A slow-setting epoxy mortar composition and its preparation method and application

Abstract

The present application provides a slow-setting epoxy mortar composition, its preparation method, and application. The composition comprises the following raw materials, measured by weight: 20 to 50 parts of epoxy resin, 10 to 30 parts of a curing agent, wherein the curing agent comprises a polyamide compound and a polyamic acid compound in a mass ratio of 1:0.2 to 5, and 30 to 120 parts of a filler. The slow-setting epoxy mortar composition provided herein can be cured under high humidity conditions and has a long working life.

Description

Technical Field

[0001] The present application relates to the technical field of polymer materials, and in particular to a slow-curing epoxy mortar composition, a preparation method thereof, and an application thereof. Background Art

[0002] Epoxy putty composition is an adhesive prepared mainly from epoxy resin. It has many significant advantages and has a good bonding effect on various metals and non-metals. It has been used in many fields.

[0003] However, with the changes in substrates, new raw materials, and usage environments, higher requirements are placed on the performance of epoxy putty compositions. Currently, commercially available epoxy putty compositions can only be strictly constructed at room temperature between 25°C and 40°C and humidity between 0% and 45%. This is because at low temperatures, commercially available products cannot cure, and at high temperatures, the curing rate is too fast and the construction time is too short, making it impossible to achieve the desired bonding effect. In addition, under high humidity conditions, water molecules in the air shield the chemical bonds of the adhesive substrate at the bonding site, resulting in low bonding strength and failure to meet the construction strength requirements. Therefore, it is necessary to improve the workability of epoxy putty compositions. Summary of the Invention

[0004] The present application provides a slow-curing epoxy mortar composition, a preparation method thereof, and an application thereof. The slow-curing epoxy mortar composition can be cured under high humidity conditions and has a long construction application time.

[0005] In the first aspect, the present application provides a slow-curing epoxy putty composition, which includes the following raw materials in parts by mass: 20 to 50 parts of epoxy resin, 10 to 30 parts of curing agent, the curing agent includes a polyamide compound and a polyamic acid compound, the mass ratio of the polyamide compound to the polyamic acid compound is 1:0.2 to 5, and 30 to 120 parts of filler.

[0006] According to the present application, a curable slow-setting epoxy putty composition can be obtained by using a certain proportion of polyamide compounds and polyamic acid compounds and mixing them with epoxy resin and filler. The polyamide compounds and polyamic acid compounds in the slow-setting epoxy putty composition work together to carry out a gradient curing reaction, so that the slow-setting epoxy putty composition can be stably cured and cross-linked under high humidity conditions, thereby improving the adhesion of the epoxy putty composition cured under high humidity, and being able to extend the curing time, so that the slow-setting epoxy putty composition has a longer construction applicability time.

[0007] In some embodiments of the present application, the epoxy resin includes at least one of bisphenol A epoxy resin, bisphenol F epoxy resin, and hydrogenated bisphenol A epoxy resin.

[0008] In some embodiments of the present application, the polyamide compound includes at least one of polyamide 300, polyamide 650, and polyamide 651; and / or the polyamide acid compound is obtained by reacting a diamino compound and a dianhydride compound in a polar solvent.

[0009] In some embodiments of the present application, the raw materials of the slow-setting epoxy putty composition, measured in parts by mass, further include 1 to 20 parts of a reactive diluent, the reactive diluent including a first reactive diluent and a second reactive diluent, the first reactive diluent including an epoxy-containing glycidyl ether, the second reactive diluent including at least one of an enamine diluent and a polyetheramine diluent; the epoxy-containing glycidyl ether includes at least one of alkylene glycidyl ether, ethylene glycol diglycidyl ether, benzyl glycidyl ether, and polypropylene glycol diglycidyl ether; the enamine diluent includes at least one of diethylenetriamine, triethylenetetramine, and tetraethylenepentamine, and the polyetheramine diluent includes at least one of polyetheramine 300, polyetheramine 400, and polyetheramine 500.

[0010] In some embodiments of the present application, the filler includes at least one of quartz powder, alumina powder, titanium dioxide, calcium carbonate powder, lithopone, and clay; and / or the raw materials of the slow-curing epoxy putty composition, in parts by mass, also include 1 to 20 parts of a thixotropic agent, and the thixotropic agent includes at least one of fumed silica, organic bentonite, hydrogenated castor oil, and polyamide wax.

[0011] In some embodiments of the present application, the raw materials of the slow-curing epoxy putty composition, calculated in parts by mass, further include 0.1 to 2 parts of pigment, and the pigment includes at least one of iron oxide red, iron oxide yellow, iron blue, and iron black; and / or the raw materials of the slow-curing epoxy putty composition, calculated in parts by mass, further include 0.1 to 5 parts of functional additives, and the functional additives include at least one of a wetting agent and a defoaming agent.

[0012] In a second aspect, the present application provides a method for preparing a slow-curing epoxy mortar composition, comprising the following steps:

[0013] The raw materials of the slow-setting epoxy putty composition according to any embodiment of the first aspect are mixed to obtain a curable slow-setting epoxy putty composition.

[0014] According to the present application, the raw materials of the slow-curing epoxy putty composition in any embodiment of the first aspect can be mixed to obtain a curable slow-curing epoxy putty composition. Therefore, the preparation method is simple, the application range is wide, and it has the beneficial effects of any embodiment of the first aspect.

[0015] In some embodiments of the present application, the preparation method specifically comprises the following steps:

[0016] S10: mixing the epoxy resin, the first reactive diluent, a portion of the filler, and a portion of the thixotropic agent to obtain component A;

[0017] S20: mixing the curing agent, the second reactive diluent, another portion of the filler, and another portion of the thixotropic agent to obtain component B;

[0018] S30: Component A and component B are mixed to obtain a curable slow-setting epoxy mortar composition.

[0019] In a third aspect, the present application provides a liquefied natural gas carrier, comprising a hull, and

[0020] An insulating box fixedly bonded to the hull by a slow-setting epoxy putty composition obtained by the slow-setting epoxy putty composition according to any embodiment of the first aspect or the preparation method according to any embodiment of the second aspect.

[0021] According to the present application, in a liquefied natural gas carrier, the hull and the insulation box are bonded using a slow-setting epoxy putty composition obtained by the preparation method according to the slow-setting epoxy putty composition described in any embodiment of the first aspect or the slow-setting epoxy putty composition described in any embodiment of the second aspect. Since the slow-setting epoxy putty composition can be cured under high humidity conditions, it can be ensured that the cured epoxy putty composition obtained during construction under high humidity conditions still has good adhesion, so that the two are stably bonded and not easily displaced, thereby improving the safety of the liquefied natural gas carrier; in addition, since the slow-setting epoxy putty composition has a long construction application time, it is suitable for large-area construction, reducing the difficulty of construction.

[0022] In some embodiments of the present application, the interior of the insulating box includes laminated wood, heavyweight boards, saddle panels, and a slow-setting epoxy putty composition obtained by the preparation method described in any embodiment of the first aspect or any embodiment of the second aspect, which is filled between the laminated wood and the heavyweight boards and saddle panels. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the present application and, together with the description, serve to explain the principles of the present application.

[0024] Figure 1 This is a schematic cross-sectional view of a liquefied natural gas storage tank in a liquefied natural gas carrier in this application.

[0025] Figure 2 These are the curing rate test results of the slow-curing epoxy putty composition of Example 1 of the present application and a commercially available epoxy putty composition.

[0026] Description of reference numerals:

[0027] 1 insulation layer, 11 main shielding protective film, 12 main insulation layer, 13 secondary shielding protective film, 14 secondary insulation layer, 2 adhesive layer, 3 hull.

[0028] The above drawings illustrate specific embodiments of the present application, which will be described in more detail below. These drawings and the textual description are not intended to limit the scope of the present application in any way, but rather to illustrate the concepts of the present application to those skilled in the art by reference to specific embodiments. DETAILED DESCRIPTION

[0029] The various embodiments or implementation schemes in this specification are described in a progressive manner, and each embodiment focuses on the differences from other embodiments.

[0030] Throughout this specification, reference to terms such as "one embodiment," "some embodiments," "illustrative embodiments," "examples," "specific examples," or "some examples" means that a specific feature, structure, material, or characteristic described in conjunction with an embodiment or example is included in at least one embodiment or example of the present application. In this specification, illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.

[0031] Furthermore, the terms "first" and "second" are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of the technical features being referred to. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one of such features. Throughout the description of this application, "plurality" means at least two, for example, two, three, etc., unless otherwise specifically defined.

[0032] As described in the background technology above, as the application of epoxy putty compositions becomes more and more extensive, the requirements for the workability of epoxy putty compositions are becoming higher and higher.

[0033] Since conventional epoxy mortar compositions have high environmental requirements, they cannot stably cure and crosslink under high humidity and low temperature conditions, resulting in poor adhesion and strength. While the use of highly reactive curing agents can increase the reactivity of the system, allowing the epoxy mortar composition to cure and crosslink under high humidity and low temperature conditions, this also shortens the curing time and the application time, making it unsuitable for large-scale construction. Therefore, workability remains largely unimproved.

[0034] In view of this, the present application provides a slow-setting epoxy putty composition, which can stably undergo curing and cross-linking under high humidity conditions, improve the adhesion of the slow-setting epoxy putty composition cured under high humidity, and can prolong the curing time, so that the slow-setting epoxy putty composition has a longer construction application time. The following is a detailed description of the slow-setting epoxy putty composition provided in this application, its preparation method, and application. The following slow-setting epoxy putty composition can be referred to as the epoxy putty composition.

[0035] In the first aspect, the present application provides a slow-curing epoxy putty composition, which includes the following raw materials in parts by mass: 20 to 50 parts of epoxy resin, 10 to 30 parts of curing agent, the curing agent includes polyamide compounds and polyamic acid compounds, the mass ratio of polyamide compounds to polyamic acid compounds is 1:0.2 to 5, and 30 to 120 parts of filler.

[0036] According to the present application, the epoxy putty composition includes a certain mass portion of epoxy resin, curing agent and filler, wherein the curing agent includes polyamide compounds and polyamic acid compounds. The inventors found that a curable epoxy putty composition is obtained by mixing a certain proportion of polyamide compounds and polyamic acid compounds with epoxy resin and filler. The two curing agents in the epoxy putty composition work together to carry out a gradient curing reaction, so that the epoxy putty composition can be stably cured and cross-linked under high humidity conditions, thereby improving the adhesion of the epoxy putty composition cured under high humidity, and being able to extend the curing time, so that the epoxy putty composition has a longer construction applicability time.

[0037] After analysis, the possible reason is that, because polyamic acid compounds contain carboxyl groups, they have good solubility and dispersibility in epoxy mortar systems, and themselves have very high reactivity, which can promote the epoxy mortar composition to undergo cross-linking and curing; In addition, since cross-linking and curing is an exothermic process, the carboxyl groups and imino groups in the polyamic acid compounds undergo intramolecular dehydration and imidization to form a ring, and this process is an endothermic process, which can reduce the promoting effect of heat on the curing reaction, and the water molecules removed can also reduce the cross-linking reaction activity and reduce the adhesion of the cured epoxy mortar composition, and then the reactivity is reduced, so when using polyamic acid compounds as curing agent, cross-linking speed is gradually reduced. At the same time, under high humidity, polyamic acid compounds undergo intramolecular dehydration and are suppressed, so under higher humidity, the speed at which the polyamic acid compound reactivity decreases is slower, which can be comparable to the cross-linking and curing speed under lower humidity environments, so that the epoxy mortar composition is stably cured and cross-linked under high humidity conditions. At the same time, in order to prevent the cross-linking speed in the early stage of curing from being too fast, which will lead to a decrease in the cross-linking degree of the epoxy putty composition, polyamide compounds with lower reaction activity are selected for compounding with polyamide acid compounds. The reaction activity of polyamide compounds is lower than that of amine compounds. The two curing agents compete with each other to reduce the initial curing reaction rate. At the same time, the polyamide acid compounds can effectively inhibit the curing thermal effect and prevent the curing reaction rate from rising too fast, thereby realizing a gradient curing reaction, thereby extending the curing time and making the epoxy putty composition have a longer construction application time.

[0038] In the present application, the epoxy resin content in the epoxy mortar composition is 20 to 50 parts, and the epoxy mortar composition has good adhesion. For example, the epoxy resin content can be 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts, 50 parts, or any range thereof.

[0039] In the present application, the mass ratio of polyamide compounds and polyamic acid compounds is specifically limited to 1:0.2~5. If the content of polyamide compounds is too much, the epoxy putty composition will not be able to stably cure and crosslink under high humidity conditions. The adhesion of the epoxy putty composition cured under high humidity is low. In addition, the effect of the polyamic acid compound on inhibiting crosslinking after internal cyclization in the late stage of curing is small, and the curing speed is relatively fast. If the content of polyamic acid compounds is too high, the crosslinking speed is too fast in the early stage of curing, and the carboxyl group and imino group in the polyamic acid compound will undergo rapid intramolecular dehydration and imidization to form a ring, resulting in a low degree of curing of the epoxy putty and poor adhesion. For example, the mass ratio of the polyamide compound to the polyamic acid compound can be 1:0.2, 1:0.3, 1:0.4, 1:0.5, 1:0.6, 1:0.7, 1:0.8, 1:0.9, 1:1, 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5, 1:5, or any range thereof. Preferably, when the mass ratio of the polyamide compound to the polyamic acid compound is 1:2 to 5, the moisture resistance of the epoxy mortar composition is better.

[0040] In addition, the curing agent content in the epoxy putty composition is 10 to 30 parts. At this time, the epoxy putty composition has good adhesion and workability. For example, the curing agent content can be 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, 20 parts, 21 parts, 22 parts, 23 parts, 24 parts, 25 parts, 26 parts, 27 parts, 28 parts, 29 parts, 30 parts, or a range consisting of any of the above values.

[0041] The type of filler is not further limited in this application. Fillers for epoxy mortar compositions known in the art can be used. The fillers can be dispersed between the epoxy mortar compositions and can be used in conjunction with the network structure formed by curing and cross-linking of the epoxy resin to disperse stress well, improve the adhesion, compressive strength and hardness of the epoxy mortar composition, and save costs. The filler content in the epoxy mortar composition is 30 to 120 parts. If the filler content is too little, it cannot effectively play the above-mentioned role, which will cause the adhesion, compressive strength and hardness of the epoxy mortar composition to decrease. If the filler content is too much, the epoxy resin that may be cured and cross-linked cannot stably bond the filler, resulting in the epoxy mortar composition pulverizing and reducing adhesion. For example, the filler content can be 30 parts, 40 parts, 50 parts, 60 parts, 70 parts, 80 parts, 90 parts, 100 parts, 110 parts, 120 parts, or the range composed of any of the above numerical values.

[0042] In some embodiments of the present application, the epoxy resin includes at least one of bisphenol A epoxy resin, bisphenol F epoxy resin, and hydrogenated bisphenol A epoxy resin.

[0043] In some of the above embodiments, several common epoxy resins in the art are listed, and those skilled in the art can select them according to actual needs. It is understood that epoxy resins include but are not limited to the above-mentioned ones, and those skilled in the art can use epoxy resins known in the art that can be used in epoxy mortar compositions according to actual needs.

[0044] In some embodiments of the present application, the polyamide compound includes at least one of polyamide 300, polyamide 650, and polyamide 651; and / or the polyamide acid compound is obtained by reacting a diamino compound and a dianhydride compound in a polar solvent.

[0045] In some of the above embodiments, several common polyamide compounds in the art are specifically listed, and those skilled in the art can select them according to actual needs. It is understood that polyamide compounds include but are not limited to the above-mentioned ones, and those skilled in the art can select polyamide compounds known in the art that can be used in epoxy putty compositions according to actual needs.

[0046] Furthermore, polyamic acid compounds can be obtained by reacting a diamino compound with a dianhydride compound in a polar solvent. Therefore, polyamic acid compounds are designable, and different properties can be obtained by selecting different reaction raw materials. For example, the use of diamino compounds or dianhydride compounds containing benzene rings can improve the thermal stability of epoxy mortar.

[0047] In some embodiments of the present application, the molar ratio of the diamino compound to the dianhydride compound is 1:0.2 to 0.9. The addition amount of the diamino compound is higher than that of the dianhydride compound. The purpose is to ensure that the terminal groups of the synthesized polyamic acid compound are active amino groups, thereby ensuring that the obtained polyamic acid compound has a good curing effect.

[0048] In some embodiments of the present application, the diamino compound is an aliphatic diamino compound and / or an aromatic diamino compound; the dianhydride compound includes one or more of pyromellitic anhydride, 3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride, hexafluorodianhydride, 4,4'-phenylenedioxydiphthalic anhydride, 4,4'-oxydiphthalic anhydride, and p-phenylenedi(trimellitic acid) dianhydride; and the polar solvent includes one or more of formamide, N,N-dimethylacetamide, N,N-dimethylformamide, and dimethyl sulfoxide.

[0049] In some embodiments of the present application, the aromatic diamino compound includes one or more of 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,4-diaminodiphenyl ether, 2,5-diamino-1,4-diphenol, 4,4'-diamino-4"-hydroxytriphenylmethane, 3,4'-diaminodiphenyl ether, 4,4'-diamino-3,3'-dichlorodiphenylmethane, 4,4'-diaminooctafluorobiphenyl, 2,6-diamino-benzoic acid, p-phenylenediamine, 4',6-diamino-3-biphenylmethane, and 3,3'-diamino-4,4'-difluorobenzophenone.

[0050] In some embodiments of the present application, the preparation method of the polyamic acid compound specifically includes the following steps:

[0051] The diamino compound is dissolved in a polar solvent, and the dianhydride compound is added under a nitrogen atmosphere, and the reaction is carried out at 0-7° C. for 4-8 hours. A poor solvent is then added to precipitate the polyamic acid compound, which is then filtered and dried to obtain the polyamic acid compound.

[0052] As an example, in some embodiments of the present application, 4,4'-diaminodiphenyl ether is selected as the diamino compound raw material for synthesizing polyamic acid compounds; pyromellitic anhydride is selected as the dianhydride compound raw material for synthesizing polyamic acid compounds; N,N-dimethylacetamide is selected as the polar solvent; and water is selected as the poor solvent.

[0053] In some embodiments of the present application, the raw materials of the epoxy putty composition, calculated in parts by mass, further include 1 to 20 parts of a reactive diluent, the reactive diluent including a first reactive diluent and a second reactive diluent, the first reactive diluent including an epoxy-containing glycidyl ether, the second reactive diluent including at least one of an enamine diluent and a polyetheramine diluent; the epoxy-containing glycidyl ether includes at least one of alkylene glycidyl ether, ethylene glycol diglycidyl ether, benzyl glycidyl ether, and polypropylene glycol diglycidyl ether; the enamine diluent includes at least one of diethylenetriamine, triethylenetetramine, and tetraethylenepentamine, and the polyetheramine diluent includes at least one of polyetheramine 300, polyetheramine 400, and polyetheramine 500.

[0054] In some of the above embodiments, in order to improve the applicability of the epoxy putty composition, 1 to 20 parts of active diluent may also be included. The active diluent can effectively reduce the viscosity of the epoxy putty composition before curing, thereby being more conducive to the uniform dispersion of the components in the epoxy putty composition, and then promoting the movement of molecular chains during the cross-linking process. Therefore, the epoxy putty composition with better dispersion has a higher cross-linking density after curing, thereby having better adhesion and compressive strength. In addition, the use of active diluents in the above embodiments can participate in the curing and cross-linking reaction. Therefore, compared with the use of ordinary diluents, on the one hand, there is no volatile component, zero VOC, and it is environmentally friendly. On the other hand, it can further improve the cross-linking density of the epoxy putty composition after curing.

[0055] The reactive diluent may also include a first reactive diluent and a second reactive diluent, wherein the first reactive diluent includes an epoxy-containing glycidyl ether, and the second reactive diluent includes at least one of an enamine diluent and a polyetheramine diluent. This is because before curing of the epoxy cement composition, the epoxy resin and curing agent in the raw materials need to be stored separately. Therefore, the first reactive diluent and the epoxy resin can be mixed, and the second reactive diluent and the curing agent can be mixed, and then the two components can be mixed. This can further improve the dispersion of the raw materials and increase the crosslink density of the epoxy cement composition after curing. In addition, both the first reactive diluent and the second reactive diluent can participate in the curing and crosslinking reaction, thereby increasing the crosslink density of the epoxy cement composition after curing.

[0056] Furthermore, some of the aforementioned embodiments list several common epoxy-containing glycidyl ethers, enamine diluents, and polyetheramine diluents in the art, and those skilled in the art may select from a variety of diluents based on actual needs. It is understood that reactive diluents include, but are not limited to, those listed above, and those skilled in the art may select reactive diluents known in the art for use in epoxy mastic compositions based on actual needs.

[0057] In some embodiments of the present application, the filler includes at least one of quartz powder, alumina powder, titanium dioxide, calcium carbonate powder, lithopone, and clay; and / or the raw materials of the epoxy putty composition, in parts by mass, further include 1 to 20 parts of a thixotropic agent, the thixotropic agent including at least one of fumed silica, organic bentonite, hydrogenated castor oil, and polyamide wax.

[0058] In some of the above embodiments, several common fillers in the art are listed, and those skilled in the art can select them according to actual needs. It is understood that fillers include but are not limited to the above-mentioned ones, and those skilled in the art can use fillers known in the art that can be used in epoxy putty compositions according to actual needs.

[0059] Furthermore, the raw materials of the epoxy putty composition may also include 1 to 20 parts of a thixotropic agent. Adding a thixotropic agent to the epoxy putty composition can further improve its workability before curing, that is, it has a lower viscosity at high shear rates during mixing and coating, and the epoxy putty composition is easier to construct due to its fluidity. In addition, since the epoxy putty composition has a long construction and usable time and a slow curing and crosslinking rate, the use of a thixotropic agent can prevent the sedimentation of the components during the crosslinking process, thereby ensuring that the epoxy resin in the epoxy putty composition is fully crosslinked and synergistically improves its adhesion with the filler and thixotropic agent.

[0060] In some of the above embodiments, several common thixotropic agents in the art are listed, and those skilled in the art can select them according to actual needs. It is understood that thixotropic agents include but are not limited to the above-mentioned ones, and those skilled in the art can select thixotropic agents known in the art that can be used in epoxy putty compositions according to actual needs.

[0061] In some embodiments of the present application, the raw materials of the epoxy putty composition, calculated by mass, further include 0.1 to 2 parts of pigment, the pigment includes at least one of iron oxide red, iron oxide yellow, iron blue, and iron black; and / or the raw materials of the epoxy putty composition, calculated by mass, further include 0.1 to 5 parts of functional additives, the functional additives include at least one of a wetting agent and a defoaming agent.

[0062] In some of the above embodiments, the raw materials of the epoxy putty composition may also include pigments. On the one hand, the role of the pigments is to obtain epoxy putty compositions of different colors according to actual needs, thereby improving their decorative properties. On the other hand, in order to judge the degree of mixing of the epoxy putty composition and thus improve its cross-linking density, different types of pigments may be added to the epoxy resin and curing agent, or pigments may be added to only one of the components. During the mixing process, the mixing may be judged by observing whether the composition has tiger stripes, thereby improving construction efficiency.

[0063] Furthermore, other functional additives may be added to the epoxy putty composition to further improve its workability. The functional additives include but are not limited to wetting agents or defoaming agents, and those skilled in the art may select them according to actual needs.

[0064] In a second aspect, the present application provides a method for preparing an epoxy mortar composition, comprising the following steps:

[0065] The raw materials of the epoxy putty composition according to any embodiment of the first aspect are mixed to obtain a curable epoxy putty composition.

[0066] According to the present application, a curable epoxy putty composition can be obtained by mixing the raw materials of the epoxy putty composition in any embodiment of the first aspect. Therefore, the preparation method is simple, the application range is wide, and it has the beneficial effects of any embodiment of the first aspect.

[0067] According to the present application, there is no limitation on the specific mixing method, and any mixing method known in the art can be used. As an example, the raw materials can be placed in a double planetary mixer for mixing.

[0068] In some embodiments of the present application, the preparation method specifically comprises the following steps:

[0069] S10: mixing the epoxy resin, the first reactive diluent, a portion of the filler, and a portion of the thixotropic agent to obtain component A;

[0070] S20: mixing the curing agent, the second reactive diluent, another portion of the filler, and another portion of the thixotropic agent to obtain component B;

[0071] S30: Mix component A and component B to obtain a curable epoxy putty composition.

[0072] In some of the above embodiments, the raw materials are divided into two components. Since a cross-linking reaction will occur after the epoxy resin and the curing agent are mixed, the two are first mixed with other raw materials to obtain component A and component B, and then component A and component B are mixed. This can further improve the dispersion effect of the epoxy putty composition before curing. The epoxy putty composition with better dispersion has a higher cross-linking density after curing and better adhesion.

[0073] The clean nature of natural gas as a fossil fuel, coupled with global efforts to protect the environment and reduce greenhouse gas emissions like carbon dioxide, has led to a significant increase in global natural gas supply and demand. Natural gas, a combustible gas recognized as the cleanest energy source on Earth, is primarily composed of methane. It is colorless, odorless, non-toxic, and non-corrosive, making it clean and safe. It condenses into a liquid upon cooling to -163°C. Transportation, as a crucial link in the liquefied natural gas (LNG) supply chain, has a direct impact on the economics of natural gas supply and consumption. Furthermore, LNG, with its advantages of safe storage and ease of transportation, has become a crucial link in the entire natural gas industry chain, further driving the development of global natural gas trade.

[0074] The transportation of liquefied natural gas mainly consists of three parts: source liquefaction station, LNG ship transportation and LNG land storage tank reception. Due to the ultra-low temperature requirement of natural gas at -163℃, both LNG transport ships and LNG land storage tanks need to be treated with low-temperature insulation. Figure 1As shown, the LNG tank (or cargo hold) containment system features an insulation layer 1 stably bonded to the ship hull 3 via an adhesive layer 2. The insulation layer 1 comprises a primary shielding layer 11, a primary insulation layer 12, a secondary shielding layer 13, and a secondary insulation layer 14. The insulation layer is constructed from numerous insulation boxes, which are secured to the hull's inner hull via an adhesive layer. Because LNG carriers often operate in high-humidity environments and are applied over a large area, an adhesive that can stably cure in high humidity and maintain a long working life is required as the adhesive layer 2.

[0075] Based on this, in a third aspect, the present application provides a liquefied natural gas carrier, comprising a hull, and

[0076] An insulating box fixedly bonded to a ship hull using an epoxy putty composition obtained by the preparation method of the epoxy putty composition according to any embodiment of the first aspect or any embodiment of the second aspect.

[0077] According to the present application, in a liquefied natural gas carrier, the hull and the insulation box are bonded using the epoxy putty composition according to any embodiment of the first aspect or the epoxy putty composition obtained by the preparation method according to any embodiment of the second aspect. Since the epoxy putty composition can be cured under high humidity conditions, it can be ensured that the cured epoxy putty composition obtained during construction under high humidity conditions still has good adhesion, so that the two are stably bonded and not easily displaced, thereby improving the safety of the liquefied natural gas carrier; in addition, since the epoxy putty composition has a long construction application time, it is suitable for large-area construction, reducing the difficulty of construction.

[0078] In some embodiments of the present application, the interior of the insulation box includes laminated wood, heavyweight boards, saddle panels, and an epoxy putty composition obtained by the preparation method of the epoxy putty composition of any embodiment of the first aspect or any embodiment of the second aspect, which is filled between the laminated wood and the heavyweight boards and saddle panels.

[0079] In some of the above embodiments, the epoxy putty composition can also be filled between the laminated wood, heavyweight board, and saddle panel inside the insulation box. Since it still has good adhesion when applied under high humidity, it can make the insulation box flatter and more stable, further improving the safety of the LCG transport ship.

[0080] Below, the embodiment of the present application is described. The embodiment described below is exemplary and is only used to explain the present application, and is not to be construed as limiting the present application. Where specific techniques or conditions are not specified in the embodiments, the techniques or conditions described in the literature in this area or the product specifications are used. Reagents or instruments used that do not specify the manufacturer are conventional products that can be obtained commercially.

[0081] Preparation of polyamic acid compounds: Dissolve 4 mol of 4,4'-diaminodiphenyl ether in 500 mL of N,N-dimethylacetamide. Under a nitrogen atmosphere, add 2 mol of pyromellitic anhydride and react in a 5°C ice-water bath for 6 hours. Then add 400 mL of deionized water for precipitation. After filtering, the precipitate is vacuum-dried at 25°C for 24 hours to obtain a light yellow solid powder, which is the polyamic acid compound.

[0082] Example 1

[0083] Preparation of component A: Mix 30 parts of epoxy resin E44, 5 parts of 1,4-cyclohexanedimethanol diglycidyl ether, 35 parts of calcium carbonate, 20 parts of titanium dioxide, 9.5 parts of silicon dioxide, 0.1 parts of color paste, 0.25 parts of wetting agent, and 0.25 parts of defoaming agent to obtain component A for later use;

[0084] Preparation of component B: Mix 25 parts of polyamide 300, 5 parts of polyamic acid compound, 5 parts of tetraethylene pentamine, 35 parts of calcium carbonate, 20 parts of titanium dioxide, 9.5 parts of silicon dioxide, 0.1 parts of color paste, 0.25 parts of wetting agent, and 0.25 parts of defoaming agent to obtain component B for later use;

[0085] Preparation of the epoxy putty composition: Component A and component B are mixed in a mass ratio of 100:65 to obtain a curable epoxy putty composition.

[0086] Example 2

[0087] Preparation of component A: Mix 30 parts of epoxy resin E44, 5 parts of 1,4-cyclohexanedimethanol diglycidyl ether, 35 parts of calcium carbonate, 20 parts of titanium dioxide, 9.5 parts of silicon dioxide, 0.1 parts of color paste, 0.25 parts of wetting agent, and 0.25 parts of defoaming agent to obtain component A for later use;

[0088] Preparation of component B: Mix 20 parts of polyamide 300, 10 parts of polyamic acid compound, 5 parts of tetraethylene pentamine, 35 parts of calcium carbonate, 20 parts of titanium dioxide, 9.5 parts of silicon dioxide, 0.1 parts of color paste, 0.25 parts of wetting agent, and 0.25 parts of defoaming agent to obtain component B for later use;

[0089] Preparation of the epoxy putty composition: Component A and component B are mixed in a mass ratio of 100:65 to obtain a curable epoxy putty composition.

[0090] Example 3

[0091] Preparation of component A: Mix 30 parts of epoxy resin E44, 5 parts of 1,4-cyclohexanedimethanol diglycidyl ether, 35 parts of calcium carbonate, 20 parts of titanium dioxide, 9.5 parts of silicon dioxide, 0.1 parts of color paste, 0.25 parts of wetting agent, and 0.25 parts of defoaming agent to obtain component A for later use;

[0092] Preparation of component B: 15 parts of polyamide 300, 15 parts of polyamic acid compound, 5 parts of tetraethylene pentamine, 35 parts of calcium carbonate, 20 parts of titanium dioxide, 9.5 parts of silicon dioxide, 0.1 parts of color paste, 0.25 parts of wetting agent, and 0.25 parts of defoaming agent are mixed to obtain component B for later use;

[0093] Preparation of the epoxy putty composition: Component A and component B are mixed in a mass ratio of 100:65 to obtain a curable epoxy putty composition.

[0094] Example 4

[0095] Preparation of component A: Mix 30 parts of epoxy resin E44, 5 parts of 1,4-cyclohexanedimethanol diglycidyl ether, 35 parts of calcium carbonate, 20 parts of titanium dioxide, 9.5 parts of silicon dioxide, 0.1 parts of color paste, 0.25 parts of wetting agent, and 0.25 parts of defoaming agent to obtain component A for later use;

[0096] Preparation of component B: 10 parts of polyamide 300, 20 parts of polyamic acid compound, 5 parts of tetraethylene pentamine, 35 parts of calcium carbonate, 20 parts of titanium dioxide, 9.5 parts of silicon dioxide, 0.1 parts of color paste, 0.25 parts of wetting agent, and 0.25 parts of defoaming agent are mixed to obtain component B for later use;

[0097] Preparation of the epoxy putty composition: Component A and component B are mixed in a mass ratio of 100:65 to obtain a curable epoxy putty composition.

[0098] Example 5

[0099] Preparation of component A: Mix 30 parts of epoxy resin E44, 5 parts of 1,4-cyclohexanedimethanol diglycidyl ether, 35 parts of calcium carbonate, 20 parts of titanium dioxide, 9.5 parts of silicon dioxide, 0.1 parts of color paste, 0.25 parts of wetting agent, and 0.25 parts of defoaming agent to obtain component A for later use;

[0100] Preparation of component B: Mix 5 parts of polyamide 300, 25 parts of polyamic acid compound, 5 parts of tetraethylene pentamine, 35 parts of calcium carbonate, 20 parts of titanium dioxide, 9.5 parts of silicon dioxide, 0.1 parts of color paste, 0.25 parts of wetting agent, and 0.25 parts of defoaming agent to obtain component B for later use;

[0101] Preparation of the epoxy putty composition: Component A and component B are mixed in a mass ratio of 100:65 to obtain a curable epoxy putty composition.

[0102] Comparative Example 1

[0103] Preparation of component A: Mix 30 parts of epoxy resin E44, 5 parts of 1,4-cyclohexanedimethanol diglycidyl ether, 35 parts of calcium carbonate, 20 parts of titanium dioxide, 9.5 parts of silicon dioxide, 0.1 parts of color paste, 0.25 parts of wetting agent, and 0.25 parts of defoaming agent to obtain component A for later use;

[0104] Preparation of component B: Mix 35 parts of polyamide 300, 5 parts of tetraethylene pentamine, 35 parts of calcium carbonate, 20 parts of titanium dioxide, 9.5 parts of silicon dioxide, 0.1 parts of color paste, 0.25 parts of wetting agent, and 0.25 parts of defoaming agent to obtain component B for later use;

[0105] Preparation of the epoxy putty composition: Component A and component B are mixed in a mass ratio of 100:65 to obtain a curable epoxy putty composition.

[0106] Comparative Example 2

[0107] Preparation of component A: Mix 30 parts of epoxy resin E44, 5 parts of 1,4-cyclohexanedimethanol diglycidyl ether, 35 parts of calcium carbonate, 20 parts of titanium dioxide, 9.5 parts of silicon dioxide, 0.1 parts of color paste, 0.25 parts of wetting agent, and 0.25 parts of defoaming agent to obtain component A for later use;

[0108] Preparation of component B: 30 parts of polyamic acid compound, 5 parts of tetraethylenepentamine, 35 parts of calcium carbonate, 20 parts of titanium dioxide, 9.5 parts of silicon dioxide, 0.1 parts of color paste, 0.25 parts of wetting agent, and 0.25 parts of defoaming agent are mixed to obtain component B for later use;

[0109] Preparation of the epoxy putty composition: Component A and component B are mixed in a mass ratio of 100:65 to obtain a curable epoxy putty composition.

[0110] Test section

[0111] 1. According to GB / T 27595-2011 "Test method for tensile shear fatigue properties of structural adhesives", samples were prepared and single shear tensile tests were performed using a universal material testing machine. Three average specimens were averaged and the average value was taken to obtain the bonding strength of the sample.

[0112] 2. Humidity bonding comparison is to perform single shear specimen bonding in a hot and humid chamber and maintain curing until complete curing. When the tensile shear strength is lower than 10MPa, it is recorded as moisture resistance failure, and the maximum HR value at this time is recorded. The larger the HR value, the better the moisture resistance.

[0113] 3. Construction time test: After mixing component A and component B, make them into a rubber rope with a diameter of 20mm. Set the curing time as t value at a specific temperature (the test results are all tested at room temperature 25℃±2℃). Use a 5KG weight to perform a compression thixotropy test. When the height after compression is greater than 5mm, the construction time is over. The recorded t value is the applicable construction time.

[0114] 4. Curing rate test: The epoxy putty composition in Example 1 and the commercially available epoxy putty composition (JM-98) were subjected to accelerated curing process test using a DMA (dynamic mechanical thermomechanical) instrument at 60°C with a vibration frequency of 10 Hz. The viscosity of the epoxy putty composition was tested over time. The faster the viscosity increased, the faster the curing reaction rate. The results are as follows: Figure 2 shown.

[0115] The epoxy mortar compositions in Examples 1 to 5 and Comparative Examples 1 to 2 and a commercially available epoxy mortar composition (JM-98) were subjected to performance tests. The test results are shown in Table 1.

[0116] Table 1

[0117]

[0118] According to Table 1, the bonding strength, moisture resistance and construction use time of each embodiment are significantly improved compared with the comparative examples and commercially available products, indicating that the epoxy putty composition provided in this application has good workability. The possible reasons have been analyzed above and will not be repeated here.

[0119] according to Figure 2 By comparing the curve of Example 1 with the curve of the commercially available product, it can be concluded that Example 1 uses two curing agents in combination, and its initial curing reaction rate is significantly suppressed, and the reaction rate increases slowly, effectively extending the construction time of the epoxy putty composition.

[0120] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present application, rather than to limit them. Although the present application has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or make equivalent replacements for some or all of the technical features therein. These modifications or replacements do not deviate the essence of the corresponding technical solutions from the scope of the technical solutions of the embodiments of the present application.

Claims

1. A slow-setting epoxy mortar composition, characterized in that: The following raw materials are included in parts by mass: 20-50 parts of epoxy resin, 10 to 30 parts of a curing agent, wherein the curing agent comprises a polyamide compound and a polyamic acid compound, and the mass ratio of the polyamide compound to the polyamic acid compound is 1:0.2 to 5, 30 to 120 parts of filler.

2. The slow-setting epoxy mortar composition according to claim 1, wherein The epoxy resin includes at least one of bisphenol A epoxy resin, bisphenol F epoxy resin, and hydrogenated bisphenol A epoxy resin.

3. The slow-setting epoxy mortar composition according to claim 1, wherein The polyamide compound includes at least one of polyamide 300, polyamide 650, and polyamide 651; and / or The polyamic acid compound is obtained by reacting a diamino compound with a dianhydride compound in a polar solvent.

4. The slow-setting epoxy mortar composition according to claim 1, characterized in that The raw materials of the slow-setting epoxy putty composition are calculated by weight and further include 1 to 20 parts of a reactive diluent, wherein the reactive diluent includes a first reactive diluent and a second reactive diluent, wherein the first reactive diluent includes a glycidyl ether containing an epoxy group, and the second reactive diluent includes at least one of an enamine diluent and a polyetheramine diluent; The epoxy-containing glycidyl ether includes at least one of alkylene glycidyl ether, ethylene glycol diglycidyl ether, benzyl glycidyl ether, and polypropylene glycol diglycidyl ether; The enamine diluent includes at least one of diethylenetriamine, triethylenetetramine and tetraethylenepentamine. The polyetheramine diluent includes at least one of polyetheramine 300, polyetheramine 400, and polyetheramine 500.

5. The slow-setting epoxy mortar composition according to claim 1, characterized in that The filler comprises at least one of quartz powder, alumina powder, titanium dioxide, calcium carbonate powder, lithopone, and clay; and / or The raw materials of the slow-setting epoxy putty composition further include 1 to 20 parts by mass of a thixotropic agent, which includes at least one of fumed silica, organic bentonite, hydrogenated castor oil, and polyamide wax.

6. The slow-setting epoxy mortar composition according to claim 1, characterized in that The raw materials of the slow-setting epoxy putty composition further include 0.1 to 2 parts by mass of a pigment, wherein the pigment includes at least one of iron oxide red, iron oxide yellow, iron blue, and iron black; and / or The raw materials of the slow-setting epoxy putty composition are calculated in parts by mass and further include 0.1 to 5 parts of functional additives, and the functional additives include at least one of a wetting agent and a defoaming agent.

7. A method for preparing a slow-setting epoxy mortar composition, characterized in that: The following steps are involved: The raw materials of the slow-setting epoxy putty composition according to any one of claims 1 to 6 are mixed to obtain a curable slow-setting epoxy putty composition.

8. The preparation method according to claim 7, characterized in that The specific steps include: S10: mixing the epoxy resin, the first reactive diluent, a portion of the filler, and a portion of the thixotropic agent to obtain component A; S20: mixing the curing agent, the second reactive diluent, another portion of the filler, and another portion of the thixotropic agent to obtain component B; S30: Component A and component B are mixed to obtain a curable slow-setting epoxy mortar composition.

9. A liquefied natural gas carrier, characterized in that: including the hull, and An insulation box fixedly bonded to the hull by the slow-setting epoxy mortar composition according to any one of claims 1 to 6 or the slow-setting epoxy mortar composition obtained by the preparation method according to claim 7 or 8.

10. The liquefied natural gas carrier according to claim 9, characterized in that: The interior of the insulating box includes laminated wood, heavyweight boards, saddle panels, and a slow-setting epoxy putty composition according to any one of claims 1 to 6 or a slow-setting epoxy putty composition obtained by the preparation method according to claim 7 or 8, which is filled between the laminated wood and the heavyweight boards and saddle panels.

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