CN114790262B - Alkaline environment soluble resin and preparation method thereof - Google Patents
Alkaline environment soluble resin and preparation method thereof Download PDFInfo
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- CN114790262B CN114790262B CN202210445835.2A CN202210445835A CN114790262B CN 114790262 B CN114790262 B CN 114790262B CN 202210445835 A CN202210445835 A CN 202210445835A CN 114790262 B CN114790262 B CN 114790262B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2438/00—Living radical polymerisation
- C08F2438/03—Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX]
Abstract
The invention belongs to the technical field of high polymer materials, and particularly relates to an alkaline environment soluble resin and a preparation method thereof. The soluble resin is prepared from the following raw materials in percentage by mass: 40-65% of DER354 epoxy resin; 25-45% of acrylic monomer; 3-10% of RAFT reagent; 0.8 to 1.8 percent of catalyst; 3.0 to 8.5 percent of other auxiliary agents; the RAFT reagent is n-dodecyl trithiocarbonate; the catalyst is tetrabutylammonium bromide; the other auxiliary agents comprise an initiator, a toughening agent and an emulsifying agent; the initiator is azodiisobutyronitrile, the toughening agent is isophorone diamine, and the emulsifier is polyvinyl alcohol. The material can be dissolved under alkaline condition, has low cost of raw materials, simple preparation process and easy industrial mass production.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to an alkaline environment soluble resin and a preparation method thereof.
Background
Petroleum is used as one of three energy sources and plays a vital role in the economic development of China. The oil gas reserves of China are quite abundant, but most of the oil gas reserves belong to unconventional oil and gas fields with low abundance and low permeability. According to the estimation of the national resource department, the amount of the recoverable shale gas resource and the total amount of the coalbed methane resource in China are the second world, and the amount of the recoverable oil sand oil resource is the fifth world. But the underground permeability of unconventional oil and gas resources is usually less than 0.1Md, and the exploitation difficulty is extremely high. The fracturing yield increasing technology is one of important means for industrially exploiting coal bed gas, shale oil/gas and densification. In the underground stratified staged fracturing, ball throwing or bridge plug insertion is needed between the intervals to seal and isolate the intervals, then the next construction is carried out, and after the construction is completed, temporary plugging tools are needed to be removed. At present, the common packing tools are mostly prepared from insoluble materials (steel, high polymer materials and the like), and the tools prepared from the insoluble materials have the defects of difficult drilling and milling, long time consumption, difficult flowback of powder/fragments after drilling and the like in use, and seriously influence the construction progress, efficiency and safety.
The underground temporary plugging tool is prepared by using the degradable material, so that the workpiece is automatically dissolved and disabled underground, drilling, grinding and recycling procedures can be omitted, engineering risks are reduced, construction efficiency is improved, and damage to a reservoir layer in the drilling and grinding process can be avoided. The degradable materials developed and applied at present mainly comprise degradable resin, soluble magnesium alloy and soluble aluminum alloy. The alloy material has higher cost, and the degradable resin composite material is used as the raw material of part of underground operation tools, so the method has the characteristics of safety, stability, low cost, convenient use and the like. In the existing technology using the degradable resin composite material as the raw material of part of the downhole operation tool, the coating has poor temperature resistance, and the downhole channel is easy to be blocked after the coating fails, so that the downhole maintenance cost is greatly increased, and the harsh downhole service condition is difficult to be satisfied.
Disclosure of Invention
Aiming at the technical problems, the invention provides the soluble resin and the preparation method thereof, wherein the material is soluble under alkaline conditions, the raw material cost is low, the preparation process is simple, and the industrial mass production is easy.
The invention is realized by the following technical scheme:
the alkali environment soluble resin is prepared from the following raw materials in percentage by mass:
40-65% of DER354 epoxy resin;
25-45% of acrylic monomer;
3-10% of RAFT reagent;
0.8 to 1.8 percent of catalyst;
3.0 to 8.5 percent of other auxiliary agents.
Further, the acrylic monomer comprises any one or more of methyl acrylate, ethyl acrylate, 2-methyl methacrylate and 2-ethyl methacrylate;
the RAFT reagent is n-dodecyl trithiocarbonate; the catalyst is tetrabutylammonium bromide; the other auxiliary agents comprise an initiator, a toughening agent and an emulsifying agent; the initiator is azodiisobutyronitrile, the toughening agent is isophorone diamine, and the emulsifier is polyvinyl alcohol.
The preparation method of the alkaline environment soluble resin is characterized in that the soluble resin is prepared by modifying epoxy resin with acrylic ester, and specifically comprises the following steps:
(1) Adding a RAFT reagent and DER354 epoxy resin into a reaction kettle, dissolving the RAFT reagent and the DER354 epoxy resin in a solvent (one of acetone, butanone, toluene, xylene, methyl ethyl ketone, cyclohexanone and n-butanol is adopted), reacting for 5-8 hours at 80-100 ℃ by taking tetrabutylammonium bromide as a catalyst, and distilling to remove the solvent to obtain epoxy ester;
(2) Mixing the epoxy ester obtained in the step (1) with acrylic ester monomers in a reaction kettle, taking acetone as a solvent, taking azodiisobutyronitrile as an initiator, carrying out polymerization reaction for 7-9 h at the temperature of 60-80 ℃, and then reducing the temperature to 50-60 ℃;
(3) Adding an emulsifying agent polyvinyl alcohol and a toughening agent isophorone diamine into a reaction kettle, heating to 70-90 ℃, and preserving heat for 1-3 hours to obtain transparent uniform resin, namely the soluble resin.
Further, the acrylic monomer comprises any one or more of methyl acrylate, ethyl acrylate, 2-methyl methacrylate and 2-ethyl methacrylate;
the RAFT reagent is n-dodecyl trithiocarbonate;
the mass of the catalyst accounts for 0.5-1.5% of the sum of the mass of the RAFT reagent and the mass of the DER354 epoxy resin;
the mass ratio of the initiator to the total mass of the reaction materials is 0.4-1.0%; the mass ratio of the emulsifier to the total mass of the reaction materials is 3-5%; the toughening agent accounts for 1.5 to 3.5 percent of the total mass of the reaction materials.
Further, in the step (1), the reaction temperature is 80 ℃, 90 ℃ or 100 ℃, and the reaction time is 5 hours, 6 hours, 7 hours or 8 hours;
in the step (2), the reaction temperature of the polymerization reaction is 60 ℃, 70 ℃ or 80 ℃; the reaction time of the polymerization reaction is 7 hours, 8 hours or 9 hours;
in the step (3), the reaction temperature is 70 ℃,80 ℃ or 90 ℃; the heat preservation time is 1h, 2h or 3h.
Further, the catalyst accounts for 0.5%, 1.0% or 1.5% of the sum of the mass of the RAFT agent and the DER354 epoxy resin.
The mass ratio of the initiator to the total mass of the reaction materials is 0.4%, 0.7% or 1.0%;
the mass ratio of the emulsifier to the total mass of the reaction materials is 3%, 4% or 5%; the toughening agent accounts for 1.5%, 2.5% or 3.5% of the total mass of the reaction materials.
The alkaline environment-soluble resin and the application of the alkaline environment-soluble resin prepared by the preparation method apply the alkaline environment-soluble resin to underground drilling and production system tools in the petroleum field, wherein the drilling and production system tools comprise underground restrictor-soluble pins, soluble ball seats and restrictor-soluble nozzles.
The beneficial technical effects of the invention are as follows:
(1) The resin provided by the invention can be automatically dissolved under alkaline conditions, and the dissolution rate of the resin matrix is more than 50% in 24 hours in an alkaline environment with pH being more than 8.
(2) The resin provided by the invention has certain temperature resistance (100 ℃), and the strength of the resin is more than 80% of an initial value after the resin is in service for 30 days in an environment with the temperature of 70 ℃ and the pH value of less than 7.
(3) The resin material provided by the invention has stable mechanical strength, the tensile strength at room temperature is more than or equal to 50MPa, the tensile strength at 90 ℃ is more than or equal to 30MPa, and the impact strength at room temperature is more than or equal to 15KJ/m 2 。
(5) The soluble resin provided by the invention is stable in neutral or acidic environment and self-decomposed in alkaline environment, the preparation process is simple and environment-friendly, the raw material cost is low, the soluble resin can be applied to raw materials of underground workpieces in the petroleum field, and after the due effect is exerted, the soluble resin can be automatically dissolved and can not cause blockage in the underground.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
On the contrary, the invention is intended to cover any alternatives, modifications, equivalents, and variations as may be included within the spirit and scope of the invention as defined by the appended claims. Further, in the following detailed description of the present invention, certain specific details are set forth in order to provide a better understanding of the present invention. The present invention will be fully understood by those skilled in the art without the details described herein.
Example 1
4.62g of DER354 epoxy resin and 8g of butyl acetate are mixed and heated to 90 ℃, 0.11g of tetrabutylammonium bromide and 0.62g of n-dodecyl trithiocarbonate dissolved in 4g of butyl acetate are added dropwise, and the mixture is reacted for 8 hours at 90 ℃.
12.06g of acetone was added to the reaction vessel, then 3.98g of butyl acrylate was added, 0.23g of azobisisobutyronitrile was added, and the reaction was carried out at 70℃for 8 hours, followed by cooling to 60 ℃.
0.32g of polyvinyl alcohol and 0.18g of isophorone diamine are added into a reaction kettle to react for 3 hours at 80 ℃ to obtain transparent uniform matrix resin, the resin prepared in the implementation is processed into cubes with the size of 20 multiplied by 20mm, and the dissolution performance test is carried out in 1mol/L sodium hydroxide solution at the temperature of 22 ℃ and the dissolution rate of 0.0232g/h.
Example 2
4.62g of DER354 epoxy resin and 9.8g of propylene glycol methyl ether are taken, mixed and heated to 80 ℃, 0.16g of tetrabutylammonium bromide and 0.68g of n-dodecyl trithiocarbonate dissolved in 3.2g of propylene glycol methyl ether are added dropwise, and the mixture is reacted for 6 hours at 80 ℃.
11.23g of acetone was added to the reaction vessel, then 4.06g of butyl acrylate was added, 0.28g of azobisisobutyronitrile was added, and the reaction was carried out at 70℃for 6 hours, followed by cooling to 60 ℃.
0.26g of polyvinyl alcohol and 0.23g of isophorone diamine are added into a reaction kettle to react for 2 hours at 70 ℃ to obtain transparent uniform matrix resin. The resin prepared in this example was processed into cubes of size 20X 20mm and tested for dissolution performance in 1mol/L sodium hydroxide solution at 22℃with a dissolution rate of 0.0587g/h.
Claims (7)
1. The alkaline environment soluble resin is characterized in that the soluble resin is prepared from acrylic ester modified epoxy resin, and the soluble resin is prepared from the following raw materials in percentage by mass:
40-65% of DER354 epoxy resin;
25-45% of acrylic monomer;
3-10% of RAFT reagent;
0.8 to 1.8 percent of catalyst;
3.0 to 8.5 percent of other auxiliary agents.
2. The alkaline environment-soluble resin of claim 1, wherein said acrylic monomer comprises any one or more of methyl acrylate, ethyl acrylate, 2-methyl methacrylate and 2-ethyl methacrylate;
the RAFT reagent is n-dodecyl trithiocarbonate; the catalyst is tetrabutylammonium bromide; the other auxiliary agents comprise an initiator, a toughening agent and an emulsifying agent; the initiator is azodiisobutyronitrile, the toughening agent is isophorone diamine, and the emulsifier is polyvinyl alcohol.
3. The preparation method of the alkaline environment soluble resin is characterized in that the soluble resin is prepared by modifying epoxy resin with acrylic ester, and the preparation method comprises the following steps:
(1) Adding a RAFT reagent and DER354 epoxy resin into a reaction kettle, dissolving the RAFT reagent and the DER354 epoxy resin by using a solvent, reacting for 5 to 8 hours at the temperature of between 80 and 100 ℃ by using tetrabutylammonium bromide as a catalyst, and distilling the solvent to obtain epoxy ester;
(2) Mixing the epoxy ester obtained in the step (1) with acrylic ester monomers in a reaction kettle, taking acetone as a solvent, taking azodiisobutyronitrile as an initiator, carrying out polymerization reaction for 7-9 h at the temperature of 60-80 ℃, and then reducing the temperature to 50-60 ℃;
(3) Adding an emulsifying agent polyvinyl alcohol and a toughening agent isophorone diamine into a reaction kettle, heating to 70-90 ℃, and preserving heat for 1-3 hours to obtain transparent uniform resin, namely the soluble resin.
4. The method for preparing an alkaline environment-soluble resin according to claim 3, wherein the acrylic monomer comprises any one or more of methyl acrylate, ethyl acrylate, 2-methyl methacrylate and 2-ethyl methacrylate;
the RAFT reagent is n-dodecyl trithiocarbonate;
the mass of the catalyst accounts for 0.5-1.5% of the sum of the mass of the RAFT reagent and the mass of the DER354 epoxy resin;
the mass ratio of the initiator to the total mass of the reaction materials is 0.4-1.0%;
the mass ratio of the emulsifier to the total mass of the reaction materials is 3-5%; the toughening agent accounts for 1.5 to 3.5 percent of the total mass of the reaction materials.
5. A process for preparing an alkaline environment-soluble resin according to claim 3, wherein in the step (1), the reaction temperature is 80 ℃, 90 ℃ or 100 ℃ and the reaction time is 5 hours, 6 hours, 7 hours or 8 hours;
in the step (2), the reaction temperature of the polymerization reaction is 60 ℃, 70 ℃ or 80 ℃; the reaction time of the polymerization reaction is 7 hours, 8 hours or 9 hours;
in the step (3), the reaction temperature is 70 ℃,80 ℃ or 90 ℃; the heat preservation time is 1h, 2h or 3h.
6. The method for preparing an alkaline environment-soluble resin according to claim 4, wherein the catalyst accounts for 0.5%, 1.0% or 1.5% of the sum of the mass of the RAFT agent and the DER354 epoxy resin;
the mass ratio of the initiator to the total mass of the reaction materials is 0.4%, 0.7% or 1.0%;
the mass ratio of the emulsifier to the total mass of the reaction materials is 3%, 4% or 5%;
the toughening agent accounts for 1.5%, 2.5% or 3.5% of the total mass of the reaction materials.
7. Use of the alkaline environment soluble resin of any one of claims 1-2 and the alkaline environment soluble resin prepared according to the method of any one of claims 3-6, wherein the alkaline environment soluble resin is applied to a downhole drilling and production system tool in the petroleum field, the drilling and production system tool comprising a downhole choke soluble pin, a soluble ball seat, a choke soluble nozzle.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202210445835.2A CN114790262B (en) | 2022-04-26 | 2022-04-26 | Alkaline environment soluble resin and preparation method thereof |
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| CN202210445835.2A CN114790262B (en) | 2022-04-26 | 2022-04-26 | Alkaline environment soluble resin and preparation method thereof |
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| CN114790262A CN114790262A (en) | 2022-07-26 |
| CN114790262B true CN114790262B (en) | 2023-06-09 |
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