A low-density hydrophobic buoyant material and a method for making the same

Abstract

The present application relates to the technical field of buoyancy material, and particularly relates to a low-density hydrophobic buoyancy material and a preparation method thereof. The low-density hydrophobic buoyancy material comprises the following components in parts by weight: 50-60 parts of epoxy resin, 35-45 parts of polyurethane modified graphene oxide-hollow glass microsphere composite material, 15-25 parts of polyaniline, 8-12 parts of short carbon fiber, 4-8 parts of diluent and 1-3 parts of curing agent. The low-density hydrophobic buoyancy material has the characteristics of low density and water absorption, excellent bulk modulus and compression strength, and good weather resistance. The preparation method of the low-density hydrophobic buoyancy material is simple in process and easy to control in operation, is conducive to industrialized mass production, and the prepared low-density hydrophobic buoyancy material is stable in quality and superior in comprehensive performance.

Description

Technical Field

[0001] This invention relates to the field of buoyancy materials technology, specifically to a low-density hydrophobic buoyancy material and its preparation method. Background Technology

[0002] Buoyancy materials are one of the key materials for deep-sea exploration equipment such as submersibles and underwater robots. They can provide these devices with sufficient buoyancy, enabling them to withstand enormous pressure in the deep sea while maintaining good floating status and maneuverability, and to complete various exploration tasks.

[0003] Due to the complex and extreme marine environment, buoyancy materials face a strong coupling effect from multiple factors during use, including high humidity, extreme temperatures, corrosion, fouling, wear, and fatigue, placing extremely high demands on their various properties. Traditional buoyancy materials generally suffer from the following defects:

[0004] 1. Poor weather resistance: During long-term use, buoyancy materials may experience performance degradation and damage due to poor aging caused by damp heat, affecting their performance and safety.

[0005] 2. Difficulty in balancing density and strength: To achieve high performance in buoyancy materials, it is necessary to ensure high strength while maintaining low density to meet the needs of different application scenarios. However, in actual production, it is difficult to accurately balance the relationship between density and strength, and often one is sacrificed for the other.

[0006] 3. Water absorption: Some buoyancy materials have a high water absorption rate. After absorbing water, the material's density increases and its buoyancy decreases, thus affecting its performance. This problem may be more severe, especially in long-term underwater environments. Summary of the Invention

[0007] In order to overcome the shortcomings and deficiencies of the existing technology, the present invention aims to provide a low-density hydrophobic buoyancy material, which has the characteristics of low density, hydrophobicity, excellent bulk modulus and compressive strength, and good weather resistance.

[0008] The preparation method of the low-density hydrophobic buoyancy material of the present invention is simple and easy to control, which is conducive to large-scale industrial production. The low-density hydrophobic buoyancy material obtained is of stable quality and has the characteristics of low density and water absorption, excellent bulk modulus of elasticity and compressive strength, and good weather resistance, with superior comprehensive performance.

[0009] The objective of this invention is achieved through the following technical solution: a low-density hydrophobic buoyancy material comprising the following components by weight: 50-60 parts epoxy resin, 35-45 parts polyurethane modified graphene oxide-hollow glass microsphere composite material, 15-25 parts polyaniline, 8-12 parts chopped carbon fiber, 4-8 parts diluent and 1-3 parts curing agent.

[0010] Furthermore, the polyurethane-modified graphene oxide-hollow glass microsphere composite material comprises the following components in parts by weight: 40-60 parts of PTMG-1000, 8-12 parts of isocyanate-grafted graphene oxide-hollow glass microsphere powder, and 10-15 parts of toluene diisocyanate.

[0011] Furthermore, the preparation method of the polyurethane-modified graphene oxide-hollow glass microsphere composite material includes the following steps: PTMG-1000 is dehydrated at 95-105℃ for 0.8-1.2h, then cooled to 80-90℃, isocyanate-grafted graphene oxide-hollow glass microsphere powder is added, stirred at 80-90℃ for 0.8-1.2h, toluene diisocyanate is slowly added dropwise at 45-55℃, reacted at 76-80℃ for 1.8-2.2h, and bubbles are removed using a vacuum pump to obtain the polyurethane-modified graphene oxide-hollow glass microsphere composite material.

[0012] Furthermore, the preparation method of the isocyanate-grafted graphene oxide-hollow glass microsphere powder includes the following steps:

[0013] A1. Graphene oxide and hollow glass microspheres were dried and then ultrasonicated in DMSO for 0.2-0.7 h to form dispersions.

[0014] A2. Add isophorone diisocyanate and DMSO to a reaction flask, stir and heat to 60-80℃, then slowly add graphene oxide dispersion, followed by 2-4 drops of catalyst, and stir at 65-75℃ for 2-4 h; then slowly add hollow glass microsphere dispersion, and stir at 65-75℃ for 7-9 h.

[0015] A3. The mixture obtained in step A2 is washed with DMSO and acetone respectively, and the solvent is removed under normal pressure to obtain isocyanate-grafted graphene oxide-hollow glass microsphere powder.

[0016] Furthermore, the mass ratio of the graphene oxide, hollow glass microspheres, and isophorone diisocyanate is 0.8-1.2:2:100.

[0017] Furthermore, the graphene oxide has a particle size of 2-5 μm; the hollow glass microspheres have an average particle size of 35-45 μm and a density of 0.3-0.4 g / cm³. 3 Its crushing strength is 25-35 MPa.

[0018] Furthermore, the catalyst is dibutyltin dilaurate.

[0019] Furthermore, the average diameter of the chopped carbon fibers is 5-9 μm, and the length is 0.8-1.2 mm.

[0020] Furthermore, the diluent is trimethylolpropane triglycidyl ether.

[0021] Furthermore, the curing agent is polyamide 650.

[0022] This invention also provides a method for preparing a low-density hydrophobic buoyancy material, comprising the following steps:

[0023] S1. Short-cut carbon fibers are treated with plasma to obtain pretreated short-cut carbon fibers.

[0024] S2. Add polyaniline and diluent to the reactor and ultrasonically disperse at 40-60℃ for 30-40 min;

[0025] S3. Add epoxy resin to the mixed solution obtained in step S2, stir for 10-20 minutes in a water bath at 75-85℃, then add polyurethane modified graphene oxide-hollow glass microsphere composite material and pretreated short-cut carbon fiber, and stir for 40-50 minutes in a water bath at 75-85℃ to make it evenly mixed.

[0026] S4. Add the curing agent to the mixture obtained in step S3, mix and stir evenly to obtain the slurry;

[0027] S5. Pour the slurry obtained in step S4 into the mold, fill and compact it, heat it to 70-90℃ and cure it for 1-3 hours, and demold to obtain a low-density hydrophobic buoyancy material.

[0028] Furthermore, in step S1, the plasma processing power is 100-200W.

[0029] The beneficial effects of the present invention are as follows: The low-density hydrophobic buoyancy material of the present invention is made by adding polyaniline, polyurethane modified graphene oxide-hollow glass microsphere composite material and short-cut carbon fiber to epoxy resin. The components work together to produce a buoyancy material with low density, hydrophobicity, excellent bulk modulus of elasticity and compressive strength, and good weather resistance. Its structure is simple and easy to use.

[0030] Meanwhile, the preparation method of low-density hydrophobic buoyancy material is simple and easy to control, which is conducive to large-scale industrial production. The low-density hydrophobic buoyancy material obtained has stable quality and features low density, hydrophobicity, excellent bulk elastic modulus and compressive strength, as well as good weather resistance, with superior comprehensive performance. Detailed Implementation

[0031] To facilitate understanding by those skilled in the art, the present invention will be further described below with reference to embodiments. The content mentioned in the embodiments is not intended to limit the present invention.

[0032] Example 1

[0033] In this embodiment, a low-density hydrophobic buoyancy material comprises the following components by weight: 50 parts epoxy resin, 35 parts polyurethane modified graphene oxide-hollow glass microsphere composite material, 15 parts polyaniline, 8 parts chopped carbon fiber, 4 parts diluent, and 1 part curing agent.

[0034] In this embodiment, the polyaniline used is polyaniline from Huanyu Chemical Co., Ltd. with CAS number 5612-44-2. The epoxy resin used is bisphenol A type epoxy resin.

[0035] Furthermore, the polyurethane-modified graphene oxide-hollow glass microsphere composite material comprises the following components in parts by weight: 50 parts of PTMG-1000, 10 parts of isocyanate-grafted graphene oxide-hollow glass microsphere powder, and 12 parts of toluene diisocyanate.

[0036] Furthermore, the preparation method of the polyurethane modified graphene oxide-hollow glass microsphere composite material includes the following steps: PTMG-1000 is dehydrated at 100℃ for 1 hour, then cooled to 85℃, isocyanate-grafted graphene oxide-hollow glass microsphere powder is added, stirred at 85℃ for 1 hour, toluene diisocyanate is slowly added dropwise at 50℃, reacted at 80℃ for 2 hours, and bubbles are removed using a vacuum pump to obtain the polyurethane modified graphene oxide-hollow glass microsphere composite material.

[0037] Furthermore, the preparation method of the isocyanate-grafted graphene oxide-hollow glass microsphere powder includes the following steps:

[0038] A1. Graphene oxide and hollow glass microspheres were dried and then ultrasonicated in DMSO for 0.5 h to form dispersions.

[0039] A2. Add isophorone diisocyanate and DMSO to a reaction flask, stir and heat to 70°C, then slowly add graphene oxide dispersion, followed by 3 drops of catalyst, and stir at 70°C for 3 h; then slowly add hollow glass microsphere dispersion, and stir at 70°C for 8 h.

[0040] A3. The mixture obtained in step A2 is washed with DMSO and acetone respectively, and the solvent is removed under normal pressure to obtain isocyanate-grafted graphene oxide-hollow glass microsphere powder.

[0041] Furthermore, the mass ratio of the graphene oxide, hollow glass microspheres, and isophorone diisocyanate is 1:2:100.

[0042] Furthermore, the graphene oxide has a particle size of 4 μm; the hollow glass microspheres have an average particle size of 40 μm and a density of 0.38 g / cm³. 3 The crushing strength is 30 MPa.

[0043] Furthermore, the catalyst is dibutyltin dilaurate.

[0044] Furthermore, the average diameter of the chopped carbon fibers is 5-9 μm, and the length is 0.8-1.2 mm.

[0045] Furthermore, the diluent is trimethylolpropane triglycidyl ether.

[0046] Furthermore, the curing agent is polyamide 650.

[0047] This embodiment also provides a method for preparing a low-density hydrophobic buoyancy material, comprising the following steps:

[0048] S1. Short-cut carbon fibers are treated with plasma to obtain pretreated short-cut carbon fibers.

[0049] S2. Add polyaniline and diluent to the reactor and ultrasonically disperse at 50°C for 35 min;

[0050] S3. Add epoxy resin to the mixed solution obtained in step S2, stir for 15 minutes in an 80°C water bath, then add polyurethane modified graphene oxide-hollow glass microsphere composite material and pretreated short-cut carbon fiber, and stir for 45 minutes in an 80°C water bath to make it evenly mixed.

[0051] S4. Add the curing agent to the mixture obtained in step S3, mix and stir evenly to obtain the slurry;

[0052] S5. Pour the slurry obtained in step S4 into the mold, fill and compact it, heat it to 80℃ and cure it for 2 hours, and demold it to obtain a low-density hydrophobic buoyancy material.

[0053] Furthermore, in step S1, the plasma processing power is 150W.

[0054] Example 2

[0055] In this embodiment, a low-density hydrophobic buoyancy material comprises the following components by weight: 55 parts epoxy resin, 40 parts polyurethane modified graphene oxide-hollow glass microsphere composite material, 20 parts polyaniline, 10 parts chopped carbon fiber, 6 parts diluent, and 2 parts curing agent.

[0056] This embodiment also provides a method for preparing a low-density hydrophobic buoyancy material, comprising the following steps:

[0057] S1. Short-cut carbon fibers are treated with plasma to obtain pretreated short-cut carbon fibers.

[0058] S2. Add polyaniline and diluent to the reactor and ultrasonically disperse at 50°C for 35 min;

[0059] S3. Add epoxy resin to the mixed solution obtained in step S2, stir for 15 minutes in an 80°C water bath, then add polyurethane modified graphene oxide-hollow glass microsphere composite material and pretreated short-cut carbon fiber, and stir for 45 minutes in an 80°C water bath to make it evenly mixed.

[0060] S4. Add the curing agent to the mixture obtained in step S3, mix and stir evenly to obtain the slurry;

[0061] S5. Pour the slurry obtained in step S4 into the mold, fill and compact it, heat it to 80℃ and cure it for 2 hours, and demold it to obtain a low-density hydrophobic buoyancy material.

[0062] The rest of this embodiment is the same as that in Embodiment 1.

[0063] Example 3

[0064] In this embodiment, a low-density hydrophobic buoyancy material comprises the following components by weight: 50 parts epoxy resin, 35 parts polyurethane modified graphene oxide-hollow glass microsphere composite material, 15 parts polyaniline, 8 parts chopped carbon fiber, 4 parts diluent, and 1 part curing agent.

[0065] This embodiment also provides a method for preparing a low-density hydrophobic buoyancy material, comprising the following steps:

[0066] S1. Short-cut carbon fibers are treated with plasma to obtain pretreated short-cut carbon fibers.

[0067] S2. Add polyaniline and diluent to the reactor and ultrasonically disperse at 50°C for 35 min;

[0068] S3. Add epoxy resin to the mixed solution obtained in step S2, stir for 15 minutes in an 80°C water bath, then add polyurethane modified graphene oxide-hollow glass microsphere composite material and pretreated short-cut carbon fiber, and stir for 45 minutes in an 80°C water bath to make it evenly mixed.

[0069] S4. Add the curing agent to the mixture obtained in step S3, mix and stir evenly to obtain the slurry;

[0070] S5. Pour the slurry obtained in step S4 into the mold, fill and compact it, heat it to 80℃ and cure it for 2 hours, and demold it to obtain a low-density hydrophobic buoyancy material.

[0071] The rest of this embodiment is the same as that in Embodiment 1.

[0072] Comparative Example 1

[0073] This comparative example differs from Example 2 in that an equal amount of epoxy resin is used instead of polyaniline. Specifically, the low-density hydrophobic buoyancy material comprises the following components by weight: 75 parts epoxy resin, 40 parts polyurethane-modified graphene oxide-hollow glass microsphere composite material, 10 parts chopped carbon fiber, 6 parts diluent, and 2 parts curing agent.

[0074] This comparative example also provides a method for preparing a low-density hydrophobic buoyancy material, comprising the following steps:

[0075] S1. Short-cut carbon fibers are treated with plasma to obtain pretreated short-cut carbon fibers.

[0076] S2. Add epoxy resin and diluent to the reactor, stir for 15 minutes in an 80°C water bath, then add polyurethane modified graphene oxide-hollow glass microsphere composite material and pretreated short-cut carbon fibers, and maintain the temperature at 80°C in a water bath for 45 minutes to mix them evenly.

[0077] S4. Add the curing agent to the mixture obtained in step S2, mix and stir evenly to obtain the slurry;

[0078] S5. Pour the slurry obtained in step S3 into the mold, fill and compact it, heat it to 80℃ and cure it for 2 hours, and demold it to obtain a low-density hydrophobic buoyancy material.

[0079] Comparative Example 2

[0080] The difference between this comparative example and Example 2 is that 8-12 parts of graphene oxide-hollow glass microsphere powder were used instead of isocyanate-grafted graphene oxide-hollow glass microsphere powder. The graphene oxide-hollow glass microsphere powder was prepared by blending graphene oxide and hollow glass microspheres at a mass ratio of 1:2. Specifically, the polyurethane-modified graphene oxide-hollow glass microsphere composite material comprises the following components by weight: 50 parts PTMG-1000, 10 parts graphene oxide-hollow glass microsphere powder, and 12 parts toluene diisocyanate.

[0081] Furthermore, the preparation method of the polyurethane-modified graphene oxide-hollow glass microsphere composite material includes the following steps: PTMG-1000 is dehydrated at 100℃ for 1 hour, then cooled to 85℃, graphene oxide-hollow glass microsphere powder and 3 drops of catalyst are added, stirred at 85℃ for 1 hour, toluene diisocyanate is slowly added dropwise at 50℃, reacted at 80℃ for 2 hours, and bubbles are removed using a vacuum pump to obtain the polyurethane-modified graphene oxide-hollow glass microsphere composite material.

[0082] Performance testing

[0083] The performance of the low-density hydrophobic buoyancy materials prepared in Example 2 and Comparative Examples 1-2 was tested.

[0084] The density, compressive strength, elastic modulus, water absorption rate, and damp heat aging of the low-density hydrophobic buoyancy materials prepared in Example 2 and Comparative Examples 1-2 were tested. The test data are shown in Table 1 below:

[0085] Table 1

[0086]

[0087] Density test: The sample is cut into regular rectangular specimens and the density is measured in accordance with GB / T 1033.1-2008 "Determination of density of non-foamed plastics".

[0088] Compression strength test; Uniaxial compression performance test was conducted in accordance with GB / T8813-2008 "Rigid Foamed Plastics Compression Test Method". The cylindrical specimen dimensions were φ (10±0.2) mm in diameter and (20±0.2) mm in height. The loading deformation rate was 1 mm / min at room temperature.

[0089] Bulk modulus test: The bulk modulus was tested according to ASTM D2926, the test method for bulk modulus of composite foam materials.

[0090] Water absorption test: The water absorption rate was tested according to the MIL-S-24154A omnidirectional hydrostatic pressure strength test.

[0091] Humid heat treatment: The low-density hydrophobic buoyancy materials prepared in Example 2 and Comparative Examples 1-2 were placed in a GDJS-150B high and low temperature alternating humid heat test chamber. The test conditions were set as follows: temperature 90℃, humidity 95%, and placed for 72 hours. The compressive strength was then tested.

[0092] The above embodiments are preferred implementations of the present invention. In addition, the present invention can be implemented in other ways. Any obvious substitutions without departing from the concept of the present invention are within the protection scope of the present invention.

Claims

1. A low-density hydrophobic buoyancy material, characterized in that, The composite material comprises the following components by weight: 50-60 parts epoxy resin, 35-45 parts polyurethane-modified graphene oxide-hollow glass microsphere composite material, 15-25 parts polyaniline, 8-12 parts chopped carbon fiber, 4-8 parts diluent, and 1-3 parts curing agent; the polyurethane-modified graphene oxide-hollow glass microsphere composite material comprises the following components by weight: PTMG-1000 The polyurethane-modified graphene oxide-hollow glass microsphere composite material comprises 40-60 parts of isocyanate-grafted graphene oxide-hollow glass microsphere powder, 8-12 parts of isocyanate-grafted graphene oxide-hollow glass microsphere powder, and 10-15 parts of toluene diisocyanate. The preparation method includes the following steps: PTMG-1000 is subjected to dehydration treatment at 95-105℃ for 0.8-1.2h, then cooled to 80-90℃, isocyanate-grafted graphene oxide-hollow glass microsphere powder is added, and the mixture is stirred at 80-90℃ for 0.8-1.2h. Then, toluene diisocyanate is slowly added dropwise at 45-55℃, and the reaction is carried out at 76-80℃ for 1.8-2.2h. The air bubbles are removed using a vacuum pump to obtain the polyurethane-modified graphene oxide-hollow glass microsphere composite material.

2. The low-density hydrophobic buoyancy material according to claim 1, characterized in that: The preparation method of the isocyanate-grafted graphene oxide-hollow glass microsphere powder includes the following steps: A1. Graphene oxide and hollow glass microspheres were dried and then ultrasonicated in DMSO for 0.2-0.7 h to form dispersions. A2. Add isophorone diisocyanate and DMSO to a reaction flask, stir and heat to 60-80℃, then slowly add graphene oxide dispersion, followed by 2-4 drops of catalyst, and stir at 65-75℃ for 2-4 h; then slowly add hollow glass microsphere dispersion, and stir at 65-75℃ for 7-9 h. A3. The mixture obtained in step A2 is washed with DMSO and acetone respectively, and the solvent is removed under normal pressure to obtain isocyanate-grafted graphene oxide-hollow glass microsphere powder.

3. The low-density hydrophobic buoyancy material according to claim 2, characterized in that: The mass ratio of graphene oxide, hollow glass microspheres and isophorone diisocyanate is 0.8-1.2:2:

100.

4. The low-density hydrophobic buoyancy material according to claim 2, characterized in that: The catalyst is dibutyltin dilaurate.

5. The low-density hydrophobic buoyancy material according to claim 1, characterized in that: The average diameter of the chopped carbon fibers is 5-9 μm, and the length is 0.8-1.2 mm.

6. The low-density hydrophobic buoyancy material according to claim 1, characterized in that: The diluent is trimethylolpropane triglycidyl ether.

7. The low-density hydrophobic buoyancy material according to claim 1, characterized in that: The curing agent is polyamide 650.

8. A method for preparing a low-density hydrophobic buoyancy material according to any one of claims 1-7, characterized in that: Includes the following steps: S1. Short-cut carbon fibers are treated with plasma to obtain pretreated short-cut carbon fibers. S2. Add epoxy resin and diluent to the reactor and stir for 15-25 minutes in a water bath at 75-85℃. S3. Add polyaniline, polyurethane-modified graphene oxide-hollow glass microsphere composite material and pretreated short-cut carbon fiber to the mixed solution obtained in step S2, and stir in a water bath at 75-85℃ for 40-50 minutes to make it evenly mixed. S4. Add the curing agent to the mixture obtained in step S3, mix and stir evenly to obtain the slurry; S5. Pour the slurry obtained in step S4 into the mold, fill and compact it, heat it to 70-90℃ and cure it for 1-3 hours, and demold to obtain a low-density hydrophobic buoyancy material.

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