High-temperature-resistant chpo curing putty

Abstract

This invention belongs to the field of coating technology and relates to a high-temperature resistant CHPO curable putty and its preparation method, which comprises the following components: unsaturated polyester resin, styrene, cobalt isooctanoate, dimethylaniline, high-temperature resistant composite dispersant, hydrogenated castor oil, silica, rutile titanium dioxide, talc, and curing agent.

Description

Technical Field

[0001] This invention belongs to the field of putty technology and relates to a high-temperature resistant CHPO curing putty. Background Technology

[0002] Cyclohexanone peroxide (CHPO) is one of the most commonly used medium-to-low temperature curing agents in free radical crosslinking systems for unsaturated polyester resins, putty, and artificial marble. Its activity originates from the "O–O" peroxide bonds in the molecule, which homolytically cleave to generate free radicals under the action of accelerators (cobalt salts, tertiary amines), initiating copolymerization and crosslinking between the resin and styrene. However, the peroxide bond has low bond energy and is sensitive to heat, shock, and metal ions, exhibiting the following common industry problems:

[0003] (1) Poor storage stability: Commercially available CHPO is usually a 50% dibutyl phthalate (DBP) paste, which will undergo self-accelerated decomposition above 35°C, and its activity will decrease by ≥15% after 6 months; (2) Large fluctuation in curing speed: In high temperature environment, the curing agent needs to be taken out immediately for use, which can easily lead to a decrease in activity under heat conditions, and the curing gel time is relatively long.

[0004] Therefore, without changing the compatibility of the main CHPO process, there is an urgent need for a synergistic system that is "micro-volume, highly efficient, low-temperature fast curing and storage stable" to solve the problem of insufficient curing speed under high temperature conditions. Summary of the Invention

[0005] This invention provides a high-temperature resistant CHPO curing putty, which has high tolerance under high temperature conditions. Even if the packaging of the curing agent and curing aid is opened and placed in a high-temperature environment for a period of time, it can still maintain a relatively fast curing efficiency, and the storage time is longer than that of the prior art.

[0006] The technical solution of the present invention is: to provide a high-temperature resistant CHPO curable putty, characterized in that the putty comprises the following components in parts by weight percentage: 45-60 parts unsaturated polyester resin, 3-5 parts styrene, 0.5-0.8 parts cobalt isooctanoate, 0.01-0.2 parts dimethylaniline, 0.35-0.55 parts high-temperature resistant composite dispersant, 0.2-0.6 parts hydrogenated castor oil, 0.1-0.5 parts fumed silica, 1-2 parts rutile titanium dioxide, 1.5-2.5 parts curing agent, 0.4-0.5 parts curing aid, and the balance being talc powder.

[0007] Furthermore, the curing agent is CHPO, the curing aid is hydrogen peroxide and modified carbon nanospheres, the mass ratio of hydrogen peroxide to modified carbon nanospheres is 98~99:1, and the diameter of the modified carbon nanospheres is less than 100nm.

[0008] Furthermore, the hydrogen peroxide is hydrogen peroxide with a mass fraction of 30%.

[0009] Furthermore, the high-temperature resistant CHPO curable putty, wherein the modified carbon nanospheres are ruthenium dioxide modified carbon nanospheres, and the modification method is as follows:

[0010] Step 1: Disperse 0.95g of raw carbon nanospheres in 50mL of 1mol / L HCl and treat with ultrasound at 150W for 30min. Then wash the carbon nanospheres with 500mL of deionized water and dry at 60℃ for 6h to obtain acidified carbon nanospheres. Step 2: Place 100mg of RuCl3·xH2O in 500mL of deionized water, add the acidified carbon nanospheres, and treat with ultrasound at 150W for 1h at room temperature. Then stir magnetically for 20min to obtain a precursor slurry. Step 3: Transfer the precursor slurry to a three-necked flask, heat to 80℃ in a water bath, and add 1mL of 30% H2O2 dropwise at a uniform rate using a burette until precipitation is complete. Then slowly cool to room temperature and wash with deionized water and 70% ethanol sequentially. Then dry at 60℃ for 12h to obtain ruthenium dioxide modified carbon nanospheres.

[0011] Furthermore, in the high-temperature resistant CHPO curable putty, the unsaturated polyester resin is composed of 196 unsaturated polyester resin and dicyclohexyl peroxide carbonate, with a mass ratio of 196 unsaturated polyester resin to dicyclohexyl peroxide carbonate of 2:3.

[0012] Furthermore, the high-temperature resistant CHPO curing putty contains a high-temperature resistant composite dispersant of model BYK-W920.

[0013] Furthermore, the present invention also provides a method for preparing the aforementioned high-temperature resistant CHPO-cured atomic putty, the specific process of which is as follows:

[0014] Weigh the specified amounts of unsaturated polyester resin, styrene, cobalt isooctanoate, dimethylaniline, high-temperature resistant composite dispersant, hydrogenated castor oil, fumed silica, rutile titanium dioxide, curing agent, curing aid, and talc. Add the specified amounts of unsaturated polyester resin to a 60°C vacuum degassing reactor, and add the specified amounts of styrene to obtain a resin base liquid. In a high-shear reactor, add the resin base liquid, the specified amounts of high-temperature resistant composite dispersant, hydrogenated castor oil, and fumed silica. Maintain 1000 rpm and shear at 50°C for 30 min. Then, maintaining 50°C, add the specified amounts of talc and rutile titanium dioxide, and stir at 400 rpm for 10 min. After cooling to 35°C, add the specified amounts of cobalt isooctanoate and dimethylaniline sequentially, and stir at 200 rpm for 5 min to obtain the main ash. Then, package the main ash separately. Mix the specified amounts of curing agent and curing aid evenly and package.

[0015] Furthermore, in the preparation method of the high-temperature resistant CHPO curable putty, the unsaturated polyester resin is composed of 196 unsaturated polyester resin and dicyclohexyl peroxide carbonate, and the mass ratio of 196 unsaturated polyester resin to dicyclohexyl peroxide carbonate is 2:3.

[0016] Furthermore, in the preparation method of the high-temperature resistant CHPO solidified putty, the high-temperature resistant composite dispersant is model BYK-W 920.

[0017] Furthermore, in the preparation method of the high-temperature resistant CHPO curing putty, the main putty, curing agent and curing aid putty are mixed evenly and then coated within 1 hour.

[0018] Cyclohexanone peroxide is a commonly used curing agent. Its active ingredient is an organic peroxide, such as cyclohexanone peroxide and benzoyl peroxide. These substances initiate a cross-linking reaction during the curing process, thereby achieving the curing effect. However, cyclohexanone peroxide has poor stability. In current technology, it is usually stored in the form of a 50% dibutyl phthalate paste to improve stability. Generally speaking, the poor stability of cyclohexanone peroxide is mainly related to its internal oxygen-oxygen single bond structure. This bond is very fragile and easily breaks, generating free radicals, which triggers a series of chain reactions, leading to decomposition or even explosion.

[0019] To enhance the curing agent's effectiveness, this application creatively incorporates a small amount of curing aids, namely hydrogen peroxide and trace amounts of carbon nanospheres. The applicant discovered that cyclohexanone peroxide (CHPO) cures faster in the presence of hydrogen peroxide. This may be because CHPO is more stable under hydrogen peroxide conditions, allowing a small amount of hydrogen peroxide to react preferentially, or the presence of hydrogen peroxide may enhance its curing initiation effect by providing additional free radicals. Furthermore, carbon nanospheres generally have antioxidant properties, inhibiting the propagation of free radical chains, which may affect the stability of the curing agent, leading to reduced curing effect and slower speed. A large number of carbon nanospheres may reduce impact resistance and adhesion. However, a small amount of ruthenium dioxide-modified carbon nanospheres, on the one hand, ruthenium dioxide has significant oxidizing properties, easily increasing the curing speed of CHPO; on the other hand, it is often used as a catalyst in materials chemistry, enhancing the initiation effect of CHPO. The applicant also discovered that a small amount of carbon nanospheres have good electrical conductivity, enabling them to participate in electron transfer reactions, altering the electronic structure and reactivity of the curing agent molecules, thereby potentially enhancing the curing reaction.

[0020] The applicant discovered through numerous experiments that:

[0021] (1) A small amount of hydrogen peroxide can preferentially form a "secondary free radical library" with CHPO, which plays a role in protecting CHPO and maintaining its relatively high activity during long-term storage. This may be because cyclohexanone peroxide is relatively stable under hydrogen peroxide conditions, and a small amount of hydrogen peroxide can preferentially react. Furthermore, the presence of hydrogen peroxide may enhance its curing initiation effect by providing additional free radicals.

[0022] (2) The carbon nanospheres modified with ruthenium dioxide (RuO2) have excellent electron transfer ability and surface oxidation activity, which can stabilize the primary free radicals generated by CHPO decomposition and inhibit chain transfer side reactions, thereby improving the curing speed while maintaining storage stability.

[0023] (3) Generally speaking, in the prior art, carbon nanospheres have antioxidant properties and can inhibit the propagation of free radical chains, which may affect the stability of the curing agent, resulting in a decrease in curing effect and a slower speed. A large number of carbon nanospheres may reduce the impact resistance and adhesion of the putty. However, the applicant found that a small amount of ruthenium dioxide modified carbon nanospheres not only have little effect on the impact resistance and adhesion of the putty, but also that ruthenium dioxide has a significant oxidizing property, which can easily improve the curing speed and initiation effect of CHPO. At the same time, the applicant found that a small amount of carbon nanospheres have good electrical conductivity and can participate in electron transfer reactions, changing the electronic structure and reactivity of the curing agent molecules, which may improve the progress of the curing reaction. Detailed Implementation

[0024] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention. Example 1

[0025] A high-temperature resistant CHPO curable putty comprises the following components in parts by weight percentage: 50 parts unsaturated polyester resin, 4 parts styrene, 0.7 parts cobalt isooctanoate, 0.2 parts dimethylaniline, 0.4 parts high-temperature resistant composite dispersant, 0.5 parts hydrogenated castor oil, 0.3 parts fumed silica, 2 parts rutile titanium dioxide, 2 parts curing agent (CHPO), 0.4 parts curing aid, and the balance being talc powder.

[0026] The curing agent consists of hydrogen peroxide and modified carbon nanospheres, with a mass ratio of 99:1. The modified carbon nanospheres have a diameter of less than 100 nm. The hydrogen peroxide used is 30% by mass. The modified carbon nanospheres are ruthenium dioxide modified carbon nanospheres, and the modification method is as follows:

[0027] Step 1: Disperse 0.95g of raw carbon nanospheres in 50mL of 1mol / L HCl and treat with ultrasound at 150W for 30min. Then wash the carbon nanospheres with 500mL of deionized water and dry at 60℃ for 6h to obtain acidified carbon nanospheres. Step 2: Place 100mg of RuCl3·xH2O in 500mL of deionized water, add the acidified carbon nanospheres, and treat with ultrasound at 150W for 1h at room temperature. Then stir magnetically for 20min to obtain a precursor slurry. Step 3: Transfer the precursor slurry to a three-necked flask, heat to 80℃ in a water bath, and add 1mL of 30% H2O2 dropwise at a uniform rate using a burette until precipitation is complete. Then slowly cool to room temperature and wash with deionized water and 70% ethanol sequentially. Then dry at 60℃ for 12h to obtain ruthenium dioxide modified carbon nanospheres.

[0028] The unsaturated polyester resin is composed of 196 unsaturated polyester resin and dicyclohexyl peroxide carbonate, with a mass ratio of 2:3 between the 196 unsaturated polyester resin and the dicyclohexyl peroxide carbonate.

[0029] Furthermore, the high-temperature resistant CHPO curing putty, wherein the high-temperature resistant composite dispersant is model BYK-W 920.

[0030] Furthermore, the present invention also provides a method for preparing high-temperature resistant CHPO-cured atomic putty, the specific process of which is as follows:

[0031] Weigh out the following components by weight: unsaturated polyester resin, styrene, cobalt isooctanoate, dimethylaniline, high-temperature resistant composite dispersant, hydrogenated castor oil, fumed silica, rutile titanium dioxide, curing agent, curing aid, and talc. Add the unsaturated polyester resin to a 60°C vacuum degassing reactor, and add the styrene to obtain a resin base liquid. In a high-shear reactor, add the resin base liquid, along with the high-temperature resistant composite dispersant, hydrogenated castor oil, and fumed silica. Maintain 1000 rpm and shear at 50°C for 30 minutes. Then, while maintaining 50°C, add the talc and rutile titanium dioxide, and stir at 400 rpm for 10 minutes. After cooling to 35°C, add the cobalt isooctanoate and dimethylaniline sequentially, and stir at 200 rpm for 5 minutes to obtain the main ash. Package the main ash separately. Mix the curing agent and curing aid thoroughly and then package.

[0032] When using, mix the main ash, hardener, and hardening aid ash evenly, and apply the coating within 1 hour. Example 2

[0033] A high-temperature resistant CHPO curable putty is provided, which differs from Example 1 in that: the curing agent is hydrogen peroxide of equal mass, and the modified carbon nanospheres are replaced with carbon nanospheres of the same specification, and the amount of carbon nanospheres used is the same as that of the modified carbon nanospheres. Example 3

[0034] A high-temperature resistant CHPO curable putty is provided, which differs from Example 1 in that the curing aids are hydrogen peroxide and powdered ruthenium dioxide. The mass of hydrogen peroxide is the same as that used in Comparative Document 1, and the amount of ruthenium dioxide is the same as that used in modified carbon nanospheres. Example 4

[0035] A high-temperature resistant CHPO curable putty is provided, which differs from Example 1 in that the amount of curing aid used remains the same. The curing aid is hydrogen peroxide and modified carbon nanospheres, and the mass ratio of hydrogen peroxide to modified carbon nanospheres is 1:99. Example 5

[0036] A high-temperature resistant CHPO curable putty is provided, which differs from Example 1 in that the amount of curing aid used remains the same. The curing aid is hydrogen peroxide and modified carbon nanospheres, and the mass ratio of hydrogen peroxide to modified carbon nanospheres is 1:1. Example 6

[0037] A high-temperature resistant CHPO curing putty is provided, with the amount of curing agent remaining the same. The difference from Example 1 is that the curing agent is only hydrogen peroxide. Example 7

[0038] A high-temperature resistant CHPO curable atomized putty is provided, with the amount of curing aid remaining the same. The difference from Example 1 is that the curing aid is only modified carbon nanospheres. Example 8

[0039] A high-temperature resistant CHPO curing putty is provided, without providing curing aids, using an equal amount of carbon black instead of curing aids, with all other conditions being the same. Example 9

[0040] A high-temperature resistant CHPO curable putty is provided, comprising the following components in parts by weight percentage: 45 parts unsaturated polyester resin, 5 parts styrene, 0.8 parts cobalt isooctanoate, 0.1 parts dimethylaniline, 0.35 parts high-temperature resistant composite dispersant, 0.6 parts hydrogenated castor oil, 0.4 parts fumed silica, 1.5 parts rutile titanium dioxide, 2.5 parts curing agent, 0.5 parts curing aid, and the balance being talc. Except for the aforementioned parts by weight, all other conditions are the same.

[0041] The high-temperature resistant CHPO cured putty from Examples 1-9 above was tested using the national standard GB / T 1728-2020, "Determination of Drying Time of Paint Film and Putty Film". The corresponding time that the putty did not stick to the filter paper was measured and recorded. The experimental result was recorded as T. one 1~T one 9. For the corresponding times in Examples 1-9, the experimental results are detailed in Table 1 below. After being dried in a 60℃ oven for 0.5 hours under forced convection, the mixture was removed and observed for cracking. Another set of experiments was conducted. The mixture of curing agent and curing aid from Examples 1-9 was removed, placed in a 40℃ environment under general convection for 30 minutes, and then mixed evenly with the main putty to prepare putty for testing. The testing method was the national standard: GB / T 1728-2020 "Determination of Drying Time of Paint Film and Putty Film". The corresponding time that did not stick to the filter paper was measured and recorded. The result of this experiment was recorded as T. two 1~T two 9. The experimental results are detailed in Table 2 below.

[0042] Table 1 Results of the first experiment

[0043]

[0044] Table 2 Results of the Second Experiment

[0045]

[0046] The above experiments show that, compared with Examples 1-9 and Tables 1 and 2, Examples 1 and 9 have the shortest surface drying time and complete curing time. However, compared with Examples 1 and 4 and 5 in Tables 1 and 2, a relatively large amount of modified carbon nanospheres may affect the crack resistance of the putty in a high-temperature environment. According to Table 3, even when placed at a higher temperature for a period of time, the increase in drying time and curing time of Examples 1 and 9 is relatively small compared with other control groups.

[0047] Table 3 shows the curing time increments, denoted as ΔT, where ΔT1 to ΔT9 correspond to the increments relative to the experimental group.

[0048] Table 3. Statistics on Curing Time Increment

[0049]

[0050] The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments. Any changes, modifications, substitutions, combinations, or simplifications made without departing from the spirit and principle of the present invention shall be considered equivalent substitutions and shall be included within the protection scope of the present invention.

Claims

1. A high-temperature resistant CHPO curing putty, characterized in that, The putty comprises the following components in parts by weight percentage: 45-60 parts unsaturated polyester resin, 3-5 parts styrene, 0.5-0.8 parts cobalt isooctanoate, 0.01-0.2 parts dimethylaniline, 0.35-0.55 parts high-temperature resistant composite dispersant, 0.2-0.6 parts hydrogenated castor oil, 0.1-0.5 parts fumed silica, 1-2 parts rutile titanium dioxide, 1.5-2.5 parts curing agent, 0.4-0.5 parts curing aid, and the balance being talc. The curing agent is CHPO, and the curing aid is hydrogen peroxide and modified carbon nanospheres, with a mass ratio of hydrogen peroxide to modified carbon nanospheres of 98-99:

1. The modified carbon nanospheres have a diameter of less than 100 nm and are modified with ruthenium dioxide. The modification method is as follows: Step 1: Disperse 0.95g of raw carbon nanospheres in 50mL of 1mol / L HCl and treat with ultrasound at 150W for 30min. Then wash the carbon nanospheres with 500mL of deionized water and dry at 60℃ for 6h to obtain acidified carbon nanospheres. Step 2: Place 100mg of RuCl3·xH2O in 500mL of deionized water, add the acidified carbon nanospheres, and treat with ultrasound at 150W for 1h at room temperature. Then stir magnetically for 20min to obtain a precursor slurry. Step 3: Transfer the precursor slurry to a three-necked flask, heat to 80℃ in a water bath, and add 1mL of 30% H2O2 dropwise at a uniform rate using a burette until precipitation is complete. Then slowly cool to room temperature and wash with deionized water and 70% ethanol sequentially. Then dry at 60℃ for 12h to obtain ruthenium dioxide modified carbon nanospheres.

2. The high-temperature resistant CHPO curing putty as described in claim 1, wherein the hydrogen peroxide has a mass fraction of 30%.

3. The high-temperature resistant CHPO curable putty as described in claim 1, wherein the unsaturated polyester resin is composed of 196 unsaturated polyester resin and dicyclohexyl peroxide carbonate, and the mass ratio of 196 unsaturated polyester resin to dicyclohexyl peroxide carbonate is 2:

3.

4. The high-temperature resistant CHPO curing putty as described in claim 1, wherein the high-temperature resistant composite dispersant is model BYK-W920.

5. The method for preparing high-temperature resistant CHPO curable putty according to any one of claims 1-2, comprising weighing the following parts by weight: unsaturated polyester resin, styrene, cobalt isooctanoate, dimethylaniline, high-temperature resistant composite dispersant, hydrogenated castor oil, fumed silica, rutile titanium dioxide, curing agent, curing aid, and talc; adding the aforementioned parts by weight of unsaturated polyester resin into a 60°C vacuum degassing reactor; adding the aforementioned parts by weight of styrene to obtain a resin base liquid; and adding the resin base liquid and the aforementioned parts by weight of styrene into a high-shear reactor. A mixture of high-temperature resistant composite dispersant, hydrogenated castor oil, and fumed silica was prepared and sheared at 50°C for 30 minutes at 1000 rpm. Then, while maintaining the temperature at 50°C, the mixture of talc powder and rutile titanium dioxide was added and stirred at 400 rpm for 10 minutes. After cooling to 35°C, the mixture of cobalt isooctanoate and dimethylaniline was added sequentially and stirred at 200 rpm for 5 minutes to obtain the main ash. The main ash was then packaged separately. The curing agent and curing aid were then mixed evenly and packaged.

6. The method for preparing high-temperature resistant CHPO curable putty as described in claim 5, wherein the unsaturated polyester resin is composed of 196 unsaturated polyester resin and dicyclohexyl peroxide carbonate, and the mass ratio of 196 unsaturated polyester resin to dicyclohexyl peroxide carbonate is 2:

3.

7. The method for preparing high-temperature resistant CHPO solidified putty as described in claim 6, wherein the high-temperature resistant composite dispersant is BYK-W 920.

8. The method for preparing high-temperature resistant CHPO curing putty as described in claim 7, wherein the main putty, curing agent and curing aid putty are mixed evenly and then coated within 1 hour.

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