CN112409758A - Solid buoyancy material and preparation method and application thereof - Google Patents
Solid buoyancy material and preparation method and application thereof Download PDFInfo
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- CN112409758A CN112409758A CN202011222301.0A CN202011222301A CN112409758A CN 112409758 A CN112409758 A CN 112409758A CN 202011222301 A CN202011222301 A CN 202011222301A CN 112409758 A CN112409758 A CN 112409758A
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- 239000000463 material Substances 0.000 title claims abstract description 98
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- 239000003795 chemical substances by application Substances 0.000 claims abstract description 66
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- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 claims description 12
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 claims description 10
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 claims description 10
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- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 claims description 10
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 10
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 claims description 9
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- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 8
- KUAUJXBLDYVELT-UHFFFAOYSA-N 2-[[2,2-dimethyl-3-(oxiran-2-ylmethoxy)propoxy]methyl]oxirane Chemical compound C1OC1COCC(C)(C)COCC1CO1 KUAUJXBLDYVELT-UHFFFAOYSA-N 0.000 claims description 8
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 claims description 8
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 8
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 8
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 8
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 claims description 8
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 8
- ZETYUTMSJWMKNQ-UHFFFAOYSA-N n,n',n'-trimethylhexane-1,6-diamine Chemical compound CNCCCCCCN(C)C ZETYUTMSJWMKNQ-UHFFFAOYSA-N 0.000 claims description 8
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- FMGBDYLOANULLW-UHFFFAOYSA-N 3-isocyanatopropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCN=C=O FMGBDYLOANULLW-UHFFFAOYSA-N 0.000 description 1
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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
-
- 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
- C08K3/041—Carbon nanotubes
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/28—Glass
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/004—Additives being defined by their length
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Epoxy Resins (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a solid buoyancy material and a preparation method and application thereof, wherein the solid buoyancy material comprises the following raw materials: modified epoxy resin, active diluent, curing agent, toughening curing agent, hollow microsphere and coupling agent; the modified epoxy resin comprises one or more of dimer acid modified epoxy resin, polyurethane modified epoxy resin, phenolic aldehyde modified epoxy resin, organic silicon modified epoxy resin, hyperbranched polymer modified epoxy resin and polybutyl acrylate modified epoxy resin. The solid buoyancy material provided by the invention adopts modified epoxy resin such as dimer acid modified epoxy resin, and the strength and toughness of the resin can be improved by using the modified epoxy resin, so that the strength and toughness of the solid buoyancy material are improved.
Description
Technical Field
The invention relates to the field of special functional materials, in particular to a solid buoyancy material and a preparation method and application thereof.
Background
With the increasing exhaustion of land resources, countries around the world are adjusting their own marine policies, and increasing the development and utilization of marine resources. At present, the maximum exploitation depth of an offshore platform in the field of offshore oil and gas resources breaks through 3000m, and various technologies in deep sea are continuously followed and perfected. Exploration and development of deep sea resources are mainly dependent on research and manufacture of underwater mining operation equipment. The buoyancy material can provide net buoyancy for the deep sea underwater operation device, plays a role in buoyancy compensation underwater, and is an important configuration material for a deep sea development device.
At present, the buoyancy material is mainly prepared from epoxy resin or phenolic resin systems in domestic research, the strength and the impact resistance of the buoyancy material are improved only by physically adding reinforcing materials, and the reinforcing effect has limitation. The reinforcing material needs to be subjected to surface treatment before use, the preparation process is complex, and the efficiency is low. In addition, the buoyancy material still can receive the collision and appear phenomena such as breakage, fracture in actual installation, use. This is because the resin itself has high strength and poor toughness, and the impact resistance can be improved only by physically adding a reinforcing material, and this problem cannot be essentially solved.
Based on the shortcomings of current buoyancy materials, there is a need to improve this.
Disclosure of Invention
In view of the above, the invention provides a solid buoyancy material, and a preparation method and an application thereof, so as to solve the defects in the prior art.
In a first aspect, the invention provides a solid buoyancy material, which comprises the following raw materials in parts by weight:
20-50 parts of modified epoxy resin, 1-10 parts of reactive diluent, 20-45 parts of curing agent, 1-10 parts of toughening curing agent, 20-150 parts of hollow microspheres and 1-5 parts of coupling agent;
the modified epoxy resin comprises one or more of dimer acid modified epoxy resin, polyurethane modified epoxy resin, phenolic aldehyde modified epoxy resin, organic silicon modified epoxy resin, hyperbranched polymer modified epoxy resin and polybutyl acrylate modified epoxy resin.
Optionally, the solid buoyancy material further comprises 0.5-2 parts by weight of a modified carbon nanotube, and the modified carbon nanotube is an amino-terminated carbon nanotube.
Optionally, in the solid buoyancy material, the amino-terminated carbon nanotubes include single-wall amino-terminated carbon nanotubes and/or multi-wall amino-terminated carbon nanotubes, and the amino-terminated carbon nanotubes have a diameter of 1-15 nm and a length of 20-50 μm.
Optionally, in the solid buoyancy material, the reactive diluent includes one or more of butyl glycidyl ether, benzyl glycidyl ether, ethylene glycol diglycidyl ether, alkylene glycidyl ether, and neopentyl glycol diglycidyl ether; the curing agent comprises one or more of methyl tetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride, isophorone diamine, m-phenylenediamine, diaminodiphenyl sulfone, trimethyl hexamethylene diamine and diethyl triamine; the toughening curing agent comprises one or more of maleic anhydride, phthalic anhydride, pyromellitic anhydride and benzophenonetetracarboxylic dianhydride; the coupling agent comprises one or more of vinyl trimethoxy silane, vinyl triethoxy silane, gamma-glycidoxypropyl trimethoxy silane, beta- (3,4 epoxy cyclohexyl) ethyl trimethoxy silane, gamma-isocyanate propyltrimethoxy silane and gamma-isocyanate propyltriethoxy silane.
Optionally, the hollow glass beads are hollow glass beads, and the density of the hollow glass beads is 0.1-0.6g/cm3The compressive strength is 1-70 MPa.
In a second aspect, the invention further provides a preparation method of the solid buoyancy material, which comprises the following steps:
adding the hollow microspheres into a kneading machine, and mixing for later use;
mixing the modified epoxy resin, the reactive diluent, the coupling agent, optionally the modified carbon
Dispersing the nanotube in a dispersing machine, then transferring to a sand mill for grinding, adding the curing agent and the toughening curing agent, and transferring to a dispersing machine for dispersing to obtain a mixture;
and adding the mixture into the kneader, kneading, discharging and curing to obtain the solid buoyancy material.
Optionally, the preparation method of the solid buoyancy material includes placing the modified epoxy resin, the reactive diluent, the coupling agent, and optionally the modified carbon nanotube in a dispersion machine at 400-600 r/min, stirring and dispersing for 10-30 min, then transferring to a sand mill at 2000-2500 r/min, grinding for 30-40 min, adding the curing agent and the toughening curing agent, transferring to a dispersion machine at 400-600 r/min, and stirring and dispersing for 10-30 min to obtain a mixture.
Optionally, in the preparation method of the solid buoyancy material, the mixture is added into the kneader and kneaded for 50-70min at a speed of 20-30r/min under a vacuum of-0.1 MPa, and the mixture is discharged and cured for 4h at a temperature of 80-150 ℃ to obtain the solid buoyancy material.
Optionally, in the preparation method of the solid buoyancy material, the hollow microspheres are added into the kneader at a speed of 15-25 r/min and mixed for 15-30 min.
In a third aspect, the invention further provides an application of the solid buoyancy material or the solid buoyancy material prepared by the preparation method in an underwater 0-5000 m operation environment.
Compared with the prior art, the solid buoyancy material provided by the invention has the following beneficial effects:
(1) according to the solid buoyancy material, the dimer acid modified epoxy resin and other modified epoxy resins are adopted, and the modified epoxy resin is used for improving the compression strength by 15-30% and the bending strength by 10-30% compared with the common epoxy resin, so that the strength and the toughness of the solid buoyancy material are improved;
(2) the solid buoyancy material also comprises the modified carbon nano tubes, compared with the common carbon nano tube resin and filler, the bonding force at the interface is stronger, the compression strength is improved by 10-20%, and the bending strength is improved by 15-25%, so that the strength and the toughness of the material can be further improved;
(3) the solid buoyancy material has the advantages of high strength, high toughness, difficult damage and cracking in collision, high use stability, heat preservation, corrosion resistance and the like.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a process flow diagram of a method for preparing the solid buoyancy material of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
Example 1
The embodiment of the application provides a solid buoyancy material, which comprises the following raw materials in parts by weight:
20-50 parts of modified epoxy resin, 1-10 parts of reactive diluent, 20-45 parts of curing agent, 1-10 parts of toughening curing agent, 20-150 parts of hollow microspheres, 1-5 parts of coupling agent and 0.5-2 parts of modified carbon nano tubes, wherein the modified carbon nano tubes are amino-terminated carbon nano tubes;
wherein the modified epoxy resin comprises one or more of dimer acid modified epoxy resin, polyurethane modified epoxy resin, phenolic aldehyde modified epoxy resin, organic silicon modified epoxy resin, hyperbranched polymer modified epoxy resin and polybutyl acrylate modified epoxy resin; specifically, the dimer acid-modified epoxy resin may be complex high-tech materials EPD-171, EPD172L from Inc. or SQE-171, SQE-72X75 from Jinnan Shengquan group, Inc.; the polyurethane modified epoxy resin can be Kunshan south Asia epoxy resin NPER-133L or 102C-2, 102C-3 of Hengchuang insulation materials Co; the phenolic aldehyde modified epoxy resin can adopt Kunshan south Asia phenolic aldehyde epoxy resin NPPN-631 or Yueyangba tomb petrochemical epoxy resin CYDBN-240 and the like; as the silicone-modified epoxy resin, Japanese Beacon ES-1023, KR-2046, etc.; the hyperbranched polymer modified epoxy resin can adopt hyperbranched epoxy resin HyPerE102 and the like of Wuhan hyperbranched resin science and technology Limited; the polybutyl acrylate modified epoxy resin is prepared by directly mixing polybutyl acrylate into epoxy resin to form an interpenetrating network structure.
Specifically, in the embodiment of the application, 30 parts by weight of phenolic aldehyde modified epoxy resin NPPN-631 is adopted as the modified epoxy resin.
Specifically, the modified carbon nanotube in the embodiment of the application is a single-wall amino-terminated carbon nanotube with the weight of 0.5 part, wherein the diameter of the single-wall amino-terminated carbon nanotube is 1-15 nm, and the length of the single-wall amino-terminated carbon nanotube is 20-50 μm; the single-wall amino-terminated carbon nanotube can adopt XFS14 of Jiangsu Xiancheng nano material science and technology Limited or C805981 of Shanghai Meclin biochemistry Limited, and the like, and in the specific embodiment, the single-wall amino-terminated carbon nanotube is XFS14, the diameter is 1-2 nm, and the length is 5-30 mu m; the diameter of the carbon nano tube is set to be 1-15 nm, and the length is set to be 20-50 μm, so that the problems of uneven mixing, long grinding and dispersing treatment time and low efficiency caused by overlarge size of the carbon nano tube are avoided.
Specifically, the reactive diluent in the embodiment of the application comprises one or more of butyl glycidyl ether, benzyl glycidyl ether, ethylene glycol diglycidyl ether, alkylene glycidyl ether and neopentyl glycol diglycidyl ether; in the embodiment of the application, the benzyl glycidyl ether is used as the reactive diluent, and the weight part of the benzyl glycidyl ether is 1.5 parts.
Specifically, the curing agent in the embodiment of the present application includes one or more of methyl tetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride, isophorone diamine, m-phenylenediamine, diamino diphenyl sulfone, trimethyl hexamethylene diamine, and diethyl triamine; the curing agent used in the examples of this application was 20 parts by weight of methyl tetrahydrophthalic anhydride.
Specifically, the toughening curing agent in the embodiment of the application comprises one or more of maleic anhydride, phthalic anhydride, pyromellitic anhydride and benzophenonetetracarboxylic dianhydride; in the embodiment of the application, the toughening curing agent adopts 2 parts by weight of maleic anhydride.
Specifically, the coupling agent in the embodiment of the application comprises one or more of vinyltrimethoxysilane, vinyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, beta- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, gamma-isocyanate propyltrimethoxysilane and gamma-isocyanate propyltriethoxysilane; in the examples of the present application, 1 part by weight of gamma-glycidoxypropyltrimethoxysilane was used as a coupling agent.
Specifically, the hollow microspheres in the embodiment of the application are hollow glass microspheres, and the density of the hollow glass microspheres is 0.1-0.6g/cm3The compression strength is 1MPa-70 MPa; specifically, in the present embodiment, the hollow glass beads are used in an amount of 20 parts by weight, and have a compressive strength of 10.6MPa and a density of 0.38g/cm330 portions of hollow glass micro-beads, 8.2Mpa of compressive strength and 0.25g/cm of density3Hollow glass beads. The density of the solid buoyancy material can be adjusted by adjusting the density of the hollow glass beads, and the compression strength is limited, so that the buoyancy material can be ensured to keep stable performance when resisting seawater pressure.
According to the solid buoyancy material, modified epoxy resin such as dimer acid modified epoxy resin is adopted, and the strength and toughness of the resin can be improved by using the modified epoxy resin, so that the strength and toughness of the solid buoyancy material are improved; the solid buoyancy material also comprises modified carbon nano tubes, so that the strength and the toughness of the material can be further improved. The solid buoyancy material is mainly used in the fields of 0-5000 m ocean detectors, deep sea operation equipment, submarine oil exploitation, buoys, submarines and the like.
Based on the same inventive concept, the embodiment of the present application further provides a preparation method of the above solid buoyancy material, as shown in fig. 1, including the following steps:
s1, adding the hollow microspheres into a kneader, and mixing for later use;
s2, placing the modified epoxy resin, the reactive diluent, the coupling agent and the modified carbon nano tube in a dispersion machine for dispersion, then transferring the dispersion machine to a sand mill for grinding, adding the curing agent and the toughening curing agent, and then transferring the dispersion machine for dispersion to obtain a mixture;
and S3, adding the mixture into a kneader, kneading, discharging and solidifying to obtain the solid buoyancy material.
Specifically, in this embodiment, S1 includes: 20 portions of the components are mixed and the density is 0.38g/cm330 portions of hollow glass micro-beads and 0.25g/cm of density3And adding the hollow glass beads into a kneader, setting the rotating speed to be 20r/min, and mixing for 30min for later use.
Specifically, in this embodiment, S2 includes: respectively putting 30 parts by weight of phenolic aldehyde modified epoxy resin, 1.5 parts by weight of benzyl glycidyl ether, 1 part by weight of gamma-glycidyl ether oxypropyltrimethoxysilane and 0.5 part by weight of single-wall amino-terminated carbon nano tube into a dispersion tank, placing the dispersion tank under a high-speed dispersion machine, setting the rotating speed to be 500r/min, stirring for 20min, then transferring the dispersion tank under a basket type sand mill, setting the rotating speed to be 2000r/min, grinding for 30min, then sequentially adding 20 parts by weight of methyl tetrahydrophthalic anhydride and 2 parts by weight of maleic anhydride, then transferring the dispersion tank under the high-speed dispersion machine, setting the rotating speed to be 500r/min, and stirring for 20min to obtain a mixture;
specifically, in this embodiment, S3 includes: and adding the mixture obtained in the step S2 into a kneader, setting the rotating speed at 30r/min under vacuum-0.1 MPa, kneading for 55min, discharging, putting into a mold, compacting, curing for 4h at 150 ℃, cooling to room temperature, and removing the buoyancy material from the mold to obtain the solid buoyancy material.
Example 2
The embodiment of the application provides a solid buoyancy material, which comprises the following raw materials in parts by weight:
20-50 parts of modified epoxy resin, 1-10 parts of reactive diluent, 20-45 parts of curing agent, 1-10 parts of toughening curing agent, 20-150 parts of hollow microspheres, 1-5 parts of coupling agent and 0.5-2 parts of modified carbon nano tubes, wherein the modified carbon nano tubes are amino-terminated carbon nano tubes;
the modified epoxy resin comprises one or more of dimer acid modified epoxy resin, polyurethane modified epoxy resin, phenolic aldehyde modified epoxy resin, organic silicon modified epoxy resin, hyperbranched polymer modified epoxy resin and polybutyl acrylate modified epoxy resin.
Specifically, in the embodiment of the application, 30 parts by weight of phenolic aldehyde modified epoxy resin NPPN-631 is adopted as the modified epoxy resin.
Specifically, the modified carbon nanotube in the embodiment of the application is 1 part by weight of an XFS14 single-wall amino-terminated carbon nanotube of jiangsu xiaofeng nano material science and technology ltd, wherein the diameter of the amino-terminated carbon nanotube is 1-2 nm, and the length of the amino-terminated carbon nanotube is 5-30 μm.
Specifically, the reactive diluent in the embodiment of the application comprises one or more of butyl glycidyl ether, benzyl glycidyl ether, ethylene glycol diglycidyl ether, alkylene glycidyl ether and neopentyl glycol diglycidyl ether; in the embodiment of the application, the reactive diluent adopts 1 part by weight of benzyl glycidyl ether.
Specifically, the curing agent in the embodiment of the present application includes one or more of methyl tetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride, isophorone diamine, m-phenylenediamine, diamino diphenyl sulfone, trimethyl hexamethylene diamine, and diethyl triamine; the curing agent used in the examples of this application was 20 parts by weight of methyl tetrahydrophthalic anhydride.
Specifically, the toughening curing agent in the embodiment of the application comprises one or more of maleic anhydride, phthalic anhydride, pyromellitic anhydride and benzophenonetetracarboxylic dianhydride; in the embodiment of the application, the toughening curing agent adopts 2 parts by weight of maleic anhydride.
Specifically, the coupling agent in the embodiment of the application comprises one or more of vinyltrimethoxysilane, vinyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, beta- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, gamma-isocyanate propyltrimethoxysilane and gamma-isocyanate propyltriethoxysilane; in the examples of the present application, 1 part by weight of gamma-glycidoxypropyltrimethoxysilane was used as a coupling agent.
Specifically, the hollow microspheres in the embodiment of the application are hollow glass microspheres, and the hollow glass microspheres are 30 parts by weight, 8.9MPa in compression strength and 0.32g/cm in density3Hollow glass beads.
Based on the same inventive concept, the embodiment of the present application further provides a preparation method of the above solid buoyancy material, as shown in fig. 1, including the following steps:
s1, adding the hollow microspheres into a kneader, and mixing for later use;
s2, placing the modified epoxy resin, the reactive diluent, the coupling agent and the modified carbon nano tube in a dispersion machine for dispersion, then transferring the dispersion machine to a sand mill for grinding, adding the curing agent and the toughening curing agent, and then transferring the dispersion machine for dispersion to obtain a mixture;
and S3, adding the mixture into a kneader, kneading, discharging and solidifying to obtain the solid buoyancy material.
Specifically, in this embodiment, S1 includes: 30 portions of the components are mixed, and the density is 0.32g/cm3And adding the hollow glass beads into a kneader, setting the rotating speed to be 20r/min, and mixing for 30min for later use.
Specifically, in this embodiment, S2 includes: respectively putting 30 parts by weight of phenolic aldehyde modified epoxy resin, 1 part by weight of benzyl glycidyl ether, 1 part by weight of gamma-glycidyl ether oxypropyltrimethoxysilane and 1 part by weight of single-wall terminal amino carbon nano tube into a dispersion tank, placing the dispersion tank under a high-speed dispersion machine, setting the rotating speed to be 600r/min, stirring for 15min, then transferring the dispersion tank to a basket type sand mill, setting the rotating speed to be 2500r/min, grinding for 30min, then sequentially adding 20 parts by weight of methyl tetrahydrophthalic anhydride and 2 parts by weight of maleic anhydride, then transferring the dispersion tank to a high-speed dispersion machine, setting the rotating speed to be 600r/min, and stirring for 20min to obtain a mixture;
specifically, in this embodiment, S3 includes: and adding the mixture obtained in the step S2 into a kneader, kneading for 60min at a set rotating speed of 25r/min under vacuum-0.1 MPa, discharging, putting into a mold, compacting, curing for 4h at 150 ℃, cooling to room temperature, and removing the buoyancy material from the mold to obtain the solid buoyancy material.
Example 3
The embodiment of the application provides a solid buoyancy material, which comprises the following raw materials in parts by weight:
20-50 parts of modified epoxy resin, 1-10 parts of reactive diluent, 20-45 parts of curing agent, 1-10 parts of toughening curing agent, 20-150 parts of hollow microspheres, 1-5 parts of coupling agent and 0.5-2 parts of modified carbon nano tubes, wherein the modified carbon nano tubes are amino-terminated carbon nano tubes;
the modified epoxy resin comprises one or more of dimer acid modified epoxy resin, polyurethane modified epoxy resin, phenolic aldehyde modified epoxy resin, organic silicon modified epoxy resin, hyperbranched polymer modified epoxy resin and polybutyl acrylate modified epoxy resin.
Specifically, in the embodiment of the application, 40 parts by weight of polyurethane modified epoxy resin NPER-133L is used as the modified epoxy resin.
Specifically, the modified carbon nanotube in the embodiment of the present application is 2 parts by weight of a multi-wall-end amino carbon nanotube, the multi-wall-end amino carbon nanotube may be 100345, 100346, 100347 and the like of Jiangsu Xiancheng nanometer materials science and technology ltd, and the multi-wall-end amino carbon nanotube is 100345, has a diameter of 8 to 15nm and a length of 50 μm in the embodiment.
Specifically, the reactive diluent in the embodiment of the application comprises one or more of butyl glycidyl ether, benzyl glycidyl ether, ethylene glycol diglycidyl ether, alkylene glycidyl ether and neopentyl glycol diglycidyl ether; in the embodiment of the application, 3 parts by weight of benzyl glycidyl ether is adopted as the reactive diluent.
Specifically, the curing agent in the embodiment of the present application includes one or more of methyl tetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride, isophorone diamine, m-phenylenediamine, diamino diphenyl sulfone, trimethyl hexamethylene diamine, and diethyl triamine; in the examples of the present application, 20 parts by weight of methylhexahydrophthalic anhydride was used as the curing agent.
Specifically, the toughening curing agent in the embodiment of the application comprises one or more of maleic anhydride, phthalic anhydride, pyromellitic anhydride and benzophenonetetracarboxylic dianhydride; in the embodiment of the application, the toughening curing agent adopts benzophenonetetracarboxylic dianhydride with the weight part of 4 parts.
Specifically, the coupling agent in the embodiment of the application comprises one or more of vinyltrimethoxysilane, vinyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, beta- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, gamma-isocyanate propyltrimethoxysilane and gamma-isocyanate propyltriethoxysilane; in the examples of the present application, 1.5 parts by weight of gamma-isocyanatopropyltriethoxysilane was used as the coupling agent.
Specifically, the hollow microspheres in the embodiment of the application are hollow glass microspheres, and the hollow glass microspheres are 30 parts by weight, 21.3MPa in compression strength and 0.6g/cm in density325 portions of hollow glass micro-beads, 8.9MPa of compressive strength and 0.32g/cm of density3Hollow glass beads.
Based on the same inventive concept, the embodiment of the present application further provides a preparation method of the above solid buoyancy material, as shown in fig. 1, including the following steps:
s1, adding the hollow microspheres into a kneader, and mixing for later use;
s2, placing the modified epoxy resin, the reactive diluent, the coupling agent and the modified carbon nano tube in a dispersion machine for dispersion, then transferring the dispersion machine to a sand mill for grinding, adding the curing agent and the toughening curing agent, and then transferring the dispersion machine for dispersion to obtain a mixture;
and S3, adding the mixture into a kneader, kneading, discharging and solidifying to obtain the solid buoyancy material.
Specifically, in this embodiment, S1 includes: 30 portions of the components are mixed, and the density is 0.6g/cm325 parts of hollow glass microspheres and 0.32g/cm of density3And adding the hollow glass beads into a kneader, setting the rotating speed to be 20r/min, and mixing for 30min for later use.
Specifically, in this embodiment, S2 includes: respectively putting 40 parts by weight of polyurethane modified epoxy resin, 3 parts by weight of benzyl glycidyl ether, 1.5 parts by weight of gamma-isocyanate propyl triethoxysilane and 2 parts by weight of multi-wall terminal amino carbon nano tube into a dispersion tank, placing the dispersion tank under a high-speed dispersion machine, setting the rotating speed to be 400r/min, stirring for 15min, then transferring the dispersion tank under a basket type sand mill, setting the rotating speed to be 2000r/min, grinding for 40min, then sequentially adding 20 parts by weight of methylhexahydrophthalic anhydride and 4 parts by weight of benzophenonetetracarboxylic dianhydride, then transferring the dispersion tank under the high-speed dispersion machine, setting the rotating speed to be 400r/min, and stirring for 20min to obtain a mixture;
specifically, in this embodiment, S3 includes: and adding the mixture obtained in the step S2 into a kneader, kneading for 50min at a set rotating speed of 30r/min under vacuum-0.1 MPa, discharging, putting into a mold, compacting, curing for 4h at 120 ℃, cooling to room temperature, and removing the buoyancy material from the mold to obtain the solid buoyancy material.
Example 4
The embodiment of the application provides a solid buoyancy material, which comprises the following raw materials in parts by weight:
20-50 parts of modified epoxy resin, 1-10 parts of reactive diluent, 20-45 parts of curing agent, 1-10 parts of toughening curing agent, 20-150 parts of hollow microspheres, 1-5 parts of coupling agent and 0.5-2 parts of modified carbon nano tubes, wherein the modified carbon nano tubes are amino-terminated carbon nano tubes;
the modified epoxy resin comprises one or more of dimer acid modified epoxy resin, polyurethane modified epoxy resin, phenolic aldehyde modified epoxy resin, organic silicon modified epoxy resin, hyperbranched polymer modified epoxy resin and polybutyl acrylate modified epoxy resin.
Specifically, in the embodiment of the application, 40 parts by weight of polyurethane modified epoxy resin NPER-133L is used as the modified epoxy resin.
Specifically, the modified carbon nanotube in the embodiment of the application is 1.5 parts by weight of an XFS14 single-walled amino-terminated carbon nanotube of jiangsu xiaofeng nano material science and technology ltd, wherein the diameter of the amino-terminated carbon nanotube is 1-2 nm, and the length of the amino-terminated carbon nanotube is 5-30 μm.
Specifically, the reactive diluent in the embodiment of the application comprises one or more of butyl glycidyl ether, benzyl glycidyl ether, ethylene glycol diglycidyl ether, alkylene glycidyl ether and neopentyl glycol diglycidyl ether; in the examples of the present application, 3 parts by weight of butyl glycidyl ether was used as the reactive diluent.
Specifically, the curing agent in the embodiment of the present application includes one or more of methyl tetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride, isophorone diamine, m-phenylenediamine, diamino diphenyl sulfone, trimethyl hexamethylene diamine, and diethyl triamine; in the examples of the present application, 18 parts by weight of methyl tetrahydrophthalic anhydride was used as the curing agent.
Specifically, the toughening curing agent in the embodiment of the application comprises one or more of maleic anhydride, phthalic anhydride, pyromellitic anhydride and benzophenonetetracarboxylic dianhydride; in the embodiment of the application, the toughening curing agent adopts benzophenonetetracarboxylic dianhydride with the weight part of 4 parts.
Specifically, the coupling agent in the embodiment of the application comprises one or more of vinyltrimethoxysilane, vinyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, beta- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, gamma-isocyanate propyltrimethoxysilane and gamma-isocyanate propyltriethoxysilane; in the examples of the present application, 1.5 parts by weight of gamma-isocyanatopropyltrimethoxysilane was used as the coupling agent.
Specifically, the hollow microspheres in the embodiment of the application are hollow glass microspheres, and the hollow glass microspheres are 20 parts by weight, 7.5Mpa in compression strength and 0.23g/cm in density3Hollow glass micro-beads, 15 weight portions, 8.5Mpa of compressive strength and 0.28g/cm of density3Hollow glass beads.
Based on the same inventive concept, the embodiment of the present application further provides a preparation method of the above solid buoyancy material, as shown in fig. 1, including the following steps:
s1, adding the hollow microspheres into a kneader, and mixing for later use;
s2, placing the modified epoxy resin, the reactive diluent, the coupling agent and the modified carbon nano tube in a dispersion machine for dispersion, then transferring the dispersion machine to a sand mill for grinding, adding the curing agent and the toughening curing agent, and then transferring the dispersion machine for dispersion to obtain a mixture;
and S3, adding the mixture into a kneader, kneading, discharging and solidifying to obtain the solid buoyancy material.
Specifically, in this embodiment, S1 includes: 20 portions of the components are mixed and the density is 0.23g/cm3The hollow glass micro-beads comprise 15 parts by weight of hollow glass micro-beads and have the density of 0.28g/cm3And adding the hollow glass beads into a kneader, setting the rotating speed to be 25r/min, and mixing for 30min for later use.
Specifically, in this embodiment, S2 includes: respectively putting 40 parts by weight of polyurethane modified epoxy resin, 3 parts by weight of butyl glycidyl ether, 1.5 parts by weight of gamma-isocyanate propyl trimethoxy silane and 1.5 parts by weight of single-wall amino carbon nanotube into a dispersion tank, placing the dispersion tank under a high-speed dispersion machine, setting the rotating speed to be 600r/min, stirring for 10min, then transferring the dispersion tank under a basket type sand mill, setting the rotating speed to be 2100r/min, grinding for 35min, then sequentially adding 18 parts by weight of methyl tetrahydrophthalic anhydride and 4 parts by weight of benzophenonetetracarboxylic dianhydride, then transferring the dispersion tank under the high-speed dispersion machine, setting the rotating speed to be 600r/min, and stirring for 10min to obtain a mixture;
specifically, in this embodiment, S3 includes: and adding the mixture obtained in the step S2 into a kneader, setting the rotating speed at 30r/min under vacuum-0.1 MPa, kneading for 65min, discharging, putting into a mold, compacting, curing at 120 ℃ for 4h, cooling to room temperature, and removing the buoyancy material from the mold to obtain the solid buoyancy material.
Example 5
The embodiment of the application provides a solid buoyancy material, which comprises the following raw materials in parts by weight:
20-50 parts of modified epoxy resin, 1-10 parts of reactive diluent, 20-45 parts of curing agent, 1-10 parts of toughening curing agent, 20-150 parts of hollow microspheres, 1-5 parts of coupling agent and 0.5-2 parts of modified carbon nano tubes, wherein the modified carbon nano tubes are amino-terminated carbon nano tubes;
the modified epoxy resin comprises one or more of dimer acid modified epoxy resin, polyurethane modified epoxy resin, phenolic aldehyde modified epoxy resin, organic silicon modified epoxy resin, hyperbranched polymer modified epoxy resin and polybutyl acrylate modified epoxy resin.
Specifically, in the embodiment of the application, 35 parts by weight of hyperbranched polymer modified epoxy resin HyPerE102 is adopted as the modified epoxy resin.
Specifically, in the embodiment of the present application, the modified carbon nanotube is 100345 multiwall terminal amino carbon nanotube of Jiangsu Xiancheng nanomaterial science and technology Limited, in which the weight part of the modified carbon nanotube is 1.5, and the diameter of the terminal amino carbon nanotube is 8-15 nm, and the length of the terminal amino carbon nanotube is 50 μm.
Specifically, the reactive diluent in the embodiment of the application comprises one or more of butyl glycidyl ether, benzyl glycidyl ether, ethylene glycol diglycidyl ether, alkylene glycidyl ether and neopentyl glycol diglycidyl ether; in the embodiment of the application, the reactive diluent adopts 3 parts by weight of ethylene glycol diglycidyl ether.
Specifically, the curing agent in the embodiment of the present application includes one or more of methyl tetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride, isophorone diamine, m-phenylenediamine, diamino diphenyl sulfone, trimethyl hexamethylene diamine, and diethyl triamine; in the examples of the present application, 20 parts by weight of isophorone diamine was used as the curing agent.
Specifically, the toughening curing agent in the embodiment of the application comprises one or more of maleic anhydride, phthalic anhydride, pyromellitic anhydride and benzophenonetetracarboxylic dianhydride; in the embodiment of the application, the toughening curing agent adopts 3 parts by weight of phthalic anhydride.
Specifically, the coupling agent in the embodiment of the application comprises one or more of vinyltrimethoxysilane, vinyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, beta- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, gamma-isocyanate propyltrimethoxysilane and gamma-isocyanate propyltriethoxysilane; in the examples of the present application, 1 part by weight of beta- (3,4 epoxycyclohexyl) ethyltrimethoxysilane was used as a coupling agent.
Specifically, the hollow microspheres in the embodiment of the application are hollow glass microspheres, and the hollow glass microspheres are 20 parts by weight, 13.2MPa in compression strength and 0.42g/cm in density3Hollow glass micro-beads, 15 weight portions, 8.9MPa of compressive strength and 0.32g/cm of density3Hollow glass beads.
Based on the same inventive concept, the embodiment of the present application further provides a preparation method of the above solid buoyancy material, as shown in fig. 1, including the following steps:
s1, adding the hollow microspheres into a kneader, and mixing for later use;
s2, placing the modified epoxy resin, the reactive diluent, the coupling agent and the modified carbon nano tube in a dispersion machine for dispersion, then transferring the dispersion machine to a sand mill for grinding, adding the curing agent and the toughening curing agent, and then transferring the dispersion machine for dispersion to obtain a mixture;
and S3, adding the mixture into a kneader, kneading, discharging and solidifying to obtain the solid buoyancy material.
Specifically, in this embodiment, S1 includes: 20 portions of the components are mixed by weight, and the density is 0.42g/cm3The hollow glass micro-beads comprise 15 parts by weight of hollow glass micro-beads and have the density of 0.32g/cm3And adding the hollow glass beads into a kneader, setting the rotating speed to be 25r/min, and mixing for 30min for later use.
Specifically, in this embodiment, S2 includes: respectively putting 35 parts by weight of hyperbranched polymer modified epoxy resin, 3 parts by weight of ethylene glycol diglycidyl ether, 1 part by weight of beta- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane and 1.5 parts by weight of multi-walled amino carbon nanotubes into a dispersion tank, placing the dispersion tank under a high-speed dispersion machine, setting the rotating speed to be 550r/min, stirring for 15min, then transferring the dispersion tank under a basket type sand mill, setting the rotating speed to be 2300r/min, grinding for 40min, then sequentially adding 20 parts by weight of isophorone diamine and 3 parts by weight of phthalic anhydride, then transferring the dispersion tank under the high-speed dispersion machine, setting the rotating speed to be 550r/min, and stirring for 10min to obtain a mixture;
specifically, in this embodiment, S3 includes: and adding the mixture obtained in the step S2 into a kneader, kneading for 50min at a set rotating speed of 30r/min under vacuum-0.1 MPa, discharging, putting into a mold, compacting, curing for 4h at 100 ℃, cooling to room temperature, and removing the buoyancy material from the mold to obtain the solid buoyancy material.
Example 6
The embodiment of the application provides a solid buoyancy material, which comprises the following raw materials in parts by weight:
20-50 parts of modified epoxy resin, 1-10 parts of reactive diluent, 20-45 parts of curing agent, 1-10 parts of toughening curing agent, 20-150 parts of hollow microspheres, 1-5 parts of coupling agent and 0.5-2 parts of modified carbon nano tubes, wherein the modified carbon nano tubes are amino-terminated carbon nano tubes;
the modified epoxy resin comprises one or more of dimer acid modified epoxy resin, polyurethane modified epoxy resin, phenolic aldehyde modified epoxy resin, organic silicon modified epoxy resin, hyperbranched polymer modified epoxy resin and polybutyl acrylate modified epoxy resin.
Specifically, in the embodiment of the application, 45 parts by weight of phenolic aldehyde modified epoxy resin NPPN-631 is adopted as the modified epoxy resin.
Specifically, in the embodiment of the present application, the modified carbon nanotube is 100345 multiwall terminal amino carbon nanotubes manufactured by Jiangsu Xiancheng nanomaterial science and technology ltd, in which the weight part of the modified carbon nanotube is 0.5, and the diameter of the terminal amino carbon nanotube is 8-15 nm, and the length of the terminal amino carbon nanotube is 50 μm.
Specifically, the reactive diluent in the embodiment of the application comprises one or more of butyl glycidyl ether, benzyl glycidyl ether, ethylene glycol diglycidyl ether, alkylene glycidyl ether and neopentyl glycol diglycidyl ether; in the examples of the present application, 3 parts by weight of benzyl glycidyl ether was used as the reactive diluent.
Specifically, the curing agent in the embodiment of the present application includes one or more of methyl tetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride, isophorone diamine, m-phenylenediamine, diamino diphenyl sulfone, trimethyl hexamethylene diamine, and diethyl triamine; in the examples of the present application, 25 parts by weight of methyltetrahydrophthalic anhydride was used as the curing agent.
Specifically, the toughening curing agent in the embodiment of the application comprises one or more of maleic anhydride, phthalic anhydride, pyromellitic anhydride and benzophenonetetracarboxylic dianhydride; in the embodiment of the application, the toughening curing agent adopts 3 parts by weight of phthalic anhydride.
Specifically, the coupling agent in the embodiment of the application comprises one or more of vinyltrimethoxysilane, vinyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, beta- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, gamma-isocyanate propyltrimethoxysilane and gamma-isocyanate propyltriethoxysilane; in the examples of the present application, 1 part by weight of beta- (3,4 epoxycyclohexyl) ethyltrimethoxysilane was used as a coupling agent.
Specifically, the hollow microspheres in the embodiment of the application are hollow glass microspheres, and the hollow glass microspheres are 30 parts by weight, 6.2MPa in compression strength and 0.15g/cm in density3Hollow glass micro-beads, 15 weight portions, 7.3Mpa of compressive strength and 0.2g/cm of density3Hollow glass beads.
Based on the same inventive concept, the embodiment of the present application further provides a preparation method of the above solid buoyancy material, as shown in fig. 1, including the following steps:
s1, adding the hollow microspheres into a kneader, and mixing for later use;
s2, placing the modified epoxy resin, the reactive diluent, the coupling agent and the modified carbon nano tube in a dispersion machine for dispersion, then transferring the dispersion machine to a sand mill for grinding, adding the curing agent and the toughening curing agent, and then transferring the dispersion machine for dispersion to obtain a mixture;
and S3, adding the mixture into a kneader, kneading, discharging and solidifying to obtain the solid buoyancy material.
Specifically, in this embodiment, S1 includes: 30 portions of the components are mixed, and the density is 0.15g/cm3The hollow glass micro-beads comprise 15 parts by weight of hollow glass micro-beads and have the density of 0.2g/cm3And adding the hollow glass beads into a kneader, setting the rotating speed to be 25r/min, and mixing for 30min for later use.
Specifically, in this embodiment, S2 includes: respectively putting 45 parts by weight of phenolic aldehyde modified epoxy resin, 3 parts by weight of benzyl glycidyl ether, 1 part by weight of beta- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane and 0.5 part by weight of multi-wall-end amino carbon nano-tubes into a dispersion tank, placing the dispersion tank under a high-speed dispersion machine, setting the rotating speed to be 400r/min, stirring for 20min, then transferring the dispersion tank under a basket type sand mill, setting the rotating speed to be 2500r/min, grinding for 35min, then sequentially adding 25 parts by weight of methyltetrahydrophthalic anhydride and 3 parts by weight of phthalic anhydride, then transferring the dispersion tank under the high-speed dispersion machine, setting the rotating speed to be 400r/min, and stirring for 20min to obtain a mixture;
specifically, in this embodiment, S3 includes: and adding the mixture obtained in the step S2 into a kneader, setting the rotating speed at 30r/min under vacuum-0.1 MPa, kneading for 55min, discharging, putting into a mold, compacting, curing for 4h at 150 ℃, cooling to room temperature, and removing the buoyancy material from the mold to obtain the solid buoyancy material.
Comparative example 1
The difference from example 1 is that conventional epoxy resin is used for the solid buoyant material.
Comparative example 2
The difference from example 1 is that conventional single-walled carbon nanotubes are used for the solid buoyant material. The density, compressive strength, underwater operation depth, bending strength, thermal conductivity and 180-day seawater immersion of the solid buoyancy materials prepared in the above examples 1 to 6 were respectively tested, and the results are shown in table 1 below.
TABLE 1 Properties of the solid buoyancy Material of the different examples
As can be seen from the above table 1, the solid buoyancy material prepared by the method has high compressive strength and bending strength, is suitable for deep operation of 5000m underwater, has low heat conductivity coefficient, has good heat preservation effect, and has good deformation stability after being soaked in seawater for 180 days.
The compressive strength and the bending strength of the solid buoyancy material prepared in example 1 and the solid buoyancy material prepared in comparative example 1 are respectively tested, and the tests show that the compressive strength is improved by 15-30% and the bending strength is improved by 10-30% compared with the solid buoyancy material prepared in comparative example 1, so that the strength and the toughness of the solid buoyancy material can be improved by adopting the modified epoxy resin.
The compressive strength and the bending strength of the solid buoyancy material prepared in the example 1 and the comparative example 2 are respectively tested, and the tests show that the compressive strength of the solid buoyancy material prepared in the example 1 is improved by 10-20% and the bending strength of the solid buoyancy material prepared in the comparative example 2 is improved by 15-25%, so that the strength and the toughness of the solid buoyancy material can be improved by adopting the modified carbon nano tubes.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. The solid buoyancy material is characterized by comprising the following raw materials in parts by weight:
20-50 parts of modified epoxy resin, 1-10 parts of reactive diluent, 20-45 parts of curing agent, 1-10 parts of toughening curing agent, 20-150 parts of hollow microspheres and 1-5 parts of coupling agent;
the modified epoxy resin comprises one or more of dimer acid modified epoxy resin, polyurethane modified epoxy resin, phenolic aldehyde modified epoxy resin, organic silicon modified epoxy resin, hyperbranched polymer modified epoxy resin and polybutyl acrylate modified epoxy resin.
2. The solid buoyancy material according to claim 1, further comprising 0.5-2 parts by weight of modified carbon nanotubes, wherein the modified carbon nanotubes are amino-terminated carbon nanotubes.
3. The solid buoyancy material according to claim 2, wherein the amino-terminated carbon nanotubes comprise single-walled amino-terminated carbon nanotubes and/or multi-walled amino-terminated carbon nanotubes, and the amino-terminated carbon nanotubes have a diameter of 1-15 nm and a length of 20-50 μm.
4. The solid buoyancy material of claim 1 wherein the reactive diluent comprises one or more of butyl glycidyl ether, benzyl glycidyl ether, ethylene glycol diglycidyl ether, alkylene glycidyl ether, neopentyl glycol diglycidyl ether; the curing agent comprises one or more of methyl tetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride, isophorone diamine, m-phenylenediamine, diaminodiphenyl sulfone, trimethyl hexamethylene diamine and diethyl triamine; the toughening curing agent comprises one or more of maleic anhydride, phthalic anhydride, pyromellitic anhydride and benzophenonetetracarboxylic dianhydride; the coupling agent comprises one or more of vinyl trimethoxy silane, vinyl triethoxy silane, gamma-glycidoxypropyl trimethoxy silane, beta- (3,4 epoxy cyclohexyl) ethyl trimethoxy silane, gamma-isocyanate propyltrimethoxy silane and gamma-isocyanate propyltriethoxy silane.
5. The solid buoyant material of claim 1 wherein the cenospheres are cenospheres of hollow glass having a density of from 0.1 to 0.6g/cm3The compressive strength is 1-70 MPa.
6. A method of manufacturing a solid buoyant material according to any one of claims 1 to 5 comprising the steps of:
adding the hollow microspheres into a kneading machine, and mixing for later use;
placing the modified epoxy resin, the active diluent, the coupling agent and the optional modified carbon nano tube into a dispersion machine for dispersion, then transferring the dispersion machine into a sand mill for grinding, then adding the curing agent and the toughening curing agent, and transferring the dispersion machine for dispersion to obtain a mixture;
and adding the mixture into the kneader, kneading, discharging and curing to obtain the solid buoyancy material.
7. The method for preparing the solid buoyancy material according to claim 6, wherein the modified epoxy resin, the reactive diluent, the coupling agent and the optional modified carbon nanotube are placed in a dispersion machine at 400-600 r/min, stirred and dispersed for 10-30 min, then transferred to a sand mill at 2000-2500 r/min, ground for 30-40 min, added with the curing agent and the toughening curing agent, transferred to a dispersion machine at 400-600 r/min, and stirred and dispersed for 10-30 min to obtain a mixture.
8. The preparation method of the solid buoyancy material as claimed in claim 6, wherein the mixture is added into the kneader and kneaded for 50-70min at 20-30r/min under vacuum-0.1 MPa, and the solid buoyancy material is obtained after discharging and curing for 4h at 80-150 ℃.
9. The method for preparing the solid buoyancy material according to claim 6, wherein the cenospheres are added into the kneader and mixed for 15-30 min at a speed of 15-25 r/min.
10. Use of the solid buoyant material according to any one of claims 1 to 5 or the solid buoyant material prepared by the preparation method according to any one of claims 6 to 9 in an underwater 0-5000 m operation environment.
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