Phenolic resin and preparation method thereof as well as proppant and preparation method thereof

Abstract

The invention provides phenolic resin with a structure shown as the formula I, wherein m ranges from 1 to 10; n ranges from 1 to 10; k ranges from 1 to 5; Q serves as a resorcinol repeating unit; and an intermediate resorcinol repeating unit and a phenol repeating unit of a molecular chain of the phenolic resin are in the weight ratio of (0.1-0.7):1. The phenolic resin provided by the invention can be solidified at low temperature. The invention also provides an oil field proppant prepared by using the phenolic resin and a preparation method of the oil field proppant shown as the formula I.

Description

technical field The invention relates to the technical field of polymer synthesis, in particular to a phenolic resin and a preparation method thereof, a proppant and a preparation method thereof. Background technique Proppant refers to a liquid additive that is brought into the fracture by fracturing fluid and used to support the fracture in the oil field after the pressure is released. It can support the fracture and keep it open, so that the fluid can flow through the fracture into the borehole. To prevent the collapse and leakage of drilling wells in hole oil fields due to fractures. At present, the synthesis technology of phenolic resin for oil field proppant in China mainly includes two kinds. The first is liquid thermoplastic phenolic resin with backward technology. The synthesis process of this oilfield proppant is as follows: phenol is used under the condition of acid catalyst (commonly used acid catalyst includes hydrochloric acid, phosphoric acid, oxalic acid), ...

Examples

Example Embodiment

The present invention also provides a preparation method of phenolic resin, including:

a) Mixing phenol, formaldehyde and resorcinol, and a condensation reaction occurs under the action of an acid catalyst; the weight ratio of resorcinol to phenol is 0.1-0.7:1;

b) subjecting the reaction product obtained in step a) to vacuum distillation to obtain a phenolic resin.

Preferably, the acid catalyst is prepared by mixing oxalic acid and phosphoric acid in a mass ratio of (0.5 to 1.5): (1.5 to 4). The mass ratio of the phenol, resorcinol, acid catalyst and formaldehyde is 1:(0.1~0.7):(0.025~0.027):(0.24~0.26); more preferably 1:(0.3~0.6):0.026: 0.255.

Preferably, the preparation method provided by the present invention can have three methods in the order of adding resorcinol. The first is to directly polymerize resorcinol, phenol and formaldehyde and then distill;

The second method is to pre-polymerize phenol and formaldehyde, distill the pre-polymerized product at atmospheric pre...

Example Embodiment

Example 1

Take 940g of phenol, 470g of resorcinol, and 37% formaldehyde into 648g, add 9.4g of oxalic acid and 18.8g of phosphoric acid (concentration of 85%), heat up to reflux reaction, react at constant temperature in this state for 4 hours, and distill to 140°C, then distilled at 170°C under reduced pressure (-0.095MPa), and put it on the tray to obtain 1328 g of resin. The properties of the phenolic resin prepared in this example are shown in Table 1.

Example Embodiment

Example 2

Take 940g of phenol and 37% formaldehyde into 648g, add 9.4g of oxalic acid, 18.8g of phosphoric acid (concentration of 85%), heat up to reflux reaction, react at constant temperature in this state for 4 hours, then distill to 105°C under normal pressure, and add to room temperature. 470 g of hydroquinone was reacted at a constant temperature for 1 hour, and then distilled at 170° C. under reduced pressure (-0.095 MPa), and placed on the tray to obtain 1348 g of resin. The properties of the phenolic resin prepared in this example are shown in Table 1.

technical field The invention relates to the technical field of polymer synthesis, in particular to a phenolic resin and a preparation method thereof, a proppant and a preparation method thereof. Background technique Proppant refers to a liquid additive that is brought into the fracture by fracturing fluid and used to support the fracture in the oil field after the pressure is released. It can support the fracture and keep it open, so that the fluid can flow through the fracture into the borehole. To prevent the collapse and leakage of drilling wells in hole oil fields due to fractures. At present, the synthesis technology of phenolic resin for oil field proppant in China mainly includes two kinds. The first is liquid thermoplastic phenolic resin with backward technology. The synthesis process of this oilfield proppant is as follows: phenol is used under the condition of acid catalyst (commonly used acid catalyst includes hydrochloric acid, phosphoric acid, oxalic acid), ...

Examples

Example Embodiment

The present invention also provides a preparation method of phenolic resin, including:

a) Mixing phenol, formaldehyde and resorcinol, and a condensation reaction occurs under the action of an acid catalyst; the weight ratio of resorcinol to phenol is 0.1-0.7:1;

b) subjecting the reaction product obtained in step a) to vacuum distillation to obtain a phenolic resin.

Preferably, the acid catalyst is prepared by mixing oxalic acid and phosphoric acid in a mass ratio of (0.5 to 1.5): (1.5 to 4). The mass ratio of the phenol, resorcinol, acid catalyst and formaldehyde is 1:(0.1~0.7):(0.025~0.027):(0.24~0.26); more preferably 1:(0.3~0.6):0.026: 0.255.

Preferably, the preparation method provided by the present invention can have three methods in the order of adding resorcinol. The first is to directly polymerize resorcinol, phenol and formaldehyde and then distill;

The second method is to pre-polymerize phenol and formaldehyde, distill the pre-polymerized product at atmospheric pre...

Example Embodiment

Example 1

Take 940g of phenol, 470g of resorcinol, and 37% formaldehyde into 648g, add 9.4g of oxalic acid and 18.8g of phosphoric acid (concentration of 85%), heat up to reflux reaction, react at constant temperature in this state for 4 hours, and distill to 140°C, then distilled at 170°C under reduced pressure (-0.095MPa), and put it on the tray to obtain 1328 g of resin. The properties of the phenolic resin prepared in this example are shown in Table 1.

Example Embodiment

Example 2

Take 940g of phenol and 37% formaldehyde into 648g, add 9.4g of oxalic acid, 18.8g of phosphoric acid (concentration of 85%), heat up to reflux reaction, react at constant temperature in this state for 4 hours, then distill to 105°C under normal pressure, and add to room temperature. 470 g of hydroquinone was reacted at a constant temperature for 1 hour, and then distilled at 170° C. under reduced pressure (-0.095 MPa), and placed on the tray to obtain 1348 g of resin. The properties of the phenolic resin prepared in this example are shown in Table 1.