CN112961360A - Preparation method of polyhedral cagelike siloxane supercritical carbon dioxide thickener - Google Patents

Preparation method of polyhedral cagelike siloxane supercritical carbon dioxide thickener Download PDF

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CN112961360A
CN112961360A CN202110152722.9A CN202110152722A CN112961360A CN 112961360 A CN112961360 A CN 112961360A CN 202110152722 A CN202110152722 A CN 202110152722A CN 112961360 A CN112961360 A CN 112961360A
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siloxane
hydrogen
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CN112961360B (en
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王彦玲
李强
刘斌
梁雷
汤龙皓
巩锦程
张传保
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China University of Petroleum East China
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Abstract

The invention relates to a preparation method of a polyhedral cagelike siloxane supercritical carbon dioxide thickener. The method comprises the following steps: (1) reacting hydroxyl double-end-capped siloxane with sodium silanol in an organic solvent to prepare double-end-capped siloxane; then, reacting the double-end sodium terminated siloxane with hydrogen-containing chlorosilane to prepare mono-hydrogen terminated siloxane; (2) under the existence of catalyst, the monohydrogen end-capped siloxane reacts in cyclohexane solution of cage-shaped stereo cyclosiloxane with the catalyst to prepare the multiangular cage-shaped siloxane polymer. The obtained siloxane polymer has good thickening capability for thickening supercritical carbon dioxide, and improves the condition of siloxane in CO2The dissolving capacity is enhanced, and the using amount of a cosolvent is reduced.

Description

Preparation method of polyhedral cagelike siloxane supercritical carbon dioxide thickener
Technical Field
The invention relates to a preparation method of a polygonal caged siloxane supercritical carbon dioxide thickener, belonging to the technical field of oil exploitation.
Background
The supercritical carbon dioxide fracturing technology can reduce the water sensitivity and water lock of the underground reservoir during the transformation of the low-permeability shale reservoir, can reduce the friction resistance of the reservoir and the formation damage aiming at the defects of low fluidity, high friction resistance and the like of the oil-based fracturing fluid, and can also improve the rheological property of crude oil. However, the low viscosity of supercritical carbon dioxide causes poor sand-carrying performance and fingering phenomenon, which is not favorable for CO2The improvement of the sweep coefficient of the fracturing fluid and the oil and gas development of a low-permeability reservoir. In order to solve this problem, researchers have conducted a great deal of research on thickeners, and research focuses on fluorine-containing polymers and hydrocarbon polymers. For example, addition of a fluorine-containing thickener to supercritical carbon dioxide, CN107043620A, provides a liquid carbon dioxide thickener [1, 6-bis (1, 3-diperfluorooctanoic acid propyl ester-2-ureido)]Hexane. Although the fluorine-containing polymer has an excellent thickening effect when used as a thickener, the fluorine-containing polymer is likely to interact with underground water and remain in a reservoir, pollute a low-permeability reservoir and water resources, further circulate in a biosphere, destroy the environment, and generate accumulation in a body to cause the accumulation of the biosphere. In addition, fluorine-containing thickeners are expensive and expensive, and are not suitable for industrial application. And the other type of hydrocarbon thickening agent has low preparation cost, but has high dissolving pressure and poor thickening effect, and cannot meet the fracturing requirement of a hypotonic reservoir stratum. Is currently available for thickening CO2The fluorine-containing thickener and the hydrocarbon thickener have limited types, and although the fluorine-containing thickener and the hydrocarbon thickener have a plurality of advantages, the defects of preparation cost, environmental pollution and the like prevent supercritical CO to a certain extent2Fracturing techniques are used for fracture stimulation of low permeability reservoirs.
More recently, studies have also been carried out on silicone polymer supercritical carbon dioxide thickeners, for example CN107236091A provides a supercritical carbon dioxide thickener having the composition: (a) polydimethylsiloxane; (b) an acrylate-based compound; (c) a styrenic compound; (d) an initiator; (e) an emulsifier; but the cosolvent has large dosage and poor solubility. CN108003349A provides a supercritical carbon dioxide thickener of siloxane polymer for fracturing, which is prepared by reacting aromatic amido end-capped side chain modified siloxane polymer with hydrogen-containing siloxane; the thickening agent has good thickening effect, but the testing temperature and pressure are low, the solvent dosage is large, and the dissolving capacity of the thickening agent in carbon dioxide needs to be further improved.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of a polygonal cage-shaped siloxane supercritical carbon dioxide thickening agent, and the obtained siloxane polymer has better thickening capacity for thickening supercritical carbon dioxide. The molecular structure of the thickening agent is added with a three-dimensional cage structure, so that the bond energy effect of carbon dioxide molecules and the thickening agent in a three-dimensional space is increased, and the dissolving capacity is enhanced.
The invention also provides the prepared polyhedral cagelike siloxane supercritical carbon dioxide thickening agent and application thereof.
Interpretation of terms:
room temperature, having a meaning well known in the art, is generally in the range of 20-26 ℃.
Hydroxyl double-terminated siloxane with a structure shown in a formula II;
a sodium-double-ended siloxane having a structure represented by formula III;
a monohydrogen terminated siloxane having a structure represented by formula IV.
Figure BDA0002933012300000021
The technical scheme of the invention is as follows:
a preparation method of a polyhedral cagelike siloxane supercritical carbon dioxide thickening agent takes hydroxyl double-terminated siloxane as an initial raw material, and comprises the following steps:
(1) preparation of one-sided active hydrogen terminated linear siloxanes
Reacting hydroxyl double-end-capped siloxane with sodium silanol in an organic solvent to prepare double-end-capped siloxane; then, reacting the double-end sodium terminated siloxane with hydrogen-containing chlorosilane to prepare mono-hydrogen terminated siloxane;
(2) preparation of polyhedral caged stereosiloxanes
Under the existence of catalyst, the monohydrogen end-capped siloxane is put into cyclohexane solution of cage-shaped stereo cyclosiloxane to react under the temperature of 35-90 ℃ with the catalyst, and the multiangular cage-shaped siloxane polymer is prepared.
The structure of the obtained product polyhedral cagelike siloxane polymer is shown as a formula I:
Figure BDA0002933012300000022
Figure BDA0002933012300000031
in the formula I, R is methyl, ethyl, allyl, active hydrogen, epoxy ether group or phenyl, the polymerization degree a is 12-47, and b is 3-20. Q is a core cage-shaped three-dimensional framework structure of cage-shaped three-dimensional cyclosiloxane, and each silicon atom is respectively connected with one R1，
R1Comprises the following steps:
Figure BDA0002933012300000037
for example, several typical polyhedral cage siloxane polymers have the structure:
Figure BDA0002933012300000032
R1is composed of
Figure BDA0002933012300000033
Figure BDA0002933012300000034
R1Is composed of
Figure BDA0002933012300000035
Or
Figure BDA0002933012300000041
R1Is composed of
Figure BDA0002933012300000042
The cage-shaped stereo cyclosiloxane is selected from methyl cyclotetrasiloxane, tetramethyl tetravinylcyclotetrasiloxane, tetramethyl tetrahydrocyclotetrasiloxane, decamethylcyclopentasiloxane, dihedral tri-square stereo cage-shaped cyclosiloxane, hexahedral all-square stereo cage-shaped cyclosiloxane or hexahedral all-pentagon stereo cage-shaped cyclosiloxane.
Preferably, in step (1), the organic solvent is one or more of toluene, cyclohexane, n-hexane, benzene, ethanol, methanol, petroleum ether and acetone; the hydrogen-containing chlorosilane is one of dimethylmonohydrochlorosilane, monomethyldihydrochlorosilane, trihydrochlorosilane, pentamethyl monohydro-hydrogen-chlorosilane and tetramethyl di-hydrogen-chlorosilane.
Preferably according to the invention, the conditions for reacting the hydroxy-bis-terminal siloxane with the sodium silanol in step (1) include one or more of the following:
i. the molar ratio of the sodium silanol to the hydroxyl double-end-capped siloxane is (2.6-6.7): 1; further preferably, the molar ratio of the sodium silanol to the hydroxyl-double-terminated siloxane is (3.5-5.6): 1;
the mass concentration of the sodium silanol and the hydroxyl double-end-capped siloxane in the organic solvent is 40-75%; further preferably, the mass concentration of the sodium silanol and the hydroxyl double-terminated siloxane in the organic solvent is 48-64%;
and iii, dropwise adding the sodium silanol into hydroxyl double-end-sealed siloxane, heating to 42-100 ℃ at the speed of 1.5-4.4 ℃/min, and reacting for 2.5-13 h. Preferably, the sodium silanol is added into the 1, 21-hydroxyl polysiloxane drop by drop, the temperature is raised to 55-80 ℃ at the speed of 2.3-3.2 ℃/min, and then the reaction is carried out for 4-9 h. Cooling the obtained product, and then carrying out suction filtration to remove impurities. Obtaining the double-sodium-end terminated siloxane.
According to the invention, in the step (1), the molar ratio of the sodium-terminated double-end siloxane to the hydrogen-containing chlorosilane is (0.85-1.73): 1; further preferably, the molar ratio of the sodium-terminated double-ended siloxane to the hydrogen-containing chlorosilane is (0.99-1.43): 1.
according to the invention, in the step (1), the reaction conditions of the sodium-terminated double-ended siloxane and the hydrogen-containing chlorosilane are as follows: hydrogen-containing chlorosilane is slowly dripped into the double-end sodium terminated siloxane and reacts for 18 to 22 hours at the temperature of between 15 ℃ below zero and 0 ℃. The slow dropping speed is 1-1.5 drops/s.
Preferably, in step (1), the sodium-terminated double-ended siloxane is reacted with hydrogen-containing chlorosilane, and the post-treatment of the obtained product is as follows: and removing residual solvent and low-boiling-point substances in vacuum under the conditions that the vacuum degree is 0.03-0.09MPa and the temperature is 60-100 ℃ to obtain the mono-hydrogen terminated siloxane. Furthermore, the residual solvent and low-boiling-point substances of the obtained product are removed in vacuum under the conditions that the vacuum degree is 0.05-0.08 MPa and the temperature is 75-90 ℃.
Preferably, according to the present invention, in step (1), the hydroxy-both terminal siloxane is 1, 21-hydroxy polysiloxane; correspondingly, the product sodium-terminated-both-end siloxane is 1, 21-sodium polysiloxane.
Preferably, in step (2), the cage-type stereo cyclosiloxane is octamethylcyclotetrasiloxane, tetramethyltetravinylcyclotetrasiloxane, tetramethyltetrahydrocyclotetrasiloxane, decamethylcyclopentasiloxane, dihedral tritetragonal tri-square stereo cage-type cyclosiloxane, hexahedral all-square stereo cage-type cyclosiloxane or hexahedral all-pentagon stereo cage-type cyclosiloxane. Among them, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dihedral trigonal tri-square three-dimensional cage-shaped cyclosiloxane, hexahedral all-square three-dimensional cage-shaped cyclosiloxane or hexahedral all-pentagon three-dimensional cage-shaped cyclosiloxane is preferable.
Preferably, in step (2), the catalyst is sodium chloroplatinate, chloroplatinic acid, ammonium chloroplatinate, sodium hexachloroplatinate hexahydrate or ammonium hexachlororuthenate and vanadium pivalate trimethyl. The molar ratio of the cage-shaped stereo cyclosiloxane to the catalyst is (84-211): 1, and more preferably the molar ratio is (98-186): 1.
according to the invention, in the step (2), the molar ratio of the cage-shaped stereo-ring siloxane to the one-side hydrogen-terminated siloxane is (0.045-0.472): 1, more preferably the molar ratio is (1.27 to 3.83): 1.
according to the present invention, in the step (2), the total concentration of the cage-shaped stereo-cyclosiloxane and the mono-hydrogen terminated siloxane in the cyclohexane is preferably 23.4% to 49.6%, and the total concentration is more preferably 31% to 42%;
according to the optimization of the method, in the step (2), a catalyst is added at the temperature of 35-90 ℃ for reaction for 4-8.5 h; preferably, the catalyst is added at 44-79 ℃ for reaction for 5.2-7.8 h.
According to a preferred embodiment of the present invention, in step (2), the product after the reaction is worked up as follows: cooling to 20-26 ℃, filtering to remove solid particle impurities, and removing residual solvent and low-boiling-point substances in vacuum from the filtered liquid product under the conditions of vacuum degree of 0.02-0.07MPa and temperature of 90-130 ℃ to obtain the polyhedral oligomeric siloxane polymer. The product was obtained as a light yellow transparent viscous liquid. Preferably, the residual solvent and low-boiling-point substances are removed from the filtered liquid product in vacuum under the conditions of 0.04-0.06MPa and 95-115 ℃.
According to the invention, a preferred embodiment is:
a preparation method of a polyhedral cage-shaped siloxane supercritical carbon dioxide thickener comprises the following steps:
(1) preparation of one-sided active hydrogen terminated linear siloxanes
Pouring 1, 21-hydroxyl polysiloxane and an organic solvent into a 500mL glass flask, heating sodium silanol to 42-100 ℃ by 1.5-4.4 ℃/min drop by drop, and reacting for 2.5-13 h; and (5) cooling, and then removing impurities in a filter flask to obtain the 1, 21-sodium polysiloxane. Adding 1, 21-sodium polysiloxane into another 250ml three-neck flask, slowly dripping hydrogen-containing chlorosilane, reacting for 20h at-15 ℃, and removing residual solvent and low-boiling-point substances in vacuum for 1.5h under the conditions of vacuum degree of 0.03-0.09MPa and temperature of 60-100 ℃ to obtain monohydrogen terminated siloxane for later use;
the solvent is one or more of toluene, cyclohexane, n-hexane, benzene, ethanol, methanol, petroleum ether and acetone; the hydrogen-containing chlorosilane is one of dimethylmonohydrochlorosilane, monomethyldihydrochlorosilane, trihydrochlorosilane, pentamethyl monohydro-hydrogen-chlorosilane and tetramethyl di-hydrogen-chlorosilane; the molar ratio of the sodium silanol to the 1, 21-hydroxyl polysiloxane is (2.6-6.7): 1, the mass concentration of the sodium silanol and the 1, 21-hydroxyl polysiloxane in the solvent is 40-75 percent; the molar ratio of the 1, 21-sodium polysiloxane to the hydrogen-containing chlorosilane is (0.85-1.73): 1.
(2) preparation of polyhedral caged stereosiloxanes
Adding the mono-hydrogen end-capped siloxane prepared in the step (1) and a cyclohexane solution of cage-shaped stereo-ring siloxane into a glass flask, and adding a catalyst at 44-79 ℃ to react for 5.2-7.8 h. Then, cooling to 25 ℃, filtering to remove solid particle impurities, and removing residual solvent and low-boiling-point substances in vacuum of the filtered liquid product under the conditions of vacuum degree of 0.04-0.06MPa and temperature of 95-115 ℃ to obtain light yellow transparent adhesive liquid, namely the polyhedral cage-shaped siloxane polymer;
the cage-shaped three-dimensional cyclosiloxane is one of octamethylcyclotetrasiloxane, tetramethyltetravinylcyclotetrasiloxane, tetramethyltetrahydrocyclotetrasiloxane, decamethylcyclopentasiloxane, dihedral triquadrate three-dimensional cage-shaped cyclosiloxane, hexahedral all-square three-dimensional cage-shaped cyclosiloxane and hexahedral all-pentagon three-dimensional cage-shaped cyclosiloxane; the catalyst is one of sodium chloroplatinite, chloroplatinic acid, ammonium chloroplatinite, sodium hexachloroplatinate hexahydrate, ammonium hexachlororuthenate and trimethyl vanadium acetate. Wherein the molar ratio of the cage-shaped stereo-ring siloxane to the unilateral hydrogen-terminated siloxane is (0.045-0.472): 1, the total concentration of cage-shaped stereo-cyclosiloxane and mono-hydrogen terminated siloxane in cyclohexane is 23.4-49.6%, and the molar ratio of the cage-shaped stereo-cyclosiloxane to noble metal acid is (84-211): 1.
the polyhedral oligomeric siloxane polymers are prepared by the process of the invention. Has a structure shown in formula I. The weight average molecular weight was 2000-8000. The preferred weight average molecular weight is 2000-.
The invention discloses application of a prepared polyhedral oligomeric silsesquioxane polymer supercritical carbon dioxide thickener. The polyhedral oligomeric siloxane polymer is used asThickener for supercritical CO2Fracturing techniques are used for fracture stimulation of low permeability reservoirs. Improvement of siloxanes in CO2The mixing and thickening ability of the compound can be reduced, and the dosage of the cosolvent is reduced.
The invention has the following technical characteristics and excellent effects:
according to the invention, 1, 21-hydroxyl polysiloxane is used as a reaction monomer, a mono-hydrogen end-capped siloxane polymer is formed by modification, and the polygonal cage-shaped siloxane supercritical carbon dioxide thickener is prepared by a hydrosilylation reaction, so that the capability of mutual collision and action of molecules of the polygonal cage-shaped thickener and carbon dioxide molecules is enhanced in the spatial three-dimensional direction, and the capability of siloxane in CO is improved2The miscibility performance and the solubility of the siloxane are effectively improved to the supercritical CO2The thickening ability of (1). Overcomes the defects of weak dissolving capacity of the thickening agent in carbon dioxide, large using amount of the thickening agent and the like in the prior art.
1. The reaction substrate involved in the preparation process has low cost, the purchase route is convenient, and the side chain of the hydroxyl-terminated siloxane can be adjusted.
2. The preparation process of the siloxane polymer has simple steps, easy realization of synthesis conditions, no need of special instruments and high safety of reactants.
3. No other reaction waste and toxic and harmful substances are generated in the reaction process, and no pollution is generated to human bodies and the environment.
4. The prepared siloxane polymer thickener has stable physical properties at normal temperature and normal pressure, is not easy to generate self-crosslinking, and can be hermetically stored for a long time at low temperature.
5. The product prepared by the invention has good compatibility with various cosolvents.
6. The addition of branched chains in the polygonal cage-shaped siloxane supercritical carbon dioxide thickener can improve the CO content of siloxane2The mixing and thickening ability of the compound can be reduced, and the dosage of the cosolvent is reduced.
In a word, the product of the invention is suitable for industrialized mass production, has better application in oilfield exploitation, does not pollute low-permeability shale reservoir and can carry out supercritical CO treatment at the high temperature of more than 70 DEG C2Has excellent mixing and thickening performance。
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of a sample of the polyhedral cagelike siloxane polymer prepared in example 1.
FIG. 2 is a nuclear magnetic carbon spectrum of a sample of the polyhedral oligomeric siloxane polymer prepared in example 1.
Detailed Description
The present invention is further illustrated by the following specific examples, but the scope of the present invention is not limited thereto, and all the raw materials in the examples are commercially available products, which are easy to purchase and have high safety. 1, 21-Hydroxypolysiloxanes are commercially available from Dow Corning, USA.
Example 1
A preparation method of a multi-end branched siloxane supercritical carbon dioxide thickener comprises the following steps:
(1) preparation of monohydrogen terminated linear siloxanes
Adding 105g of 1, 21-hydroxyl polysiloxane, 124mL of cyclohexane and 6.59g of sodium silanol into a 500mL dry three-neck flask which is provided with a stirrer, a nitrogen introducing pipe and a thermometer, raising the temperature to 75 ℃ at the speed of 2.6 ℃/min, and reacting for 8.5 h; cooling to room temperature, and performing suction filtration to remove impurities to obtain the sodium-terminated siloxane (1, 21-sodium polysiloxane). Pouring the prepared 1, 21-sodium polysiloxane into another 250mL glass flask, reacting 9.73g of dimethylmonohydrochlorosilane at-15 ℃ for 20h, and removing impurities under the conditions of vacuum degree of 0.05MPa and temperature of 78 ℃ to obtain 108g of monohydrogen terminated linear siloxane (R is methyl) for later use; the yield thereof was found to be 89.27%.
Figure BDA0002933012300000081
(2) Preparation of polyhedral oligomeric silsesquioxane thickeners
Under the protection of nitrogen, 0.04mol of the mono-hydrogen end-capped linear siloxane prepared in the step (1) and 84mL of cyclohexane solution containing 0.002mol of the dihedral triangular three-square three-dimensional cage-shaped ring siloxane are added into a three-neck flask, the mixture is uniformly stirred, and 2.7 multiplied by 10-5Reacting mol chloroplatinic acid for 6.4h, filtering to remove impurities, and keeping the vacuum degree of a liquid product at 0The residual solvent and low-boiling-point substances are removed under the vacuum condition at the temperature of 90 ℃ under the pressure of 05MPa to obtain light yellow transparent liquid, namely the polyhedral oligomeric siloxane, the weight-average molecular weight is 4220, 23.2g of products are obtained, and the yield is 74.3%.
The resulting product has the following structural formula:
Figure BDA0002933012300000082
R1is composed of
Figure BDA0002933012300000083
a＝13，b＝7。
The nuclear magnetic spectra of the obtained product are shown in fig. 1 and fig. 2, and only two hydrogen peaks (delta is 0.14 and delta is 0.21) of the side chain methyl group appear in the nuclear magnetic hydrogen spectrum, while only two carbon peaks (delta is 5.34 and delta is 5.82, the rest hydrogen peaks and carbon peaks do not appear in the nuclear magnetic carbon spectrum, and reactants do not appear in the nuclear magnetic spectrum, and hydrogen peaks and carbon peaks of other groups do not exist, which indicates that the thickener product is successfully synthesized.
Example 2
The procedure was as described in example 1, except that the cage-type stereo-cyclosiloxane used in step (2) was a six-sided all-square stereo-cage-cyclosiloxane. The resulting product has the following structural formula (a ═ 13, b ═ 7):
Figure BDA0002933012300000091
r1 is
Figure BDA0002933012300000092
Example 3
Except that 1, 21-hydroxy-2-naphthyl-siloxane was added in step (1) as described in example 1. The resulting product has the following structural formula (a ═ 13, b ═ 7):
Figure BDA0002933012300000093
R1is composed of
Figure BDA0002933012300000094
Example 4
As described in example 1, except that the solvent used in step (1) was 138mL of toluene.
Example 5
As described in example 1, except that in step (1) the temperature was raised to 75 ℃ in a three-necked flask at an increase rate of 5.0 ℃/min.
Example 6
As described in example 1, except that in step (2) the catalyst was replaced with sodium hexachloroplatinate hexahydrate, the amount used was the same.
Example 7
As in example 1, except that the molar ratio of cage-stereo cyclosiloxane to mono-hydrogen terminated siloxane in step (2) was 3.8: 1.
example 8
As described in example 1, except that the molar ratio of cage-stereo cyclosiloxane to catalyst in step (2) was 183: 1.
example 9:
113g of 1, 21-hydroxyl polysiloxane, 119mL of cyclohexane and 8.2g of sodium silanol are added into a 500mL dry three-neck flask which is provided with a stirrer, a nitrogen introducing pipe and a thermometer, the temperature is raised to 90 ℃ at the speed of 4.1 ℃/min, and then the mixture reacts for 4 hours; removing impurities at room temperature to obtain the sodium bi-end terminated siloxane. Pouring the prepared 1, 21-sodium polysiloxane into another 250mL glass flask, reacting 8.75 pentamethyl-hydrochlorodisilane at-7 ℃ for 13h, and removing impurities under the conditions of vacuum degree of 0.07MPa and temperature of 89 ℃ to obtain 101g of mono-hydrogen terminated linear siloxane for later use; the yield was 77.69%.
(2) Preparation of polyhedral oligomeric silsesquioxane thickeners
Under the protection of nitrogen, 0.04mol of monohydrogen terminated linear siloxane prepared in the step (1) and 0.002mol of dihedral triangular trisquare84mL of cyclohexane solution of the three-dimensional caged cyclosiloxane was stirred uniformly and 2.7X 10 added at 75 deg.C-5Reacting mol chloroplatinic acid for 6.4h, filtering to remove impurities, and removing residual solvent and low-boiling-point substances in vacuum at the temperature of 90 ℃ under the vacuum degree of 0.05MPa of a liquid product to obtain light yellow transparent liquid, namely the polyhedral cagelike siloxane. The weight average molecular weight was 3852, giving 17.2g of product in 55.1% yield.
Example 10:
adding 105g of 1, 21-hydroxyl polysiloxane, 124mL of cyclohexane and 6.59g of sodium silanol into a 500mL dry three-neck flask which is provided with a stirrer, a nitrogen introducing pipe and a thermometer, raising the temperature to 90 ℃ at the speed of 4.1 ℃/min, and reacting for 4 h; removing impurities at room temperature to obtain the sodium bi-end terminated siloxane. Pouring the prepared double-end sodium terminated siloxane into another 250mL glass flask, reacting 9.73g of dimethylmonohydrochlorosilane at-15 ℃ for 20h, and removing impurities under the conditions of vacuum degree of 0.05MPa and temperature of 78 ℃ to obtain 108g of monohydrogen terminated linear siloxane for later use; the yield was 89.27%.
(2) Preparation of polyhedral oligomeric silsesquioxane thickeners
Under the protection of nitrogen, 0.02mol of the mono-hydrogen end-capped linear siloxane prepared in the step (1) and 84mL of cyclohexane solution containing 0.002mol of dihedral triangular three-square three-dimensional cage-shaped ring siloxane are added into a three-neck flask and stirred uniformly, and 2.7 multiplied by 10 is added at 75 DEG C-5Reacting ammonium hexachlororuthenate for 6.4h, filtering to remove impurities, and removing residual solvent and low-boiling-point substances in vacuum at 90 ℃ under the vacuum degree of 0.05MPa to obtain light yellow transparent liquid 11.4g, namely the polyhedral cagelike siloxane. The weight average molecular weight is 2157.
Comparative example 1
As in example 1, except that dimethylmonohydrochlorosilane was not added to the monomers.
Comparative example 2
Comparative example 2 is dimethicone produced by dow corning corporation of america.
Experimental example: comparison of the Properties of the polyhedral oligomeric silsesquioxane Polymer products of the examples and of the comparative examples
Preparing the siloxane thickener by using 0.5 times of cyclohexane solutionIs 3% of supercritical CO2Fracturing fluid solution, 8MPa, 55 ℃ and 170s-1Under the condition that the thickening agent is in CO2The miscibility and solubility of the samples are shown in Table 1, the different samples are on CO2The viscosity and viscosity ratio (compared to pure carbon dioxide) data for the fracturing fluid are shown in table 2.
TABLE 1 results of evaluation of miscibility and solubility
Sample numbering Appearance of mixed liquid Whether or not to dissolve completely
Example 1 Clarification Is that
Example 2 Clarification Is that
Example 3 Clarification Is that
Example 4 Clarification Is that
Example 5 Clarification Is that
Practice ofExample 6 Clarification Is that
Example 7 Clarification Is that
Example 8 Clarification Is that
Example 9 Clarification Is that
Example 10 Clarification Is that
Comparative example 1 Turbidity Whether or not
Comparative example 2 Clarification Is that
TABLE 2 thickening Performance evaluation results
Figure BDA0002933012300000111
Figure BDA0002933012300000121

Claims (10)

1. A preparation method of a polyhedral cagelike siloxane supercritical carbon dioxide thickening agent takes hydroxyl double-terminated siloxane as an initial raw material, and comprises the following steps:
(1) preparation of one-sided active hydrogen terminated linear siloxanes
Reacting hydroxyl double-end-capped siloxane with sodium silanol in an organic solvent to prepare double-end-capped siloxane; then, the user can use the device to perform the operation,
reacting double-end sodium terminated siloxane with hydrogen-containing chlorosilane to prepare mono-hydrogen terminated siloxane;
(2) preparation of polyhedral caged stereosiloxanes
Under the existence of catalyst, the monohydrogen end-capped siloxane is put into cyclohexane solution of cage-shaped stereo cyclosiloxane to react under the temperature of 35-90 ℃ with the catalyst, and the multiangular cage-shaped siloxane polymer is prepared.
2. The method for preparing the polyhedral cagelike siloxane supercritical carbon dioxide thickener according to claim 1, wherein in the step (1), the organic solvent used is one or more of toluene, cyclohexane, n-hexane, benzene, ethanol, methanol, petroleum ether and acetone; the hydrogen-containing chlorosilane is one of dimethylmonohydrochlorosilane, monomethyldihydrochlorosilane, trihydrochlorosilane, pentamethyl monohydro-hydrogen-chlorosilane and tetramethyl di-hydrogen-chlorosilane.
3. The method of claim 1, wherein the conditions for reacting the hydroxy-terminated bis-siloxane with the sodium silanol in step (1) comprise one or more of the following:
i. the molar ratio of the sodium silanol to the hydroxyl double-end-capped siloxane is (2.6-6.7): 1; further preferably, the molar ratio of the sodium silanol to the hydroxyl-double-terminated siloxane is (3.5-5.6): 1;
the mass concentration of the sodium silanol and the hydroxyl double-end-capped siloxane in the organic solvent is 40-75%; further preferably, the mass concentration of the sodium silanol and the hydroxyl double-terminated siloxane in the organic solvent is 48-64%;
iii, dropwise adding the sodium silanol into hydroxyl double-end-sealed siloxane, heating to 42-100 ℃ at the speed of 1.5-4.4 ℃/min, and reacting for 2.5-13 h; preferably, the sodium silanol is added into the 1, 21-hydroxyl polysiloxane drop by drop, the temperature is raised to 55-80 ℃ at the speed of 2.3-3.2 ℃/min, and then the reaction is carried out for 4-9 h.
4. The method of claim 1, wherein in step (1), the reaction conditions of the sodium-terminated double-ended siloxane with the hydrogen-containing chlorosilane comprise one or more of the following:
i. the molar ratio of the sodium-terminated double-end siloxane to the hydrogen-containing chlorosilane is (0.85-1.73): 1; preferably, the molar ratio of the sodium-terminated double-end siloxane to the hydrogen-containing chlorosilane is (0.99-1.43): 1;
slowly dripping the hydrogen-containing chlorosilane into double-end sodium terminated siloxane, and reacting for 18-22h at the temperature of-15-0 ℃;
the molar ratio of the sodium-double-ended terminated siloxane to the hydrogen-containing chlorosilane is (0.85-1.73): 1; preferably, the molar ratio of the sodium-terminated double-end siloxane to the hydrogen-containing chlorosilane is (0.99-1.43): 1;
work-up of the product obtained was: and removing residual solvent and low-boiling-point substances in vacuum under the conditions that the vacuum degree is 0.03-0.09MPa and the temperature is 60-100 ℃ to obtain the mono-hydrogen terminated siloxane.
5. The method for producing a polyhedral cagelike siloxane-based supercritical carbon dioxide thickener according to claim 1, wherein in step (2), the cagelike stereo cyclosiloxane is octamethylcyclotetrasiloxane, tetramethyltetravinylcyclotetrasiloxane, tetramethyltetrahydrocyclotetrasiloxane, decamethylcyclopentasiloxane, dihedral triquetrous stereo cagelike siloxane, hexahedral all-square stereo cagelike siloxane or hexahedral all-pentagon stereo cagelike siloxane.
6. The method for preparing a polygonal caged siloxane supercritical carbon dioxide thickener according to claim 1 wherein in step (2) said catalyst is sodium chloroplatinite, chloroplatinic acid, ammonium chloroplatinite, sodium hexachloroplatinate hexahydrate or ammonium hexachlororuthenate and vanadium trimethylacetate.
7. The method for producing a polyhedral cagelike supercritical carbon dioxide thickener according to claim 1 wherein the reaction conditions in step (2) include one or more of the following:
i. the molar ratio of the cage-shaped stereo cyclosiloxane to the catalyst is (84-211): 1, preferably the molar ratio is (98-186): 1;
the molar ratio of the cage-shaped stereo-ring siloxane to the unilateral hydrogen-terminated siloxane is (0.045-0.472): 1, preferably the molar ratio is (1.27 to 3.83): 1;
the total concentration of cage-shaped stereo-cyclosiloxane and mono-hydrogen terminated siloxane in cyclohexane is 23.4-49.6%, preferably the total concentration is 31-42%;
iv, adding a catalyst at the temperature of 35-90 ℃ to react for 4-8.5 h; preferably, adding a catalyst at 44-79 ℃ for reaction for 5.2-7.8 h;
v. work-up of the product after the end of the reaction is as follows: cooling to 20-26 ℃, filtering to remove solid particle impurities, and removing residual solvent and low-boiling-point substances in vacuum from the filtered liquid product under the conditions of vacuum degree of 0.02-0.07MPa and temperature of 90-130 ℃ to obtain the polyhedral cagelike siloxane polymer; preferably, the residual solvent and low-boiling-point substances of the filtered liquid product are removed in vacuum under the conditions of 0.04-0.06MPa and the temperature of 95-115 ℃.
8. The method of preparing a polyhedral caged siloxane supercritical carbon dioxide thickener according to claim 1, comprising the steps of:
(1) preparation of one-sided active hydrogen terminated linear siloxanes
Pouring 1, 21-hydroxyl polysiloxane and an organic solvent into a 500mL glass flask, heating sodium silanol to 42-100 ℃ by 1.5-4.4 ℃/min drop by drop, and reacting for 2.5-13 h; cooling, and removing impurities in a filter flask to obtain 1, 21-sodium polysiloxane; adding 1, 21-sodium polysiloxane into another 250ml three-neck flask, slowly dripping hydrogen-containing chlorosilane, reacting for 20h at-15 ℃, and removing residual solvent and low-boiling-point substances in vacuum for 1.5h under the conditions of vacuum degree of 0.03-0.09MPa and temperature of 60-100 ℃ to obtain monohydrogen terminated siloxane for later use;
the solvent is one or more of toluene, cyclohexane, n-hexane, benzene, ethanol, methanol, petroleum ether and acetone; the hydrogen-containing chlorosilane is one of dimethylmonohydrochlorosilane, monomethyldihydrochlorosilane, trihydrochlorosilane, pentamethyl monohydro-hydrogen-chlorosilane and tetramethyl di-hydrogen-chlorosilane; the molar ratio of the sodium silanol to the 1, 21-hydroxyl polysiloxane is (2.6-6.7): 1, the mass concentration of the sodium silanol and the 1, 21-hydroxyl polysiloxane in the solvent is 40-75 percent; the molar ratio of the 1, 21-sodium polysiloxane to the hydrogen-containing chlorosilane is (0.85-1.73): 1;
(2) preparation of polyhedral caged stereosiloxanes
Adding the cyclohexane solution of the mono-hydrogen terminated siloxane and the cage-shaped stereo-ring siloxane prepared in the step (1) into a glass flask, adding a catalyst at 44-79 ℃ for reacting for 5.2-7.8 h, then cooling to 25 ℃, filtering to remove solid particle impurities, and removing residual solvent and low-boiling-point substances in vacuum of a filtered liquid product under the conditions of vacuum degree of 0.04-0.06MPa and temperature of 95-115 ℃ to obtain light yellow transparent adhesive liquid, namely the polygonal cage-shaped siloxane;
the cage-shaped three-dimensional cyclosiloxane is one of octamethylcyclotetrasiloxane, tetramethyltetravinylcyclotetrasiloxane, tetramethyltetrahydrocyclotetrasiloxane, decamethylcyclopentasiloxane, dihedral triquadrate three-dimensional cage-shaped cyclosiloxane, hexahedral all-square three-dimensional cage-shaped cyclosiloxane and hexahedral all-pentagon three-dimensional cage-shaped cyclosiloxane; the catalyst is one of sodium chloroplatinite, chloroplatinic acid, ammonium chloroplatinite, sodium hexachloroplatinate hexahydrate, ammonium hexachlororuthenate and trimethyl vanadium acetate; wherein the molar ratio of the cage-shaped stereo-ring siloxane to the unilateral hydrogen-terminated siloxane is (0.045-0.472): 1, the total concentration of cage-shaped stereo-cyclosiloxane and mono-hydrogen terminated siloxane in cyclohexane is 23.4-49.6%, and the molar ratio of the cage-shaped stereo-cyclosiloxane to noble metal acid is (84-211): 1.
9. the polyhedral oligomeric siloxane polymer of any one of claims 1 to 8, having the structure of formula I:
Figure FDA0002933012290000031
in the formula I, R is methyl, ethyl, allyl, active hydrogen, epoxy ether group or phenyl, the polymerization degree a is 12-47, and b is 3-20; q is a core cage-shaped three-dimensional framework structure of cage-shaped three-dimensional cyclosiloxane, and each silicon atom is respectively connected with one R1，
R1Comprises the following steps:
Figure FDA0002933012290000041
10. use of the polyhedral oligomeric cage siloxane polymers prepared by the process according to any of claims 1 to 8 as thickeners for supercritical CO2Fracturing techniques are used for fracture stimulation of low permeability reservoirs.
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