CN109796955A - A kind of preparation method of trapezoidal branch modified siloxane polymer supercritical carbon dioxide thickener - Google Patents
A kind of preparation method of trapezoidal branch modified siloxane polymer supercritical carbon dioxide thickener Download PDFInfo
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Abstract
The present invention relates to a kind of preparation methods of trapezoidal branch modified siloxane polymer supercritical carbon dioxide thickener.This method comprises: the preparation of (1) functional group endcapped linear polydimethylsiloxanepolymer polymer, (2) preparation of the hydrogeneous phenylmethylsiloxane polymers of scalariform, (3) functional group's endcapped linear polydimethylsiloxanepolymer polymer and the hydrogeneous phenylmethylsiloxane polymers of scalariform are instilled at a temperature of 65 DEG C~125 DEG C chloroplatinic acid catalyst, reacts and the trapezoidal branch modified siloxane polymer of product is made.Branch containing functional group is introduced into thickener molecule by the present invention, is not only improved solubility of the thickener in supercritical carbon dioxide, but also can have excellent thickening properties, is improved the ability for carrying proppant, reduces leakoff coefficent.
Description
Technical field
The present invention relates to a kind of preparation method of trapezoidal branch modified siloxane polymer supercritical carbon dioxide thickener,
Belong to technical field of petroleum extraction.
Background technique
As the raising recovery efficiency technique of a quasi-tradition, hydraulic fracturing has great advantages in oilfield stimulation exploitation.
But the disadvantages of existing water consumption is larger, reservoir damage, groundwater resources pollution still hampers the development of technique.In view of
Many defects of hydraulic fracturing technology, finding the free of contamination novel fracturing technique of a kind of clean and effective becomes the pass of oilfield stimulation
Key.As the measure of a kind of emerging oilfield stimulation augmented injection, carbon dioxide pressure break technology has improvement greenhouse effects, low reservoir damage
Low water pollution and use are injured, economic benefits, frictional resistance ability is poor, there is preferable relaxation effect to water-sensitive formation, at
For the well stimulation with preferable development prospect.Although there is many performance advantages for carbon dioxide pressure break technology, pure super
The ultralow viscosity of the carbon dioxide of critical state is not still able to satisfy the viscosity demand of the fracturing fluid in fracturing process, stores up in oil gas
The pressure break stage of layer especially low permeability reservoir, it is easier to flow, the carbon dioxide of pure above-critical state is lower due to the density of itself
It is easy to cause gas channeling phenomenon, fingering phenomenon is more serious, and the residence time in shale reservoir is short, and leak-off is caused due to low-viscosity
It is larger, big pore pressure cannot be formed and carry out pressure break.In addition, its low-viscosity having is also easy to cause proppant and gravel
Performance is carried obviously to weaken, since the gas channeling phenomenon and fingering phenomenon of appearance can also cause the reduction of sweep efficiency, so as to cause
The rate of oil and gas recovery is decreased obviously.
Fluorine-containing quasi polymer, which is focused primarily upon, for the goal in research object of carbon dioxide thickener at present closes hydrocarbon Type of Collective
Object.Thickening effect is excellent when fluorine-containing quasi polymer is as thickener, but easily interacts with underground water and remain on reservoir, pollutes
Water resource, and can be generated in body and gather the accumulation for causing biosphere.In addition, the high price of fluorine-containing quasi polymer itself is also
It is hindered to be applied to the critical bottleneck of carbon dioxide pressure break technology.Hydrocarbon quasi polymer although price compared to fluorine-containing quasi polymer
Price it is lower, and can be directly dissolved in supercritical carbon dioxide, but thickening effect is significantly lower than fluoropolymer.Above-mentioned two class
Thickener due to itself there are the drawbacks of hinder application and popularization in fracturing yield increasing.Therefore, need research and development it is a kind of cheap,
Not polluted underground water resource, the damage of reduction reservoir and the polymer-thickened supercritical carbon dioxide with excellent thickening property are
Industrial foundation is established in the development of supercritical carbon dioxide fracturing technique.The present invention is proposed thus.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provide it is a kind of can be used for oil field fracturing technology to gather cricoid branch chain modified
Siloxanes supercritical carbon dioxide thickener and preparation method thereof.Supercritical carbon dioxide thickener prepared by the present invention is improving
Dissolubility is taken into account while thickening property, and production cost is low, preparation step is simple.
Summary of the invention:
The present invention obtains the property of the viscosity of excellent thickening supercritical carbon dioxide by the modification to siloxane polymer
Energy.Using several cyclosiloxane classes as reaction monomers, it is high that straight-chain is generated to annular siloxane open loop through ring-opening polymerization first
Then molecular precursor introduces the branch containing functional group by hydrosilylation, is improved by the branch of introducing and dioxy
The interaction for changing carbon molecules not only significantly improves the solubility in supercritical carbon dioxide, reduces cosolvent dosage, and
The thickening capabilities to supercritical carbon dioxide can be improved.
Term explanation:
Room temperature: there is meaning well known in the art, generally refer to 20~25 DEG C；The temperature being not particularly limited in the present invention
Condition refers both to room temperature.
Room temperature: there is meaning well known in the art, generally refer to 23 DEG C ± 2 DEG C.
Detailed description of the invention:
Technical scheme is as follows:
A kind of preparation method of trapezoidal branch modified siloxane polymer supercritical carbon dioxide thickener, comprising steps of
(1) preparation of functional group's endcapped linear polydimethylsiloxanepolymer polymer
Annular siloxane, small molecule end-capping reagent, toluene and basic catalyst are added in reaction kettle, nitrogen is passed through, it will be anti-
It answers kettle to seal, 2-11h is reacted at a temperature of 100-115 DEG C, then temperature is increased to react 30-40min at 140-155 DEG C, drop
To room temperature, vacuum removal toluene solvant and small molecule siloxanes low-boiling-point substance obtain functional group's endcapped linear dimethyl silicone polymer
Polymer；
The annular siloxane is octamethylcy-clotetrasiloxane, t etram-ethyltetravinylcyclotetrasiloxane, eight ethylene basic rings
Tetrasiloxane, tetramethyl tetrahydro cyclotetrasiloxane, hexamethyl dihydro cyclotetrasiloxane, hexamethyl cyclotrisiloxane, octaphenyl ring
One of tetrasiloxane, tetramethyl tetraphenyl cyclotetrasiloxane are a variety of；
The small molecule end-capping reagent is tetramethyl disiloxane, hexamethyldisiloxane, heptamethyltrisiloxane, prestox
Trisiloxanes, pentamethyl disiloxane, six vinyl disiloxane, hexaphenyldisiloxane or seven phenyl trisiloxanes；
The molar ratio of the annular siloxane and small molecule end-capping reagent is (1.7-15): 1；Annular siloxane and small molecule are sealed
Holding mass concentration of the agent in toluene is 30%~85%；The molar ratio of annular siloxane and basic catalyst is (92-224):
1；
(2) preparation of the hydrogeneous phenylmethylsiloxane polymers of scalariform
At a temperature of 160-270 DEG C, react chlorine-containing silane with phenylenediamine, the molar ratio of the chlorine-containing silane and phenylenediamine
For (0.55~3.2): 1, the phenylenediamine is dissolved in tetrahydrofuran solvent, and chlorine-containing silane and phenylenediamine are in tetrahydrofuran
Mass concentration is 30%~74%；Then,
Deionized water, which is added, makes its mass concentration 0.1%~4.3% in the system, anti-at 140-210 DEG C
Answer 1.5-4.2h；It is cooled to room temperature；
Then it filters, is separated off solid matter, evaporation removes remaining small molecule low-boiling-point substance and tetrahydrofuran, obtains dense
Contracting filtrate；Concentration filtrate is stirred into 3-5h, is cleaned with saturated salt solution to pH=7, is rotated drying, obtain the hydrogeneous methyl silicon of scalariform
Oxygen alkane polymer；
(3) preparation of trapezoidal branch modified siloxane polymer
By the scalariform of functional group's endcapped linear polydimethylsiloxanepolymer polymer of step (1) preparation and step (2) preparation
Hydrogeneous phenylmethylsiloxane polymers are dissolved in toluene together, and chloroplatinic acid catalyst is instilled at a temperature of 65 DEG C~125 DEG C, react 2-
7.5h is cooled to room temperature；Chloroplatinic acid catalyst is removed, then revolving removes small molecule low-boiling-point substance, obtains product, i.e., trapezoidal branch changes
Property siloxane polymer；
Wherein, functional group's endcapped linear polydimethylsiloxanepolymer polymer and the hydrogeneous phenylmethylsiloxane polymers of scalariform
Molar ratio be (0.4~5.3): 1, the molar ratio of the hydrogeneous phenylmethylsiloxane polymers of the scalariform and chloroplatinic acid be (41~
132): 1.
The trapezoidal branch modified siloxane polymer of final product of the invention is the thick liquid of light yellow clear.
Preferred according to the present invention, in step (1), the annular siloxane is octamethylcy-clotetrasiloxane, tetramethyl four
Vinyl cyclotetrasiloxane, eight vinyl cyclotetrasiloxanes, octaphenylcyclotetrasiloxane, in tetramethyl tetraphenyl cyclotetrasiloxane
It is one or more.
Preferred according to the present invention, in step (1), the small molecule end-capping reagent is hexamethyldisiloxane, seven methyl three
Siloxanes, octamethyltrisiloxane, pentamethyl disiloxane, six vinyl disiloxane or hexaphenyldisiloxane.
Preferred according to the present invention, in step (1), the basic catalyst is tetramethylammonium hydroxide, sodium hydroxide, hydrogen
Potassium oxide, aluminium hydroxide or lithium hydroxide；Further preferably, the basic catalyst is selected from tetramethylammonium hydroxide, hydroxide
Sodium or potassium hydroxide.
, according to the invention it is preferred to, in step (1), the molar ratio of annular siloxane and small molecule end-capping reagent is (4.5-
14): 1, the molar ratio of annular siloxane and basic catalyst is (113-185): 1, annular siloxane and small molecule end-capping reagent exist
Quality total concentration in toluene is 35%~70%.
, according to the invention it is preferred to, in step (1), the flow velocity of nitrogen is 0.5Lmin-1, incited somebody to action after being passed through nitrogen 30min
Reaction kettle sealing, and be put in High Temperature Rotating roller furnace.
, according to the invention it is preferred to, the annular siloxane in reaction kettle, small molecule end-capping reagent, toluene in step (1) and
Basic catalyst reacts at 110 DEG C；Reaction time is 4-10h.Reactant is under the conditions of vacuum degree 0.06MPa, 90 DEG C of temperature
Vacuum removal toluene solvant and small molecule siloxanes low-boiling-point substance；The vacuum removal time is 0.7~5h.
Preferred according to the present invention, in step (2), the chlorine-containing silane is trichloromethyl silane, trichlorosilane alkane, three hydrogen
Chlorosilane, trim,ethylchlorosilane, trichloroethyl silane, two kinds in three hydrogen trimethoxy silanes.Mole of two kinds of chlorine-containing silanes
Than for (0.5~4.5): 1.
, according to the invention it is preferred to, in step (2), the molar ratio of chlorine-containing silane and phenylenediamine is (0.85~2.7): 1,
The mass concentration of chlorine-containing silane and phenylenediamine in tetrahydrofuran is 35%~68%, the matter of deionized water in the reaction system
Measuring concentration is 0.3%~3.2%.
, according to the invention it is preferred to, in step (2), the reaction temperature of the chlorine-containing silane and phenylenediamine mixture is 180
DEG C~240 DEG C.
, according to the invention it is preferred to, in step (2), chlorine-containing silane and phenylenediamine reaction time are 0.3-2.3h, further
It is preferred that the reaction time is 0.6~1.7h.
, according to the invention it is preferred to, in step (2), the deionized water and chlorine-containing silane, toluene and phenylenediamine mixture
Reaction temperature be 170 DEG C~220 DEG C；Reaction time is 1.8~2.2h.
, according to the invention it is preferred to, in step (2), evaporation removes the item of remaining small molecule low-boiling-point substance and tetrahydrofuran
Part is 85 DEG C of vacuum degree 0.07MPa, temperature.
, according to the invention it is preferred to, in step (2), the revolving drying condition is at vacuum degree 0.09MPa, 75 DEG C
It carries out.
, according to the invention it is preferred to, in step (3), functional group's endcapped linear polydimethylsiloxanepolymer polymer with
The molar ratio of the hydrogeneous phenylmethylsiloxane polymers of scalariform is (0.9~4.1): 1, the hydrogeneous phenylmethylsiloxane polymers of scalariform and chlorine platinum
The molar ratio of acid is (68~112): 1.
, according to the invention it is preferred to, in step (3), functional group's endcapped linear polydimethylsiloxanepolymer polymer and
Mass concentration of the hydrogeneous phenylmethylsiloxane polymers of scalariform in toluene is 30%~73%, further preferably, functional group's sealing end
The mass concentration of linear polydimethylsiloxane- polymer and the hydrogeneous phenylmethylsiloxane polymers of scalariform in toluene be 33%~
60%.
, according to the invention it is preferred to, in step (3), the reaction temperature be 85 DEG C~105 DEG C, the reaction time be 4~
7h。
, according to the invention it is preferred to, in step (3), the removal chloroplatinic acid catalyst is: taking active carbon that reactant is added
For adsorbing chloroplatinic acid solid particle in solution, it is separated by filtration and removes active carbon and chloroplatinic acid.
, according to the invention it is preferred to, in step (3), the vacuum degree of the product revolving is 0.03MPa~0.09MPa, rotation
Steaming temperature is 65 DEG C~110 DEG C；Further preferably, revolving vacuum degree be 0.05MPa~0.08MPa, revolving temperature be 75 DEG C~
95℃。
The trapezoidal branch modified siloxane polymer supercritical carbon dioxide thickener of the method for the present invention preparation, has Formulas I
Shown in structure.
In method of the invention, product functional group's endcapped linear polydimethylsiloxanepolymer polymer of step (1), structural formula
As shown in Formula Il:
The hydrogeneous phenylmethylsiloxane polymers of product scalariform of step (2)；Shown in the following formula III of structural formula, shape such as ladder:
R1, R2, R3, a, b, m meaning in above formula II, formula III is identical as Formulas I.
According to the method for the present invention, the final product of step (3) has structure shown in Formulas I:
In Formulas I, R1 is methyl, ethyl or vinyl, and degree of polymerization m is between 3~16；R2 is methyl, ethyl, phenyl, second
Alkenyl or active hydrogen, degree of polymerization a is between 22~54, and b is between 17~48；R3 is methyl, phenyl or vinyl.
, according to the invention it is preferred to, in the final product Formulas I of step (3), R1 is methyl or ethyl, and degree of polymerization m is 4~10
Between；R2 is methyl, ethyl or phenyl, and degree of polymerization a is between 27~43；B is between 23~41；R3 is methyl or vinyl.
Most preferably, R1, R2, R3 are methyl, and degree of polymerization m is 6；Degree of polymerization a is 29；B is 25.
According to the present invention, the reaction condition of embodiment 1 is optimum reaction condition: the molar ratio of two kinds of cyclosiloxane is 1:1,
The molar ratio of annular siloxane and hexamethyldisiloxane is 9.1:1, and annular siloxane and hexamethyldisiloxane are in toluene
Quality total concentration be 58%, the molar ratio 2:1 of trichloromethyl silane, trichlorosilane alkane and phenylenediamine, chlorine-containing silane and benzene two
Mass concentration of the amine in tetrahydrofuran is 66%, and the mass concentration of deionized water in the reaction system is 2%, methyl blocking
The molar ratio of linear polydimethylsiloxane- polymer and the hydrogeneous phenylmethylsiloxane polymers of scalariform is 3:1, the hydrogeneous methyl of scalariform
The molar ratio of siloxane polymer and chloroplatinic acid is 98:1, and methyl blocking linear polydimethylsiloxane- polymer and scalariform are hydrogeneous
Mass concentration of the phenylmethylsiloxane polymers in toluene is 55%.
Technical characterstic and excellent results of the invention:
Dissolubility of the siloxanes thickener in supercritical carbon dioxide interacts due to being difficult to exist between the two,
Lamination is obvious, and solubility is lower, need to be in the cosolvents such as toluene or hexamethylene as raising siloxanes thickening under intermediary
Solubility of the agent in supercritical carbon dioxide.In addition, the hydrotropy that common siloxane polymer under cosolvent assistance, needs
Agent volume is larger, and is only dissolved in supercritical carbon dioxide under large volume cosolvent, and thickening effect is unobvious, so as to cause
The performance of low pressure break efficiency and carrying proppant.The present invention will contain functional group by being modified to siloxane polymer
Branch be introduced into thickener molecule, not only improve solubility of the thickener in supercritical carbon dioxide, reduce cosolvent
Dosage, and can have the performance of excellent thickening supercritical carbon dioxide, the ability for carrying proppant is improved, leak-off is reduced
Coefficient.
Since thickener generally relates to the high-molecular compounds such as polymer, thickening properties are not only considered, but also super
Solubility property in critical carbon dioxide is also important aspect.It takes into account thickening property and dissolubility is the technical problem of ability, this
Invention is introduced into the branch containing functional group to improve dissolubility of the siloxane polymer in supercritical carbon dioxide and thickening energy
Power.
Excellent results of the invention are as follows:
1, the various monomer materials that the present invention uses can directly be bought by market, and compared to fluorinated monomer, price is bright
Show relatively low.It is easy to get and price is relatively cheap, preparation condition is mild.
2, the reaction step that the present invention designs is easy to operate, will not relate to expensive laboratory apparatus, and operating procedure is not numerous
It is trivial.
3, the reaction that the present invention carries out to prepare products collection efficiency higher, waste is not present, will not be to environmental effects.
4, the physicochemical properties of trapezoidal branch modified siloxane polymer are stablized, and changing over time is not in chemical knot
The variation of structure and thickening properties.
5, the introducing of side chain helps to improve the raising of type siloxane thickener in trapezoidal branch modified siloxane polymer
The performance of the viscosity of supercritical carbon dioxide fracturing fluid.
6, the compatibility of trapezoidal branch modified siloxane polymer prepared by the present invention and toluene and supercritical carbon dioxide
It can be excellent.
7, products of the present invention is not soluble in water, and polarity is small, small with rock surface contact angle, is easy to return row from reservoir.
To sum up, trapezoidal branch modified siloxane polymer prepared by the present invention can industrial mass production, it is excellent
The performance of thickening supercritical carbon dioxide can be developed in oil field fracturing, especially in the exploitation of the petroleum resources of shale reservoir
With good application effect.
Detailed description of the invention
Fig. 1 is the infrared spectrum of the trapezoidal branched chain methyl sealing end polydimethylsiloxanepolymer polymer of 1 products therefrom of embodiment.
Specific embodiment
The present invention will be further described combined with specific embodiments below, but the scope of the present invention is not limited only to this, real
Applying raw material described in example is regular market purchase product.
Embodiment 1
A kind of preparation method of trapezoidal branch modified siloxane polymer supercritical carbon dioxide thickener, including step is such as
Under:
1) preparation of methyl blocking linear polydimethylsiloxane- polymer
29.6g octamethylcy-clotetrasiloxane, 34.4g tetramethyl tetravinyl ring four are added in the synthesis reaction vessel of 250mL
Siloxanes, 3.6g hexamethyldisiloxane, 115mL toluene and 0.15g tetramethylammonium hydroxide, and the nitrogen usually under temperature
0.5L·min-1Flow velocity under synthesis reaction vessel is sealed after 30min, and be put in High Temperature Rotating roller furnace and reacted at 110 DEG C
8h, after raise the temperature at 150 DEG C react 40min after be reduced to room temperature, reactant is at 90 DEG C of vacuum degree 0.06MPa, temperature
Under the conditions of vacuum removal toluene solvant and low-boiling-point substance 4h, obtain methyl blocking linear polydimethylsiloxane- polymer 42g.
(2) preparation of the hydrogeneous phenylmethylsiloxane polymers of scalariform
To equipped with condensing unit, dropping funel, agitating device three-necked flask in pour into 14.9g trichloromethyl silane and
13.5g trichlorosilane alkane, and the 68mL tetrahydrofuran mixed solution containing 11g phenylenediamine is poured into three-necked flask, in 220 DEG C
Lower reaction 0.9h.2g deionized water is poured into mixed reactant solution afterwards and reacts 2h at 190 DEG C.It will be through after being cooled to room temperature
It is separated by filtration removing solid matter, and is evaporated remaining small molecule low-boiling-point substance and four under the conditions of 0.07MPa, 85 DEG C of temperature
Hydrogen furans obtains concentration filtrate.After stirring 5h under filtrate room temperature, cleaned with saturated salt solution to pH=7, in 0.09MPa
Vacuum degree and 75 DEG C of backspins be evaporated dry, obtain white solid product 27g, the i.e. hydrogeneous phenylmethylsiloxane polymers of scalariform.
(3) preparation of trapezoidal branched chain methyl sealing end polydimethylsiloxanepolymer polymer
The 115mL toluene that the 35g of preparation is linearly blocked dimethyl silicone polymer and the hydrogeneous methylsiloxane of 20g scalariform is molten
Liquid pours into three-necked flask, after 0.0003g chloroplatinic acid reaction 6h is instilled at 85 DEG C, is cooled to room temperature down active carbon and reaction is added
Filter operation is separated off active carbon and chloroplatinic acid after 5h in object solution, by the product after absorption in 0.08MPa and 87 DEG C of backspin
It steams 3h and removes small molecule low-boiling-point substance, obtain the thick liquid 38g of light yellow clear, yield 69.10%.As siloxanes
Polymer supercritical carbon dioxide thickener.With structure shown in Formulas I, wherein R1 is methyl, and degree of polymerization m is 6；R2 is first
Base, degree of polymerization a are 29；B is 25；R3 is methyl.
Products therefrom infrared spectrum is as shown in Fig. 1.In infrared spectrum, 2964cm-1It is the hydrocarbon absorption peak of methyl
(vC-H), in addition, the absorption peak (δ of methylas C-H) appear in 1412cm-1；1261cm-1It is the symmetric deformation absorption peak of methyl,
1024cm-1To 1093cm-1Broad peak be silicon oxygen bond characteristic absorption peak, 800.327cm-1It is then the absorption peak of silicon-carbon bonds
(vas Si-C), the symmetrical stretching vibration (v of silicon-carbon bondss Si-C) mainly in 718.759cm-1。
Embodiment 2
As described in Example 1, operating procedure is consistent, except that basic catalyst used in step (1) is hydrogen-oxygen
Change potassium, usage amount is 0.13g.
Embodiment 3
As described in Example 1, operating procedure is consistent, except that cyclosiloxane used in step (1) is tetramethyl
Tetravinyl cyclotetrasiloxane and tetraphenyl tetramethyl-ring tetrasiloxane, dosage are respectively 34.4g and 55g.
Products therefrom has structure shown in Formulas I, wherein R1 is methyl, and degree of polymerization m is 6；R2 is phenyl, and degree of polymerization a is
29；R3 is methyl.
Embodiment 4
As described in Example 1, operating procedure is consistent, except that in step (1), octamethylcy-clotetrasiloxane and tetramethyl
The dosage of base tetravinyl cyclotetrasiloxane is respectively 15g and 69g.Products therefrom has structure shown in Formulas I, wherein R1 is
Methyl, degree of polymerization m are 4；R2 is methyl, and degree of polymerization a is 29；B is 41；R3 is methyl.
Embodiment 5
As described in Example 1, except that the molar ratio of cyclosiloxane and hexamethyldisiloxane is in step (1)
14:1。
Embodiment 6
As described in Example 1, except that in step (2), the quality of trichloromethyl silane and trichlorosilane alkane is distinguished
For 22.4g and 7g.The molar ratio of two kinds of chlorine-containing silanes is 3:1.
Embodiment 7
As described in Example 1, except that the usage amount of phenylenediamine is 8.2g in step (2).
Embodiment 8
As described in Example 1, except that the dosage of deionized water is 0.21g in step (2).
Embodiment 9
As described in Example 1, except that catalyst is chlordene rhodium (III) sour potassium in step (3), dosage is
0.0008g。
Embodiment 10
As described in Example 1, except that in step (3) reaction time be 7h, reaction temperature be 105 DEG C.
Comparative example 1
Comparative example 1 is the linear polydimethylsiloxane- of Dow corning company production.
Comparative example 2
Comparative example 2 is the vinyl phenyl silicone oil of Jiande City's polymerized new material Co., Ltd production.
Embodiment and the evaluation of comparative example properties of product:
With 3 times of volumes in the toluene prepared polymer concentration of siloxane polymer be 1.9wt% siloxane polymer it is molten
Liquid, with capillary viscosity measuring device in 10MPa, 30 DEG C and 170s~1Shear rate under test each polymer, toluene and
The viscosity of supercritical carbon dioxide mixed high-voltage liquid, viscosity numerical value are as shown in table 1.
1 anti-shear performance measurement result of table
| Sample number into spectrum | Viscosity, mPas |
| Embodiment 1 | 231 |
| Embodiment 2 | 137 |
| Embodiment 3 | 82 |
| Embodiment 4 | 109 |
| Embodiment 5 | 170 |
| Embodiment 6 | 73 |
| Embodiment 7 | 97 |
| Embodiment 8 | 113 |
| Comparative example 1 | 24 |
| Comparative example 2 | 50 |
Claims (10)
1. a kind of preparation method of trapezoidal branch modified siloxane polymer supercritical carbon dioxide thickener, comprising steps of
(1) preparation of functional group's endcapped linear polydimethylsiloxanepolymer polymer
Annular siloxane, small molecule end-capping reagent, toluene and basic catalyst are added in reaction kettle, nitrogen is passed through, by reaction kettle
Sealing, reacts 2-11h, then temperature is increased to react 30-40min at 140-155 DEG C, is down to room at a temperature of 100-115 DEG C
Temperature, vacuum removal toluene solvant and small molecule siloxanes low-boiling-point substance obtain the polymerization of functional group's endcapped linear dimethyl silicone polymer
Object；
The annular siloxane is octamethylcy-clotetrasiloxane, t etram-ethyltetravinylcyclotetrasiloxane, eight ethylene basic rings, four silicon
Oxygen alkane, tetramethyl tetrahydro cyclotetrasiloxane, hexamethyl dihydro cyclotetrasiloxane, hexamethyl cyclotrisiloxane, four silicon of octaphenyl ring
One of oxygen alkane, tetramethyl tetraphenyl cyclotetrasiloxane are a variety of；
The small molecule end-capping reagent is tetramethyl disiloxane, hexamethyldisiloxane, heptamethyltrisiloxane, three silicon of prestox
Oxygen alkane, pentamethyl disiloxane, six vinyl disiloxane, hexaphenyldisiloxane or seven phenyl trisiloxanes；
The molar ratio of the annular siloxane and small molecule end-capping reagent is (1.7-15): 1；Annular siloxane and small molecule end-capping reagent
Mass concentration in toluene is 30%~85%；The molar ratio of annular siloxane and basic catalyst is (92-224): 1；
(2) preparation of the hydrogeneous phenylmethylsiloxane polymers of scalariform
At a temperature of 160-270 DEG C, react chlorine-containing silane with phenylenediamine, the molar ratio of the chlorine-containing silane and phenylenediamine is
(0.55~3.2): 1, the phenylenediamine is dissolved in tetrahydrofuran solvent, the matter of chlorine-containing silane and phenylenediamine in tetrahydrofuran
Measuring concentration is 30%~74%；Then,
Deionized water, which is added, makes its mass concentration 0.1%~4.3% in the system, reacts at 140-210 DEG C
1.5-4.2h；It is cooled to room temperature；
Then it filters, is separated off solid matter, evaporation removes remaining small molecule low-boiling-point substance and tetrahydrofuran, obtains concentration filter
Liquid；Concentration filtrate is stirred into 3-5h, is cleaned with saturated common salt aqueous solution to pH=7, is rotated drying, obtain the hydrogeneous methyl silicon of scalariform
Oxygen alkane polymer；
(3) preparation of trapezoidal branch modified siloxane polymer
The scalariform of functional group's endcapped linear polydimethylsiloxanepolymer polymer of step (1) preparation and step (2) preparation is hydrogeneous
Phenylmethylsiloxane polymers are dissolved in toluene together, and chloroplatinic acid catalyst is instilled at a temperature of 65 DEG C~125 DEG C, react 2-
7.5h is cooled to room temperature；Chloroplatinic acid catalyst is removed, then revolving removes small molecule low-boiling-point substance, obtains product, i.e., trapezoidal branch changes
Property siloxane polymer；
Wherein, functional group's endcapped linear polydimethylsiloxanepolymer polymer and the hydrogeneous phenylmethylsiloxane polymers of scalariform rub
You are than being (0.4~5.3): 1, the molar ratio of the hydrogeneous phenylmethylsiloxane polymers of the scalariform and chloroplatinic acid is (41~132): 1.
2. the preparation side of trapezoidal branch modified siloxane polymer supercritical carbon dioxide thickener as described in claim 1
Method, it is characterised in that in step (1), the annular siloxane is octamethylcy-clotetrasiloxane, four silicon of tetramethyl tetravinyl ring
One of oxygen alkane, eight vinyl cyclotetrasiloxanes, octaphenylcyclotetrasiloxane, tetramethyl tetraphenyl cyclotetrasiloxane are more
Kind；Preferably, the small molecule end-capping reagent is hexamethyldisiloxane, heptamethyltrisiloxane, octamethyltrisiloxane, five first
Base disiloxane, six vinyl disiloxane or hexaphenyldisiloxane.
3. the preparation side of trapezoidal branch modified siloxane polymer supercritical carbon dioxide thickener as described in claim 1
Method, which is characterized in that in step (1), the basic catalyst is tetramethylammonium hydroxide, sodium hydroxide, potassium hydroxide, hydrogen-oxygen
Change aluminium or lithium hydroxide.
4. the preparation side of trapezoidal branch modified siloxane polymer supercritical carbon dioxide thickener as described in claim 1
Method, which is characterized in that, in step (1), the molar ratio of annular siloxane and small molecule end-capping reagent is (4.5-14): 1, cyclic annular silicon
The molar ratio of oxygen alkane and basic catalyst is (113-185): 1, annular siloxane and quality of the small molecule end-capping reagent in toluene
Total concentration is 35%~70%.
5. the preparation side of trapezoidal branch modified siloxane polymer supercritical carbon dioxide thickener as described in claim 1
Method, which is characterized in that the reaction in step (1) includes one or more of the following conditions:
A. the flow velocity of nitrogen is 0.5Lmin-1, reaction kettle is sealed after being passed through nitrogen 30min, and be put in High Temperature Rotating roller furnace
In；
B. the annular siloxane in reaction kettle, small molecule end-capping reagent, toluene and basic catalyst react at 110 DEG C；
C. reactant vacuum removal toluene solvant and small molecule siloxanes low boiling under the conditions of vacuum degree 0.06MPa, 90 DEG C of temperature
Object；
Preferred according to the present invention, in step (2), the chlorine-containing silane is trichloromethyl silane, trichlorosilane alkane, three hydrogen chlorine silicon
Alkane, trim,ethylchlorosilane, trichloroethyl silane, two kinds in three hydrogen trimethoxy silanes, the molar ratio of two kinds of chlorine-containing silanes are
(0.5~4.5): 1.
6. the preparation side of trapezoidal branch modified siloxane polymer supercritical carbon dioxide thickener as described in claim 1
Method, which is characterized in that in step (2), the molar ratio of chlorine-containing silane and phenylenediamine is (0.85~2.7): 1, chlorine-containing silane and benzene
Mass concentration of the diamines in tetrahydrofuran is 35%~68%, and the mass concentration of deionized water in the reaction system is
0.3%~3.2%.
7. the preparation side of trapezoidal branch modified siloxane polymer supercritical carbon dioxide thickener as described in claim 1
Method, which is characterized in that reaction described in step (2) includes one or more of the following conditions:
A. the reaction temperature of the chlorine-containing silane and phenylenediamine mixture is 180 DEG C~240 DEG C；
B. chlorine-containing silane and phenylenediamine reaction time are 0.3-2.3h；
C. the deionized water and the reaction temperature of chlorine-containing silane, toluene and phenylenediamine mixture are 170 DEG C~220 DEG C；
D. it is 85 DEG C of vacuum degree 0.07MPa, temperature that evaporation, which removes remaining small molecule low-boiling-point substance and the condition of tetrahydrofuran,；
E. the revolving drying condition is carried out at the vacuum degree of 0.09MPa and 75 DEG C；
, according to the invention it is preferred to, in step (3), functional group's endcapped linear polydimethylsiloxanepolymer polymer and scalariform
The molar ratio of hydrogeneous phenylmethylsiloxane polymers is (0.9~4.1): 1, the hydrogeneous phenylmethylsiloxane polymers of scalariform and chloroplatinic acid
Molar ratio is (68~112): 1.
8. the preparation side of trapezoidal branch modified siloxane polymer supercritical carbon dioxide thickener as described in claim 1
Method, which is characterized in that in step (3), functional group's endcapped linear polydimethylsiloxanepolymer polymer and the hydrogeneous methyl of scalariform
Mass concentration of the siloxane polymer in toluene is 30%~73%；It is preferred that functional group's endcapped linear dimethyl silicone polymer
The mass concentration of polymer and the hydrogeneous phenylmethylsiloxane polymers of scalariform in toluene is 33%~60%.
9. the preparation side of trapezoidal branch modified siloxane polymer supercritical carbon dioxide thickener as described in claim 1
Method, which is characterized in that reaction described in step (3) includes one or more of the following conditions:
A. the reaction temperature is 85 DEG C~105 DEG C, and the reaction time is 4~7h；
B. the vacuum degree of the product revolving is 0.03MPa~0.09MPa, and revolving temperature is 65 DEG C~110 DEG C；It is preferred that revolving
Vacuum degree is 0.05MPa~0.08MPa, and revolving temperature is 75 DEG C~95 DEG C.
10. the trapezoidal overcritical titanium dioxide of branch modified siloxane polymer of the described in any item method preparations of claim 1-9
Carbon thickener, the trapezoidal branch modified siloxane polymer have structure shown in Formulas I:
In Formulas I, R1 is methyl, ethyl or vinyl, and degree of polymerization m is between 3~16；R2 is methyl, ethyl, phenyl, vinyl
Or active hydrogen, degree of polymerization a is between 22~54, and b is between 17~48；R3 is methyl, phenyl or vinyl.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110862541A (en) * | 2019-12-04 | 2020-03-06 | 中国石油大学(华东) | Preparation method of acrylate/siloxane polymer supercritical carbon dioxide thickener |
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| CN112708138A (en) * | 2019-10-25 | 2021-04-27 | 中国石油化工股份有限公司 | Preparation method and application of sesqui-cyclic siloxane supercritical carbon dioxide thickener |
| CN112961360A (en) * | 2021-02-04 | 2021-06-15 | 中国石油大学(华东) | Preparation method of polyhedral cagelike siloxane supercritical carbon dioxide thickener |
| CN113024816A (en) * | 2021-03-30 | 2021-06-25 | 中国日用化学研究院有限公司 | Comb-type aminosiloxane-allyl polydimethylsiloxane co-modified organic silicon and preparation method thereof |
| CN113929915A (en) * | 2021-10-26 | 2022-01-14 | 中国石油大学(华东) | Preparation method and application of modified siloxane supercritical carbon dioxide thickener |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5006584A (en) * | 1988-11-23 | 1991-04-09 | Chevron Research And Technology Company | Polydialkylsilalkylene polymer useful in enhanced oil recovery using carbon dioxide flooding |
| CN1590390A (en) * | 2003-06-23 | 2005-03-09 | 气体产品与化学公司 | Stabilizers to inhibit the polymerization of substituted cyclotetrasiloxane |
| CN101671436A (en) * | 2009-10-13 | 2010-03-17 | 广州天赐有机硅科技有限公司 | Preparation method for polysiloxane with extra high molecular weight |
| CN102443172A (en) * | 2011-08-02 | 2012-05-09 | 中国科学院化学研究所 | Polysiloxane polymer and preparation method thereof |
| WO2015094693A1 (en) * | 2013-12-20 | 2015-06-25 | Praxair Technology, Inc. | Fracturing fluid composition and method utilizing same |
| CN107236091A (en) * | 2016-03-28 | 2017-10-10 | 中国石油化工股份有限公司 | A kind of supercritical carbon dioxide thickener and its preparation method and application |
-
2019
- 2019-01-30 CN CN201910090496.9A patent/CN109796955B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5006584A (en) * | 1988-11-23 | 1991-04-09 | Chevron Research And Technology Company | Polydialkylsilalkylene polymer useful in enhanced oil recovery using carbon dioxide flooding |
| CN1590390A (en) * | 2003-06-23 | 2005-03-09 | 气体产品与化学公司 | Stabilizers to inhibit the polymerization of substituted cyclotetrasiloxane |
| CN101671436A (en) * | 2009-10-13 | 2010-03-17 | 广州天赐有机硅科技有限公司 | Preparation method for polysiloxane with extra high molecular weight |
| CN102443172A (en) * | 2011-08-02 | 2012-05-09 | 中国科学院化学研究所 | Polysiloxane polymer and preparation method thereof |
| WO2015094693A1 (en) * | 2013-12-20 | 2015-06-25 | Praxair Technology, Inc. | Fracturing fluid composition and method utilizing same |
| CN107236091A (en) * | 2016-03-28 | 2017-10-10 | 中国石油化工股份有限公司 | A kind of supercritical carbon dioxide thickener and its preparation method and application |
Non-Patent Citations (3)
| Title |
|---|
| QIANG LI: "Study on the optimization of silicone copolymer synthesis and the evaluation of its thickening performance", 《RSC ADVANCES》 * |
| 硅氧烷增稠 CO2压裂液高压流变性: "李宾飞", 《中国石油大学学报( 自然科学版)》 * |
| 黄 洲: "液态 CO2增稠剂的研究现状", 《现代化工》 * |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110862541B (en) * | 2019-12-04 | 2021-07-16 | 中国石油大学(华东) | Preparation method of acrylate/siloxane polymer supercritical carbon dioxide thickener |
| CN110862541A (en) * | 2019-12-04 | 2020-03-06 | 中国石油大学(华东) | Preparation method of acrylate/siloxane polymer supercritical carbon dioxide thickener |
| CN111849449B (en) * | 2020-06-28 | 2021-10-22 | 中国石油大学(北京) | Supercritical CO2Oil displacement system and oil displacement method |
| CN111849449A (en) * | 2020-06-28 | 2020-10-30 | 中国石油大学(北京) | Supercritical CO2Oil displacement system and oil displacement method |
| CN112961360A (en) * | 2021-02-04 | 2021-06-15 | 中国石油大学(华东) | Preparation method of polyhedral cagelike siloxane supercritical carbon dioxide thickener |
| CN113024816A (en) * | 2021-03-30 | 2021-06-25 | 中国日用化学研究院有限公司 | Comb-type aminosiloxane-allyl polydimethylsiloxane co-modified organic silicon and preparation method thereof |
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