CN104448719B - Organic and inorganic hollow microsphere compounded deepwater buoyancy material and preparation method thereof - Google Patents

Abstract

The invention provides an organic and inorganic hollow microsphere compounded deepwater buoyancy material and a preparation method thereof. The material is prepared from the following components in parts by mass: 100 parts of unsaturated resin, 2-4 parts of a curing agent, 0.5-2 parts of an accelerant, 10-15 parts of organic hollow microspheres and 40 parts of inorganic hollow microspheres. The invention provides the buoyancy material which provides buoyancy to an underwater device for ocean deepwater detection, ocean development and related use. The buoyancy material is low in density, high in strength and excellent in machinable property. The density of the prepared deepwater buoyancy material is 0.40-0.45g/cm<3> and the compression strength is 30-35MPa, so that the buoyancy material meets the request for deepwater universal materials.

Description

Deep-water buoyancy material compounded with organic and inorganic hollow microspheres and its preparation method

technical field

The invention relates to a buoyancy material, and also relates to a preparation method of the buoyancy material. Specifically, it is a buoyancy material for providing buoyancy to underwater devices for ocean deep-water exploration, ocean development and related purposes and a preparation method thereof.

Background technique

With the increasing demand for natural resources and the depletion of land resources, people turn their attention to the resource-rich ocean. Oceanic polymetallic nodules of various elements are widely distributed in the depths of the ocean, and the seabed oil and gas reserves account for about 45% of the world's total. To develop and detect resources in deep water is inseparable from marine equipment, and deep-sea marine equipment requires buoyant materials to provide sufficient net buoyancy. The density and compressive strength of deep-water buoyancy materials directly determine the working performance and working depth of deep-sea equipment. How to reduce the density of deep-water buoyant materials and improve the strength of deep-water buoyant materials has attracted more and more attention.

At present, most of the deep-sea buoyancy materials at home and abroad use resin as the matrix, filled with inorganic hollow microspheres to reduce the density, but the filling of inorganic hollow microspheres is limited by the maximum filling ratio. After exceeding the maximum filling ratio, although the density can continue to decrease , but the resin cannot completely wrap the inorganic hollow microspheres, and the interfacial bonding performance between the resin and the inorganic hollow microspheres is poor, and the finally prepared buoyant material has low compressive strength and high water absorption. In the patent document with the publication number CN103665758, a method for preparing a high-strength solid buoyancy material is disclosed. The method uses hollow microspheres to add fiber pellets to prepare the buoyancy material. This type of material can be used in water depths of 3000 meters, but its density is greater than 0.5g/cm ³ , high water absorption for long-term service. The patent document with the application number 200410030821.6 introduces a solid buoyant material prepared by chemical foaming method. The density of the material is less than 0.33g/cm ³ , and the compressive strength is only 5.5MPa, which cannot be used in water depths above 1000m. In the patent application documents with application numbers 201010552911.7 and 201310065622.8, glass microspheres are used to fill unsaturated resin to prepare buoyant materials at room temperature, but the buoyant materials prepared by the buoyant materials have a strength less than 13 MPa when the density is less than 0.45 g/ ^cm3 , and a density greater than 30 MPa when the strength is greater than 30 MPa. 0.56g/cm ³ . None of the above public documents report that it can be applied to deep water buoyancy materials prepared at room temperature with a water depth of more than 2000m, a compressive strength greater than 30MPa, and a density less than 0.45g/cm ³ .

Contents of the invention

The object of the present invention is to provide a deep-water buoyancy material compounded with organic and inorganic hollow microspheres with low density, high strength and excellent processability. The object of the present invention is also to provide a method for preparing deep-water buoyancy material compounded with organic and inorganic hollow microspheres, which requires less equipment, simple molding process and low cost.

The deep-water buoyancy material compounded by organic and inorganic hollow microspheres of the present invention is composed of 100 parts in parts by mass of unsaturated resin, 2-4 parts of curing agent, 0.5-2 parts of accelerator, 10-15 parts of organic hollow microspheres and Consists of 40 parts of inorganic hollow microspheres.

The organic hollow microspheres are polymer organic microspheres with a hollow structure, a particle diameter of 20 μm, and a density of 0.15 g/cm ³ .

The polymer organic microspheres are hollow epoxy resin microspheres and/or polyethylene hollow microspheres.

The inorganic hollow microspheres are hollow glass microspheres with a particle diameter of 80 μm and a density of 0.3 g/cm ³ .

The hollow of the hollow glass microsphere is filled with air or vacuum.

The unsaturated resin is epoxy vinyl resin. The curing agent selects methyl ethyl ketone peroxide as an initiator. The accelerator is selected from cobalt naphthenate or cobalt isooctanoate accelerator.

The preparation method of the deep-water buoyancy material compounded by organic and inorganic hollow microspheres of the present invention is:

(1) In terms of parts by mass, take 100 parts of unsaturated resin, 2 to 4 parts of curing agent, and 0.5 to 2 parts of accelerator, add them to the reaction kettle, stir and mix evenly with a stirring rod, and obtain resin glue;

(2) In terms of parts by mass, take 10-15 parts of organic hollow microspheres and 40 parts of inorganic hollow microspheres and add them to a vacuum mixer, and mix them uniformly to obtain mixed microspheres;

(3) Add the resin glue into the mixed microspheres, stir in vacuum, the stirring speed is 25r/min, the stirring time is 40min, and mix evenly to obtain the mixed material;

(4) The mixed material is put into a vacuum drying oven, and vacuum degassing at normal temperature;

(5) Pouring into the mold, curing and forming at room temperature.

The invention provides a buoyancy buoyancy material for underwater devices used in ocean deep water exploration, ocean development and related applications. The buoyancy material is a deep water buoyancy material with low density, high strength and excellent processability. Its main feature is a deep-water buoyancy material prepared by compounding organic hollow microspheres and inorganic hollow microspheres.

The main features of the preparation method of the present invention are: low-speed stirring and mixing method of organic hollow glass microspheres and inorganic hollow microspheres. The unsaturated resin is epoxy vinyl resin; the curing agent is a room temperature curing curing agent, which is methyl ethyl ketone peroxide; the accelerator is cobalt naphthenate or cobalt isooctanoate; the organic hollow microspheres are hollow epoxy Resin microspheres and/or polyethylene hollow microspheres, the selected particle size is 20 μm, and the density is 0.15 g/cm ³ ; the inorganic hollow microspheres are hollow glass microspheres, and the selected particle size of the hollow glass microspheres is 80 μm, and the density is 0.15 g/cm 3 . It is 0.3 g/cm ³ . Through reasonable matching of various raw material components and suitable technological process, the deep-water buoyancy material prepared by the present invention has a low density of 0.40 to 0.45g/cm ³ , and a compressive strength of 30 to 35MPa, which meets the requirements of deep-sea general-purpose materials. The forming method of the present invention has lower requirements on equipment, simple forming process and low cost.

detailed description

The following examples describe the present invention in more detail.

Example 1:

The deep-water buoyancy material was prepared by compounding the organic/inorganic hollow microspheres according to the ratio in Table 1, and the specific preparation method was as follows:

(1) In terms of parts by mass, take 100 parts of unsaturated resin, 2 parts of curing agent, and 1 part of accelerator, add them into the reaction kettle, mix them evenly, and obtain the resin glue;

(2) In terms of parts by mass, 10 parts of organic hollow microspheres and 40 parts of inorganic hollow microspheres are added to a vacuum mixer and mixed evenly;

(3) Add the resin glue solution obtained in the above step 1 and the mixed hollow microspheres obtained in step 2 to a vacuum mixer, stir in a vacuum, the stirring speed is 25r/min, the stirring time is 40min, and mix evenly;

(4) Put the mixed material obtained in the above step 3 into a vacuum drying oven, and vacuum degassing at normal temperature;

(5) pour the material obtained in the above step 4 into various molds, and solidify and form at room temperature.

Table 1 Organic/inorganic hollow microsphere compound preparation deep water buoyancy material components by weight

epoxy vinyl resin Hardener Initiator Organic hollow microspheres Inorganic hollow microspheres Example 1 100 2 1 10 40

In Table 1: methyl ethyl ketone peroxide is selected as the curing agent; cobalt naphthenate or cobalt isooctanoate is selected as the accelerator; the organic hollow microspheres are hollow epoxy resin microspheres and/or polyethylene hollow microspheres, and the selected particle size is 20 μm , with a density of 0.15g/cm ³ ; the inorganic hollow microspheres are hollow glass microspheres with a particle size of 80 μm and a density of 0.3 g/cm ³ .

The performance test was carried out on the material formed in Example 1. The size of the compressive strength test piece was 50×50×50mm, the size of the water absorption test piece was 100×100×100mm, and the test conditions were hydrostatic pressure 20MPa, pressure holding 24h.

The relevant performance of table 2 embodiment 1

It can be seen from Table 2 that the deep-water buoyancy material prepared by compounding the organic/inorganic hollow microspheres involved in the present invention has a low density, with a density of 0.45g/cm ³ and a compressive strength of 35MPa, which can be applied to oceans with a water depth of more than 2000m Environment, especially under the isostatic pressure of 20MPa, the water absorption rate is less than 1% for 24 hours under pressure. The deep-water buoyancy material prepared by compounding the organic/inorganic hollow microspheres can still be subjected to mechanical processing such as sawing, planing, grinding, inlaying and related follow-up processing after solidification and molding. And a variety of flexible waterproof coatings can be used for surface coating, and the base material and the top coat are tightly bonded.

Example 2:

Prepare the deep-water buoyancy material according to the ratio of organic/inorganic hollow microspheres in Table 3. The specific preparation method is as follows:

(1) In terms of parts by mass, take 100 parts of unsaturated resin, 2 parts of curing agent, and 1 part of accelerator, add them into the reaction kettle, mix them evenly, and obtain the resin glue;

(2) In terms of parts by mass, 12 parts of organic hollow microspheres and 40 parts of inorganic hollow microspheres are added to a vacuum mixer and mixed evenly;

(3) Add the resin glue solution obtained in the above step 1 and the mixed hollow microspheres obtained in step 2 to a vacuum mixer, stir in a vacuum, the stirring speed is 25r/min, the stirring time is 40min, and mix evenly;

(4) Put the mixed material obtained in the above step 3 into a vacuum drying oven, and vacuum degassing at normal temperature;

(5) pour the material obtained in the above step 4 into various molds, and solidify and form at room temperature.

Table 3 Composition by weight of lightweight thermal insulation materials for marine deep-water pipelines

epoxy vinyl resin Hardener Initiator Organic hollow microspheres Inorganic hollow microspheres Example 2 100 2 1 12 40

In Table 3: methyl ethyl ketone peroxide is selected as the curing agent; cobalt naphthenate or cobalt isooctanoate is selected as the accelerator; the organic hollow microspheres are hollow epoxy resin microspheres and/or polyethylene hollow microspheres, and the selected particle size is 20 μm , with a density of 0.15g/cm ³ ; the inorganic hollow microspheres are hollow glass microspheres with a particle size of 80 μm and a density of 0.3 g/cm ³ .

The performance of the material molded in Example 2 was tested. The size of the compressive strength test piece was 50×50×50mm, the size of the water absorption test piece was 100×100×100mm, and the test conditions were hydrostatic pressure 20MPa, pressure holding 24h.

The relevant performance of table 4 embodiment 2

It can be seen from Table 4 that the deep-water buoyancy material prepared by compounding the organic/inorganic hollow microspheres involved in the present invention has a low density of 0.44g/cm ³ and a compressive strength of 33MPa, which can be applied to oceans with a water depth of more than 2000m Environment, especially under the isostatic pressure of 20MPa, the water absorption rate is less than 1% for 24 hours under pressure. The deep-water buoyancy material prepared by compounding the organic/inorganic hollow microspheres can still be subjected to mechanical processing such as sawing, planing, grinding, inlaying and related follow-up processing after solidification and molding. And a variety of flexible waterproof coatings can be used for surface coating, and the base material and the top coat are tightly bonded.

Example 3:

The deep-water buoyancy material was prepared by compounding the organic/inorganic hollow microspheres according to the ratio in Table 5, and the specific preparation method was as follows:

(1) In terms of parts by mass, take 100 parts of unsaturated resin, 2 parts of curing agent, and 1 part of accelerator, add them into the reaction kettle, mix them evenly, and obtain the resin glue;

(2) In terms of parts by mass, 12 parts of organic hollow microspheres and 40 parts of inorganic hollow microspheres are added to a vacuum mixer and mixed evenly;

(3) Add the resin glue solution obtained in the above step 1 and the mixed hollow microspheres obtained in step 2 to a vacuum mixer, stir in a vacuum, the stirring speed is 25r/min, the stirring time is 40min, and mix evenly;

(4) Put the mixed material obtained in the above step 3 into a vacuum drying oven, and vacuum degassing at normal temperature;

(5) pour the material obtained in the above step 4 into various molds, and solidify and form at room temperature.

Table 5 Composition by weight of lightweight thermal insulation materials for marine deep-water pipelines

epoxy vinyl resin Hardener Initiator Organic hollow microspheres Inorganic hollow microspheres Example 3 100 2 1 15 40

In Table 5: methyl ethyl ketone peroxide is selected as the curing agent; cobalt naphthenate or cobalt isooctanoate is selected as the accelerator; the organic hollow microspheres are hollow epoxy resin microspheres and/or polyethylene hollow microspheres, and the selected particle size is 20 μm , with a density of 0.15g/cm ³ ; the inorganic hollow microspheres are hollow glass microspheres with a particle size of 80 μm and a density of 0.3 g/cm ³ .

The performance test was carried out on the material formed in Example 3. The size of the compressive strength test piece was 50×50×50mm, the size of the water absorption test piece was 100×100×100mm, and the test conditions were hydrostatic pressure 20MPa, pressure holding 24h.

The relevant performance of table 6 embodiment 3

It can be seen from Table 6 that the deep-water buoyancy material prepared by compounding the organic/inorganic hollow microspheres involved in the present invention has a low density of 0.41g/cm ³ and a compressive strength of 30MPa, which can be applied to oceans with a water depth of more than 2000m Environment, especially under the isostatic pressure of 20MPa, the water absorption rate is less than 1% for 24 hours under pressure. The deep-water buoyancy material prepared by compounding the organic/inorganic hollow microspheres can still be subjected to mechanical processing such as sawing, planing, grinding, inlaying and related follow-up processing after solidification and molding. And a variety of flexible waterproof coatings can be used for surface coating, and the base material and the top coat are tightly bonded.

The deep-water buoyancy material is prepared by compounding the organic/inorganic hollow microspheres of the invention, wherein the organic hollow glass microspheres and the inorganic hollow microspheres are stirred and mixed at a low speed.

The content not described in this embodiment is the prior art, so it will not be described in detail.

The advantages of the deep-water buoyancy material prepared by compounding organic/inorganic hollow microspheres of the present invention: the material formula is flexible, and the dosage of each component can be adjusted within the formula range according to the water depth of the product to achieve a lightweight material that matches the depth of use; The combination of microspheres and inorganic hollow microspheres greatly reduces the density of the buoyancy material, and at the same time has higher strength; the density is 0.40 to 0.45g/cm ³ , the compressive strength is 30 to 35MPa, which meets the requirements of deep-sea general-purpose materials, and the quality Excellent, and the molding method has lower requirements on equipment, simple molding process and low cost.

The unsaturated resin in the present invention is an epoxy vinyl resin, which has the characteristics of low viscosity, low density and high strength after curing.

The organic hollow microspheres used in the invention have uniform particle size, high compressive strength, and high interface bonding force with the matrix resin.

The inorganic microsphere hollow glass microsphere used in the invention has uniform particle size, high floating rate and good pressure resistance.

The curing agent used in the present invention is a curing agent at room temperature, which can effectively protect the mechanical properties of the organic hollow microspheres and ensure the quality of the buoyancy material. The accelerator used is cobalt salt, which can effectively control the reaction time and effectively control the uniform mixing of materials. The organic hollow microspheres are hollow epoxy resin microspheres and/or polyethylene hollow microspheres, the selected particle diameter is 20 μm, and the density is 0.15 g/cm ³ ; the inorganic hollow microspheres are hollow glass microspheres, the The hollow glass microspheres have a particle size of 80 μm and a density of 0.3 g/cm ³ . According to the principle of compounding, the closest packing is achieved, the amount of microspheres is increased, the density of the system is reduced, and the quality of the material is guaranteed.

In the present invention, organic hollow microspheres, inorganic hollow microspheres and unsaturated resins are reasonably matched and organically combined and prepared according to a scientific solidification molding process, so that the prepared deep-water buoyancy material has the performance characteristics of light weight, high strength and good compactness , and the preparation method is simple, efficient and easy to operate.

The above are only preferred embodiments of the present invention, and are not intended to limit the present invention in any form. Any simple modifications, equivalent changes and modifications made to the above embodiments according to the technical essence of the present invention still belong to within the scope of the technical solutions of the present invention.

Claims (4)

1. a kind of organic deep water buoyant material being compounded with inorganic hollow microspheres, be is characterized in that: is oxireme by mass fraction 100 parts of base resin, 2 parts of methyl ethyl ketone peroxide, cobalt naphthenate or 1 part of cobalt iso-octoate, particle diameter are 20 μm and density is 0.15g/cm³ Hollow epoxide resin microballoon and/or 10 parts of polyethylene tiny balloon and particle diameter is 80 μm and density is 0.3g/cm³Hollow glass 40 parts of compositions of glass microballoon.

2. organic deep water buoyant material being compounded with inorganic hollow microspheres according to claim 1, be is characterized in that: described sky Heart glass microsphere hollow be filled with air or be vacuum.

3. a kind of preparation method of organic deep water buoyant material being compounded with inorganic hollow microspheres, be is characterized in that:

(1) in terms of mass fraction, 100 parts of epoxy vingl ester resin, 2 parts of methyl ethyl ketone peroxide, cobalt naphthenate or cobalt iso-octoate 1 are taken Part, add in reactor, be uniformly mixed with stirring rod, obtain resin adhesive liquid；

(2) in terms of mass fraction, take particle diameter be 20 μm and density be 0.15g/cm³Hollow epoxide resin microballoon and/or polyethylene 10 parts of tiny balloon is 80 μm with particle diameter and density is 0.3g/cm³40 parts of addition de-airing mixers of hollow glass microballoon in, mix Close and uniformly obtain mixing microballoon；

(3) described resin adhesive liquid is added in described mixing microballoon, vacuum stirring, mixing speed 25r/min, mixing time 40min, mixes and obtains mixed material；

(4) described mixed material is put in vacuum drying chamber, normal-temperature vacuum deaeration；

(5) it is poured in mould, normal temperature cure is molded.

4. the preparation method of organic deep water buoyant material compounding with inorganic hollow microspheres according to claim 3, it is special Levying is: described hollow glass micro-ball hollow be filled with air or be vacuum.