Preparation method and application of high-performance epoxy resin, curing agent and sealant

Abstract

The invention relates to a preparation method and application of high-performance epoxy resin, a curing agent and a sealant thereof, accurate regulation and control of four functionality are realized by introducing 3-chloro-1, 2-propylene glycol into hydrogenated bisphenol A, and epoxy resin 1 is prepared by reacting with epoxy chloropropane and has high crosslinking density, excellent weather resistance and prolonged yellowing time. The epoxy resin 2 with higher crosslinking density is synthesized by further adopting an epoxy group grafting strategy, and the mechanical property of the epoxy resin 2 is remarkably improved. The problems that traditional epoxy resin is poor in yellowing resistance and low in mechanical property are effectively solved, and the epoxy resin is widely applied to the fields of building decoration, seam beautifying materials, high-performance coatings and the like and has important actual value.

Description

Technical Field

[0001] The invention relates to the field of epoxy resin processing, and in particular to a preparation method and application of a high-performance epoxy resin, a curing agent and a seam-beautifying agent thereof. Background Art

[0002] With the development of the building decoration industry, the application of caulking agents in building materials is becoming more and more extensive. In the traditional method, conventional epoxy-based caulking agents mainly use bisphenol A epoxy resin as the main raw material. However, due to the presence of benzene ring structure in bisphenol A epoxy resin, its yellowing resistance is poor, and it is easy to change color during long-term use, affecting the appearance.

[0003] In recent years, in order to solve this problem, a variety of improved methods have emerged in the patent field. The following are two recent patent examples for reference:

[0004] Patent name: A modified epoxy-based seam beautifier. The patent mainly consists of modified bisphenol A epoxy resin, curing agent, filler and additives. By introducing other functional groups into bisphenol A epoxy resin, its yellowing resistance is improved. However, in actual application, this patent may have problems such as unstable modification effect and high cost.

[0005] Patent name: A hydrogenated bisphenol A epoxy resin seam beautifying agent. This patent uses hydrogenated bisphenol A epoxy resin as the main raw material. Due to the loss of the benzene ring structure, its mechanical properties have declined. This patent improves the mechanical properties by adding an appropriate amount of toughening agent and curing agent. However, while improving the mechanical properties, this patent may have problems such as difficulty in controlling the amount of toughening agent and curing agent added and high cost.

[0006] Although the existing patent solutions have solved the problems of yellowing resistance and mechanical properties to a certain extent, there are still some shortcomings. Summary of the invention

[0007] In order to solve the above problems, the present invention provides a preparation method and application of a high-performance epoxy resin, a curing agent and a seam-beautifying agent, which can effectively solve the deficiencies in the prior art.

[0008] The present invention is achieved through the following technical scheme: A method for preparing a high-performance epoxy resin comprises the following steps:

[0009] S1.1, mix and dissolve hydrogenated bisphenol A and methyl tert-butyl ether, add metallic sodium under vacuum conditions, and react at 40°C until the metallic sodium completely disappears;

[0010] S1.2, add 10 wt % sodium hydroxide solution, add 3-chloro-1,2-propylene glycol dropwise, and react at 110° C. for 5 hours to obtain the intermediate HBPA-4OH;

[0011] S1.3. The intermediate HBPA-4OH was mixed with epichlorohydrin, stirred at 70° C. for 30 minutes, and then tetramethylammonium hydroxide catalyst was added. The reaction was continued for 5 hours to obtain resin 1.

[0012] As a preferred technical solution, the intermediate HBPA-4OH is filtered through deionized water, extracted with a mixture of n-butanol and deionized water, and purified by rotary evaporation and recrystallization.

[0013] As a preferred technical solution, the purification of the resin 1 comprises the following steps:

[0014] Step 2.1, cooling the reaction product to room temperature and centrifuging it in a centrifuge;

[0015] Step 2.2, filter the obtained filtrate, and wash with deionized water until the pH of the aqueous phase is 7;

[0016] Step 2.3, after adding anhydrous alumina to adsorb impurities, the purified resin 1 is obtained by rotary evaporation.

[0017] A method for preparing a modified epoxy resin of the present invention comprises the following steps:

[0018] Step 3.1, mixing hydrogenated bisphenol A epoxy resin and 2-ethyl chloroisocyanate in a molar ratio of 1:1, and stirring at 60-70° C. for 10 minutes;

[0019] Step 3.2, adding 0.1% of an organic tin catalyst, maintaining the temperature at 60-70°C for 6 hours to obtain an intermediate;

[0020] Step 3.3, the intermediate and glycidol were mixed in a molar ratio of 1:1, a certain amount of sodium hydroxide solution was evenly added, and the mixture was reacted at 100-110° C. for 5 hours to obtain resin 2.

[0021] As a preferred technical solution, the intermediate is purified by low-temperature recrystallization to improve the purity.

[0022] A method for preparing a curing agent of the present invention comprises the following steps:

[0023] 6.1. Weigh the polyetheramine (T403) in a conical flask according to the proportion, "titrate with the modified hydrogenated resin, and adjust the performance according to the set ratio), control the temperature at 70-80℃, and react for 1h after the titration is completed;

[0024] 6.2. When the temperature is cooled to 50-60°C, weigh 1,3-cyclohexanedimethylamine (1.3BAC) and isophoronediamine (IPDA) in a conical flask, titrate with the remaining modified hydrogenated resin, control the temperature at 50-60°C, and react for 2 hours;

[0025] 6.3. After the reaction is completed, let it stand and test the basic properties of the curing agent (amine value titration, gel time test, hardness test at different times)

[0026] 6.4. Used to improve the cross-linking density and flexibility of resin.

[0027] As a preferred technical solution, it further includes adding a reinforcing agent to the curing agent to improve the heat resistance and mechanical properties after curing.

[0028] A seam beautifying agent of the present invention is characterized by comprising the following components:

[0029] Epoxy resin 1 and resin 2;

[0030] Curing agent;

[0031] Antioxidants, leveling agents and pigment fillers;

[0032] Add anti-ultraviolet agent.

[0033] As a preferred technical solution, the mixing ratio of the epoxy resin 1 to the resin 2 is 1:1 to 3:1.

[0034] The epoxy resin composition for improving yellowing performance of the present invention is prepared by mixing epoxy resin 1 and epoxy resin 2 in a certain proportion and curing them with a curing agent.

[0035] The beneficial effects of the present invention are as follows: the present invention successfully introduces 3-chloro-1,2-propylene glycol into hydrogenated bisphenol A through an innovative chemical modification strategy, achieves precise regulation of the four functionalities, and reacts with epichlorohydrin (ECH) to obtain a high-performance epoxy resin 1. The following are the beneficial effects of the present invention compared to the prior art:

[0036] First, the modification strategy provided by the present invention significantly improves the crosslinking density and structural stability of epoxy resin. Due to the introduction of 3-chloro-1,2-propylene glycol, the crosslinking density of resin 1 is greatly improved, thereby enhancing the physical properties of the resin, making it more reliable and durable in application. At the same time, the improvement in structural stability also means that resin 1 can better maintain its shape and performance during processing and use, and is not prone to deformation or degradation.

[0037] Secondly, the modified epoxy resin 1 exhibits excellent weather resistance and effectively prolongs the yellowing time. This improvement is particularly important for epoxy resin products that are used outdoors or need to be exposed to harsh environmental conditions for a long time, which can significantly extend the service life of the material and reduce maintenance costs.

[0038] However, in the process of hydrogenation, the present invention successfully eliminated the influence of benzene ring on the color of the resin, but sacrificed its mechanical properties to a certain extent. In order to overcome this shortcoming, the present invention further adopted a strategy of grafting epoxy groups on hydrogenated bisphenol A epoxy resin to synthesize epoxy resin 2 with higher crosslinking density. This advanced synthesis strategy not only significantly enhances the structural stability of the resin, but also effectively improves its yellowing resistance and mechanical properties, achieving comprehensive optimization of the comprehensive properties of the resin.

[0039] More importantly, the present invention ingeniously mixes resin 1 and resin 2 in a certain ratio and uses them as raw materials of agent A. This ratio scheme not only effectively alleviates the negative impact of hydrogenation treatment on the benzene ring structure, but also achieves complementary and enhanced performance through the synergistic effect of the two resins. This mixed use method not only improves the comprehensive performance of the final product, but also expands the application field of epoxy resin.

[0040] The beneficial effects of the present invention are embodied in the following aspects:

[0041] Significantly improved the cross-linking density and structural stability of epoxy resin, and enhanced its physical properties;

[0042] It effectively prolongs the yellowing time of epoxy resin and exhibits excellent weather resistance;

[0043] The mechanical properties of the resin were improved by the strategy of grafting epoxy groups;

[0044] By mixing and using different modified epoxy resins, complementary and enhanced performance is achieved;

[0045] It provides new ideas for the modification of epoxy resin and lays a solid foundation for the development and application of high-performance epoxy resin materials.

[0046] In summary, the present invention has significant advantages in improving the performance of epoxy resin, which not only meets the demand for high-performance materials, but also provides strong support for technological progress in related industries. BRIEF DESCRIPTION OF THE DRAWINGS

[0047] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0048] Figure 1 is a synthetic route diagram of resin 1 of the present invention;

[0049] Figure 2The synthetic route of resin 2 of the present invention is shown in FIG. DETAILED DESCRIPTION

[0050] All features disclosed in this specification, or steps in all methods or processes disclosed, except mutually exclusive features and / or steps, can be combined in any manner.

[0051] Any feature disclosed in this specification (including any additional claims, abstract and drawings), unless otherwise stated, may be replaced by other equivalent or alternative features with similar purposes. That is, unless otherwise stated, each feature is only an example of a series of equivalent or similar features.

[0052] Example 1: Preparation of Resin 1

[0053] Preparation of intermediate HBPA-4OH

[0054] 100 g of hydrogenated bisphenol A (H-BPA) was added into a four-necked flask, and then 200 mL of methyl tert-butyl ether was added to dissolve the mixture and stirred evenly.

[0055] At 40°C, turn on the vacuum pump to maintain the vacuum state.

[0056] Slowly add 46 g of metallic sodium at a molar ratio of 1:2.1, and react at 40° C. until the metallic sodium is completely dissolved, and keep stirring during the reaction.

[0057] 200 mL of 10 wt% sodium hydroxide solution was added, and 150 g of 3-chloro-1,2-propanediol was slowly added dropwise for 1-2 hours.

[0058] The temperature was raised to 110° C. and the reaction was continued with stirring for 5 hours. After cooling, a crude intermediate HBPA-4OH product was obtained.

[0059] like Figure 1 As shown, the preparation of epoxy resin 1

[0060] The prepared intermediate HBPA-4OH (80 g) was mixed with 120 g of epichlorohydrin (ECH) and added into a reaction kettle.

[0061] The vacuum pump was turned on to a vacuum state, and the temperature was raised to 70°C and stirred for 30 minutes.

[0062] 5 g of tetramethylammonium hydroxide catalyst was added and the reaction was continued at 70° C. for 5 hours.

[0063] After the reaction was completed, the mixture was cooled to room temperature to obtain a crude product of epoxy resin 1.

[0064] Purification of epoxy resin 1

[0065] The crude product was added to deionized water and filtered, and the filtrate was collected.

[0066] The filtrate was extracted with a mixture of n-butanol and deionized water (volume ratio 3:1), and the organic phase was separated by rotary evaporation.

[0067] The separated organic phase was mixed with a mixture of ethyl acetate and anhydrous ethanol (volume ratio 1:1) and heated until completely dissolved.

[0068] After the filtrate was frozen for 1 hour, it was recrystallized twice to finally obtain the purified epoxy resin 1.

[0069] Example 2: Preparation of Resin 2

[0070] like Figure 2 As shown, the first reaction stage

[0071] Hydrogenated bisphenol A epoxy resin (100 g) and 2-ethyl chloroisocyanate (120 g) were added into a reaction kettle at a molar ratio of 1:1.

[0072] The temperature was gradually increased to 60-70°C and stirred for 10 minutes to mix the two evenly.

[0073] Add 0.1% of an organic tin catalyst (calculated by mass ratio) and continue to react at 60-70° C. for 6 hours to generate an intermediate.

[0074] Second reaction stage

[0075] The obtained intermediate (100 g) was mixed with propylene oxide (120 g), and added into the reactor in a molar ratio of 1:1.

[0076] The temperature was raised to 100-110°C, stirred for 10 minutes to make it uniform, and then 10 wt% sodium hydroxide solution was added.

[0077] The reaction lasted for 5 hours. After the reaction was completed, the product was cooled, filtered, extracted, and the solvent was evaporated to finally obtain the purified epoxy resin 2.

[0078] Example 3: Preparation of curing agent

[0079] Material selection and proportion

[0080] 1,3-cyclohexanedimethylamine (1.3BAC), isophoronediamine (IPDA) and polyetheramine (T403) are used as main raw materials.

[0081] The raw materials are accurately weighed to ensure the uniformity of chemical composition.

[0082] Preparation steps

[0083] Weigh the polyetheramine (T403) in a conical flask according to the proportion, titrate it with the modified hydrogenated resin, control the temperature at 70-80°C, and react for 1 hour after the titration is completed;

[0084] When the temperature is cooled to 50-60°C, 1,3-cyclohexanedimethylamine (1.3BAC) and isophoronediamine (IPDA) are weighed in a conical flask and titrated with the remaining modified hydrogenated resin. The temperature is controlled at 50-60°C and the reaction is carried out for 2 hours.

[0085] After the reaction is completed, let it stand and test the basic properties of the curing agent (amine value titration, gel time test, hardness test at different times).

[0086] Control the speed during the mixing process to avoid component separation and ensure the uniformity and stability of the final curing agent.

[0087] The obtained curing agent can be directly used for epoxy resin curing.

[0088] Preparation of seam beautifier

[0089] Raw material combination

[0090] The epoxy resin 1 prepared in Example 1 and the epoxy resin 2 prepared in Example 2 were mixed in a ratio of 2:1 to form component A.

[0091] The curing agent prepared in Example 3 was used as component B, and the volume ratio of A:B was 3:1.

[0092] Adding additives

[0093] An antioxidant (mass ratio 0.5 wt%), a leveling agent (mass ratio 0.2 wt%) and a pigment filler (mass ratio 20 wt%) were added to component A.

[0094] Stir evenly to fully blend all ingredients.

[0095] Preparation of seam beautifier

[0096] Raw material combination:

[0097] The epoxy resin 1 prepared in Example 1 and the epoxy resin 2 prepared in Example 2 were mixed in a ratio of 2:1 to form component A.

[0098] The curing agent prepared in Example 3 was used as component B, and the volume ratio of A:B was 3:1.

[0099] Additives:

[0100] An antioxidant (mass ratio 0.5 wt%), a leveling agent (mass ratio 0.2 wt%) and a pigment filler (mass ratio 20 wt%) were added to component A.

[0101] 5 wt % of fumed silica was added to component A and component B respectively as an anti-sagging agent, and the mixture was stirred evenly to ensure full fusion of the components.

[0102] Mixing and Preparation:

[0103] After mixing component A and component B in proportion, stir them thoroughly at 25°C until a uniform adhesive system is formed.

[0104] The prepared seam-beautifying agent has excellent anti-sagging performance, leveling and mechanical properties, and is suitable for application scenarios such as building decoration.

[0105] Example 5: Performance Test

[0106] Crosslink density test

[0107] Epoxy resin 1 and epoxy resin 2 were cured and standard test samples were prepared. The crosslink density was determined by the solvent swelling method. The test results show that:

[0108] The cross-linking density of epoxy resin 1 is increased by more than 20% compared with that of conventional bisphenol A epoxy resin.

[0109] After grafting epoxy groups, the crosslinking density of epoxy resin 2 increased by more than 30%. This high crosslinking density significantly enhanced the physical properties of epoxy resin, including heat resistance, dimensional stability, and durability under extreme conditions.

[0110] Thermal performance test

[0111] The glass transition temperature (Tg) of the two resins was measured using a differential scanning calorimeter (DSC). The results showed that:

[0112] The Tg of resin 1 is 140°C, which is about 15°C higher than that of conventional bisphenol A epoxy resin.

[0113] After grafting modification, the Tg of resin 2 is further increased to 155° C. This result shows that the epoxy resin of the present invention can maintain its mechanical properties and stability under high temperature conditions and is suitable for application scenarios requiring higher thermal stability.

[0114] Yellowing resistance test

[0115] Expose the sealant sample to the UV accelerated aging test equipment for yellowing test:

[0116] Light intensity: 800W / m2.

[0117] Test time: 500 hours. According to the yellowing grade standard of GB / T 28983, the yellowing grade of the epoxy resin composition of the present invention reaches grade 0. Compared with the traditional seam beautifier, its yellowing time is extended by more than 50%, which significantly improves the weather resistance of the product.

[0118] Mechanical properties test

[0119] According to GB / T 2567-2008 standard, test tensile strength, elongation at break and flexural strength:

[0120] Tensile strength: 48MPa, 25% higher than traditional products.

[0121] Elongation at break: 6.5%, showing good toughness.

[0122] Bending strength: 90MPa, 30% higher than traditional products. This result shows that the epoxy resin composition is significantly better than traditional epoxy resin materials in mechanical properties.

[0123] Example 6: Practical application case

[0124] Application in architectural decoration:

[0125] The caulking agent prepared in Example 4 is used to fill the gaps between tiles:

[0126] Apply the grouting agent evenly on the cleaned tile surface;

[0127] The curing time at room temperature is about 12 hours (the standard curing conditions are 23°C, humidity RH50%, the initial curing time is 3-4 hours, and the residual material can be cleaned up). After complete curing, it shows excellent gloss and wear resistance.

[0128] Application in balcony tile caulking:

[0129] Scenarios for applying caulking agent to the caulking of balcony tiles:

[0130] Apply the grouting agent evenly in the cleaned tile gaps;

[0131] After curing, the weather resistance test was carried out. The test results showed that after the caulking material was exposed to a hot and humid environment for 1,000 hours (equivalent to 7 months of actual use), there was no obvious performance degradation, showing excellent durability and waterproofness.

[0132] An epoxy resin composition for improving yellowing performance of the present invention:

[0133] The epoxy resin 1 and the epoxy resin 2 are mixed in a certain ratio and cured by the curing agent described in Example 3. The composition has a significant advantage in yellowing performance.

[0134] The beneficial effects of the present invention are as follows: the present invention successfully introduces 3-chloro-1,2-propylene glycol into hydrogenated bisphenol A through an innovative chemical modification strategy, achieves precise regulation of the four functionalities, and reacts with epichlorohydrin (ECH) to obtain a high-performance epoxy resin 1. The following are the beneficial effects of the present invention compared to the prior art:

[0135] First, the modification strategy provided by the present invention significantly improves the crosslinking density and structural stability of epoxy resin. Due to the introduction of 3-chloro-1,2-propylene glycol, the crosslinking density of resin 1 is greatly improved, thereby enhancing the physical properties of the resin, making it more reliable and durable in application. At the same time, the improvement in structural stability also means that resin 1 can better maintain its shape and performance during processing and use, and is not prone to deformation or degradation.

[0136] Secondly, the modified epoxy resin 1 exhibits excellent weather resistance and effectively prolongs the yellowing time. This improvement is particularly important for epoxy resin products that are used outdoors or need to be exposed to harsh environmental conditions for a long time, which can significantly extend the service life of the material and reduce maintenance costs.

[0137] However, in the process of hydrogenation, the present invention successfully eliminated the influence of benzene ring on the color of the resin, but sacrificed its mechanical properties to a certain extent. In order to overcome this shortcoming, the present invention further adopted a strategy of grafting epoxy groups on hydrogenated bisphenol A epoxy resin to synthesize epoxy resin 2 with higher crosslinking density. This advanced synthesis strategy not only significantly enhances the structural stability of the resin, but also effectively improves its yellowing resistance and mechanical properties, achieving comprehensive optimization of the comprehensive properties of the resin.

[0138] More importantly, the present invention ingeniously mixes resin 1 and resin 2 in a certain ratio and uses them as raw materials of agent A. This ratio scheme not only effectively alleviates the negative impact of hydrogenation treatment on the benzene ring structure, but also achieves complementary and enhanced performance through the synergistic effect of the two resins. This mixed use method not only improves the comprehensive performance of the final product, but also expands the application field of epoxy resin.

[0139] The above is only a specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Any changes or substitutions that are not conceived through creative work should be included in the protection scope of the present invention. Therefore, the protection scope of the present invention should be based on the protection scope defined in the claims.

Claims

1. A method for preparing a high-performance epoxy resin, characterized in that: The following steps are involved: S1.1, mix and dissolve hydrogenated bisphenol A and methyl tert-butyl ether, add metallic sodium under vacuum conditions, and react at 40°C until the metallic sodium completely disappears; S1.2, add 10wt% sodium hydroxide solution, add 3-chloro-1,2-propylene glycol dropwise, and react at 110°C for 5 hours to obtain the intermediate HBPA-4OH; S1.

3. The intermediate HBPA-4OH was mixed with epichlorohydrin, stirred at 70° C. for 30 minutes, and then tetramethylammonium hydroxide catalyst was added. The reaction was continued for 5 hours to obtain resin 1.

2. The method for preparing a high performance epoxy resin according to claim 1, characterized in that: The intermediate HBPA-4OH is filtered through deionized water, extracted with a mixture of n-butanol and deionized water, and purified by rotary evaporation and recrystallization.

3. The method for preparing a high performance epoxy resin according to claim 1, characterized in that: The purification of the resin 1 comprises the following steps: Step 2.1, cooling the reaction product to room temperature and centrifuging it in a centrifuge; Step 2.2, filter the obtained filtrate, and wash with deionized water until the pH of the aqueous phase is 7; Step 2.3, after adding anhydrous alumina to adsorb impurities, the purified resin 1 is obtained by rotary evaporation.

4. A method for preparing a modified epoxy resin, characterized in that: The following steps are involved: Step 3.1, mixing hydrogenated bisphenol A epoxy resin and 2-ethyl chloroisocyanate in a molar ratio of 1:1, and stirring at 60-70° C. for 10 minutes; Step 3.2, adding 0.1% of an organic tin catalyst, maintaining the temperature at 60-70°C for 6 hours to obtain an intermediate; Step 3.3, the intermediate and glycidol were mixed in a molar ratio of 1:1, a certain amount of sodium hydroxide solution was evenly added, and the mixture was reacted at 100-110° C. for 5 hours to obtain resin 2.

5. The method for preparing the modified epoxy resin according to claim 4, characterized in that: The intermediate is purified by low temperature recrystallization to improve the purity.

6. A method for preparing a curing agent, characterized in that: The following steps are involved: 6.

1. Weigh the polyetheramine (T403) in a conical flask according to the proportion, and titrate it with the modified hydrogenated resin. The performance can be adjusted according to the set ratio). The temperature is controlled at 70-80°C. After the titration is completed, react for 1 hour; 6.

2. When the temperature is cooled to 50-60°C, weigh 1,3-cyclohexanedimethylamine (1.3BAC) and isophoronediamine (IPDA) in a conical flask, titrate with the remaining modified hydrogenated resin, control the temperature at 50-60°C, and react for 2 hours; 6.

3. Used to improve the cross-linking density and flexibility of resin.

7. The method for preparing a curing agent according to claim 6, characterized in that: The method further comprises adding a reinforcing agent to the curing agent to improve the heat resistance and mechanical properties after curing.

8. A seam beautifying agent, characterized in that: Contains the following ingredients: Epoxy resin 1 and resin 2 prepared according to claim 1 or claim 4; The curing agent according to claim 6; Antioxidants, leveling agents and pigment fillers; Add anti-ultraviolet agent.

9. The seam beautifying agent according to claim 8, characterized in that: The mixing ratio of the epoxy resin 1 to the resin 2 is 1:1 to 3:

1.

10. An epoxy resin composition for improving yellowing performance, characterized in that: The epoxy resin 1 and the epoxy resin 2 are mixed in a certain proportion and then cured by the curing agent of claim 6.

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