CN106589259B - Heat Resistant and Salt Tolerant Polymer microballoon and preparation method - Google Patents
Heat Resistant and Salt Tolerant Polymer microballoon and preparation method Download PDFInfo
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Abstract
The present invention relates to a kind of using Heat Resistant and Salt Tolerant Polymer microballoon and preparation method thereof, it mainly solves big conversed phase micro emulsion copolymerization conventional emulsifier dosage existing in the prior art, reverse micro emulsion stability difference and polymer microballoon early period, expansion was more rapid in the prior art, late expansion is slow, the low problem of plugging strength in macropore.For the present invention by a kind of Heat Resistant and Salt Tolerant Polymer microballoon, the Heat Resistant and Salt Tolerant Polymer microballoon is as Reverse Microemulsion System through made from Raolical polymerizable；The Reverse Microemulsion System, in terms of mass fraction, including following components: 20~80 parts of base oil；10~70 parts of water；10~50 parts of water-soluble monomers；0.5~18 part of sulfonate compound emulsifying agent；0.01~10 part of emulsion adjuvant etc., the sulfonate compound emulsifying agent include the technical solution of sulfosalt surfactant shown in formula I, preferably solve the problems, such as this, can be used for improving oil recovery factor in tertiary oil production in oil field.
Description
Technical field
The present invention relates to a kind of Heat Resistant and Salt Tolerant Polymer microballoon and preparation methods.
Background technique
Currently, China major part oil field comes into tertiary phase, Produced Liquid moisture content is up to 98% or more, very much
Mine loses extraction value.But it is found by oil pool analysis, still with the presence of oil reservoir in the oil reservoir exploited.This phenomenon is non-equal
Matter is serious and high permeability reservoir in it is very common.And the main means for improving recovery ratio at present are still water drive and chemical flooding, therefore,
The Novel technique of in-depth profile control of heterogeneous reservoir is just particularly important.
But due to leading to stratum through fracturing reform in tertiary oil recovery, there are a large amount of cracks, high permeable strip, through long-term subsequent
Waterflooding extraction, development degree difference is big in layer, and water injection profile phenomenon of advancing by leaps and bounds is serious.In addition, low permeability pay permeability is low, hole
Spend small, water absorbing capacity is low, and stratum easily blocks in addition, and water absorbing capacity constantly reduces, and water injection pressure constantly rises, and causes water injection well
It is formed about higher-pressure region, deep injection is difficult.In this regard, increasing oil recovery to improve the sweep efficiency that different permeable formations inject water and producing
Amount, must just be adjusted water injection profile, i.e. introducing water plugging profile control agent.Generally, to profile control agent require be are as follows: into must go,
It is so stifled that live, can move.And there is certain defect in traditional profile control agent such as Inorganic Profile Modification, polymer agent, foaming agent, to microballoon tune
It is significant to steady oil control water with application to cut open research.
Polymer microballoon technology is a kind of novel deep profile controlling water-plugging technique, can direct waste water, cost is relatively low, injection
Without viscosity, the expandable microballoon of water is met by nano/micron grade to block the effect that formation pore throat realizes its deep profile controlling water blockoff step by step
Fruit.Its profile control mechanism are as follows: block high permeability formation, deformed between ground layer gap, migrate, block again, water is injected after making and changes flow direction, is expanded
Big water drive sweep efficiency, reaches deep profile correction.Therefore, the technological means is to the oil reservoirs such as hypotonic, high temperature, high salinity in raising
Recovery ratio is of great significance.
In addition, when preparing nanoscale/micron order expansiveness polymer microballoon using conversed phase micro emulsion copolymerization at present, often
It has been often used a large amount of surfactant and has made the stable emulsifier of oil-water interfaces, such as alkyl phenol polyoxyethylene ether class, Sorbitan
Sugar alcohol fatty acid ester, polyoxyethylene sorbitan aliphatic ester and its compound etc., considerably increase production cost.
And alkyl phenol polyoxyethylene ether class is to aquatic toxicity and to the biological degradability of skin irritation, teratogenesis and difference, in recent years
Come in its use of majority state and territorial restrictions；Sorbitan fatty ester interfacial activity is poor, substantially right
Displacement efficiency is improved without contribution function.Therefore, seek it is a kind of can substitution or part substitute above-mentioned conventional surfactants for matching
Stable, transparent Reverse Microemulsion System is made, so that the water plugging and profile controlling effect that preparation has had has both the displacement of reservoir oil and tune blocks up dual function
The microemulsion system of effect is significant and far-reaching.
Summary of the invention
The first technical problem to be solved by the present invention is the conventional cream of conversed phase micro emulsion copolymerization existing in the prior art
Agent dosage is big, reverse micro emulsion stability is poor and expands more rapid, late expansion polymer microballoon early period in the prior art
Slowly, it is poly- to provide a kind of temperature-resistant anti-salt using the preparation of sulfonate compound emulsifying agent for the low problem of plugging strength in macropore
Close object microballoon, the water plugging and profile controlling effect that prepared Heat Resistant and Salt Tolerant Polymer microballoon has had, while obtained Emulsions
System also have both washing oil displacement of reservoir oil effect, can satisfy make in tertiary oil production in oil field water blockoff, deep profile controlling and displacement etc. improve crude oil adopt
The requirement of yield field operation, economy are good.
The second technical problem to be solved by the present invention is to provide a kind of use sulfonate solved in one of technical problem
The preparation method of the Heat Resistant and Salt Tolerant Polymer microballoon of compound emulsifying agent.
One of to solve above-mentioned technical problem, The technical solution adopted by the invention is as follows:
A kind of Heat Resistant and Salt Tolerant Polymer microballoon, the Heat Resistant and Salt Tolerant Polymer microballoon is by Reverse Microemulsion System through freedom
Made from base polymerization reaction；The Reverse Microemulsion System, in terms of mass fraction, including following components:
(1) 20~80 part of base oil；
(2) 10~70 parts of water；
(3) 10~50 parts of water-soluble monomer；
(4) 0.5~18 parts of sulfonate compound emulsifying agent；
Wherein, the water-soluble monomer is selected from nonionic monomers, anionic monomer, cationic monomer；The sulphur
Hydrochlorate compound emulsifying agent includes general formula sulfosalt surfactant as shown in Formulas I structure:
In formula, R C1~C18Aliphatic hydrocarbon or aromatic hydrocarbon；Y is oxygroup, imido grpup or carbonyl oxygroup；M=0~50；N=2
~55；M is selected from alkali metal, alkaline-earth metal or ammonium salt, and x is selected from 1 or 2, and when M is selected from alkali metal or ammonium salt, x=1, when M is selected
When from alkaline-earth metal, x=2.
In above-mentioned technical proposal, the Reverse Microemulsion System, in terms of mass fraction, it is also preferable to include following components:
(5) 0.01~10 parts of emulsion adjuvant；
(6) 0.001~5 parts of oxidant；
(7) 0.001~5 parts of reducing agent；
(8) 0.001~5 parts of crosslinking agent；
(9) 0.1~5 parts of pH adjusting agent.
In above-mentioned technical proposal, the base oil preferably is selected from thiacyclohexane, hexane, heptane, octane, isooctane, benzene, first
At least one of benzene, ethylbenzene, dimethylbenzene, isopropylbenzene, atoleine, vegetable oil, white oil, gasoline, diesel oil and kerosene.
In above-mentioned technical proposal, it is also preferable to include spans surfactant and tweens for the sulfonate compound emulsifying agent
Class surfactant, wherein spans surfactant and Tweens surfactant are surfactants commonly used in the art,
Those skilled in the art can carry out conventional selection, such as but not limit spans surfactant be more preferably sapn
20, sorbester p17, span 85 etc., Tweens surfactant are more preferably polysorbas20, polysorbate60, Tween 80 etc., described
HLB value after sulfonate compound emulsifying agent compounding is preferably 3~9；In order to improve stability of emulsion, emulsification can also be added and helped
Agent, the emulsion adjuvant preferably are selected from ethyl alcohol, propyl alcohol, isopropanol, n-butanol, isobutanol, the tert-butyl alcohol, amylalcohol, hexanol, second two
Alcohol, propylene glycol, butanediol, pentanediol, hexylene glycol, glycerol, polyglycerol ester, sodium formate, potassium formate, ammonium formate, sodium acetate, acetic acid
At least one of potassium, ammonium acetate, hexanedioic acid sodium, sodium malonate.
In above-mentioned technical proposal, the preparation method of the sulfosalt surfactant preferably includes following steps:
(1) preparation of the alkyl polycyclic oxygen alkylene halides of Formula II structure:
Wherein, X is chlorine atom or bromine atom；
By alkyl polycyclic oxygen alkene based surfactants shown in thionyl chloride or thionyl bromide and formula III structure mole
Than for 1~15:1 be uniformly mixed, under 10~160 DEG C of reaction temperatures, react 2~15 hours, after reaction through lye, go from
Sub- water process obtains alkyl polycyclic oxygen alkylene halides shown in Formula II structure；
(2) preparation of sulfosalt surfactant shown in Formulas I structure:
Sulfonating agent sulfurous acid is added in synthesized alkyl polycyclic oxygen alkylene halides under stirring in step (1)
The molar ratio of potassium and/or potassium bisulfite, sulfonating agent and halides is 1~10:1, at a temperature of 30~220 DEG C, reaction 2~16
Hour, it handles to obtain sulfosalt surfactant shown in Formulas I structure after reaction through lye, deionized water.
In above-mentioned technical proposal, the preferred acrylamide of the nonionic monomers, Methacrylamide, N- isopropyl third
Acrylamide, N hydroxymethyl acrylamide, N,N-DMAA, N, N- acrylamide, N- vinylpyridine, N-
At least one of vinyl pyrrolidone；Anionic monomer preferred vinyl sulfonic acid, vinylbenzenesulfonic acid, allyl sulphur
Acid, allyl benzene sulfonic acid, 2- acrylamide-2-methylpro panesulfonic acid and/or at least one of its alkali metal salt and ammonium salt；Sun
The preferred dimethyl ethyl allyl ammonium chloride of ionic comonomer, dimethyl diallyl ammonium chloride, acrylyl oxy-ethyl-trimethyl
Ammonium chloride, acryloxyethyldimethyl ethyl phosphonium bromide ammonium, MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, 2- acrylamide
At least one of base -2- trimethoxysilyl propyl methacrylate ammonium chloride.
In above-mentioned technical proposal, the oxidant preferably is selected from ammonium persulfate, potassium peroxydisulfate, at least one in sodium peroxydisulfate
Kind；The reducing agent preferably is selected from sodium hydrogensulfite, potassium bisulfite, sodium sulfite, potassium sulfite, sodium thiosulfate, chlorination
At least one of ferrous iron；The crosslinking agent preferably is selected from divinylbenzene, methylene-bisacrylamide, two propylene of polyethylene glycol
At least one of acid esters, pentaerythritol triacrylate.
In above-mentioned technical proposal, the pH adjusting agent preferably is selected from natrium carbonicum calcinatum, sodium bicarbonate, sodium hydroxide, carbonic acid
At least one of potassium, saleratus, potassium hydroxide or ammonium hydroxide.
In order to solve the above-mentioned technical problem two, The technical solution adopted by the invention is as follows: any in above-mentioned technical proposal
The preparation method of the Heat Resistant and Salt Tolerant Polymer microballoon, comprising the following steps:
(1) the desired amount of reducing agent is soluble in water, stirring is allowed to dissolve, and obtains reducing agent aqueous solution；It will be the desired amount of
Water-soluble monomer, oxidant, crosslinking agent are soluble in water, are stirred well to solution clarification and adjust without insoluble matter, and with pH adjusting agent
PH value of water solution obtains monomer solution to 7~12；And the summation of water in reducing agent aqueous solution and monomer solution is made to be institute
The water of requirement；
(2) sulfonate compound emulsifying agent, emulsion adjuvant are dissolved in base oil, are sufficiently stirred and are uniformly dissolved, monomer is added
Aqueous solution stirs to get transparent or semitransparent Reverse Microemulsion System；
(3) it is passed through inert gas, the reducing agent aqueous solution prepared in step (1), mixing is added in the oxygen in displacement system
Uniformly, initiated polymerization 0.5~6 hour at a temperature of 15~60 DEG C is obtained containing the saturating of the Heat Resistant and Salt Tolerant Polymer microballoon
Bright or translucent microemulsion system obtains the Heat Resistant and Salt Tolerant Polymer microballoon for microemulsion system is post-treated；Wherein
Heat Resistant and Salt Tolerant Polymer microspherulite diameter is 50~300nm, particle diameter distribution less than 0.5.
The inert gas is selected from least one of nitrogen, argon gas.
The key of the method for the present invention is that the interface for not only increasing system is living by adding sulfosalt surfactant
Property, water plugging and profile controlling and displacement multi-efficiency are also had both, " one multiple-effect " effect is reached.The microemulsion system can satisfy oil field three
Make water blockoff, deep profile controlling and displacement etc. in secondary oil recovery and improve the requirement of oil recovery factor field operation, economy is good.
Using technical solution of the present invention, polymer microballoon initial particle, can up to 300nm in obtained microemulsion system
Slowly expansion, 45 days expansion multiples are up to 14.5 times, with Pu 2-529 output oil oil water interfacial tension up to 7.0 × 10-3MN/m,
Achieve preferable technical effect.
Below by specific embodiment, the present invention will be further elaborated.
Specific embodiment
[embodiment 1]
1, the synthesis of sulfosalt surfactant:
(1) synthesis of chloro isomery myristyl alcohol polyoxypropylene base (10) polyoxyethylene groups (2) ether:
In the glass reaction kettle equipped with reflux condensate device, thermometer, blender and gas absorbing device, 92g is added
Isomery myristyl alcohol polyoxypropylene base (10) polyoxyethylene groups (2) ether, 13g pyridine, it is slow with dropping funel at a temperature of 68 DEG C
Slowly it is added dropwise to 26.5g thionyl chloride, is stirred when being added dropwise and is allowed to uniformly mixed, the reaction was continued 5.5 hours after being added dropwise, and terminates
Reaction is stood, cooling layering, adjusts upper liquid pH value to 7.4 with 30% sodium hydroxide solution, the saturated salt solution of reusable heat
It washs upper layer three times, obtains chloro isomery myristyl alcohol polyoxypropylene base (10) polyoxyethylene groups (2) ether after dry, yield is
87.9%.
(2) synthesis of isomery myristyl alcohol polyoxypropylene base (10) polyoxyethylene groups (2) ether sulfonic acid potassium:
Chloro isomery myristyl alcohol polyoxypropylene base (10) polyoxyethylene groups (2) the ether 90g synthesized in step (1) is added
Enter equipped with reflux condensate device, thermometer, blender glass reaction kettle in, 76 DEG C are heated to, with dropping funel by 68g
30% bisulfite aqueous solutions of potassium is slowly added dropwise in kettle, and after being added dropwise, the reaction was continued 9 hours, reaction is terminated, through depressurizing
After distillation, thick product isomery myristyl alcohol polyoxypropylene base (10) polyoxyethylene groups (2) ether sulfonic acid potassium is obtained.
2, the preparation of microemulsion system:
120g white oil, 7g isomery myristyl alcohol polyoxypropylene base (10) polyoxyethylene groups (2) ether are added into reaction kettle
Potassium sulfonate, 32g span 40,10g polysorbate65, stirring are allowed to uniformly mixed, and control temperature in the kettle is 33 DEG C, and stirring rate is
270rpm.90g water, 100g acrylamide, 20g sodium acrylate, 10g n-vinyl pyrrolidone, 1.7g are added in batching kettle
Polyethyleneglycol diacrylate, 1.3g hexylene glycol, 2g adipic acid sodium, 1.8g ammonium persulfate, stirring are allowed to be uniformly dissolved, and use carbonic acid
Hydrogen sodium solid adjusts pH value to 7.8；In addition, 2.8g sodium hydrogensulfite is dissolved in 16.2g deionized water, it is spare.By monomer water
Solution imports in reaction kettle, and stirring is allowed to fully emulsified, and 15g aqueous solution of sodium bisulfite is added, and system temperature rise continues to 75 DEG C
Reaction 3 hours, after terminating reaction, discharging.
2000 type Particle Size Analyzer of Zetasizer Nano is produced using Malvern instrument company, Britain and tests microemulsion system
Microballoon initial particle and distribution；7 days, 15 days, 30 are placed under total salinity 160000mg/L salt water under 92 DEG C, oxygen free condition
It, after 45 days microballoon partial size, calculate the expansion multiple of microballoon；TX-500 type rotation drop circle is produced using Texas ,Usa university
Face tensiometer measures the interfacial tension between microemulsion system and Pu 2-529 output oil.The results are shown in Table 1.
[embodiment 2]
The synthesis of sulfosalt surfactant and the preparation process of microemulsion system, with [embodiment 1], only by third
Olefin(e) acid sodium replaces with 2- acrylamide-2-methylpro panesulfonic acid.Zetasizer Nano is produced using Malvern instrument company, Britain
The microballoon initial particle and distribution of 2000 type Particle Size Analyzers test microemulsion system；The total salinity under 92 DEG C, oxygen free condition
The partial size of microballoon, calculates the expansion multiple of microballoon after placing 7 days, 15 days, 30 days, 45 days under 160000mg/L salt water；Using beauty
University of Texas, state produces the boundary between TX-500 type rotating interfacial tensimeter measurement microemulsion system and Pu 2-529 output oil
Face tension.The results are shown in Table 1.
[embodiment 3]
The synthesis of sulfosalt surfactant and the preparation process of microemulsion system only will be newborn with [embodiment 1]
The dosage of agent isomery myristyl alcohol polyoxypropylene base (10) polyoxyethylene groups (2) ether sulfonic acid potassium and polysorbate65 is transformed to respectively
3.6g,13.9g.2000 type Particle Size Analyzer of Zetasizer Nano is produced using Malvern instrument company, Britain and tests microemulsion
The microballoon initial particle of system and distribution；7 days, 15 are placed under total salinity 160000mg/L salt water under 92 DEG C, oxygen free condition
It, 30 days, after 45 days microballoon partial size, calculate the expansion multiple of microballoon；The rotation of TX-500 type is produced using Texas ,Usa university
Turn the interfacial tension between drop interfacial tensimeter measurement microemulsion system and Pu 2-529 output oil.The results are shown in Table 1.
[embodiment 4]
The synthesis of sulfosalt surfactant and the preparation process of microemulsion system only will be newborn with [embodiment 1]
The dosage of agent isomery myristyl alcohol polyoxypropylene base (10) polyoxyethylene groups (2) ether sulfonic acid potassium and polysorbate65 is transformed to respectively
10g,8g.2000 type Particle Size Analyzer of Zetasizer Nano is produced using Malvern instrument company, Britain and tests microemulsion system
Microballoon initial particle and distribution；7 days, 15 days, 30 are placed under total salinity 160000mg/L salt water under 92 DEG C, oxygen free condition
It, after 45 days microballoon partial size, calculate the expansion multiple of microballoon；TX-500 type rotation drop circle is produced using Texas ,Usa university
Face tensiometer measures the interfacial tension between microemulsion system and Pu 2-529 output oil.The results are shown in Table 1.
[embodiment 5]
1, the synthesis of sulfosalt surfactant:
(1) synthesis of bromo n-octadecane base polyoxyethylene groups (12) amine:
In the glass reaction kettle equipped with reflux condensate device, thermometer, blender and gas absorbing device, 15g is added
Pyridine, 95g n-octadecane base polyoxyethylene groups (12) amine are slowly added dropwise with dropping funel into 45g thionyl at a temperature of 72 DEG C
Bromine stirs when being added dropwise and is allowed to uniformly mixed, and the reaction was continued 6.5 hours after being added dropwise, and reaction was completed, stands, divides after cooling
Layer adjusts upper layer pH to neutrality with 30% sodium hydroxide solution, the saturated common salt water washing upper layer of reusable heat three times, after dry
Obtain bromo n-octadecane base polyoxyethylene groups (12) amine, yield 92.1%.
(2) synthesis of n-octadecane base amino polyoxyethylene groups (12) potassium sulfonate:
Bromo n-octadecane base polyoxyethylene groups (12) the amine 75g synthesized in step (1) is added and is filled equipped with reflux condensation mode
It sets, in the glass reaction kettle of thermometer, blender, is heated to 79 DEG C, with dropping funel by the potassium bisulfite water of 70g 30%
Solution is slowly added dropwise in kettle, and after being added dropwise, the reaction was continued 9 hours, terminates reaction, after being evaporated under reduced pressure, obtains thick
Product n-octadecane base amino polyoxyethylene groups (12) potassium sulfonate.
2, the preparation of microemulsion system:
150g normal octane, 10g n-octadecane base amino polyoxyethylene groups (12) potassium sulfonate, 34g department are added into reaction kettle
Disk 80 and 8g Tween61, stirring are allowed to uniformly mixed, and control temperature in the kettle is 35 DEG C, stirring rate 250rpm.In batching kettle
Middle addition 90g water, 125g acrylamide, 20g 2- acrylamide-2-methylpro panesulfonic acid, 5g 2- acrylamido -2- methyl
Hydroxypropyltrimonium chloride, 1.5g methylene-bisacrylamide, 1.5g ammonium formate, 1g glycerol, 2g ammonium persulfate, stirring are allowed to molten
Solution uniformly, with sodium hydrate aqueous solution adjusts pH value to 7.2；In addition, 2.8g sodium sulfite is dissolved in 20g deionized water, it is standby
With.Monomer solution is imported in reaction kettle, stirring is allowed to fully emulsified, 18g sodium sulfite aqueous solution is added, system temperature rise is extremely
67 DEG C, the reaction was continued 2 hours, after terminating reaction, discharging.
2000 type Particle Size Analyzer of Zetasizer Nano is produced using Malvern instrument company, Britain and tests microemulsion system
Microballoon initial particle and distribution；7 days, 15 days, 30 are placed under total salinity 160000mg/L salt water under 92 DEG C, oxygen free condition
It, after 45 days microballoon partial size, calculate the expansion multiple of microballoon；TX-500 type rotation drop circle is produced using Texas ,Usa university
Face tensiometer measures the interfacial tension between microemulsion system and Pu 2-529 output oil.The results are shown in Table 1.
[embodiment 6]
The synthesis of sulfosalt surfactant and the preparation process of microemulsion system, with [embodiment 5], only by portion
Acrylamide is divided to replace with N,N-DMAA, dosage 25g.It is produced using Malvern instrument company, Britain
The microballoon initial particle and distribution of 2000 type Particle Size Analyzer of Zetasizer Nano test microemulsion system；In 92 DEG C, anaerobic
Under the conditions of place 7 days, 15 days, 30 days, 45 days under total salinity 160000mg/L salt water after microballoon partial size, calculate the swollen of microballoon
Swollen multiple；TX-500 type rotating interfacial tensimeter measurement microemulsion system and Pu 2-529 are produced using Texas ,Usa university
Interfacial tension between output oil.The results are shown in Table 1.
[embodiment 7]
The synthesis of sulfosalt surfactant and the preparation process of microemulsion system only will be newborn with [embodiment 5]
Agent n-octadecane base amino polyoxyethylene groups (12) potassium sulfonate, Tween61 dosage be transformed to 3g, 15g respectively.Using Britain
Malvern instrument company produce 2000 type Particle Size Analyzer of Zetasizer Nano test microemulsion system microballoon initial particle and
Distribution；Microballoon after being placed 7 days, 15 days, 30 days, 45 days under total salinity 160000mg/L salt water under 92 DEG C, oxygen free condition
Partial size calculates the expansion multiple of microballoon；It is micro- that the measurement of TX-500 type rotating interfacial tensimeter is produced using Texas ,Usa university
Interfacial tension between emulsion system and Pu 2-529 output oil.The results are shown in Table 1.
[embodiment 8]
The synthesis of sulfosalt surfactant and the preparation process of microemulsion system only will be newborn with [embodiment 5]
Agent n-octadecane base amino polyoxyethylene groups (12) potassium sulfonate, Tween61 dosage be transformed to 12g, 5.56g respectively.Using English
Malvern instrument company, state produces the microballoon initial particle of 2000 type Particle Size Analyzer of Zetasizer Nano test microemulsion system
And distribution；Microballoon after being placed 7 days, 15 days, 30 days, 45 days under total salinity 160000mg/L salt water under 92 DEG C, oxygen free condition
Partial size, calculate the expansion multiple of microballoon；The measurement of TX-500 type rotating interfacial tensimeter is produced using Texas ,Usa university
Interfacial tension between microemulsion system and Pu 2-529 output oil.The results are shown in Table 1.
[comparative example 1]
The preparation process of microemulsion system is with [embodiment 4], only by emulsifier isomery myristyl alcohol polyoxypropylene base
(10) polyoxyethylene groups (2) ether sulfonic acid potassium replaces with Tween 80.Zetasizer Nano is produced using Malvern instrument company, Britain
The microballoon initial particle and distribution of 2000 type Particle Size Analyzers test microemulsion system；The total salinity under 92 DEG C, oxygen free condition
The partial size of microballoon, calculates the expansion multiple of microballoon after placing 7 days, 15 days, 30 days, 45 days under 160000mg/L salt water；Using beauty
University of Texas, state produces the boundary between TX-500 type rotating interfacial tensimeter measurement microemulsion system and Pu 2-529 output oil
Face tension.The results are shown in Table 1.
[comparative example 2]
Isomery ten will be only added with [comparative example 1] in the preparation process of microemulsion system in the microemulsion system after discharging
Tetraalkyl alcohol polyoxypropylene base (10) polyoxyethylene groups (2) ether sulfonic acid potassium 10g.It is produced using Malvern instrument company, Britain
The microballoon initial particle and distribution of 2000 type Particle Size Analyzer of Zetasizer Nano test microemulsion system；In 92 DEG C, anaerobic
Under the conditions of place 7 days, 15 days, 30 days, 45 days under total salinity 160000mg/L salt water after microballoon partial size, calculate the swollen of microballoon
Swollen multiple；TX-500 type rotating interfacial tensimeter measurement microemulsion system and Pu 2-529 are produced using Texas ,Usa university
Interfacial tension between output oil.The results are shown in Table 1.
[comparative example 3]
The preparation process of microemulsion system is only poly- by isomery myristyl alcohol polyoxypropylene base (10) with [embodiment 4]
Oxyethylene group (2) ether sulfonic acid potassium replaces with isomery myristyl alcohol polyoxyethylene groups (2) polyoxypropylene base (10) ether sulfonic acid potassium (such as
Shown in formula IV).2000 type Particle Size Analyzer of Zetasizer Nano is produced using Malvern instrument company, Britain and tests Emulsions
The microballoon initial particle of system and distribution；Placed under total salinity 160000mg/L salt water under 92 DEG C, oxygen free condition 7 days, 15 days,
The partial size of microballoon, calculates the expansion multiple of microballoon after 30 days, 45 days；TX-500 type rotation drop is produced using Texas ,Usa university
Interfacial tensimeter measures the interfacial tension between microemulsion system and Pu 2-529 output oil.The results are shown in Table 1.
Table 1
Claims (10)
1. a kind of Heat Resistant and Salt Tolerant Polymer microballoon, the Heat Resistant and Salt Tolerant Polymer microballoon is by Reverse Microemulsion System through free radical
Made from polymerization reaction；The Reverse Microemulsion System, in terms of mass fraction, including following components:
(1) 20~80 part of base oil；
(2) 10~70 parts of water；
(3) 10~50 parts of water-soluble monomer；
(4) 0.5~18 parts of sulfonate compound emulsifying agent；
Wherein, the water-soluble monomer is selected from nonionic monomers, anionic monomer, cationic monomer；The sulfonate
Compound emulsifying agent includes general formula sulfosalt surfactant as shown in Formulas I structure:
In formula, R C1~C18Aliphatic hydrocarbon or aromatic hydrocarbon；Y is oxygroup, imido grpup or carbonyl oxygroup；M=0~50；N=2~
55；M is selected from alkali metal, alkaline-earth metal or ammonium salt, and x is selected from 1 or 2, and when M is selected from alkali metal or ammonium salt, x=1, when M is selected from
When alkaline-earth metal, x=2.
2. Heat Resistant and Salt Tolerant Polymer microballoon according to claim 1, it is characterised in that the sulfonate compound emulsifying agent is also
Including spans surfactant and/or Tweens surfactant.
3. Heat Resistant and Salt Tolerant Polymer microballoon according to claim 1 or 2, it is characterised in that the base oil is selected from hexamethylene
Alkane, hexane, heptane, octane, isooctane, benzene, toluene, ethylbenzene, dimethylbenzene, isopropylbenzene, atoleine, vegetable oil, white oil, vapour
At least one of oil, diesel oil and kerosene.
4. Heat Resistant and Salt Tolerant Polymer microballoon according to claim 1 or 2, it is characterised in that the Reverse Microemulsion System,
Further include following components in terms of mass fraction:
(5) 0.01~10 parts of emulsion adjuvant；
(6) 0.001~5 parts of oxidant；
(7) 0.001~5 parts of reducing agent；
(8) 0.001~5 parts of crosslinking agent；
(9) 0.1~5 parts of pH adjusting agent.
5. Heat Resistant and Salt Tolerant Polymer microballoon according to claim 4, it is characterised in that the emulsion adjuvant is selected from ethyl alcohol, third
Alcohol, isopropanol, n-butanol, isobutanol, the tert-butyl alcohol, amylalcohol, hexanol, ethylene glycol, propylene glycol, butanediol, pentanediol, hexylene glycol,
Glycerol, polyglycerol ester, sodium formate, potassium formate, ammonium formate, sodium acetate, potassium acetate, ammonium acetate, adipic acid sodium, in sodium malonate
It is at least one.
6. Heat Resistant and Salt Tolerant Polymer microballoon according to claim 1, it is characterised in that the nonionic monomers are selected from third
Acrylamide, Methacrylamide, n-isopropyl acrylamide, N hydroxymethyl acrylamide, N,N-DMAA, N, N-
At least one of acrylamide, N- vinylpyridine, n-vinyl pyrrolidone；Anionic monomer is selected from ethylene
Base sulfonic acid, vinylbenzenesulfonic acid, allyl sulphonic acid, allyl benzene sulfonic acid, 2- acrylamide-2-methylpro panesulfonic acid and/or its
At least one of alkali metal salt and ammonium salt；Cationic monomer is selected from dimethyl ethyl allyl ammonium chloride, dimethyl diene
Propyl ammonium chloride, acrylyl oxy-ethyl-trimethyl salmiac, acryloxyethyldimethyl ethyl phosphonium bromide ammonium, methacryloxypropyl
At least one of ethyl-trimethyl salmiac, 2- acrylamido -2- trimethoxysilyl propyl methacrylate ammonium chloride.
7. Heat Resistant and Salt Tolerant Polymer microballoon according to claim 4, it is characterised in that the oxidant be selected from ammonium persulfate,
At least one of potassium peroxydisulfate, sodium peroxydisulfate；The reducing agent is selected from sodium hydrogensulfite, potassium bisulfite, sodium sulfite, Asia
At least one of potassium sulfate, sodium thiosulfate, frerrous chloride；The crosslinking agent is selected from divinylbenzene, methylene bisacrylamide
At least one of amide, polyethyleneglycol diacrylate, pentaerythritol triacrylate.
8. Heat Resistant and Salt Tolerant Polymer microballoon according to claim 4, it is characterised in that the pH adjusting agent is selected from anhydrous carbon
At least one of sour sodium, sodium bicarbonate, sodium hydroxide, potassium carbonate, saleratus, potassium hydroxide, calcium oxide or ammonium hydroxide.
9. a kind of preparation method of any Heat Resistant and Salt Tolerant Polymer microballoon of claim 1~8, comprising the following steps:
(1) the desired amount of reducing agent is soluble in water, stirring is allowed to dissolve, and obtains reducing agent aqueous solution；It will be the desired amount of water-soluble
Property monomer, oxidant, crosslinking agent it is soluble in water, be stirred well to solution clarification without insoluble matter, and adjusted with pH adjusting agent water-soluble
Liquid pH value obtains monomer solution to 7~12；And the summation of water in reducing agent aqueous solution and monomer solution is made to be aequum
Water；
(2) sulfonate compound emulsifying agent, emulsion adjuvant are dissolved in base oil, are sufficiently stirred and are uniformly dissolved, it is water-soluble that monomer is added
Liquid stirs to get transparent or semitransparent Reverse Microemulsion System；
(3) it is passed through inert gas, the reducing agent aqueous solution prepared in step (1) is added in the oxygen in displacement system, and mixing is equal
Even, initiated polymerization 0.5~6 hour at a temperature of 15~60 DEG C is obtained containing the transparent of the Heat Resistant and Salt Tolerant Polymer microballoon
Or translucent microemulsion system, the Heat Resistant and Salt Tolerant Polymer microballoon is obtained by microemulsion system is post-treated；It is wherein resistance to
Warm salt-resistant polymer microspherulite diameter is 50~300nm, particle diameter distribution less than 0.5.
10. the preparation method of Heat Resistant and Salt Tolerant Polymer microballoon according to claim 9, it is characterised in that the inert gas
Selected from least one of nitrogen, argon gas.
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