WO2020204748A1 - Procédé de production d'un hydrogel à base de polyméthylsilsesquioxane - Google Patents

Procédé de production d'un hydrogel à base de polyméthylsilsesquioxane Download PDF

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Publication number
WO2020204748A1
WO2020204748A1 PCT/RU2019/000889 RU2019000889W WO2020204748A1 WO 2020204748 A1 WO2020204748 A1 WO 2020204748A1 RU 2019000889 W RU2019000889 W RU 2019000889W WO 2020204748 A1 WO2020204748 A1 WO 2020204748A1
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WO
WIPO (PCT)
Prior art keywords
hydrolysis
mol
water
solution
methyltriethoxysilane
Prior art date
Application number
PCT/RU2019/000889
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English (en)
Russian (ru)
Inventor
Леонид Яковлевич РАБИНОВИЧ
Олег Геннадиевич СИЛАНТЬЕВ
Original Assignee
Общество с ограниченной ответственностью "Тульская фармацевтическая фабрика"
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Publication of WO2020204748A1 publication Critical patent/WO2020204748A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/06—Preparatory processes
    • C08G77/08—Preparatory processes characterised by the catalysts used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C08G77/16—Polysiloxanes containing silicon bound to oxygen-containing groups to hydroxyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/38—Polysiloxanes modified by chemical after-treatment

Definitions

  • the present invention relates to the production of organosilicon adsorbent, which can be used in various industries, mainly in pharmacy and healthcare, as well as chemistry and construction, as a sorbing agent for various substances, including for various types of pathology of the gastrointestinal tract and poisoning.
  • the patent of Ukraine for invention No UA 27434 (prototype) is known, which discloses a method for producing an adsorbent gel by hydrolysis of an alkoxysilane in an organic solvent in the presence of an acid catalyst, followed by alkaline treatment, gel maturation, grinding and washing the finished product. product, while the hydrolysis is carried out at a molar ratio of alkoxyxilane: water: acid catalyst - 1: (6, 5-7, 5): (0.04-0.05) for 1-2 hours at a temperature of 20-35 ° C ...
  • the disadvantage of this method is the high consumption of organic solvent.
  • the organic solvent is taken in an amount of 7 to 11 mol per 1 mol of methyltriethoxysilane (MTEOS).
  • MTEOS methyltriethoxysilane
  • the problem underlying the present invention and the achieved technical result is to reduce the consumption of organic solvent in the production of polymethylsilsesquioxane hydrogel.
  • the problem is solved using a method for producing polymethylsiloxane polyhydrate, which consists in the hydrolysis of alkoxysilane in an organic solvent in the presence of a catalyst, followed by maturation and washing of the hydrogel, where an alkaline catalyst is used and the hydrolysis is carried out in an alkaline medium.
  • a method for producing polymethylsiloxane polyhydrate which consists in the hydrolysis of alkoxysilane in an organic solvent in the presence of a catalyst, followed by maturation and washing of the hydrogel, where an alkaline catalyst is used and the hydrolysis is carried out in an alkaline medium.
  • the resulting product remains soluble only in very dilute solutions.
  • polymethylsilsequioxane falls out of the reaction zone as an amorphous product instead of the required hydrogel.
  • the adsorption capacity of the resulting product does not meet any requirements.
  • a negative charge is formed on the surface of the formed macromolecule upon coordination of hydroxyl groups with alkali, which helps to maintain the solubility of the product in more concentrated solutions and allows the process to be carried out with a smaller amount of organic solvent to obtain a hydrogel.
  • methyltriethoxysilane as an alkoxysilane
  • ethanol as an organic solvent
  • KOH or NaOH as an alkaline catalyst
  • the alkaline catalyst in the form of an aqueous solution, the water of which is used for the hydrolysis reaction, while the molar ratio of alkoxysilane and water for hydrolysis is 1 to 7.8 ... 13.6.
  • the acid for neutralizing the product can be used
  • hydrolysis is carried out in an alkaline medium in the absence of sulfuric acid, which is necessary to obtain 1, 1, 3,3-tetrahydroxy-1, 3-dimethyldisiloxane polyhydrate.
  • 1, 1,3,3-tetrahydroxy-1,3-dimethyldisiloxane polyhydrate is not formed.
  • the resulting product also meets the requirements for silicone adsorbents.
  • the resulting gel is crushed to the required size, while diluting with water twice by the volume of the mixture. Then it is transferred to a filter and washed with water until the wash water is neutral for phenolphthalein. In the same place on the filter at the end of washing, the density of the mixture is adjusted by dry residue. A white to translucent gel is obtained with a dry residue of 6.1% and sorption of 5.5 ⁇ mol / g.
  • the resulting gel is crushed to the required size, while diluting with water twice by the volume of the mixture. Then it is transferred to a filter and washed with water until the wash water is neutral for phenolphthalein. A white to translucent gel is obtained with a dry residue of 5.2% and sorption of 4.3 ⁇ mol / g.
  • the resulting gel is crushed to the required size, while diluting with water twice by the volume of the mixture. Then it is transferred to a filter and washed with water until the wash water is neutral for phenolphthalein. In the same place on the filter at the end of washing, the density of the mixture is adjusted by dry residue. A white to translucent gel is obtained with a dry residue of 5.4% and sorption of 3.0 ⁇ mol / g.
  • Example 4 92 g of 95% ethanol are added to 178.3 g (1 mol) of methyltriethoxysilane and a solution of 12 g (0.3 mol) of sodium hydroxide in 157 g of water is added with stirring. The reaction mass spontaneously heats up to 35 ° C. Stirred for 20 minutes and add 20 g of 10% aqueous hydrochloric acid solution (0.05 mol of hydrogen chloride). Stir for 1 minute and pour into a gelling vessel. Kept at room temperature for 8 hours.
  • the resulting gel is crushed to the required size, while diluting with water twice by the volume of the mixture. Then it is transferred to a filter and washed with water until the wash water is neutral for phenolphthalein. In the same place on the filter at the end of washing, the density of the mixture is adjusted by dry residue. A white to translucent gel is obtained with a solid residue of 5.1% and a sorption of 3.1 ⁇ mol / g.
  • the resulting gel is crushed to the required size, while diluting with water twice by the volume of the mixture. Then it is transferred to a filter and washed with water until the wash water is neutral for phenolphthalein. In the same place on the filter at the end of washing, the density of the mixture is adjusted by dry residue. A white to translucent gel is obtained with a dry residue of 5.3% and a sorption of 3.7 ⁇ mol / g.
  • the resulting gel is crushed to the required size, while diluting with water twice by the volume of the mixture. Then it is transferred to a filter and washed with water until the wash water is neutral for phenolphthalein. In the same place on the filter at the end of washing, the density of the mixture is adjusted by dry residue. A white to translucent gel is obtained with a dry residue of 5.5% and sorption of 5.5 ⁇ mol / g.
  • the resulting gel is crushed to the required size, while diluting with water twice by the volume of the mixture. Then it is transferred to a filter and washed with water until the wash water is neutral for phenolphthalein. A white to translucent gel is obtained with a dry residue of 5.5% and a sorption of 3.8 ⁇ mol / g.
  • the optical density of the resulting solution is measured on a spectrophotometer at the absorption maximum at a wavelength of 492 nm in a cuvette with layer thickness of 10 mm, using 0.02 M sodium chloride solution as a reference solution.
  • the optical density of the Congo red solution Kk1 solution is measured.
  • the adsorption activity (X) of the drug in micromoles per gram is calculated by the formula: a 0 2 50 50 1000000 (L 0 - A) a 0 50 000 a - 1000 ⁇ 50 ⁇ 2 ⁇ M ” A 0 ⁇ a ⁇ M
  • a 0 is the optical density of the Congo red solution (Kk1 solution);
  • A is the optical density of the Congo red solution after contact with the drug; ao - weight of Congo red, in g; a - sample of the drug, in g;
  • M is the molecular weight of Congo red (696.7)
  • 1.170 g of sodium chloride is placed in a volumetric flask with a capacity of 1000 ml, dissolved in 50 ml of water, the volume of the solution is brought to the mark with water and stirred.
  • the pH of the water taken to prepare the solution should be between 6.0 and 6.5.
  • the pH of the water is adjusted with 0.1 M sodium hydroxide solution or 0.1 M hydrochloric acid.
  • the obtained adsorbent has sufficient adsorption capacity compared to the prototype, from 3.0 to 8.1 ⁇ mol / g.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Silicon Polymers (AREA)

Abstract

L'invention concerne un procédé de production d'un polyhydrate de polyméthylsiloxane qui consiste à effectuer une hydrolyse d'alcoxysilane dans un solvant organique en présence d'un catalyseur suivi d'une maturation et d'un rinçage de l'hydrogel, dans lequel on utilise un catalyseur alcalin et l'hydrolyse se fait dans un milieu alcalin. Ce procédé permet de réduire la consommation en en solvant organique et d'augmenter les capacités d'adsorption du produit.
PCT/RU2019/000889 2019-03-29 2019-12-04 Procédé de production d'un hydrogel à base de polyméthylsilsesquioxane WO2020204748A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
RU2019109257A RU2714728C1 (ru) 2019-03-29 2019-03-29 Способ получения полиметилсилсесквиоксанового гидрогеля
RU2019109257 2019-03-29

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WO2020204748A1 true WO2020204748A1 (fr) 2020-10-08

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RU (1) RU2714728C1 (fr)
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3842110A (en) * 1973-10-11 1974-10-15 Gen Electric Process for producing octaphenyltetracyclosiloxane
CN102079754A (zh) * 2010-12-27 2011-06-01 蓝星化工新材料股份有限公司江西星火有机硅厂 一甲基三乙氧基硅烷制备工艺
WO2011075095A1 (fr) * 2009-12-16 2011-06-23 Kabachnyi Gennadii Ivanovych Procédé de production d’hydrogel d’acide méthylsilicique
RU2632465C1 (ru) * 2016-12-13 2017-10-05 Федеральное государственное бюджетное учреждение науки Институт элементоорганических соединений им. А.Н. Несмеянова Российской академии наук (ИНЭОС РАН) Способ получения симметричных алкокси(органо)дисилоксанов

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SU1004410A1 (ru) * 1980-10-23 1983-03-15 Предприятие П/Я Г-4236 Способ получени олигометилфенилсилоксанов

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3842110A (en) * 1973-10-11 1974-10-15 Gen Electric Process for producing octaphenyltetracyclosiloxane
WO2011075095A1 (fr) * 2009-12-16 2011-06-23 Kabachnyi Gennadii Ivanovych Procédé de production d’hydrogel d’acide méthylsilicique
CN102079754A (zh) * 2010-12-27 2011-06-01 蓝星化工新材料股份有限公司江西星火有机硅厂 一甲基三乙氧基硅烷制备工艺
RU2632465C1 (ru) * 2016-12-13 2017-10-05 Федеральное государственное бюджетное учреждение науки Институт элементоорганических соединений им. А.Н. Несмеянова Российской академии наук (ИНЭОС РАН) Способ получения симметричных алкокси(органо)дисилоксанов

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