A high elastic modulus epoxy resin composition and steel structure adhesive

Abstract

The present invention relates to the field of organic resin materials, in particular to a high elastic modulus epoxy resin composition and a steel structural adhesive, comprising a component A and a component B, wherein the component A comprises an epoxy resin and a modifier, the component B is a curing agent, and the structural formula of the modifier is as follows: #imgabs0# wherein Ar1 and Ar2 are the same and are any one of cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. After testing, the epoxy resin composition of the present invention has excellent mechanical properties after curing, with a tensile strength of ≥110MPa, a tensile elastic modulus of ≥3.1GPa, and an impact strength of ≥23kJ / m 2 .

Description

Technical Field

[0001] The invention relates to the field of organic resin materials, in particular to a high elastic modulus epoxy resin composition and steel structure adhesive. Background Art

[0002] Epoxy resin is generally superior to most other types of resins in many aspects such as mechanical strength and resistance to environmental degradation. It also has the advantages of excellent bonding and creep properties, low shrinkage, electrical insulation, and good dimensional stability. Therefore, it is considered to be a multifunctional material and an indispensable basic material in many fields.

[0003] The properties of polymer materials are often closely related to their structural composition. Before curing, epoxy resin itself is an epoxy oligomer. Only after adding a curing agent will it form a thermosetting resin with a high cross-linking density and a three-dimensional network structure. How to improve the elastic modulus of epoxy resin so that it can withstand greater external forces, including stretching, compression, and shearing, thereby ensuring the stability and reliability of polymer materials during use, is one of the technical issues that need to be urgently addressed. Summary of the invention

[0004] Purpose of the invention: In view of the above technical problems, the present invention proposes a high elastic modulus epoxy resin composition and steel structure adhesive.

[0005] The technical solutions adopted are as follows:

[0006] A high elastic modulus epoxy resin composition, comprising component A and component B;

[0007] The A component includes epoxy resin and a modifier;

[0008] The B component is a curing agent;

[0009] The structural formula of the modifier is as follows:

[0010] ;

[0011] Wherein, Ar1 and Ar2 are the same and are any one of cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl.

[0012] Furthermore, the preparation method of the modifier is as follows:

[0013] After allyl epoxy resin and cycloalkyl mercaptan are uniformly mixed, a photoinitiator is added, and the mixture is stirred and reacted for 1-10 hours under ultraviolet light.

[0014] Furthermore, the photoinitiator is 1173 photoinitiator (chemical name is 2-hydroxy-2-methyl-1-phenyl-1-propanone, referred to as HMPP) and / or 184 photoinitiator (chemical name is 1-hydroxycyclohexyl phenyl ketone, referred to as UV-184).

[0015] Furthermore, the photoinitiator is 1173 photoinitiator.

[0016] Furthermore, the amount of the photoinitiator used is 1-5% of the total mass of the allyl epoxy resin and the cycloalkyl mercaptan.

[0017] Furthermore, the amount of the photoinitiator is 1% of the total mass of the allyl epoxy resin and cycloalkyl mercaptan.

[0018] Furthermore, the curing agent is 1,3-bis(2′-aminoethylidene)-2-methylimidazole amino acid salt.

[0019] Furthermore, the 1,3-bis(2′-aminoethylidene)-2-methylimidazole amino acid salt is any one or a combination of two or more of 1,3-bis(2′-aminoethylidene)-2-methylimidazole alanine salt, 1,3-bis(2′-aminoethylidene)-2-methylimidazole arginine salt, and 1,3-bis(2′-aminoethylidene)-2-methylimidazole glutamate.

[0020] Furthermore, the 1,3-bis(2′-aminoethylidene)-2-methylimidazole amino acid salt is 1,3-bis(2′-aminoethylidene)-2-methylimidazole alanine salt.

[0021] Furthermore, the mass ratio of component A to component B is 5-20:1.

[0022] Furthermore, the mass ratio of component A to component B is 12:1.

[0023] Furthermore, the mass ratio of the epoxy resin to the modifier is 5-20:1.

[0024] Furthermore, the mass ratio of the epoxy resin to the modifier is 19:1.

[0025] The invention also provides a steel structure adhesive containing the high elastic modulus epoxy resin composition.

[0026] Beneficial effects of the present invention:

[0027] The invention provides an epoxy resin composition with a high elastic modulus. A modifier containing a cycloalkyl long chain is added to form physical entanglements during curing, thereby providing physical crosslinking points for the system. The physical crosslinking points serve as stress concentration centers, inducing a large number of silver streaks in a matrix. When an external force acts, the silver streaks consume a large amount of energy, so that they do not develop into destructive cracks. The cycloalkyl group with axial flexibility and rigidity improves the strength of the physical crosslinking points, so that the epoxy resin composition has better mechanical properties. The amino groups on both sides of the cation in 1,3-di(2′-aminoethyl)-2-methylimidazole amino acid salt and the carboxyl group and amino group of the amino acid can all undergo nucleophilic addition reaction with the epoxy group, so that high-density curing and crosslinking of the epoxy resin is achieved. After being cured, the epoxy resin composition of the invention has excellent mechanical properties through testing, with a tensile strength of ≥110MPa, a tensile elastic modulus of ≥3.1GPa, and an impact strength of ≥23kJ / m 2 . BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 This is the SEM morphology of the tensile fracture surface of the sample prepared in Example 1. DETAILED DESCRIPTION

[0029] If the specific conditions are not specified in the examples, the experiments were carried out under conventional conditions or the conditions recommended by the manufacturer. If the manufacturer of the reagents or instruments is not specified, they are all conventional products that can be purchased commercially. The techniques not mentioned in the present invention are all referenced to the prior art. Unless otherwise specified, the following examples and comparative examples are parallel experiments, using the same processing steps and parameters.

[0030] Embodiment 1:

[0031] A high elastic modulus epoxy resin composition comprises a component A and a component B in a mass ratio of 12:1, wherein the component A comprises epoxy resin E-51 and a modifier in a mass ratio of 19:1, and the component B is 1,3-bis(2′-aminoethylidene)-2-methylimidazole alanine salt;

[0032] The epoxy resin E-51 and the modifier in component A were mixed, stirred at a speed of 200 r / min for 10 min, and then component B, 1,3-di(2′-aminoethyl)-2-methylimidazole alanine salt, was added and stirred for 5 min. The obtained mixture was transferred to a polytetrafluoroethylene mold for vacuum degassing for 30 min, and cured according to the process flow of 90℃ / 3h +120℃ / 3h +150℃ / 1h. Finally, the sample was demoulded to obtain a sample. Figure 1 This is the SEM morphology of the tensile fracture surface of the sample. A large number of wavy silver streaks can be seen. During the stretching process, the generation and development of these silver streaks consume a lot of energy.

[0033] The structural formula of the modifier is shown below:

[0034] ;

[0035] The preparation method of the modifier is as follows:

[0036] ;

[0037] 0.1 mol of allyl epoxy resin DADGEBA and 0.2 mol of cyclohexyl methyl mercaptan were mixed evenly, and then 1173 photoinitiator was added. The amount of 1173 photoinitiator was 1.5% of the total mass of allyl epoxy resin DADGEBA and cyclohexyl methyl mercaptan. Then, the reaction device was placed in an environment of 365 nm UV-LED ultraviolet light source and stirred for 5 hours. ESI-MS (m / z) (M + ): Theoretical value 681.05, measured value 681.24.

[0038] The preparation method of 1,3-bis(2′-aminoethylidene)-2-methylimidazole alanine salt is as follows:

[0039] 1 g of 1,3-bis(2′-aminoethylidene)-2-methylimidazolium bromide (customized from Lander Energy) was dissolved in 50 ml of deionized water and passed through an anion exchange resin to obtain a 1,3-bis(2′-aminoethylidene)-2-methylimidazolium hydroxide solution. A sample was taken and titrated with hydrochloric acid to calculate the required amount of alanine. The required alanine was dissolved in a small amount of deionized water and added to the 1,3-bis(2′-aminoethylidene)-2-methylimidazolium hydroxide solution. The solution was stirred at room temperature for 24 hours, and the solution was rotary evaporated to remove water and low-boiling substances. The obtained product was dried in vacuum at 55°C for 48 hours.

[0040] Embodiment 2:

[0041] It is basically the same as Example 1, except that the structural formula of the modifier is as follows:

[0042] ;

[0043] The preparation method of the modifier is as follows:

[0044] ;

[0045] 0.1 mol of allyl epoxy resin DADGEBA and 0.2 mol of cyclopentyl methyl mercaptan were mixed evenly, and then 1173 photoinitiator was added. The amount of 1173 photoinitiator was 1.5% of the total mass of allyl epoxy resin DADGEBA and cyclopentyl methyl mercaptan. Then, the reaction device was placed in an environment of 365 nm UV-LED ultraviolet light source and stirred for 5 hours. ESI-MS (m / z) (M +): Theoretical value 652.99, measured value 652.15.

[0046] Embodiment 3:

[0047] It is basically the same as Example 1, except that the structural formula of the modifier is as follows:

[0048] ;

[0049] The preparation method of the modifier is as follows:

[0050] ;

[0051] 0.1 mol of allyl epoxy resin DADGEBA and 0.2 mol of cycloheptyl methyl mercaptan were mixed evenly, and then 1173 photoinitiator was added. The amount of 1173 photoinitiator was 1.5% of the total mass of allyl epoxy resin DADGEBA and cycloheptyl methyl mercaptan. Then, the reaction device was placed in an environment of 365 nm UV-LED ultraviolet light source and stirred for 5 hours. ESI-MS (m / z) (M + ): Theoretical value 709.10, measured value 709.56.

[0052] Embodiment 4:

[0053] It is basically the same as Example 1, except that the structural formula of the modifier is as follows:

[0054] ;

[0055] The preparation method of the modifier is as follows:

[0056] ;

[0057] 0.1 mol of allyl epoxy resin DADGEBA and 0.2 mol of cyclooctyl methyl mercaptan were mixed evenly, and then 1173 photoinitiator was added. The amount of 1173 photoinitiator was 1.5% of the total mass of allyl epoxy resin DADGEBA and cyclooctyl methyl mercaptan. Then, the reaction device was placed in an environment of 365 nm UV-LED ultraviolet light source and stirred for 5 hours. ESI-MS (m / z) (M + ): Theoretical value 737.15, measured value 737.37.

[0058] Comparative Example 1:

[0059] The method is substantially the same as Example 1, except that 1,3-bis(2′-aminoethylidene)-2-methylimidazolium bromide is used instead of 1,3-bis(2′-aminoethylidene)-2-methylimidazolium alanine.

[0060] Comparative Example 2:

[0061] It is basically the same as Example 1, except that no modifier is added.

[0062] Comparative Example 3:

[0063] It is basically the same as Example 1, except that the structural formula of the modifier is as follows:

[0064] ;

[0065] The preparation method of the modifier is as follows:

[0066] ;

[0067] 0.1 mol of allyl epoxy resin DADGEBA and 0.2 mol of n-decyl mercaptan were mixed evenly, and then 1173 photoinitiator was added. The amount of 1173 photoinitiator was 1.5% of the total mass of allyl epoxy resin DADGEBA and n-decyl mercaptan. Then, the reaction device was placed in an environment of 365 nm UV-LED ultraviolet light source and stirred for 5 hours. ESI-MS (m / z) (M + ): Theoretical value 769.24, measured value 769.61.

[0068] Performance Test:

[0069] The performance tests were performed on the samples prepared in Examples 1-4 and Comparative Examples 1-3;

[0070] The tensile properties were tested according to GB / T 1040-2006, and the tensile speed was set at 50 mm / min;

[0071] Impact performance is tested according to GB / T 2567-2008;

[0072] The above test results are shown in Table 1 below:

[0073] ;

[0074] It can be seen from Table 1 above that the samples prepared from the epoxy resin composition of the present invention have excellent mechanical properties.

[0075] By comparing Examples 1-4, it can be seen that the structure of the modifier has a certain influence on the mechanical properties of the sample. When the cycloalkyl group in the modifier structure is a cyclohexyl group, the epoxy resin composition has the best mechanical properties after curing. By comparing Example 1 with Comparative Example 1, it can be seen that compared with 1,3-bis(2′-aminoethyl)-2-methylimidazolium bromide, the addition of 1,3-bis(2′-aminoethyl)-2-methylimidazolium alanine salt can improve the mechanical properties of the sample to a greater extent.

[0076] By comparing Example 1 with Comparative Example 2, it can be seen that the addition of the modifier can greatly improve the mechanical properties of the sample; by comparing Example 1 with Comparative Example 3, it can be seen that the modifier containing cycloalkyl groups can improve the mechanical properties of the sample to a greater extent than the modifier containing long-chain alkyl groups.

[0077] The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit the same. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that the technical solutions described in the aforementioned embodiments may still be modified, or some of the technical features may be replaced by equivalents. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A high elastic modulus epoxy resin composition, characterized in that: It includes component A and component B; The A component includes epoxy resin and a modifier; The B component is a curing agent; The structural formula of the modifier is shown below: ; Wherein, Ar1 and Ar2 are the same and are any one of cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl; The curing agent is 1,3-bis(2′-aminoethylidene)-2-methylimidazole amino acid salt.

2. The high elastic modulus epoxy resin composition according to claim 1, characterized in that The preparation method of the modifier is as follows: After allyl epoxy resin and cycloalkyl mercaptan are uniformly mixed, a photoinitiator is added, and the mixture is stirred and reacted for 1-10 hours under ultraviolet light.

3. The high elastic modulus epoxy resin composition according to claim 2, characterized in that: The photoinitiator is 1173 photoinitiator and / or 184 photoinitiator.

4. The high elastic modulus epoxy resin composition according to claim 3, characterized in that: The amount of the photoinitiator used is 1-5% of the total mass of the allyl epoxy resin and the cycloalkyl mercaptan.

5. The high elastic modulus epoxy resin composition according to claim 1, characterized in that: The 1,3-bis(2′-aminoethylidene)-2-methylimidazole amino acid salt is any one of 1,3-bis(2′-aminoethylidene)-2-methylimidazole alanine salt, 1,3-bis(2′-aminoethylidene)-2-methylimidazole arginine salt, and 1,3-bis(2′-aminoethylidene)-2-methylimidazole glutamate, or a combination of two or more thereof.

6. The high elastic modulus epoxy resin composition according to claim 1, characterized in that: The mass ratio of component A to component B is 5-20:

1.

7. The high elastic modulus epoxy resin composition according to claim 1, characterized in that: The mass ratio of the epoxy resin to the modifier is 5-20:

1.

8. A steel structure adhesive, characterized in that: A high elastic modulus epoxy resin composition comprising the composition described in any one of claims 1 to 7.

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