Lubricant for drilling fluids composition and preparation method thereof and water-base drilling fluid and its application
Technical field
The invention belongs to drilling liquid technology fields in oil and natural gas industry, are related to a kind of lubricant for drilling fluids combination
Object and preparation method thereof and water-base drilling fluid and its application.
Background technique
It is well known that the greasy property of drilling fluid is very big to drilling well work influence in oil field development industry, it is accordingly used in
Lubricant in drilling fluid, it is desirable that drilling fluid can be enable to reduce torque, abrasion and the fatigue of drilling tool, extend making for bit bearing
With the service life, while adherency bit freezing is prevented, reduces balled bit etc..Many classes can be divided into for lubricant for drilling fluid, there are mineral
Oils also has animals and plants oils.Wherein mineral oils lubricant due to environmental pollution it is bigger, and fluorescence grade is high, right
It the analysis of geologic data and is affected, gradually loses competitive advantage.And animals and plants oils has lower fluorescence grade, it is good
Good greasy property, it is biodegradable, therefore developing vegetable oil as lubricant base oil is green lubricants research
Main trend.
However, the lubricant of most of animals and plants oils does not have characteristic resistant to high temperature at present, once encounter high temperature and pressure
The case where will degrade so that greasy property reduce, cause the greasy property of drilling fluid to be not enough to reach above-mentioned requirements.Together
When, some drilling fluid vegetable oil lubricating agents do not have good wear-resistant, antifriction quality although having characteristic resistant to high temperature again
Energy.
In view of the above-mentioned problems, having to be developed a kind of while there is favorable lubricating property, also there is high temperature resistant, wear-resistant, easy
The good environmentally-friendly lubricant for drilling fluid of degradation, cloud point stability.
Summary of the invention
It is resistant to high temperature the purpose of the invention is to overcome the lubricant of animals and plants oils of the existing technology not have
Though the lubricant of defect or animals and plants oils has characteristic resistant to high temperature, but does not have wear-resistant, antifriction performance well
Defect, and provide a kind of lubricant for drilling fluids composition and preparation method thereof and water-base drilling fluid and its application.The present invention mentions
The lubricant for drilling fluids composition of confession, introduces capsule grain, is not affected by high temperatures it in drilling fluid, and degradable, cloud point is steady
It is qualitative good, it is small on the influence of the rheological property of drill-in fluid, drilling fluid lubricating performance requirement can be better adapted to.
To achieve the goals above, first aspect present invention provides a kind of lubricant for drilling fluids composition, wherein should
Lubricant compositions contain modified vegetable oil, biodiesel, capsule grain, the first dispersing agent, extreme pressure anti-wear additives and defoaming agent;Wherein,
The capsule grain includes intracapsular material and the capsule casing material that is coated on outside the intracapsular material, and the capsule casing material is phenolic resin,
The intracapsular material contains sulfonated polyimide, water and the second dispersing agent.
Second aspect of the present invention provides a kind of preparation method of aforementioned lubricant for drilling fluids composition,
In, this method comprises: under agitation, modified vegetable oil and biodiesel are carried out first and are mixed, then successively with capsule
Grain, the first dispersing agent and extreme pressure anti-wear additives carry out second and are mixed, then carry out third mixing with defoaming agent.
Third aspect present invention provides a kind of water-base drilling fluid, wherein the water-base drilling fluid contains the aforementioned profit
The lubricant compositions that lubricant composition or the aforementioned preparation method are prepared.
Fourth aspect present invention provides the aforementioned water-base drilling fluid of one kind in oil and gas well drilling construction
Using.
Through the above technical solutions, compared with prior art, the present invention has following spy using technical solution of the present invention
Point:
(1) lubricant for drilling fluid of the invention is the compound good with biological degradabilities such as biodiesel, modified vegetable oils
Based on oil, capsule grain is added, extreme pressure anti-wear additives, the first dispersing agent and defoaming agent reconcile, there is excellent abrasion resistance
And biological degradability, the other performance of drilling fluid, such as viscosity, fluid loss are had not significant impact, they are a kind of environmentally friendly
Lubricant for drilling fluid.
(2) present invention significantly improves its oxidation stability and greasy property by carrying out chemical modification to vegetable oil, former
Expect abundance, environment is absolutely not polluted, to no damage to human body, excellent lubricating properties.
(3) capsule grain is the phenolic resin in the pan coating nanoscale thickness of sulfonated polyimide as cyst wall in the present invention,
Microencapsulation structure is formed, is introduced into lubricant system, is not affected by high temperatures as speciality polymer, it is degradable, and pass through sulphur
Change to stablize cloud point, to better adapt to the needs of drilling fluid, thus solve existing lubricant for drilling fluid cause serious pollution to the environment,
Fluorescence grade is high, it is unstable to be not easy biological degradation, higher cost, poor high temperature stability, cloud point, and most of product is in drilling well
There is the problems such as thickening, blistering in liquid.
(4) lubricant for drilling fluid of the present invention passes through the weight proportion of strict control different additive, so that between additive
It is able to interact to have played best effect in the lubricant, and then ensure that the good greasy property of drilling fluid, have
Effect reduces the torque and frictional resistance in drilling process, reaches protection surface of drill stem, extends the purpose of drilling tool service life, and
It is still able to maintain good lubricity at high temperature under high pressure, and there is excellent wear-resistant, antifriction performance, to the rheological characteristic of drill-in fluid
Energy influence is small, has a good application prospect.
Specific embodiment
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
First aspect present invention provides a kind of lubricant for drilling fluids composition, wherein the lubricant compositions contain
Modified vegetable oil, biodiesel, capsule grain, the first dispersing agent, extreme pressure anti-wear additives and defoaming agent;Wherein, the capsule grain includes intracapsular
Material and the capsule casing material being coated on outside the intracapsular material, the capsule casing material are phenolic resin, and the intracapsular material contains
Sulfonated polyimide, water and the second dispersing agent.
In the present invention, the lubricant for drilling fluids composition contains above-mentioned each component, the profit enabled to
Lubrication prescription has excellent abrasion resistance and biological degradability, is a kind of environmental-friendly type drilling liquid lubricant.
According to the present invention, although the lubricant for drilling fluids composition can obtain as long as containing above-mentioned each component
Good effect is obtained, still, in the present invention, by the content of each component of strict control, so that being able between each component
Interaction ensure that the good greasy property of drilling fluid to have played best effect in the lubricant, effectively drop
Torque and frictional resistance in low drilling process reach protection surface of drill stem, extend the purpose of drilling tool service life, and in height
Still it is able to maintain good lubricity under warm high pressure, and there is excellent wear-resistant, antifriction performance, to the rheological property shadow of drill-in fluid
Sound is small.Therefore, in the lubricant compositions, the modified vegetable oil, the biodiesel, the capsule grain, the extreme pressure
The weight ratio of antiwear additive, first dispersing agent and the defoaming agent is (20-50): (30-60): (5-16): (4-8): (1-
5): (3-10);Preferably, the modified vegetable oil, the biodiesel, the capsule grain, the extreme pressure anti-wear additives, described first
The weight ratio of dispersing agent and the defoaming agent is (20-50): (30-60): (5-16): (4-8): 3:(3-10) when, effect is more preferable.
It is a kind of lubricant for drilling fluids combination containing the capsule grain that softgel shell is phenolic resin provided by according to the present invention
Object, wherein the capsule casing material with a thickness of 1-100nm, preferably 20-60nm;Preferably, sulfonation is poly- in the intracapsular material
The weight ratio of acid imide and the capsule casing material is (4-6): 1;That is, in the present invention, capsule grain can be microcapsules knot
Structure, as phenolic resin are coated with sulfonated polyimide microcapsules, be sulfonated polyimide pan coating nanoscale it is thick (usually
1-100nm thickness) phenolic resin as cyst wall, that is, use microwave curing method make the surface coated of sulfonated polyimide
The rapid film-forming of phenolic resin forms microencapsulation structure, is introduced into lubricant system, is not affected by high temperatures as capsule grain,
It is degradable, and cloud point is stablized by sulfonation, to better adapt to the needs of drilling fluid.
According to the present invention, the partial size of the capsule grain can be 5-10 μm.
According to the present invention, the sulfonated polyimide is the sulfonated polyimide polymerization that the structural unit shown in Formulas I forms
Object,
Wherein, X1Refer to that a kind of residue, structural formula are formula (II) shown,
Wherein, Ar1It is a kind of sulfonated diamine residue, structural formula is formula (III) shown,
In the present invention, the value of weight average molecular weight is not particularly limited, and can be more wide in range value, for example, can be 1
Ten thousand-50 ten thousand, preferably 50,000-10 ten thousand.
In the present invention, the sulfonated polyimide can be prepared by the following method:
Sulfonated diamine and tertiary amine are dissolved in the phenol solvent of nitrogen protection, double naphthalene dianhydrides and catalyst are added;First rise
Temperature is to 60-100 DEG C of reaction 1-24h, then is warming up to 160-200 DEG C the reaction was continued 4-48h, and solution poured into precipitating reagent after cooling
In, it is washed after collecting precipitating, it is dry, obtain sulfonated polyimide polymer.
Wherein, the phenol solvent can be one of phenol, metacresol, cresols and parachlorphenol or a variety of;Institute
Stating catalyst can be bis- for zinc chloride, benzoic acid, isoquinolin, quinoline, triethylene diamine, benzyltrimethylammonium hydroxide and 1,8-
One of dimethylamino naphthalene is a variety of;The precipitating reagent can be one of acetone, methanol, ethyl alcohol and isopropanol or more
Kind.
Wherein, the tertiary amine can be one of triethylamine, Tri-n-Propylamine and tri-n-butylamine or a variety of, preferable case
Under, the ratio between amount of substance of tertiary amine and sulfonated diamine is (2-3): 1.
According to the present invention, the capsule grain preparation method the following steps are included:
(a) sulfonated polyimide, water and the second dispersing agent sonic oscillation are obtained into dispersion liquid;
(b) phenolic resin prepolymer and the dispersion liquid are mixed, then carry out microwave curing.
In step (a), it is sub- that sulfonation polyamides can be added in the mulser equipped with supersonic wave cleaning machine and blender
Amine, water and the second dispersing agent, supersonic oscillations, wherein the sonic oscillation can carry out at room temperature, for example, temperature is 18-
25 DEG C, the supersonic oscillations time can be 20-45min, disperse sulfonated polyimide in water;Preferably, sulfonation polyamides is sub-
The mass ratio of the dosage of amine, water and the second dispersing agent is (2-3): (10-15): 1.In addition, second dispersing agent can be ten
Dialkyl benzene sulfonic acids sodium, sodium dodecyl benzene sulfonate, SPAN 80, sldium lauryl sulfate, two
One of octyl sodium sulfosuccinate, sodium glycocholate, benzalkonium chloride, benzalkonium bromide and lecithin are a variety of;In the present invention,
Second dispersing agent can be commercially available, for example, Suzhou high energy fine chemistry industry Science and Technology Ltd., type can be purchased from
It number for example can be SDBS.
In step (b), phenolic resin prepolymer is then added, wherein the concentration of phenolic resin prepolymer in water can
Think 0.1-0.16g/ml;Preferably, phenolic resin prepolymer is thermosetting-resoles;Then in 500-800r/min
Revolving speed under stir 4-6min after, by microwave radiation device microwave curing effect solidified, wherein the microwave curing
Condition include: the power of the microwave radiation device be 480-520W, time 10-15min, form fine and close phenolic aldehyde tree
Adipose membrane is coated on sulfonated polyimide surface, is filtered, washed, is dried, and phenolic resin is made and is coated with the micro- glue of sulfonated polyimide
Capsule, that is, the capsule grain of microcapsule structure.
According to the present invention, the modified vegetable oil may include epoxy-modified vegetable oil and/or organic-silicon-modified vegetable oil;
Preferably, when the modified vegetable oil includes epoxy-modified vegetable oil and organic-silicon-modified vegetable oil, the epoxy-modified plant
The weight ratio of the content of object oil and the organic-silicon-modified vegetable oil is 1:(0.5-3);
Preferably, the epoxy-modified vegetable oil is epoxy-modified rapeseed oil;
Preferably, the organic-silicon-modified vegetable oil is organic-silicon-modified rapeseed oil.
According to the present invention, the preparation of the epoxy-modified rapeseed oil may comprise steps of:
(1) potassium hydroxide methanol solution is added dropwise in rapeseed oil and carries out the first reaction;
(2) existing for the catalyst under the conditions of, by H2O2Solution is added dropwise to the fatty acid methyl ester and acetic acid that step (1) obtains
Mixture in carry out epoxidation reaction.
In step (1), rapeseed oil is added in reactor, potassium hydroxide methanol solution is then added dropwise, in 60- after dripping off
1-1.5h is reacted at 70 DEG C, is washed after reaction to neutrality, is removed water drying, obtain fatty acid methyl ester;
Preferably, the mass concentration of potassium hydroxide methanol solution is 6-8 mass %;
Preferably, the mass ratio of the dosage of potassium hydroxide methanol solution and the rapeseed oil is 1:(2-4).
In step (2), fatty acid methyl ester, acetic acid and catalyst storng-acid cation exchange resin at 60-70 DEG C
H is added dropwise in mixture2O2Solution drips off rear insulation reaction 2-4h, is washed after reaction to neutrality, removes water drying, obtain ring
Oxygen modified colza;
Preferably, H2O2Molar ratio with the dosage of acetic acid is (1-1.2): 1;
Preferably, relative to the acetic acid of 12-15mL, the dosage of fatty acid methyl ester is 8-12g;In more preferable situation, relatively
In the acetic acid of 12mL, the dosage of fatty acid methyl ester is 8-12g;
Preferably, the catalyst is storng-acid cation exchange resin;It is highly preferred that with the total weight of fatty acid methyl ester
On the basis of, the dosage of the catalyst is 3-5 weight %, and the strong acidic ion resin is the examination of Chinese medicines group chemistry
The 732# cation exchange resin of agent Co., Ltd production.
According to the present invention, the preparation method of the organic-silicon-modified rapeseed oil may comprise steps of:
(1) potassium hydroxide methanol solution is added dropwise in rapeseed oil and carries out the first reaction;
(2) existing for the catalyst under the conditions of, by H2O2Solution is added dropwise to the fatty acid methyl ester and acetic acid that step (1) obtains
Mixture in carry out epoxidation reaction;
(3) acetic acid is added dropwise to progress third reaction in the epoxy-modified rapeseed oil that step (2) obtains;
(4) under conditions of ice-water bath and nitrogen protection, the pure and mild triethylamine of rapeseed oil that step (3) obtains is added dropwise to three
The 4th reaction is carried out in the diethyl ether solution of methyl chloride SiClx.
Wherein, step (1) and (2) are as previously mentioned, details are not described herein.
In step (3), acetic acid is added dropwise into epoxy-modified rapeseed oil at 50-60 DEG C, drips off rear insulation reaction 2-3h,
It is washed after reaction to neutrality, removes water drying, obtain vegetable seed oleyl alcohol;
Preferably, relative to the acetic acid of 2-4mL, the dosage of the epoxy-modified rapeseed oil is 10-15g;It is highly preferred that phase
For the acetic acid of 2mL, the dosage of the epoxy-modified rapeseed oil is 10-15g.
In step (4), trimethylsilyl chloride is dissolved in the diethyl ether solution that trimethylsilyl chloride is obtained in anhydrous ether,
Under conditions of ice-water bath and nitrogen protection, into the diethyl ether solution of trimethylsilyl chloride be added dropwise vegetable seed oleyl alcohol diethyl ether solution and
Triethylamine is washed after reaction in 36-40 DEG C of reaction 1-3h after dripping off to neutrality, after revolving removes solvent and is dried in vacuo,
Obtain organic-silicon-modified rapeseed oil.
Preferably, relative to the ether of 10mL, the dosage of trimethylsilyl chloride is 2.4-2.8mL, and the dosage of triethylamine is
5.6-5.8mL。
In the present invention, the rapeseed oil can be non-transgenic rapeseed oil, level-one squeezing.
In the present invention, the molar ratio of the trimethylsilyl chloride and vegetable seed oleyl alcohol can be 1:1.
According to the present invention, used modified vegetable oil has lower fluorescence grade, and good greasy property is gone back simultaneously
It is biodegradable, therefore can avoid lubricant and pollute the environment.
According to the present invention, the biodiesel is also known as fatty acid methyl ester, by with oil crops, Wild oil plant and work
The water plants such as Cheng Weizao grease and animal fat, food garbage oil etc. are feedstock oil, are being catalyzed with alcohol (usually methanol)
There are under type ester exchange reactions for agent, generate long chain fatty acids monoalkyl ester, have good lubricity.Biodiesel sulfur content
Low, biological degradability is good, and the biological degradability of biodiesel is up to 98%, and degradation cycle is short, and degradation rate is ordinary diesel oil
Twice, pollution when can mitigate accidental release significantly to environment, is a kind of base oil of environment-friendly type, and therefore, biodiesel can be with
The pollution to environment is reduced as the base oil of lubricant for drilling fluid to reduce the use of mineral type lubricating oil.In the present invention
In, the biodiesel can be commercially available, for example, Henan Tianguan Enterprise Group Co, model can be purchased from
For BioDiesel.And the parameter of the biodiesel are as follows: flash-point is 130-150 DEG C, and at a temperature of 40 DEG C, kinematic viscosity is
1.9-6.0mm2/s。
According to the present invention, first dispersing agent be octyl phenol polyoxyethylene ether, low nitrogen type polyisobutene succinimide,
One of boronation polyisobutene succinimide, alkyl phenol polyoxyethylene ether and sorbitan ester are a variety of;In the present invention
In, first dispersing agent is limited to above range, can effectively ensure that can be uniformly mixed between each component, will not go out
The phenomenon that now reuniting is to influence lubricant properties.In the present invention, first dispersing agent can be commercially available, example
Such as, the prosperous blue star Science and Technology Ltd. in Xingtai, model NP-15 can be purchased from.
According to the present invention, the extreme pressure anti-wear additives are one of kodalk, potassium metaborate and three potassium borates or a variety of;
In the present invention, the extreme pressure anti-wear additives are limited to above range, enable to lubricant that there is good wear-resistant, antifriction quality
Energy.In the present invention, the extreme pressure anti-wear additives can be commercially available, for example, can be purchased from the good boat chemical products in Zhengzhou
Co., Ltd, model 325PPSN.
According to the present invention, the defoaming agent is silicone emulsion, polyoxyethylene polyoxypropylene pentaerythrite ether, polyoxyethylene gather
One of oxygen propyl alcohol amidogen ether, polypropylene glycerol aether, polyoxyethylene polyoxypropylene glycerin ether and dimethyl silicone polymer are more
Kind;In the present invention, the defoaming agent is limited to above range, can effectively inhibits the blistering of lubricant in use
Tendency, and generated foam is made to vanish rapidly.In the present invention, the defoaming agent can be commercially available, for example, can
To be purchased from Jiangsu Hai'an Petrochemical Plant, model DEFORM.
Second aspect of the present invention provides a kind of preparation method of aforementioned lubricant compositions, wherein this method
Include: under agitation, modified vegetable oil and biodiesel are carried out first and are mixed, then successively with capsule grain, first point
Powder and extreme pressure anti-wear additives carry out second and are mixed, then carry out third mixing with defoaming agent.
Preferably, it is 45-60 DEG C that the condition of the stirring, which includes: temperature, stirring rate 1500-2000r/min;
Preferably, it is described first be mixed condition include: the time be 1.5-2h;
Preferably, it is described second be mixed condition include: the time be 0.8-1.2h;
Preferably, the condition that the third is mixed include: be 0.8-1.2h the time.
The preparation method of a kind of water-base drilling fluid highly-efficient lubricant of a kind of preferred embodiment according to the present invention, should
Method the following steps are included:
Step (1): stock up by following components and parts by weight: 20-50 parts of modified vegetable oil, 30-60 parts of biodiesel,
4-8 parts of extreme pressure anti-wear additives, 5-16 parts of sulfonated polyimide microcapsules of phenolic resin coating, 1-5 parts of dispersing agent and defoaming agent 3-
10 parts;
Step (2): modified vegetable oil, biodiesel are added in stirred tank by weight, are heated with stirring to 45-60
DEG C, then phenolic resin coating sulfonated polyimide microcapsules, dispersing agent, extreme pressure anti-wear additives are sequentially added by weight, continue to stir
0.8-1.2h is mixed, defoaming agent is added, continues to stir 0.8-1.2h, obtains water-base drilling fluid with lubricator.
Third aspect present invention provides a kind of water-base drilling fluid, wherein the water-base drilling fluid contains the aforementioned profit
The lubricant compositions that lubricant composition or the aforementioned preparation method are prepared.
According to the present invention, cost is relatively low, simple process for lubricant compositions (lubricant) provided by the present invention.According to brill
Well liquid type and drilled strata lithological characteristic, on the basis of the total weight of the water-base drilling fluid of 100mL, the lubricant group
The dosage for closing object can be 0.8-2.4 weight %.
According to the present invention, which can contain bentonite slurry, tackifier, fluid loss additive, inhibitor, sodium chloride
Close barite, also, in the present invention, it is preferred in the case of, in the water-base drilling fluid test base slurry formula be 2% bentonite slurry
+ 10% sodium chloride+300g barite of+3% inhibitor of+2.0% fluid loss additive of+0.3% tackifier.
Fourth aspect present invention provides the aforementioned water-base drilling fluid of one kind in oil and gas well drilling construction
Using.Under preferable case, application of the water-base drilling fluid in the wellbore construction of extended reach well KT-1 well.
Lubricant for drilling fluids composition provided by the invention, introduces capsule grain, makes it in drilling fluid not by high temperature shadow
It rings, degradable, cloud point stability is good, and small on the influence of the rheological property of drill-in fluid, can better adapt to drilling fluid lubricating performance needs
It asks.
The present invention will be described in detail by way of examples below.
In following embodiment and comparative example:
(1) method according to specified in standard GB/T/T16783.1-2006 and SY/T6094-94 measures apparent viscosity
(AV), plastic viscosity (PV), yield value (YP) and extreme boundary lubrication coefficient.
Wherein, in the present invention, apparent viscosity (AV) is a physical concept, refers under certain speed gradient, uses phase
The shear stress answered only is made one to mobility quality and opposite is substantially compared divided by the resulting quotient of shear rate.Plasticity
Viscosity (PV) characterizes the complexity that the static rear colloid system of mud is destroyed.Yield value (YP) is that reflection drilling fluid exists
The intensity of inside gel networks, also referred to as yield value when flowing.
(2) environmental-protecting performance test (fluorescence property test)
According to QCNPC 88-2003 drilling fluid fluid lubricant technical requirements, fluorescence property test is carried out.
(3) Luminous bacteria is used, bio-toxicity EC50 test is carried out
EC50, half-maximal effect concentration (concentration for 50%of maximal effect, EC50) refers to
It can cause the concentration of 50% ceiling effect.EC50It is drug safety index.It is meant that: causing the 50% effective drug of individual
Concentration.LD50/ED50、TD50/ED50、TC50/EC50It is the safety index of a kind of drug etc. being referred to as therapeutic index, its usual value
More bigger, safer.
Embodiment 1
The present embodiment prepares lubricant compositions and water-base drilling fluid using method of the invention for illustrating.
The present embodiment lubricant compositions include following components and parts by weight: 32 parts by weight of modified vegetable oil, biodiesel
45 parts by weight, 6 parts by weight of extreme pressure anti-wear additives, phenolic resin are coated with sulfonated polyimide microcapsules (capsule grain) 9 parts by weight, first point
7 parts by weight of 3 parts by weight of powder and defoaming agent.
Wherein, modified vegetable oil is epoxy-modified rapeseed oil, and the preparation method of the epoxy-modified rapeseed oil includes following step
It is rapid:
Step (A): rapeseed oil 18g is added in reactor, and the methanolic potassium hydroxide that 6g mass concentration 6% is then added dropwise is molten
Liquid, reacts 1h at 60 DEG C after dripping off, washed after reaction to neutrality, remove water drying, obtain fatty acid methyl ester;
Step (B): to 10g fatty acid methyl ester, 15mL acetic acid and catalyst storng-acid cation exchange resin at 60 DEG C
Mixture in H is added dropwise2O2Solution, wherein H2O2Molar ratio with acetic acid is 1.2:1, drips off rear insulation reaction 3h, reaction terminates
After wash to neutrality, remove water drying, obtain epoxy-modified rapeseed oil.
Wherein, rapeseed oil is non-transgenic rapeseed oil, level-one squeezing;The molar ratio of trimethylsilyl chloride and vegetable seed oleyl alcohol is
1:1;In epoxidation reaction the additive amount of catalyst be fatty acid methyl ester quality 4%, and the catalyst be highly acid sun from
Subtree rouge is the 732# cation exchange resin of Sinopharm Chemical Reagent Co., Ltd.'s production.
Wherein, capsule grain the preparation method comprises the following steps: in the mulser equipped with supersonic wave cleaning machine and blender, it is poly- that sulfonation is added
Acid imide, water and dispersing agent, supersonic oscillations 30min, disperse sulfonated polyimide in water;Then phenolic resin prepolymer is added
After polymers stirs 5min under the revolving speed of 600r/min, 10min is acted on by the microwave curing of microwave radiation device, is formed fine and close
Phenolic resin film be coated on sulfonated polyimide surface, be filtered, washed, dried, be made phenolic resin be coated with sulfonation polyamides
Imines microcapsules, that is, the capsule grain of microcapsule structure.
Wherein, the weight ratio of sulfonated polyimide and phenolic resin is in phenolic resin coating sulfonated polyimide microcapsules
The mass ratio of 4:1, sulfonated polyimide, water and dispersing agent are 3:10:1, and the concentration of phenolic resin prepolymer in water is
0.12g/mL, phenolic resin prepolymer are thermosetting-resoles, and the power of microwave radiation device is 480W, and dispersing agent is
Neopelex.
Wherein, sulfonated polyimide polymer the preparation method comprises the following steps:
Sulfonated diamine and tertiary amine are dissolved in the phenol solvent of nitrogen protection, double naphthalene dianhydrides and catalyst are added;First rise
Temperature is to 80 DEG C of reaction 10h, then is warming up to 180 DEG C the reaction was continued 12h, pours into solution in precipitating reagent after cooling, after collecting precipitating
It is washed, it is dry, obtain sulfonated polyimide polymer;
Wherein, sulfonated polyimide is the sulfonated polyimide polymer that the structural unit shown in formula (I) forms:
Wherein, X1For residue shown in formula (II);
Wherein, Ar1For sulfonated diamine residue shown in formula (III);
Wherein, the weight average molecular weight of sulfonated polyimide is 50,000.
Wherein, phenol solvent is phenol, and catalyst is zinc chloride, and precipitating reagent is acetone, methanol.Tertiary amine is triethylamine, and
The ratio between amount of substance of tertiary amine and sulfonated diamine is 2:1.
Wherein, extreme pressure anti-wear additives are kodalk, and dispersing agent is sorbitan ester, and defoaming agent is polyoxyethylene polyoxy third
Alkene pentaerythrite ether.
The preparation method of the present embodiment water-base drilling fluid lubricant compositions includes:
Modified vegetable oil, biodiesel are added in stirred tank according to above-mentioned parts by weight, are heated with stirring to 52 DEG C, then press
Parts by weight sequentially add phenolic resin coating sulfonated polyimide microcapsules, the first dispersing agent, extreme pressure anti-wear additives, continue to stir
1h adds defoaming agent, continues to stir 1h, obtains water-base drilling fluid lubricant compositions, is labeled as S1.
Embodiment 2
The present embodiment prepares lubricant compositions and water-base drilling fluid using method of the invention for illustrating.
The present embodiment lubricant compositions include following components and parts by weight: 40 parts by weight of modified vegetable oil, biodiesel
50 parts by weight, 7 parts by weight of extreme pressure anti-wear additives, phenolic resin are coated with 12 parts by weight of sulfonated polyimide microcapsules, 4 weight of dispersing agent
Part and 8 parts by weight of defoaming agent.
Wherein, modified vegetable oil is epoxy-modified rapeseed oil, and the preparation method of the epoxy-modified rapeseed oil includes following step
It is rapid:
Step (A): rapeseed oil 16g is added in reactor, and the methanolic potassium hydroxide that 5g mass concentration 7% is then added dropwise is molten
Liquid, reacts 1.5h at 62 DEG C after dripping off, washed after reaction to neutrality, remove water drying, obtain fatty acid methyl ester;
Step (B): to 8g fatty acid methyl ester, 14mL acetic acid and catalyst storng-acid cation exchange resin at 62 DEG C
H is added dropwise in mixture2O2Solution, wherein H2O2Molar ratio with acetic acid is 1.1:1, drips off rear insulation reaction 4h, after reaction
Washing removes water drying, obtains epoxy-modified rapeseed oil to neutrality.
Wherein, rapeseed oil is non-transgenic rapeseed oil, level-one squeezing;The molar ratio of trimethylsilyl chloride and vegetable seed oleyl alcohol is
1:1;In epoxidation reaction the additive amount of catalyst be fatty acid methyl ester quality 3%, and the catalyst be highly acid sun from
Subtree rouge is the 732# cation exchange resin of Sinopharm Chemical Reagent Co., Ltd.'s production.
Wherein, capsule grain the preparation method comprises the following steps: in the mulser equipped with supersonic wave cleaning machine and blender, it is poly- that sulfonation is added
Acid imide, water and dispersing agent, supersonic oscillations 20min, disperse sulfonated polyimide in water;Then phenolic resin prepolymer is added
After polymers stirs 4min under the revolving speed of 500r/min, 12min is acted on by the microwave curing of microwave radiation device, is formed fine and close
Phenolic resin film be coated on sulfonated polyimide surface, be filtered, washed, dried, it is poly- to obtain phenolic resin coating sulfonation
Acid imide microcapsules, that is, the capsule grain of microcapsule structure.
Wherein, the weight ratio of sulfonated polyimide and phenolic resin is in phenolic resin coating sulfonated polyimide microcapsules
5:1, the mass ratio of sulfonated polyimide, water and dispersing agent are 2:12:1, and the concentration of phenolic resin prepolymer in water is 0.1g/
ML, phenolic resin prepolymer are thermosetting-resoles, and the power of microwave radiation device is 500W, and dispersing agent is dodecane
Base phenyl-hydrogen-sulfate sodium mixes in mass ratio for 1:2:1 with sldium lauryl sulfate, lecithin.
Wherein, sulfonated polyimide polymer the preparation method comprises the following steps:
Sulfonated diamine and tertiary amine are dissolved in the phenol solvent of nitrogen protection, double naphthalene dianhydrides and catalyst are added;First rise
Temperature is to 100 DEG C of reaction 1h, then is warming up to 200 DEG C the reaction was continued 4h, pours into precipitating reagent solution after cooling, passes through after collecting precipitating
Washing, it is dry, obtain sulfonated polyimide polymer;Wherein, sulfonated polyimide is what the structural unit shown in formula (I) formed
The weight average molecular weight of sulfonated polyimide polymer and sulfonated polyimide is 100,000.
Wherein, phenol solvent is metacresol, and catalyst is benzoic acid, and precipitating reagent is acetone, methanol and ethyl alcohol.Tertiary amine is three just
Propylamine, and the ratio between amount of substance of tertiary amine and sulfonated diamine is 2.5:1.
Wherein, extreme pressure anti-wear additives are potassium metaborate, and dispersing agent is boronation polyisobutene succinimide, and defoaming agent is polyoxy
Propylene glycerin ether.
The preparation method of the present embodiment water-base drilling fluid lubricant compositions includes:
Modified vegetable oil, biodiesel are added in stirred tank according to above-mentioned parts by weight, are heated with stirring to 45 DEG C, then press
Parts by weight sequentially add phenolic resin coating sulfonated polyimide microcapsules, the first dispersing agent, extreme pressure anti-wear additives, continue to stir
0.8h adds defoaming agent, continues to stir 0.8h, obtains water-base drilling fluid lubricant compositions, is labeled as S2.
Embodiment 3
The present embodiment prepares lubricant compositions and water-base drilling fluid using method of the invention for illustrating.
The present embodiment lubricant compositions include following components and parts by weight: 21 parts by weight of modified vegetable oil, biodiesel
34 parts by weight, 5 parts by weight of extreme pressure anti-wear additives, phenolic resin are coated with 6 parts by weight of sulfonated polyimide microcapsules, 2 weight of dispersing agent
Part and 4 parts by weight of defoaming agent.
Wherein, modified vegetable oil is epoxy-modified rapeseed oil, and the preparation method of the epoxy-modified rapeseed oil includes following step
It is rapid:
Step (A): rapeseed oil 20g is added in reactor, and the methanolic potassium hydroxide that 7g mass concentration 8% is then added dropwise is molten
Liquid, reacts 1h at 70 DEG C after dripping off, washed after reaction to neutrality, remove water drying, obtain fatty acid methyl ester;
Step (B): to 12g fatty acid methyl ester, 12mL acetic acid and catalyst storng-acid cation exchange resin at 70 DEG C
Mixture in H is added dropwise2O2Solution, wherein H2O2Molar ratio with acetic acid is 1:1, drips off rear insulation reaction 2h, after reaction
Washing removes water drying, obtains epoxy-modified rapeseed oil to neutrality.
Wherein, rapeseed oil is non-transgenic rapeseed oil, level-one squeezing;The molar ratio of trimethylsilyl chloride and vegetable seed oleyl alcohol is
1:1;In epoxidation reaction the additive amount of catalyst be fatty acid methyl ester quality 5%, and the catalyst be highly acid sun from
Subtree rouge is the 732# cation exchange resin of Sinopharm Chemical Reagent Co., Ltd.'s production.
Wherein, capsule grain the preparation method comprises the following steps: in the mulser equipped with supersonic wave cleaning machine and blender, it is poly- that sulfonation is added
Acid imide, water and dispersing agent, supersonic oscillations 35min, disperse sulfonated polyimide in water;Then phenolic resin prepolymer is added
After polymers stirs 5min under the revolving speed of 600r/min, 15min is acted on by the microwave curing of microwave radiation device, is formed fine and close
Phenolic resin film be coated on sulfonated polyimide surface, be filtered, washed, dried, it is poly- to obtain phenolic resin coating sulfonation
Acid imide microcapsules, that is, the capsule grain of microcapsule structure.
Wherein, the weight ratio of sulfonated polyimide and phenolic resin is in phenolic resin coating sulfonated polyimide microcapsules
6:1, the mass ratio of sulfonated polyimide, water and dispersing agent are 2:12:1, and the concentration of phenolic resin prepolymer in water is 0.1g/
ML, phenolic resin prepolymer are thermosetting-resoles, and the power of microwave radiation device is 510W, and dispersing agent is glycocholic acid
Sodium mixes in mass ratio for 1:1:1 with sldium lauryl sulfate, lecithin.
Wherein, sulfonated polyimide polymer the preparation method comprises the following steps:
Sulfonated diamine and tertiary amine are dissolved in the phenol solvent of nitrogen protection, double naphthalene dianhydrides and catalyst are added;First rise
Temperature is to 95 DEG C of reaction 6h, then is warming up to 185 DEG C the reaction was continued 5h, pours into precipitating reagent solution after cooling, passes through after collecting precipitating
Washing, it is dry, obtain sulfonated polyimide polymer;Wherein, sulfonated polyimide is what the structural unit shown in formula (I) formed
The weight average molecular weight of sulfonated polyimide polymer and sulfonated polyimide is 10,000.
Wherein, it with cresols is that 1:2 is mixed that phenol solvent is benzoic acid in mass ratio, catalyst 1, the bis- diformazans of 8-
Amino naphthalenes, precipitating reagent are isopropanol.Tertiary amine is tri-n-butylamine, and the ratio between amount of substance of tertiary amine and sulfonated diamine is 3:1.
Wherein, extreme pressure anti-wear additives are three potassium borates, and dispersing agent is alkyl phenol polyoxyethylene ether, and defoaming agent is poly- for polyoxyethylene
Oxygen propyl alcohol amidogen ether.
The preparation method of the present embodiment water-base drilling fluid lubricant compositions includes:
Modified vegetable oil, biodiesel are added in stirred tank according to above-mentioned parts by weight, are heated with stirring to 58 DEG C, then press
Parts by weight sequentially add phenolic resin coating sulfonated polyimide microcapsules, the first dispersing agent, extreme pressure anti-wear additives, continue to stir
1.2h adds defoaming agent, continues to stir 1.2h, obtains water-base drilling fluid lubricant compositions, is labeled as S3.
Embodiment 4
The present embodiment prepares lubricant compositions and water-base drilling fluid using method of the invention for illustrating.
The present embodiment lubricant compositions include following components and parts by weight: 28 parts by weight of modified vegetable oil, biodiesel
46 parts by weight, 7 parts by weight of extreme pressure anti-wear additives, phenolic resin are coated with 10 parts by weight of sulfonated polyimide microcapsules, 4 weight of dispersing agent
Part and 8 parts by weight of defoaming agent.
Wherein, modified vegetable oil be organic-silicon-modified rapeseed oil, the preparation method of the organic-silicon-modified rapeseed oil include with
Lower step:
Step (A '): rapeseed oil 18g is added in reactor, and the methanolic potassium hydroxide of 6g mass concentration 7% is then added dropwise
Solution, reacts 1.2h at 65 DEG C after dripping off, washed after reaction to neutrality, remove water drying, obtain fatty acid methyl ester;
Step (B '): to 10g fatty acid methyl ester, 12mL acetic acid and catalyst storng-acid cation exchange resin at 65 DEG C
Mixture in H is added dropwise2O2Solution, wherein H2O2Molar ratio with acetic acid is 1.1:1, drips off rear insulation reaction 3h, reaction terminates
After wash to neutrality, remove water drying, obtain epoxy-modified rapeseed oil;
Step (C '): being added dropwise 3mL acetic acid into the epoxy-modified rapeseed oil of 12g at 55 DEG C, drip off rear insulation reaction 2.5h,
It is washed after reaction to neutrality, removes water drying, obtain vegetable seed oleyl alcohol;
2.6mL trimethylsilyl chloride: being dissolved in the diethyl ether solution that trimethylsilyl chloride is obtained in anhydrous ether by step (D '),
Under conditions of ice-water bath and nitrogen protection, into the diethyl ether solution of trimethylsilyl chloride be added dropwise vegetable seed oleyl alcohol diethyl ether solution with
And 5.7mL triethylamine is washed after reaction to neutrality, revolving removes solvent and is dried in vacuo in 38 DEG C of reaction 2h after dripping off
Afterwards, organic-silicon-modified rapeseed oil is obtained.
Wherein, rapeseed oil is non-transgenic rapeseed oil, level-one squeezing;The molar ratio of trimethylsilyl chloride and vegetable seed oleyl alcohol is
1:1;In epoxidation reaction the additive amount of catalyst be fatty acid methyl ester quality 4%, and the catalyst be highly acid sun from
Subtree rouge is the 732# cation exchange resin of Sinopharm Chemical Reagent Co., Ltd.'s production.
Wherein, capsule grain the preparation method comprises the following steps: in the mulser equipped with supersonic wave cleaning machine and blender, it is poly- that sulfonation is added
Acid imide, water and dispersing agent, supersonic oscillations 25min, disperse sulfonated polyimide in water;Then phenolic resin prepolymer is added
After polymers stirs 4min under the revolving speed of 800r/min, 12min is acted on by the microwave curing of microwave radiation device, is formed fine and close
Phenolic resin film be coated on sulfonated polyimide surface, be filtered, washed, dried, it is poly- to obtain phenolic resin coating sulfonation
Acid imide microcapsules.
Wherein, the weight ratio of sulfonated polyimide and phenolic resin is in phenolic resin coating sulfonated polyimide microcapsules
The mass ratio of 5:1, sulfonated polyimide, water and dispersing agent are 3:12:1, and the concentration of phenolic resin prepolymer in water is
0.14g/mL, phenolic resin prepolymer are thermosetting-resoles, and the power of microwave radiation device is 490W, and dispersing agent is
Dioctyl succinate disulfonate acid.
Wherein, sulfonated polyimide polymer the preparation method comprises the following steps:
Sulfonated diamine and tertiary amine are dissolved in the phenol solvent of nitrogen protection, double naphthalene dianhydrides and catalyst are added;First rise
Temperature for 24 hours, then is warming up to 160 DEG C the reaction was continued 48h to 60 DEG C of reactions, pours into solution in precipitating reagent after cooling, after collecting precipitating
It is washed, it is dry, obtain sulfonated polyimide polymer;Wherein, sulfonated polyimide is that the structural unit shown in formula (I) forms
Sulfonated polyimide polymer and sulfonated polyimide weight average molecular weight be 60,000.
Wherein, phenol solvent is parachlorphenol, and catalyst is benzyltrimethylammonium hydroxide, and precipitating reagent is isopropanol.Tertiary amine is
Tri-n-butylamine mixes in mass ratio for 2:1 with triethylamine, and the ratio between amount of substance of tertiary amine and sulfonated diamine is 3:1.
Wherein, extreme pressure anti-wear additives are three potassium borates, and dispersing agent is octyl phenol polyoxyethylene ether, and defoaming agent is silicone emulsion.
The preparation method of the present embodiment water-base drilling fluid lubricant compositions includes:
Modified vegetable oil, biodiesel are added in stirred tank according to above-mentioned parts by weight, are heated with stirring to 55 DEG C, then press
Parts by weight sequentially add phenolic resin coating sulfonated polyimide microcapsules, the first dispersing agent, extreme pressure anti-wear additives, continue to stir
1h adds defoaming agent, continues to stir 1h, obtains water-base drilling fluid lubricant compositions, is labeled as S4.
Embodiment 5
The present embodiment prepares lubricant compositions and water-base drilling fluid using method of the invention for illustrating.
The present embodiment lubricant compositions include following components and parts by weight: 42 parts by weight of modified vegetable oil, biodiesel
60 parts by weight, 8 parts by weight of extreme pressure anti-wear additives, phenolic resin are coated with 16 parts by weight of sulfonated polyimide microcapsules, 4 weight of dispersing agent
Part and 10 parts by weight of defoaming agent.
Wherein, modified vegetable oil be organic-silicon-modified rapeseed oil, the preparation method of the organic-silicon-modified rapeseed oil include with
Lower step:
Step (A '): rapeseed oil 16g is added in reactor, and the methanolic potassium hydroxide of 5g mass concentration 6% is then added dropwise
Solution, reacts 1.5h at 60 DEG C after dripping off, washed after reaction to neutrality, remove water drying, obtain fatty acid methyl ester;
Step (B '): to 8g fatty acid methyl ester, 14mL acetic acid and catalyst storng-acid cation exchange resin at 60 DEG C
Mixture in H is added dropwise2O2Solution, wherein H2O2Molar ratio with acetic acid is 1:1, drips off rear insulation reaction 4h, after reaction
Washing removes water drying, obtains epoxy-modified rapeseed oil to neutrality;
Step (C '): 2mL acetic acid is added dropwise into the epoxy-modified rapeseed oil of 10g at 50 DEG C, drips off rear insulation reaction 2h, instead
Washing removes water drying, obtains vegetable seed oleyl alcohol to neutrality after answering;
2.4mL trimethylsilyl chloride: being dissolved in the diethyl ether solution that trimethylsilyl chloride is obtained in anhydrous ether by step (D '),
Under conditions of ice-water bath and nitrogen protection, into the diethyl ether solution of trimethylsilyl chloride be added dropwise vegetable seed oleyl alcohol diethyl ether solution with
And 5.6mL triethylamine is washed after reaction to neutrality, revolving removes solvent and is dried in vacuo in 36 DEG C of reaction 3h after dripping off
Afterwards, organic-silicon-modified rapeseed oil is obtained.
Wherein, rapeseed oil is non-transgenic rapeseed oil, level-one squeezing;The molar ratio of trimethylsilyl chloride and vegetable seed oleyl alcohol is
1:1;In epoxidation reaction the additive amount of catalyst be fatty acid methyl ester quality 3%, and the catalyst be highly acid sun from
Subtree rouge is the 732# cation exchange resin of Sinopharm Chemical Reagent Co., Ltd.'s production.
Wherein, capsule grain the preparation method comprises the following steps: in the mulser equipped with supersonic wave cleaning machine and blender, it is poly- that sulfonation is added
Acid imide, water and dispersing agent, supersonic oscillations 36min, disperse sulfonated polyimide in water;Then phenolic resin prepolymer is added
After polymers stirs 4min under the revolving speed of 750r/min, 12min is acted on by the microwave curing of microwave radiation device, is formed fine and close
Phenolic resin film be coated on sulfonated polyimide surface, be filtered, washed, dried, it is poly- to obtain phenolic resin coating sulfonation
Acid imide microcapsules.
Wherein, the weight ratio of sulfonated polyimide and phenolic resin is in phenolic resin coating sulfonated polyimide microcapsules
The mass ratio of 4:1, sulfonated polyimide, water and dispersing agent are 2.5:15:1, and the concentration of phenolic resin prepolymer in water is
0.11g/mL, phenolic resin prepolymer are thermosetting-resoles, and the power of microwave radiation device is 500W, and dispersing agent is
SPAN 80.
Wherein, sulfonated polyimide polymer the preparation method comprises the following steps:
Sulfonated diamine and tertiary amine are dissolved in the phenol solvent of nitrogen protection, double naphthalene dianhydrides and catalyst are added;First rise
Temperature is to 78 DEG C of reaction 18h, then is warming up to 172 DEG C the reaction was continued 40h, pours into solution in precipitating reagent after cooling, after collecting precipitating
It is washed, it is dry, obtain sulfonated polyimide polymer;Wherein, sulfonated polyimide is that the structural unit shown in formula (I) forms
Sulfonated polyimide polymer and sulfonated polyimide weight average molecular weight be 70,000.
Wherein, phenol solvent is parachlorphenol, and catalyst is triethylene diamine, and precipitating reagent is acetone.Tertiary amine is tri-n-butylamine, and
And the ratio between amount of substance of tertiary amine and sulfonated diamine is 2:1.
Wherein, extreme pressure anti-wear additives are three potassium borates, and dispersing agent is low nitrogen type polyisobutene succinimide, and defoaming agent is poly-
Oxypropylene polyoxyethylene glycerol ether.
The preparation method of the present embodiment water-base drilling fluid lubricant compositions includes:
Modified vegetable oil, biodiesel are added in stirred tank according to above-mentioned parts by weight, are heated with stirring to 45 DEG C, then press
Parts by weight sequentially add phenolic resin coating sulfonated polyimide microcapsules, the first dispersing agent, extreme pressure anti-wear additives, continue to stir
1.2h adds defoaming agent, continues to stir 1.2h, obtains water-base drilling fluid lubricant compositions, is labeled as S5.
Embodiment 6
The present embodiment prepares lubricant compositions and water-base drilling fluid using method of the invention for illustrating.
The present embodiment lubricant compositions include following components and parts by weight: 50 parts by weight of modified vegetable oil, biodiesel
57 parts by weight, 6 parts by weight of extreme pressure anti-wear additives, phenolic resin are coated with 14 parts by weight of sulfonated polyimide microcapsules, 2 weight of dispersing agent
Part and 9 parts by weight of defoaming agent.
Wherein, modified vegetable oil be organic-silicon-modified rapeseed oil, the preparation method of the organic-silicon-modified rapeseed oil include with
Lower step:
Step (A '): rapeseed oil 20g is added in reactor, and the methanolic potassium hydroxide of 7g mass concentration 8% is then added dropwise
Solution, reacts 1h at 70 DEG C after dripping off, washed after reaction to neutrality, remove water drying, obtain fatty acid methyl ester;
Step (B '): to 12g fatty acid methyl ester, 15mL acetic acid and catalyst storng-acid cation exchange resin at 70 DEG C
Mixture in H is added dropwise2O2Solution, wherein H2O2Molar ratio with acetic acid is 1.2:1, drips off rear insulation reaction 2h, reaction terminates
After wash to neutrality, remove water drying, obtain epoxy-modified rapeseed oil;
Step (C '): 4mL acetic acid is added dropwise into the epoxy-modified rapeseed oil of 15g at 60 DEG C, drips off rear insulation reaction 3h, instead
Washing removes water drying, obtains vegetable seed oleyl alcohol to neutrality after answering;
2.8mL trimethylsilyl chloride: being dissolved in the diethyl ether solution that trimethylsilyl chloride is obtained in anhydrous ether by step (D '),
Under conditions of ice-water bath and nitrogen protection, into the diethyl ether solution of trimethylsilyl chloride be added dropwise vegetable seed oleyl alcohol diethyl ether solution with
And 5.8mL triethylamine is washed after reaction to neutrality, revolving removes solvent and is dried in vacuo in 40 DEG C of reaction 1h after dripping off
Afterwards, organic-silicon-modified rapeseed oil is obtained.
Wherein, rapeseed oil is non-transgenic rapeseed oil, level-one squeezing;The molar ratio of trimethylsilyl chloride and vegetable seed oleyl alcohol is
1:1;In epoxidation reaction the additive amount of catalyst be fatty acid methyl ester quality 5%, and the catalyst be highly acid sun from
Subtree rouge is the 732# cation exchange resin of Sinopharm Chemical Reagent Co., Ltd.'s production.
Wherein, capsule grain the preparation method comprises the following steps: in the mulser equipped with supersonic wave cleaning machine and blender, it is poly- that sulfonation is added
Acid imide, water and dispersing agent, supersonic oscillations 40min, disperse sulfonated polyimide in water;Then phenolic resin prepolymer is added
After polymers stirs 5min under the revolving speed of 640r/min, 15min is acted on by the microwave curing of microwave radiation device, is formed fine and close
Phenolic resin film be coated on sulfonated polyimide surface, be filtered, washed, dried, it is poly- to obtain phenolic resin coating sulfonation
Acid imide microcapsules.
Wherein, the weight ratio of sulfonated polyimide and phenolic resin is in phenolic resin coating sulfonated polyimide microcapsules
The mass ratio of 6:1, sulfonated polyimide, water and dispersing agent are 2:14:1, and the concentration of phenolic resin prepolymer in water is
0.16g/mL, phenolic resin prepolymer are thermosetting-resoles, and the power of microwave radiation device is 500W, and dispersing agent is
Benzalkonium chloride, benzalkonium bromide and sldium lauryl sulfate mix in mass ratio for 1:1:3.
Wherein, that the preparation method is the same as that of Example 1 is identical for sulfonated polyimide, and the sulfonated polyimide being prepared is by formula
(I) the sulfonated polyimide polymer of the composition of structural unit shown in and the weight average molecular weight of sulfonated polyimide are 80,000.
Wherein, extreme pressure anti-wear additives are three potassium borates, and dispersing agent is alkyl phenol polyoxyethylene ether, and defoaming agent is poly dimethyl silicon
Oxygen alkane.
The preparation method of the present embodiment water-base drilling fluid with lubricator, comprising the following steps:
The preparation method of the present embodiment water-base drilling fluid lubricant compositions includes:
Modified vegetable oil, biodiesel are added in stirred tank according to above-mentioned parts by weight, are heated with stirring to 60 DEG C, then press
Parts by weight sequentially add phenolic resin coating sulfonated polyimide microcapsules, the first dispersing agent, extreme pressure anti-wear additives, continue to stir
0.8h adds defoaming agent, continues to stir 0.8h, obtains water-base drilling fluid lubricant compositions, is labeled as S6.
Embodiment 7
The present embodiment prepares lubricant compositions and water-base drilling fluid using method of the invention for illustrating.
In the present embodiment, the preparation method of epoxy-modified rapeseed oil is in the same manner as in Example 2, organic-silicon-modified rapeseed oil
Preparation method is in the same manner as in Example 4, institute the difference is that: modified vegetable oil be epoxy-modified rapeseed oil with it is organic-silicon-modified
Rapeseed oil mixes in mass ratio for 1:3;And in the present embodiment formula, extreme pressure anti-wear additives are kodalk and three boric acid
Potassium mixes in mass ratio for 1:1;Dispersing agent is low nitrogen type polyisobutene succinimide and boronation polyisobutene succinyl
Imines mixes in mass ratio for 3:2;Defoaming agent is polyoxyethylene polyoxypropylene pentaerythrite ether and polypropylene glycerol aether
It is mixed in mass ratio for 1:2.
Remaining is the same as embodiment 4.
As a result water-base drilling fluid lubricant compositions are made, are labeled as S7.
Embodiment 8
The present embodiment prepares lubricant compositions and water-base drilling fluid using method of the invention for illustrating.
In the present embodiment, the preparation method of epoxy-modified rapeseed oil is in the same manner as in Example 2, organic-silicon-modified rapeseed oil
Preparation method is in the same manner as in Example 4, institute the difference is that: modified vegetable oil be epoxy-modified rapeseed oil with it is organic-silicon-modified
Rapeseed oil mixes in mass ratio for 1:1;And in the present embodiment formula, extreme pressure anti-wear additives are kodalk, metaboric acid
Potassium mixes in mass ratio for 1:1:2 with three potassium borates;Dispersing agent is that low nitrogen type polyisobutene succinimide and boronation are poly-
Isobutene succimide mixes in mass ratio for 1:2.
Remaining is the same as embodiment 5.
As a result water-base drilling fluid lubricant compositions are made, are labeled as S8.
Embodiment 9
The present embodiment prepares lubricant compositions and water-base drilling fluid using method of the invention for illustrating.
In the present embodiment, the preparation method of epoxy-modified rapeseed oil is in the same manner as in Example 2, organic-silicon-modified rapeseed oil
Preparation method is in the same manner as in Example 4, institute the difference is that: modified vegetable oil be epoxy-modified rapeseed oil with it is organic-silicon-modified
Rapeseed oil mixes in mass ratio for 2:1;And in the present embodiment formula, extreme pressure anti-wear additives are kodalk, metaboric acid
Potassium mixes in mass ratio for 1:1:1 with three potassium borates;Dispersing agent is that low nitrogen type polyisobutene succinimide and boronation are poly-
Isobutene succimide mixes in mass ratio for 4:3.
Remaining is the same as embodiment 6.
As a result water-base drilling fluid lubricant compositions are made, are labeled as S9.
Comparative example 1
Prepare lubricant compositions and water-base drilling fluid in the same manner as shown in Example 1, institute the difference is that:
When preparing water-base drilling fluid, lubricant (lubricant compositions) of the invention is not used, but uses commercial liquid lubricant,
Such as oil lubricant LUBE.
As a result water-base drilling fluid lubricant compositions are made, are labeled as DS1.
Comparative example 2
Prepare lubricant compositions and water-base drilling fluid in the same manner as shown in Example 1, institute the difference is that:
When preparing water-base drilling fluid, lubricant (lubricant compositions) of the invention is not used, but by lubricant group of the invention
The capsule grain closed in object replaces with biodiesel.
As a result water-base drilling fluid lubricant compositions are made, are labeled as DS2.
Comparative example 3
Prepare lubricant compositions and water-base drilling fluid in the same manner as shown in Example 1, institute the difference is that: institute
State capsule grain not instead of microcapsule structure, phenolic resin, sulfonated polyimide, water and the second dispersing agent mixture.
As a result water-base drilling fluid lubricant compositions are made, are labeled as DS3.
Comparative example 4
Prepare lubricant compositions and water-base drilling fluid in the same manner as shown in Example 1, institute the difference is that: capsule
Shell material is 7:1 with a thickness of the weight ratio of 0.5nm and the intracapsular material and the capsule casing material.
As a result water-base drilling fluid lubricant compositions are made, are labeled as DS4.
Comparative example 5
Prepare lubricant compositions and water-base drilling fluid in the same manner as shown in Example 1, institute the difference is that: will
Modified vegetable oil replaces with rapeseed oil.
As a result water-base drilling fluid lubricant compositions are made, are labeled as DS5.
Comparative example 6
Prepare lubricant compositions and water-base drilling fluid in the same manner as shown in Example 1, institute the difference is that: institute
The weight ratio for stating the content of epoxy-modified vegetable oil and the organic-silicon-modified vegetable oil is 1:5.
As a result water-base drilling fluid lubricant compositions are made, are labeled as DS6.
Test case 1
The effect of embodiment 1-9 and comparative example 1-6 are tested below.
Base slurry is prepared:
The formula for testing base slurry is+3% inhibitor+10% of+2.0% fluid loss additive of+0.3% tackifier of 2% bentonite slurry
Sodium chloride+300g barite.
" base starches+2% embodiment, base slurry+2% comparative example (commercial liquid lubricant) " rheological characteristic is tested, drilling well
Liquid rheological property test result is as shown in table 1.
Table 1
: AV- drilling fluid apparent viscosity, PV are drilling fluid plastic viscosity;YP is drilling fluid yield value.
As shown in Table 1, after embodiment, comparative example being added, drilling fluid extreme boundary lubrication coefficient is significantly reduced, wherein embodiment
Greasy property be better than comparative example;Comparative example 1-6 is added, significantly affects the rheological property of drilling fluid, apparent viscosity AV, plasticity
Viscosity PV, yield value YP are significantly increased;And embodiment 1-9 is added, drilling fluid rheology performance is held essentially constant, this just illustrates
Water-base drilling fluid provided by the invention highly-efficient lubricant composition will not also shadow while performance " antifriction " effect
Ring the rheological property of drilling fluid.
Test case 2
The fluorescence of embodiment 1-9 and comparative example 1-6 are tested below, the results are shown in Table 2.
Table 2
By environmental-protecting performance test it is found that the EC of the water-base drilling fluid highly-efficient lubricant composition of 1-9 of the embodiment of the present invention50
Value is up to 30000mg/L or more, for example, the EC of the water-base drilling fluid highly-efficient lubricant composition of the embodiment of the present invention 650Value is
80000mg/L, is no biotoxicity rank, and fluorescence grade is respectively less than 4 grades;And the EC of comparative example 1-650Value is below 20000mg/
L, for example, the EC of commercial liquid lubricant comparative example 150Value is 18000mg/L, is Ecotoxicology, fluorescence grade is up to 6 grades.
As can be seen from Table 2, water-base drilling fluid highly-efficient lubricant composition provided by the invention, is not only able to effectively play
" antifriction " function and effect, or a kind of environmental-friendly type drilling liquid lubricant, help to solve existing drilling fluid lubricating
Agent causes serious pollution to the environment, fluorescence grade is high, the unstable, influence that is not easy biological degradations, higher cost, poor high temperature stability, cloud point
The problems such as rheology.
Test case 3
The lubricant for drilling fluid composition of the embodiment of the present invention 7 is applied in oil and gas well drilling construction, for example,
The application in wellbore construction in extended reach well KT-1, and uses existing commercially available conventional liq lubricant for drilling fluid (comparative example 1)
Lin Jing (KT-2) compare, torque reduces 38-42%, and rate of penetration improves 29%, and drilling period shortens 39%.Thus
As it can be seen that lubricant for drilling fluid composition provided by the invention, can effectively play " antifriction " function and effect, drilling well is improved
Profession of constructing efficiency, helps to realize safe, high-quality, efficient wellbore target.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention
In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to
Protection scope of the present invention.