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KR-20260065806-A - Modified spherical silicon dioxide containing closed isocyanate groups, method of preparation thereof, and application

KR20260065806AKR 20260065806 AKR20260065806 AKR 20260065806AKR-20260065806-A

Abstract

The present application discloses modified spherical silicon dioxide containing closed isocyanate groups, a method for manufacturing the same, and applications, and belongs to the field of functional materials technology. The method comprises spraying an isocyanate coupling agent onto the surface of silicon dioxide to obtain silicon dioxide powder modified with isocyanate; dispersing the silicon dioxide powder modified with isocyanate in a solvent, adding an oxime-based closing agent A solution and reacting at 100–140°C for 4–8 hours, and cooling to 20–80°C after the reaction is finished; adding an oxime-based closing agent B solution to the cooled reaction system and reacting at 20–80°C for 2–4 hours; and after the reaction is finished, washing the precipitate several times and drying it to produce modified spherical silicon dioxide containing closed isocyanate groups. The present application can effectively improve the stability of isocyanate groups by closing an isocyanate coupling agent using a suitable closing agent to form an aqueous closed isocyanate, and by using the said aqueous closed isocyanate as a modifier to modify spherical silicon dioxide.

Inventors

  • 카오, 지아카이
  • 장, 지안핑
  • 헤, 유촨
  • 선, 샤오야오

Assignees

  • 노보레이 코포레이션

Dates

Publication Date
20260511
Application Date
20250623
Priority Date
20241030

Claims (18)

  1. Modified spherical silicon dioxide containing closed isocyanate groups, wherein the modified spherical silicon dioxide containing closed isocyanate groups is characterized by having a carbon content <0.65% when left for 0 days; a carbon content <0.62% and a moisture content <0.028% when left for 6 months.
  2. In paragraph 1, The modified spherical silicon dioxide containing closed isocyanate groups is characterized by having a carbon content <0.65% when left for 0 days; a carbon content <0.62% and a moisture content <0.027% when left for 6 months.
  3. In paragraph 1 or 2, Modified spherical silicon dioxide containing closed isocyanate groups, characterized by a carbon content of 0.580 to 0.619% when the modified spherical silicon dioxide containing closed isocyanate groups is left for 6 months.
  4. A method for producing modified spherical silicon dioxide containing closed isocyanate groups as described in any one of claims 1 to 3, wherein the method comprises the following steps: A step of spraying an isocyanate coupling agent onto the surface of silicon dioxide powder having a moisture content of less than 0.03% to obtain silicon dioxide powder after isocyanate modification; wherein the isocyanate coupling agent is a methoxy group-containing isocyanate, an ethoxy group-containing isocyanate, a pyridine group-containing isocyanate, or a benzene ring-containing isocyanate; A step of dispersing the silicon dioxide powder after isocyanate modification in a solvent, adding an oxime-based occlusive agent A solution, reacting at 100–140°C for 4–8 hours, and cooling to 20–80°C after the reaction is completed; A step of adding an oxime-based closing agent B solution to the above-described cooled reaction system and reacting at 20–80°C for 2–4 hours, and after the reaction is completed, washing the precipitate several times and drying it under conditions of 35–45°C to produce modified spherical silicon dioxide containing closed isocyanate groups; A method for manufacturing characterized in that the oxime-based clotting agent A is at least one of pyruvate oxime, glyoxylate oxime, and 2-oxocyclopentanethate oxime; and the oxime-based clotting agent B is at least one of acetaldehyde oxime, acetone oxime, butanone oxime, pentanone oxime, cyclopentanone oxime, and cyclohexanone oxime.
  5. In paragraph 4, A manufacturing method characterized by obtaining silicon dioxide powder with a moisture content of less than 0.03% by drying silicon dioxide raw materials in a roller furnace.
  6. In paragraph 4, A manufacturing method characterized by a mass ratio of silicon dioxide powder with a moisture content of less than 0.03% and an isocyanate coupling agent of 100: 0.1 to 1.5.
  7. In paragraph 4 or 6, A method for manufacturing characterized in that the above isocyanate coupling agent is at least one of 3-isocyanate propyltrimethoxysilane, 2-isocyanate pyridine, isocyanate propyltriethoxysilane, triphenylmethane triisocyanate, and 2-(trifluoromethoxy)phenyl isocyanate.
  8. In paragraph 4, A manufacturing method characterized by the molar ratio of the above isocyanate coupling agent, oxime-based clotting agent A, and oxime-based clotting agent B being 1:1~5:0.01~5.
  9. In paragraph 8, A manufacturing method characterized by the molar ratio of the above isocyanate coupling agent, oxime-based clotting agent A, and oxime-based clotting agent B being 1:1~5:0.01~1.
  10. In paragraph 4, A manufacturing method characterized in that the above-mentioned oxime-based occlusive agent A is two of pyruvate oxime, glyoxylate oxime, and 2-oxocyclopentanethate oxime, and the molar ratio of the two is 1~3:1~3.
  11. In Paragraph 10, A method for manufacturing characterized in that the above-mentioned oxime-based occlusive agent A is a pyruvate oxime and a 2-oxocyclopentanethate oxime, or a glyoxylate oxime and a 2-oxocyclopentanethate oxime.
  12. In paragraph 4, A manufacturing method characterized in that the above-mentioned oxime-based occlusive agent B is two of acetaldehyde oxime, acetone oxime, butanone oxime, pentanone oxime, cyclopentanone oxime, and cyclohexanone oxime, and the molar ratio of the two is 1 to 3:1 to 3.
  13. In Paragraph 12, A method for manufacturing characterized in that the above-mentioned oxime-based occlusive agent B is acetaldehyde oxime and acetone oxime, or acetone oxime and butanone oxime, or butanone oxime and cyclohexanone oxime, or butanone oxime and cyclopentanone oxime, or acetone oxime and pentanone oxime, or pentanone oxime and cyclohexanone oxime, or acetaldehyde oxime and pentanone oxime, or acetaldehyde oxime and cyclopentanone oxime, or acetone oxime and cyclohexanone oxime.
  14. In paragraph 4, A manufacturing method characterized in that the solvent in the above oxime-based clotting agent A solution is anhydrous toluene; and the molar volume ratio of the above oxime-based clotting agent A to anhydrous toluene is 0.01 to 0.3 mol: 50 to 150 mL.
  15. In paragraph 4, A manufacturing method characterized in that the solvent in the above oxime-based occlusive agent B solution is anhydrous toluene; and the molar volume ratio of the above oxime-based occlusive agent B to anhydrous toluene is 0.001 to 0.1 mol: 0.1 to 15 mL.
  16. In paragraph 4, A manufacturing method characterized by the above drying being carried out in a vacuum drying oven.
  17. Application in a package substrate of modified spherical silicon dioxide containing closed isocyanate groups as described in any one of claims 1 to 3, or modified spherical silicon dioxide containing closed isocyanate groups obtained by a manufacturing method according to any one of claims 4 to 16.
  18. Applications of modified spherical silicon dioxide containing closed isocyanate groups as described in any one of claims 1 to 3, or modified spherical silicon dioxide containing closed isocyanate groups obtained by a manufacturing method according to any one of claims 4 to 16, in paints, adhesives, polymer materials, catalysts, drug transport, or adsorption separation.

Description

Modified spherical silicon dioxide containing closed isocyanate groups and its manufacturing method and applications **Applied** The present application claims priority to a Chinese patent application filed with the Chinese Intellectual Property Office on October 30, 2024, with application number CN202411528356.2 and title of the invention “Spherical silicon dioxide modified with isocyanate groups and method for manufacturing the same,” the entire contents of which are incorporated into the present application by reference. The present application relates to the field of functional materials technology, specifically to modified spherical silicon dioxide containing closed isocyanate groups, a method for manufacturing the same, and applications. In the chemical industry, isocyanate groups are commonly used as modifiers or for the treatment of spherical silicon dioxide. However, due to the high activity of isocyanate groups, they react easily with substances such as moisture, leading to the consumption of the isocyanate groups and a decrease in the stability and sustainability of the modification effect. To facilitate the transportation and storage of isocyanates, the industry enhances their stability by protecting the isocyanate groups with closure agents. Closed isocyanates can form stable compounds by reacting the isocyanate groups with the closure agent at low temperatures, and can restore reaction activity by generating isocyanate groups again at high temperatures. Considering the high reactive activity of the -NCO group, many compounds containing active hydrogen, such as phenols, alcohols, and oximes, can all react with isocyanates to form closed-type isocyanates. CN113121791A disclosed a low-temperature unclogging isocyanate curing agent and a method for manufacturing the same. Two types of organic and inorganic closing agents were reacted with hexamethylene diisocyanate (HDI) to form a closed-type isocyanate curing agent. The manufactured isocyanate curing agent can be completely unclogged at a relatively low temperature of 70 to 85°C, but the amount of hydrogen sulfite used is more than three times that of the isocyanate group, and if the treatment after unclogging is improper, it may remain in the product and cause adverse effects. CN117567724A disclosed an aqueous closed-type isocyanate crosslinking agent, and a nonionic aqueous closed-type isocyanate crosslinking agent was obtained by selecting and using an isocyanate compound, a hydrophilic diol, and a fluorine-containing diol. The crosslinking agent has excellent hydrophobicity but contains a fluorine element that is not environmentally friendly, so its use is limited. Carbon content was detected using a German inductar CS cube carbon-sulfur analyzer, by burning carbon and sulfur in the sample with high-temperature induction combustion to produce carbon dioxide and sulfur dioxide gases, and then using an infrared detector to detect the concentration of these gases to calculate the carbon content in the sample (in this application, the carbon content specifically refers to the mass content of carbon); moisture was detected using a Kunya moisture meter SFY-118, by drying the sample to a constant weight under a constant temperature and calculating the moisture content of the sample from the reduced mass of the sample (in this application, the moisture content specifically refers to the mass content of moisture); infrared radiation was detected using a Fourier infrared spectrometer, which is based on the fact that all chemical bonds present in a molecule have a specific vibration frequency, and since these vibration frequencies can coincide with the wavelength of infrared radiation, the molecule absorbs a specific frequency of infrared radiation to produce a peak. Since isocyanate reacts with water to produce CO2 , the method for detecting the release temperature of the closed isocyanate is to heat the closed-agent-treated modified spherical silicon dioxide on a moist molecular sieve and consider the lowest temperature detected when CO2 evaporates as the release temperature of the closed isocyanate. The present application will be further explained through the following examples, but the scope of protection of the present application is not limited thereto: Example 1 Step 1: The silicon dioxide raw material is dried in a roller furnace, and the moisture content of the silicon dioxide powder after drying is 0.023%. Step 2: 240g of dried silicon dioxide powder is fed into a high-speed mixer, and 2.4g of 3-isocyanatepropyltrimethoxysilane (0.01 mol) is sprayed onto the surface of the dried silicon dioxide powder to modify it, and then sieved to remove impurities to obtain silicon dioxide powder after isocyanate modification. Step 3: Disperse the silicon dioxide powder after isocyanate modification in 960 mL of anhydrous toluene and place it in a three-necked flask; using an isobaric dropping funnel, slowly add a mixed solution of 0.018 mol oxime-based