked copolymer
Weight.
Embodiment 1
The present embodiment is used to illustrate weak cross-linked copolymer of the invention and preparation method thereof and sealing agent.
By the Methacrylamide of 0.615mol total amounts (about 74g), 2- acrylamide-2-methyl propane sulfonics and metering system
(mol ratio is 30 to sour cetyl ester：10：1) it is added in the water of 100g, regulation pH is 7；Add the persulfuric acid of 1.75mmol
Crosslinking agent N, the N- methylene-bisacrylamide of potassium and 0.3g, and mixing 40min is stirred at 200rpm, 25 DEG C；Then add
The atoleine (purchased from the PARAFFIN of An Naiji companies) of 120g, the sorbitan fatty ester of 8g (are purchased from An Naiji
The SPAN-80 of company) and 5g polyoxyethylene sorbitan fatty acid ester (purchased from An Naiji companies TWEEN60), and will
Gained mixture emulsifies 1min on emulsification instrument；Nitrogen 15min is subsequently passed with deoxygenation；Then it is added dropwise to the sulfurous of 0.7mmol
Sour hydrogen sodium (aqueous solution form with concentration as 0.07mol/L) (about 10min drops finish), and in reacting 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 is 3, is detected through infrared, proton nmr spectra and carbon analysis of spectrum, the knot shown in formula (1)
Structure unit (R1It is methyl, R1'Be H), the construction unit (R shown in formula (2)2And R2'It is H, R3It is the alkylidene of C0, R4Selected from-CO-
NH-C(CH3)2-CH2-SO3M construction unit (the R) and shown in formula (3)6It is methyl, R6'It is H, R7Selected from positive decyl) mol ratio
It is 29.4：9.2：1, crosslinking minor structure content is 0.4 weight %, and expansion multiple is 40.
Embodiment 2
The present embodiment is used to illustrate weak cross-linked copolymer of the invention and preparation method thereof and sealing agent.
By the acrylamide of 0.572mol total amounts (about 76.5g), 2- acrylamide-2-methyl propane sulfonics and methacrylic acid
(mol ratio is 15 to stearyl：10：1) it is added in the water of 100g, regulation pH is 7；Add 1.9mmol ammonium persulfate and
Crosslinking agent N, the N- ethylenebisacrylamide of 0.34g, and mixing 50min is stirred at 220rpm, 25 DEG C；Then add 120g
Atoleine (purchased from the PARAFFIN of An Naiji companies), the sorbitan fatty ester of 7g (be purchased from An Naiji companies
SPAN-60) and 7g polyoxyethylene sorbitan fatty acid ester (purchased from the TWEEN80 of An Naiji companies), and by gained
Mixture emulsifies 2min on emulsification instrument；Nitrogen 15min is subsequently passed with deoxygenation；Then it is added dropwise to the thiosulfuric acid of 0.95mmol
Sodium (aqueous solution form with concentration as 0.095mol/L) (about 12min drops finish), and in reacting 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 is 2, is detected through infrared, proton nmr spectra and carbon analysis of spectrum, the structure shown in formula (1)
Unit (R1And R1'Be H), the construction unit (R shown in formula (2)2And R2'It is H, R3It is the alkylidene of C0, R4Selected from-CO-NH-C
(CH3)2-CH2-SO3M construction unit (the R) and shown in formula (3)6It is methyl, R6'It is H, R7Selected from dodecyl) mol ratio
It is 14.2：9.1：1, crosslinking minor structure content is 0.44 weight %, and expansion multiple is 35.
Embodiment 3
The present embodiment is used to illustrate weak cross-linked copolymer of the invention and preparation method thereof and sealing agent.
By the acrylamide of 0.8mol total amounts (about 64.4g), acrylic acid and lauryl methacrylate, (mol ratio is
13：6：1) it is added in the water of 100g, regulation pH is 7；Add the potassium peroxydisulfate of 1.5mmol and crosslinking agent N, the N- Asia of 0.23g
Bisacrylamide, and mixing 60min is stirred at 210rpm, 20 DEG C；Then add the atoleine of 120g (resistance to purchased from peace
The PARAFFIN of Ji companies), the polyoxy of the sorbitan fatty ester of 7g (purchased from the SPAN-80 of An Naiji companies) and 5g
Ethene sorbitan fatty acid ester (purchased from the TWEEN60 of An Naiji companies), and gained mixture is emulsified on emulsification instrument
1min；Nitrogen 20min is subsequently passed with deoxygenation；Then the sodium hydrogensulfite of 0.9mmol is added dropwise to (with concentration as 0.09mol/L
Aqueous solution form) (about 10min drops finish), and in reacting 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
It is 4, is detected through infrared, proton nmr spectra and carbon analysis of spectrum, the construction unit (R shown in formula (1)1And R1'Be H), formula (2) institute
Construction unit (the R for showing2And R2'It is H, R3It is the alkylidene of C0, R4Selected from-COOH) and formula (3) shown in construction unit (R6It is first
Base, R6'It is 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
Method according to embodiment 1, unlike, the consumption of potassium peroxydisulfate is 2.4mmol, the use of sodium hydrogensulfite
It is 0.96mmol to measure, so that 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 is 2.8, through infrared, nuclear magnetic resonance
Hydrogen is composed and the detection of carbon analysis of spectrum, the construction unit (R shown in formula (1)1It is methyl, R1'Be H), the construction unit (R shown in formula (2)2
And R2'It is H, R3It is the alkylidene of C0, R4Selected from-CO-NH-C (CH3)2-CH2-SO3M construction unit (the R) and shown in formula (3)6For
Methyl, R6'It is 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
Method according to embodiment 1, unlike, the consumption of potassium peroxydisulfate is 1mmol, the consumption of sodium hydrogensulfite
It is 0.34mmol, so that final gained emulsion is sealing agent A5, wherein the content of weak cross-linked copolymer is 23.3 weight %, should
The weight average molecular weight of weak cross-linked copolymer is 6.5 × 106G/mol, molecular weight distribution index is 3.1, through infrared, hydrogen nuclear magnetic resonance
Spectrum and the detection of carbon analysis of spectrum, the construction unit (R shown in formula (1)1It is methyl, R1'Be H), the construction unit (R shown in formula (2)2With
R2'It is H, R3It is the alkylidene of C0, R4Selected from-CO-NH-C (CH3)2-CH2-SO3M construction unit (the R) and shown in formula (3)6It is first
Base, R6'It is 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
Method according to embodiment 1, unlike, n-BMA replaces methacrylic acid octadecyl
Ester, so that 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 is 3.2, through infrared, proton nmr spectra and carbon
Analysis of spectrum detection, the construction unit (R shown in formula (1)1It is methyl, R1'Be H), the construction unit (R shown in formula (2)2And R2'It is H,
R3It is the alkylidene of C0, R4Selected from-CO-NH-C (CH3)2-CH2-SO3M) and octadecyl methacrylate provide structure list
The mol ratio of unit is 29.1：9：1, crosslinking minor structure content is 0.4 weight %, and expansion multiple is 39.
Comparative example 2
Method according to embodiment 1, unlike, 2- acrylamide-2-methyl propane sulfonics are not used, but are used
Mol ratio is 30：1 Methacrylamide and methacrylic acid cetyl ester is used as monomer, so that 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 is 2.7, is detected through infrared, proton nmr spectra and carbon analysis of spectrum, the knot shown in formula (1)
Structure unit (R1It is methyl, R1'Be H) and the mol ratio of construction unit that provides of octadecyl methacrylate be 28.6：1, hand over
Connection minor structure content is 0.4 weight %, and expansion multiple is 44.
Comparative example 3
Method according to embodiment 1, unlike, the consumption of crosslinking agent N, N- methylene-bisacrylamide is
0.05g, so that 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 is 2.86, through infrared, proton nmr spectra
With the detection of carbon analysis of spectrum, the construction unit (R shown in formula (1)1It is methyl, R1'Be H), the construction unit (R shown in formula (2)2And R2'
It is H, R3It is the alkylidene of C0, R4Selected from-CO-NH-C (CH3)2-CH2-SO3M construction unit (the R) and shown in formula (3)6It is first
Base, R6'It is 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
Method according to embodiment 1, unlike, the consumption of crosslinking agent N, N- methylene-bisacrylamide is 1g,
So as to 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 is 3.2, is composed through infrared, proton nmr spectra and carbon
Analysis detection, the construction unit (R shown in formula (1)1It is methyl, R1'Be H), the construction unit (R shown in formula (2)2And R2'It is H, R3
It is the alkylidene of C0, R4Selected from-CO-NH-C (CH3)2-CH2-SO3M construction unit (the R) and shown in formula (3)6It is methyl, R6'For
H, R7Selected from positive decyl) mol ratio be 29.3：9：1, crosslinking minor structure content is 1.4 weight %, and expansion multiple is 53.
Drilling fluid embodiment 1
The present embodiment is used to illustrate water-base drilling fluid of the invention.
Drilling fluid composition：The water of 100 weight portions, (weight portion is with the copolymer in sealing agent for the sealing agent A1 of 1 weight portion
Dry weight meter), the sodium bentonite (China ties up bentonite Technical Research Center purchased from Weifang) of 2.5 weight portions, 0.15 weight portion
Na2CO3, the salt resistant filter loss reduction agent (purchased from the Henan marine chemical industry Co., Ltd PAC trade mark) of 1 weight portion, the temperature resistance drop of 3 weight portions
Fluid loss agents (are purchased from Shijiazhuang Hualai Dingsheng Technology Co., Ltd. KJAN trades mark), and the anti-sloughing agent of 3 weight portions (is purchased from Henan ocean
The work Co., Ltd DWFT-I trades mark), the anti-sloughing agent emulsified asphalt powder of 1.5 weight portions (is purchased from Renqiu City Ren Yuan chemical plant YK-H boards
Number), the sulfonated gilsonite powder of 2 weight portions (purchased from the Henan marine chemical industry Co., Ltd FT-1 trade mark), the KCl of 5 weight portions, 10 weight
The heavy weight additive (being purchased from Shijiazhuang Hualai Dingsheng Technology Co., Ltd. Weigh2 trades mark) of part, the barite of 45 weight portions (is purchased from stone
The prosperous Science and Technology Ltd. of Lay of village China of family)；So as to obtain drilling fluid Y1.
Drilling fluid embodiment 2-5
The present embodiment is used to illustrate water-base drilling fluid of the invention.
According to drilling fluid embodiment 1, unlike, sealing agent A2-A5 is respectively adopted instead of above-mentioned A1, so as to respectively obtain
Drilling fluid Y2-Y5.
Drilling fluid comparative example 1-4
According to drilling fluid embodiment 1, unlike, sealing agent DA1-DA4 is respectively adopted instead of above-mentioned A1, so that respectively
To drilling fluid DY1-DY4.
Drilling fluid comparative example 5
The present embodiment is used to illustrate water-base drilling fluid of the invention.
According to drilling fluid embodiment 1, unlike, sealing agent A1 is not used, so as to obtain drilling fluid DY5.
Test case 1
The rheological characteristic and filtration property to 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 aging near room temperatures of 6h at 120 DEG C
(G10 "/10 ') and middle press filtration vector (API)
Apparent viscosity (AV) is using the fast viscosimeter of normal form six side according to specified in standard GB/T/T29170-2012
What method was measured, unit is mPas,
Plastic viscosity (PV) is using the fast viscosimeter of normal form six side according to specified in standard GB/T/T29170-2012
What method was measured, unit is mPas, PV=θ600-θ300。
Yield value (YP) is using the fast viscosimeter method according to specified in standard GB/T/T29170-2012 of normal form six
Measure, YP=0.511 × (2 × φ 300- φ 600), unit is Pa.
First egress (G10 "/10 ') it is to be specified according in standard GB/T/T29170-2012 according to the fast viscosimeter of normal form six
Method measure, unit is Pa/Pa.
API refers to middle press filtration vector, 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 is mL.
Table 1
After the data of table 1 can be seen that and add sealing agent in drilling fluid system, the change of the rheological characteristic of system compared with
It is small, illustrate good with drilling fluid compatibility；Filter loss is substantially reduced, and illustrates that sealing agent has good sealing characteristics.
Test case 2
The sealing characteristics to 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, misses instrument and determines plugging effect using HTHP casting bed respectively, and measurement result is shown in Table 2.
HTHP casting bed misses instrument assay method：(specific mesh number is shown in Table 2 institutes to take the quartz sand 200g of corresponding mesh number
Show) leakage instrument lower floor is filled in, drilling fluid to graduation mark is loaded thereto；Booster is loaded into connection valve rod upper end, by back pressure
Device loads lower connection valve rod lower end, and two ends will insert positioning finger setting, connect source of the gas；Adjustment increases, back pressure device handle indicates it
0.7MPa pressure values；Open overhead-valve and keep 0.7MPa pressure, temperature is up to 120 DEG C, then rapidly adjusts to 4.2MPa booster, beats
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, but, the present invention is not limited in above-mentioned implementation method
Detail, in range of the technology design of the invention, various 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 specific 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 is no longer separately illustrated.
Additionally, can also be combined between a variety of implementation methods of the invention, 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 (18)
1. a kind of weak cross-linked copolymer, it is characterised in that the weak cross-linked copolymer contains construction unit, the formula (2) shown in formula (1)
Construction unit shown in shown construction unit and formula (3), and the content of crosslinking minor structure is in the weak cross-linked copolymer
0.1-1 weight %, wherein：
Wherein, R1、R1'、R2、R2'、R6And R6'It is each independently selected from the alkyl of H and C1-C6；R3Selected from the alkylidene of C0-C6；R4
Selected from-COOM ,-SO3M or-CO-NH-R5-SO3M, R5Selected from the alkylidene of C0-C6, M is selected from H or alkali metal；R7Selected from H
Or the alkyl of C1-C20.
2. weak cross-linked copolymer according to claim 1, wherein, R1、R1'、R2、R2'、R6And R6'It is each independently selected from H
With the alkyl of C1-C4；R3Selected from the alkylidene of C0-C4；R4Selected from-COOM ,-SO3M or-CO-NH-R5-SO3M, R5Selected from C1-C6
Alkylidene, M be selected from H, Na or K；R7Selected from the alkyl of C2-C16；
Preferably, R1、R1'、R2、R2'、R6And R6'It is each independently selected from H, methyl, ethyl and n-propyl；R3Selected from the alkylene of C0
Base ,-CH2-、-CH2-CH2-、-CH2-CH2-CH2-、-CH(CH3)-CH2-、-CH2-CH(CH3)-or-CH2-(CH2)2-CH2-；R4
Selected 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.
3. weak cross-linked copolymer according to claim 1 and 2, wherein, shown in the construction unit, formula (2) shown in formula (1)
The mol ratio of the construction unit shown in construction unit and formula (3) is 10-50：3-20：1, preferably 12-40：5-15：1；
Preferably, the content that minor structure is crosslinked in the weak cross-linked copolymer is 0.3-0.6 weight %.
4. the weak cross-linked copolymer according to any one in claim 1-3, wherein, the weight of the weak cross-linked copolymer is equal
Molecular weight is 3 × 106-10×106G/mol, preferably 3.5 × 106-7×106G/mol, more preferably 4 × 106-5.5×
106g/mol。
5. the weak cross-linked copolymer according to any one in claim 1-4, wherein, the friendship in the weak cross-linked copolymer
One or more offer in crosslinking agent of the connection minor structure as shown in following formula (4)：
N is selected from the integer of 1-6.
6. a kind of preparation method of weak cross-linked copolymer, it is characterised in that the method includes：In aqueous solvent, aoxidizing-going back
In the presence of former initiation system, crosslinking agent and emulsifying agent, by the (2') shown compound of the (1') shown compound of formula, formula and formula
(3') shown compound carries out emulsion polymerization, wherein, the consumption of the crosslinking agent causes to be handed in the weak cross-linked copolymer of gained
The content for joining minor structure is 0.1-1 weight %,
Wherein, R1、R1'、R2、R2'、R6And R6'It is each independently selected from the alkyl of H and C1-C6；R3Selected from the alkylidene of C0-C6；R4
Selected from-COOM ,-SO3M or-CO-NH-R5-SO3M, R5Selected from the alkylidene of C0-C6, M is selected from H or alkali metal；R7Selected from H
Or the alkyl of C1-C20.
7. method according to claim 6, wherein, R1、R1'、R2、R2'、R6And R6'It is each independently selected from H's and C1-C4
Alkyl；R3Selected from the alkylidene of C0-C4；R4Selected from-COOM ,-SO3M or-CO-NH-R5-SO3M, R5Selected from the alkylidene of C1-C6,
M is selected from H, Na or K；R7Selected from the alkyl of C2-C16；
Preferably, R1、R1'、R2、R2'、R6And R6'It is each independently selected from H, methyl, ethyl and n-propyl；R3Selected from the alkylene of C0
Base ,-CH2-、-CH2-CH2-、-CH2-CH2-CH2-、-CH(CH3)-CH2-、-CH2-CH(CH3)-or-CH2-(CH2)2-CH2-；R4
Selected 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.
8. the method according to claim 6 or 7, wherein, the (2') shown compound of the (1') shown compound of formula, formula and
The mole dosage ratio of the (3') shown compound of formula is 10-50：3-20：1, preferably 12-40：5-15：1；
Preferably, the consumption of the crosslinking agent cause gained weak cross-linked copolymer in be crosslinked minor structure content be 0.3-0.6
Weight %；
Preferably, the aqueous solvent relative to 100g, the (2') shown compound of the (1') shown compound of formula, formula and formula
(3') mole total amount of shown compound is 0.1-5mol, more preferably preferably 0.2-2mol, 0.5-1mol.
9. the method according to claim 6 or 7, wherein, the crosslinking agent is selected from the crosslinking agent shown in following formula (4)
Plant or various：
N is selected from the integer of 1-6.
10. the method according to claim 6 or 7, wherein, the oxidant in the oxidation-reduction trigger system was selected from
One or more in sodium sulphate, potassium peroxydisulfate, ammonium persulfate and hydrogen peroxide, going back in the oxidation-reduction trigger system
Former agent be selected from ferrous sulfate, frerrous chloride, sodium sulfite, sodium hydrogensulfite, potassium sulfite and sodium thiosulfate in one kind or
It is various；It is highly preferred that the mol ratio 1 of the Oxidizing and Reducing Agents：0.2-1, preferably 1：0.3-0.8；
Preferably, the (2') shown compound of the (1') shown compound of the formula relative to 1mol, formula and the (3') shown change of formula
Mole total amount of compound, the consumption of the oxidation-reduction trigger system is 1-10mmol, more preferably preferably 2-5mmol, 2-
3mmol。
11. method according to any one in claim 6-10, wherein, the emulsifying agent is sorbitan fatty
One kind or many in acid esters, APES, polyoxyethylene sorbitan fatty acid ester and polyglyceryl fatty acid ester
Kind；
Preferably, the aqueous solvent and the weight ratio of the consumption of the emulsifying agent are 100：10-20, preferably 100：12-14；
Preferably, the method is carried out in the presence of being included in oils reagent, and the oils reagent is liquefied petrolatum；The emulsifying agent and
The weight ratio of the consumption of oils reagent is 100：500-2000.
12. method according to any one in claim 6-11, wherein, the condition of the emulsion polymerization includes：Temperature
It it is 30-60 DEG C, the time is 5-10h.
13. method according to any one in claim 6-12, wherein, the method includes：In the case where pH is 6-8, first will
The (3') shown compound of the (1') shown compound of formula, formula (2') shown compound, formula, the aqueous solvent, the oxygen
Oxidant and the crosslinking agent in change-reduction initiating system are mixed, and then introduce the emulsifying agent and oils reagent simultaneously
Emulsified, then under an inert atmosphere, the reducing agent being introduced into the oxidation-reduction trigger system simultaneously carries out the emulsion and gathers
Close.
Weak cross-linked copolymer obtained in 14. method as described in any one in claim 6-13.
Weak cross-linked copolymer in 15. claim 1-5 and 14 described in any one is in drilling fluid as the application of sealing agent.
A kind of 16. weak cross-linked copolymers containing described in any one in claim 1-5 and 14 as sealing agent water base brill
Well liquid.
17. water-base drilling fluids according to claim 16, wherein, relative to the water in the water-base drilling fluid of 100 weight portions,
The content of the weak cross-linked copolymer is 1-3 weight portions.
The application of water-base drilling fluid described in 18. claims 16 or 17 in oil/gas drilling.
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