CN108558691B - Star-shaped compound carrying dense charges and preparation method thereof - Google Patents

Abstract

The invention discloses a star-shaped compound carrying dense charges and a preparation method thereof, wherein the compound is prepared by the following steps: dropwise adding a quantitative trimethylolpropane-tri (3-aziridinyl propionate) reaction solution into a reaction bottle filled with methylamine (or ethylamine) aqueous solution and an acid catalyst to perform a first step aziridine ring-opening reaction; then adding quantitative 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride into the reaction solution to carry out second quaternization reaction, and obtaining a star-shaped compound carrying dense charges.

Description

A kind of star-shaped compound carrying dense charge and preparation method thereof

technical field

The invention relates to the technical field of preparation of polyquaternary ammonium salt cationic surfactants, in particular to a star-shaped compound carrying dense charges and a preparation method thereof.

Background technique

The aziridine ring structure in the aziridine crosslinking agent has a large tension and high activity. It can react with the amine group, the carboxyl group and the hydroxyl group to form a compound with a star structure or a network structure. The introduction of polycationic quaternary ammonium salt groups in the preparation of new compounds for application in oil and gas exploitation is a difficulty in current research.

There are clay minerals such as montmorillonite, kaolin, chlorite and other clay minerals in oil and gas reservoirs. When they come into contact with incompatible foreign fluids, they will hydrate, expand and disperse and migrate to block the channels of oil and gas reservoirs. The use of clay stabilizers can Prevent and reduce the damage of clay expansion and dispersion to the formation. At present, there are many types of clay stabilizers, including inorganic salts, inorganic bases, inorganic polymers, non-ionic polymers and cationic polymers. Polymers, quaternary ammonium salt cationic clay stabilizers are easily adsorbed preferentially by clay, which will promote dehydration between clay crystal layers, reduce swelling force, effectively inhibit clay hydration, and can be embedded between clay crystal layers to prevent water molecules from entering and reducing clay. Hydration swelling, due to its firm adsorption on clay particles, has a long-term stabilization effect. However, the existing quaternary ammonium salt clay stabilizers have problems such as large dosage, low anti-swelling rate and great damage to the formation.

SUMMARY OF THE INVENTION

In order to expand the types of polycationic quaternary ammonium salt surfactants and the quantity of polycationic quaternary ammonium salts, the present invention reacts with a highly active aziridine crosslinking agent and an active amine group to form a star-shaped surfactant carrying an active secondary amine, The quaternary ammonium salt reagent carrying the quaternary ammonium salt is then introduced to react to obtain a star-shaped compound carrying a dense charge. One of the objects of the present invention is to provide a star-shaped compound carrying dense charges, and the second object of the present invention is to provide a preparation method of the compound.

To achieve the above object, the present invention adopts the following technical solutions:

A star-shaped compound carrying a dense charge, its structural formula is:

Wherein, R1- is -CH ₃ or -CH ₂ CH ₃ .

A method for preparing a star-shaped compound carrying a dense electric charge as claimed in claim 1, comprising the steps of:

Add trimethylolpropane-tris(3-aziridinyl propionate) reaction solution to methylamine (or ethylamine) aqueous solution and acidic catalyst to carry out aziridine ring-opening reaction, and react at 40～70 ℃ for 5 ~7h;

Under weak alkaline conditions, 3-chloro-2-hydroxypropyl-trimethylammonium chloride aqueous solution was added to the above reactants for quaternary amination reaction, and the reaction was carried out at 50 to 70 ° C for 4 to 8 hours; Insoluble matter, the reaction solution was concentrated, purified by toluene column chromatography to isolate the product, and vacuum dried to constant weight to obtain the product.

In the aziridine ring-opening reaction, the molar ratio of trimethylolpropane-tris(3-aziridinyl propionate) and methylamine (or ethylamine) is 1:3.

In the aziridine ring-opening reaction, the acidic catalyst is an aqueous phosphoric acid solution with a mass fraction of 85%, and the amount thereof is 1% of the total mass of the raw materials.

In the quaternary amination reaction, the pH of the weakly alkaline condition is 9-10, and the reaction solution is adjusted to weakly alkaline with K ₂ CO ₃ .

In the quaternary amination reaction, the amount of 3-chloro-2-hydroxypropyl-trimethylammonium chloride was 6 times that of trimethylolpropane-tris(3-aziridinyl propionate).

Application of a star-shaped compound carrying a dense electric charge as a clay stabilizer in oil and gas production.

The addition amount of the clay stabilizer is 0.2-1% of the total mass.

Compared with the prior art, the present invention has the following advantages:

The aziridine ring structure in the aziridine crosslinking agent has a large tension and high activity, and can react with amine groups, carboxyl groups and hydroxyl groups to form compounds with a star structure or a network structure. The polycationic quaternary ammonium salt group is introduced in the present invention, and the high-activity aziridine crosslinking agent reacts with the active amine group to form an independent star structure, and then the quaternary amination reagent carrying the quaternary ammonium salt group is introduced to react, A novel structure of star-shaped compounds carrying dense charges was obtained. Such star-shaped compounds carrying dense charges can be widely used in the preparation of new materials, fungicides, inhibition of metal corrosion, fabric dyeing and finishing, oil extraction and other fields.

In the present invention, a high-activity aziridine crosslinking agent is reacted with an active amine group to form a star-shaped surfactant carrying an active secondary amine, and then a quaternary ammonium salt reagent carrying a quaternary ammonium salt is introduced to react to obtain a star-shaped surfactant carrying a dense charge. A simple preparation method is provided for the preparation of star-shaped compounds carrying dense charges.

The densely charged clay stabilizer contains 18 quaternary ammonium salt groups in the molecule, which can act on negatively charged clay particles at multiple points at the same time, and has a high degree of adsorption, thus achieving the purpose of low dosage and high anti-swelling rate. .

Description of drawings

Fig. 1 is the chemical structural formula of the present invention;

Fig. 2 is the reaction synthesis route diagram of the present invention.

Detailed ways

As shown in Figure 1 and Figure 2, the reaction equation of the present invention is:

wherein, R ₁ - is -CH ₃ or -CH ₂ CH ₃ .

According to the above reaction mechanism, the present invention adopts the following technical solutions

A star-shaped compound carrying a dense charge, the compound has the structural formula:

wherein, R ₁ - is -CH ₃ or -CH ₂ CH ₃ .

To prepare the above-mentioned star-shaped compound carrying a dense charge, the steps of the method are:

Trimethylolpropane-tris(3-aziridinyl propionate) reaction solution was added dropwise to a reaction flask equipped with a 20-70% mass fraction of methylamine (or ethylamine) aqueous solution and an acidic catalyst for nitrogen purification. Propylene ring-opening reaction, wherein the molar ratio of methylolpropane-tris(3-aziridinyl propionate) and methylamine (or ethylamine) is 1:3, and the reaction is carried out at 40～70℃ for 5～7h; The above reaction solution was then adjusted to alkaline (pH=9～10) with K ₂ CO ₃ , and 3-chloro-2-hydroxypropyl-trimethylammonium chloride was added to carry out the second-step quaternary amination reaction, wherein 3 -The amount of chloro-2-hydroxypropyl-trimethylammonium chloride is 6 times that of trimethylolpropane-tris(3-aziridinyl propionate), and the reaction is carried out at 50～70℃ for 4～ 8h; after the reaction was completed, insoluble substances were removed, the reaction solution was concentrated, the product was purified and isolated by toluene column chromatography, and the product was obtained by vacuum drying to constant weight.

Example 1

A 20% mass fraction of methylamine aqueous solution (23.25g, which contained methylamine 4.65g, 0.15mol) and an acidic catalyst (85% H ₃ PO ₄ , 0.25g) was heated to 40° C., and the mass fraction was added dropwise. It is a 70% trimethylolpropane-tris(3-aziridinyl propionate) aqueous solution (35.42g, which contains 21.25g of trimethylolpropane-tris(3-aziridinyl propionate), 0.05mol), the dropwise addition time was 40min. After the dropwise addition, the temperature was raised to 50°C for 7h; the above reaction solution was adjusted to weakly alkaline (pH=9～10) with K ₂ CO ₃ , and 3-chloro-2-hydroxypropane with a mass fraction of 80% was added dropwise. Hydroxypropyl-trimethylammonium chloride aqueous solution (70.50g, which contains 56.40g of 3-chloro-2-hydroxypropyl-trimethylammonium chloride, 0.30mol), the dropwise addition time is 60min, and the reaction is carried out at 50°C for 8h; After the reaction, insoluble substances were removed, the reaction solution was concentrated, the product was purified and isolated by toluene column chromatography, and the product was obtained by vacuum drying to constant weight.

The structural formula of embodiment 1 products therefrom is:

¹ H NMR (300MHz, DMSO): δ4.77～4.84(m, 24H), 3.94(s, 6H), 3.63～3.68(m, 18H), 3.25～3.51(m, 48H), 3.30(s, 117H) ), 2.70 (t, 6H), 1.69 (m, 2H), 0.84 (t, 3H) ppm.

¹³ C NMR (300 MHz, DMSO): δ 173.2, 68.1, 65.7, 58.4, 55.1, 50.7, 35.7, 27.3, 22.9, 7.1 ppm.

Example 2

A solution containing 70% ethylamine aqueous solution (9.54g, which contains 6.75g of ethylamine, 0.15mol) and an acidic catalyst (85% H ₃ PO ₄ , 0.25g) with a mass fraction of 70% was added, the temperature was raised to 50° C., and the mass fraction was added dropwise. It is a 70% trimethylolpropane-tris(3-aziridinyl propionate) aqueous solution (35.42g, which contains 21.25g of trimethylolpropane-tris(3-aziridinyl propionate), 0.05mol), the dropwise addition time was 40min. After the dropwise addition, the temperature was raised to 70° C. for reaction for 5h; the above reaction solution was adjusted to weakly alkaline (pH=9～10) with K ₂ CO ₃ , and 3-chloro-2-hydroxypropane with a mass fraction of 80% was added dropwise. Hydroxypropyl-trimethylammonium chloride aqueous solution (70.50g, which contains 3-chloro-2-hydroxypropyl-trimethylammonium chloride 56.40g, 0.30mol), the dropwise addition time is 60min, and the reaction is performed at 70°C for 4h; After the reaction, insoluble substances were removed, the reaction solution was concentrated, the product was purified and isolated by toluene column chromatography, and the product was obtained by vacuum drying to constant weight.

The structural formula of embodiment 2 products therefrom is:

¹ H NMR (300MHz, DMSO): δ4.84(m, 12H), 4.77(d, 12H), 3.63～3.68(m, 18H), 3.25～3.51(m, 54H), 3.30(s, 108H), 2.69 (t, 6H), 1.69 (m, 2H), 1.25 (t, 9H), 0.84 (t, 3H) ppm.

¹³ C NMR (300 MHz, DMSO): δ 173.1, 72.5, 65.6, 58.4, 55.6, 35.7, 27.3, 22.9, 7.7-8.3 ppm.

Characterization of Clay Stabilizers

(1) Anti-swelling rate and water-washing resistance test of clay stabilizer

With reference to the standard SY/T 5971-2016 "Evaluation Method for the Performance of Clay Stabilizers for Fracturing, Acidizing and Water Injection in Oil and Gas Fields" and the centrifugal method in Q/SH 0053-2010 "Technical Requirements for Clay Stabilizers", the determination of sodium bentonite in clay stabilizer The swelling resistance was evaluated by the swelling increase in solution and in distilled water. The anti-swelling rate and water-washing resistance rate of the clay stabilizers of Example 1 and Example 2 in water were measured. The results are shown in Table 1.

Table 1 Anti-swelling rate and washing resistance rate of clay stabilizer

It can be seen from the table that the anti-swelling rate of the clay stabilizer of the present invention in the clear water fracturing fluid is higher than 85% under the addition of 0.2%, and the water washing resistance rate is more than 90%; Under the added amount, the anti-swelling rate in the clear water fracturing fluid is higher than 90%, and the water washing resistance rate is more than 94%. The anti-swelling rate is lower than 70% under the same amount.

(2) Compatibility test

The compatibility of the clay stabilizers of Examples 1 and 2 with the fracturing fluid base fluid and acid fluid was observed, and the results are shown in Table 2.

Table 2 Compatibility test of clay stabilizer

As can be seen from Table 2, the clay stabilizer of the present invention is mixed with the fracturing fluid base fluid and the acid fluid, and no stratification, precipitation and suspension phenomena occur, and the compatibility is good.

The above content is a further detailed description of the present invention, and it cannot be considered that the specific embodiments of the present invention are limited to this. Several simple deductions or substitutions should be regarded as belonging to the protection scope of the present invention determined by the submitted claims.

Claims (3)

1. The preparation method of the star-shaped compound carrying dense charges is characterized in that the structural formula of the star-shaped compound is as follows:

wherein R1-is-CH₃or-CH₂CH₃；

The preparation method of the star-shaped compound comprises the following steps:

adding trimethylolpropane-tris (3-aziridinyl propionate) reaction liquid into methylamine or ethylamine water solution and an acid catalyst to perform aziridine ring-opening reaction, and reacting at 40-70 ℃ for 5-7 h;

under the alkalescent condition, adding 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride aqueous solution into the reactant to carry out quaternization reaction, and reacting for 4-8 h at 50-70 ℃; removing insoluble substances after the reaction is finished, concentrating the reaction solution, purifying and separating a product by using a toluene column chromatography, and drying in vacuum until the weight is constant to obtain the product;

in the aziridine ring opening reaction, trimethylolpropane-tris (3-aziridinylpropionate) and methylamine or ethylamine were in a molar ratio of 1: 3.

2. The method of claim 1 for preparing a star-shaped compound carrying dense charges, comprising: in the aziridine ring-opening reaction, the acidic catalyst is a phosphoric acid aqueous solution with the mass fraction of 85 percent, and the dosage of the acidic catalyst is 1 percent of the total mass of the raw materials.

3. The method for preparing a star-shaped compound with dense charges according to claim 1, wherein the pH value is 9-10 under weak alkaline condition in the quaternization reaction, and the reaction solution is K₂CO₃And adjusting to alkalescence.

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