CN109796955B - Preparation method of trapezoidal branched chain modified siloxane polymer supercritical carbon dioxide thickener - Google Patents
Preparation method of trapezoidal branched chain modified siloxane polymer supercritical carbon dioxide thickener Download PDFInfo
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Abstract
The invention relates to a preparation method of a trapezoidal branched chain modified siloxane polymer supercritical carbon dioxide thickener. The method comprises the following steps: (1) preparing a functional group end-capped linear polydimethylsiloxane polymer, (2) preparing a ladder-shaped hydrogenous methylsiloxane polymer, (3) dripping a chloroplatinic acid catalyst into the functional group end-capped linear polydimethylsiloxane polymer and the ladder-shaped hydrogenous methylsiloxane polymer at the temperature of 65-125 ℃, and reacting to obtain the product of the ladder-shaped branched chain modified siloxane polymer. The invention introduces the branched chain containing functional groups into the thickener molecules, thereby not only improving the solubility of the thickener in supercritical carbon dioxide, but also having excellent thickening performance, improving the capacity of carrying the proppant and reducing the fluid loss coefficient.
Description
Technical Field
The invention relates to a preparation method of a trapezoidal branched chain modified siloxane polymer supercritical carbon dioxide thickener, belonging to the technical field of oil exploitation.
Background
As a traditional technology for improving recovery efficiency, hydraulic fracturing has great advantages in oilfield stimulation development. However, the development of the technology is still hindered by the defects of large water consumption, reservoir damage, underground water resource pollution and the like. In view of the defects of the hydraulic fracturing technology, finding a clean, efficient and pollution-free novel fracturing technology becomes the key for increasing the yield of the oil field. As a new measure for increasing the yield and the injection of the oil field, the carbon dioxide fracturing technology has the advantages of improving the greenhouse effect, reducing the reservoir damage, reducing the water pollution and using, having considerable economic benefit and poorer friction resistance, having better relieving effect on the water-sensitive stratum and becoming a yield increasing measure with better development prospect. Although the carbon dioxide fracturing technology has many performance advantages, the ultra-low viscosity of the pure supercritical carbon dioxide still cannot meet the viscosity requirement of the fracturing fluid in the fracturing process, the pure supercritical carbon dioxide is easy to flow in the fracturing stage of an oil and gas reservoir, particularly a low-permeability reservoir, the pure supercritical carbon dioxide is easy to cause a gas channeling phenomenon due to low density, the fingering phenomenon is serious, the retention time in a shale reservoir is short, the filtration loss is large due to low viscosity, and large pore pressure cannot be formed for fracturing. In addition, the low viscosity of the oil-gas mixture also easily causes the carrying performance of propping agents and gravel to be obviously weakened, and the sweep efficiency is also reduced due to the occurrence of gas channeling phenomenon and fingering phenomenon, so that the oil-gas recovery rate is obviously reduced.
The current research targets for carbon dioxide thickeners are mainly focused on fluorine-containing polymers and hydrocarbon polymers. The fluorine-containing polymer has excellent thickening effect when used as a thickening agent, but is easy to interact with underground water to remain in a reservoir stratum, pollutes water resources, and can generate accumulation in a body to cause the accumulation of biospheres. In addition, the high price of the fluorine-containing polymer itself is a key bottleneck preventing the application of the fluorine-containing polymer in the carbon dioxide fracturing technology. Although the hydrocarbon polymer has a lower price than the fluorine-containing polymer and is directly soluble in supercritical carbon dioxide, the thickening effect is significantly lower than that of the fluorine-containing polymer. The two thickening agents hinder the application and popularization in fracturing yield increase due to the defects of the two thickening agents. Therefore, the development of a polymer thickening supercritical carbon dioxide which is cheap, does not pollute underground water resources, reduces reservoir damage and has excellent thickening property is urgently needed, and an industrial foundation is laid for the development of a supercritical carbon dioxide fracturing technology. The invention is therefore proposed.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a poly-cyclic branched chain modified siloxane supercritical carbon dioxide thickener used for an oil field fracturing technology and a preparation method thereof. The supercritical carbon dioxide thickener prepared by the invention improves the thickening property and simultaneously considers the solubility, and has low production cost and simple preparation steps.
Summary of the invention:
the invention obtains excellent performance of thickening the viscosity of the supercritical carbon dioxide by modifying the siloxane polymer. Several cyclosiloxanes are used as reaction monomers, firstly, the cyclosiloxanes are subjected to ring opening polymerization reaction to generate straight-chain polymer precursors, then, a branched chain containing functional groups is introduced through hydrosilylation reaction, and the interaction with carbon dioxide molecules is improved through the introduced branched chain, so that the solubility in supercritical carbon dioxide is obviously improved, the using amount of a cosolvent is reduced, and the thickening capacity of the supercritical carbon dioxide can be improved.
Description of terms:
normal temperature: has the meaning known in the field, and generally refers to 20-25 ℃; the temperature conditions not particularly limited in the present invention are all normal temperatures.
Room temperature: having the meaning well known in the art, generally 23 ℃. + -. 2 ℃.
Detailed description of the invention:
the technical scheme of the invention is as follows:
a preparation method of a trapezoidal branched chain modified siloxane polymer supercritical carbon dioxide thickener comprises the following steps:
(1) preparation of functional group-terminated linear polydimethylsiloxane polymers
Adding cyclic siloxane, a small molecular end-capping agent, toluene and a basic catalyst into a reaction kettle, introducing nitrogen, sealing the reaction kettle, reacting at 100-115 ℃ for 2-11h, then increasing the temperature to 140-155 ℃ for reaction for 30-40min, cooling to room temperature, and removing a toluene solvent and a small molecular siloxane low-boiling-point substance in vacuum to obtain a functional group end-capped linear polydimethylsiloxane polymer;
the cyclic siloxane is one or more of octamethylcyclotetrasiloxane, tetramethyltetravinylcyclotetrasiloxane, octavinylcyclotetrasiloxane, tetramethyltetrahydrocyclotetrasiloxane, hexamethyldihydrocyclotetrasiloxane, hexamethylcyclotrisiloxane, octaphenylcyclotetrasiloxane and tetramethyltetraphenylcyclotetrasiloxane;
the micromolecule end-capping agent is tetramethyl disiloxane, hexamethyl disiloxane, heptamethyl trisiloxane, octamethyl trisiloxane, pentamethyl disiloxane, hexavinyl disiloxane, hexaphenyl disiloxane or heptaphenyl trisiloxane;
the molar ratio of the cyclic siloxane to the small molecule end-capping reagent is (1.7-15) to 1; the mass concentration of the cyclic siloxane and the micromolecule end-capping agent in the toluene is 30-85 percent; the molar ratio of cyclic siloxane to basic catalyst is (92-224): 1;
(2) preparation of ladder-shaped hydrogenous methylsiloxane polymer
Reacting chlorosilane and phenylenediamine at a temperature of 160-270 ℃, wherein the molar ratio of the chlorosilane to the phenylenediamine is (0.55-3.2): 1, dissolving the phenylenediamine in a tetrahydrofuran solvent, wherein the mass concentration of the chlorosilane and the phenylenediamine in the tetrahydrofuran is 30-74%; then, the user can use the device to perform the operation,
deionized water is added to ensure that the mass concentration of the deionized water in the system is 0.1 to 4.3 percent, and the mixture reacts for 1.5 to 4.2 hours at the temperature of between 140 and 210 ℃; cooling to room temperature;
then filtering, separating to remove solid substances, evaporating to remove residual micromolecular low-boiling-point substances and tetrahydrofuran, and obtaining concentrated filtrate; stirring the concentrated filtrate for 3-5h, washing with saturated saline solution until the pH value is 7, and performing rotary evaporation and drying to obtain a ladder-shaped hydrogenous methylsiloxane polymer;
(3) preparation of ladder-branched modified siloxane polymers
Dissolving the functional group-terminated linear polydimethylsiloxane polymer prepared in the step (1) and the ladder-shaped hydrogenous methylsiloxane polymer prepared in the step (2) into toluene, dripping a chloroplatinic acid catalyst at the temperature of 65-125 ℃, reacting for 2-7.5h, and cooling to room temperature; removing the chloroplatinic acid catalyst, and then removing micromolecular low-boiling-point substances by rotary evaporation to obtain a product, namely the trapezoidal branched chain modified siloxane polymer;
wherein the molar ratio of the functional group-terminated linear polydimethylsiloxane polymer to the ladder-shaped hydrogenous methylsiloxane polymer is (0.4-5.3): 1, the molar ratio of the ladder-shaped hydrogenmethylsiloxane polymer to the chloroplatinic acid is (41-132): 1.
the final product of the trapezoidal branched chain modified siloxane polymer is light yellow clear transparent viscous liquid.
Preferably, in step (1), the cyclic siloxane is one or more of octamethylcyclotetrasiloxane, tetramethyltetravinylcyclotetrasiloxane, octavinylcyclotetrasiloxane, octaphenylcyclotetrasiloxane and tetramethyltetraphenylcyclotetrasiloxane.
According to the present invention, in step (1), the small molecule blocking agent is hexamethyldisiloxane, heptamethyltrisiloxane, octamethyltrisiloxane, pentamethyldisiloxane, hexavinyldisiloxane or hexaphenyldisiloxane.
Preferably, in step (1), the basic catalyst is tetramethylammonium hydroxide, sodium hydroxide, potassium hydroxide, aluminum hydroxide or lithium hydroxide; further preferably, the basic catalyst is selected from tetramethylammonium hydroxide, sodium hydroxide or potassium hydroxide.
According to the invention, in the step (1), the molar ratio of the cyclic siloxane to the small molecule end-capping agent is (4.5-14):1, the molar ratio of the cyclic siloxane to the basic catalyst is (113-185):1, and the total concentration of the cyclic siloxane to the small molecule end-capping agent in the toluene is 35-70%.
According to the present invention, it is preferable that the flow rate of nitrogen gas in the step (1) is 0.5 L.min-1And introducing nitrogen for 30min, sealing the reaction kettle, and placing the reaction kettle in a high-temperature rotary roller furnace.
According to the invention, preferably, the cyclic siloxane, the small molecule blocking agent, the toluene and the alkaline catalyst in the reaction kettle in the step (1) react at 110 ℃; the reaction time is 4-10 h. Removing the toluene solvent and the micromolecular siloxane low-boiling-point substances from the reactants in vacuum under the conditions that the vacuum degree is 0.06MPa and the temperature is 90 ℃; the vacuum removal time is 0.7-5 h.
Preferably, in step (2), the chlorosilane is two of trichloromethylsilane, trichlorosilane, trihydrochlorosilane, trimethylchlorosilane, trichloroethylsilane and trihydrotrimethoxysilane. The molar ratio of the two kinds of the chlorine-containing silane is (0.5-4.5): 1.
According to the present invention, in step (2), the molar ratio of chlorosilane to phenylenediamine is preferably (0.85 to 2.7): 1, the mass concentration of the chlorosilane and the phenylenediamine in tetrahydrofuran is 35-68 percent, and the mass concentration of deionized water in a reaction system is 0.3-3.2 percent.
According to the present invention, it is preferable that the reaction temperature of the mixture containing chlorosilane and phenylenediamine in the step (2) is 180 to 240 ℃.
According to the invention, in the step (2), the reaction time of the chlorosilane and the phenylenediamine is preferably 0.3-2.3h, and more preferably 0.6-1.7 h.
According to the invention, in step (2), the reaction temperature of the deionized water and the mixture containing chlorosilane, toluene and phenylenediamine is preferably 170-220 ℃; the reaction time is 1.8-2.2 h.
According to the present invention, it is preferred that in the step (2), the conditions for removing the remaining small molecule low boiling substances and tetrahydrofuran by evaporation are a vacuum degree of 0.07MPa and a temperature of 85 ℃.
According to the present invention, it is preferable that the spin-drying condition in the step (2) is performed under a vacuum degree of 0.09MPa at 75 ℃.
According to the invention, in step (3), the molar ratio of the functional group-terminated linear polydimethylsiloxane polymer to the ladder-shaped hydrogenous methylsiloxane polymer is (0.9-4.1): 1, the molar ratio of the ladder-shaped hydrogenmethylsiloxane polymer to the chloroplatinic acid is (68-112): 1.
according to the present invention, in step (3), the mass concentration of the functional group-terminated linear polydimethylsiloxane polymer and the ladder-shaped hydrogencontaining methylsiloxane polymer in toluene is preferably 30% to 73%, and further preferably, the mass concentration of the functional group-terminated linear polydimethylsiloxane polymer and the ladder-shaped hydrogencontaining methylsiloxane polymer in toluene is 33% to 60%.
According to the invention, in the step (3), the reaction temperature is preferably 85-105 ℃, and the reaction time is preferably 4-7 h.
According to the present invention, it is preferable that, in the step (3), the chloroplatinic acid removing catalyst is: adding activated carbon into the reactant solution for adsorbing chloroplatinic acid solid particles, and filtering and separating to remove the activated carbon and the chloroplatinic acid.
According to the invention, preferably, in the step (3), the vacuum degree of the rotary evaporation of the product is 0.03MPa to 0.09MPa, and the rotary evaporation temperature is 65 ℃ to 110 ℃; further preferably, the rotary evaporation vacuum degree is 0.05MPa to 0.08MPa, and the rotary evaporation temperature is 75 ℃ to 95 ℃.
The ladder-shaped branched chain modified siloxane polymer supercritical carbon dioxide thickener prepared by the method has a structure shown in a formula I.
In the method of the present invention, the product of step (1) is a functional group-terminated linear polydimethylsiloxane polymer having the structural formula shown in formula II below:
the product of step (2) is a ladder-like hydrogenmethylsiloxane polymer; the structural formula is shown as the following formula III, and the shape is as a ladder:
r1, R2, R3, a, b and m in the formula II and the formula III are the same as those in the formula I.
According to the method of the invention, the final product of step (3) has the structure shown in formula I:
in the formula I, R1 is methyl, ethyl or vinyl, and the polymerization degree m is 3-16; r2 is methyl, ethyl, phenyl, vinyl or active hydrogen, the degree of polymerization a is between 22 and 54, and the degree of polymerization b is between 17 and 48; r3 is methyl, phenyl or vinyl.
According to the invention, preferably, in the final product of the step (3), R1 is methyl or ethyl, and the polymerization degree m is between 4 and 10; r2 is methyl, ethyl or phenyl, and the polymerization degree a is between 27 and 43; b is between 23 and 41; r3 is methyl or vinyl. Most preferably, R1, R2 and R3 are all methyl groups, and the polymerization degree m is 6; the degree of polymerization a is 29; b is 25.
According to the invention, the reaction conditions of example 1 are optimal reaction conditions: the molar ratio of the two cyclosiloxanes was 1:1, the molar ratio of the cyclic siloxane to hexamethyldisiloxane was 9.1: the total mass concentration of cyclic siloxane and hexamethyldisiloxane in toluene is 58%, the molar ratio of trichloromethylsilane, trichlorosilane and phenylenediamine is 2:1, the mass concentration of chlorosilane and phenylenediamine in tetrahydrofuran is 66%, the mass concentration of deionized water in the reaction system is 2%, the molar ratio of methyl-terminated linear polydimethylsiloxane polymer to ladder-shaped hydrogenmethylsiloxane polymer is 3:1, the molar ratio of ladder-shaped hydrogenmethylsiloxane polymer to chloroplatinic acid is 98:1, and the mass concentration of methyl-terminated linear polydimethylsiloxane polymer and ladder-shaped hydrogenmethylsiloxane polymer in toluene is 55%.
The invention has the technical characteristics and excellent effects that:
the solubility of the siloxane thickener in the supercritical carbon dioxide is difficult to interact, the delamination phenomenon is obvious, the solubility is low, and the solubility of the siloxane thickener in the supercritical carbon dioxide needs to be improved under the condition that cosolvent such as toluene or cyclohexane is used as an intermediate medium. In addition, the common siloxane polymer needs a larger volume of cosolvent with the help of the cosolvent, and is only dissolved in supercritical carbon dioxide under the large volume of cosolvent, so that the thickening effect is not obvious, and the low fracturing efficiency and the performance of carrying the proppant are caused. According to the invention, siloxane polymer is modified, and a branched chain containing a functional group is introduced into a thickener molecule, so that the solubility of the thickener in supercritical carbon dioxide is improved, the dosage of a cosolvent is reduced, the thickener has excellent performance of thickening supercritical carbon dioxide, the capacity of carrying a propping agent is improved, and the fluid loss coefficient is reduced.
Since the thickener generally relates to a polymer compound such as a polymer, not only the thickening property but also the solubility in supercritical carbon dioxide are important aspects. The technical problem of combining thickening property and solubility is that the invention introduces the branch chain containing the functional group to improve the solubility and thickening capacity of the siloxane polymer in the supercritical carbon dioxide.
The invention has the following excellent effects:
1. the various monomer materials used in the invention can be directly purchased from the market, and the price is obviously lower compared with the fluorine-containing monomer. Easy to obtain, relatively cheap and mild in preparation condition.
2. The reaction steps designed by the invention are simple to operate, expensive experimental instruments cannot be involved, and the operation steps are not complicated.
3. The reaction of the present invention has high product yield, no waste and no environmental influence.
4. The physical and chemical properties of the trapezoidal branched chain modified siloxane polymer are stable, and the change of a chemical structure and thickening performance can not occur along with the change of time.
5. The introduction of the side chain in the trapezoidal branched chain modified siloxane polymer is beneficial to improving the performance of the siloxane thickener for improving the viscosity of the supercritical carbon dioxide fracturing fluid.
6. The trapezoidal branched chain modified siloxane polymer prepared by the invention has excellent miscibility with toluene and supercritical carbon dioxide.
7. The product prepared by the method is insoluble in water, has small polarity, has small contact angle with the surface of rock, and is easy to flow back from a reservoir.
In conclusion, the trapezoid branched chain modified siloxane polymer prepared by the invention can be industrially produced in large scale, and the excellent performance of thickening supercritical carbon dioxide can have good application effect in oil field fracturing development, especially in development of oil and gas resources of shale reservoirs.
Drawings
FIG. 1 is an IR spectrum of a trapezoidal branched methyl terminated polydimethylsiloxane polymer of the product obtained 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 the raw materials described in the examples are all conventional commercially available products.
Example 1
A preparation method of a trapezoidal branched chain modified siloxane polymer supercritical carbon dioxide thickener comprises the following steps:
1) preparation of methyl terminated linear polydimethylsiloxane polymers
A250 mL synthesis reaction vessel was charged with 29.6g of octamethylcyclotetrasiloxane, 34.4g of tetramethyltetravinylcyclotetrasiloxane, 3.6g of hexamethyldisiloxane, 115mL of toluene, and 0.15g of tetramethylammonium hydroxide under normal temperature with nitrogen at 0.5 L.min-1Sealing the synthesis reaction kettle after the flow rate is lower than 30min, placing the synthesis reaction kettle in a high-temperature rotary roller furnace to react for 8h at 110 ℃, then raising the temperature to 150 ℃ to react for 40min, then reducing the temperature to room temperature, and removing the toluene solvent and low-boiling-point substances in vacuum for 4h under the conditions of the vacuum degree of 0.06MPa and the temperature of 90 ℃ of the reactants to obtain 42g of methyl terminated linear polydimethylsiloxane polymer.
(2) Preparation of ladder-shaped hydrogenous methylsiloxane polymer
14.9g of trichloromethylsilane and 13.5g of trichlorosilane were poured into a three-necked flask equipped with a condensing device, a dropping funnel and a stirring device, and 68mL of a tetrahydrofuran mixed solution containing 11g of phenylenediamine was poured into the three-necked flask and reacted at 220 ℃ for 0.9 h. Then 2g of deionized water was poured into the mixed reactant solution to react at 190 ℃ for 2 h. Cooling to room temperature, filtering to remove solid substances, and evaporating residual micromolecular low-boiling-point substances and tetrahydrofuran at the temperature of 85 ℃ under the pressure of 0.07MPa to obtain concentrated filtrate. The filtrate was stirred at room temperature for 5 hours, washed with saturated brine to pH 7, and then spin-dried at 75 ℃ under a vacuum of 0.09MPa to obtain 27g of a white solid, i.e., a ladder-like hydrogenmethylsiloxane polymer.
(3) Preparation of trapezoidal branched chain methyl terminated polydimethylsiloxane polymer
Pouring prepared 35g of linear end-capped polydimethylsiloxane and 20g of ladder-shaped hydrogen-containing methyl siloxane into a three-neck flask in 115mL of toluene solution, dripping 0.0003g of chloroplatinic acid at 85 ℃ for reaction for 6h, cooling to room temperature, adding activated carbon into the reactant solution for 5h, filtering to separate and remove the activated carbon and the chloroplatinic acid, and performing rotary evaporation on the adsorbed product at 0.08MPa and 87 ℃ for 3h to remove small-molecular low-boiling-point substances to obtain 38g of light yellow clear and transparent viscous liquid, wherein the yield is 69.10%. Namely the siloxane polymer supercritical carbon dioxide thickener. The compound has a structure shown in a formula I, wherein R1 is methyl, and the polymerization degree m is 6; r2 is methyl, the degree of polymerization a is 29; b is 25; r3 is methyl.
The obtained product has an infrared spectrum shown in figure 1. 2964cm in infrared spectrum-1Hydrocarbon absorption peak (v) of methyl groupC-H) In addition, absorption peak of methyl group: (as C-H) Appear at 1412cm-1；1261cm-1Is a symmetric deformation absorption peak of methyl group, 1024cm-1To 1093cm-1The broad peak of (A) is a characteristic absorption peak of a silicon-oxygen bond of 800.327cm-1Is the absorption peak of the silicon-carbon bond (v)as Si-C) Symmetric stretching vibration of silicon-carbon bond (v)s Si-C) Mainly at 718.759cm-1。
Example 2
The procedure was as in example 1, except that the basic catalyst used in step (1) was potassium hydroxide and the amount used was 0.13 g.
Example 3
The procedure was as described in example 1, except that the cyclosiloxanes used in step (1) were tetramethyltetravinylcyclotetrasiloxane and tetraphenyltetramethylcyclotetrasiloxane, in amounts of 34.4g and 55g, respectively.
The obtained product has a structure shown in formula I, wherein R1 is methyl, and the polymerization degree m is 6; r2 is phenyl, the degree of polymerization a is 29; r3 is methyl.
Example 4
The procedure was as described in example 1, except that octamethylcyclotetrasiloxane and tetramethyltetravinylcyclotetrasiloxane were used in amounts of 15g and 69g, respectively, in step (1). The obtained product has a structure shown in formula I, wherein R1 is methyl, and the polymerization degree m is 4; r2 is methyl, the degree of polymerization a is 29; b is 41; r3 is methyl.
Example 5
As in example 1, except that the molar ratio of cyclosiloxane to hexamethyldisiloxane in step (1) was 14: 1.
Example 6
Except that the masses of trichloromethylsilane and trichlorosilane were 22.4g and 7g, respectively, in step (2), as described in example 1. The molar ratio of the two chlorosilanes was 3: 1.
Example 7
The procedure was as described in example 1, except that 8.2g of phenylenediamine was used in the step (2).
Example 8
Except that the amount of deionized water used in step (2) was 0.21g as described in example 1.
Example 9
The procedure is as in example 1, except that in step (3) the catalyst is potassium hexachlororhodium (III) in an amount of 0.0008 g.
Example 10
As described in example 1, except that the reaction time in step (3) was 7 hours and the reaction temperature was 105 ℃.
Comparative example 1
Comparative example 1 is a linear polydimethylsiloxane manufactured by dow corning corporation.
Comparative example 2
Comparative example 2 is a vinylphenyl silicone oil produced by New Polymer materials Co.Ltd of Jiand.
The performance of the products of the examples and the comparative examples is evaluated:
preparing a siloxane polymer solution with the polymer concentration of 1.9 wt% by using toluene with 3 times volume of the siloxane polymer, and measuring the viscosity of the siloxane polymer solution at 10MPa, 30 ℃ and 170s by using a capillary viscosity measuring device～1The viscosity of each polymer, toluene and supercritical carbon dioxide mixed high pressure liquid was tested at shear rates and the viscosity values are shown in table 1.
TABLE 1 determination of shear resistance
| Sample numbering | Viscosity, mPas |
| Example 1 | 231 |
| Example 2 | 137 |
| Example 3 | 82 |
| Example 4 | 109 |
| Example 5 | 170 |
| Example 6 | 73 |
| Example 7 | 97 |
| Example 8 | 113 |
| Comparative example 1 | 24 |
| Comparative example 2 | 50 |
Claims (13)
1. A preparation method of a trapezoidal branched chain modified siloxane polymer supercritical carbon dioxide thickener comprises the following steps:
(1) preparation of functional group-terminated linear polydimethylsiloxane polymers
Adding cyclic siloxane, a small molecular end-capping agent, toluene and a basic catalyst into a reaction kettle, introducing nitrogen, sealing the reaction kettle, reacting at 100-115 ℃ for 2-11h, then increasing the temperature to 140-155 ℃ for reaction for 30-40min, cooling to room temperature, and removing a toluene solvent and a small molecular siloxane low-boiling-point substance in vacuum to obtain a functional group end-capped linear polydimethylsiloxane polymer;
the cyclic siloxane is a combination of octamethylcyclotetrasiloxane and tetramethyltetravinylcyclotetrasiloxane or a combination of tetramethyltetravinylcyclotetrasiloxane and tetraphenyltetramethylcyclotetrasiloxane;
the micromolecule end-capping agent is tetramethyl disiloxane, hexamethyl disiloxane, heptamethyl trisiloxane, octamethyl trisiloxane, pentamethyl disiloxane, hexavinyl disiloxane, hexaphenyl disiloxane or heptaphenyl trisiloxane;
the molar ratio of the cyclic siloxane to the small molecule end-capping reagent is (1.7-15) to 1; the mass concentration of the cyclic siloxane and the micromolecule end-capping agent in the toluene is 30-85 percent; the molar ratio of cyclic siloxane to basic catalyst is (92-224): 1;
(2) preparation of ladder-shaped hydrogenous methylsiloxane polymer
Reacting chlorosilane and phenylenediamine at a temperature of 160-270 ℃, wherein the molar ratio of the chlorosilane to the phenylenediamine is (0.55-3.2): 1, dissolving the phenylenediamine in a tetrahydrofuran solvent, wherein the mass concentration of the chlorosilane and the phenylenediamine in the tetrahydrofuran is 30-74%; then, the user can use the device to perform the operation,
adding deionized water to ensure that the mass concentration of the deionized water in a reaction system is 0.1-4.3 percent, and reacting for 1.5-4.2h at the temperature of 140-210 ℃; cooling to room temperature;
then filtering, separating to remove solid substances, evaporating to remove residual micromolecular low-boiling-point substances and tetrahydrofuran, and obtaining concentrated filtrate; stirring the concentrated filtrate for 3-5h, washing with saturated salt solution until pH =7, and rotary steaming and drying to obtain ladder-shaped hydrogenous methylsiloxane polymer;
the chlorine-containing silane is trichloromethylsilane and trichlorosilane;
(3) preparation of ladder-branched modified siloxane polymers
Dissolving the functional group-terminated linear polydimethylsiloxane polymer prepared in the step (1) and the ladder-shaped hydrogenous methylsiloxane polymer prepared in the step (2) into toluene, dripping a chloroplatinic acid catalyst at the temperature of 65-125 ℃, reacting for 2-7.5h, and cooling to room temperature; removing the chloroplatinic acid catalyst, and then removing micromolecular low-boiling-point substances by rotary evaporation to obtain a product, namely the trapezoidal branched chain modified siloxane polymer;
wherein the molar ratio of the functional group-terminated linear polydimethylsiloxane polymer to the ladder-shaped hydrogenous methylsiloxane polymer is (0.4-5.3): 1, the molar ratio of the ladder-shaped hydrogenmethylsiloxane polymer to the chloroplatinic acid is (41-132): 1.
2. the method for preparing the ladder-shaped branched modified siloxane polymer supercritical carbon dioxide thickener according to claim 1, wherein in step (1), the alkaline catalyst is tetramethylammonium hydroxide, sodium hydroxide, potassium hydroxide, aluminum hydroxide or lithium hydroxide.
3. The method for preparing the ladder-shaped branched chain modified siloxane polymer supercritical carbon dioxide thickener according to claim 1, wherein in the step (1), the molar ratio of the cyclic siloxane to the small molecule end-capping agent is (4.5-14):1, the molar ratio of the cyclic siloxane to the basic catalyst is (113-185):1, and the total concentration of the cyclic siloxane to the small molecule end-capping agent in the toluene is 35-70%.
4. The method of preparing a ladder-branched modified siloxane polymer supercritical carbon dioxide thickener according to claim 1, wherein the reaction in step (1) comprises one or more of the following conditions:
a. nitrogen is present inThe flow rate of gas is 0.5 L.min-1Introducing nitrogen for 30min, sealing the reaction kettle, and placing the reaction kettle in a high-temperature rotary roller furnace;
b. reacting cyclic siloxane, a micromolecular end-capping agent, toluene and an alkaline catalyst in a reaction kettle at 110 ℃;
c. the toluene solvent and the micromolecular siloxane low-boiling-point substance are removed from the reactant in vacuum under the conditions that the vacuum degree is 0.06MPa and the temperature is 90 ℃.
5. The method for preparing the trapezoidal branched modified siloxane polymer supercritical carbon dioxide thickener according to claim 1, wherein in the step (2), the molar ratio of the two chlorine-containing silanes is (0.5-4.5): 1.
6. The method for preparing the trapezoidal branched modified siloxane polymer supercritical carbon dioxide thickener according to claim 1, wherein in the step (2), the molar ratio of the chlorosilane to the phenylenediamine is (0.85-2.7): 1, the mass concentration of the chlorosilane and the phenylenediamine in tetrahydrofuran is 35-68 percent, and the mass concentration of deionized water in a reaction system is 0.3-3.2 percent.
7. The method of preparing a ladder-branched modified siloxane polymer supercritical carbon dioxide thickener according to claim 1, wherein the reacting in step (2) comprises one or more of the following conditions:
a. the reaction temperature of the mixture containing chlorosilane and phenylenediamine is 180-240 ℃;
b. the reaction time of the chlorosilane and the phenylenediamine is 0.3 to 2.3 hours;
c. the reaction temperature of the deionized water and the mixture containing chlorosilane, methylbenzene and phenylenediamine is 170-220 ℃;
d. the conditions for removing the residual micromolecular low-boiling-point substances and tetrahydrofuran by evaporation are that the vacuum degree is 0.07MPa and the temperature is 85 ℃;
e. the rotary evaporation drying condition is carried out under the vacuum degree of 0.09MPa and the temperature of 75 ℃.
8. The method for preparing the ladder-shaped branched modified siloxane polymer supercritical carbon dioxide thickener according to claim 1, wherein in the step (3), the molar ratio of the functional group-terminated linear polydimethylsiloxane polymer to the ladder-shaped hydrogencontaining methylsiloxane polymer is (0.9-4.1): 1, the molar ratio of the ladder-shaped hydrogenmethylsiloxane polymer to the chloroplatinic acid is (68-112): 1.
9. the method for preparing the ladder-shaped branched modified siloxane polymer supercritical carbon dioxide thickener according to claim 1, wherein in the step (3), the mass concentration of the functional group-terminated linear polydimethylsiloxane polymer and the ladder-shaped hydrogencontaining methylsiloxane polymer in toluene is 30-73%.
10. The method for preparing the ladder-shaped branched modified siloxane polymer supercritical carbon dioxide thickener according to claim 1, wherein in the step (3), the mass concentration of the functional group-terminated linear polydimethylsiloxane polymer and the ladder-shaped hydrogencontaining methylsiloxane polymer in toluene is 33-60%.
11. The method of preparing a ladder-branched modified siloxane polymer supercritical carbon dioxide thickener according to claim 1, wherein the reacting in step (3) comprises one or more of the following conditions:
a. the reaction temperature is 85-105 ℃, and the reaction time is 4-7 h;
b. the vacuum degree of the rotary evaporation of the product is 0.03MPa to 0.09MPa, and the rotary evaporation temperature is 65 ℃ to 110 ℃.
12. The method for preparing the trapezoidal branched modified siloxane polymer supercritical carbon dioxide thickener according to claim 1, wherein the rotary evaporation vacuum degree of the product in the step (3) is 0.05MPa to 0.08MPa, and the rotary evaporation temperature is 75 ℃ to 95 ℃.
13. A ladder-branched modified siloxane polymer supercritical carbon dioxide thickener prepared by the process of any of claims 1 to 12, having the structure shown in formula I:
in the formula I, R1 is methyl, ethyl or vinyl, and the polymerization degree m is 3-16; r2 is methyl, ethyl, phenyl, vinyl or active hydrogen, the degree of polymerization a is between 22 and 54, and the degree of polymerization b is between 17 and 48; r3 is methyl, phenyl or vinyl.
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| CN110862543B (en) * | 2019-12-03 | 2021-11-09 | 中国石油大学(华东) | Preparation method of hyperbranched hydrogen-containing siloxane supercritical carbon dioxide thickener |
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| CN112961360B (en) * | 2021-02-04 | 2022-06-07 | 中国石油大学(华东) | Preparation method of polyhedral cagelike siloxane supercritical carbon dioxide thickener |
| CN113024816B (en) * | 2021-03-30 | 2022-12-23 | 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 |
| CN113929915B (en) * | 2021-10-26 | 2022-10-28 | 中国石油大学(华东) | Preparation method and application of modified siloxane supercritical carbon dioxide thickener |
| CN115073749B (en) * | 2022-05-05 | 2024-02-27 | 黑龙江八一农垦大学 | Preparation method of multi-terminal branched siloxane supercritical carbon dioxide thickener |
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