CN117603557A - Room-temperature casting type solid buoyancy material and preparation method thereof - Google Patents

Abstract

The invention provides a room-temperature casting type solid buoyancy material and a preparation method thereof, wherein the solid buoyancy material comprises a component A and a component B, and the component A comprises the following components in parts by weight: 100 parts of matrix resin, 5-15 parts of diluent, 0.1-2 parts of coupling agent, 0.1-1 part of dispersing agent, 1-5 parts of anti-settling agent, 0.1-0.5 part of defoamer and 10-40 parts of hollow glass microsphere; the component B comprises the following components in parts by weight: 100 parts of curing agent, 3-10 parts of diluent, 0.1-0.5 part of defoamer and 10-15 parts of hollow glass beads; the mass ratio of the component A to the component B is 100:30-60. Mixing and stirring the component A and the component B, defoaming, and pouring; solidifying the mould filled with the casting solution for 24-48 hours at room temperature, and demoulding to obtain the casting solid buoyancy material. The resin curing agent system used in the invention has low viscosity, good fluidity, small reaction heat release and low curing shrinkage, and is beneficial to the implementation of the casting process. And the curing is performed at normal temperature, the curing time is short, the casting construction can be performed on the using site, and the process adaptability is strong.

Description

Room-temperature casting type solid buoyancy material and preparation method thereof

Technical Field

The invention relates to the technical field of solid buoyancy materials, in particular to a room-temperature casting type solid buoyancy material and a preparation method thereof.

Background

The deep sea equipment is operated frequently by adopting an unpowered floating technology, so that the material of the deep sea equipment is required to have certain pressure resistance and can provide certain buoyancy to ensure the effective load quantity and the underwater safety performance of the submersible. The solid buoyancy material is a polymer-based solid material with low density, high strength and low water absorption rate, has a density smaller than that of water, and can provide certain buoyancy, so that the solid buoyancy material is widely applied to ocean development equipment such as deep sea drilling, deep diving equipment, deep sea mining and the like. At present, most of solid buoyancy materials prepared at home and abroad are composite light buoyancy materials, and the material is mainly formed by taking epoxy resin as a binder and filling a large amount of hollow glass beads and other additives. The traditional solid buoyancy material product is a prefabricated block material, and is processed into corresponding dimensions according to the drawing requirements of structural members and then fixed on a framework of the equipment in actual use. The prefabricated massive solid buoyancy material is difficult to fill the complex structure of certain marine equipment in practical use, especially the edge and the inner area of the complex structure, so that the application range of the solid buoyancy material is greatly limited. The casting type solid buoyancy material is applied abroad, and mature products exist, but is subject to technical control reasons, and is not sold in China, so that the products cannot be purchased normally in China; although mature products are developed and partially applied in domestic Ha engineering, partial performances, particularly density and casting thickness, are quite different from those of foreign products, and the overall performance of equipment is affected.

Patent application CN1261479C reports a solid buoyancy material prepared by a chemical foaming method, the solid buoyancy material is a prefabricated and cast solid buoyancy material, the compression strength is only 5.5MPa, and the solid buoyancy material needs to be cured for 2 hours at 100 ℃ after demolding. The patent application CN110628180A adopts two or three hollow glass beads as density regulators to be filled into an epoxy resin matrix and poured into a mold to prepare a solid buoyancy material, after the pouring is completed, the solid buoyancy material is required to be solidified after the temperature is 100 ℃ and 140 ℃, and the solid buoyancy material is obtained after cooling to room temperature and demolding. The patent application CN103709607A is prepared by mixing a first component consisting of epoxy resin, hollow glass beads, epoxy diluent and the like with a second component consisting of a curing agent and a catalyst, and pouring the mixture into a mold to be cured for one week at room temperature for complete curing, wherein the thickness of single pouring is 25-50mm; the single casting thickness of the product is smaller, so that when the casting requirement of a large-size large-thickness structural member is met, the whole casting time is too long, and the casting efficiency is seriously influenced. After uniformly mixing epoxy resin and a curing agent, adding a light filler, uniformly stirring, removing bubbles and pouring into a mold in the patent application CN 109251483A; the buoyancy material prepared by the method can be completely solidified in one week, and the casting material is required to be prepared on site, so that the requirement on site test conditions is high, and the applicability is not strong. The casting buoyancy material prepared by the patent application is long in solidification and high in on-site casting condition, so that the applicability is not strong.

Disclosure of Invention

In view of the above, the invention aims to provide a room temperature casting type solid buoyancy material and a preparation method thereof, so as to solve the problems of long curing time, high in-situ casting condition and low applicability of the solid buoyancy material.

In order to achieve the above purpose, the technical scheme of the invention is realized as follows:

on one hand, the invention provides a room-temperature casting type solid buoyancy material, which comprises an A component and a B component, wherein the A component comprises the following components in parts by weight: 100 parts of matrix resin, 5-15 parts of diluent, 0.1-2 parts of coupling agent, 0.1-1 part of dispersing agent, 1-5 parts of anti-settling agent, 0.1-0.5 part of defoamer and 10-40 parts of hollow glass microsphere; the component B comprises the following components in parts by weight: 100 parts of curing agent, 3-10 parts of diluent, 0.1-0.5 part of defoamer and 10-15 parts of hollow glass beads; the mass ratio of the component A to the component B is 100:30-60.

Further, the matrix resin is bisphenol A epoxy resin, and one of E51 and LY1564 is adopted.

Further, the curing agent is an epoxy curing agent matched with the epoxy resin, and one of a polyether amine epoxy curing agent T403, an amine curing agent 3486 and an aromatic amine curing agent ZTGR-3008 is adopted.

Further, the diluent is an epoxy reactive diluent, and one of propylene oxide butyl ether 660A, C-14 aliphatic glycidyl ether AGE, n-butyl glycidyl ether BGE and diglycidyl ether is adopted. The diluent is used for reducing the viscosity of the casting solution material and increasing the fluidity.

Further, the coupling agent is a silane coupling agent, and one of 3- (2, 3-epoxypropoxy) propyl trimethoxy silane KH560, 3-aminopropyl trimethoxy silane KH550 and r-methacryloxypropyl trimethoxy silane KH570 is adopted. The coupling agent is used for improving the bonding strength between the filler and the resin.

Further, the dispersing agent adopts one of BYK110, BYK130 and BYK 163. The dispersing agent is used for improving the dispersion uniformity of the filler and preventing particles from gathering.

Furthermore, the anti-settling agent adopts one of calcium carbonate, fumed silica and organic bentonite. The anti-settling agent is used for enhancing the mechanical strength of the resin matrix and preventing the filler from settling.

Further, the defoamer adopts one of BYK011, BYK022, BYK085 and ACP-0001. The defoamer is used for eliminating foam formed during liquid material mixing.

Further, the average particle diameter of the hollow glass beads is 30-65 microns, and the density is 0.125-0.23g/cm ³ The compressive strength is 5-20MPa. The hollow glass beads are used for reducing the overall density of the buoyancy material.

The principle of the invention is as follows: the filler is uniformly distributed in the component A mainly comprising resin and the component B mainly comprising curing agent respectively, and is sealed and preserved after vacuum defoamation treatment to avoid air from entering. In the process of pouring in a test site, A, B components are stirred and mixed in proportion, then vacuum defoamation treatment is carried out again, and air in liquid is discharged, so that the formation of air holes in the buoyancy material in the process of pouring can be reduced. Meanwhile, the resin curing agent system selected by the invention can carry out curing reaction at room temperature, has less heat release, and avoids the phenomenon of burning caused by a large amount of accumulation of reaction heat in the buoyancy material; the system has small curing shrinkage rate, so that the shrinkage degree of the resin matrix after curing is controllable, and the shrinkage cracking phenomenon after curing is avoided.

In another aspect of the present invention, a method for preparing a room temperature casting type solid buoyancy material is also provided, the method comprising the following steps:

s1, weighing matrix resin, a diluent, a coupling agent, a dispersing agent, an anti-settling agent, a defoaming agent and hollow glass beads according to a proportion, putting into a stirrer, uniformly mixing, vacuumizing and exhausting to obtain a casting solution A component, and sealing for later use;

s2, weighing the curing agent, the diluent, the defoaming agent and the hollow glass beads according to a proportion, putting into a stirrer, uniformly mixing, vacuumizing and exhausting to obtain a casting solution B component, and sealing for later use;

s3, mixing the component A and the component B according to the mass ratio of 100:30-60, uniformly stirring, pouring into a vacuum deaeration machine for deaeration treatment, and pouring into a mold coated with a release agent;

s4, solidifying the mould filled with the casting solution for 24-48 hours at room temperature, and demoulding to obtain the casting solid buoyancy material.

Compared with the prior art, the room-temperature casting type solid buoyancy material and the preparation method thereof have the following advantages:

(1) The resin curing agent system used by the invention has low viscosity, good fluidity, room temperature curing, small reaction heat release and low curing shrinkage rate through the formula design, and is beneficial to the implementation of the casting process.

(2) Compared with the traditional thermal curing process, the method for preparing the casting type solid buoyancy material by adopting the room temperature curing method does not need heating curing, can carry out casting construction, curing and forming on the site, has the curing time of not more than 48 hours, has strong process adaptability, and does not need subsequent processing, installation and other procedures.

(3) The room temperature casting type solid buoyancy material has excellent density, uniaxial compression strength and hydrostatic pressure resistance, small water absorption and low shrinkage after solidification molding, and can be used in deep sea areas of 0-500 m.

(4) The single casting thickness of the room temperature casting type solid buoyancy material is 50-200mm, and when the casting requirement of a large-size large-thickness structural member is met, the whole casting time is short, so that the casting efficiency is improved.

Detailed Description

The invention is further described below in conjunction with the detailed description. It should be noted that the data in the following examples are obtained by the inventors through a lot of experiments, and are only shown in some of the descriptions, and those skilled in the art can understand and practice the present invention under the data. These examples are only for illustrating the present invention and are not intended to limit the scope of the present invention. Further, it should be understood that after reading the present disclosure, those skilled in the art may make various changes or modifications to the present disclosure, which also fall within the scope of the present disclosure.

The room-temperature casting type solid buoyancy material comprises a component A and a component B, wherein the component A comprises the following components in parts by weight: 100 parts of matrix resin, 5-15 parts of diluent, 0.1-2 parts of coupling agent, 0.1-1 part of dispersing agent, 1-5 parts of anti-settling agent, 0.1-0.5 part of defoamer and 10-40 parts of hollow glass microsphere; the component B comprises the following components in parts by weight: 100 parts of curing agent, 3-10 parts of diluent, 0.1-0.5 part of defoamer and 10-15 parts of hollow glass beads; the mass ratio of the component A to the component B is 100:30-60. The resin curing system obtained by the formula design has low viscosity and good fluidity, can be cured at room temperature, avoids high-temperature curing, ensures that the solid buoyancy material is not limited in casting, can be cast on site, and has high applicability. Meanwhile, the reaction heat release is small, the curing shrinkage rate is low, and the implementation of the casting process and the improvement of the casting efficiency are facilitated.

The matrix resin is bisphenol A epoxy resin and adopts one of E51 and LY 1564.

The curing agent is an epoxy curing agent matched with the epoxy resin, and adopts one of polyether amine epoxy curing agent T403, amine curing agent 3486 and aromatic amine curing agent ZTGR-3008. Specifically, the amine curing agent 3486 is an amine curing agent 3486 of Huntsman corporation.

The diluent is an epoxy reactive diluent, and is one of propylene oxide butyl ether 660A, C-14 aliphatic glycidyl ether AGE, n-butyl glycidyl ether BGE and diglycidyl ether. The diluent is used for reducing the viscosity of the casting solution material and increasing the fluidity.

The coupling agent is a silane coupling agent, and adopts one of 3- (2, 3-epoxypropoxy) propyl trimethoxy silane KH560, 3-aminopropyl trimethoxy silane KH550 and r-methacryloxypropyl trimethoxy silane KH 570. The coupling agent is used for improving the bonding strength between the filler and the resin.

The dispersing agent adopts one of BYK110, BYK130 and BYK 163. The dispersing agent is used for improving the dispersion uniformity of the filler and preventing particles from gathering.

The anti-settling agent adopts one of calcium carbonate, fumed silica and organic bentonite. The anti-settling agent is used for enhancing the mechanical strength of the resin matrix and preventing the filler from settling.

The defoamer adopts one of BYK011, BYK022, BYK085 and ACP-0001. The defoamer is used for eliminating foam formed during liquid material mixing.

The average grain diameter of the hollow glass microsphere is 30-65 micrometers, and the density is 0.125-0.23g/cm ³ The compressive strength is 5-20MPa. Specifically, the hollow glass bead adopts one of K series, S series of 3M company and HS series of new material of Zhengzhou holly hollow glass bead. The hollow glass beads are used for reducing the whole buoyancy materialBulk density.

The preparation method of the room-temperature casting type solid buoyancy material comprises the following steps:

s1, weighing matrix resin, a diluent, a coupling agent, a dispersing agent, an anti-settling agent, a defoaming agent and hollow glass beads according to a proportion, putting into a stirrer, uniformly mixing, vacuumizing and exhausting to obtain a casting solution A component, and sealing for later use;

s2, weighing the curing agent, the diluent, the defoaming agent and the hollow glass beads according to a proportion, putting into a stirrer, uniformly mixing, vacuumizing and exhausting to obtain a casting solution B component, and sealing for later use;

s3, mixing the component A and the component B according to the mass ratio of 100:30-60, uniformly stirring, pouring into a vacuum deaeration machine for deaeration treatment, and pouring into a mold coated with a release agent;

s4, solidifying the mould filled with the casting solution for 24-48 hours at room temperature, and demoulding to obtain the casting solid buoyancy material.

The casting type solid buoyancy material prepared by using the hollow glass beads as a filler and using the epoxy resin as a matrix resin through a room temperature curing molding process has a single casting thickness of 50-200mm, and can be applied to marine equipment materials in the sea depth of 0-500 m. Through the formula design, the used resin curing agent system has low viscosity, good fluidity, room temperature curing, small reaction heat release and low curing shrinkage, and is beneficial to the implementation of the casting process. Meanwhile, the hollow glass microspheres are added into the component A and the component B, so that the fluidity of the component A and the component B is improved, and the purpose of densely filling logistics can be achieved without adopting a vibration and stirring mode when large-scale equipment is cast on site, the operation is simplified, and the use convenience is improved. In addition, because the heating and curing are not needed, the curing time is not more than 48 hours, and the casting construction curing molding can be carried out on the using site, thereby being convenient for the subsequent processing and installation and other procedures. And because the liquid pouring method is adopted, the inside of the complex structure of the marine equipment can be effectively filled, the situation that the edge or the inner area of the complex structure cannot be well filled is avoided, the maximization of the weight reduction effect in water is realized, the construction and installation efficiency of the solid buoyancy material is improved, the use reliability of the solid buoyancy material is greatly improved, and the process links are reduced.

Example 1

Weighing 100 parts of E51 epoxy resin, 10 parts of propylene oxide butyl ether 660A, 0.2 part of 3-aminopropyl trimethoxy silane KH550, 1 part of BYK130, 3 parts of calcium carbonate, 0.2 part of BYK011 and 18 parts of S15 hollow glass microspheres of 3M company, putting into a stirrer, uniformly mixing, vacuumizing and exhausting to obtain a casting solution A component, and sealing for later use;

weighing 100 parts of polyether amine epoxy curing agent T403, 5 parts of propylene oxide butyl ether 660A, 0.1 part of BYK011 and 10 parts of S15 hollow glass beads of 3M company, putting into a stirrer, uniformly mixing, vacuumizing and exhausting to obtain a casting solution B component, and sealing for later use;

mixing the component A and the component B according to the mass ratio of 100:45, uniformly stirring, pouring into a vacuum deaeration machine for deaeration treatment, and pouring into a mold coated with a release agent;

and solidifying the mould filled with the casting solution at room temperature, and demoulding to obtain the casting solid buoyancy material.

Example 2

Weighing 100 parts of E51 epoxy resin, 15 parts of C12-14 fatty glycidyl ether AGE, 1 part of 3- (2, 3-epoxypropoxy) propyl trimethoxy silane KH560, 0.5 part of BYK110, 3 parts of organic bentonite, 0.2 part of ACP-0001 and 30 parts of K20 hollow glass microspheres of 3M company, putting into a stirrer, uniformly mixing, vacuumizing and exhausting to obtain a casting solution A component, and sealing for later use;

weighing 100 parts of aromatic amine curing agent ZTGR-3008, 3 parts of C12-14 fatty glycidyl ether AGE, 0.2 part of ACP-0001 and 12 parts of K20 hollow glass microspheres of 3M company, putting into a stirrer, uniformly mixing, vacuumizing and exhausting to obtain a casting solution B component, and sealing for later use;

mixing the component A and the component B according to the mass ratio of 100:55, uniformly stirring, pouring into a vacuum deaeration machine for deaeration treatment, and pouring into a mold coated with a release agent;

and solidifying the mould filled with the casting solution at room temperature, and demoulding to obtain the casting solid buoyancy material.

Example 3

Weighing 100 parts of LY1564 epoxy resin, 5 parts of n-butyl glycidyl ether BGE, 2 parts of r-methacryloxypropyl trimethoxysilane KH570, 0.5 part of BYK163, 3 parts of fumed silica, 0.1 part of BYK085 and 40 parts of HS28 hollow glass beads of new material company of Santa Clay hollow glass beads, zheng, putting into a stirrer, uniformly mixing, vacuumizing, exhausting to obtain a casting solution A component, and sealing for later use;

weighing 100 parts of Huntsman company amine curing agent 3486, 10 parts of n-butyl glycidyl ether BGE, 0.5 part of BYK085 and 15 parts of HS28 hollow glass beads of new material limited company of Zhengzhou holt hollow glass beads, putting into a stirrer, uniformly mixing, vacuumizing and exhausting to obtain a casting solution B component, and sealing for later use;

mixing the component A and the component B according to the mass ratio of 100:30, uniformly stirring, pouring into a vacuum deaeration machine for deaeration treatment, and pouring into a mold coated with a release agent;

and solidifying the mould filled with the casting solution at room temperature, and demoulding to obtain the casting solid buoyancy material.

Comparative example 1

Weighing 100 parts of E51 epoxy resin, 10 parts of propylene oxide butyl ether 660A, 0.2 part of 3-aminopropyl trimethoxy silane KH550, 1 part of BYK130, 3 parts of calcium carbonate, 0.2 part of BYK011 and 18 parts of S15 hollow glass microspheres of 3M company, putting into a stirrer, uniformly mixing, vacuumizing and exhausting to obtain a casting solution A component, and sealing for later use;

weighing 100 parts of a medium-high temperature curing agent aromatic amine curing agent ZTGR-2219, 5 parts of propylene oxide butyl ether 660A, 0.1 part of BYK011 and 10 parts of S15 hollow glass beads of 3M company, putting into a stirrer, uniformly mixing, vacuumizing and exhausting to obtain a casting solution B component, and sealing for later use;

mixing the component A and the component B according to the mass ratio of 100:50, uniformly stirring, pouring into a vacuum deaeration machine for deaeration treatment, and pouring into a mold coated with a release agent;

and solidifying the mould filled with the casting solution at room temperature, and demoulding to obtain the casting solid buoyancy material.

The properties of the buoyancy materials prepared by casting in examples 1-3 and comparative example 1 are shown in Table 1.

TABLE 1

For comparison, the same mold was used in examples 1 to 3 and comparative example 1.

As can be seen from Table 1, the cast solid buoyancy materials of examples 1-3 have higher uniaxial compression strength, can reach 19.6-22.7MPa, have hydrostatic pressure resistance strength of 7.0-7.2MPa, have water absorption rate of 0.5-0.8% in 24h, and are suitable for marine equipment materials in the sea depth of 0-500 m. And the shrinkage rate after curing molding is less than or equal to 0.84%, and the shrinkage rate after curing is smaller, so that the shrinkage degree of the resin matrix after curing is controllable, and the shrinkage cracking phenomenon after curing is avoided. In addition, the cast solid buoyancy material systems of examples 1-3 were ready for initial cure within 24 hours and fully cured within 48 hours, greatly reducing the on-site casting time. The thickness of the single casting in the embodiment 1-3 can reach 50-200mm, and when the casting requirement of a large-size and large-thickness structural member is met, the whole casting time is short, so that the casting efficiency is improved. The casting type solid buoyancy material of comparative example 1 was changed in formulation, and it took 120 hours for curing to complete at room temperature, and the uniaxial compressive strength, hydrostatic pressure resistance, water absorption and shrinkage after curing molding were inferior to those of examples 1 to 3.

The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.

Claims (10)

1. The room temperature casting type solid buoyancy material is characterized by comprising a component A and a component B, wherein the component A comprises the following components in parts by weight: 100 parts of matrix resin, 5-15 parts of diluent, 0.1-2 parts of coupling agent, 0.1-1 part of dispersing agent, 1-5 parts of anti-settling agent, 0.1-0.5 part of defoamer and 10-40 parts of hollow glass microsphere; the component B comprises the following components in parts by weight: 100 parts of curing agent, 3-10 parts of diluent, 0.1-0.5 part of defoamer and 10-15 parts of hollow glass beads; the mass ratio of the component A to the component B is 100:30-60.

2. The room temperature casting type solid buoyancy material according to claim 1, wherein the matrix resin is bisphenol a epoxy resin, and one of E51 and LY1564 is adopted.

3. The room temperature casting type solid buoyancy material according to claim 2, wherein the curing agent is an epoxy curing agent matched with the epoxy resin, and one of a polyether amine epoxy curing agent T403, an amine curing agent 3486 and an aromatic amine curing agent ZTGR-3008 is adopted.

4. The room temperature casting type solid buoyancy material according to claim 1, wherein the diluent is an epoxy reactive diluent, and one of propylene oxide butyl ether 660A, C-14 aliphatic glycidyl ether AGE, n-butyl glycidyl ether BGE and diglycidyl ether is adopted.

5. The room temperature casting type solid buoyancy material according to claim 1, wherein the coupling agent is a silane coupling agent, and one of 3- (2, 3-glycidoxy) propyl trimethoxysilane KH560, 3-aminopropyl trimethoxysilane KH550 and r-methacryloxypropyl trimethoxysilane KH570 is adopted.

6. The room temperature casting type solid buoyancy material according to claim 1, wherein the dispersing agent is one of BYK110, BYK130 and BYK 163.

7. The room temperature casting type solid buoyancy material according to claim 1, wherein the anti-settling agent is one of calcium carbonate, fumed silica and organic bentonite.

8. The room temperature casting type solid buoyancy material according to claim 1, wherein the defoaming agent is one of BYK011, BYK022, BYK085 and ACP-0001.

9. The room temperature casting type solid buoyancy material as claimed in claim 1, wherein the hollow glass beads have an average particle size of 30-65 microns and a density of 0.125-0.23g/cm ³ The compressive strength is 5-20MPa.

10. A method of preparing a room temperature castable solid buoyancy material as claimed in any one of claims 1 to 9, comprising the steps of:

s1, weighing matrix resin, a diluent, a coupling agent, a dispersing agent, an anti-settling agent, a defoaming agent and hollow glass beads according to a proportion, putting into a stirrer, uniformly mixing, vacuumizing and exhausting to obtain a casting solution A component, and sealing for later use;

s2, weighing the curing agent, the diluent, the defoaming agent and the hollow glass beads according to a proportion, putting into a stirrer, uniformly mixing, vacuumizing and exhausting to obtain a casting solution B component, and sealing for later use;

s3, mixing the component A and the component B according to the mass ratio of 100:30-60, uniformly stirring, pouring into a vacuum deaeration machine for deaeration treatment, and pouring into a mold coated with a release agent;

s4, solidifying the mould filled with the casting solution for 24-48 hours at room temperature, and demoulding to obtain the casting solid buoyancy material.