CN112694713A - Anti-aging drillable composite material and preparation method thereof - Google Patents
Anti-aging drillable composite material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an anti-aging drillable composite material which comprises the following raw materials in parts by weight: 100 parts of epoxy resin, 20-100 parts of aromatic curing agent, 5-30 parts of active diluent, 0.1-1 part of antioxidant, 1-10 parts of silane coupling agent, 1-10 parts of hydrophobic modifier, 10-50 parts of reinforcing fiber, 10 parts of protective polymer, 5-10 parts of inorganic nano material and 50-100 parts of absolute ethyl alcohol; firstly, dissolving an aromatic curing agent in an active diluent, then adding epoxy resin, a silane coupling agent and a hydrophobic modifier, then forming and curing the mixture and reinforcing fibers according to a certain process, preparing a composite material tool after the completion, dispersing a protective polymer and an inorganic nano material into absolute ethyl alcohol to prepare a coating ethanol dispersion liquid, coating the coating ethanol dispersion liquid on the surface of the composite material tool, and drying and curing at 80 ℃. The drillable composite material has excellent mechanical property, thermal aging resistance and water resistance, and can be used for preparing drillable composite material tools with higher requirements on aging property, water resistance and corrosion resistance in the oil and gas exploitation process.
Description
Technical Field
The invention belongs to the technical field of materials for downhole tools, and particularly relates to an anti-aging drillable composite material and a preparation method thereof.
Background
The composite material has the characteristics of easy drilling and milling, low specific gravity of chips, easy circular discharge of a shaft and the like, and simultaneously has designability, so technical research on applying the non-metal composite material to the petroleum downhole tool is started at home and abroad, and a mature composite downhole tool, mainly a bridge plug, is developed at home and abroad at present. The application field of the fiber composite material is continuously expanded, the fiber composite material is gradually applied to the technologies of layered water injection, layered oil extraction, layered sand prevention and the like, and higher requirements on the long-term durability, corrosion resistance and the like of the drillable composite material are provided for ensuring the long-term and effective work of tools.
The drillable composite material is inevitably corroded and aged by various media such as temperature, oxygen, water and the like in underground service, so that the surface of a product is damaged, resin degradation is caused, and the macroscopic mechanical property is degraded. At present, the composite material is applied more in the fields of ocean, aerospace and civil use, the research on the corrosion performance of the composite material is also carried out under the use conditions of the related fields, and methods for improving the long-acting performance of the composite material are formed at present: firstly, the variety and the curing degree of a resin matrix are improved; secondly, the types and surface physical properties of the materials and the additives are enhanced; interface bonding performance of the matrix and the base material; the corrosion-resistant layer is formed; and fifthly, improving the processing technology.
The composite material has the following problems in the well: soaking the resin for a long time to deform and expand; severe corrosion of the surface of the material in the well; thirdly, the resin and the fiber are separated and fall off after being soaked. The above problems seriously affect the service life and reliability of composite downhole tools, and thus, the improvement of material performance is urgently needed. The improvement of the performance of the composite material directly influences the design and reliability of the downhole tool, directly influences the technical level of the downhole tool even the whole process can reach, improves the long-term effect of the composite material, can expand the application field of the tool, realizes scale and industrialization, and has extremely important significance for realizing the non-metallization of the downhole tool and solving the problems existing on site at present.
CN201710149125.4 discloses a method for increasing the drilling and grinding speed of drillable composite material, in the process of preparing drillable composite material, an expanding agent is introduced, and the expanding agent is uniformly dispersed in the matrix material of the composite material; the drilling and grinding speed of the composite material is improved without replacing the reinforced fiber material and sacrificing the overall mechanical property of the composite material. When the composite material is specifically applied, the type and the proportion of the introduced expanding agent can be adjusted according to different well conditions, the controllability and the adaptability are better, and the drilling and grinding speed of the composite material can be further improved on the basis of optimizing the drilling and grinding process.
Chinese literature chemical research and application (2016.9,1294-1300) discloses preparation and performance research of a polyester fiber cloth hybrid reinforced epoxy resin drillable composite material, and the polyester fiber cloth, carbon fiber and Kevlar fiber are respectively mixed and reinforced with epoxy resin to prepare the high-performance composite material for drillable bridge plugs meeting the requirements of oil field development. The discovery that the liquid arylamine is used for replacing the solid arylamine, and the similar glass transition temperature and mechanical strength can still be maintained; the TDE is used in an amount of 30 percent, and the reactive diluent is used in an amount of 10 percent, so that the resin can be ensured to fully infiltrate the fibers, and better mechanical properties are achieved; the polyester fiber/carbon fiber reinforced epoxy resin composite material has the advantages that the polyester fiber, the carbon fiber and the Kevlar fiber are mixed and reinforced, the tensile modulus and the breaking strength are increased along with the increase of the contents of the carbon fiber and the Kevlar fiber, and the polyester fiber/carbon fiber reinforced epoxy resin composite material has lower breaking elongation; through indoor drilling and grinding experiment tests, the epoxy resin composite material is high in drilling and grinding speed, and rapid removal of tools can be achieved.
The materials in the above patents and documents can improve the drilling and grinding speed to some extent, but the influence of the aging of the materials on the performance of the composite material is not considered.
Disclosure of Invention
Aiming at the defects of the existing drillable composite material in aging resistance and long-term effect, one of the invention is to provide an aging-resistant drillable composite material which can delay the aging rate of a downhole drillable composite material tool and prolong the service life, and the technical scheme is as follows:
an aging-resistant drillable composite material, comprising the following raw materials in parts by weight:
100 parts of epoxy resin;
20-100 parts of aromatic curing agent;
5-30 parts of a reactive diluent;
0.1-1 part of antioxidant;
1-10 parts of a silane coupling agent;
1-10 parts of a hydrophobic modifier;
10-50 parts of reinforcing fiber;
10 parts of a protective polymer;
5-10 parts of inorganic nano material;
50-100 parts of absolute ethyl alcohol;
the protective polymer is one or a mixture of polyaniline and epoxy resin;
the inorganic nano material is one or a mixture of two of nano titanium dioxide and nano zirconium dioxide.
Preferably, the ageing-resistant drillable composite material comprises the following raw materials in parts by weight:
100 parts of epoxy resin;
20 parts of aromatic curing agent;
5 parts of a reactive diluent;
0.1 part of antioxidant;
1 part of a silane coupling agent;
1 part of a hydrophobic modifier;
10 parts of reinforcing fiber;
5 parts of polyaniline;
5 parts of epoxy resin;
5 parts of nano zirconium dioxide;
50 parts of absolute ethyl alcohol.
Preferably, the ageing-resistant drillable composite material comprises the following raw materials in parts by weight:
100 parts of epoxy resin;
100 parts of aromatic curing agent;
30 parts of a reactive diluent;
1 part of an antioxidant;
10 parts of a silane coupling agent;
10 parts of a hydrophobic modifier;
50 parts of reinforcing fiber;
10 parts of epoxy resin;
10 parts of nano titanium dioxide;
100 parts of absolute ethyl alcohol.
Preferably, the ageing-resistant drillable composite material comprises the following raw materials in parts by weight:
100 parts of epoxy resin;
60 parts of aromatic curing agent;
18 parts of a reactive diluent;
0.5 part of antioxidant;
5 parts of a silane coupling agent;
5 parts of a hydrophobic modifier;
30 parts of reinforcing fiber;
10 parts of polyaniline;
2.5 parts of nano titanium dioxide;
2.5 parts of nano zirconium dioxide;
80 parts of absolute ethyl alcohol.
Further, the epoxy resin is liquid epoxy resin or epoxy resin with the softening temperature close to room temperature.
Further, the aromatic curing agent is an aromatic polyamine.
Further, the reactive diluent is glycidyl ether with a diepoxy functional group.
Further, the antioxidant is an antioxidant 1010.
Further, the silane coupling agent is one or more of KH-550, KH-560 or KH 570.
Further, the hydrophobic modifier is one or more of amino silicone oil and fluorine-containing long-chain alkyl trimethoxy siloxane.
Furthermore, the reinforcing fiber is one or more of glass fiber, carbon fiber and Kevlar fiber, and the weaving form adopts plain cloth, twill cloth, monofilament or chopped fiber.
Further, the aromatic polyamine is one or more of m-phenylenediamine, p-phenylenediamine, 4,4' -diaminodiphenylmethane, toluene diethyldiamine, 4-aminobenzenesulfonamide, 4,4' -diaminodiphenyl ether or 4,4' -diaminodiphenylsulfone.
Further, the glycidyl ether is one or more of ethylene glycol diglycidyl ether, butanediol diglycidyl ether or resorcinol diglycidyl ether.
The second invention provides a preparation method of an anti-aging drillable composite material, which adopts the technical scheme that:
firstly, dissolving an aromatic curing agent in an active diluent, then adding epoxy resin, a silane coupling agent and a hydrophobic modifier, uniformly stirring, then forming the aromatic curing agent and reinforcing fibers by winding forming, hand pasting forming or compression molding forming processes, curing according to a certain curing process, processing into a composite material tool after curing, dispersing a protective polymer and an inorganic nano material into absolute ethyl alcohol to prepare a coating ethanol dispersion liquid, coating the coating ethanol dispersion liquid on the surface of the composite material tool, and drying and curing.
The drying and curing temperature is 80 ℃.
The curing process comprises three stages of low-temperature normal-pressure curing at room temperature to 120 ℃ for 24 hours, medium-temperature vacuum curing at 80-160 ℃ for 12 hours and high-temperature vacuum curing at 120-200 ℃ for 4 hours, and after the gel is cured at the low temperature and normal pressure, vacuumizing and raising the temperature to the medium-high temperature for post-curing.
Compared with the prior art, the invention has the following advantages: the hydrophilicity is reduced and the oxidation resistance is increased through the formula of the epoxy resin matrix, the interface action between the epoxy resin matrix and the reinforced fiber reinforcement is improved, and the anti-aging coating is coated on the surface of the composite material, so that the failure of the fiber composite material is slowed down and the service life is prolonged on the basis of ensuring the high strength, high modulus and good drillability of the composite material. The drillable composite material prepared by the invention has excellent mechanical property, thermal aging resistance and water resistance, and can be used for preparing drillable composite material tools with higher requirements on aging property, water resistance and corrosion resistance in the oil and gas exploitation process.
Drawings
FIG. 1 is a graph of tensile stress-strain curves before and after aging of composites of examples 1-3 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
It should be noted that all directional indications (such as up, down, left, right, front, and back … …) in the embodiments of the present invention are limited to relative positions on a given view, not absolute positions.
In addition, the descriptions related to "first", "second", etc. in the present invention are only for descriptive purposes and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature. In the description of the present invention, "a plurality" means at least two, e.g., two, three, etc., unless specifically limited otherwise.
An aging-resistant drillable composite material comprises the following raw materials in parts by weight:
100 parts of epoxy resin;
20-100 parts of aromatic curing agent;
5-30 parts of a reactive diluent;
0.1-1 part of antioxidant;
1-10 parts of a silane coupling agent;
1-10 parts of a hydrophobic modifier;
10-50 parts of reinforcing fiber;
10 parts of a protective polymer;
5-10 parts of inorganic nano material;
50-100 parts of absolute ethyl alcohol;
the protective polymer is one or a mixture of polyaniline and epoxy resin;
the inorganic nano material is one or a mixture of two of nano titanium dioxide and nano zirconium dioxide.
The epoxy resin is liquid epoxy resin or epoxy resin with the softening temperature close to room temperature.
The aromatic curing agent is aromatic polyamine, and the aromatic polyamine is one or more of m-phenylenediamine, p-phenylenediamine, 4,4' -diaminodiphenylmethane, toluene diethyldiamine, 4-aminobenzenesulfonamide, 4,4' -diaminodiphenyl ether or 4,4' -diaminodiphenyl sulfone.
The reactive diluent is glycidyl ether with a diepoxy functional group, and the glycidyl ether is one or more of ethylene glycol diglycidyl ether, butanediol diglycidyl ether or resorcinol diglycidyl ether.
The antioxidant is antioxidant 1010.
The silane coupling agent is one or more of KH-550, KH-560 or KH 570.
The hydrophobic modifier is one or more of amino silicone oil and fluorine-containing long-chain alkyl trimethoxy siloxane.
The reinforcing fiber is one or more of glass fiber, carbon fiber and Kevlar fiber, and the weaving form adopts plain cloth, twill cloth, monofilament or chopped fiber.
The above products are all commercially available, such as: the resin is produced by Shanghai petrochemical Balng division, the aromatic curing agent 4,4' -diaminobenzene is produced by Shanghai Arlatin Biotechnology, Inc., the active diluent 622 is produced by Shanghai Delaun chemical, Inc., the antioxidant 1010 is produced by Singapofibuff factory, the silane coupling agent is produced by Ruixiang chemical, Inc., the hydrophobic modifier is produced by Dow Corning, the carbon fiber cloth (Dongli protofilament) in the reinforced fiber is produced by Nanjing Manka technology, the chopped glass fiber is produced by Kyolite, the Kevlar protofilament is produced by DuPont, the polyaniline, the nano titanium dioxide and the nano zirconium dioxide are produced by Shanghai Arlatin Biotechnology, and the absolute ethyl alcohol is produced by Dow chemical.
As mentioned in the background of the specification, the drillable composite material may have the problems of soaking deformation, corrosion aging, resin and fiber shedding and the like in the underground, and the invention respectively improves the aging resistance of the composite material from the angles of the interface bonding performance of a resin matrix, the matrix and a reinforcement, a corrosion-resistant layer, a processing technology and the like. In the resin matrix, the molecular structure of the epoxy resin and the aromatic curing agent is relatively stable, the oxidation resistance and the dissolution resistance are good, and the stability of the epoxy resin and the aromatic curing agent is basically ensured on the basis of the molecular structure; in the resin matrix, the silane coupling agent is incorporated into the cross-linked network, so that the oxidation resistance of the molecular structure is improved, and meanwhile, the hydrophobic modifier can reduce the diffusion rate of water in the matrix and improve the water resistance. The existence of the silane coupling agent improves the interface strength of the resin matrix and the interface of the reinforced fiber, reduces the diffusion of water molecules in the interface and reduces the possibility of interlayer peeling. The anti-aging coating is coated on the surface of the composite material, so that the rate of molecules such as oxygen, water and chemical media entering the composite material is reduced, and the service life of the composite material is prolonged. In the preparation process, before the gel is solidified, the gel is solidified at normal pressure and low temperature, so that micro bubbles or pores formed by volatilization of low-boiling-point substances are reduced, and during medium-high temperature solidification, the vacuum is pumped, so that the oxidation generated before a sufficient cross-linked network is not formed in the solidification process is reduced.
Specific examples are given below:
example 1
(1) Dissolving 20 parts by weight of aromatic amine curing agent 4,4' -diaminodiphenylmethane in 5 parts by weight of reactive diluent ethylene glycol diglycidyl ether, then adding 100 parts by weight of liquid epoxy resin, 1 part by weight of silane coupling agent KH550, 1 part by weight of hydrophobic modifier amino silicone oil and 0.1 part by weight of antioxidant 1010, and uniformly stirring to obtain an anti-aging resin matrix;
(2) and then arranging the anti-aging resin matrix and 10 parts by weight of carbon fibers on a rigid flat plate die in a plain mode, and preparing the composite material laminated board containing 8 layers of carbon fiber plain cloth by adopting a hand lay-up forming process. The curing process conditions of the laminated board are three stages of curing at 60 ℃ under normal pressure for 24 hours, curing at 120 ℃ under medium temperature and vacuum for 12 hours and curing at 160 ℃ under high temperature and vacuum for 4 hours. After curing, the laminate was processed to 10cm × 10 cm. The retention of carbon fibers therein was 65%.
(3) And dip-coating the laminated board with a coating ethanol dispersion liquid consisting of 5 parts by weight of polyaniline, 5 parts by weight of epoxy resin, 5 parts by weight of nano zirconium dioxide and 50 parts by weight of absolute ethyl alcohol, and drying and curing at 80 ℃ to prepare the aging-resistant drillable composite laminated board.
In this embodiment, if the room temperature is low, the aromatic amine curing agent is dissolved, and the epoxy resin and the carbon fiber plain cloth are soaked by heating properly. In this embodiment, the thermal-oxidative aging resistance of the material is improved, and referring to fig. 1, the tensile strength retention rate of the prepared drillable composite material is 91.8% after thermal-oxidative aging at 120 ℃ for 60 days.
Example 2
(1) Firstly, dissolving 100 parts by weight of aromatic amine curing agent 4-aminobenzenesulfonamide in 30 parts by weight of active diluent butanediol diglycidyl ether, then adding 100 parts by weight of epoxy resin with the softening temperature of 60 ℃,1 part by weight of antioxidant 1010, 10 parts by weight of silane coupling agent KH560 and 10 parts by weight of hydrophobic modifier heptadecafluorodecyltrimethylsilane trimethoxy silane, properly heating to liquefy the epoxy resin, and uniformly stirring to obtain an anti-aging resin matrix;
(2) and uniformly stirring the anti-aging resin matrix and 50 parts by weight of chopped glass fibers to prepare a prepreg, placing the prepreg in a rectangular mold, and carrying out compression molding. The curing process conditions of the mould pressing material are three stages of curing for 24 hours at the temperature of 80 ℃ under normal pressure, curing for 12 hours at the temperature of 120 ℃ in vacuum and curing for 4 hours at the temperature of 180 ℃ in vacuum. After curing, the material is processed into 10cm × 20cm molded plates.
(3) And dip-coating the molded plate with a coating ethanol dispersion solution consisting of 10 parts by weight of epoxy resin, 10 parts by weight of nano titanium dioxide and 100 parts by weight of absolute ethyl alcohol, and drying and curing at 80 ℃ to prepare the aging-resistant drillable composite material molded plate.
In the embodiment, the chopped glass fiber prepreg is generally molded, and the water resistance of the composite material is mainly improved. Referring to fig. 1, the tensile strength retention of the composite material in this example was 90% after 60 days of water immersion aging at 80 ℃.
Example 3
(1) Firstly, dissolving a mixture of 30 parts by weight of 4,4' -diaminodiphenyl sulfone and 30 parts by weight of toluene diethyl diamine in 18 parts by weight of butanediol diglycidyl ether serving as an active diluent, then adding 100 parts by weight of liquid epoxy resin, 0.5 part by weight of antioxidant 1010, 5 parts by weight of silane coupling agent KH570 and 5 parts by weight of tridecafluorooctyltrimethoxysilane serving as a hydrophobic modifier, and uniformly mixing to prepare the anti-aging resin matrix.
(2) Immersing the Kevlar fiber precursor into an anti-aging resin matrix, and then winding and forming the Kevlar fiber precursor on a square core mold, wherein the dosage of the Kevlar fiber is controlled at 30 parts by weight. The curing process conditions of the winding body are three stages of curing at 60 ℃ under normal pressure for 24 hours, curing at 100 ℃ under medium temperature in vacuum for 12 hours and curing at 160 ℃ under high temperature in vacuum for 4 hours. And demolding after curing is finished, and processing into a 10cm × 20cm plate.
(3) And (3) dip-coating the plate with a coating ethanol dispersion consisting of 10 parts by weight of polyaniline, 2.5 parts by weight of nano titanium dioxide, 2.5 parts by weight of nano zirconium dioxide and 80 parts by weight of absolute ethyl alcohol, and drying and curing at 80 ℃ to prepare the anti-aging drillable composite plate.
In the embodiment, the used fiber protofilaments are generally formed by winding, the aging resistance of the composite material under the high-salinity damp-heat condition is mainly improved, and for the convenience of later-stage test, the used core mold is square so as to obtain a flat plate. Referring to fig. 1, the tensile strength retention of the composite material in this example was 91.2% after aging in 120 ℃ simulated geothermal water for 60 days.
The composite material obtained in example 1 was subjected to tensile strength tests before and after heat aging, the composite material obtained in example 2 was subjected to tensile strength tests before and after water resistance tests, and the composite material obtained in example 3 was subjected to tensile strength tests before and after aging under high salinity and high humidity conditions.
The aging-resistant drillable composite materials prepared in the above examples 1-3 have excellent mechanical properties, thermal aging resistance, and water resistance, as detailed in table 1 (characterization of technical properties of aging-resistant drillable composite materials).
TABLE 1 characterization of technical Properties of ageing-resistant drillable composites
As can be seen from table 1, the tensile strength before aging of the aging-resistant drillable composite material prepared in example 1 is 390MPa, the tensile strength before aging is 358MPa and the tensile strength retention is 91.8% after 60 days of 120 ℃ thermo-oxidative aging, the tensile strength before aging of the aging-resistant drillable composite material prepared in example 2 is 151MPa, the tensile strength after 80 ℃ soaking in water and aging is 136MPa and the tensile strength retention is 90% after 60 days of 80 ℃ soaking in water, the tensile strength before aging of the aging-resistant drillable composite material prepared in example 3 is 250MPa, and the tensile strength after 120 ℃ simulated geothermal water and aging is 60 days, the tensile strength is 228MPa and the tensile strength retention is 91.2%.
To further verify the technical effects of the present invention, the following examples were further made on the basis of the above examples 1 to 3.
Example 4
(1) Firstly, dissolving 25 parts by weight of aromatic amine curing agent 4,4' -diaminodiphenylmethane in 10 parts by weight of reactive diluent ethylene glycol diglycidyl ether, then adding 100 parts by weight of liquid epoxy resin, 2 parts by weight of silane coupling agent KH550, 2 parts by weight of hydrophobic modifier amino silicone oil and 0.2 part by weight of antioxidant 1010, and uniformly stirring to obtain an anti-aging resin matrix;
(2) and then arranging the anti-aging resin matrix and 15 parts by weight of carbon fibers on a rigid flat plate die in a plain mode, and preparing the composite material laminated board containing 8 layers of carbon fiber plain cloth by adopting a hand lay-up forming process. The curing process conditions of the laminated board are three stages of curing at 60 ℃ under normal pressure for 24 hours, curing at 120 ℃ under medium temperature and vacuum for 12 hours and curing at 160 ℃ under high temperature and vacuum for 4 hours. After curing, the laminate was processed to 10cm × 10 cm. The retention of carbon fibers therein was 65%.
(3) And dip-coating the laminated board with a coating ethanol dispersion liquid consisting of 4 parts by weight of polyaniline, 6 parts by weight of epoxy resin, 6 parts by weight of nano zirconium dioxide and 55 parts by weight of absolute ethyl alcohol, and drying and curing at 80 ℃ to prepare the aging-resistant drillable composite laminated board.
In this embodiment, if the room temperature is low, the aromatic amine curing agent is dissolved, and the epoxy resin and the carbon fiber plain cloth are soaked by heating properly. In the embodiment, the thermal-oxidative aging resistance of the material is improved, and the tensile strength retention rate of the prepared drillable composite material is 91.0 after the drillable composite material is aged for 60 days at 120 ℃ by thermal oxidation.
Example 5
(1) Firstly, dissolving 90 parts by weight of aromatic amine curing agent 4-aminobenzenesulfonamide in 25 parts by weight of active diluent butanediol diglycidyl ether, then adding 100 parts by weight of epoxy resin with the softening temperature of 60 ℃, 0.8 part by weight of antioxidant 1010, 8 parts by weight of silane coupling agent KH560 and 9 parts by weight of hydrophobic modifier heptadecafluorodecyltrimethylsilane, properly heating to liquefy the epoxy resin, and uniformly stirring to obtain an anti-aging resin matrix;
(2) and uniformly stirring the anti-aging resin matrix and 45 parts by weight of chopped glass fibers to prepare a prepreg, placing the prepreg in a rectangular mold, and carrying out compression molding. The curing process conditions of the mould pressing material are three stages of curing for 24 hours at the temperature of 80 ℃ under normal pressure, curing for 12 hours at the temperature of 120 ℃ in vacuum and curing for 4 hours at the temperature of 180 ℃ in vacuum. After curing, the material is processed into 10cm × 20cm molded plates.
(3) And dip-coating the molded plate with a coating ethanol dispersion consisting of 8 parts by weight of epoxy resin, 9 parts by weight of nano titanium dioxide and 85 parts by weight of absolute ethyl alcohol, and drying and curing at 80 ℃ to prepare the aging-resistant drillable composite material molded plate.
In the embodiment, the chopped glass fiber prepreg is generally molded, and the water resistance of the composite material is mainly improved. In the embodiment, the tensile strength retention rate of the composite material is 89.5% after the composite material is soaked in water and aged at 80 ℃ for 60 days.
Example 6
(1) Firstly, dissolving a mixture of 25 parts by weight of 4,4' -diaminodiphenyl sulfone and 35 parts by weight of toluene diethyl diamine in 20 parts by weight of butanediol diglycidyl ether serving as an active diluent, then adding 100 parts by weight of liquid epoxy resin, 0.4 part by weight of antioxidant 1010, 6 parts by weight of silane coupling agent KH570 and 4 parts by weight of tridecafluorooctyltrimethoxysilane serving as a hydrophobic modifier, and uniformly mixing to prepare the anti-aging resin matrix.
(2) Dipping the Kevlar fiber precursor into an anti-aging resin matrix, and then winding and forming the Kevlar fiber precursor on a square core mold, wherein the dosage of the Kevlar fiber is controlled to be 25 parts by weight. The curing process conditions of the winding body are three stages of curing at 60 ℃ under normal pressure for 24 hours, curing at 100 ℃ under medium temperature in vacuum for 12 hours and curing at 160 ℃ under high temperature in vacuum for 4 hours. And demolding after curing is finished, and processing into a 10cm × 20cm plate.
(3) And (3) dip-coating the plate with a coating ethanol dispersion solution consisting of 8 parts by weight of polyaniline, 3 parts by weight of nano titanium dioxide, 2 parts by weight of nano zirconium dioxide and 75 parts by weight of absolute ethyl alcohol, and drying and curing at 80 ℃ to prepare the anti-aging drillable composite plate.
In the embodiment, the used fiber protofilaments are generally formed by winding, the aging resistance of the composite material under the high-salinity damp-heat condition is mainly improved, and for the convenience of later-stage test, the used core mold is square so as to obtain a flat plate. In the embodiment, the tensile strength retention rate of the composite material is 90.8% after the composite material is aged in 120 ℃ simulated geothermal water for 60 days.
The composite material obtained in example 4 was subjected to tensile strength tests before and after heat aging, the composite material obtained in example 5 was subjected to tensile strength tests before and after water resistance tests, and the composite material obtained in example 6 was subjected to tensile strength tests before and after aging under high salinity and high humidity conditions. The parameters of the aging-resistant drillable composite materials obtained in the examples 4 to 6 are basically equivalent to those of the examples 1 to 3, and the aging-resistant drillable composite materials have excellent mechanical property, thermal aging resistance and water resistance.
The present invention is not limited to the above-described embodiments, and various changes can be made within the knowledge of those skilled in the art without departing from the gist of the present invention, and the contents of the changes still fall within the scope of the present invention.
Claims (12)
1. An aging-resistant drillable composite material is characterized by comprising the following raw materials in parts by weight:
100 parts of epoxy resin;
20-100 parts of aromatic curing agent;
5-30 parts of a reactive diluent;
0.1-1 part of antioxidant;
1-10 parts of a silane coupling agent;
1-10 parts of a hydrophobic modifier;
10-50 parts of reinforcing fiber;
10 parts of a protective polymer;
5-10 parts of inorganic nano material;
50-100 parts of absolute ethyl alcohol;
the protective polymer is one or a mixture of polyaniline and epoxy resin;
the inorganic nano material is one or a mixture of two of nano titanium dioxide and nano zirconium dioxide.
2. The weathering-resistant drillable composite of claim 1 wherein the epoxy resin is a liquid epoxy resin or an epoxy resin having a softening temperature near room temperature.
3. The age resistant drillable composite material of claim 1, wherein the aromatic curing agent is an aromatic polyamine.
4. The age resistant drillable composite material of claim 1, wherein the reactive diluent is a glycidyl ether having a diepoxy functionality.
5. The weathering-resistant drillable composite material in accordance with claim 1 wherein the antioxidant is antioxidant 1010.
6. The weathering-resistant drillable composite of claim 1 wherein the silane coupling agent is one or more of KH-550, KH-560 or KH 570.
7. The age resistant drillable composite material of claim 1, wherein the hydrophobic modifier is one or more of an amino silicone oil, a fluoro long chain alkyl trimethoxy siloxane.
8. The weathering-resistant drillable composite material of claim 1 wherein the reinforcing fibers are one or more of glass fibers, carbon fibers, kevlar fibers, woven in plain, twill, monofilament or chopped fibers.
9. The age-resistant drillable composite material of claim 3, wherein the aromatic polyamine is one or more of m-phenylenediamine, p-phenylenediamine, 4,4' -diaminodiphenylmethane, toluene diethyldiamine, 4-aminobenzenesulfonamide, 4,4' diaminodiphenyl ether, or 4,4' diaminodiphenylsulfone.
10. The age resistant drillable composite material of claim 4, wherein the glycidyl ether is one or more of ethylene glycol diglycidyl ether, butanediol diglycidyl ether, or resorcinol diglycidyl ether.
11. The method of any one of claims 1-10, wherein the method comprises dissolving an aromatic curing agent in a reactive diluent, adding epoxy resin, silane coupling agent, and hydrophobic modifier, stirring, forming with reinforcing fiber by winding, hand lay-up or compression molding, curing by a curing process, processing into a composite tool after curing, dispersing the protective polymer and the inorganic nanomaterial in absolute ethanol to prepare a coating ethanol dispersion, coating the coating ethanol dispersion on the surface of the composite tool, and drying and curing.
12. The method as claimed in claim 11, wherein the curing process comprises three stages of low-temperature normal-pressure curing at room temperature to 120 ℃ for 24 hours, medium-temperature vacuum curing at 80-160 ℃ for 12 hours, and high-temperature vacuum curing at 120-200 ℃ for 4 hours, after the gel is cured at low temperature and normal pressure, vacuumizing and raising the temperature to medium and high temperature for post-curing.
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| CN117467246A (en) * | 2023-12-05 | 2024-01-30 | 东莞市维斯德新材料技术有限公司 | Carbon fiber/glass fiber reinforced epoxy resin composite material and preparation method thereof |
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