WO2021133213A1 - Procédé de production de polydiéthylsiloxanes - Google Patents

Procédé de production de polydiéthylsiloxanes Download PDF

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Publication number
WO2021133213A1
WO2021133213A1 PCT/RU2020/000653 RU2020000653W WO2021133213A1 WO 2021133213 A1 WO2021133213 A1 WO 2021133213A1 RU 2020000653 W RU2020000653 W RU 2020000653W WO 2021133213 A1 WO2021133213 A1 WO 2021133213A1
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WO
WIPO (PCT)
Prior art keywords
polydiethylsiloxanes
producing
molecular weight
polymerization
hexaethylcyclotrisiloxane
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/RU2020/000653
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English (en)
Russian (ru)
Inventor
Марина Алексеевна ОБРЕЗКОВА
Азиз Мансурович МУЗАФАРОВ
Александра Александровна КАЛИНИНА
Нина Васильевна ДЕМЧЕНКО
Александра Валерьевна БЫСТРОВА
Мартин МЕЛЛЕР
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
AN Nesmeyanov Institute of Organoelement Compounds of Russian Academy of Sciences INEOS RAS
Original Assignee
AN Nesmeyanov Institute of Organoelement Compounds of Russian Academy of Sciences INEOS RAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by AN Nesmeyanov Institute of Organoelement Compounds of Russian Academy of Sciences INEOS RAS filed Critical AN Nesmeyanov Institute of Organoelement Compounds of Russian Academy of Sciences INEOS RAS
Publication of WO2021133213A1 publication Critical patent/WO2021133213A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C08G77/06—Preparatory processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/10—Metal compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C08L83/06—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C08L83/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen

Definitions

  • the invention relates to the chemistry and technology of organosilicon polymers and can be used in the preparation of polymers with a given structure and properties, in particular in the preparation of polymacromonomers, block copolymers and polymers of a star-shaped structure.
  • This invention relates to a new method for producing "living" polydiethylsiloxane polymers.
  • Polydiethylsiloxanes are flexible siloxane chain silicone polymers that exhibit complex phase behavior. Polydiethylsiloxanes with molecular weights above 30,000 g / mol are characterized by the presence of a mesophase at about room temperature and two or more crystalline phases at lower temperatures [Lee CL, Johannson OK, Flanigan OL, Hahn P. ACS Polym. Prepr. 1969,10 (2), 1319-26; Beaty CL, Pochan JM, Froix MF, Hinman DD Macromolecules. 1975,8 (4), 547-51; Froix MF, Beaty CL, Pochan JM, Hinman DD J Polym. Sci .: Polym. Phys.
  • the main method for producing polydiethylsiloxanes is anionic polymerization of hexaethylcyclotrisiloxane.
  • the specified polymerization method makes it possible to relatively easily synthesize polydiethylsiloxanes with end hydroxysilyl groups at room temperature; however, the synthesized samples are characterized by high values of polydispersity: even for a polymer with a molecular weight of 6,000, the polydispersity is 1.27 , and for polydiethylsiloxane with a molecular weight equal to 58000, it reaches 1.91.
  • This method makes it possible to obtain polydiethyl siloxanes with a polydispersity of 1.10 in the range of number average molecular weights from 11800 to 66700.
  • the polydispersity of the samples varies from 1.11 for polydiethylsiloxane with a molecular weight of 11,800 to 1.39 for a sample with a molecular weight of 430,000.
  • cryptand [221] is used as a polymerization activator is the need to carry out the process under high vacuum conditions and in the absence of moisture, which requires special equipment.
  • cryptand [221] is distinguished by its high cost, extreme sensitivity to moisture and various impurities, and requires laborious preliminary cleaning for its application.
  • the objective of the claimed invention was to create a new method for producing polydiethylsiloxanes, providing the formation of "living" monofunctional polydiethylsiloxanes with an OLi-group at the end of the chain with a narrow monomodal molecular weight distribution, using an affordable and cheap activator.
  • n denotes integers from 15 to 500.
  • the reaction scheme is presented below: where n denotes integers from 15 to 500,
  • Dimethylformamide used as an activator in the claimed method does not require special conditions for purification and storage: it is simply dried by distillation under reduced pressure over barium oxide, in contrast to cryptand [211], an activator used in the prototype, which must first be distilled in a high vacuum in a quartz container and store at -20 ° C.
  • FIG. 1 shows the GPC curve of polydiethylsiloxane prepared under the conditions described below in Example 3.
  • the molecular weight of the polydiethylsiloxanes synthesized by the inventive method can be adjusted by changing the ratio of the initial reagents and the duration of the process. This results in the formation of polydiethyl siloxanes with a molecular weight of 1600 to 51000 s monomodal molecular weight distribution and polydispersity
  • the technical result consists in the development of a new technological method that allows to obtain "live” monofunctional polydiethylsiloxanes with an OLi group at the end of the chain with a narrow monomodal molecular weight distribution from available reagents.
  • the polymerization is carried out in an inert atmosphere.
  • a mixture of 0.6988 g (2.28 s 10 ' mol) of hexaethylcyclotrisiloxane, 4.4 ⁇ l (6.98 s 10 mol) of n-BuLi and 0.35 ml of toluene is stirred at room temperature for 20 h, then 1, 62 ⁇ l of DMF (6.98 s 10 6 mol) and the reaction mixture is stirred at 60 ° C for 6 h. Then trimethylchlorosilane is added to neutralize OLi-groups.
  • the polymerization is carried out in an inert atmosphere.

Landscapes

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

Abstract

L'invention concerne des procédés de production de polymères à base de silicium organique. . L'invention concerne un procédé de production de polydiéthylsiloxanes par la polymérisation anionique d'hexaéthylcyclotrisiloxane, laquelle se fait dans du toluol à 60°C en présence d'un initiateur de n-butyllithium, et on utilise du DMF en qualité d'activateur de polymérisation. Le résultat technique consiste en un procédé permettant de produire des polydiéthylsiloxanes polyfonctionnels "vivants" possédant un groupe OLi à la fin de la chaîne, et possédant un distribution moléculaire-massique monomodale étroite, qui peuvent être utilisés lors de la production de copolymères séquencés à mémoire de formes.
PCT/RU2020/000653 2019-12-27 2020-12-01 Procédé de production de polydiéthylsiloxanes Ceased WO2021133213A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
RU2019144326 2019-12-27
RU2019144326A RU2732410C1 (ru) 2019-12-27 2019-12-27 Способ получения полидиэтилсилоксанов

Publications (1)

Publication Number Publication Date
WO2021133213A1 true WO2021133213A1 (fr) 2021-07-01

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/RU2020/000653 Ceased WO2021133213A1 (fr) 2019-12-27 2020-12-01 Procédé de production de polydiéthylsiloxanes

Country Status (2)

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RU (1) RU2732410C1 (fr)
WO (1) WO2021133213A1 (fr)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10052183A1 (de) * 1999-09-21 2002-05-02 Chi Mei Corp Katalysatorzusammensetzung zur Hydrierung von Synthesekautschuken auf der Grundlage konjugierter Diene
EP2584005A1 (fr) * 2010-06-18 2013-04-24 Tosoh Corporation Composition de polysiloxane contenant des métaux types, son procédé de fabrication et ses utilisations
RU2700937C1 (ru) * 2016-07-22 2019-09-24 Публичное акционерное общество "СИБУР Холдинг" Способ получения разветвленно-модифицированного каучука и резиновая смесь, содержащая полученный данным способом разветвленно-модифицированный каучук, а также ее применение

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10052183A1 (de) * 1999-09-21 2002-05-02 Chi Mei Corp Katalysatorzusammensetzung zur Hydrierung von Synthesekautschuken auf der Grundlage konjugierter Diene
EP2584005A1 (fr) * 2010-06-18 2013-04-24 Tosoh Corporation Composition de polysiloxane contenant des métaux types, son procédé de fabrication et ses utilisations
RU2700937C1 (ru) * 2016-07-22 2019-09-24 Публичное акционерное общество "СИБУР Холдинг" Способ получения разветвленно-модифицированного каучука и резиновая смесь, содержащая полученный данным способом разветвленно-модифицированный каучук, а также ее применение

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
AART MOLENBERG, STEFAN SIFFRIN, MARTIN MÖLLER, SYLVIE BOILEAU, DOMINIQUE TEYSSIÉ: "Well defined columnar liquid crystalline polydiethylsiloxane", MACROMOLECULAR SYMPOSIA, vol. 102, no. 1, 1 January 1996 (1996-01-01), pages 199 - 207, XP055834930, ISSN: 1022-1360, DOI: 10.1002/masy.19961020125 *

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