WO2017145690A1 - Polysilsesquioxane en échelle ayant un groupe acide phosphonique et groupe phosphonate dans ses chaînes latérales, stratifié de polysilsesquioxane en échelle, procédé de production d'un polysilsesquioxane en échelle, et procédé de production d'un stratifié de polysilsesquioxane - Google Patents

Polysilsesquioxane en échelle ayant un groupe acide phosphonique et groupe phosphonate dans ses chaînes latérales, stratifié de polysilsesquioxane en échelle, procédé de production d'un polysilsesquioxane en échelle, et procédé de production d'un stratifié de polysilsesquioxane Download PDF

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Publication number
WO2017145690A1
WO2017145690A1 PCT/JP2017/003756 JP2017003756W WO2017145690A1 WO 2017145690 A1 WO2017145690 A1 WO 2017145690A1 JP 2017003756 W JP2017003756 W JP 2017003756W WO 2017145690 A1 WO2017145690 A1 WO 2017145690A1
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ladder
type polysilsesquioxane
formula
laminate
type
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PCT/JP2017/003756
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English (en)
Japanese (ja)
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芳郎 金子
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国立大学法人 鹿児島大学
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Priority to JP2018501100A priority Critical patent/JP6842777B2/ja
Publication of WO2017145690A1 publication Critical patent/WO2017145690A1/fr

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    • 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
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/30—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen phosphorus-containing groups

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  • the present invention relates to a ladder-type polysilsesquioxane having a phosphonic acid group and a phosphonate group in the side chain, a ladder-type polysilsesquioxane laminate, a method for producing a ladder-type polysilsesquioxane, and a ladder-type polysil
  • the present invention relates to a method for producing a sesquioxane laminate.
  • Silsesquioxane is a compound having a structure of (RSiO 1.5 ) n in which one organic substituent (R) and an average of 1.5 oxygen atoms (O) are bonded to a silicon atom (Si). It is a generic name. Silsesquioxane has been attracting attention in recent years mainly in the field of organic-inorganic hybrid materials because it is excellent in heat resistance and durability and has excellent compatibility with organic materials due to the presence of organic substituents.
  • Ladder-type polysilsesquioxane has a one-dimensionally extending polymer main chain, and ladder-type polysilsesquioxane containing a proton-conductive substituent (for example, sulfo group or phosphonic acid group) in the side chain is It is expected to have excellent thermal stability and good proton conductivity. For this reason, utilization of such a ladder-type polysilsesquioxane as a solid electrolyte in a polymer electrolyte fuel cell is being studied. Regarding the application of ladder-type polysilsesquioxane to solid electrolytes, for example, Patent Documents 1 and 2 disclose proton conductive membranes.
  • the proton conductive membranes of Patent Documents 1 and 2 are obtained by combining various silsesquioxanes including ladder types with organic polymer materials having carbon having a sulfonic acid group as a main skeleton.
  • the portion responsible for proton conduction in this proton conducting film is mainly an organic polymer material.
  • Some silsesquioxanes containing sulfonic acid groups have also been used, but the structure is unclear.
  • the present invention has been made in view of the above circumstances, and has a ladder-type polysilsesquioxane, a ladder-type polysilsesquioxane laminate, and a ladder having a phosphonic acid group and a phosphonate group that are more excellent in heat resistance in the side chain. It aims at providing the manufacturing method of a type polysilsesquioxane, and the manufacturing method of a ladder type polysilsesquioxane laminated body.
  • the ladder-type polysilsesquioxane according to the first aspect of the present invention is: Represented by Formula 1 or Formula 2, (In Formula 1 and Formula 2, R 1 represents an alkylene group having 1 to 6 carbon atoms, n represents a positive real number, and in Formula 2, X represents an alkali metal cation, an alkaline earth metal cation, an ammonium cation, Or represents an imidazolium cation.) It is characterized by that.
  • the main chain may have a twisted rod structure.
  • a plurality of ladder-type polysilsesquioxanes represented by Formula 2 and having a rod structure in which the main chain is twisted are laminated on hexagonal,
  • X is an alkali metal cation, alkaline earth metal cation, ammonium cation, or imidazolium cation
  • R 1 is an alkylene group having 1 to 6 carbon atoms
  • n is a positive real number.
  • the method for producing a ladder-type polysilsesquioxane according to the third aspect of the present invention is as follows.
  • the compound represented by Formula 3 is hydrolyzed and condensed to obtain a ladder-type polysilsesquioxane represented by Formula 1.
  • R 1 represents an alkylene group having 1 to 6 carbon atoms
  • R 2 represents an alkyl group having 1 to 4 carbon atoms.
  • R 1 represents an alkylene group having 1 to 6 carbon atoms
  • n represents a positive real number.
  • the method for producing a ladder-type polysilsesquioxane laminate according to the fourth aspect of the present invention includes: The ladder-type polysilsesquioxane obtained by the method for producing a ladder-type polysilsesquioxane according to the third aspect of the present invention is treated with a base, Obtaining a laminate in which a plurality of ladder-type polysilsesquioxanes represented by formula 2 and having a rod structure in which the main chain is twisted is laminated on hexagonal, (In Formula 2, X is an alkali metal cation, alkaline earth metal cation, ammonium cation, or imidazolium cation, R 1 is an alkylene group having 1 to 6 carbon atoms, and n is a positive real number.) It is characterized by that.
  • the ladder-type polysilsesquioxane according to the present embodiment is represented by Formula 1 or Formula 2.
  • R 1 represents an alkylene group having 1 to 6 carbon atoms
  • n represents a positive real number.
  • X represents an alkali cation, an alkaline earth metal cation, an ammonium cation, or an imidazolium cation.
  • a phosphonic acid group or a phosphonate group is bonded as a side chain to Si of the polymer main chain. That is, one phosphonic acid group or phosphonate group is bonded to one Si of the polymer main chain. Due to the repulsion of charges between the side chains, the ladder-type polysilsesquioxane represented by Formula 1 and Formula 2 has a one-dimensional extension of the polymer main chain and a twist of the main chain as shown in FIG. It has a rod structure.
  • the side chain phosphonic acid groups form a continuous proton transfer path and exhibit high proton conductivity.
  • the ladder-type polysilsesquioxane according to the present embodiment is derived from the excellent heat resistance and durability derived from the Si—O—Si bond of the main chain, and the rigid main chain of the double chain structure. With a high glass transition point. Therefore, the ladder type polysilsesquioxane can be suitably used as a solid electrolyte of a polymer electrolyte fuel cell at a high temperature exceeding 100 ° C. (for example, 150 ° C. to 200 ° C.).
  • the ladder-type polysilsesquioxane according to the present embodiment also has flame retardancy derived from a phosphonic acid group or a phosphonate group. For this reason, the ladder type polysilsesquioxane according to the present embodiment can be suitably used as a flame retardant material. And ladder type polysilsesquioxane is excellent in compatibility with an aqueous solvent or a highly polar organic solvent, and is soluble. For example, a solution in which a ladder type polysilsesquioxane is dissolved in a solvent can be coated on various materials to form a film, and can also be used as a flame retardant coating material.
  • the ladder-type polysilsesquioxane represented by the above formula 1 is obtained by hydrolysis and polycondensation of the compound represented by the formula 3.
  • R 1 is an alkylene group having 1 to 6 carbon atoms.
  • the alkylene group is longer than this, regular steric coordination becomes difficult, and the formation of a ladder structure may be hindered. Furthermore, the heat resistance and durability of the resulting ladder-type polysilsesquioxane may be lowered.
  • R 2 is an alkyl group having 1 to 4 carbon atoms. If the alkyl chain is long, hydrolysis described later may be difficult to occur.
  • Hydrolysis and polycondensation of the compound represented by Formula 3 can be performed by mixing the compound represented by Formula 3 with a strong acidic aqueous solution such as concentrated hydrochloric acid and stirring under reflux.
  • a strong acidic aqueous solution such as concentrated hydrochloric acid and stirring under reflux.
  • the temperature may be about 100 ° C. and the reaction time may be about 12 hours.
  • Concentrated hydrochloric acid is preferably added in excess (for example, 120 times in molar ratio) with respect to the compound represented by Formula 3. This is because when there is little concentrated hydrochloric acid, hydroxylation of the alkoxy group bonded to phosphorus is difficult to proceed.
  • the ladder-type polysilsesquioxane represented by Formula 1 is obtained by heating in an open system (about 50 to 60 ° C.) and evaporating and removing the solvent.
  • the ladder type polysilsesquioxane represented by Formula 1 by neutralizing the ladder-type polysilsesquioxane represented by Formula 1 with a base, as shown in the following synthesis examples, the hydroxyl group H is substituted with various cations, and the phosphonic acid group A ladder-type polysilsesquioxane represented by the formula 2 that becomes a phosphonate group is obtained. And the ladder type polysilsesquioxane represented by Formula 2 constructs a hexagonal laminate in which polymer main chains are regularly arranged as shown in FIG.
  • a ladder-type polysilsesquioxane represented by formula 1 is treated with KOH, and a synthesis example of a ladder-type polysilsesquioxane represented by formula 2 is shown.
  • the obtained product was dissolved in heavy water, and a 1 H NMR spectrum was measured.
  • IR spectrum and 29 Si NMR spectrum of the product were measured.
  • the 1 H NMR spectrum, IR spectrum, and 29 Si NMR spectrum are shown in FIGS. 3, 4, and 5, respectively.
  • PSGA-PO (OH) 2 was subjected to TGA (Thermogravimetric Analysis) measurement in an oxygen atmosphere and a nitrogen atmosphere. The results are shown in FIGS.
  • PSQ-PO (OH) 2 is thermally stable up to about 200 ° C., and can be used even under temperature conditions exceeding 100 ° C. when used as a solid electrolyte.
  • PSQ-PO (OK) 2 a ladder-type polysilsesquioxane having a phosphonate group represented by Formula 5 in the side chain, in which —OH of the phosphonic acid group was converted to —OK, was obtained.
  • the synthesized PSQ-PO (OK) 2 was subjected to XRD measurement.
  • the measurement results are shown in FIG.
  • a diffraction peak having a ratio of d value of 1: 1 / ⁇ 3: 1/2: 1 / ⁇ 7: 1/3 from the low angle side was observed.
  • This is a typical hexagonal phase diffraction pattern, which shows that a rod-shaped PSQ-PO (OK) 2 has a regularly laminated structure.
  • the diameter of the rod-shaped PSQ-PO (OK) 2 calculated from the XRD pattern was 2 nm or less, and the T 3 peak was mainly observed from the 29 Si NMR spectrum of FIG. It is considered that a network structure composed of Si—O—Si bonds is formed in the space. That is, it was suggested that the synthesized PSQ-PO (OK) 2 has a ladder-like structure in which 8-membered rings composed of Si—O—Si bonds are connected in a one-dimensional direction.
  • PSQ-PO (OK) 2 having a ladder-like structure forms a twisted structure (rod structure) that is considered to be the conformation in which the distance between the side chains is farthest due to the repulsion of the charges between the side chain anions, It is thought that a hexagonal laminate is constructed.
  • FIG. 1 a TEM (Transmission Electron Microscope) photograph of PSQ-PO (OK) 2 is shown in FIG. It can be seen from the TEM photograph that PSQ-PO (OK) 2 is a hexagonal laminate.
  • the ladder type polysilsesquioxane according to the present invention is expected to be used for fuel cell electrolytes and the like because the phosphonic acid groups in the side chain form a continuous proton transfer path and show high proton conductivity.
  • the flame retardancy derived from the phosphonic acid group or phosphonate group is expected to be used as a flame retardant material.

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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)
  • Silicon Polymers (AREA)

Abstract

La présente invention concerne un polysilsesquioxane en échelle représenté par la formule 1 ou la formule 2. Dans la formule 1 et la formule 2, R1 représente un groupe alcylène ayant de 1 à 6 atomes de carbone, et n représente un nombre réel positif. Dans la formule 2, X représente un cation de métal alcalin, un cation de métal alcalino-terreux, un cation d'ammonium ou un cation d'imidazolium.
PCT/JP2017/003756 2016-02-26 2017-02-02 Polysilsesquioxane en échelle ayant un groupe acide phosphonique et groupe phosphonate dans ses chaînes latérales, stratifié de polysilsesquioxane en échelle, procédé de production d'un polysilsesquioxane en échelle, et procédé de production d'un stratifié de polysilsesquioxane WO2017145690A1 (fr)

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JP2018501100A JP6842777B2 (ja) 2016-02-26 2017-02-02 ホスホン酸基およびホスホネート基を側鎖に有するラダー型ポリシルセスキオキサン、ラダー型ポリシルセスキオキサン積層体、及び、ラダー型ポリシルセスキオキサン積層体の製造方法

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108467407A (zh) * 2018-04-09 2018-08-31 山东大学 一种增强二维层状稀土有机膦酸盐质子传导能力的方法
CN109054023A (zh) * 2018-07-23 2018-12-21 德清顾舒家华高分子材料有限公司 一种有机硅磷协同阻燃剂的制备方法
CN109912799A (zh) * 2019-03-29 2019-06-21 太原理工大学 一种含磷有机硅阻燃剂及其制备和应用
WO2020128860A1 (fr) * 2018-12-18 2020-06-25 3M Innovative Properties Company Composition comprenant un phosphate ou un phosphonate de polysiloxane et procédé de fabrication d'un article traité
CN114031779A (zh) * 2021-11-01 2022-02-11 兰州瑞朴科技有限公司 一种含磷梯形聚硅氧烷及其制备方法和作为阻燃协效剂的应用

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US3780127A (en) * 1972-10-02 1973-12-18 Union Carbide Corp Catalytic process for dehydration of alcohols
US3816550A (en) * 1972-10-02 1974-06-11 Union Carbide Corp Catalytic process for hydration of olefins
JP2004022393A (ja) * 2002-06-18 2004-01-22 Tdk Corp プロトン伝導性電解質およびこれを用いた固体電解質膜と燃料電池、ならびにこれらの製造方法

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US3780127A (en) * 1972-10-02 1973-12-18 Union Carbide Corp Catalytic process for dehydration of alcohols
US3816550A (en) * 1972-10-02 1974-06-11 Union Carbide Corp Catalytic process for hydration of olefins
JP2004022393A (ja) * 2002-06-18 2004-01-22 Tdk Corp プロトン伝導性電解質およびこれを用いた固体電解質膜と燃料電池、ならびにこれらの製造方法

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GRACE JONES D. KALAW: "Novel polysilsesquioxane hybrid membranes for proton exchange membrane fuel cell (PEMFC) applications", SEPARATION SCIENCE AND TECHNOLOGY, vol. 43, 2008, pages 3981 - 4008, XP055411996 *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108467407A (zh) * 2018-04-09 2018-08-31 山东大学 一种增强二维层状稀土有机膦酸盐质子传导能力的方法
CN109054023A (zh) * 2018-07-23 2018-12-21 德清顾舒家华高分子材料有限公司 一种有机硅磷协同阻燃剂的制备方法
CN109054023B (zh) * 2018-07-23 2021-02-12 德清顾舒家华高分子材料有限公司 一种有机硅磷协同阻燃剂的制备方法
WO2020128860A1 (fr) * 2018-12-18 2020-06-25 3M Innovative Properties Company Composition comprenant un phosphate ou un phosphonate de polysiloxane et procédé de fabrication d'un article traité
CN109912799A (zh) * 2019-03-29 2019-06-21 太原理工大学 一种含磷有机硅阻燃剂及其制备和应用
CN109912799B (zh) * 2019-03-29 2021-03-26 太原理工大学 一种含磷有机硅阻燃剂及其制备和应用
CN114031779A (zh) * 2021-11-01 2022-02-11 兰州瑞朴科技有限公司 一种含磷梯形聚硅氧烷及其制备方法和作为阻燃协效剂的应用
CN114031779B (zh) * 2021-11-01 2023-02-28 兰州瑞朴科技有限公司 一种含磷梯形聚硅氧烷及其制备方法和作为阻燃协效剂的应用

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