1. The ultra-high-strength low-density full-sea-depth solid buoyancy material is characterized by comprising the following raw material components in parts by weight: 100 parts of epoxy resin, 25-100 parts of pretreated hollow glass beads, 10-50 parts of diluent, 50-120 parts of curing agent and 0.1-3 parts of catalyst.

2. The ultra-high strength low density full sea depth solid buoyancy material of claim 1,the method is characterized in that: the density of the hollow glass beads before pretreatment is 0.3-0.6 g/cm³Particle size distribution D₅₀15 to 70 μm, 1 to 2 μm in wall thickness and 30 to 120MPa in compressive strength.

3. The ultra-high strength low density full sea depth solid buoyancy material of claim 1, wherein: the epoxy resin is one of bisphenol A epoxy resin, bisphenol F epoxy resin, hybrid epoxy resin or mixed epoxy resin.

4. The ultra-high strength low density full sea depth solid buoyancy material of claim 1, wherein: the catalyst is one of N, N-dimethylbenzylamine, 2,4, 6-tri (dimethylaminomethyl) phenol, bisphenol A, polythiol or salicylic acid.

5. The ultra-high strength low density full sea depth solid buoyancy material of claim 1, wherein: the curing agent is one of methyl tetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride, polyamide, diethylenetriamine and triethylene tetramine.

6. The ultra-high strength low density full sea depth solid buoyancy material of claim 1, wherein: the diluent is one or a mixture of butyl glycidyl ether, ethylene glycol diglycidyl ether, phenyl glycidyl ether, benzyl glycidyl ether and o-tolyl glycidyl ether.

7. The method for preparing the ultrahigh-strength low-density full-sea-depth solid buoyancy material according to any one of claims 1 to 6, wherein the method comprises the following steps:

(1) the compression resistance of the hollow glass beads is preferably as follows: putting the hollow glass beads into a self-made water isostatic pressing screening machine, applying isostatic pressing optimization of more than or equal to 30MPa, performing bleaching, taking the bleaching material, and drying to obtain the hollow glass beads with optimized compression resistance;

(2) grading the hollow glass beads: putting the hollow glass beads obtained in the step (1) into an airflow classifier for particle size classification to obtain classified hollow glass beads;

(3) surface modification of hollow glass beads: reacting the graded hollow glass beads obtained in the step (2) with a surface modifier to obtain surface-modified hollow glass beads, wherein the surface modifier is one or a mixture of silane coupling agent, titanate coupling agent and surfactant;

(4) stirring epoxy resin, surface modified hollow glass beads and a diluent in corresponding parts by weight in a vacuum defoaming stirrer at 50-60 ℃ for 20-30 min, adding a curing agent and a catalyst in corresponding parts by weight, continuously stirring for 20min, injecting the obtained mixture into a mold, carrying out vacuum defoaming for 30min, putting the mold into a vacuum drying oven for curing and molding, sequentially carrying out curing at 110 ℃ for 2h and at 130 ℃ for 4h, cooling, and demolding to prepare the ultrahigh-strength low-density full-sea-depth solid buoyancy material.

Background

With the rise and development of ocean development science, human beings have more and more exploration on the seabed world, and the submerging depth is deeper and deeper, so that a buoyancy material which can be applied to deep sea is urgently needed to ensure the safe use of deep water equipment.

At present, 6000-meter grade buoyancy materials are developed in Europe, America, Japan and Russia, and standard series commercial products are formed. A few companies are also able to provide 11000 meters of buoyant material, such as the European Trelleberg Offshore, the American Telleborg Offshore, the American Engineered Synthesis Systems, ESS, the Australian Ron alcohol deep sea series, and others. However, the high-end technologies in foreign countries basically set barriers to China, and the existing large-depth buoyancy materials in China, particularly 11000 meters, can only depend on import, so that the investment of deepwater engineering is increased.

Compared with countries such as America, Japan, Russia and the like with developed deep diving technology, the research on the solid buoyancy material is started late in China and has a large difference with developed countries, most of the 6000-plus-11000-meter buoyancy materials prepared in China still adopt hollow glass beads produced by America 3M company, although the performance of the buoyancy material is improved to meet the requirement of the water depth environment by optimizing the mixing ratio of the buoyancy material and adopting polyurea coatings and other means, the performance of the buoyancy material is unstable due to the compressive strength of the glass beads, and especially the performance of the buoyancy material is rapidly reduced after the coatings are damaged.

Disclosure of Invention

The invention aims to solve the first technical problem of providing an ultrahigh-strength low-density full-sea-depth solid buoyancy material which is high in strength, low in density and good in compression resistance.

The second technical problem to be solved by the invention is to provide the preparation method of the ultrahigh-strength low-density full-sea-depth solid buoyancy material, which has the advantages of simple steps, convenience in construction and low cost.

In order to solve the first technical problem, the invention provides an ultrahigh-strength low-density full-sea-depth solid buoyancy material which comprises the following raw material components in parts by weight: 100 parts of epoxy resin, 25-100 parts of pretreated hollow glass beads, 10-50 parts of diluent, 50-120 parts of curing agent and 0.1-3 parts of catalyst.

Preferably, the density of the hollow glass beads before pretreatment is 0.3-0.6 g/cm³Particle size distribution D₅₀15 to 70 μm, 1 to 2 μm in wall thickness and 30 to 120MPa in compressive strength.

Preferably, the epoxy resin is one of bisphenol a type epoxy resin, bisphenol F type epoxy resin, hybrid type epoxy resin or hybrid type epoxy resin.

Preferably, the catalyst is one of N, N-dimethylbenzylamine, 2,4, 6-tris (dimethylaminomethyl) phenol, bisphenol A, polythiol or salicylic acid.

Preferably, the curing agent is one of methyl tetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride, polyamide, diethylenetriamine and triethylene tetramine.

Preferably, the diluent is one or a mixture of more of butyl glycidyl ether, ethylene glycol diglycidyl ether, phenyl glycidyl ether, benzyl glycidyl ether and o-tolyl glycidyl ether.

For the sake of simplicity, the ultra-high strength low density full-sea-depth solid buoyancy material of the present invention is referred to as the present material hereinafter.

The material has the advantages that: the material has high strength, low density and good compression resistance effect.

In order to solve the second technical problem, the invention provides a preparation method of an ultrahigh-strength low-density full-sea-depth solid buoyancy material, which comprises the following steps:

(1) the compression resistance of the hollow glass beads is preferably as follows: putting the hollow glass beads into a self-made water isostatic pressing screening machine, applying isostatic pressing optimization of more than or equal to 30MPa, performing bleaching, taking the bleaching material, and drying to obtain the hollow glass beads with optimized compression resistance;

(2) grading the hollow glass beads: putting the hollow glass beads obtained in the step (1) into an airflow classifier for particle size classification to obtain classified hollow glass beads;

(3) surface modification of hollow glass beads: reacting the graded hollow glass beads obtained in the step (2) with a surface modifier to obtain surface-modified hollow glass beads, wherein the surface modifier is one or a mixture of silane coupling agent, titanate coupling agent and surfactant;

(4) stirring epoxy resin, surface modified hollow glass beads and a diluent in corresponding parts by weight in a vacuum defoaming stirrer at 50-60 ℃ for 20-30 min, adding a curing agent and a catalyst in corresponding parts by weight, continuously stirring for 20min, injecting the obtained mixture into a mold, carrying out vacuum defoaming for 30min, putting the mold into a vacuum drying oven for curing and molding, sequentially carrying out curing at 110 ℃ for 2h and at 130 ℃ for 4h, cooling, and demolding to prepare the ultrahigh-strength low-density full-sea-depth solid buoyancy material.

For the sake of simple explanation, the preparation method of the ultra-high-strength low-density full-sea-depth solid buoyancy material is simply referred to as the method below.

The method has the advantages that: according to the method, the high-quality ultrahigh-strength hollow glass beads are obtained by adopting a hollow glass bead pretreatment method, the hollow glass beads with low compressive strength are firstly removed through compressive optimization, the particle size distribution of the hollow glass beads is narrower through grading, the compressive strength of the hollow glass beads with close particle sizes is also close, so that the compressive strength of the hollow glass beads is obviously improved, and finally, the dispersibility and compatibility of the hollow glass beads in an epoxy matrix are improved through surface treatment, so that the prepared solid buoyancy material shows that the existing solid buoyancy material has higher strength and lower density in the same water depth environment. The method has the advantages of simple steps, convenient construction and low cost.

Drawings

FIG. 1 is a photograph of a preferred front polarizing microscope for compression resistance according to an embodiment.

FIG. 2 is a photograph of a preferred rear deflection microscope with compression resistance according to one embodiment.

FIG. 3 is a photograph of a polarization microscope before the two-stage classification of the examples.

FIG. 4 is a two-step rear polarization microscope picture of the embodiment.

FIG. 5 is a polarized microscope photograph of the buoyant material prepared before surface modification of the hollow glass microspheres of example two.

FIG. 6 is a polarized microscope photograph of the buoyant material prepared before surface modification of the hollow glass microspheres of example two.

Detailed Description

The first embodiment is as follows:

an ultrahigh-strength low-density full-sea deep solid buoyancy material comprises the following raw material components in parts by weight: 100 parts of epoxy resin, 70 parts of pretreated hollow glass beads, 15 parts of diluent, 80 parts of curing agent and 0.5 part of catalyst.

The density of the hollow glass beads before pretreatment is 0.36-0.38 g/cm³Particle size distribution D₅₀47 mu m, 1-2 mu m of wall thickness and 38Mpa of compressive strength, and a product of type 38P5500 of Kaishan base materials, Inc. of Anhui.

The epoxy resin is bisphenol A epoxy resin 8125 with an epoxy value of 0.51eq/100g, which is purchased from Nantong star plastics, Inc.

The catalyst is 2,4, 6-tri (dimethylaminomethyl) phenol, and is purchased from Zhang hong Kong Yuanbang chemical materials Co.

The curing agent is methyl tetrahydrophthalic anhydride which is purchased from Nantong star synthetic materials Co.

The diluent is butyl glycidyl ether and is purchased from Shanghai Homing chemical company Limited.

The preparation method of the ultrahigh-strength low-density full-sea-depth solid buoyancy material comprises the following steps:

(1) the compression resistance of the hollow glass beads is preferably as follows: putting the hollow glass beads into a self-made water isostatic pressing screening machine, applying isostatic pressing optimization of 30MPa, carrying out bleaching, taking floating objects and drying to obtain the hollow glass beads with optimized compression resistance, wherein the compressive strength of the hollow glass beads with optimized compression resistance is 50MPa, and the polarized light microscope pictures before and after the optimized compression resistance are shown in the figure 1 and the figure 2;

(2) grading the hollow glass beads: placing the hollow glass beads obtained in the step (1) into an airflow classifier for particle size classification to obtain classified hollow glass beads, wherein the particle size distribution D of the classified hollow glass beads₅₀26 μm;

(3) surface modification of hollow glass beads: reacting the graded hollow glass microspheres obtained in the step (2) with a surface modifier to obtain surface-modified hollow glass microspheres, wherein the surface modifier is a mixture of silane coupling agents KH-550 and CG-104, the mass ratio of the silane coupling agents KH-550 to CG-104 is 3:1, and the surface modifier is purchased from Jiangxi Chenguang New materials GmbH;

(4) stirring epoxy resin, surface modified hollow glass beads and a diluent in corresponding parts by weight in a vacuum defoaming stirrer at 50 ℃ for 30min, adding a curing agent and a catalyst in corresponding parts by weight, continuously stirring for 20min, injecting the obtained mixture into a mold, carrying out vacuum defoaming for 30min, putting the mold into a vacuum drying oven for curing and molding, cooling and demolding to prepare the ultrahigh-strength low-density full-sea-depth solid buoyancy material, wherein the curing temperature is 2h at 110 ℃ and 4h at 130 ℃.

Through inspection, the density of the ultra-high-strength low-density full-sea-depth solid buoyancy material prepared by the embodiment is 0.63g/cm³The compression strength is 80MPa, and the water absorption rate under the hydrostatic pressure environment of 100MPa is 0.41 percent.

Example two:

an ultrahigh-strength low-density full-sea deep solid buoyancy material comprises the following raw material components in parts by weight: 100 parts of epoxy resin, 80 parts of pretreated hollow glass beads, 15 parts of diluent, 80 parts of curing agent and 0.5 part of catalyst.

The density of the hollow glass beads before pretreatment is 0.42-0.45 g/cm³Particle size distribution D₅₀35 mu M, 1-2 mu M of wall thickness and 82Mpa of compressive strength, and the product is M45 model of Anhui Kaishan base materials Co.

The epoxy resin is bisphenol A epoxy resin 8125 with an epoxy value of 0.51eq/100g, which is purchased from Nantong star plastics, Inc.

The catalyst is 2,4, 6-tri (dimethylaminomethyl) phenol, and is purchased from Zhang hong Kong Yuanbang chemical materials Co.

The curing agent is methyl tetrahydrophthalic anhydride which is purchased from Nantong star synthetic materials Co.

The diluent is butyl glycidyl ether and is purchased from Shanghai Homing chemical company Limited.

The preparation method of the ultrahigh-strength low-density full-sea-depth solid buoyancy material comprises the following steps:

(1) the compression resistance of the hollow glass beads is preferably as follows: putting the hollow glass beads into a self-made water isostatic pressing screening machine, applying 100MPa isostatic pressing optimization, then carrying out bleaching, taking floating objects and drying to obtain the hollow glass beads with optimized compression resistance, wherein the compression strength of the hollow glass beads with optimized compression resistance is 110 MPa;

(2) grading the hollow glass beads: placing the hollow glass beads obtained in the step (1) into an airflow classifier for particle size classification to obtain classified hollow glass beads, wherein the particle size distribution D of the classified hollow glass beads₅₀The size of the sample is 21 μm, and the images of the polarizing microscope before and after grading are shown in FIGS. 3 and 4;

(3) surface modification of hollow glass beads: reacting the graded hollow glass microspheres obtained in the step (2) with a surface modifier to obtain surface-modified hollow glass microspheres, wherein the surface modifier is a mixture of silane coupling agents KH-550 and CG-104, the mass ratio of the silane coupling agents KH-550 to CG-104 is 3:1, the mixture is purchased from Jiangxi Cheng Guang New materials GmbH, and the polarized microscope pictures of the buoyancy materials prepared before and after the surface modification of the hollow glass microspheres are shown in figures 5 and 6;

(4) stirring epoxy resin, surface modified hollow glass beads and a diluent in corresponding parts by weight in a vacuum defoaming stirrer at 50 ℃ for 30min, adding a curing agent and a catalyst in corresponding parts by weight, continuously stirring for 20min, injecting the obtained mixture into a mold, carrying out vacuum defoaming for 30min, putting the mold into a vacuum drying oven for curing and molding, cooling and demolding to prepare the ultrahigh-strength low-density full-sea-depth solid buoyancy material, wherein the curing temperature is 2h at 110 ℃ and 4h at 130 ℃.

Through inspection, the density of the ultra-high-strength low-density full-sea-depth solid buoyancy material prepared by the embodiment is 0.67g/cm³The water absorption rate under the hydrostatic pressure environment with the compression strength of 118MPa and 140MPa is 0.49 percent.

Comparative experiment:

comparative example 1:

the difference between the comparative example and the second example is that: the adopted hollow glass bead pretreatment process does not undergo pressure-resistant optimization and classification, and only one surface treatment process is carried out. The density of the prepared ultra-high-strength low-density full-sea-depth solid buoyancy material is 0.68g/cm³The compressive strength is 97MPa, and the water absorption rate under the hydrostatic pressure environment of 125MPa is 0.62 percent.

Comparative example 2:

the difference between the comparative example and the second example is that: the hollow glass beads used were not pretreated. The density of the prepared ultra-high-strength low-density full-sea-depth solid buoyancy material is 0.71g/cm³The compressive strength is 85MPa, and the water absorption rate under the hydrostatic pressure environment of 120MPa is 0.87%.