CN106220797B - Diblock copolymer suitable for oil base drilling fluid viscosity reduction and its preparation method and application and oil base drilling fluid and application - Google Patents

Diblock copolymer suitable for oil base drilling fluid viscosity reduction and its preparation method and application and oil base drilling fluid and application Download PDF

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CN106220797B
CN106220797B CN201610726812.3A CN201610726812A CN106220797B CN 106220797 B CN106220797 B CN 106220797B CN 201610726812 A CN201610726812 A CN 201610726812A CN 106220797 B CN106220797 B CN 106220797B
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diblock copolymer
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CN106220797A (en
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蒋官澄
彭双磊
贺垠博
邓正强
李新亮
史亚伟
王凯
王春蕾
马光长
赵利
屈刚
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China University of Petroleum Beijing
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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
    • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
    • C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
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    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/02—Well-drilling compositions
    • C09K8/03—Specific additives for general use in well-drilling compositions
    • C09K8/035—Organic additives

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Abstract

The present invention relates to the drilling applications of petroleum industry, in particular it relates to a kind of diblock copolymer suitable for oil base drilling fluid viscosity reduction and its preparation method and application and oil base drilling fluid and application.The diblock copolymer is mainly made up of block A and B block, wherein, block A is constituted by selected from the construction unit shown in formula (1), and B block is constituted by selected from the construction unit shown in formula (2), and the number-average molecular weight of the block A is 1,500 10000.Diblock copolymer of the invention can be used in oil base drilling fluid as thinner, be especially applicable to it is highdensity without in native phase oil base drilling fluid as thinner, it is in HTHP stratum, in the case where appropriate shear force is ensured, the apparent viscosity and plastic viscosity of oil base drilling fluid can be largely reduced, in order to accelerating rate of penetration, reducing drilling well difficulty.

Description

Diblock copolymer suitable for oil base drilling fluid viscosity reduction and its preparation method and application And oil base drilling fluid and application
Technical field
The present invention relates to the drilling applications of petroleum industry, in particular it relates to a kind of suitable for the double of oil base drilling fluid viscosity reduction Block copolymer and its preparation method and application and oil base drilling fluid and application.
Background technology
With the expansion and the development of depth of exploration of Exploration Domain, bore HTHP stratum and have become oil gas drilling operation Normality.HTHP means that excessive risk, high cost, while the requirement of the performance to drill-well operation, equipment and drilling fluid Also it is higher.
When HTHP stratum is drilled, there is requirement very high to the high temperature resistant property and density of drilling fluid used.For Ensure the high temperature resistant property of drilling fluid, can typically select the good oil base drilling fluid of high-temperature resistance as the drilling well of hp-ht well Working solution.Even if being the oil base drilling fluid of function admirable, with the increase of density, system solid phase is also inevitably led to Content increase, then one side solid-solid, solid-liquid friction increase cause drilling fluid system plastic viscosity increase, on the other hand in order to Suspension high solid loading will not be settled, and the shear force of drilling fluid system will certainly be strengthened by adding extracting and cutting agent etc., and often at present The apparent viscosity and plastic viscosity of system can also be increased while shear force is increased with drilling fluid extracting and cutting agent.And it is excessive apparent viscous Degree and plastic viscosity can cause：(1) rate of penetration reduction, extension drilling period；(2) cyclic pressure dissipation increases, drilling pump load increases Plus；(3) circulation equal yield density increases, and easily induces the down hole problems such as leakage, differential sticking, ultimately increases drillng operation Cost and difficulty.
Therefore, thinner would generally be added for high density drilling fluid, in the case where appropriate shear force is ensured, is significantly dropped The apparent viscosity and plastic viscosity of low system, accelerate rate of penetration, reduce drilling well difficulty, save drilling cost, prevent underground thing Therefore, it is ensured that drillng operation is carried out safe efficiently.
Current water-base drilling fluid thinner species is various and is widely used, and oil base drilling fluid is due to long recognized The features such as good rheological property, viscosity are low and easy to control, rarely has the research for oil base drilling fluid thinner and product always.But As hp-ht well is to the heat-resisting property and density requirements more and more higher of drilling fluid, even oil base drilling fluid is without native phase oil base Drilling fluid, in density 2g/cm3Its apparent viscosity and plastic viscosity also can greatly exceed zone of reasonableness during the above, it is difficult to control, And generally Applicable temperature is also no more than 150 DEG C.
The content of the invention
It is difficult to be applied to high density oil base drilling fluid it is an object of the invention to be directed to existing oil base drilling fluid thinner Viscosity reduction and the undesirable defect of heat-resisting property, there is provided one kind can be applied to high density oil base drilling fluid viscosity reduction and with good Diblock copolymer suitable for oil base drilling fluid viscosity reduction of heat-resisting property and its preparation method and application and oil base drilling fluid And application.
To achieve these goals, the present invention provides a kind of diblock copolymer, and the copolymer is main by block A and block B is constituted, wherein, block A is constituted by selected from the construction unit shown in formula (1), construction unit of the B block as shown in selected from formula (2) Constitute, the number-average molecular weight of the block A is 1500-10000,
Formula (1)Formula (2)
Wherein, R1、R1'、R4、R4'And R6It is each independently selected from the alkyl of H and C1-C6；R2And R2'It is each independently selected from The alkyl of H, C1-C6 ,-O-C (O)-R3With-COOR3, and R2And R2'In at least one be selected from-O-C (O)-R3Or-COOR3, R3 Selected from the alkyl of C1-C6；R5Selected from the alkylidene of C1-C8；X is selected from-NH- or-O-.
Present invention also offers a kind of preparation method of diblock copolymer, the method includes：
(1) in the presence of chain-transferring agent and the first azo initiator, in the first organic solvent, prepare formula is (1') shown Compound carry out polymerisation, obtain number-average molecular weight be 1500-10000 polymer A；
(2) in the presence of the second azo initiator, in a second organic solvent, by polymer A and the (2') shown change of formula Compound carries out copolymerization；
Formula is (1')Formula is (2')
Wherein, R1、R1'、R4、R4'And R6It is each independently selected from the alkyl of H and C1-C6；R2And R2'It is each independently selected from The alkyl of H, C1-C6 ,-O-C (O)-R3With-COOR3, and R2And R2'In at least one be selected from-O-C (O)-R3Or-COOR3, R3 Selected from the alkyl of C1-C6；R5Selected from the alkylidene of C1-C8；X is selected from-NH- or-O-；X' is selected from halogen.
Diblock copolymer is obtained present invention also offers by the above method.
Present invention also offers above-mentioned diblock copolymer in drilling fluid as the application of thinner.
Present invention also offers it is a kind of containing above-mentioned diblock copolymer as thinner oil base drilling fluid.
Present invention also offers application of the above-mentioned oil base drilling fluid in oil/gas drilling.
The diblock copolymer that the present invention is provided can be used in oil base drilling fluid as thinner, be especially applicable to highly dense Degree without in native phase oil base drilling fluid as thinner, its can in HTHP stratum, in the case where appropriate shear force is ensured, compared with Big degree ground reduces the apparent viscosity and plastic viscosity of oil base drilling fluid, in order to accelerating rate of penetration, reducing drilling well difficulty, section About drilling cost, prevents down-hole accident, it is ensured that drillng operation is carried out safe efficiently.Particularly, of the invention pair of block copolymerization More than 200 DEG C of high temperature can be resisted when thing is as thinner, it is 2g/cm that can be applied to density3High density oil base above is bored Well liquid.
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 diblock copolymer, and the copolymer is mainly made up of block A and B block, wherein, block A Constituted by selected from the construction unit shown in formula (1), B block is constituted by selected from the construction unit shown in formula (2), the block A's Number-average molecular weight is 1500-10000,
Formula (1)Formula (2)
Wherein, R1、R1'、R4、R4'And R6It is each independently selected from the alkyl of H and C1-C6；R2And R2'It is each independently selected from The alkyl of H, C1-C6 ,-O-C (O)-R3With-COOR3, and R2And R2'In at least one be selected from-O-C (O)-R3Or-COOR3, R3 Selected from the alkyl of C1-C6；R5Selected from the alkylidene of C1-C8；X is selected from-NH- or-O-.
According to the present invention, the diblock copolymer is mainly made up of block A and B block, i.e., described diblock copolymer In double blocks refer to just block A and B block here, it is believed that be the double blocks being made up of block A and B block linearly altogether Polymers, it is also possible to be expressed as A-B, but be not particularly limited to the end moieties of block A and B block, can be for not The diblock copolymer is influenceed as the various groups of the performance of thinner, usually H.This pair of block that the present invention is provided is total to In polymers, block A is the nonpolar long chain polymeric section that can unfold in oil, and B block is poly- containing positively charged ammonium long-chain Close section.When during diblock copolymer of the invention is applied into oil base drilling fluid as thinner, should be containing positively charged Ammonium long chain polymeric section can be preferentially adsorbed on the particle surfaces such as barite by electrostatic interaction, break barite that overlap is reunited etc. Particle, repulsion is larger between powered particle, it is easier to dispersed, reduces system viscosity；Oil-soluble Long-chain block A exists simultaneously Stretched in oil phase, increase solubility of the polymer in oil, between increasing steric hindrance and reducing particle, particle contact between liquid phase； And the drilling fluid containing diblock copolymer of the invention flowing when due to the protection of diblock copolymer of the invention, It is Elastic Contact between grain, reduces internal friction, reduces plastic viscosity.In the case where appropriate shear force is ensured, largely Reduce oil base drilling fluid apparent viscosity and plastic viscosity, in order to accelerate rate of penetration, reduce drilling well difficulty, save drilling well into This, prevents down-hole accident, it is ensured that drillng operation is carried out safe efficiently.
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 of above-mentioned C1-C8 for example can be upper State alkylidene and heptamethylene, octamethylene that the alkyl of C1-C6 is formed.
In order to preferably play effect of the diblock copolymer as thinner, under preferable case, R1、R1'、 R4、R4'And R6It is each independently selected from the alkyl of H and C1-C4；R2And R2'It is each independently selected from the alkyl ,-O-C of H, C1-C4 (O)-R3With-COOR3, and R2And R2'In at least one be selected from-O-C (O)-R3Or-COOR3, R3Selected from the alkyl of C1-C4；R5 Selected from the alkylidene of C1-C6.
It is highly preferred that R1、R1'、R4、R4'And R6It is each independently selected from H, methyl, ethyl, n-propyl, isopropyl and positive fourth Base；R2And R2'It is each independently selected from H, methyl, ethyl, n-propyl, isopropyl, normal-butyl ,-O-C (O)-CH3、-O-C(O)- CH2CH3、-O-C(O)-CH2CH2CH3、-O-C(O)-CH(CH3)CH3、-COOCH3、-COOCH2CH3、-COOCH2CH2CH3With- COOCH(CH3)CH3, and R2And R2'In at least one be selected from-O-C (O)-CH3、-O-C(O)-CH2CH3、-O-C(O)- CH2CH2CH3、-O-C(O)-CH(CH3)CH3、-COOCH3、-COOCH2CH3、-COOCH2CH2CH3Or-COOCH (CH3)CH3；R5Choosing From-CH2-、-CH2-CH2-、-CH2-CH2-CH2-、-CH(CH3)-CH2-、-CH2-CH(CH3)-、-CH2-(CH2)2-CH2-、-CH2- CH(CH3)-CH2-、-C(CH3)2-CH2-、-CH2-C(CH3)2-、-CH2-(CH2)3-CH2- or-CH2-(CH2)4-CH2-。
It is of the invention it is a kind of preferred embodiment in, R1'It is H, R1It is methyl.Of the invention another preferred In implementation method, R1And R1'It is H.In another preferred embodiment of the invention, R2'It is H, R2Selected from-O-C (O)- CH3、-O-C(O)-CH2CH3、-O-C(O)-CH2CH2CH3、-O-C(O)-CH(CH3)CH3、-COOCH3、-COOCH2CH3、- COOCH2CH2CH3Or-COOCH (CH3)CH3.In another preferred embodiment of the invention, R2'And R2From independently selecting From-O-C (O)-CH3、-O-C(O)-CH2CH3、-O-C(O)-CH2CH2CH3、-O-C(O)-CH(CH3)CH3、-COOCH3、- COOCH2CH3、-COOCH2CH2CH3With-COOCH (CH3)CH3。
In terms of the invention, it is understood that the construction unit shown in formula (2) should contain anionicsite, this To the anionicsite, there is no particular limitation for invention, as long as not interfering with the property of drilling fluid, for example the anion can Think F-、Cl-、Br-、I-Deng.
According to the present invention, in order to obtain viscosity-reducing performance preferably double block copolymerizations in the case where the appropriate shear force of drilling fluid is ensured Thing, under preferable case, the number-average molecular weight of the block A is 1500-9000, more preferably preferably 2000-8000,2500- 6000, still more preferably it is 3500-5500.The molecular weight distribution index of the block A for example can be 1-1.5, preferably 1-1.3。
According to the present invention, although shown in construction unit and formula (2) shown in formula (1) described in the diblock copolymer Construction unit can with content can be changed in relative broad range, it is contemplated that construction unit and formula shown in the formula (1) (2) the block A and B block that the construction unit shown in is formed respectively can preferably cooperate with to a greater degree to drilling fluid Viscosity reduction is carried out, under preferable case, the content mol ratio of the construction unit shown in construction unit and formula (2) shown in the formula (1) It is 1：0.2-5, preferably 1：0.5-2, more preferably 1：0.6-1.6, for example, 1：0.8-1.5.Meeting the condition and above-mentioned Under the conditions of the molecular weight of block A, the number-average molecular weight of diblock copolymer of the invention is preferably 5000-25000, preferably 6000-24000, more preferably 8000-20000, are still more preferably 8500-16000, for example, 10000-15000.
According to the present invention, although without particularly illustrating, it will be understood that in diblock copolymer of the invention, block A is Constituted by selected from one or more in the construction unit shown in formula (1), in construction unit of the B block as shown in selected from formula (2) One or more composition.
Present invention also offers a kind of preparation method of diblock copolymer, the method includes：
(1) in the presence of chain-transferring agent and the first azo initiator, in the first organic solvent, prepare formula is (1') shown Compound carry out polymerisation, obtain number-average molecular weight be 2000-10000 polymer A；(2) in the second azo initiator In the presence of, in a second organic solvent, polymer A and the (2') shown compound of formula are carried out into copolymerization；
Formula is (1')Formula is (2')
Wherein, R1、R1'、R4、R4'And R6It is each independently selected from the alkyl of H and C1-C6；R2And R2'It is each independently selected from The alkyl of H, C1-C6 ,-O-C (O)-R3With-COOR3, and R2And R2'In at least one be selected from-O-C (O)-R3Or-COOR3, R3 Selected from the alkyl of C1-C6；R5Selected from the alkylidene of C1-C8；X is selected from-NH- or-O-；X' is selected from halogen.In the present invention, the halogen Element for example can be F, Cl, Br, I etc..X' is preferably selected from F, Cl or Br.
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 and formula can also be according to the specific knot of copolymer described above Structure unit species is 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, R2'It is H, R2For-COOCH3(also referred to as methyl acrylate)；In formula (1'-2)：R1 And R1'It is H, R2'It is H, R2For-COOCH2CH3(also referred to as ethyl acrylate)；In formula (1'-3)：R1It is methyl, R1'It is H, R2'For H, R2For-COOCH3(also referred to as methyl methacrylate)；In formula (1'-4)：R1It is methyl, R1'It is H, R2'It is H, R2For- COOCH2CH3(also referred to as EMA)；In formula (1'-5)：R1And R1'It is H, R2'And R2For-COOCH3It is (also referred to as suitable Butene dioic acid dimethyl ester)；In formula (1'-6)：R1And R1'It is H, R2'And R2For-COOCH2CH3(also referred to as maleic acid diethyl Ester)；In formula (1'-7)：R1And R1'It is H, R2'It is H, R2It is-O-C (O)-CH3(also referred to as vinyl acetate)；In formula (1'-8)：R1 And R1'It is H, R2'It is H, R2It is-O-C (O)-CH2CH3(also referred to as propionate).
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)：R4And R4'It is H, X is selected from-O-, R5Selected from-CH2-CH2-, R6Selected from methyl, X' is selected from Cl (also referred to as Make (2- acrylyl oxy-ethyls) trimethyl ammonium chloride)；In formula (2'-2)：R4It is methyl, R4'It is H, X is selected from-O-, R5Selected from-CH2- CH2-, R6Selected from methyl, X' is selected from Cl (also referred to as (2- methylacryoyloxyethyls) trimethyl ammonium chloride)；In formula (2'-3)：R4 And R4'It is H, X is selected from-O-, R5Selected from-CH2-CH2-CH2-, R6Selected from methyl, X' is selected from Cl (also referred to as (3- acryloyl-oxies third Base) trimethyl ammonium chloride)；In formula (2'-4)：R4It is methyl, R4'It is H, X is selected from-O-, R5Selected from-CH2-CH2-CH2-, R6It is selected from Methyl, X' is selected from Cl (also referred to as (3- methacryloxypropyls) trimethyl ammonium chloride)；In formula (2'-5)：R4And R4'It is H, X Selected from-O-, R5Selected from-CH2-(CH2)2-CH2-, R6Selected from methyl, X' is selected from Cl (also referred to as (4- acryloyl-oxies butyl) trimethyls Ammonium chloride)；In formula (2'-6)：R4It is methyl, R4'It is H, X is selected from-O-, R5Selected from-CH2-(CH2)2-CH2-, R6Selected from methyl, X' Selected from Cl (also referred to as (4- methacryls oxygen-butyl) trimethyl ammonium chloride)；In formula (2'-7)：R4And R4'It is H, X is selected from- NH-, R5Selected from-CH2-CH2-, R6Selected from methyl, X' is selected from Cl (also referred to as (2- acrylamides ethyl) trimethyl ammonium chloride)；Formula In (2'-8)：R4It is methyl, R4'It is H, X is selected from-NH-, R5Selected from-CH2-CH2-, R6Selected from methyl, X' is selected from Cl (also referred to as (2- Methacrylamides ethyl) trimethyl ammonium chloride)；In formula (2'-9)：R4And R4'It is H, X is selected from-NH-, R5Selected from-CH2- CH2-CH2-, R6Selected from methyl, X' is selected from Cl (also referred to as (3- acrylamide propyls) trimethyl ammonium chloride)；In formula (2'-10)： R4It is methyl, R4'It is H, X is selected from-NH-, R5Selected from-CH2-CH2-CH2-, R6Selected from methyl, X' is selected from Cl (also referred to as (3- methyl Acrylamide propyl) trimethyl ammonium chloride)；In formula (2'-11)：R4And R4'It is H, X is selected from-NH-, R5Selected from-CH2-(CH2)2- CH2-, R6Selected from methyl, X' is selected from Cl (also referred to as (4- acrylamides butyl) trimethyl ammonium chloride)；In formula (2'-12)：R4For Methyl, R4'It is H, X is selected from-NH-, R5Selected from-CH2-(CH2)2-CH2-, R6Selected from methyl, X' is selected from Cl (also referred to as (4- methyl-props Acrylamide butyl) trimethyl ammonium chloride).
According to the present invention, in order to obtain viscosity-reducing performance preferably double block copolymerizations in the case where the appropriate shear force of drilling fluid is ensured Thing, under preferable case, the number-average molecular weight of the polymer A obtained by step (1) is 1500-9000, preferably 2000-8000, More preferably 2500-6000, is still more preferably 3500-5500.The consumption of above-mentioned monomer can be according to required copolymer Construction unit accounting and molecular weight selected, under preferable case, in step (2), form the formula of polymer A (1') institute The compound for showing is 1 with the mol ratio of the consumption of the (2') shown compound of formula：0.2-5, preferably 1：0.5-2, more preferably 1：0.6-1.6, for example, 1：0.8-1.5.The compound that the formula of formation polymer A here is (1') shown should be understood that Participating in the compound (2') shown with formula of step (2) carries out the partial polymer A of copolymerization, gathers the part is prepared The consumption of the (1') shown compound of formula needed for compound A.
In order to be suitable to the carrying out of the polymerisation, and the reasonably molecular weight of copolymer obtained by control, preferable case Under, step (1), the (1') shown compound of formula relative to 1mol, the consumption of first organic solvent is 200-600mL, Preferably 200-400mL.First organic solvent can be the conventional various polymer A that can be formed in this area without shadow Ring any organic solvent for being smoothed out of reaction, preferably benzene, toluene, ethylbenzene, dimethylbenzene, Isosorbide-5-Nitrae-dioxane, ethanol and different One or more in propyl alcohol.
According to the present invention, various chain-transferring agents that the chain-transferring agent can routinely be used using this area, it is contemplated that To that can obtain more particularly suitable molecular weight, under preferable case, the chain-transferring agent is 2- (dodecyl trithiocarbonates Base) -2 Methylpropionic acid, 3- benzyl trithio carbonate groups propionic acid, dithiobenzoic acid (4- cyanopentanoic acids) ester and double thio phenyl first One or more in sour isopropyl phenyl ester.The consumption of the chain-transferring agent can change in relative broad range, it is preferable that relative to The (1') shown compound of the formula of 1mol, the consumption of the chain-transferring agent is 15-55mmol, preferably 20-50mmol, more enters one Step is preferably 24-35mmol, for example, 25-30mmol.It should be appreciated that the part chain-transferring agent will be protected with polymer A Stay, it is possible to participate in the copolymerization of step (2), it is believed that polymer A the step of the method described in (1) is one The polymer of the (1') shown compound of the formula of kind and the mixture of chain-transferring agent etc., this is also that this area is recognized the routine of polymer Know, be not particularly limited.
According to the present invention, first azo initiator can be the conventional various azo initiators in this area, it is preferable that First azo initiator is 4,4'- azos (4- cyanopentanoic acids), azo-bis-isobutyrate hydrochloride, azodiisobutyronitrile, idol One or more in the different heptonitrile of nitrogen two and the isobutyl imidazoline hydrochloride of azo two, such azo initiator can be with above-mentioned chain Transfer agent forms the required reaction system of RAFT polymerizations so that polymerisation of the invention and copolymerization can be controllably Polymerization obtains the diblock copolymer.The consumption of first azo initiator can change in relative broad range, it is preferable that The (1') shown compound of formula relative to 1mol, the consumption of first azo initiator is 8-25mmol, preferably 8- 20mmol, more preferably 9.5-17mmol, for example, 10-14mmol.
, according to the invention it is preferred in the case of, step (1), the condition of the polymerisation includes：Temperature is 50-80 DEG C (excellent Elect 55-70 DEG C as), the time is 2-6h (preferably 3-5h).
According to the present invention, in order to keep the activity of initiator etc., the step (1) can also include：So that described poly- Close reaction is carried out in an inert atmosphere, for example can be to being passed through nitrogen, helium, neon, argon gas etc. in system one or more simultaneously Replace atmosphere therein (process can for example carry out 5-300min, mainly deoxygenation).
According to the present invention, in order to the polymer A is extracted, the step (1) can also include：Will be described poly- The reacted product of compound carries out vacuum distillation and removes solvent and unreacted monomer, so as to obtain required polymer A.
According to the initiation that the present invention, step (2) pass through further second azo initiator so that the (2') shown change of formula Compound carries out initiation copolymerization at an active end of polymer A, the diblock copolymer needed for obtaining the present invention.
According to the present invention, in order to be suitable to the carrying out of the copolymerization, and copolymer point reasonably obtained by control Son amount, under preferable case, step (2), the (2') shown compound of formula relative to 1mol, the consumption of second organic solvent It is 400-1200mL, preferably 440-800mL.Second organic solvent can form institute for the various of this area routine State any organic solvent that diblock copolymer is smoothed out without influence reaction, preferably DMF, THF, dichloromethane, chlorine One or more in imitative and carbon tetrachloride.
According to the present invention, second azo initiator can be the conventional various azo initiators in this area, it is preferable that Second azo initiator is 4,4'- azos (4- cyanopentanoic acids), azo-bis-isobutyrate hydrochloride, azodiisobutyronitrile, idol One or more in the different heptonitrile of nitrogen two and the isobutyl imidazoline hydrochloride of azo two, such azo initiator has as described above Characteristic needed for the present invention.The consumption of second azo initiator can change in relative broad range, it is preferable that relative to The (2') shown compound of the formula of 1mol, the consumption of second azo initiator is 3-10mmol, preferably 3-6mmol.
, according to the invention it is preferred in the case of, step (2), the condition of the copolymerization includes：Temperature is 80-140 DEG C (preferably 100-120 DEG C), the time is 12-36h (preferably 18-24h).
According to the present invention, in order to keep the activity of initiator etc., the step (2) can also include：So that described common Polymerisation is carried out in an inert atmosphere, for example can be to being passed through nitrogen, helium, neon, argon gas etc. in system one or more And replace atmosphere therein (process can for example carry out 5-300min, mainly deoxygenation).
According to the present invention, in order to the diblock copolymer is extracted, the method can also include：Will be described The product of copolymer reaction is mixed and is precipitated with methyl alcohol, and filtration washing is precipitated and dried, so as to can obtain of the invention Diblock copolymer.
Present invention also offers the diblock copolymer obtained by the above method.The diblock copolymer may be considered The diblock copolymer introduced of text it should be appreciated that can be with by the diblock copolymer obtained by the above method The other end including the somewhat random copolymerization section in two ends, or block A ends can also somewhat shown in formula (2) Construction unit, but what the formation of such copolymer was brought in itself by polymerization methodses, it is believed that it is that this area can allow Error, it should also be included within the scope of the invention.
Present invention also offers above-mentioned diblock copolymer in drilling fluid as the application of thinner.
Present invention also offers it is a kind of containing above-mentioned diblock copolymer as thinner oil base drilling fluid.
The diblock copolymer that the present invention is provided can be used in oil base drilling fluid as thinner, and the thinner can pass through Oil phase and particulate component in two blocks of itself and oil base drilling fluid are acted on, and are rubbed with reducing in oil base drilling fluid Power is wiped, so as to be effectively reduced the apparent viscosity and plastic viscosity of oil base drilling fluid, even density is in 2g/cm3Height above Density oil base drilling fluid is also applicable；And the thinner has preferable temperature resistance, the even temperature more than 200 DEG C Under, it is also possible to play preferable viscosity reduction effect.There is no particular limitation for content of the present invention to the copolymer, can be using conventional Thinner consumption, naturally it is also possible to suitably adjusted according to different well situations and drilling fluid, it is preferable that relative to Oil phase in the oil base drilling fluid of 100 weight portions, the content of the diblock copolymer is 0.5-3 weight portions.
According to the present invention, the oil phase in the oil base drilling fluid can be the conventional various oil phases in this area, such as diesel oil (for example, (flash-point is 220 DEG C to 3# white oils, and 40 DEG C of kinematic viscosity are 3mm with white oil2/ s, proportion be 0.85), 5# white oil (flash-points It it is 220 DEG C, 40 DEG C of kinematic viscosity are 3.5mm2/ s, proportion be 0.85) in one or more.Also added in the oil base drilling fluid There is a certain amount of CaCl2The aqueous solution (preferably using CaCl2Concentration is the CaCl of 20-40 weight %2The aqueous solution), such as phase For the oil phase in the drilling fluid of 100 weight portions, the CaCl2The aqueous solution consumption be 15-40 weight portions.
According to the present invention, the oil base drilling fluid can also containing oil base drilling fluid in conventional additive, preferred feelings Under condition, the oil base drilling fluid contains in emulsifying agent, extracting and cutting agent, wetting agent, fluid loss additive, alkalinity regulator and heavy weight additive Plant or various.
, according to the invention it is preferred in the case of, the emulsifying agent is one or more in the compound shown in lower formula (I)：
Formula (I)
In formula (I), two R1It is each independently selected from the alkyl of the C14-C30 for optionally being replaced by group Y and optionally by base The unsaturated alkyl of the C14-C30 with carbon-carbon double bond of group's Y substitutions, group Y is each independently selected from the group shown in following formula：
N is the integer of 1-8；
N X' is each independently selected from H and-C (O)-R2, and at least one X' is-C (O)-R2, R2Selected from carboxyl, C1- The alkyl of C6, the cycloalkyl of C3-C8, by carboxyl replace C1-C6 alkyl, by carboxyl replace C3-C8 cycloalkyl, by carboxylic It is the cycloalkyl of the alkyl-substituted C3-C8 of base and C1-C4, the unsaturated alkyl of the C2-C6 with carbon-carbon double bond, double with carbon carbon The unsaturation ring alkyl of the C3-C8 of key, replaced by carboxyl and C2-C6 with carbon-carbon double bond unsaturated alkyl and quilt The unsaturation ring alkyl of alkyl-substituted and with carbon-carbon double bond the C3-C8 of carboxyl and C1-C4.
According to the present invention, the emulsifying agent is one or more in the compound shown in above-mentioned formula (I).Shown in formula (I) Compound there is long-chain saturation for two ends and/or unsaturated alkyl long-chain and the middle comb shaped structure with short alkyl chain Compound.The compound of such comb shaped structure can by increase emulsification interfacial film strength effect, and with the extracting and cutting agent Coordinated to cause that oil base drilling fluid of the invention is obtaining appropriate shear force, suspending power with the thinner obtained by the present invention Under, can be applicable at more preferable temperature, and obtain excellent viscosity reducing effect.
Wherein, under preferable case, in formula (I), two R1It is each independently selected from the C14-C20 for optionally being replaced by group Y Alkyl and optionally by group Y replace with carbon-carbon double bond, (preferably less than 5, for example, can be 1,2 or 3 carbon Carbon double bond) C14-C20 unsaturated alkyl；N is the integer of 1-6；R2Selected from carboxyl, the alkyl of C1-C4, C4-C6 cycloalkanes Base, by carboxyl replace C1-C4 alkyl, by carboxyl replace C4-C6 cycloalkyl, by carboxyl and methyl substituted C4-C6 Cycloalkyl, with carbon-carbon double bond (preferably 1-3 carbon-carbon double bond for example can be 1,2 or 3 carbon-carbon double bond) The unsaturated alkyl of C2-C4, with carbon-carbon double bond (preferably less than 5, such as can be 1,2 or 3 carbon-carbon double bond) C4-C6 unsaturation ring alkyl, replaced by carboxyl and with carbon-carbon double bond, (preferably 1-3 carbon-carbon double bond, for example can be with Be 1,2 or 3 carbon-carbon double bond) C2-C4 unsaturated alkyl and by carboxyl and methyl substituted and double with carbon carbon The unsaturation ring alkyl of the C4-C7 of key (preferably less than 5, such as, can be 1,2 or 3 carbon-carbon double bond).
It is highly preferred that in formula (I), two R1Be each independently selected from the C15-C18 for optionally being replaced by group Y alkyl and The unsaturated alkyl of the C15-C18 with carbon-carbon double bond for optionally being replaced by group Y；N is the integer of 1-4, such as 1,2,3 or 4.
According to the present invention, two R1Selected independently of one another, can be the same or different, wherein, as R1Tool Body example can for example include following group：-(CH2)7- CH=CH- (CH2)7-CH3、-(CH2)8-CH(Y)-(CH2)7-CH3、- (CH2)7-CH(Y)-(CH2)8-CH3、-(CH2)7-CH(Y)-CH(Y)-(CH2)7-CH3、-(CH2)16-CH3、-(CH2)7- CH= CH-CH2- CH=CH- (CH2)4-CH3、-(CH2)7- CH=CH-CH2-CH2-CH(Y)-(CH2)4-CH3、-(CH2)7- CH=CH- CH2-CH(Y)-(CH2)5-CH3、-(CH2)8-CH(Y)-CH2- CH=CH- (CH2)4-CH3、-(CH2)7-CH(Y)-CH2-CH2-CH =CH- (CH2)4-CH3、-(CH2)7- CH=CH-CH2-CH(Y)-CH(Y)-(CH2)4-CH3、-(CH2)7-CH(Y)-CH(Y)- CH2- CH=CH- (CH2)4-CH3、-(CH2)7-CH(Y)-CH(Y)-CH2-CH(Y)-(CH2)5-CH3、-(CH2)8-CH(Y)-CH2- CH(Y)-CH(Y)-(CH2)4-CH3、-(CH2)7-CH(Y)-CH2-CH2-CH(Y)-CH(Y)-(CH2)4-CH3、-(CH2)7-CH (Y)-CH(Y)-CH2-CH2-CH(Y)-(CH2)4-CH3、-(CH2)7-CH(Y)-CH(Y)-CH2-CH(Y)-CH(Y)-(CH2)4- CH3、-(CH2)14-CH3、-(CH2)13-CH3.Wherein, group Y as described above, is selected from The dotted line connected on these groups represents connection R1 On carbon atom connection site.
According to the present invention, wherein, as group R2Instantiation can for example include：Carboxyl, methyl, ethyl, propyl group, Cyclopenta, cyclohexyl ,-CH2- COOH (being considered by a C1 alkyl for carboxyl substitution) ,-(CH2)2- COOH (is considered by one The C2 alkyl of individual carboxyl substitution) ,-CH (CH2-COOH)2(being considered by two C3 alkyl of carboxyl substitution), -CH2- CH=CH2、- CH=CH2-COOH、-CH2- CH=CH2- COOH ,-CH=CH-CH2-COOH、
According to the present invention, mentioned emulsifier can be commercially available product, it is also possible to be obtained by the conventional method in this area, preferably In the case of, the preparation method of the emulsifying agent includes：By the polyamine compounds shown in formula (II) and formula R1'Carboxylic acid shown in-COOH In carry out amidation process one or more, by reacted product and R2Shown in-COOH in carboxylic acid and its acid anhydrides one Kind or various carry out haptoreaction；
Formula (II)Wherein, R2It is described above with n, this is repeated no more.
And R1'The unsaturated alkyl of the alkyl selected from C14-C30 and the C14-C30 with carbon-carbon double bond.
Wherein, as formula R1'The instantiation of the carboxylic acid shown in-COOH can for example include：COOH-(CH2)7- CH= CH-(CH2)7-CH3(also referred to as oleic acid), COOH- (CH2)7- CH=CH-CH2- CH=CH- (CH2)4-CH3(also referred to as sub- oil Acid), COOH- (CH2)16-CH3(also referred to as octadecanoid acid), COOH- (CH2)14-CH3(also referred to as hexadecanoic acid or palmitic acid), COOH-(CH2)13-CH3(also referred to as pentadecanoic acid).
Wherein, as formula R2The instantiation of carboxylic acid and its acid anhydrides shown in-COOH can for example include：HOOC-COOH (oxalic acid), CH3- COOH (acetic acid), CH3-COO-CO-CH3(acetic anhydride), HOOC-CH2- COOH (malonic acid), HOOC-CH2- CH2- COOH (succinic acid), HOOC-CH2-CH(COOH)-CH2- COOH (the third three acid),(succinic anhydride),(1,2- cyclohexane diacids),(1,2- cyclohexane diacids acid anhydride),Maleic Diacid,(maleic anhydride),(methylnadic anhydride),(Na Dike Acid anhydrides).
According to the present invention, the instantiation of the polyamine compounds shown in formula (II) can for example include：(referred to as diethylenetriamine),(referred to as triethylene four Amine),(referred to as TEPA),(referred to as Pentaethylene hexamine).
According to the present invention, polyamine compounds and formula R shown in above-mentioned formula (II)1'The acid amides that carboxylic acid shown in-COOH is carried out Change primary amine and formula R that reaction is primarily referred to as the polyamine compounds shown in formula (II)1'Between the carboxylic acid group of the carboxylic acid shown in-COOH Amidation process, sloughs hydrone and forms amido link, so as to obtain formula (I ') One or more in the also unsubstituted compound of parahelium in the middle part of shown such chain.Under preferable case, formula (II) institute The polyamine compounds for showing and formula R1'The consumption mol ratio of the carboxylic acid shown in-COOH is 1：1.8-3, preferably 1：1.8-2.2.
, according to the invention it is preferred in the case of, the condition of the amidation process includes：Temperature is 220-230 DEG C, and pH value is 7-9, the time is 3-5 hours.In order to cause amidation process more abundant, the method can also include：First by formula (II) Shown polyamine compounds and formula R1'One or more in carboxylic acid shown in-COOH is under the mixing speed of 80-300r/min Amidation process is carried out under the mixing speed of 80-300r/min again after carrying out mixing 10-30min, also, in amidation process During use fraction water device water-dividing.
According to the present invention, by the product after the amidation process and formula R2In carboxylic acid and its acid anhydrides shown in-COOH Carry out haptoreaction one or more, you can obtain emulsifying agent of the invention.Wherein, the product after the amidation process can be with Carry out purification acquisitionShown compound, but can also purify, Directly by the product after amidation process and formula R2Carry out for one or more in carboxylic acid and its acid anhydrides shown in-COOH contacting anti- Should, so as to-C (O)-R in connection on the parahelium between two amido links2Substitution base, so as to form the formula with comb shaped structure (I) compound shown in.Under preferable case, polyamine compounds and R shown in formula (II)2Carboxylic acid and its acid anhydrides shown in-COOH Consumption mol ratio be 1：0.5-20, for example, polyamine compounds and R shown in formula (II)2Carboxylic acid and its acid anhydrides shown in-COOH Consumption mol ratio be 1：1.8-2.2、1：3.6-4.4、1：5.4-6.6、1：7.2-8.8、1：9-11、1：10.8-13.2.
According to the present invention, work as R1'When carboxylic acid shown in-COOH is the unsaturated carboxylic acid with carbon-carbon double bond, and connect described Touch the formula R used in course of reaction2Carboxylic acid and its acid anhydrides shown in-COOH there is also carbon-carbon double bond, then anti-in the contact During answering, it is also possible to generating polynomial R2The carbon-carbon double bond of carboxylic acid and its acid anhydrides shown in-COOH and the product of the amidation process The addition reaction that the carbon-carbon double bond having in thing is carried out, so as to obtain the R shown in formula (I)1The chemical combination replaced by group Y Thing.Although the present invention is to this, and there is no particular limitation, the compound obtained by such case also include with it is of the present invention Emulsifying agent in.
, according to the invention it is preferred in the case of, the catalytic condition includes：Temperature is 75-90 DEG C, and pH value is 7-9, Time is 6-10 hours.In order to cause amidation process more abundant, the method can also include：First by amidation process Products therefrom and formula R2Stirred under one or more 200-500r/min in carboxylic acid and its acid anhydrides shown in-COOH and contacted Reaction, also, fraction water device water-dividing is used during haptoreaction.
According to the present invention, it is necessary to explanation, emulsifying agent of the invention both can be in the compound shown in formula (I) Kind, if being prepared by above-mentioned preparation method, then the emulsifying agent can be just by obtained by above-mentioned preparation method Product carries out the one kind in the compound shown in the formula (I) of the gained after purification ＆ isolation.But, highly efficient operation is, this The emulsifying agent of invention both can be various in the compound shown in formula (I), i.e., if being prepared by above-mentioned preparation method, So described emulsifying agent can, by the product of the direct gained of above-mentioned preparation method, be needed not move through purification and can be used, and change sentence Talk about, it is also possible to think, emulsifying agent of the invention is the above method product obtained in the case where not purified.
It is highly preferred that relative to the oil phase in the oil base drilling fluid of 100 weight portions, the consumption of the emulsifying agent is 1- 5 weight portions.
According to the present invention, the extracting and cutting agent is preferably dimeric dibasic acid-organic amine copolymer, and the copolymer includes coming from dimeric dibasic acid Construction unit, the construction unit from alkylamine and the construction unit from aromatic amine, wherein, the dimeric dibasic acid is oleic acid With linoleic dimer, the alkylamine is one or more in the kiber alkyl amine of C10-C20, and the aromatic amine is aniline It is preferably with extracting and cutting agent described in one or more in aniline replaced by the alkyl single-point of C1-C3 on phenyl ring or that multiple spot replaces Dimeric dibasic acid-organic amine copolymer.Wherein, the dimeric dibasic acid is that, containing 2 dimer (fatty acid) yls of hydroxy-acid group, it is oleic acid (CH3 (CH2)7CH=CH (CH2)7)) and linoleic acid (CH COOH3(CH2)4CH=CHCH2CH=CH (CH2)7COOH dimer).This The dimeric dibasic acid of sample can be obtained by method of the invention conventional, for example document " Zhang Shulin, synthesis and the application of dimeric dibasic acid,《Essence Thin petrochemical industry》, 1995 " described in method, or commercially available product (preferably using purity in more than 98 weight %).It is excellent Selection of land, the alkylamine is dodecyl primary amine, tridecyl primary amine, myristyl primary amine, pentadecyl primary amine, cetyl One or more in primary amine, heptadecyl primary amine and octadecyl primary amine, more preferably dodecyl primary amine and/or octadecane Base primary amine.Preferably, the aromatic amine is aniline, 2-aminotoluene, 3- methylanilines, 4- methylanilines, 2- MEAs, 3- One or more in MEA, 4- MEAs, 2- propyl group aniline, 3- propyl group aniline and 4- propyl group aniline, more preferably One or more in aniline, 2-aminotoluene, 3- methylanilines and 4- methylanilines.
It is of the invention it is a kind of preferred embodiment in, the dimeric dibasic acid be oleic acid and linoleic dimer, it is described Alkylamine is dodecyl primary amine or octadecyl primary amine, and the aromatic amine is aniline or 3- methylanilines.
In accordance with the present invention it is preferred that, the construction unit from dimeric dibasic acid, the construction unit from alkylamine and come Mol ratio from the construction unit of aromatic amine is 1：0.3-1：0.2-1, more preferably 1：0.3-0.8：0.2-0.7, further Preferably 1：0.4-0.7：0.3-0.6.
Under preferable case, the weight average molecular weight of the dimeric dibasic acid-organic amine copolymer is 2200-9000g/mol, definitely viscous It is 20000-150000cp to spend.From obtain more suitable for improve oil base drilling fluid suspending power and heat-resisting property composition on Consider, it is highly preferred that the weight average molecular weight of the dimeric dibasic acid-organic amine copolymer is 4000-9000g/mol, absolute viscosity is 100000-150000cp.It is highly preferred that the weight average molecular weight of the dimeric dibasic acid-organic amine copolymer is 5000-9000g/mol, Absolute viscosity is 100000-150000cp.In the present invention, weight average molecular weight is the weight measured using GPC gel chromatographies Average molecular weight, absolute viscosity is the absolute viscosity measured by Brookfield viscometer.
According to the present invention, can be using the conventional side in this area as the dimeric dibasic acid-organic amine copolymer of extracting and cutting agent Method is obtained, such as the preparation method of described dimeric dibasic acid-organic amine copolymer includes：Dimeric dibasic acid, alkylamine and aromatic amine are carried out Copolymerization, wherein, the dimeric dibasic acid is oleic acid and linoleic dimer, and the alkylamine is the alkyl primary of C10-C20 One or more in amine, the aromatic amine is by the substitution of the alkyl single-point or multiple spot substitution of C1-C3 on aniline and phenyl ring One or more in aniline.In the method, the dimeric dibasic acid, alkylamine and aromatic amine are as described above, herein Repeat no more.
According to the present invention, above-mentioned dimeric dibasic acid, copolymerization mainly carboxylic acid and amine are carried out between alkylamine and aromatic amine Dehydration condensation between base.As long as can although carrying out combined polymerization using dimeric dibasic acid of the invention, alkylamine and aromatic amine To obtain the dimeric dibasic acid-organic amine copolymer with advantageous property as the extracting and cutting agent in oil base drilling fluid, but in order to obtain Obtain absolute viscosity and molecular weight is more suitable for the extracting and cutting agent of full oil base drilling fluid, the dimeric dibasic acid, alkylamine and aromatic amine Mole dosage ratio is 1：0.3-1：0.2-1, more preferably 1：0.3-0.8：0.2-0.7, is still more preferably 1：0.4-0.7： 0.3-0.6。
According to the present invention, the copolymerization can using this area it is conventional by the way of carry out, as long as being obtained in that Can be used as the dimeric dibasic acid of extracting and cutting agent-organic amine copolymer, it is preferable that be total to dimeric dibasic acid, alkylamine and aromatic amine First the dimeric dibasic acid, alkylamine and aromatic amine are mixed before polymerisation, obtains monomer mixture；Exist in the concentrated sulfuric acid again Under, the monomer mixture of gained carries out copolymerization.
According to the present invention, if first mixed the dimeric dibasic acid, alkylamine and aromatic amine, monomer mixture is obtained, can be with So that be more fully contacted reaction in monomer polymerisation behind, due to relatively gluing for above-mentioned monomer mixture, preferably compared with Mixed at temperature high, the condition of the mixing for particularly preferably using includes：Temperature is 100-130 DEG C, and the time is 20- 30min。
According to the present invention, the above-mentioned concentrated sulfuric acid does not have spy as the catalyst of copolymerization of the invention to its consumption Other restriction, as long as copolymerization of the invention can be catalyzed carrying out, it is preferable that relative to the dimeric dibasic acid, alkyl The gross weight of amine and aromatic amine, the consumption of the concentrated sulfuric acid is 0.3-1 weight %.The concentrated sulfuric acid can be that the concentration of sulfuric acid is The sulfuric acid solution (preferably 98 weight %) of more than 95 weight %.
, according to the invention it is preferred in the case of, the condition of the copolymerization includes：Temperature is 150-180 DEG C, and the time is 2-6h.It is highly preferred that the condition of the copolymerization includes：Temperature is 155-175 DEG C, and the time is 2-6h.Further preferably Ground, the condition of the copolymerization includes：Temperature is 160-170 DEG C, and the time is 2-6h.
In order to promote the carrying out of the copolymerization, can be by the water byproduct produced by copolymerization from anti- Removing in system is answered, the mode of the removing water byproduct is the conventional method of this area, be will not be repeated here.
When using dimeric dibasic acid-organic amine copolymer obtained in the above method, such extracting and cutting agent both can be above-mentioned side Method has been obtained dimeric dibasic acid-organic amine copolymer, can be after the above method has been obtained dimeric dibasic acid-organic amine copolymer, directly The concentration of 50-70 weight % is diluted to (i.e. relative to the dimeric dibasic acid after dilution-organic amine copolymer solution using diluent Gross weight, the wherein content of dimeric dibasic acid-organic amine copolymer is 50-70 weight %), or other modes well known in the art The extracting and cutting agent of the invention containing the dimeric dibasic acid-organic amine copolymer is obtained.
It will be apparent to a skilled person that it is general all without separation as the product of copolymerization, but Think that used monomer substantially completely reacts, and be also that directly the product of copolymerization is carried out directly as copolymer Use, therefore for the sake of convenience, the diluent can be in the combined polymerization in the preparation method of above-mentioned dimeric dibasic acid-organic amine copolymer It is added directly into after the completion of reaction in the product of the copolymerization, and without dimeric dibasic acid-organic amine therein is common Polymers carries out purifies and separates.On ordinary meaning, after signified dimeric dibasic acid-organic amine copolymer is also copolymerization in the present invention The product of purifies and separates is not carried out, or is only the product of the copolymerization after removing water byproduct as described above Thing.
The diluent for example can be the diluent that this area routinely uses, such as tall oil and/or ready denier oil acid. It is highly preferred that relative to the oil phase in the oil base drilling fluid of 100 weight portions, the consumption of the extracting and cutting agent is 1-5 weight portions.
Wherein, the wetting agent can improve drilling fluid wettability, prevent the underground such as bit freezing complicated state, for example can be with For modified phospholipid (such as purchased from the modified phospholipid of the Shanghai You Chuan Industrial Co., Ltd.s FHGT-G trades mark) and fatty glyceride with One or more in surfactant mixture (such as the trade mark is FK-1), preferably FHGT-G modified phospholipids.It is highly preferred that phase For the oil phase in the oil base drilling fluid of 100 weight portions, the consumption of the lubricant is 0.5-2 weight portions.
Wherein, the fluid loss additive can improve wellbore liquid leaching loss wave making machine, for example, can be oxidized asphalt, modified humic Acid and polymerization species oil base fluid loss additive (such as sulfonated polystyrene, the HFLO type oil base filtrate reducings purchased from Sichuan Hong Hua companies Agent) in one or more, preferably be modified humic acid and/or polymer oil-base fluid loss additive.Preferably, relative to 100 weights The oil phase in the oil base drilling fluid of part is measured, the consumption of the fluid loss additive is 1-3 weight portions.
Wherein, the alkalinity regulator has stable emulsion, improves the effect of emulsion-breaking voltage, for example, can be CaO.It is preferred that Ground, relative to the oil phase in the oil base drilling fluid of 100 weight portions, the consumption of the alkalinity regulator is 2-5 weight portions.
Wherein, the density for acting as adjusting drilling fluid of the heavy weight additive reaches required density, for example, can be barite (for example can be barite of the barium sulfate content in more than 90 weight %) etc..Preferably, relative to the oil of 100 weight portions Oil phase in base drilling fluid, the consumption of the heavy weight additive is 400-600 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.
According to the present invention, thinner is used as by adding the diblock copolymer obtained by the present invention, gained can be caused Density reaches 2g/cm3After oil base drilling fluid above is aging at 200 DEG C, remain able to obtain more than 20% viscosity break ratio, or even More than 30% can be reached, more than 40% is preferably reached.
Present invention also offers application of the above-mentioned oil base drilling fluid in oil/gas drilling.
Below will the present invention will be described in detail by embodiment.
In following examples and comparative example：
Infared spectrum is red using the Fourier transformation of the models of SpectraLab Scientific company MAGNA-IR 560 External spectrum instrument is measured.
Proton nmr spectra and carbon spectrum are measured using the NMR of the models of Bruker companies AVANCE 400.
Emulsifying agent preparation example 1
(1) by reactant TEPA in molar ratio:Linoleic acid=1:2.2 (four ethene five i.e. in terms of primary amine group The consumption of amine is 1 with the mol ratio of linoleic consumption:1.1) mix, and 40min is stirred under 250r/min, then will obtain The pH value of mixture adjust to 9, then reacted 3 hours at 230 DEG C, while using fraction water device water-dividing, being then cooled to room Temperature；(2) product of step (1) is mixed into (the mol ratio of the consumption of TEPA and the consumption of malonic acid with malonic acid It is 1:0.6) pH value of the mixture that, then will be obtained is adjusted to 8, then at 90 DEG C, and is stirred under the speed of 400r/min Reaction 6h is mixed, emulsifying agent A1 is obtained.Detected through infrared, proton nmr spectra and carbon analysis of spectrum, amide groups is contained in emulsifying agent A1 Group, unsaturated double-bond and carboxyl, and with comb shaped structure.
Extracting and cutting agent preparation example 1
(1) it is 1 by mol ratio：0.5：0.5 dimeric dibasic acid (NCM trade mark Pripol 1013, It is as follows), dodecyl primary amine and aniline be added in reaction vessel, stir 30min at 120 ± 2 DEG C, be well mixed Monomer mixture；(2) to the concentrated sulfuric acid is added dropwise in above-mentioned monomer mixture, (concentration is 98 weight %, and addition is mixed for monomer 0.5 weight % of the amount of compound) (about 2min is added), in the case where condensed water outlet device is configured with, 2h, institute are reacted at 160 ± 5 DEG C It is dimeric dibasic acid-organic amine copolymer to obtain product, and its weight average molecular weight is 6500g/mol, and absolute viscosity is 125000cp.To Added in dimeric dibasic acid-organic amine copolymer diluent tall oil (be purchased from Jinan Jin Quan Chemical Co., Ltd.s, trade mark F1, below Together), dimeric dibasic acid-organic amine copolymer is diluted to the concentration of 50 weight %, extracting and cutting agent B1 of the invention is obtained, the liquid is orange Color liquid.
Embodiment 1
The present embodiment is used to illustrate diblock copolymer of the invention and preparation method thereof.
(1) by methyl methacrylate 12g (120mmol) and chain-transferring agent 2- (dodecyl trithiocarbonic acid ester group)- 2 Methylpropionic acid (DMP) 1.27g (3.49mmol) is dissolved in 25mL benzene, and is passed through nitrogen 60min, is subsequently adding initiator idol Nitrogen bis-isobutyronitrile 0.27g (1.65mmol) reacts 4h in 60 DEG C, and vacuum distillation removes solvent and unreacted monomer, obtains 11.4g Thick liquid PMMA-1.Its number-average molecular weight is 3800, and molecular weight distributing index is 1.2.
(2) PMMA-1 of (3- acrylamide propyls) trimethyl ammonium chloride 23.4g (100mmol) and 11.4g is dissolved in In the DMF of 70mL, and nitrogen 60min is passed through, is subsequently adding initiator azodiisobutyronitrile 0.08g (0.49mmol) in 100 DEG C Reaction 24h, is cooled to room temperature (about 25 DEG C) to terminate polymerization.Crude product is precipitated in absolute methanol, crosses afterwards be filtered dry repeatedly for three times It is dry, obtain diblock copolymer, as thinner TFO-1.Wherein, the diblock copolymer is by PMMA and (3- acrylamides Propyl group) trimethyl ammonium chloride polymer segments constitute diblock copolymer, its number-average molecular weight be 11000, the knot shown in formula (1) Structure unit (R1It is methyl, R1'It is H, R2'It is H, R2For-COOCH3) and formula (2) shown in construction unit (R4And R4'It is H, X choosings From-NH-, R5Selected from-CH2-CH2-CH2-, R6Selected from methyl, X' is selected from Cl) content mol ratio be 1：0.8.
Embodiment 2
The present embodiment is used to illustrate diblock copolymer of the invention and preparation method thereof.
(1) by dimethyl maleate 16g (110mmol) and chain-transferring agent 2- (dodecyl trithiocarbonates Base) -2 Methylpropionic acid (DMP) 1.09g (3mmol) is dissolved in 40mL benzene, and nitrogen 50min is passed through, it is subsequently adding initiator Azo-bis-isobutyrate hydrochloride 0.32g (1.2mmol) reacts 3.5h in 70 DEG C, and vacuum distillation removes solvent and unreacted monomer, Obtain 16.4g thick liquids PDM-1.Its number-average molecular weight is 5400, and molecular weight distributing index is 1.3.
(2) PDM-1 of (3- acrylamide propyls) trimethyl ammonium chloride 29.2g (130mmol) and 16.4g is dissolved in 60mL In DMF, and nitrogen 50min is passed through, is subsequently adding initiator azo-bis-isobutyrate hydrochloride 0.14g (0.5mmol) anti-in 110 DEG C 22h is answered, is cooled to room temperature to terminate polymerization.Crude product is precipitated in absolute methanol, repeatedly for three times rear filtration drying, obtains double embedding Section copolymer, as thinner TFO-2.Wherein, the diblock copolymer is by PDM and (3- acrylamide propyls) trimethyl chlorine Change the diblock copolymer that ammonium polymer section is constituted, its number-average molecular weight is 15000, the construction unit (R shown in formula (1)1And R1' It is H, R2'And R2For-COOCH3) and formula (2) shown in construction unit (R4And R4'It is H, X is selected from-NH-, R5Selected from-CH2-CH2- CH2-, R6Selected from methyl, X' is selected from Cl) content mol ratio be 1：1.1.
Embodiment 3
The present embodiment is used to illustrate diblock copolymer of the invention and preparation method thereof.
(1) (1) prepares PMMA-1 according to the step of embodiment 1.
(2) it is the PMMA-1 of (2- methylacryoyloxyethyls) trimethyl ammonium chloride 36.6g (180mmol) and 11.4g is molten In 80mL DMF, and nitrogen 70min is passed through, is subsequently adding initiator azodiisobutyronitrile 0.1g (0.61mmol) in 120 DEG C Reaction 18h, is cooled to room temperature to terminate polymerization.Crude product is precipitated in absolute methanol, repeatedly for three times rear filtration drying, obtains double Block copolymer, as thinner TFO-3.Wherein, the diblock copolymer is by PMMA and (2- methylacryoyloxyethyls) The diblock copolymer that trimethyl ammonium chloride polymer segments are constituted, its number-average molecular weight is 16000, the structure list shown in formula (1) Unit (R1It is methyl, R1'It is H, R2'It is H, R2For-COOCH3) and formula (2) shown in construction unit (R4It is methyl, R4'It is H, X choosings From-O-, R5Selected from-CH2-CH2-, R6Selected from methyl, X' is selected from Cl) content mol ratio be 1：1.5.
Embodiment 4
The present embodiment is used to illustrate diblock copolymer of the invention and preparation method thereof.
(1) by methyl methacrylate 12g (120mmol) and chain-transferring agent 2- (dodecyl trithiocarbonic acid ester group)- 2 Methylpropionic acid (DMP) 1.64g (4.5mmol) is dissolved in 25mL benzene, and is passed through nitrogen 60min, is subsequently adding initiator idol Nitrogen bis-isobutyronitrile 0.33g (2mmol) reacts 3h in 65 DEG C, and vacuum distillation removes solvent and unreacted monomer, obtains 11.5g sticky Liquid PMMA-2.Its number-average molecular weight is 2800, and molecular weight distributing index is 1.15.
(2) (2) are prepared according to the step of embodiment 1, the difference is that PMMA-1 is replaced using the PMMA-2 of 11.5g, As thinner TFO-4.Wherein, the diblock copolymer is to be polymerized by PMMA and (3- acrylamide propyls) trimethyl ammonium chloride The diblock copolymer that thing section is constituted, its number-average molecular weight is 8500, the construction unit (R shown in formula (1)1It is methyl, R1'It is H, R2'It is H, R2For-COOCH3) and formula (2) shown in construction unit (R4And R4'It is H, X is selected from-NH-, R5Selected from-CH2-CH2- CH2-, R6Selected from methyl, X' is selected from Cl) content mol ratio be 1：0.9.
Embodiment 5
The present embodiment is used to illustrate diblock copolymer of the invention and preparation method thereof.
(1) by methyl methacrylate 12g (120mmol) and chain-transferring agent 2- (dodecyl trithiocarbonic acid ester group)- 2 Methylpropionic acid (DMP) 1.1g (3mmol) is dissolved in 25mL benzene, and is passed through nitrogen 60min, is subsequently adding initiator azo two Isobutyronitrile 0.2g (1.2mmol) reacts 6h in 55 DEG C, and vacuum distillation removes solvent and unreacted monomer, obtains 11g thick liquids PMMA-3.Its number-average molecular weight is 4500, and molecular weight distributing index is 1.2.
(2) (2) are prepared according to the step of embodiment 1, the difference is that PMMA-1 is replaced using the PMMA-3 of 11g, i.e., It is thinner TFO-5.Wherein, the diblock copolymer is by PMMA and (3- acrylamide propyls) trimethyl ammonia chloride ammonium polymer The diblock copolymer that section is constituted, its number-average molecular weight is 14000, the construction unit (R shown in formula (1)1It is methyl, R1'It is H, R2'It is H, R2For-COOCH3) and formula (2) shown in construction unit (R4And R4'It is H, X is selected from-NH-, R5Selected from-CH2-CH2- CH2-, R6Selected from methyl, X' is selected from Cl) content mol ratio be 1：0.9.
Embodiment 6
The present embodiment is used to illustrate diblock copolymer of the invention and preparation method thereof.
(1) by methyl methacrylate 12g (120mmol) and chain-transferring agent 2- (dodecyl trithiocarbonic acid ester group)- 2 Methylpropionic acid (DMP) 2.18g (6mmol) is dissolved in 25mL benzene, and is passed through nitrogen 60min, is subsequently adding initiator azo Bis-isobutyronitrile 0.39g (2.4mmol) reacts 2.5h in 75 DEG C, and vacuum distillation removes solvent and unreacted monomer, obtains 11.6g and glues Thick liquid PMMA-4.Its number-average molecular weight is 2000, and molecular weight distributing index is 1.2.
(2) (2) are prepared according to the step of embodiment 1, the difference is that PMMA-1 is replaced using the PMMA-4 of 11.6g, As thinner TFO-6.Wherein, the diblock copolymer is to be polymerized by PMMA and (3- acrylamide propyls) trimethyl ammonium chloride The diblock copolymer that thing section is constituted, its number-average molecular weight is 6000, the construction unit (R shown in formula (1)1It is methyl, R1'It is H, R2'It is H, R2For-COOCH3) and formula (2) shown in construction unit (R4And R4'It is H, X is selected from-NH-, R5Selected from-CH2-CH2- CH2-, R6Selected from methyl, X' is selected from Cl) content mol ratio be 1：0.9.
Embodiment 7
The present embodiment is used to illustrate diblock copolymer of the invention and preparation method thereof.
(1) by methyl methacrylate 12g (120mmol) and chain-transferring agent 2- (dodecyl trithiocarbonic acid ester group)- 2 Methylpropionic acid (DMP) 0.87g (2.4mmol) is dissolved in 25mL benzene, and is passed through nitrogen 60min, is subsequently adding initiator idol Nitrogen bis-isobutyronitrile 0.16g (1mmol) reacts 6h in 50 DEG C, and vacuum distillation removes solvent and unreacted monomer, obtains 11.2g sticky Liquid PMMA-5.Its number-average molecular weight is 8000, and molecular weight distributing index is 1.3.
(2) (2) are prepared according to the step of embodiment 1, the difference is that PMMA-1 is replaced using the PMMA-5 of 11.2g, As thinner TFO-6.Wherein, the diblock copolymer is to be polymerized by PMMA and (3- acrylamide propyls) trimethyl ammonium chloride The diblock copolymer that thing section is constituted, its number-average molecular weight is 24000, the construction unit (R shown in formula (1)1It is methyl, R1'For H, R2'It is H, R2For-COOCH3) and formula (2) shown in construction unit (R4And R4'It is H, X is selected from-NH-, R5Selected from-CH2-CH2- CH2-, R6Selected from methyl, X' is selected from Cl) content mol ratio be 1：0.9.
Comparative example 1
By methyl methacrylate 12g (120mmol), (3- acrylamide propyls) trimethyl ammonium chloride 23.4g (100mmol) and chain-transferring agent 2- (dodecyl trithiocarbonic acid ester group) -2 Methylpropionic acid (DMP) 2.54g (7mmol) dissolve In the DMF of 70mL, and nitrogen 60min is passed through, is subsequently adding initiator azodiisobutyronitrile 0.7g (4.2mmol) in 100 DEG C Reaction 15h, is cooled to room temperature to terminate polymerization.Crude product is precipitated in absolute methanol, and rear filtration drying, obtains nothing repeatedly for three times Rule copolymer, as thinner D1.Wherein, the number-average molecular weight of the random copolymer is 20000, the structure list shown in formula (1) Unit (R1It is methyl, R1'It is H, R2'It is H, R2For-COOCH3) and formula (2) shown in construction unit (R4And R4'It is H, X is selected from- NH-, R5Selected from-CH2-CH2-CH2-, R6Selected from methyl, X' is selected from Cl) content mol ratio be 1：0.8.
Drilling fluid embodiment 1
The present embodiment is used to illustrate drilling fluid of the invention.
Drilling fluid composition is：The diesel oil (purchased from Beijing treasure profit company 0# diesel oil, same as below) of 100 weight portions, 20 weights Measure the CaCl of part2The aqueous solution (CaCl in the solution2Concentration is 30 weight %), the thinner TFO-1 of 1 weight portion, 3 weight portions Emulsifying agent A1, the extracting and cutting agent B1 of 2 weight portions, 1 weight portion wetting agent modified phospholipid (for example purchased from Shanghai help wound industry it is limited The modified phospholipid of company's FHGT-G trades mark, same as below), (purchased from Sichuan, deep China is public for the polymer oil-base fluid loss additive of 2 weight portions The HFLO type oil bases fluid loss additive of department), the CaO of 3 weight portions, the barite of 450 weight portions (is purchased from Sichuan Zheng Rong companies, below It is identical)；So as to drilling fluid X1 is obtained, density is 2.6g/cm3。
Drilling fluid embodiment 2-7
The present embodiment is used to illustrate drilling fluid of the invention.
Formula according to drilling fluid embodiment 1, unlike, thinner TFO-2 to TFO-7 replacements are respectively adopted TFO-1, so as to obtain drilling fluid X2-X7, their density is 2.6g/cm3。
Comparative example 1
Formula according to drilling fluid embodiment 1, unlike, thinner TFO-1 is added without, so as to drilling fluid is obtained DX1。
Comparative example 2
Formula according to drilling fluid embodiment 1, unlike, thinner TFO-1 is replaced using thinner D1, so that Drilling fluid DX2 is obtained.
Comparative example 3
Formula according to drilling fluid embodiment 1, unlike, thinner TFO-1 is replaced using PMMA-1, so as to make Obtain drilling fluid DX3.
Test case 1
It is respectively 55 DEG C by drilling fluid temperature after above-mentioned drilling fluid high-speed stirred 20 minutes, is kept, surveys its apparent viscosity (AV), plastic viscosity (PV), yield value (YP) and viscosity break ratio is calculated；Then test object is fitted into ageing can at 200 DEG C Heat rolling 16 hours, is cooled to room temperature, moves into jar high speed and stirs 20 minutes, and it is 55 DEG C to keep drilling fluid temperature, surveys its stream Become performance (AV, PV, YP and viscosity break ratio)；The results are shown in Table shown in 1.
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.Apparent viscosity (AV) is according to state using the fast viscosimeter of normal form six What method specified in family standard GB/T29170-2012 was measured, unit is mPas,Yield value (YP) Measured using the fast viscosimeter method according to specified in standard GB/T/T29170-2012 of normal form six, YP=0.5 (2θ300-θ600), unit is Pa.Thinner viscosity reducing effect plastic viscosity reduced rate Rpv(hereinafter referred to as viscosity break ratio) is represented, its meter Point counting formula is as follows：RPV=[(PV0–PV)/PV0] × 100%, in formula, RPV- viscosity break ratio, %；PV0- not with thinner drilling fluid Plastic viscosity；The plastic viscosity (i.e. drilling fluid DX1) of PV-addition thinner drilling fluid.
Table 1
Note："/" is unmeasured.
The oil base drilling fluid containing diblock copolymer of the invention as thinner is can be seen that by the data of table 1 Viscosity break ratio can reach more than 20%, can be applied to common oil base drilling fluid viscosity reduction, viscosity break ratio even can with 30% with On, what is had can reach more than 40%, while the shear force influence on the oil base drilling fluid is little, and the thinner is at 200 DEG C Aged properties viscosity-reducing performance can keep good heat endurance still without too big change.
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 (45)

1. a kind of diblock copolymer, it is characterised in that the copolymer is mainly made up of block A and B block, wherein, block A by Constituted selected from the construction unit shown in formula (1), B block is constituted by selected from the construction unit shown in formula (2), the number of the block A Average molecular weight is 1500-10000,
Formula (1)Formula (2)
Wherein, R1、R1'、R4、R4'And R6It is each independently selected from the alkyl of H and C1-C6；R2And R2'It is each independently selected from H, C1- The alkyl of C6 ,-O-C (O)-R3With-COOR3, and R2And R2'In at least one be selected from-O-C (O)-R3Or-COOR3, R3It is selected from The alkyl of C1-C6；R5Selected from the alkylidene of C1-C8；X is selected from-NH- or-O-.
2. diblock copolymer according to claim 1, wherein, R1、R1'、R4、R4'And R6It is each independently selected from H and C1- The alkyl of C4；R2And R2'It is each independently selected from alkyl ,-O-C (O)-R of H, C1-C43With-COOR3, and R2And R2'In at least One is selected from-O-C (O)-R3Or-COOR3, R3Selected from the alkyl of C1-C4；R5Selected from the alkylidene of C1-C6.
3. diblock copolymer according to claim 2, wherein, R1、R1'、R4、R4'And R6It is each independently selected from H, first Base, ethyl, n-propyl, isopropyl and normal-butyl；R2And R2'Be each independently selected from H, methyl, ethyl, n-propyl, isopropyl, Normal-butyl ,-O-C (O)-CH3、-O-C(O)-CH2CH3、-O-C(O)-CH2CH2CH3、-O-C(O)-CH(CH3)CH3、-COOCH3、- COOCH2CH3、-COOCH2CH2CH3With-COOCH (CH3)CH3, and R2And R2'In at least one be selected from-O-C (O)-CH3、-O-C (O)-CH2CH3、-O-C(O)-CH2CH2CH3、-O-C(O)-CH(CH3)CH3、-COOCH3、-COOCH2CH3、-COOCH2CH2CH3 Or-COOCH (CH3)CH3；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-、-CH2-C(CH3)2-、-CH2-(CH2)3- CH2- or-CH2-(CH2)4-CH2-。
4. the diblock copolymer according to any one in claim 1-3, wherein, the structure list shown in the formula (1) The content mol ratio of the construction unit shown in unit and formula (2) is 1：0.2-5.
5. diblock copolymer according to claim 4, wherein, shown in the construction unit and formula (2) shown in the formula (1) Construction unit content mol ratio be 1：0.5-2.
6. diblock copolymer according to claim 5, wherein, shown in the construction unit and formula (2) shown in the formula (1) Construction unit content mol ratio be 1：0.6-1.6.
7. diblock copolymer according to claim 4, wherein, the number-average molecular weight of the block A is 5000-25000.
8. diblock copolymer according to claim 7, wherein, the number-average molecular weight of the block A is 6000-24000.
9. diblock copolymer according to claim 8, wherein, the number-average molecular weight of the block A is 8000-20000.
10. diblock copolymer according to claim 9, wherein, the number-average molecular weight of the block A is 8500- 16000。
11. a kind of preparation methods of diblock copolymer, it is characterised in that the method includes：
(1) in the presence of chain-transferring agent and the first azo initiator, in the first organic solvent, prepare the (1') shown change of formula Compound carries out polymerisation, obtains the polymer A that number-average molecular weight is 1500-10000；
(2) in the presence of the second azo initiator, in a second organic solvent, by polymer A and the (2') shown compound of formula Carry out copolymerization；
Formula is (1')Formula is (2')
Wherein, R1、R1'、R4、R4'And R6It is each independently selected from the alkyl of H and C1-C6；R2And R2'It is each independently selected from H, C1- The alkyl of C6 ,-O-C (O)-R3With-COOR3, and R2And R2'In at least one be selected from-O-C (O)-R3Or-COOR3, R3It is selected from The alkyl of C1-C6；R5Selected from the alkylidene of C1-C8；X is selected from-NH- or-O-；X' is selected from halogen.
12. methods according to claim 11, wherein, R1、R1'、R4、R4'And R6It is each independently selected from the alkane of H and C1-C4 Base；R2And R2'It is each independently selected from alkyl ,-O-C (O)-R of H, C1-C43With-COOR3, and R2And R2'In at least one choosing From-O-C (O)-R3Or-COOR3, R3Selected from the alkyl of C1-C4；R5Selected from the alkylidene of C1-C6；X' is selected from F, Cl or Br.
13. methods according to claim 12, wherein, R1、R1'、R4、R4'And R6Be each independently selected from H, methyl, ethyl, N-propyl, isopropyl and normal-butyl；R2And R2' be each independently selected from H, methyl, ethyl, n-propyl, isopropyl, normal-butyl ,- O-C(O)-CH3、-O-C(O)-CH2CH3、-O-C(O)-CH2CH2CH3、-O-C(O)-CH(CH3)CH3、-COOCH3、- COOCH2CH3、-COOCH2CH2CH3With-COOCH (CH3)CH3, and R2And R2'In at least one be selected from-O-C (O)-CH3、-O-C (O)-CH2CH3、-O-C(O)-CH2CH2CH3、-O-C(O)-CH(CH3)CH3、-COOCH3、-COOCH2CH3、-COOCH2CH2CH3 Or-COOCH (CH3)CH3；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-、-CH2-C(CH3)2-、-CH2-(CH2)3- CH2- or-CH2-(CH2)4-CH2-。
14. method according to any one in claim 11-13, wherein, the number of the polymer A obtained by step (1) is equal Molecular weight is 5000-25000.
15. methods according to claim 14, wherein, the number-average molecular weight of the polymer A obtained by step (1) is 6000- 24000。
16. methods according to claim 15, wherein, the number-average molecular weight of the polymer A obtained by step (1) is 8000- 20000。
17. methods according to claim 16, wherein, the number-average molecular weight of the polymer A obtained by step (1) is 8500- 16000。
18. methods according to claim 14, wherein, in step (2), form the (1') shown change of the formula of polymer A Compound is 1 with the mol ratio of the consumption of the (2') shown compound of formula：0.2-5.
19. methods according to claim 18, wherein, in step (2), form the (1') shown change of the formula of polymer A Compound is 1 with the mol ratio of the consumption of the (2') shown compound of formula：0.5-2.
20. methods according to claim 19, wherein, in step (2), form the (1') shown change of the formula of polymer A Compound is 1 with the mol ratio of the consumption of the (2') shown compound of formula：0.6-1.6.
21. methods according to claim 11, wherein, in step (1), the chain-transferring agent is 2- (dodecyl trithios For carbonate group) -2 Methylpropionic acid, 3- benzyl trithio carbonate groups propionic acid, dithiobenzoic acid (4- cyanopentanoic acids) ester and double One or more in thiobenzoate isopropyl phenyl ester.
22. methods according to claim 21, wherein, in step (1), the (1') shown chemical combination of formula relative to 1mol Thing, the consumption of the chain-transferring agent is 15-55mmol.
23. methods according to claim 22, wherein, in step (1), the (1') shown chemical combination of formula relative to 1mol Thing, the consumption of the chain-transferring agent is 20-50mmol.
24. methods according to claim 23, wherein, in step (1), the (1') shown chemical combination of formula relative to 1mol Thing, the consumption of the chain-transferring agent is 24-35mmol.
25. methods according to claim 21, wherein, in step (1), first azo initiator is 4,4'- azos (4- cyanopentanoic acids), azo-bis-isobutyrate hydrochloride, azodiisobutyronitrile, ABVN and the isobutyl imidazoline salt of azo two One or more in hydrochlorate.
26. methods according to claim 25, wherein, in step (1), the (1') shown chemical combination of formula relative to 1mol Thing, the consumption of first azo initiator is 8-25mmol.
27. methods according to claim 26, wherein, in step (1), the (1') shown chemical combination of formula relative to 1mol Thing, the consumption of first azo initiator is 8-20mmol.
28. methods according to claim 27, wherein, in step (1), the (1') shown chemical combination of formula relative to 1mol Thing, the consumption of first azo initiator is 9.5-17mmol.
29. methods according to claim 21, wherein, in step (1), first organic solvent is benzene, toluene, second One or more in benzene, dimethylbenzene, 1,4- dioxane, ethanol and isopropanol.
30. methods according to claim 29, wherein, the (1') shown compound of formula relative to 1mol, described first The consumption of organic solvent is 200-600mL.
31. methods according to claim 11, wherein, in step (2), second azo initiator is 4,4'- azos (4- cyanopentanoic acids), azo-bis-isobutyrate hydrochloride, azodiisobutyronitrile, ABVN and the isobutyl imidazoline salt of azo two One or more in hydrochlorate.
32. methods according to claim 31, wherein, in step (2), the (2') shown chemical combination of formula relative to 1mol Thing, the consumption of second azo initiator is 3-10mmol.
33. methods according to claim 32, wherein, in step (2), the (2') shown chemical combination of formula relative to 1mol Thing, the consumption of second azo initiator is 3-6mmol.
34. methods according to claim 31, wherein, in step (2), second organic solvent is DMF, THF, dichloro One or more in methane, chloroform and carbon tetrachloride.
35. methods according to claim 34, wherein, in step (2), the (2') shown chemical combination of formula relative to 1mol Thing, the consumption of second organic solvent is 400-1200mL.
36. methods according to claim 11, wherein, step (1), the condition of the polymerisation includes：Temperature is 50- 80℃；Time is 2-6h.
37. methods according to claim 36, wherein, step (1), the condition of the polymerisation includes：Temperature is 55- 70℃；Time is 3-5h.
38. methods according to claim 36, wherein, step (2), the condition of the copolymerization includes：Temperature is 80-140℃；Time is 12-36h.
39. method according to claim 38, wherein, step (2), the condition of the copolymerization includes：Temperature is 100-120℃；Time is 18-24h.
Diblock copolymer obtained in method in a kind of 40. 11-39 as claim described in any one.
Diblock copolymer in 41. claim 1-10 and 40 described in any one in drilling fluid as thinner should With.
A kind of 42. diblock copolymers containing described in any one in claim 1-10 and 40 are bored as the oil base of thinner Well liquid.
43. oil base drilling fluids according to claim 42, wherein, relative in the oil base drilling fluid of 100 weight portions Oil phase, the content of the diblock copolymer is 0.5-3 weight portions.
44. oil base drilling fluids according to claim 42, wherein, the density of the oil base drilling fluid is 2g/cm3More than.
The application of oil base drilling fluid in 45. claim 42-44 described in any one in oil/gas drilling.
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CN111778004B (en) * 2020-08-12 2021-04-13 中国石油大学(北京) Amphiphilic block polymer ultra-low permeability agent and intelligent temporary plugging type water-based drilling fluid
CN112680202B (en) * 2020-12-25 2022-06-07 河北峻极化工科技有限公司 Oil-gas well underground solid-phase deposition eliminating agent and preparation method thereof
CN115926763A (en) * 2021-08-24 2023-04-07 中国石油天然气股份有限公司 Viscosity reducer for oil-based drilling fluid and preparation method thereof
CN114316936B (en) * 2022-03-15 2022-05-13 华睿致诚化学(山东)有限公司 Bifunctional depolymerization scale dissolver for oil extraction, and preparation and application thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101531886A (en) * 2009-04-20 2009-09-16 中国石油大学(华东) High-temperature resistant polymer viscosity reducer for drilling fluid and preparation method thereof
WO2013019704A1 (en) * 2011-07-29 2013-02-07 M-I L.L.C. Hydrocarbon fluid flow improver
CN103484084A (en) * 2013-09-18 2014-01-01 新疆贝肯能源工程股份有限公司 Multifunctional oligomerization lubricant for drilling fluid and preparation method of lubricant
CN103980421A (en) * 2014-05-30 2014-08-13 陕西科技大学 Water-base macromolecular shale inhibitor and preparation method thereof

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060106180A1 (en) * 2004-11-18 2006-05-18 Aquaspecialties S.A. Polymeric stabilizing agent for water-in-oil polymerization processes

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101531886A (en) * 2009-04-20 2009-09-16 中国石油大学(华东) High-temperature resistant polymer viscosity reducer for drilling fluid and preparation method thereof
WO2013019704A1 (en) * 2011-07-29 2013-02-07 M-I L.L.C. Hydrocarbon fluid flow improver
CN103484084A (en) * 2013-09-18 2014-01-01 新疆贝肯能源工程股份有限公司 Multifunctional oligomerization lubricant for drilling fluid and preparation method of lubricant
CN103980421A (en) * 2014-05-30 2014-08-13 陕西科技大学 Water-base macromolecular shale inhibitor and preparation method thereof

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