CN113292825A - High-toughness epoxy composite buoyancy material and preparation method thereof - Google Patents
High-toughness epoxy composite buoyancy material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high-toughness epoxy-based composite buoyancy material and a preparation method thereof.A modified epoxy resin is obtained by directly heating and melting polyvinyl formal copolymerized acrylic acid and epoxy resin, and then is mixed with a carbon nano tube and hollow glass beads, and the compatibility of the hollow glass beads, the carbon nano tube and the epoxy resin is improved by utilizing the hydrogen bonding action of polar groups of the polyvinyl formal copolymerized acrylic acid and amino and hydroxyl groups on the surfaces of the carbon nano tube and the hollow glass beads; the preparation process is simple and convenient, the method is suitable for industrial production, and the prepared buoyancy material is high in compressive strength, good in impact toughness and low in water absorption.
Description
Technical Field
The invention belongs to the field of solid buoyancy materials for marine equipment, and particularly relates to a high-toughness epoxy-based composite buoyancy material and a preparation method thereof.
Background
The development and treatment of ocean resources are the focus of international attention all the time, and with the further development of ocean resources, people face more and more complex ocean environments, and higher requirements are put forward on buoyancy materials. The solid buoyancy material is also called composite foam material, is prepared by adding hollow microspheres into a resin matrix, has the comprehensive characteristics of low density, high strength, low water absorption, corrosion resistance and the like, and is widely used for ocean exploration systems, deep sea diving equipment, offshore oil exploration and other deep sea development equipment. Most of high-strength solid buoyancy materials belong to brittle materials, and the materials are difficult to avoid brittle failure caused by impact or collision in the using process of the materials, so that the application and development of the materials in some high-technology fields with high requirements on durability and reliability are limited. Therefore, on the premise of ensuring high compressive strength, the improvement of the toughness of the buoyancy material plays an important role.
The existing toughening mode of the solid buoyancy material is mainly to add materials such as polymer elastic microspheres, rubber elastomers, thermoplastic polymers and the like into the buoyancy material to improve the toughness of the material, but the compressive strength is often reduced. Chinese patent CN 108329656A introduces that elastic microspheres are adopted to replace hollow glass microspheres, and toughening agents such as nitrile rubber, polyether sulfone and the like are matched to improve the toughness of the solid buoyancy material, so that the elongation at break of the prepared buoyancy material is well improved, but the compressive strength of the prepared solid buoyancy material is lower due to the poor compressive strength of the polymer elastic microspheres. Chinese patent CN106380786 describes that the toughness of the solid buoyancy material is improved by using thermoplastic plastic foaming microspheres and hollow glass beads, and the material density and the addition amount of the hollow glass beads are further reduced by using the thermal expansion of the foaming microspheres. Chinese patent CN200610043524 introduces a method of adding toughening agents such as polysulfide rubber, liquid nitrile rubber and the like in a mechanical blending mode to toughen a solid buoyancy material, and because the toughening effect of rubber is in positive correlation with the addition amount, excessive addition can cause the problems of material density increase, uneven dispersion and the like, and the toughening effect is influenced.
Disclosure of Invention
In order to solve the problem that the compressive strength of the material is reduced due to uneven dispersion of the traditional toughening agent in the buoyancy material, the invention provides the high-toughness epoxy group composite buoyancy material and the preparation method thereof, wherein carboxyl-terminated polyvinyl formal is adopted to copolymerize acrylic acid modified epoxy resin, and the carboxylic acid group and the epoxy resin are crosslinked, so that the compatibility of the two is effectively improved; meanwhile, the modified epoxy resin is firmly attached to the hollow glass beads and the carbon nano tubes through hydrogen bonds of each polar unit, so that the overall impact resistance of the buoyancy material is improved, and the compressive strength of the material is not reduced. The toughening mechanism is as follows:
in order to realize the purpose, the invention is implemented by the following technical scheme:
the high-toughness epoxy-based composite buoyancy material comprises the following components in parts by mass:
100 parts of epoxy resin; 30-100 parts of a curing agent; 6-10 parts of a toughening agent; 25-100 parts of hollow glass microspheres; 0.5-2 parts of carbon nano tubes; 5-15 parts of a reactive diluent; 0.5-3 parts of an accelerator; 0-2 parts of a surface treating agent. Wherein the epoxy resin is one or a mixture of two of bisphenol A epoxy resin, alicyclic epoxy resin, novolac epoxy resin and the like; the epoxy resin toughening agent is polyvinyl formal copolymerized acrylic acid containing terminal carboxyl; the curing agent is one of acid anhydride curing agent or amine curing agent; the accelerator is one of 2-ethyl-4-methylimidazole or 2,4, 6-tris (dimethylaminomethyl) phenol; the reactive diluent is one of butyl glycidyl ether or neopentyl glycol glycidyl ether;
further, the hollow glass beads are one or two hollow glass beads pretreated by the surface treating agent and compounded, the particle size difference is 5-40um, the real density of the beads is 0.25-0.6g/cm3, and the compressive strength is 5-125 MPa;
the surface pretreatment method comprises the following steps: adding the hollow glass beads into a sodium hydroxide solution with the concentration of 0.1mol/L, refluxing for 2h at 80 ℃, then washing with clear water until the pH value is 7, and finally, carrying out suction filtration, drying and sieving by using 200-mesh filter cloth. Adding the dried microspheres into a mixed solution of absolute ethyl alcohol and distilled water, then adding a KH560 silane solution with the mass of 1-6% of that of the hollow glass microspheres, refluxing for 2h at 80 ℃, filtering, drying and sieving; further, the surface pretreatment agent of the hollow glass microsphere is one of silane coupling agents KH550 or KH 560;
further, the carbon nanotube powder is one of a hydroxylated carbon nanotube, a carboxylated carbon nanotube, an aminated carbon nanotube and the like;
the preparation method of the high-toughness epoxy-based composite buoyancy material is characterized by comprising the following steps of:
(1) placing the epoxy resin in an oven, heating at 80-100 deg.C for 2-5h, dehydrating and degassing;
(2) adding an epoxy resin toughening modifier in the step (1), and stirring for 3-4h at the temperature of 130-140 ℃ to completely dissolve the epoxy resin toughening modifier;
(3) adding carbon nanotube powder and an active diluent into the modified epoxy resin obtained in the step (2), sanding the mixture in a stirrer for 2-3h, and filtering to obtain a uniformly mixed resin premix;
(4) adding a curing agent, an accelerator and the hollow glass micro subjected to surface pretreatment into the resin premix in the step (3), and stirring for 20min in vacuum at 70 ℃;
(5) and (3) injecting the premix obtained in the step (4) into a mold, vacuumizing at 70 ℃, standing at room temperature for 3-4h for defoaming, and finally performing gradient heating and curing for 2h, 2h and 1h in sequence at the heating temperature of 80-100 ℃, 100 ℃ and 120 ℃ and 160 ℃ to obtain the solid buoyancy material.
The invention has the following remarkable advantages:
the carboxyl-terminated polyvinyl formal copolymerized acrylic acid is directly heated and melted to obtain the modified epoxy resin, and the carboxyl group and the epoxy resin are used for crosslinking, so that the compatibility of the carboxyl-terminated polyvinyl formal copolymerized acrylic acid and the epoxy resin is effectively improved; meanwhile, the modified epoxy resin is firmly attached to the hollow glass beads and the carbon nano tubes through hydrogen bonds of all polar units, so that the overall impact resistance of the buoyancy material is improved, and the compressive strength of the material is not reduced; the preparation process is simple and convenient, the method is suitable for industrial production, and the prepared buoyancy material is high in compressive strength, good in impact toughness and low in water absorption.
Drawings
FIG. 1 is a macroscopic view of samples of the solid buoyant material prepared in comparative example 1, example 2 and example 6;
FIG. 2 is an SEM image of a compressed section of the solid buoyancy material prepared in example 2;
fig. 3 is a SEM image of a compressed cross-section of the solid buoyant material prepared in comparative example 1.
Detailed Description
The invention provides a high-toughness epoxy-based composite buoyancy material and a preparation method thereof, and in order to make the purposes, technical schemes and effects of the invention clearer and clearer, the invention is further explained by combining specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Example 1
(1) 100 parts of epoxy resin E44 and 7 parts of carboxyl-terminated polyvinyl formal copolymerized acrylic acid (VINYLEC) toughening agent are stirred at the temperature of 130-140 ℃ for 3-4h to be completely dissolved, and vacuum defoaming treatment is carried out on the mixture. Adding 30 parts of polyetheramine curing agent D230 and 1.5 parts of 2-ethyl-4-methylimidazole accelerator, and stirring at a certain temperature for 20min in vacuum to obtain mixed epoxy resin liquid for later use;
(2) hollow glass microspheres with the particle size D50 of 65um (true density of 0.25 g/cm)3Compressive strength of 5 MPa) and particle size D50 of 35um (true density of 0.6 g/cm)3Compressive strength of 125 MPa) by massUniformly mixing the components in a ratio of 4:1, adding the mixture into the liquid in the mixed epoxy resin, and stirring the mixture for 20min in vacuum at 70 ℃;
(3) and (3) injecting the premix in the step (2) into a mold, vacuumizing at 80 ℃, standing at room temperature for 3-4h for defoaming, and finally performing gradient heating and curing for 2h, 2h and 1h in sequence at the heating temperature of 80-100 ℃, 100 ℃ and 120 ℃ and 160 ℃ to obtain the solid buoyancy material.
The density of the solid buoyancy material obtained in the embodiment is 0.680g/cm3The compressive strength is 76.86MPa, the water absorption is 0.32 percent, and the impact strength is 7.83KJ/m2。
Example 2
(1) 100 parts of epoxy resin E54 and 8 parts of carboxyl-terminated polyvinyl formal copolymerized acrylic acid (VINYLEC) toughening agent are stirred at the temperature of 130-140 ℃ for 3-4h to be completely dissolved, and vacuum defoaming treatment is carried out on the mixture. Adding 90 parts of methyl hexahydrophthalic anhydride curing agent and 2 parts of 2,4, 6-tri (dimethylaminomethyl) phenol accelerator, and stirring at a certain temperature in vacuum for 20min to obtain mixed epoxy resin liquid for later use;
(2) hollow glass microspheres with the particle size D50 of 60um (true density of 0.25 g/cm)3The compressive strength was 5. 18 MPa) and 20um particle diameter D50 (true density 0.46 g/cm)3The compressive strength is 110 MPa) is uniformly mixed according to the mass ratio of 1:1, then the mixture is added into KH560 ethanol aqueous solution with the mass of 3 percent of that of the hollow glass microspheres for surface pretreatment, the mixture is refluxed for 2 hours at the temperature of 80 ℃, and then is filtered, dried and sieved by 200-mesh filter cloth;
(3) adding the hollow glass microspheres subjected to surface pretreatment in the step (2) into the liquid in the mixed epoxy resin in the step (1), and stirring for 20min in vacuum at 70 ℃;
(4) and (3) injecting the premix in the step (3) into a mold, vacuumizing at 80 ℃, standing at room temperature for 3-4h for defoaming, and finally performing gradient heating and curing for 2h, 2h and 1h in sequence at the heating temperature of 80-100 ℃, 100 ℃ and 120 ℃ and 160 ℃ to obtain the solid buoyancy material.
The density of the solid buoyancy material obtained in the embodiment is 0.667g/cm3The compressive strength is 84.22MPa, the water absorption is 0.29 percent, and the impact strength is 7.99KJ/m2。
Example 3
(1) 100 parts of epoxy resin E51 and 8 parts of carboxyl-terminated polyvinyl formal copolymerized acrylic acid (VINYLEC) toughening agent are stirred at the temperature of 130-140 ℃ for 3-4h to be completely dissolved, and vacuum defoaming treatment is carried out on the mixture. Adding 85 parts of methyl tetrahydrophthalic anhydride curing agent and 2 parts of 2-ethyl-4-methylimidazole accelerator, and stirring at a certain temperature in vacuum for 20min to obtain mixed epoxy resin liquid for later use;
(2) hollow glass microspheres with the particle size D50 of 55um (true density of 0.25 g/cm)3Compressive strength of 5.17 MPa) and a particle size D50 of 20um (true density of 0.46 g/cm)3The compressive strength is 110 MPa) is uniformly mixed according to the mass ratio of 1:1, added into KH550 ethanol aqueous solution with the mass of 3 percent of that of the hollow glass microspheres for surface pretreatment, refluxed for 2 hours at the temperature of 80 ℃, filtered, dried and sieved by 200-mesh filter cloth;
(3) adding the hollow glass microspheres subjected to surface pretreatment in the step (2) into the liquid in the mixed epoxy resin in the step (1), and stirring for 20min in vacuum at 70 ℃;
(4) and (3) injecting the premix in the step (3) into a mold, vacuumizing at 80 ℃, standing at room temperature for 3-4h for defoaming, and finally performing gradient heating and curing for 2h, 2h and 1h in sequence at the heating temperature of 80-100 ℃, 100 ℃ and 120 ℃ and 160 ℃ to obtain the solid buoyancy material.
The density of the solid buoyancy material obtained in the embodiment is 0.678g/cm3The compressive strength is 83.51MPa, the water absorption is 0.25 percent, and the impact strength is 8.83KJ/m2. As shown in fig. 2(a), a compressed cross section SEM of the solid buoyancy material shows that the modified microbeads have good interface compatibility with epoxy resin and strong binding force.
Example 4
(1) Stirring 100 parts of epoxy resin CYD-128 and 7 parts of carboxyl-terminated polyvinyl formal copolymerized acrylic acid (VINYLEC) toughening agent at the temperature of 130-140 ℃ for 3-4h to be completely dissolved, carrying out vacuum defoaming treatment on the mixture, then adding 1.5 parts of hydroxylated carbon nanotube powder and 12 parts of butyl glycidyl ether reactive diluent, sanding the mixture in a stirrer for 2-3h, and filtering the mixture to obtain a uniformly mixed resin premix;
(2) adding 35 parts of polyetheramine curing agent D230 and 1.5 parts of 2,4, 6-tris (dimethylaminomethyl) phenol accelerator into the step (1), and stirring at a certain temperature for 20min in vacuum to obtain mixed epoxy resin liquid for later use;
(3) hollow glass beads (true density 0.38 g/cm) having a particle size D50 of 40um3Compressive strength of 38 MPa) and a particle size D50 of 30um (true density of 0.46 g/cm)3The compressive strength is 41.37 MPa) is uniformly mixed according to the mass ratio of 2:1, then the mixture is added into the liquid in the epoxy resin mixture obtained in the step (2), and the mixture is stirred for 20min under vacuum at 70 ℃;
(4) and (3) injecting the premix in the step (3) into a mold, vacuumizing at 80 ℃, standing at room temperature for 3-4h for defoaming, and finally performing gradient heating and curing for 2h, 2h and 1h in sequence at the heating temperature of 80-100 ℃, 100 ℃ and 120 ℃ and 160 ℃ to obtain the solid buoyancy material.
The density of the solid buoyancy material obtained in the embodiment is 0.655g/cm3The compressive strength is 80.86 MPa, the water absorption is 0.35 percent, and the impact strength is 8.03KJ/m2。
Example 5
(1) Stirring 100 parts of epoxy resin E51 and 8 parts of carboxyl-terminated polyvinyl formal copolymerized acrylic acid (VINYLEC) toughening agent at the temperature of 130-140 ℃ for 3-4h to be completely dissolved, carrying out vacuum defoaming treatment on the mixture, then adding 1.5 parts of carboxylated carbon nanotube powder and 12 parts of neopentyl glycol glycidyl ether active diluent, sanding the mixture in a stirrer for 2-3h, and filtering the mixture to obtain a uniformly mixed resin premix;
(2) adding 85 parts of methyl tetrahydrophthalic anhydride curing agent and 1.5 parts of 2,4, 6-tris (dimethylaminomethyl) phenol accelerator into the step (1), and stirring at a certain temperature in vacuum for 20min to obtain mixed epoxy resin liquid for later use;
(3) hollow glass beads (true density 0.38 g/cm) having a particle size D50 of 40um3Compressive strength of 37.9 MPa) and a particle size D50 of 40um (true density of 0.46 g/cm)3The compressive strength is 41.34 MPa) according to the mass ratio of 2:1Mixing uniformly, adding into the liquid in the mixed epoxy resin in the step (2), and stirring in vacuum at 70 ℃ for 20 min;
(4) and (3) injecting the premix in the step (3) into a mold, vacuumizing at 80 ℃, standing at room temperature for 3-4h for defoaming, and finally performing gradient heating and curing for 2h, 2h and 1h in sequence at the heating temperature of 80-100 ℃, 100 ℃ and 120 ℃ and 160 ℃ to obtain the solid buoyancy material.
The density of the solid buoyancy material obtained in the embodiment is 0.662g/cm3The compressive strength is 82.86 MPa, the water absorption is 0.33 percent, and the impact strength is 8.61KJ/m2。
Example 6
(1) Stirring 100 parts of epoxy resin E44 and 8 parts of carboxyl-terminated polyvinyl formal copolymerized acrylic acid (VINYLEC) toughening agent at the temperature of 130-140 ℃ for 3-4h to be completely dissolved, carrying out vacuum defoaming treatment on the mixture, then adding 1.2 parts of carboxylated carbon nanotube powder and 10 parts of neopentyl glycol glycidyl ether active diluent, sanding the mixture in a stirrer for 2-3h, and filtering the mixture to obtain a uniformly mixed resin premix;
(2) adding 75 parts of methyl tetrahydrophthalic anhydride curing agent and 2.0 parts of 2,4, 6-tris (dimethylaminomethyl) phenol accelerator into the step (1), and stirring at a certain temperature for 20min in vacuum to obtain mixed epoxy resin liquid for later use;
(3) hollow glass microspheres with the particle size D50 of 55um (true density of 0.25 g/cm)3Compressive strength of 5.17 MPa) and a particle size D50 of 30um (true density of 0.6 g/cm)3Compressive strength of 124.02 MPa) is uniformly mixed according to the mass ratio of 1:1, added into KH550 ethanol aqueous solution with the mass of 3 percent of that of the hollow glass microspheres for surface pretreatment, refluxed for 2 hours at 80 ℃, filtered, dried and sieved by 200-mesh filter cloth;
(4) adding the hollow glass microspheres subjected to surface pretreatment in the step (3) into the liquid in the mixed epoxy resin in the step (2), and stirring for 20min in vacuum at 70 ℃;
(5) and (3) injecting the premix in the step (4) into a mold, vacuumizing at 80 ℃, standing at room temperature for 3-4h for defoaming, and finally performing gradient heating and curing for 2h, 2h and 1h in sequence at the heating temperature of 80-100 ℃, 100 ℃ and 120 ℃ and 160 ℃ to obtain the solid buoyancy material.
The density of the solid buoyancy material obtained in the example was 0.691g/cm3The compressive strength is 85.75 MPa, the water absorption is 0.27 percent, and the impact strength is 10.23KJ/m2。
Comparative example 1
(1) Stirring 100 parts of epoxy resin E51, 85 parts of methyl hexahydrophthalic anhydride curing agent and 2 parts of 2-ethyl-4-methylimidazole accelerator at a certain temperature in vacuum for 20min to obtain mixed epoxy resin liquid for later use;
(2) hollow glass beads (true density 0.38 g/cm) having a particle size D50 of 40um3Compressive strength of 38 MPa) and a particle size D50 of 35um (true density of 0.6 g/cm)3Compressive strength of 125 MPa) is uniformly mixed according to the mass ratio of 3:2, added into the liquid in the mixed epoxy resin, and stirred for 20min under vacuum at 70 ℃;
(3) and (3) injecting the premix in the step (2) into a mold, vacuumizing at 80 ℃, standing at room temperature for 3-4h for defoaming, and finally performing gradient heating and curing for 2h, 2h and 1h in sequence at the heating temperature of 80-100 ℃, 100 ℃ and 120 ℃ and 160 ℃ to obtain the solid buoyancy material.
The density of the solid buoyancy material obtained by the comparative example is 0.668g/cm3The compressive strength is 73.05MPa, the water absorption is 0.23 percent, and the impact strength is 6.10KJ/m2. As shown in fig. 3(b), the SEM of the compressed cross section of the solid buoyancy material shows that the floating body material without the modified microspheres and epoxy resin has poor compatibility of the microsphere-epoxy interface, low binding force between the two, and a large number of hollow glass microspheres are peeled off.
Comparative example 2
(1) 100 parts of epoxy resin CYD-128, 90 parts of methyl tetrahydrophthalic anhydride curing agent and 2 parts of 2,4, 6-tris (dimethylaminomethyl) phenol accelerator are stirred for 20min in vacuum at a certain temperature to obtain mixed epoxy resin liquid.
(2) And (2) injecting the mixed resin liquid obtained in the step (1) into a mold, vacuumizing at 80 ℃, standing at room temperature for 3-4h for defoaming, and finally performing gradient heating curing at the heating temperature of 80-100 ℃, 100-120 ℃ and 160 ℃ for 2h, 2h and 1h in sequence to obtain the pure epoxy resin curing material.
This comparative example is a pure epoxy curing system and gives a material density of 1.189g/cm3The compressive strength is 121.115MPa, the water absorption is 0.08 percent, and the impact strength is 11.33KJ/m2。
Comparative example 3
(1) 100 parts of epoxy resin E51 and 8 parts of carboxyl-terminated polyvinyl formal copolymerized acrylic acid (VINYLEC) toughening agent are stirred at the temperature of 130-140 ℃ for 3-4h to be completely dissolved, and vacuum defoaming treatment is carried out on the mixture. Adding 35 parts of polyether amine curing agent and 2 parts of 2-ethyl-4-methylimidazole accelerator, and stirring at a certain temperature for 20min in vacuum to obtain mixed epoxy resin liquid.
(2) Injecting the modified epoxy resin liquid obtained in the step (1) into a mold, vacuumizing at 80 ℃, standing at room temperature for 3-4h for defoaming, and finally performing gradient heating curing at the heating temperature of 80-100 ℃, 100-120 ℃ and 160 ℃ for 2h, 2h and 1h in sequence to obtain the modified epoxy resin curing material.
In order to verify the toughening effect of the carboxyl-terminated polyvinyl formal copolymerized acrylic acid directly heated and melted modified epoxy resin, the hollow glass beads and the carbon nano tubes are not added in the comparative example. The resulting material had a density of 1.174g/cm3The compressive strength is 117.45MPa, the water absorption is 0.11 percent, and the impact strength is 18.85KJ/m2。
The above-mentioned preferred embodiments, further illustrating the objects, technical solutions and advantages of the present invention, should be understood that the above-mentioned are only preferred embodiments of the present invention and should not be construed as limiting the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The high-toughness epoxy-based composite buoyancy material is characterized by comprising the following components in parts by mass:
100 parts of epoxy resin; 30-100 parts of a curing agent; 6-10 parts of a toughening agent; 25-100 parts of hollow glass microspheres; 0.5-2 parts of carbon nano tubes; 5-15 parts of a reactive diluent; 0.5-3 parts of an accelerator; 0-2 parts of a surface treating agent.
2. A high toughness epoxy based composite buoyancy material according to claim 1, wherein: the epoxy resin is one or a mixture of two of bisphenol A epoxy resin, alicyclic epoxy resin, novolac epoxy resin and the like.
3. A high toughness epoxy based composite buoyancy material according to claim 1, wherein: the epoxy resin toughening agent is polyvinyl formal copolymerized acrylic acid containing terminal carboxyl.
4. A high toughness epoxy based composite buoyancy material according to claim 1, wherein: the carbon nano tube powder is one of hydroxylated carbon nano tube, carboxylated carbon nano tube, aminated carbon nano tube and the like.
5. A high toughness epoxy based composite buoyancy material according to claim 1, wherein: the curing agent is one of acid anhydride or amine curing agents; the accelerator is one of 2-ethyl-4-methylimidazole or 2,4, 6-tris (dimethylaminomethyl) phenol; the reactive diluent is one of butyl glycidyl ether or neopentyl glycol glycidyl ether.
6. A high toughness epoxy based composite buoyancy material according to claim 1, wherein: the hollow glass beads are compounded by one or two beads pretreated by a surface treating agent, the particle size difference is between 5 and 40 mu m, and the real density of the beads is between 0.25 and 0.6g/cm3The compressive strength is 5-125 MPa; the surface pretreatment method comprises the following steps: adding hydrogen with the concentration of 0.1mol/L into hollow glass microspheresRefluxing the sodium oxide solution at 80 ℃ for 2h, washing with clear water until the pH is 7, performing suction filtration, drying and sieving with 200-mesh filter cloth, adding the dried microspheres into a mixed solution of absolute ethyl alcohol and distilled water, adding a silane solution accounting for 1-6% of the mass of the hollow glass microspheres, refluxing at 80 ℃ for 2h, performing suction filtration, drying and sieving with 200-mesh filter cloth.
7. A high toughness epoxy based composite buoyancy material according to claim 1, wherein: the surface pretreatment agent of the hollow glass microsphere is one of silane coupling agents KH550 or KH 560.
8. A method for preparing a high toughness epoxy based composite buoyancy material according to any one of claims 1 to 7, wherein the method comprises the following steps: the method comprises the following steps:
(1) placing the epoxy resin in an oven, heating at 80-100 deg.C for 2-5h, dehydrating and degassing;
(2) adding an epoxy resin toughening modifier in the step (1), and stirring for 3-4h at the temperature of 130-140 ℃ to completely dissolve the epoxy resin toughening modifier;
(3) adding carbon nanotube powder and an active diluent into the modified epoxy resin obtained in the step (2), sanding the mixture in a stirrer for 2-3h, and filtering to obtain a uniformly mixed resin premix;
(4) adding a curing agent, an accelerator and the hollow glass micro subjected to surface pretreatment into the resin premix in the step (3), and stirring for 20min in vacuum at 70 ℃;
(5) and (4) injecting the premix in the step (4) into a mold, vacuumizing, standing at room temperature for 3-4h for defoaming, and finally heating, curing and demolding.
9. The method for preparing the high-toughness epoxy-based composite buoyancy material according to claim 8, wherein the method comprises the following steps: the die in the step (5) is a polytetrafluoroethylene or stainless steel die which is sprayed with a release agent in advance and is subjected to preheating treatment at 80-100 ℃ in an oven.
10. The method for preparing the high-toughness epoxy-based composite buoyancy material according to claim 8, wherein the method comprises the following steps: and (5) performing gradient temperature rise curing for 2h, 2h and 1h at the curing temperature of 80-100 ℃, 100-120 ℃ and 160 ℃ sequentially to obtain the solid buoyancy material.
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| CN102329428A (en) * | 2011-07-26 | 2012-01-25 | 广东生益科技股份有限公司 | Block copolymer modified epoxy resin and preparation method thereof |
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| CN110016204A (en) * | 2019-03-01 | 2019-07-16 | 谷佑芽 | A kind of preparation method of high-strength lightweight buoyancy material |
| CN112409758A (en) * | 2020-11-05 | 2021-02-26 | 青岛爱尔家佳新材料股份有限公司 | Solid buoyancy material and preparation method and application thereof |
| CN112694717A (en) * | 2020-12-01 | 2021-04-23 | 河北汉光重工有限责任公司 | Preparation method of mixed hollow glass bead solid buoyancy material |
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2021
- 2021-06-22 CN CN202110692782.XA patent/CN113292825A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102329428A (en) * | 2011-07-26 | 2012-01-25 | 广东生益科技股份有限公司 | Block copolymer modified epoxy resin 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 |
| CN110016204A (en) * | 2019-03-01 | 2019-07-16 | 谷佑芽 | A kind of preparation method of high-strength lightweight buoyancy material |
| CN112409758A (en) * | 2020-11-05 | 2021-02-26 | 青岛爱尔家佳新材料股份有限公司 | Solid buoyancy material and preparation method and application thereof |
| CN112694717A (en) * | 2020-12-01 | 2021-04-23 | 河北汉光重工有限责任公司 | Preparation method of mixed hollow glass bead solid buoyancy material |
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Application publication date: 20210824 |