CN103897094B - Drilling fluid unstressed configuration nanometer additive and preparation method thereof - Google Patents

Drilling fluid unstressed configuration nanometer additive and preparation method thereof Download PDF

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CN103897094B
CN103897094B CN201410141841.4A CN201410141841A CN103897094B CN 103897094 B CN103897094 B CN 103897094B CN 201410141841 A CN201410141841 A CN 201410141841A CN 103897094 B CN103897094 B CN 103897094B
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water
monomer
drilling fluid
carbon
nanometer additive
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CN103897094A (en
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王绪美
赵福祥
解洪祥
李洪俊
王绮
田野
贾东民
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China National Petroleum Corp
CNPC Bohai Drilling Engineering Co Ltd
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CNPC Bohai Drilling Engineering Co Ltd
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Abstract

The invention discloses a kind of drilling fluid unstressed configuration nanometer additive and preparation method thereof, adopt the non-water-soluble monomer of at least one and at least one water-soluble monomer under non-oxygen atmosphere, adopt the method for letex polymerization to synthesize, the Nano grade of nanometer additive is 10nm-5000nm, its surface containing having carboxylic acid group or carboxylate radical hydrophilic radical, and has the structure of nucleocapsid.The present invention relates to the water soluble nanometer particles with nucleocapsid structure of carboxylate radical modification, nanometer ball uniform particle diameter, stably can be dispersed in drilling fluid the drilling fluid forming nanometer additive and add.This nanometer additive unstressed configuration, does not produce interference to well logging, has the effect of high temperature resistance filtrate reducing, extreme boundary lubrication and suppression shale expansion, and has no significant effect drilling fluid rheology, reach the multi-functional object of potion.

Description

Drilling fluid unstressed configuration nanometer additive and preparation method thereof
Technical field
The present invention relates to for the nano material in drilling fluid field, especially a kind of unstressed configuration nanometer additive for oil or gas drilled hole liquid and preparation method thereof.
Background technology
When the size of material is reduced to the rank of nanometer, it can show the remarkable property being different from macroscopic material, and the properties such as such as small-size effect, surface effects and Selective adsorption, these special performances make it be applied in drilling fluid field becomes possibility.This is because the small-size effect of nano material, the duct of Nano grade can be blocked; The surface energy that nano material is large, can make it adsorb some macromolecule polymer materials, is then used for the large formation pore of blockage ratio own dimensions by bridge joint, these all make its mud cake formed than conventional material formed finer and close; During the network that the functional group of nano-material surface can participate in clay is formed, play the effect of filtrate reducing; Nano material has stronger surface adsorption, can be adsorbed on the surface of drilling tool, forms the film of one deck densification in surface of drill stem, reduces frictional force; Easily be adsorbed in micro-hole of the wearing and tearing of drilling tool, play the function of reparation, utilize " micro-bearing " principle of nanometer bead, can wearing and tearing be reduced, prevent bit freezing, play the effect of lubrication.The specific heat ratio conventional material of nano material is much larger, if apply it in drilling fluid field, it can be allowed to absorb more heat, play the effect improving drilling fluid other additive inner and superpolymer performance, and then the overall performance of stable drilling fluid, thus improve the thermostability of drilling fluid.
In view of above analysis, if nano material be incorporated in drilling fluid field, a lot of problems in existing drilling fluid field can be solved, promise to be the multi-functional additive for drilling fluid that a class is novel.
Summary of the invention
Technical problem to be solved by this invention is, provides a kind of and significantly can reduce drilling fluid filtration and have drilling fluid unstressed configuration nanometer additive of suppression and lubricating function and preparation method thereof.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is: a kind of preparation method of drilling fluid unstressed configuration nanometer additive, adopt the non-water-soluble monomer of at least one and at least one water-soluble monomer, under non-oxygen atmosphere, adopt the method synthesis of letex polymerization, the Nano grade of nanometer additive is 10nm-5000nm, and its surface, containing having carboxylic acid group or carboxylate radical hydrophilic radical, has the structure of nucleocapsid.
Described letex polymerization is seeded emulsion polymerization method, comprises the following steps:
(1) synthesis of nano seed emulsion, adopt at least one non-water soluble monomers, under the condition that non-oxygen atmosphere also stirs, be that the mode that solvent adopts free radical to cause synthesizes nanometer seed with water, temperature of reaction is 20-96 DEG C, time 0.05-2 hour, the massfraction of initiator is 0.005%-3%, and the total mass mark of monomer is between 0.1%-50%;
(2) then at least one is joined in nanometer seed emulsion with the monomer of carboxylic acid group or carboxylate radical and at least one non-water soluble monomers, make its 0-2 hour that coexists, again non-oxygen atmosphere and stir condition under, the mode adopting free radical to cause reacts 0.1-4 hour, i.e. synthesis of nano additive for drilling fluid, the massfraction of initiator is 0.005%-3%; Temperature of reaction is 20-96 DEG C, and the total mass mark of monomer is between 0.2%-70%, and the total mass mark of described monomer refers to the summation of non-water soluble monomers and water-soluble monomer in step (1), (2).
Described letex polymerization is the method for emulsion copolymerization, comprise the following steps: at least one is added to the water with the water-soluble monomer of carboxylate radical or carboxylic acid group and at least one non-water soluble monomers, under the condition that non-oxygen atmosphere also stirs, the mode adopting free radical to cause reacts 0.1-8 hour, namely synthesize nano-drilling fluid treating agent, the massfraction of initiator is 0.005%-3%; Temperature of reaction is 20-96 DEG C, and the massfraction of non-water soluble monomers is between 0.1%-50%; The massfraction of water-soluble monomer is between 0.1%-30%.
Described non-water soluble monomers is the monomer of following structure:
R 1for the saturated alkane substituting group of H or 1-4 carbon; R 2for the alkane substituting group of 1-5 carbon; X is O or S.
Described non-water soluble monomers is the monomer of following structure:
R 1for the alkane substituting group of 1-5 carbon; R 2for the alkane substituting group of 1-5 carbon; X is O or S; Y is O or S; The configuration of alkene is cis or trans.
Described non-water soluble monomers be vinylbenzene, p-methylstyrene, to methoxy styrene with to the one in benzene diene.
Described water-soluble monomer is the monomer of following structure:
R 1for the saturated alkane substituting group of H or 1-4 carbon; M is H, basic metal or amido.
Described water-soluble monomer is the monomer of following structure:
M is H, basic metal or amido; The configuration of alkene is cis or trans.
Described radical initiator can be single dose, as Diisopropyl azodicarboxylate, Diisopropyl azodicarboxylate amidine hydrochloride, dibenzoyl peroxide, Na 2s 2o 8, K 2s 2o 8or (NH 4) 2s 2o 8; Also can be redox system, as Na 2s 2o 8/ NaHSO 3, K 2s 2o 8/ NaHSO 3, (NH 4) 2s 2o 8/ NaHSO 3, Na 2s 2o 8/ FeSO 4, K 2s 2o 8/ FeSO 4, (NH 4) 2s 2o 8/ FeSO 4, Na 2s 2o 8/ Na 2s 2o 3, K 2s 2o 8/ Na 2s 2o 3, (NH 4) 2s 2o 8/ Na 2s 2o 3, Na 2s 2o 8/ Na 2sO 3, K 2s 2o 8/ Na 2sO 3, (NH 4) 2s 2o 8/ Na 2sO 3, Na 2s 2o 8/ aliphatic amide, K 2s 2o 8/ aliphatic amide or (NH 4) 2s 2o 8/ aliphatic amide, described aliphatic amide is RNH 2, R 2nH, R 3n, R are the alkyl of 1-8 carbon.When described initiator is redox system, the mol ratio of oxygenant and reductive agent is 1:0.1-1:10.
Adopt the drilling fluid unstressed configuration nanometer additive of aforesaid method synthesis.
The invention has the beneficial effects as follows: gained treatment agent unstressed configuration, does not produce interference to well logging; Make the mud cake of formation thin and fine and close; Significantly can reduce drilling fluid filtration, leak-off reduced rate can reach more than 60%; And the extreme boundary lubrication coefficient of drilling fluid can be reduced, extreme boundary lubrication coefficient can reduce by more than 70%; Effective suppression shale expansion, comes compared with clear water, suppresses shale expansion rate to reduce by more than 70%; High temperature resistance can reach 180 DEG C; Anti-salt can reach 15%; And significant impact can not be produced on the rheological of drilling fluid.
Accompanying drawing explanation
Fig. 1 is the stereoscan photograph of unstressed configuration nanometer additive of the present invention.
Fig. 2 is the transmission electron microscope photo of unstressed configuration nanometer additive of the present invention.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in further detail:
The preparation method of drilling fluid unstressed configuration nanometer additive of the present invention, adopt the non-water-soluble monomer of at least one and at least one water-soluble monomer, under non-oxygen atmosphere, adopt the method synthesis of letex polymerization, the Nano grade of nanometer additive is 10nm-5000nm, its surface, containing having similar carboxylic acid group or carboxylate radical hydrophilic radical, has the structure of similar nucleocapsid.
Described letex polymerization is seeded emulsion polymerization method, comprises the following steps:
(1) synthesis of nano seed emulsion, adopt at least one non-water soluble monomers, under the condition that non-oxygen atmosphere also stirs, be that the mode that solvent adopts free radical to cause synthesizes nanometer seed with water, temperature of reaction is 20-96 DEG C, time 0.05-2 hour, the massfraction of initiator is 0.005%-3%, and the total mass mark of monomer is between 0.1%-50%;
(2) then at least one is joined in nanometer seed emulsion with the monomer of carboxylic acid group or carboxylate radical and at least one non-water soluble monomers, make its 0-2 hour that coexists, again non-oxygen atmosphere and stir condition under, the mode adopting free radical to cause reacts 0.1-4 hour, i.e. synthesis of nano additive for drilling fluid, the massfraction of initiator is 0.005%-3%; Temperature of reaction is 20-96 DEG C, and the total mass mark of monomer is between 0.2%-70%, and the total mass mark of described monomer refers to the summation of non-water soluble monomers and water-soluble monomer in step (1), (2).
Described letex polymerization is the method for emulsion copolymerization, comprise the following steps: at least one is added to the water with the water-soluble monomer of carboxylate radical or carboxylic acid group and at least one non-water soluble monomers, under the condition that non-oxygen atmosphere also stirs, the mode adopting free radical to cause reacts 0.1-8 hour, namely synthesize nano-drilling fluid treating agent, the massfraction of initiator is 0.005%-3%; Temperature of reaction is 20-96 DEG C, and the massfraction of non-water soluble monomers is between 0.1%-50%; The massfraction of water-soluble monomer is between 0.1%-30%.
Described non-water soluble monomers is the monomer of following structure:
R 1for the saturated alkane substituting group of H or 1-4 carbon; R 2for the alkane substituting group of 1-5 carbon; X is O or S.
Described non-water soluble monomers is the monomer of following structure:
R 1for the alkane substituting group of 1-5 carbon; R 2for the alkane substituting group of 1-5 carbon; X is O or S; Y is O or S; The configuration of alkene is cis or trans.
Described non-water soluble monomers be vinylbenzene, p-methylstyrene, to methoxy styrene with to the one in benzene diene.
Described water-soluble monomer is the monomer of following structure:
R 1for the saturated alkane substituting group of H or 1-4 carbon; M is H, basic metal or amido.
Described water-soluble monomer is the monomer of following structure:
M is H, basic metal or amido; The configuration of alkene is cis or trans.
Described radical initiator can be single dose, as Diisopropyl azodicarboxylate, Diisopropyl azodicarboxylate amidine hydrochloride, dibenzoyl peroxide, Na 2s 2o 8, K 2s 2o 8or (NH 4) 2s 2o 8; Also can be redox system, as Na 2s 2o 8/ NaHSO 3, K 2s 2o 8/ NaHSO 3, (NH 4) 2s 2o 8/ NaHSO 3, Na 2s 2o 8/ FeSO 4, K 2s 2o 8/ FeSO 4, (NH 4) 2s 2o 8/ FeSO 4, Na 2s 2o 8/ Na 2s 2o 3, K 2s 2o 8/ Na 2s 2o 3, (NH 4) 2s 2o 8/ Na 2s 2o 3, Na 2s 2o 8/ Na 2sO 3, K 2s 2o 8/ Na 2sO 3, (NH 4) 2s 2o 8/ Na 2sO 3, Na 2s 2o 8/ aliphatic amide, K 2s 2o 8/ aliphatic amide or (NH 4) 2s 2o 8/ aliphatic amide, described aliphatic amide is RNH 2, R 2nH, R 3n, R are the alkyl of 1-8 carbon.When described initiator is redox system, the mol ratio of oxygenant and reductive agent is 1:0.1-1:10.
Adopt the drilling fluid unstressed configuration nanometer additive of aforesaid method synthesis.
Below, the polymethyl methacrylate nano ball containing carboxylate radical for surface is described.
1, the preparation of unstressed configuration nanometer additive
1.1 experimental formulas and condition
Unstressed configuration nanometer additive of the present invention is the material with nucleocapsid structure that hydrophilic radical is contained on surface that a class has a nano-scale.What synthesize that this nanometer additive adopts is the non-water-soluble monomer of at least one and at least one water-soluble monomer at non-oxygen atmosphere and under the condition stirred, and adopts the method synthesis of letex polymerization.The initiator adopted can be single dose, as Diisopropyl azodicarboxylate, Diisopropyl azodicarboxylate amidine hydrochloride, dibenzoyl peroxide, Na 2s 2o 8, K 2s 2o 8or (NH 4) 2s 2o 8; Also can be redox system, as Na 2s 2o 8/ NaHSO 3, K 2s 2o 8/ NaHSO 3, (NH 4) 2s 2o 8/ NaHSO 3, Na 2s 2o 8/ FeSO 4, K 2s 2o 8/ FeSO 4, (NH 4) 2s 2o 8/ FeSO 4, Na 2s 2o 8/ Na 2s 2o 3, K 2s 2o 8/ Na 2s 2o 3, (NH 4) 2s 2o 8/ Na 2s 2o 3, Na 2s 2o 8/ Na 2sO 3, K 2s 2o 8/ Na 2sO 3, (NH 4) 2s 2o 8/ Na 2sO 3, Na 2s 2o 8(aliphatic amide is RNH to/aliphatic amide 2, R 2nH, R 3n, R are the alkyl of 1-8 carbon), K 2s 2o 8(aliphatic amide is RNH to/aliphatic amide 2, R 2nH, R 3n, R are the alkyl of 1-8 carbon) or (NH 4) 2s 2o 8/ aliphatic amide (RNH 2, R 2nH, R 3n, R are the alkyl of 1-8 carbon).Temperature of reaction is 20-96 DEG C.
The preparation of 1.2 novel unstressed configuration nanometer fluid loss agents
The method of seeded emulsion polymerization:
Embodiment 1
First seed is synthesized, 0.029gK 2s 2o 8join in 100mL distilled water, logical nitrogen after it dissolves also heats, and when temperature reaches 70 DEG C, adds 8mL methyl methacrylate, after reacting 2h, namely obtains the emulsion of polymethyl methacrylate nano particle, be then cooled to room temperature under agitation condition.In above-mentioned emulsion, add 4mL methyl acrylate, 2mL vinylbenzene and 4mL vinylformic acid, after making its 2h that mutually coexists, add 0.03gK 2s 2o 8make it dissolve, react 3h under nitrogen environment, stirring and 70 DEG C of conditions after, namely emulsion obtains unstressed configuration nanometer additive through centrifugal and dry operating process, or without process, and direct as unstressed configuration nanometer additive in the form of an emulsion.
Embodiment 2
First seed is synthesized, 0.4g (NH 4) 2s 2o 8join in 100mL distilled water, logical argon gas after it dissolves also heats, and when temperature reaches 80 DEG C, adds 15mL methyl acrylate, after reacting 3h, namely obtains the emulsion of polymethyl acrylate nanoparticle, be then cooled to room temperature under agitation condition.In above-mentioned emulsion, add 20mL methyl acrylate and 20mL vinylformic acid, after making its 0.2h that mutually coexists, add 0.4g (NH 4) 2s 2o 8make it dissolve, react 4h under ar gas environment, stirring and 80 DEG C of conditions after, namely emulsion obtains unstressed configuration nanometer additive through centrifugal and dry operating process, or without process, and direct as unstressed configuration nanometer additive in the form of an emulsion.
Embodiment 3
First seed is synthesized, 0.3gK 2s 2o 8and 0.4gNaHSO 3join in 100mL tap water, logical nitrogen after it dissolves also heats, when temperature reaches 45 DEG C, add 5mL methyl methacrylate and 5mL methyl acrylate, after reacting 2h under agitation condition, namely obtain the emulsion of polymer nano-particle, be then cooled to room temperature.In above-mentioned emulsion, add 6mL methyl methacrylate, 3mL dimethyl maleate and 6mL sodium acrylate, after making its 0.5h that mutually coexists, add 0.1gK 2s 2o 8and 0.15gNaHSO 3make it dissolve, react 5h under nitrogen environment, stirring and 45 DEG C of conditions after, namely emulsion obtains unstressed configuration nanometer additive through centrifugal and dry operating process, or without process, and direct as unstressed configuration nanometer additive in the form of an emulsion.
Embodiment 4
First seed is synthesized, 0.1g (NH 4) 2s 2o 8join in 100mL distilled water with 0.4g aqueous methylamine solution, logical argon gas after it dissolves also heats, when temperature reaches 60 DEG C, add 20mL methyl methacrylate and 5mL FUMARIC ACID TECH GRADE methyl esters, after reacting 2h under agitation condition, namely obtain the emulsion of polymer nano-particle, be then cooled to room temperature.In above-mentioned emulsion, add 20mL methyl methacrylate 10mL FUMARIC ACID TECH GRADE, after making it mutually be total to 0.2h, add 0.1g (NH 4) 2s 2o 8with 0.4g aqueous methylamine solution, react 4h under ar gas environment, stirring and 60 DEG C of conditions after, namely emulsion obtains unstressed configuration nanometer additive through centrifugal and dry operating process, or without process, and direct as unstressed configuration nanometer additive in the form of an emulsion.
Embodiment 5
First seed is synthesized, 0.3g Diisopropyl azodicarboxylate joins in 100mL distilled water, logical nitrogen after it dissolves also heats, when temperature reaches 80 DEG C, add 5mL methyl acrylate and 1mL to methoxy styrene, after reacting 2h under agitation condition, namely obtain the emulsion of polymer nano-particle, be then cooled to room temperature.6mL methyl acrylate and 6mL vinylformic acid is added in above-mentioned emulsion, after making its 0.5h that mutually coexists, add 0.2g Diisopropyl azodicarboxylate, react 3h under nitrogen environment, stirring and 80 DEG C of conditions after, namely emulsion obtains unstressed configuration nanometer additive through centrifugal and dry operating process, or without process, and direct as unstressed configuration nanometer additive in the form of an emulsion.
The method of the letex polymerization of copolymerization:
Embodiment 6
Under the condition that nitrogen protection is also stirred, by 8mL methyl acrylate, 4mL vinylformic acid, 100mL distilled water and 0.048gK 2s 2o 8join in the three-necked flask with prolong.Stirring reaction 3h when 70 DEG C.Namely reaction solution obtains novel unstressed configuration nanometer additive through centrifugal and dry operating process, also can without process, directly in the form of an emulsion as unstressed configuration nanometer additive.
Embodiment 7
Under the condition that argon shield is also stirred, by 10mL methyl methacrylate, 2mL ethyl propenoate, 3mL methacrylic acid, 3mL vinylformic acid, 100mL tap water, 0.1gK 2s 2o 8and 0.15gNaHSO 3join in the three-necked flask with prolong.Stirring reaction 4h when 60 DEG C.Namely reaction solution obtains novel unstressed configuration nanometer additive through centrifugal and dry operating process, also can without process, directly in the form of an emulsion as unstressed configuration nanometer additive.
Embodiment 8
Under the condition that nitrogen protection is also stirred, by 40mL methyl acrylate, 5mL maleic acid methyl esters, 15mL methacrylic acid, 5mL maleic acid, 100mL tap water, 0.1gK 2s 2o 8and 0.15gNaHSO 3join in the three-necked flask with prolong.Stirring reaction 4h when 60 DEG C.Namely reaction solution obtains novel unstressed configuration nanometer additive through centrifugal and dry operating process, also can without process, directly in the form of an emulsion as unstressed configuration nanometer additive.
2, the application case of unstressed configuration nanometer additive in drilling fluid field
Unstressed configuration nanometer additive is joined in base slurry, make the massfraction of the solid content of unstressed configuration nanometer additive be respectively 0.5%, 1% and 2%, after high speed agitator stirs 20min, survey its rheological parameter, middle pressure drop leak-off and extreme boundary lubrication coefficient.See the following form:
Note: AV--apparent viscosity; PV--plastic viscosity; Y--yield value; FL aPI--middle press filtration vector.Base is starched: join in 400mL water by 16g In Xiazijie Region, xinjiang swelling sodium soil and 0.8g anhydrous sodium carbonate, high-speed stirring 20min, static aquation 24h.
As can be seen from the above table, the rheology impact of this kind of nanometer additive to drilling fluid is less; And there is good filtrate reducing effect, come compared with base slurry, leak-off reduced rate can reach 62%, the fluid loss that can significantly reduce drilling fluid and also the mud cake formed thin and fine and close, all illustrate that novel nano treatment agent serves good filtrate reducing effect above; Compared with starching with base, its extreme boundary lubrication coefficient can reduce by more than 65%, and this illustrates that this nano material can be adsorbed onto on metallic surface preferably, reduces the friction between metal and metal, serve the effect of good extreme boundary lubrication, be applicable to being applied in horizontal well and extended reach well.
In addition, add the base slurry of the treatment agent synthesized by embodiment 1 of massfraction 1%, at 220 DEG C, heat rolls 16h, and High Temperature High Pressure (180 DEG C, 3.5MPa, 30min) filtrate reducing amount is less than 35mL, illustrates that this type for the treatment of agent also has good high temperature resistance effect; Such treatment agent obviously can suppress the hydration swelling of mud shale, and add the aqueous solution of the treatment agent synthesized by embodiment 1 of massfraction 1% compared with clear water, rate of expansion reduced rate can reach 70%.
In sum, such treatment agent has the multiple performances such as outstanding filtrate reducing, extreme boundary lubrication and suppression, and has no significant effect the rheological of drilling fluid, reaches the multi-functional object of potion.
Unstressed configuration nanometer additive of the present invention is from the appearance the pulverulent solids of white.From scanning electron microscope data, the product of synthesis is spherical (see figure 1), and particle diameter is comparatively homogeneous, and size is at about 380nm; Zeta electric potential characterization result shows, and its surface is with negative charge.And this kind of nano material has the structure (see Fig. 2) of similar nucleocapsid.
The present invention in drilling fluid field, improves the over-all properties of drilling fluid the Application of micron of modification.Specifically, utilize the functional group of nano-material surface that nano material is better disperseed in aqueous, and the surface functional group of nano material can with clay-phase mutual effect, play the protective colloid effect to clay; Utilize the characteristic of the small size of nano material and strong absorption to block the duct of Nano grade, and be adsorbed in duct, near opening of the channel, form crane span structure, form fine and close mud cake outward at opening of the channel, play the effect of shutoff and filtrate reducing; Utilize " micro-bearing " principle and the surface adsorption characteristic of nanometer, improve the lubricant effect of drilling fluid; The Specific Heat Capacity utilizing nano material large is to improve the thermostability of drilling fluid.Finally reach the multi-functional object of potion.
In sum, content of the present invention is not limited in the above-described embodiment, and the knowledgeable people in same area can propose other embodiment easily within technical director's thought of the present invention, but this embodiment all comprises within the scope of the present invention.

Claims (4)

1. the drilling fluid preparation method of unstressed configuration nanometer additive, it is characterized in that, adopt the non-water-soluble monomer of at least one and at least one water-soluble monomer, under non-oxygen atmosphere, adopt the method synthesis of letex polymerization, the Nano grade of nanometer additive is 10nm-5000nm, and its surface, containing having carboxylic acid group or carboxylate radical hydrophilic radical, has the structure of nucleocapsid;
Described letex polymerization is seeded emulsion polymerization method, comprises the following steps:
(1) synthesis of nano seed emulsion, adopt at least one non-water soluble monomers, under the condition that non-oxygen atmosphere also stirs, be that the mode that solvent adopts free radical to cause synthesizes nanometer seed with water, temperature of reaction is 20-96 DEG C, time 0.05-2 hour, the massfraction of initiator is 0.005%-3%, and the total mass mark of monomer is between 0.1%-50%;
(2) then at least one is joined in nanometer seed emulsion with the monomer of carboxylic acid group or carboxylate radical and at least one non-water soluble monomers, make its 0-2 hour that coexists, again non-oxygen atmosphere and stir condition under, the mode adopting free radical to cause reacts 0.1-4 hour, i.e. synthesis of nano additive for drilling fluid, the massfraction of initiator is 0.005%-3%; Temperature of reaction is 20-96 DEG C, and the total mass mark of monomer is between 0.2%-70%, and the total mass mark of described monomer refers to the summation of non-water soluble monomers and water-soluble monomer in step (1), (2);
Described non-water soluble monomers is the monomer of following structure:
R 1for the saturated alkane substituting group of H or 1-4 carbon; R 2for the alkane substituting group of 1-5 carbon; X is O or S; Or
Described non-water soluble monomers is the monomer of following structure:
R 1for the alkane substituting group of 1-5 carbon; R 2for the alkane substituting group of 1-5 carbon; X is O or S; Y is O or S; The configuration of alkene is cis or trans; Or
Described non-water soluble monomers be vinylbenzene, p-methylstyrene, to the one in methoxy styrene;
Described water-soluble monomer is the monomer of following structure:
R 1for the saturated alkane substituting group of H or 1-4 carbon; M is H, basic metal or amido; Or
Described water-soluble monomer is the monomer of following structure:
M is H, basic metal or amido; The configuration of alkene is cis or trans.
2. the drilling fluid preparation method of unstressed configuration nanometer additive, it is characterized in that, adopt the non-water-soluble monomer of at least one and at least one water-soluble monomer, under non-oxygen atmosphere, adopt the method synthesis of letex polymerization, the Nano grade of nanometer additive is 10nm-5000nm, and its surface, containing having carboxylic acid group or carboxylate radical hydrophilic radical, has the structure of nucleocapsid;
Described letex polymerization is the method for emulsion copolymerization, comprise the following steps: at least one is added to the water with the water-soluble monomer of carboxylate radical or carboxylic acid group and at least one non-water soluble monomers, under the condition that non-oxygen atmosphere also stirs, the mode adopting free radical to cause reacts 0.1-8 hour, namely synthesize nano-drilling fluid treating agent, the massfraction of initiator is 0.005%-3%; Temperature of reaction is 20-96 DEG C, and the massfraction of non-water soluble monomers is between 0.1%-50%; The massfraction of water-soluble monomer is between 0.1%-30%;
Described non-water soluble monomers is the monomer of following structure:
R 1for the saturated alkane substituting group of H or 1-4 carbon; R 2for the alkane substituting group of 1-5 carbon; X is O or S; Or
Described non-water soluble monomers is the monomer of following structure:
R 1for the alkane substituting group of 1-5 carbon; R 2for the alkane substituting group of 1-5 carbon; X is O or S; Y is O or S; The configuration of alkene is cis or trans; Or
Described non-water soluble monomers be vinylbenzene, p-methylstyrene, to the one in methoxy styrene;
Described water-soluble monomer is the monomer of following structure:
R 1for the saturated alkane substituting group of H or 1-4 carbon; M is H, basic metal or amido; Or
Described water-soluble monomer is the monomer of following structure:
M is H, basic metal or amido; The configuration of alkene is cis or trans.
3. the preparation method of drilling fluid unstressed configuration nanometer additive according to claim 1 and 2, is characterized in that, described radical initiator is Diisopropyl azodicarboxylate, azo-bis-isobutyrate hydrochloride, dibenzoyl peroxide, Na 2s 2o 8, K 2s 2o 8, (NH 4) 2s 2o 8, Na 2s 2o 8/ NaHSO 3, K 2s 2o 8/ NaHSO 3, (NH 4) 2s 2o 8/ NaHSO 3, Na 2s 2o 8/ FeSO 4, K 2s 2o 8/ FeSO 4, (NH 4) 2s 2o 8/ FeSO 4, Na 2s 2o 8/ Na 2s 2o 3, K 2s 2o 8/ Na 2s 2o 3, (NH 4) 2s 2o 8/ Na 2s 2o 3, Na 2s 2o 8/ Na 2sO 3, K 2s 2o 8/ Na 2sO 3, (NH 4) 2s 2o 8/ Na 2sO 3, Na 2s 2o 8/ aliphatic amide, K 2s 2o 8/ aliphatic amide, (NH 4) 2s 2o 8one in/aliphatic amide, described aliphatic amide is RNH 2, R 2nH, R 3n, R are the alkyl of 1-8 carbon.
4. the unstressed configuration nanometer additive of drilling fluid prepared of a method as claimed in claim 1 or 2.
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