阅读说明：本技术 一种高性能固体浮力材料及其制备方法 (High-performance solid buoyancy material and preparation method thereof ) 是由 刘刚 于 2020-08-17 设计创作，主要内容包括：本发明提供了一种高性能固体浮力材料及其制备方法,固体浮力材料以重量份数计,包括以下组分：双环戊二烯40～70份、钌卡宾络合物催化剂0.2～5.0份、硅烷偶联剂0.2～5.0份、阻聚剂5～40份和空心玻璃微珠20～60份。本发明提供的固体浮力材料在上述组分的共同作用下具有较低密度、高强度和低吸水率特性,适用于载人潜水器等要求极高的应用场景。(The invention provides a high-performance solid buoyancy material and a preparation method thereof, wherein the solid buoyancy material comprises the following components in parts by weight: 40-70 parts of dicyclopentadiene, 0.2-5.0 parts of ruthenium carbene complex catalyst, 0.2-5.0 parts of silane coupling agent, 5-40 parts of polymerization inhibitor and 20-60 parts of hollow glass beads. The solid buoyancy material provided by the invention has the characteristics of low density, high strength and low water absorption under the combined action of the components, and is suitable for application scenes with extremely high requirements such as manned submersible vehicles and the like.)

1. A high-performance solid buoyancy material comprises the following components in parts by weight:

40-70 parts of dicyclopentadiene, 0.2-5.0 parts of ruthenium carbene complex catalyst, 0.2-5.0 parts of silane coupling agent, 5-40 parts of polymerization inhibitor and 20-60 parts of hollow glass beads.

2. The high-performance solid buoyancy material according to claim 1, wherein the hollow glass beads have a diameter of 5 to 200 μm and a true density of 50 to 800kg/cm³The isostatic strength is 1-250 MPa.

3. The high performance solid buoyancy material according to claim 1, wherein the silane coupling agent is selected from trimethoxysilane and/or tetrakis (2-methoxyethoxy) silane;

the polymerization inhibitor is selected from one or more of styrene, acetone and methanol.

4. A preparation method of the high-performance solid buoyancy material according to any one of claims 1 to 3 comprises the following steps:

a) mixing dicyclopentadiene, a ruthenium carbene complex catalyst, a silane coupling agent and a polymerization inhibitor to obtain a mixture;

b) adding hollow glass beads into the mixture, and stirring to obtain a liquid buoyancy material;

c) vibrating the liquid buoyancy material for 5 min-24 h to divide the material into three layers, wherein the bottom layer is provided with sunken glass beads, the middle layer is provided with redundant liquid material and the upper layer is provided with well-packed glass bead material;

d1) heating and curing the layered materials, and cutting off the bottom layer material and the middle layer material to obtain the high-performance solid buoyancy material;

or d2) discharging the bottom layer material and the middle layer material in the layered materials, then heating and curing to obtain the high-performance solid buoyancy material.

5. The method of claim 4, wherein the vibrating is performed in a mold;

the bottom of the mould is provided with a discharge outlet.

6. The preparation method according to claim 4, wherein the heating temperature is 60-80 ℃ and the heating time is 6-12 h.

7. The preparation method according to claim 4, wherein the curing temperature is 115-130 ℃ and the curing time is 2-8 h.

Technical Field

The invention belongs to the technical field of buoyancy materials, and particularly relates to a high-performance solid buoyancy material and a preparation method thereof.

Background

Compared with the common solid buoyancy material, the solid buoyancy material applied to the manned submersible has higher performance and reliability requirements. For example, the solid buoyancy material applied to the manned submersible requires that the compressive strength is more than 1.5 times of the working water pressure, and the water absorption rate is not more than one thousandth after 24 hours under the working water pressure; the compressive strength of the solid buoyancy material applied to the autonomous submersible or underwater robot is only 1.25 times of the working water pressure, and the water absorption rate of the solid buoyancy material is not more than one percent after 24 hours under the working water pressure. Meanwhile, as the manned submersible is larger in load and more limited in space, a lower density of solid buoyancy material is required to achieve higher buoyancy and increase load capacity at the same volume.

The traditional solid buoyancy material is generally formed by heating, curing and molding after uniformly stirring epoxy resin, curing agent and hollow glass beads. Due to the fact that the epoxy resin is high in viscosity and the hollow glass beads are brittle, the hollow glass beads are broken frequently in the stirring process, and performance of the solid buoyancy material product is reduced.

Disclosure of Invention

In view of the above, the present invention is directed to a high performance solid buoyancy material with low density, high strength and low water absorption rate, and a method for preparing the same.

The invention provides a high-performance solid buoyancy material which comprises the following components in parts by weight:

40-70 parts of dicyclopentadiene, 0.2-5.0 parts of ruthenium carbene complex catalyst, 0.2-5.0 parts of silane coupling agent, 5-40 parts of polymerization inhibitor and 20-60 parts of hollow glass beads.

Preferably, the diameter of the hollow glass bead is 5-200 microns, and the true density is 50-800 kg/cm³The isostatic strength is 1-250 MPa.

Preferably, the silane coupling agent is selected from trimethoxysilane and/or tetrakis (2-methoxyethoxy) silane;

the polymerization inhibitor is selected from one or more of styrene, acetone and methanol.

The invention provides a preparation method of a high-performance solid buoyancy material, which comprises the following steps:

a) mixing dicyclopentadiene, a ruthenium carbene complex catalyst, a silane coupling agent and a polymerization inhibitor to obtain a mixture;

b) adding hollow glass beads into the mixture, and stirring to obtain a liquid buoyancy material;

c) vibrating the liquid buoyancy material for 5 min-24 h to divide the material into three layers, wherein the bottom layer is provided with sunken glass beads, the middle layer is provided with redundant liquid material and the upper layer is provided with well-packed glass bead material;

d1) heating and curing the layered materials, and cutting off the bottom layer material and the middle layer material to obtain the high-performance solid buoyancy material;

or d2) discharging the bottom layer material and the middle layer material in the layered materials, and then heating and curing to obtain the high-performance solid buoyancy material.

Preferably, the vibration is performed in a mould;

the bottom of the mould is provided with a discharge outlet.

Preferably, the heating temperature is 60-80 ℃, and the heating time is 6-12 h.

Preferably, the curing temperature is 115-130 ℃, and the curing time is 2-8 h.

The invention provides a high-performance solid buoyancy material which comprises the following components in parts by weight: 40-70 parts of dicyclopentadiene, 0.2-5.0 parts of ruthenium carbene complex catalyst, 0.2-5.0 parts of silane coupling agent, 5-40 parts of polymerization inhibitor and 20-60 parts of hollow glass beads. The solid buoyancy material provided by the invention has the characteristics of low density, high strength and low water absorption under the combined action of the components, and is suitable for application scenes with extremely high requirements such as manned submersible vehicles and the like.

Drawings

Fig. 1 is a schematic structural diagram of a mold used in the method provided by the present invention.

Detailed Description

The invention provides a high-performance solid buoyancy material which comprises the following components in parts by weight:

40-70 parts of dicyclopentadiene, 0.2-5.0 parts of ruthenium carbene complex catalyst, 0.2-5.0 parts of silane coupling agent, 5-40 parts of polymerization inhibitor and 20-60 parts of hollow glass beads.

In the invention, the polymerization inhibitor is a volatile solvent, mainly plays a role in slowing down the polymerization reaction of dicyclopentadiene, prolonging the operable time, and volatilizes in the reaction process to further reduce the density of the solid buoyancy material. The polymerization inhibitor is preferably selected from styrene, acetone, methanol, and the like.

In the invention, the diameter of the hollow glass bead is 5-200 microns, and the true density is 50-800 kg/cm³The isostatic strength is 1-250 MPa. In specific embodiments, the hollow glass microspheres are selected from the group consisting of hollow glass microspheres having a true density of 0.15g/cc, crushing strength of 2.0 MPa; or hollow glass beads having a true density of 0.46g/cc and a crushing strength of 110 MPa.

The silane coupling agent is selected from trimethylsilane and/or tetra (2-methoxyethoxy) silane.

The solid buoyancy material provided by the invention has the advantages of lower density, high strength and low water absorption.

The invention provides a preparation method of a high-performance solid buoyancy material, which comprises the following steps:

a) mixing dicyclopentadiene, a ruthenium carbene complex catalyst, a silane coupling agent and a polymerization inhibitor to obtain a mixture;

b) adding hollow glass beads into the mixture, and stirring to obtain a liquid buoyancy material;

c) vibrating the liquid buoyancy material for 5 min-24 h to divide the material into three layers, wherein the bottom layer is provided with sunken glass beads, the middle layer is provided with redundant liquid material and the upper layer is provided with well-packed glass bead material;

d1) heating and curing the layered materials, and cutting off the bottom layer material and the middle layer material to obtain the high-performance solid buoyancy material;

or d2) discharging the bottom layer material and the middle layer material in the layered materials, and then heating and curing to obtain the high-performance solid buoyancy material.

The method provided by the invention adopts a vibration-assisted phase splitting method, and can obtain high performance of low density, high strength and low water absorption rate due to the removal of damaged hollow glass beads and redundant liquid materials and the tight packing of intact hollow glass beads in material products.

In the invention, the dicyclopentadiene, the catalyst, the silane coupling agent and the polymerization inhibitor are preferably uniformly stirred under vacuum. After the hollow glass microspheres are added, stirring is preferably carried out under vacuum.

According to the invention, the liquid buoyancy material is poured into the mold, and the mold is placed on a vibration platform to vibrate, wherein the vibration frequency is 0.1-20 Hz. In a specific embodiment, the vibration has a frequency of 1Hz or 15Hz and a time of 30min or 12 hours. The heating temperature is preferably 60-80 ℃, and the heating time is 6-12 h; in a specific embodiment, the heating temperature is 60 ℃ or 80 ℃, and the time is 6h or 12 h. The curing temperature is preferably 115-130 ℃, and more preferably 120-125 ℃; the time is preferably 2-8 h, and more preferably 3-6 h; in specific embodiments, the curing temperature is 120 ℃ and the curing time is 6 hours or 3 hours.

Fig. 1 is a schematic structural diagram of a mold used in the method provided by the present invention. The vibration is carried out in the mould; the bottom of the mould is provided with a discharge outlet.

In the vibration process, the damaged hollow glass beads sink under the action of gravity; the intact hollow glass microspheres float upwards and are closely stacked under the action of buoyancy; between which is excess liquid material.

According to the invention, the mould with the material is preferably moved into an oven to be heated; when the polymerization inhibitor volatilizes in the heating process, the dicyclopentadiene generates polymerization reaction under the action of the catalyst, so that the buoyancy material is solidified. And (3) removing the cured buoyancy material from the mold, cutting off the sunk glass beads and the redundant liquid material, and obtaining the residual cured material, namely the high-performance solid buoyancy material.

The material after vibrating for 5 min-24 h is divided into three layers, wherein the bottom layer is sunken glass beads, the middle layer is redundant liquid material and the upper layer is intact glass bead material containing compact packing; and discharging the bottom layer material and the middle layer material through a discharge hole, and then heating for curing and demoulding to obtain the high-performance solid buoyancy material.

In order to further illustrate the present invention, the following examples are provided to describe the high performance solid buoyancy material and the preparation method thereof in detail, but they should not be construed as limiting the scope of the present invention.