CN109486116B - Deep sea buoyancy material and preparation method thereof - Google Patents

Deep sea buoyancy material and preparation method thereof Download PDF

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CN109486116B
CN109486116B CN201811423172.4A CN201811423172A CN109486116B CN 109486116 B CN109486116 B CN 109486116B CN 201811423172 A CN201811423172 A CN 201811423172A CN 109486116 B CN109486116 B CN 109486116B
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deep sea
epoxy resin
graphene
buoyancy material
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CN109486116A (en
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易杰
李书卿
代正伟
董军
杨群
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Jiaxing University
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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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/5033—Amines aromatic
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/042—Graphene or derivatives, e.g. graphene oxides

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Abstract

The invention discloses a deep sea buoyancy material and a preparation method thereof, and relates to the technical field of chemical materials. According to the deep sea buoyancy material and the preparation method thereof provided by the invention, a modification process is designed aiming at graphene with low bulk density and high strength, so that the uniform dispersion performance of the graphene in an epoxy resin system is improved, the deep sea buoyancy material is prepared by taking the modified graphene, epoxy resin and a curing agent as raw materials through an optimized preparation process, and the obtained deep sea buoyancy material has the material properties of low density, high hydrostatic pressure resistance and low water absorption rate, and can be applied to the preparation of deep sea instruments and equipment, so that the use environment of the deep sea instruments and equipment can be greatly expanded. The invention can solve the technical problems of large density and low hydrostatic pressure resistance of the deep sea buoyancy material, and achieves the technical effects of reducing the material density of the deep sea buoyancy material, improving the hydrostatic pressure resistance and reducing the water absorption rate.

Description

Deep sea buoyancy material and preparation method thereof
Technical Field
The invention relates to the technical field of chemical materials, in particular to a deep sea buoyancy material and a preparation method thereof.
Background
With the promotion of global deep sea strategy and the continuous development of deep sea development technology, more and more deep sea instruments and equipment are put into use. The working environment of the deep sea instrument and equipment is usually extremely high in hydrostatic pressure, and the deep sea instrument and equipment are made of deep sea buoyancy materials to provide net buoyancy, so that normal operation and safe recovery of the deep sea instrument and equipment in the extremely high hydrostatic pressure working environment are guaranteed, and the working performance and the working depth of the deep sea instrument and equipment are directly determined by the density, the hydrostatic pressure resistance, the water absorption rate and other properties of the deep sea buoyancy materials.
The structure of the existing deep sea buoyancy material usually takes epoxy resin as a matrix and hollow glass as a micro-structureThe beads form a solid syntactic foam for the filler. For example, chinese patent CN 101735566 a discloses a machinable full-sea deep buoyancy material and a manufacturing method thereof, wherein the deep-sea buoyancy material disclosed in the patent has a hydrostatic strength of about 115 MPa, but has a high density of about 0.70 g/cm3Thereby greatly limiting the use environment of the deep sea instrument and equipment.
In the process of implementing the invention, the inventor finds that the related art has at least the following problems:
the hollow glass microspheres used in the deep sea buoyancy material provided by the prior art are generally high in density (more than or equal to 0.50 g/cm)3) And the hollow glass microspheres are easy to be damaged in the processing process, and the density of the hollow glass microspheres is further increased, so that the density of the deep sea buoyancy material obtained by subsequent preparation is higher, and the use performance of the deep sea buoyancy material is limited.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a deep sea buoyancy material and a preparation method thereof. The technical scheme of the invention is as follows:
according to a first aspect of the embodiments of the present invention, there is provided a method for preparing a deep sea buoyant material, the method comprising:
adding the pretreated epoxy resin into a stirring barrel of a vacuum defoaming stirrer, heating the temperature of the stirring barrel to 80-90 ℃, adding a curing agent into the stirring barrel, and uniformly stirring;
adding the modified graphene into the stirring barrel, adjusting the vacuum degree of the stirring barrel to be minus 0.08 to minus 0.10atm, and continuously and uniformly stirring to obtain a mixture;
transferring the mixture from the stirring barrel to a mold, heating the mold to 120-140 ℃, preserving heat for 5-10 h, then completing the curing and forming of the mixture, and then reducing the temperature of the cured and formed mixturePerforming warm demoulding to prepare the deep sea buoyancy material, wherein the density of the deep sea buoyancy material is 0.50-0.56 g/cm3The hydrostatic pressure strength is 115-140 MPa, and the water absorption rate is less than or equal to 2%;
the mass part ratio of the pretreated epoxy resin, the curing agent and the modified graphene is 100: 20-40: 1-5.
In a preferred embodiment, the preparation method of the modified graphene comprises the following steps:
adding graphene into absolute ethyl alcohol, and performing ultrasonic dispersion for 30-90 min to prepare a graphene solution, wherein the mass part ratio of graphene to absolute ethyl alcohol in the graphene solution is 1-5: 200-400;
mixing absolute ethyl alcohol and deionized water to form a mixed solution, adding acetic acid into the mixed solution, adjusting the pH value of the mixed solution to 3.5-4.5, then slowly dropwise adding a silane coupling agent into the mixed solution, and stirring and dispersing the mixed solution at a high speed for 30-60 min to prepare a silane coupling agent solution, wherein the mass part ratio of the absolute ethyl alcohol to the deionized water to the silane coupling agent in the silane coupling agent solution is 100-200: 20-60: 0.5-1.0;
slowly adding the silane coupling agent solution into the graphene solution to form a reaction solution, controlling the reaction solution to react for 4-8 hours at a reaction temperature of 70-90 ℃, and performing suction filtration and drying on the reaction solution to prepare the modified graphene.
In a preferred embodiment, the epoxy resin pretreatment method comprises:
heating epoxy resin to 85-95 ℃, adding an epoxy active diluent when the epoxy resin is in a complete molten state, uniformly stirring at 85-95 ℃ for 10-20 min, and cooling to 55-65 ℃ to prepare the pretreated epoxy resin, wherein the mass part ratio of the epoxy resin to the epoxy active diluent is 100: 15-25.
In a preferred embodiment, the epoxy resin contains three or four epoxy groups and the epoxy reactive diluent contains two epoxy groups.
In a preferred embodiment, the curing agent is an aromatic amine curing agent.
In a preferred embodiment, the silane coupling agent is at least one of gamma-aminopropyltriethoxysilane or gamma-glycidoxypropyltrimethoxysilane.
In a preferred embodiment, the density of the graphene is 0.01-0.10 g/cm3。
In a preferred embodiment, the working pressure of a vulcanizer used in the curing and molding process is 10 to 15 MPa.
According to a second aspect of the embodiments of the present invention, there is provided a deep sea buoyant material, wherein the deep sea buoyant material is prepared by any one of the methods for preparing a deep sea buoyant material shown above, and the deep sea buoyant material comprises the following components in parts by weight: 80-120 parts of epoxy resin, 15-25 parts of epoxy active diluent, 20-40 parts of curing agent and 1-5 parts of modified graphene, wherein the density of the deep sea buoyancy material is 0.50-0.56 g/cm3The hydrostatic pressure strength is 115-140 MPa, and the water absorption rate is less than or equal to 2%.
Compared with the prior art, the deep sea buoyancy material and the preparation method thereof provided by the invention have the following advantages:
according to the deep sea buoyancy material and the preparation method thereof provided by the invention, a modification process is designed aiming at graphene with low bulk density and high strength, so that the uniform dispersion performance of the graphene in an epoxy resin system is improved, the deep sea buoyancy material is prepared by taking the modified graphene, epoxy resin and a curing agent as raw materials through an optimized preparation process, and the obtained deep sea buoyancy material has the material properties of low density, high hydrostatic pressure resistance and low water absorption rate, and can be applied to the preparation of deep sea instruments and equipment, so that the use environment of the deep sea instruments and equipment can be greatly expanded. The invention can solve the technical problems of large density and low hydrostatic pressure resistance of the deep sea buoyancy material, and achieves the technical effects of reducing the material density of the deep sea buoyancy material, improving the hydrostatic pressure resistance and reducing the water absorption rate.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the invention and together with the description, serve to explain the principles of the invention.
FIG. 1 is a method flow diagram illustrating a method of making a deep sea buoyant according to an exemplary embodiment.
Fig. 2 is a schematic diagram illustrating a preparation of a modified graphene according to an exemplary embodiment.
Detailed Description
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
According to the invention, the deep sea buoyancy material is prepared by modifying graphene and then combining the modified graphene with epoxy resin and a curing agent. The prepared deep sea buoyancy material has the advantages of low density, high hydrostatic pressure resistance, low water absorption and the like, and is realized by the following technical scheme:
fig. 1 is a flow chart illustrating a method of manufacturing a deep sea buoyant material according to an exemplary embodiment, the method comprising, as shown in fig. 1:
step 101: and adding the pretreated epoxy resin into a stirring barrel of a vacuum defoaming stirrer, heating the temperature of the stirring barrel to 80-90 ℃, adding a curing agent into the stirring barrel, and uniformly stirring.
In one possible implementation, the epoxy resin pretreatment method includes:
heating epoxy resin to 85-95 ℃, adding an epoxy active diluent when the epoxy resin is in a complete molten state, uniformly stirring at 85-95 ℃ for 10-20 min, and cooling to 55-65 ℃ to prepare the pretreated epoxy resin, wherein the mass part ratio of the epoxy resin to the epoxy active diluent is 100: 15-25.
Wherein, the epoxy resin contains three or four epoxy groups, and the epoxy reactive diluent contains two epoxy groups. For example, the epoxy resin may be at least one of resorcinol formaldehyde tetraglycidyl ether epoxy resin, 1,2, 2-tetra (p-hydroxyphenyl) ethane tetraglycidyl ether epoxy resin, triphenol methane triglycidyl ether epoxy resin, and phloroglucinol triglycidyl ether epoxy resin.
The curing agent is an aromatic amine curing agent. For example, the curing agent may be at least one of m-xylylenediamine, diaminodiphenylmethane, and m-phenylenediamine.
Step 102: adding the modified graphene into the stirring barrel, adjusting the vacuum degree of the stirring barrel to be-0.08 to-0.10 atm, and continuously and uniformly stirring to obtain a mixture.
The preparation method of the modified graphene comprises the following steps:
(1) adding graphene into absolute ethyl alcohol, and performing ultrasonic dispersion for 30-90 min to prepare a graphene solution, wherein the mass part ratio of graphene to absolute ethyl alcohol in the graphene solution is 1-5: 200-400.
Wherein the density of the graphene is 0.01-0.10 g/cm3。
(2) Mixing absolute ethyl alcohol and deionized water to form a mixed solution, adding acetic acid into the mixed solution, adjusting the pH value of the mixed solution to 3.5-4.5, then slowly dropwise adding a silane coupling agent into the mixed solution, stirring and dispersing the mixed solution at a high speed for 30-60 min to prepare a silane coupling agent solution, wherein the mass part ratio of the absolute ethyl alcohol to the deionized water to the silane coupling agent in the silane coupling agent solution is 100-200: 20-60: 0.5-1.0.
Wherein the silane coupling agent is at least one of gamma-aminopropyltriethoxysilane (KH-550) or gamma-glycidoxypropyltrimethoxysilane (KH-560).
(3) Slowly adding the silane coupling agent solution into the graphene solution to form a reaction solution, controlling the reaction solution to react for 4-8 hours at a reaction temperature of 70-90 ℃, and performing suction filtration and drying on the reaction solution to prepare the modified graphene.
The traditional graphene has the characteristics of low bulk density and high strength, and the density of the deep sea buoyancy material can be reduced while the hydrostatic pressure resistance of the deep sea buoyancy material is ensured. However, the traditional graphene has the material characteristic of easy agglomeration, and is difficult to uniformly disperse in an epoxy resin system, so that the traditional graphene cannot be applied to the preparation of deep sea buoyancy materials. According to the invention, graphene with low bulk density and high strength is modified, so that the uniform dispersion performance of the modified graphene in an epoxy resin system is improved, and the application of the modified graphene in a deep sea buoyancy material is possible.
In order to better illustrate the graphene modification process of the embodiment of the present invention, a schematic diagram of the preparation of modified graphene is specifically shown, as shown in fig. 2.
Step 103: transferring the mixture from the stirring barrel to a mold, heating the mold to 120-140 ℃, preserving heat for 5-10 hours, then completing the curing and molding of the mixture, cooling and demolding the cured and molded mixture to prepare the deep sea buoyancy material, wherein the density of the deep sea buoyancy material is 0.50-0.56 g/cm3The hydrostatic pressure strength is 115-140 MPa, and the water absorption rate is less than or equal to 2%.
In the invention, the working pressure of a vulcanizing machine used for carrying out the curing and forming process on the mixture in the mold is 10-15 MPa.
The mass part ratio of the pretreated epoxy resin, the curing agent and the modified graphene is 100: 20-40: 1-5.
In conclusion, according to the deep sea buoyancy material and the preparation method thereof provided by the invention, a modification process is designed for graphene with low bulk density and high strength, so that the uniform dispersion performance of graphene in an epoxy resin system is improved, the deep sea buoyancy material is prepared by taking the modified graphene, epoxy resin and a curing agent as raw materials through an optimized preparation process, and the obtained deep sea buoyancy material has the material properties of low density, high hydrostatic pressure resistance and low water absorption rate. The invention can solve the technical problems of large density and low hydrostatic pressure resistance of the deep sea buoyancy material, and achieves the technical effects of reducing the material density of the deep sea buoyancy material, improving the hydrostatic pressure resistance and reducing the water absorption rate.
In order to better illustrate the beneficial effects of the deep sea buoyant material and the preparation method thereof provided by the invention, the following embodiments 1 to 3 are shown for illustration:
example 1
(1) Preparing modified graphene:
calculated by weight portion, the density is 0.04 g/cm3Adding 5 parts of graphene into 300 parts of absolute ethyl alcohol, and performing ultrasonic dispersion for 60min to prepare a graphene solution; mixing 200 parts of absolute ethyl alcohol and 40 parts of deionized water to form a mixed solution, adding acetic acid into the mixed solution, adjusting the pH value of the mixed solution to 3.5-4.5, then slowly dropwise adding 0.5 part of silane coupling agent into the mixed solution, and stirring and dispersing the mixed solution at a high speed for 60min to prepare a silane coupling agent solution; and slowly adding the silane coupling agent solution into the graphene solution to form a reaction solution, controlling the reaction solution to react for 6 hours at a reaction temperature of 80 ℃, and performing suction filtration and drying on the reaction solution to prepare the modified graphene.
(2) Pretreatment of epoxy resin:
according to the mass parts, heating 15 parts of resorcinol formaldehyde tetraglycidyl ether epoxy resin and 70 parts of 1,1,2, 2-tetra (p-hydroxyphenyl) ethane tetraglycidyl ether epoxy resin to 90 ℃, adding 15 parts of ethylene glycol diglycidyl ether when each epoxy resin is in a completely molten state, uniformly stirring at 90 ℃ for 10 min, and cooling to 60 ℃ to prepare the pretreated epoxy resin.
(3) Preparing the deep sea buoyancy material:
adding 100 parts of the pretreated epoxy resin into a stirring barrel of a vacuum defoaming stirrer, heating the temperature of the stirring barrel to 80 ℃, adding 20 parts of m-phenylenediamine into the stirring barrel, and uniformly stirring by using a high-shear stirrer; adding 5 parts of modified graphene into the stirring barrel, adjusting the vacuum degree of the stirring barrel to be minus 0.08 to minus 0.10atm, and continuously and uniformly stirring to obtain a mixture; and transferring the mixture from the stirring barrel to a mold, carrying out curing molding by using a vulcanizing machine, then heating the mold to 120 ℃, carrying out heat preservation for 8 hours, then finishing the curing molding of the mixture, and then cooling and demolding the cured and molded mixture to prepare the deep sea buoyancy material.
Example 2
(1) Preparing modified graphene:
calculated by weight portion, the density is 0.03 g/cm3Adding 4 parts of graphene into 300 parts of absolute ethyl alcohol, and performing ultrasonic dispersion for 90min to prepare a graphene solution; mixing 200 parts of absolute ethyl alcohol and 40 parts of deionized water to form a mixed solution, adding acetic acid into the mixed solution, adjusting the pH value of the mixed solution to 3.5-4.5, then slowly dropwise adding 0.8 part of silane coupling agent into the mixed solution, and stirring and dispersing the mixed solution at a high speed for 60min to prepare a silane coupling agent solution; and slowly adding the silane coupling agent solution into the graphene solution to form a reaction solution, controlling the reaction solution to react for 7 hours at a reaction temperature of 80 ℃, and performing suction filtration and drying on the reaction solution to prepare the modified graphene.
(2) Pretreatment of epoxy resin:
heating 15 parts of resorcinol formaldehyde tetraglycidyl ether epoxy resin and 70 parts of triphenol methane triglycidyl ether epoxy resin to 90 ℃, adding 10 parts of ethylene glycol diglycidyl ether and 5 parts of diglycidyl ether when each epoxy resin is in a completely molten state, uniformly stirring at 90 ℃ for 15min, and cooling to 60 ℃ to prepare the pretreated epoxy resin.
(3) Preparing the deep sea buoyancy material:
adding 100 parts of pretreated epoxy resin into a stirring barrel of a vacuum defoaming stirrer, heating the temperature of the stirring barrel to 90 ℃, adding 10 parts of m-phenylenediamine and 15 parts of diaminodiphenylmethane into the stirring barrel, and uniformly stirring by using a high-shear stirrer; adding 4 parts of modified graphene into the stirring barrel, adjusting the vacuum degree of the stirring barrel to be minus 0.08 to minus 0.10atm, and continuously and uniformly stirring to obtain a mixture; and transferring the mixture from the stirring barrel to a mold, carrying out curing molding by using a vulcanizing machine, then heating the mold to 130 ℃, carrying out heat preservation for 8 hours, then finishing the curing molding of the mixture, and then cooling and demolding the cured and molded mixture to prepare the deep sea buoyancy material.
Example 3
(1) Preparing modified graphene:
calculated by weight portion, the density is 0.02 g/cm3Adding 3 parts of graphene into 400 parts of absolute ethyl alcohol, and performing ultrasonic dispersion for 90min to prepare a graphene solution; mixing 200 parts of absolute ethyl alcohol and 60 parts of deionized water to form a mixed solution, adding acetic acid into the mixed solution, adjusting the pH value of the mixed solution to 3.5-4.5, then slowly dropwise adding 1.0 part of silane coupling agent into the mixed solution, and stirring and dispersing the mixed solution at a high speed for 60min to prepare a silane coupling agent solution; and slowly adding the silane coupling agent solution into the graphene solution to form a reaction solution, controlling the reaction solution to react for 8 hours at a reaction temperature of 80 ℃, and performing suction filtration and drying on the reaction solution to prepare the modified graphene.
(2) Pretreatment of epoxy resin:
according to the mass portion, 30 portions of 1,1,2, 2-tetra (p-hydroxyphenyl) ethane tetraglycidyl ether epoxy resin and 50 portions of phloroglucinol triglycidyl ether epoxy resin are heated to 90 ℃, 10 portions of ethylene glycol diglycidyl ether and 10 portions of diglycidyl ether are added when each epoxy resin is in a complete melting state, the mixture is stirred uniformly at the temperature of 90 ℃ for 20min, and then the temperature is reduced to 60 ℃, so that the pretreated epoxy resin is prepared.
(3) Preparing the deep sea buoyancy material:
adding 100 parts of the pretreated epoxy resin into a stirring barrel of a vacuum defoaming stirrer, heating the stirring barrel to 80 ℃, adding 10 parts of m-phenylenediamine and 15 parts of m-xylylenediamine into the stirring barrel, and uniformly stirring by using a high-shear stirrer; adding 3 parts of modified graphene into the stirring barrel, adjusting the vacuum degree of the stirring barrel to be minus 0.08 to minus 0.10atm, and continuously and uniformly stirring to obtain a mixture; and transferring the mixture from the stirring barrel to a mold, carrying out curing molding by using a vulcanizing machine, heating the mold to 140 ℃, preserving heat for 10 hours, then finishing the curing molding of the mixture, and then cooling and demolding the cured and molded mixture to prepare the deep sea buoyancy material.
Mechanical detection is carried out on the deep sea buoyancy material prepared in the embodiment 1-3, and the obtained performance data are shown in a table I:
density of material Hydrostatic strength Water absorption rate
Example 1 0.56 g/cm3 140 MPa ≤2%
Example 2 0.53 g/cm3 125 MP ≤2%
Example 3 0.50 g/cm3 115 MPa ≤2%
Watch 1
In the table I, the water absorption rate is measured under the test environment of 115 MPa hydrostatic pressure for 24 h for each deep sea buoyancy material.
As can be seen from the table I, the deep sea buoyant material prepared in example 1 has a density of 0.56g/cm3The hydrostatic pressure resistance is 140MPa, and the water absorption is less than or equal to 2 percent; the deep sea buoyant material prepared in example 2 has a density of 0.53 g/cm3The hydrostatic pressure strength is 125 MPa, and the water absorption rate is less than or equal to 2 percent; example 3 the density of the deep sea graphene buoyancy material prepared in example 3 is 0.50 g/cm3The hydrostatic pressure strength is 115 MPa, and the water absorption is less than or equal to 2 percent.
Obviously, the hydrostatic strength of the deep sea buoyancy material prepared by the various examples is higher than 115 MPa, and the density of the material is far lower than 0.70 g/cm3Therefore, the material performance of the deep sea buoyancy material provided by the invention is superior to that of the traditional solid deep sea buoyancy material.
The results of various analysis tests show that: according to the deep sea buoyancy material prepared by the preparation method provided by the invention, the traditional hollow glass microspheres are replaced by the low-density and high-strength modified graphene, so that the density of the deep sea buoyancy material is greatly reduced, the hydrostatic pressure resistance is enhanced, the low water absorption rate is kept, the working performance of deep sea equipment and instruments can be greatly improved, and the use environment of the deep sea equipment and instruments is widened.
In conclusion, according to the deep sea buoyancy material and the preparation method thereof provided by the invention, a modification process is designed for graphene with low bulk density and high strength, so that the uniform dispersion performance of graphene in an epoxy resin system is improved, the deep sea buoyancy material is prepared by taking the modified graphene, epoxy resin and a curing agent as raw materials through an optimized preparation process, and the obtained deep sea buoyancy material has the material properties of low density, high hydrostatic pressure resistance and low water absorption rate. The invention can solve the technical problems of large density and low hydrostatic pressure resistance of the deep sea buoyancy material, and achieves the technical effects of reducing the material density of the deep sea buoyancy material, improving the hydrostatic pressure resistance and reducing the water absorption rate.
In addition, the preparation process of the deep sea buoyancy material provided by the invention is simple and practical, and is suitable for large-scale production of a production line.
While the invention has been described in detail in the foregoing by way of general description, and specific embodiments and experiments, it will be apparent to those skilled in the art that modifications and improvements can be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Other embodiments of the invention will be apparent to those skilled in the art from consideration of the specification and practice of the invention disclosed herein. This invention is intended to cover any variations, uses, or adaptations of the invention following, in general, the principles of the invention and including such departures from the present disclosure as come within known or customary practice within the art to which the invention pertains. It will be understood that the invention is not limited to the precise arrangements described above and shown in the drawings and that various modifications and changes may be made without departing from the scope thereof.

Claims (7)

1. A preparation method of a deep sea buoyancy material is characterized by comprising the following steps: adding the pretreated epoxy resin into a stirring barrel of a vacuum defoaming stirrer, heating the temperature of the stirring barrel to 80-90 ℃, adding a curing agent into the stirring barrel, and uniformly stirring; adding the modified graphene into the stirring barrel, adjusting the vacuum degree of the stirring barrel to be minus 0.08 to minus 0.10atm, and continuously and uniformly stirring to obtain a mixture; transferring the mixture from the mixing drum to a mold, thenHeating the mold to 120-140 ℃, preserving heat for 5-10 hours, then completing curing molding of the mixture, cooling and demolding the cured and molded mixture, and preparing the deep sea buoyancy material, wherein the density of the deep sea buoyancy material is 0.50-0.56 g/cm3The hydrostatic pressure strength is 115-140 MPa, and the water absorption rate is less than or equal to 2%; the mass part ratio of the pretreated epoxy resin, the curing agent and the modified graphene is 100: 20-40: 1-5; the preparation method of the modified graphene comprises the following steps: adding graphene into absolute ethyl alcohol, and performing ultrasonic dispersion for 30-90 min to prepare a graphene solution, wherein the mass part ratio of graphene to absolute ethyl alcohol in the graphene solution is 1-5: 200-400, and the density of the graphene is 0.01-0.10 g/cm3(ii) a Mixing absolute ethyl alcohol and deionized water to form a mixed solution, adding acetic acid into the mixed solution, adjusting the pH value of the mixed solution to 3.5-4.5, then slowly dropwise adding a silane coupling agent into the mixed solution, and stirring and dispersing the mixed solution at a high speed for 30-60 min to prepare a silane coupling agent solution, wherein the mass part ratio of the absolute ethyl alcohol to the deionized water to the silane coupling agent in the silane coupling agent solution is 100-200: 20-60: 0.5-1.0; slowly adding the silane coupling agent solution into the graphene solution to form a reaction solution, controlling the reaction solution to react for 4-8 hours at a reaction temperature of 70-90 ℃, and performing suction filtration and drying on the reaction solution to prepare the modified graphene.
2. The method of claim 1, wherein the epoxy resin pretreatment comprises: heating epoxy resin to 85-95 ℃, adding an epoxy active diluent when the epoxy resin is in a complete molten state, uniformly stirring at 85-95 ℃ for 10-20 min, and cooling to 55-65 ℃ to prepare the pretreated epoxy resin, wherein the mass part ratio of the epoxy resin to the epoxy active diluent is 100: 15-25.
3. The method of claim 2, wherein the epoxy resin contains three or four epoxy groups and the epoxy reactive diluent contains two epoxy groups.
4. The method of claim 1, wherein the curing agent is an aromatic amine curing agent.
5. The method of claim 1, wherein the silane coupling agent is at least one of gamma-aminopropyltriethoxysilane or gamma-glycidoxypropyltrimethoxysilane.
6. The method according to claim 1, wherein the working pressure of a vulcanizer used in the curing step is 10 to 15 MPa.
7. The deep sea buoyancy material is characterized by being prepared by the preparation method of any one of the deep sea buoyancy materials in claims 1-6, and comprising the following components in parts by weight: 80-120 parts of epoxy resin, 15-25 parts of epoxy active diluent, 20-40 parts of curing agent and 1-5 parts of modified graphene, wherein the density of the deep sea buoyancy material is 0.50-0.56 g/cm3And the hydrostatic pressure strength is 115-140 MPa.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102732037A (en) * 2011-04-08 2012-10-17 中国科学院金属研究所 Graphene foam/polymer high-conductivity composite material preparation method and application thereof
CN103483773A (en) * 2013-09-24 2014-01-01 滕州市华海新型保温材料有限公司 Deep-sea solid buoyancy material and manufacture method thereof
CN105566857A (en) * 2016-03-10 2016-05-11 四川大学 Light-weight epoxy resin composite material and preparation method thereof
CN107474486A (en) * 2017-09-13 2017-12-15 北京理工大学 A kind of solid buoyancy material and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102732037A (en) * 2011-04-08 2012-10-17 中国科学院金属研究所 Graphene foam/polymer high-conductivity composite material preparation method and application thereof
CN103483773A (en) * 2013-09-24 2014-01-01 滕州市华海新型保温材料有限公司 Deep-sea solid buoyancy material and manufacture method thereof
CN105566857A (en) * 2016-03-10 2016-05-11 四川大学 Light-weight epoxy resin composite material and preparation method thereof
CN107474486A (en) * 2017-09-13 2017-12-15 北京理工大学 A kind of solid buoyancy material and preparation method thereof

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