Sealant

Abstract

The invention relates to the technical field of sealing materials, in particular to a sealant which comprises a first component and a second component. The first component comprises epoxy resin; the second component comprises polyether amine, a curing accelerator and a catalyst; the catalyst comprises a phenol catalyst. According to the sealant, the hardness of the cured sealant can be controlled by adjusting the curing temperature, and the formula of the sealant does not need to be further adjusted.

Description

Technical Field

[0001] The present application relates to the technical field of sealing materials, and in particular to a sealant. Background Art

[0002] Traditional sealants include polyurethane sealants, silicone sealants, polysulfide sealants, etc., with a hardness of 25-90 Shore A and good elasticity. Epoxy resin has excellent mechanical properties, bonding properties, and weather resistance, but usually has a high cross-linking density, a hard and brittle texture, poor flexibility, and almost no elasticity.

[0003] In order to increase the flexibility of epoxy resin and obtain elastic epoxy glue, various approaches have been adopted at home and abroad to toughen epoxy resin, mainly in the following aspects: (1) by adding rubber elastomers, such as amino-terminated liquid nitrile rubber, hydroxyl-terminated liquid polybutylene rubber, liquid polysulfide rubber, etc., an elastomer dispersed phase is formed inside after curing to improve the flexibility of epoxy resin; (2) synthesizing high-elasticity epoxy resin, such as introducing flexible long-chain fatty alcohols in the synthesis to obtain glycidyl ether-type epoxy resins with different elasticities; (3) by using flexible chain segment curing agents, such as amino-terminated polyurethane, polyether amine, low molecular weight polyamide, etc., microscopic phase separation is produced during the curing process to form a dense and loose phase network structure, thereby improving the toughness of the system.

[0004] The above technical solutions can improve the flexibility of epoxy resin, but cannot control the hardness after curing without changing the sealant formula. Generally, changing the hardness of the sealant after curing requires changing the sealant formula, such as changing the sealant curing system, adjusting the amount of filler, adding plasticizer, etc.

[0005] Therefore, it is crucial to develop a sealant that can control the hardness after curing without changing the sealant formulation. Summary of the invention

[0006] In view of the above problems, the present application provides a sealant, which can control the hardness of the sealant after curing by adjusting the curing temperature without further adjusting the formula of the sealant.

[0007] The present application provides a sealant, which comprises a first component and a second component;

[0008] The first component includes epoxy resin;

[0009] The second component includes polyetheramine, curing accelerator and catalyst;

[0010] The catalyst includes a phenol catalyst.

[0011] In the technical solution of the implementation mode of the present application, the catalyst is selected in the second component, combined with the polyetheramine and the curing accelerator. In actual use, the hardness of the cured sealant can be controlled by adjusting the curing temperature, without further adjusting the formula of the sealant, especially adding additives or adjusting the filler content.

[0012] In some embodiments, the polyetheramine comprises a difunctional polyetheramine.

[0013] In some embodiments, the polyetheramine includes a first polyetheramine and a second polyetheramine;

[0014] The number average molecular weight of the first polyetheramine is greater than the number average molecular weight of the second polyetheramine.

[0015] In some embodiments, the number average molecular weight of the first polyetheramine is 1500-5000 g / mol.

[0016] In some embodiments, the number average molecular weight of the second polyetheramine is 200-500 g / mol.

[0017] In some embodiments, based on 100% by mass of the first polyetheramine, the mass of the second polyetheramine is 10%-20%.

[0018] In the technical solution of the implementation mode of the present application, the addition amount of high molecular weight polyether amine is greater than the addition amount of low molecular weight polyether amine, and the formed sealant can control the hardness of the cured sealant by adjusting the curing temperature without further adjusting the formula of the sealant.

[0019] In some embodiments, the phenol catalyst includes 2,4,6-tris(dimethylaminomethyl)phenol and / or dimethylaminomethylphenol.

[0020] In some embodiments, based on 100% of the mass of the polyetheramine, the mass of the phenol catalyst is 3%-12%.

[0021] In the technical solution of the embodiment of the present application, the mass of the phenol catalyst is controlled within the above range, and the hardness of the cured sealant can be controlled by adjusting the curing temperature without adjusting the sealant formula.

[0022] In some embodiments, based on 100% of the mass of the polyetheramine, the mass of the phenol catalyst is 4%-10%.

[0023] In some embodiments, based on 100% of the mass of the polyetheramine, the mass of the curing accelerator is 4%-12%.

[0024] In some embodiments, based on 100% of the mass of the first polyetheramine, the mass of the curing accelerator is 5%-10%.

[0025] In some embodiments, the curing accelerator includes any one or a combination of at least two of triethanolamine, m-phenylenediamine, m-phenylenediamine, N-aminoethylpiperazine, 1,4-diacetylpiperazine, isophoronediamine or hexahydropyridine.

[0026] In some embodiments, the epoxy value of the epoxy resin is 0.2-0.6 mol / 100g.

[0027] In some embodiments, the epoxy resin includes bisphenol A type epoxy resin.

[0028] In some embodiments, the mass ratio of the first component to the second component is 10:(12-18).

[0029] In some embodiments, the sealant further includes a third component, and the third component includes a filler.

[0030] In some embodiments, the filler includes any one of fumed silica, titanium dioxide, calcium carbonate, or kaolin, or a combination of at least two thereof.

[0031] In some embodiments, the mass ratio of the first component to the third component is 10:(0-3).

[0032] In some embodiments, the hardness of the sealant after curing is adjusted by the curing temperature.

[0033] The above description is only an overview of the technical solution of the present application. In order to more clearly understand the technical means of the present application, it can be implemented in accordance with the contents of the specification. In order to make the above and other purposes, features and advantages of the present application more obvious and easy to understand, the specific implementation methods of the present application are listed below. DETAILED DESCRIPTION

[0034] The following is a detailed description of the embodiments of the technical solution of the present application. The following embodiments are only used to more clearly illustrate the technical solution of the present application, and are therefore only used as examples, and cannot be used to limit the scope of protection of the present application.

[0035] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by technicians in the technical field to which this application belongs; the terms used herein are only for the purpose of describing specific embodiments and are not intended to limit this application; the terms "including" and "having" in the description and claims of this application and any variations thereof are intended to cover non-exclusive inclusions.

[0036] In the description of the embodiments of the present application, the technical terms "first", "second", etc. are only used to distinguish different objects, and cannot be understood as indicating or implying relative importance or implicitly indicating the number, specific order or primary and secondary relationship of the indicated technical features. In the description of the embodiments of the present application, the meaning of "multiple" is more than two, unless otherwise clearly and specifically defined.

[0037] Reference to "embodiments" herein means that a particular feature, structure, or characteristic described in conjunction with the embodiments may be included in at least one embodiment of the present application. The appearance of the phrase in various locations in the specification does not necessarily refer to the same embodiment, nor is it an independent or alternative embodiment that is mutually exclusive with other embodiments. It is explicitly and implicitly understood by those skilled in the art that the embodiments described herein may be combined with other embodiments.

[0038] The "range" disclosed in the present application is defined in the form of a lower limit and an upper limit, and a given range is defined by selecting a lower limit and an upper limit, and the selected lower limit and upper limit define the boundaries of the particular range. The range defined in this way can be inclusive or exclusive of the end values, and can be arbitrarily combined, that is, any lower limit can be combined with any upper limit to form a range. For example, if a range of 60 to 120 and 80 to 110 is listed for a particular parameter, it is understood that a range of 60 to 110 and 80 to 120 is also expected. In addition, if the minimum range values ​​1 and 2 are listed, and if the maximum range values ​​3, 4 and 5 are listed, the following ranges can all be expected: 1-3, 1-4, 1-5, 2-3, 2-4 and 2-5. In the present application, unless otherwise specified, the numerical range "ab" represents an abbreviation of any real number combination between a and b, where a and b are both real numbers. For example, the numerical range "2-10" means that all real numbers between "2-10" are listed in this document, and "2-10" is just an abbreviation of these numerical combinations. In addition, when a parameter is expressed as an integer ≥ 2, it is equivalent to disclosing that the parameter is, for example, an integer of 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.

[0039] In the description of the embodiments of the present application, the term "and / or" is only a description of the association relationship of associated objects, indicating that three relationships may exist. For example, A and / or B can represent: A exists, A and B exist at the same time, and B exists. In addition, the character " / " in this article generally indicates that the associated objects before and after are in an "or" relationship.

[0040] In the prior art, for sealants, especially epoxy sealants, generally changing the hardness of the sealant after curing requires changing the sealant formula, such as changing the sealant curing system, adjusting the amount of filler, adding plasticizer, etc. It is generally impossible to control the hardness after curing without changing the sealant formula.

[0041] The present application selects the catalyst of the second component to include a phenolic catalyst, so that the sealant can control the hardness of the cured sealant by adjusting the curing temperature without further adjusting the formula of the sealant.

[0042] [Sealant]

[0043] The present application provides a sealant, which comprises a first component and a second component;

[0044] The first component includes epoxy resin;

[0045] The second component includes polyetheramine, curing accelerator and catalyst;

[0046] The catalyst includes a phenol catalyst.

[0047] In the technical solution of the embodiment of the present application, the catalyst is selected in the second component, combined with the polyetheramine and the curing accelerator. In actual use, the hardness of the cured sealant can be controlled by adjusting the curing temperature, without further adjusting the formula of the sealant, especially adding additives or adjusting the filler content.

[0048] In some embodiments, the polyetheramine comprises a difunctional polyetheramine.

[0049] In some embodiments, the polyetheramine includes a first polyetheramine and a second polyetheramine;

[0050] The number average molecular weight of the first polyetheramine is greater than the number average molecular weight of the second polyetheramine.

[0051] In some embodiments, the number average molecular weight of the first polyetheramine is 1500-5000 g / mol, for example, 2000 g / mol, 2500 g / mol, 3000 g / mol, 3500 g / mol, 4000 g / mol, 4500 g / mol, etc.

[0052] In some embodiments, the number average molecular weight of the second polyetheramine is 200-500 g / mol, for example, 250 g / mol, 100 g / mol, 350 g / mol, 400 g / mol, 450 g / mol, etc.

[0053] In some embodiments, based on the mass of the first polyetheramine being 100%, the mass of the second polyetheramine is 10%-20%, for example, 12%, 14%, 16%, 18%, etc.

[0054] In the technical solution of the embodiment of the present application, the addition amount of high molecular weight polyetheramine is greater than the addition amount of low molecular weight polyetheramine, and the formed sealant can control the hardness of the cured sealant by adjusting the curing temperature without further adjusting the formula of the sealant.

[0055] In some embodiments, the phenol catalyst includes 2,4,6-tris(dimethylaminomethyl)phenol (DMP-30) and / or dimethylaminomethylphenol.

[0056] In some embodiments, based on 100% of the mass of the polyetheramine, the mass of the phenol catalyst is 3%-12%, for example, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, etc.

[0057] In the technical solution of the embodiment of the present application, the mass of the phenol catalyst is controlled within the above range, and the hardness of the cured sealant can be controlled by adjusting the curing temperature without adjusting the sealant formula.

[0058] In some embodiments, based on 100% of the mass of the polyetheramine, the mass of the phenol catalyst is 4%-10%, for example, 5%, 6%, 7%, 8%, 9%, etc.

[0059] In some embodiments, based on 100% of the mass of the polyetheramine, the mass of the curing accelerator is 4%-12%, for example, 5%, 6%, 7%, 8%, 9%, 10%, 11%, etc.

[0060] In some embodiments, based on 100% of the mass of the first polyetheramine, the mass of the curing accelerator is 5%-10%, for example, 6%, 7%, 8%, 9%, etc.

[0061] In some embodiments, the curing accelerator includes any one of triethanolamine, m-phenylenediamine, m-phenylenediamine, N-aminoethylpiperazine, 1,4-diacetylpiperazine, isophoronediamine or hexahydropyridine, or a combination of at least two thereof.

[0062] In some embodiments, the epoxy value of the epoxy resin is 0.2-0.6 mol / 100 g, such as 0.35 mol / 100 g, 0.4 mol / 100 g, 0.5 mol / 100 g, etc.

[0063] In the present application, the epoxy value refers to the amount (number of moles) of substances containing epoxy groups per 100 grams of epoxy resin, usually in units of mol / 100g.

[0064] In some embodiments, the epoxy resin includes bisphenol A epoxy resin.

[0065] As an example, the epoxy resin is selected from epoxy resin E51 and / or epoxy resin E44, wherein the epoxy value of epoxy resin E51 is 0.48-0.54 mol / 100 g, and the epoxy value of epoxy resin E44 is 0.42-0.48 mol / 100 g.

[0066] In some embodiments, the mass ratio of the first component to the second component is 10:(12-18), wherein 12-18 can be 13, 14, 15, 16, 17, etc.

[0067] In some embodiments, the sealant further comprises a third component, wherein the third component comprises a filler.

[0068] In some embodiments, the filler includes any one of fumed silica, titanium dioxide, calcium carbonate, or kaolin, or a combination of at least two thereof.

[0069] In some embodiments, the mass ratio of the first component to the third component is 10:(0-3), for example, 0.5, 1, 1.5, 2, 2.5, etc.

[0070] In some embodiments, the hardness of the sealant after curing is adjusted by the curing temperature.

[0071] As an example, the sealant includes a first component, a second component and a third component in a mass ratio of 10:(12-18):(0-3);

[0072] The first component includes bisphenol A epoxy resin, and the epoxy value is 0.2-0.6 mol / 100 mol;

[0073] Based on the total mass of the polyetheramine being 100%, the second component comprises 100% polyetheramine, 4%-12% curing accelerator and 3%-12% phenol catalyst;

[0074] The polyetheramine comprises a first polyetheramine and a second polyetheramine in a mass ratio of 100:(10-20);

[0075] The number average molecular weight of the first polyetheramine is greater than the number average molecular weight of the second polyetheramine.

[0076] The third component includes a filler.

[0077] As an example, the sealant includes a first component, a second component and a third component in a mass ratio of 10:(12-18):(0-3);

[0078] The first component includes bisphenol A epoxy resin, and the epoxy value is 0.2-0.6 mol / 100 mol;

[0079] Based on the total mass of the first polyetheramine being 100%, the second component comprises 100% of the first polyetheramine, 10%-20% of the second polyetheramine, 5%-10% of a curing accelerator and 4%-10% of a phenol catalyst;

[0080] The number average molecular weight of the first polyetheramine is greater than the number average molecular weight of the second polyetheramine.

[0081] The third component includes a filler.

[0082] In actual use, the components in the second component are first mixed according to the formula amount, and then the first component, the second component and the third component are mixed according to the formula amount, and a high-speed mixer or a three-roll grinder is used for mixing, and the mixed sealant is loaded into a mold.

[0083] As an example, in actual use, the first component and the second component can be prepolymerized and then applied to the part that needs to be sealed and fully cured. The third component can be mixed with the first component and the second component before prepolymerization, or can be used after mixing with the prepolymer.

[0084] [Examples and performance results]

[0085] Example 1 and Comparative Examples 1-2

[0086] The sealant consists of a first component and a second component in a mass ratio of 10:14.

[0087] The first component: epoxy resin E-51, epoxy value is 0.51 mol / 100g.

[0088] The formula of the second component is shown in Table 1.

[0089] Table 1

[0090]

[0091] In the table, the polyetheramines described in the present application were purchased from Huntsman Corporation with the grades D2000 and D230, wherein the number average molecular weight of D2000 is 2000 g / mol, and that of D230 is 230 g / mol.

[0092] The components of the sealants described in Example 1 and Comparative Examples 1-2 were mixed according to the formula amounts, and then cured according to the conditions shown in Table 2. The hardness values ​​were tested according to the method of GB / T 531.

[0093] Table 2

[0094] Curing conditions Example 1 Comparative Example 1 Comparative Example 2 Room temperature curing 7d 94 65 64 Curing at 60℃ for 4h 82 68 67 Curing at 60℃ for 24h 82 68 69 120℃ curing for 4h 58 68 69 120℃ curing for 24h 58 68 69

[0095] It can be seen from Table 2 that, when the curing is basically complete, the hardness of the sealant described in the present application at different curing temperatures has obvious differences, while the hardness difference after curing under different conditions in the control example is not much. A few numerical differences are caused by incomplete curing. If the curing is continued, the final hardness after complete curing is not much different.

[0096] Example 2 and Comparative Example 3

[0097] The sealant consists of a first component and a second component in a mass ratio of 10:16.

[0098] The first component: epoxy resin E-44, epoxy value is 0.44 mol / 100g.

[0099] The formula of the second component is shown in Table 3.

[0100] Table 3

[0101]

[0102] The components of the sealants described in Example 2 and Comparative Example 3 were mixed according to the formula amount, and then cured according to the conditions shown in Table 4. The hardness value was tested according to the method of GB / T 531, and the shear strength value was tested according to the method of GB / T 7124.

[0103] Table 4

[0104] Curing conditions Example 2 Comparative Example 3 60℃ cured for 24h hardness, Shore A 85 71 120℃ cured for 24h hardness, Shore A 68 72 Shear strength after curing at 60℃, MPa 11.3 6.4 Shear strength after curing at 120℃, MPa 6.0 6.6

[0105] It can be seen from Table 4 that, when the curing is basically complete, the hardness of the sealant described in the present application at different curing temperatures is significantly different and affects the mechanical properties after curing. Therefore, the mechanical properties of the sealant can be adjusted by controlling the temperature to make it suitable for sealing parts with different mechanical property requirements.

[0106] Example 3

[0107] The sealant consists of a first component, a second component and a third component in a mass ratio of 10:17:1.

[0108] The first component: epoxy resin E-51, epoxy value is 0.51 mol / 100g.

[0109] The formula of the second component is shown in Table 5.

[0110] The third component: titanium dioxide.

[0111] Table 5

[0112]

[0113]

[0114] The components of the sealant described in Example 4 were mixed according to the formula, and then cured according to the conditions shown in Table 6. The hardness value was tested according to the method of GB / T 531.

[0115] Table 6

[0116] Curing conditions Example 3 60℃ cured for 24h hardness, Shore A 90 120℃ cured for 24h hardness, Shore A 48

[0117] It can be seen from Table 6 that, when the curing is substantially complete, the hardness of the sealant described in the present application at different curing temperatures has obvious differences.

[0118] In summary, the hardness of the sealant described in the present application at different curing temperatures is significantly different and affects the mechanical properties after curing. Therefore, the sealant described in the present application can adjust the hardness and mechanical properties of the sealant by controlling the temperature, so that it is suitable for sealing parts with different hardness and mechanical property requirements.

[0119] 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 replace some or all of the technical features therein by equivalents; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the scope of the technical solutions of the embodiments of the present application, and they should all be included in the scope of the claims and specification of the present application. In particular, as long as there is no structural conflict, the various technical features mentioned in the various embodiments can be combined in any way. The present application is not limited to the specific embodiments disclosed herein, but includes all technical solutions that fall within the scope of the claims.

Claims

1. A sealant, characterized in that: The sealant comprises a first component and a second component; The first component includes epoxy resin; The second component includes polyetheramine, curing accelerator and catalyst; The catalyst includes a phenol catalyst.

2. The sealant according to claim 1, characterized in that: The polyetheramine includes a difunctional polyetheramine; Preferably, the polyetheramine comprises a first polyetheramine and a second polyetheramine; The number average molecular weight of the first polyetheramine is greater than the number average molecular weight of the second polyetheramine; Preferably, the number average molecular weight of the first polyetheramine is 1500-5000 g / mol; Preferably, the number average molecular weight of the second polyetheramine is 200-500 g / mol.

3. The sealant according to claim 2, characterized in that: Taking the mass of the first polyetheramine as 100%, the mass of the second polyetheramine is 10%-20%.

4. The sealant according to any one of claims 1 to 3, characterized in that: Based on the mass of the polyetheramine being 100%, the mass of the curing accelerator is 4%-12%; Preferably, based on 100% of the mass of the first polyetheramine, the mass of the curing accelerator is 5%-10%; Preferably, the curing accelerator includes any one of triethanolamine, m-phenylenediamine, m-phenylenediamine, N-aminoethylpiperazine, 1,4-diacetylpiperazine, isophoronediamine or hexahydropyridine, or a combination of at least two thereof.

5. The sealant according to any one of claims 1 to 4, characterized in that: The phenol catalyst includes 2,4,6-tris(dimethylaminomethyl)phenol and / or dimethylaminomethylphenol.

6. The sealant according to any one of claims 1 to 5, characterized in that: Based on the mass of the polyetheramine being 100%, the mass of the phenol catalyst is 3%-12%; Preferably, based on 100% of the mass of the first polyetheramine, the mass of the phenol catalyst is 4%-10%.

7. The sealant according to any one of claims 1 to 6, characterized in that: The epoxy value of the epoxy resin is 0.2-0.6 mol / 100g; Preferably, the epoxy resin comprises bisphenol A type epoxy resin.

8. The sealant according to any one of claims 1 to 7, characterized in that: The mass ratio of the first component to the second component is 10:(12-18).

9. The sealant according to any one of claims 1 to 8, characterized in that: The sealant further comprises a third component, and the third component comprises a filler; Preferably, the filler comprises any one or a combination of at least two of fumed silica, titanium dioxide, calcium carbonate or kaolin; Preferably, the mass ratio of the first component to the third component is 10:(0-3).

10. The sealant according to any one of claims 1 to 9, characterized in that: The hardness of the sealant after curing is adjusted by the curing temperature.

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