JPWO2017145690A1 - Ladder type polysilsesquioxane having phosphonic acid group and phosphonate group in side chain, ladder type polysilsesquioxane laminate, method for producing ladder type polysilsesquioxane, and ladder type polysilsesquioxane laminate Body manufacturing method - Google Patents
Ladder type polysilsesquioxane having phosphonic acid group and phosphonate group in side chain, ladder type polysilsesquioxane laminate, method for producing ladder type polysilsesquioxane, and ladder type polysilsesquioxane laminate Body manufacturing method Download PDFInfo
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- 229920000734 polysilsesquioxane polymer Polymers 0.000 title claims abstract description 65
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphonic acid group Chemical group P(O)(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 title description 28
- -1 alkali metal cation Chemical class 0.000 claims abstract description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 16
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 8
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims description 10
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 239000002585 base Substances 0.000 claims description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract 1
- 229940006487 lithium cation Drugs 0.000 abstract 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 229910002808 Si–O–Si Inorganic materials 0.000 description 7
- 238000002329 infrared spectrum Methods 0.000 description 7
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 4
- 239000007784 solid electrolyte Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000002411 thermogravimetry Methods 0.000 description 4
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 3
- 239000003063 flame retardant Substances 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- XLYOFNOQVPJJNP-ZSJDYOACSA-N Heavy water Chemical compound [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 239000005518 polymer electrolyte Substances 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- AQRLNPVMDITEJU-UHFFFAOYSA-N triethylsilane Substances CC[SiH](CC)CC AQRLNPVMDITEJU-UHFFFAOYSA-N 0.000 description 2
- 239000013585 weight reducing agent Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910004856 P—O—P Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 125000001918 phosphonic acid ester group Chemical group 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- CASUWPDYGGAUQV-UHFFFAOYSA-M potassium;methanol;hydroxide Chemical compound [OH-].[K+].OC CASUWPDYGGAUQV-UHFFFAOYSA-M 0.000 description 1
- UIDUKLCLJMXFEO-UHFFFAOYSA-N propylsilane Chemical compound CCC[SiH3] UIDUKLCLJMXFEO-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- REWDXIKKFOQRID-UHFFFAOYSA-N tetrabutylsilane Chemical compound CCCC[Si](CCCC)(CCCC)CCCC REWDXIKKFOQRID-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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
- C08G77/22—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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- 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
ラダー型ポリシルセスキオキサンは、式１又は式２で表される。式１及び式２中、Ｒ１は炭素数１〜６のアルキレン基、ｎは正の実数を表し、式２中、Ｘはアルカリ金属陽イオン、アルカリ土類金属陽イオン、アンモニウム陽イオン、又はイミダゾリウム陽イオンを表す。Ladder type polysilsesquioxane is represented by Formula 1 or Formula 2. In Formula 1 and Formula 2, R1 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 an imidazo. Represents a lithium cation.
Description
本発明は、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、ラダー型ポリシルセスキオキサンの製造方法、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に関する。 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.
シルセスキオキサンは、ケイ素原子（Ｓｉ）に対して１つの有機置換基（Ｒ）と平均１．５個の酸素原子（Ｏ）が結合した（ＲＳｉＯ１．５）ｎの構造を持つ化合物の総称である。シルセスキオキサンは耐熱性、耐久性に優れるとともに、有機置換基の存在により有機材料との相溶性に優れることから、有機−無機ハイブリッド材料の分野を中心に近年注目されている。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 silsesquioxane is excellent in heat resistance and durability and has excellent compatibility with organic materials due to the presence of organic substituents.
ラダー型ポリシルセスキオキサンは、一次元的にポリマー主鎖が延びており、側鎖にプロトン伝導性を示す置換基（例えばスルホ基やホスホン酸基）を含むラダー型ポリシルセスキオキサンは、熱安定性に優れ、かつ良好なプロトン伝導性を示すことが期待されている。このため、このようなラダー型ポリシルセスキオキサンは、固体高分子形燃料電池の固体電解質としての利用が検討されている。ラダー型ポリシルセスキオキサンの固体電解質への応用に関し、例えば、特許文献１、２などにプロトン伝導性膜が開示されている。 Ladder-type polysilsesquioxane has a one-dimensionally extended polymer main chain, and a ladder-type polysilsesquioxane containing a substituent (for example, sulfo group or phosphonic acid group) showing proton conductivity 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 of 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.
特許文献１、２のプロトン伝導性膜は、スルホン酸基を有する炭素を主骨格とする有機高分子材料にラダー型も含む種々のシルセスキオキサンが複合化されたものである。このプロトン伝導製膜のプロトン伝導を担う部分は、主に有機高分子材料である。一部、スルホン酸基を含むシルセスキオキサンも用いられているが、その構造については不明瞭である。 The proton conductive membranes of Patent Documents 1 and 2 are obtained by combining various silsesquioxanes including a ladder type with an organic polymer material 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.
本発明は、上記実情に鑑みてなされたものであり、より耐熱性に優れる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、ラダー型ポリシルセスキオキサンの製造方法、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を提供することを目的とする。 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.
本発明の第１の観点に係るラダー型ポリシルセスキオキサンは、
式１又は式２で表される、
（式１及び式２中、Ｒ１は炭素数１〜６のアルキレン基、ｎは正の実数を表し、式２中、Ｘはアルカリ金属陽イオン、アルカリ土類金属陽イオン、アンモニウム陽イオン、又はイミダゾリウム陽イオンを表す。）
ことを特徴とする。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.
また、主鎖がねじれたロッド構造になっていてもよい。 The main chain may have a twisted rod structure.
本発明の第２の観点に係るラダー型ポリシルセスキオキサン積層体は、
式２で表され、主鎖がねじれたロッド構造になっている複数のラダー型ポリシルセスキオキサンがヘキサゴナルに積層されている、
（式２中、Ｘはアルカリ金属陽イオン、アルカリ土類金属陽イオン、アンモニウム陽イオン、又はイミダゾリウム陽イオン、Ｒ１は炭素数１〜６のアルキレン基、ｎは正の実数を表す。）
ことを特徴とする。The ladder-type polysilsesquioxane laminate according to the second aspect of the present invention,
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,
(In Formula 2, X represents an alkali metal cation, an alkaline earth metal cation, an ammonium cation, or an imidazolium cation, R 1 represents an alkylene group having 1 to 6 carbon atoms, and n represents a positive real number.)
It is characterized by that.
本発明の第３の観点に係るラダー型ポリシルセスキオキサンの製造方法は、
式３で表される化合物を加水分解、縮合させて、式１で表されるラダー型ポリシルセスキオキサンを得る、
（式３中、Ｒ１は炭素数１〜６のアルキレン基、Ｒ２は炭素数１〜４のアルキル基を表す。）
（式１中、Ｒ１は炭素数１〜６のアルキレン基、ｎは正の実数を表す。）
ことを特徴とする。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.
(In Formula 3, R 1 represents an alkylene group having 1 to 6 carbon atoms, and R 2 represents an alkyl group having 1 to 4 carbon atoms.)
(In Formula 1, R 1 represents an alkylene group having 1 to 6 carbon atoms, and n represents a positive real number.)
It is characterized by that.
本発明の第４の観点に係るラダー型ポリシルセスキオキサン積層体の製造方法は、
本発明の第３の観点に係るラダー型ポリシルセスキオキサンの製造方法で得られたラダー型ポリシルセスキオキサンを塩基で処理し、
式２で表され、主鎖がねじれたロッド構造になっている複数のラダー型ポリシルセスキオキサンがヘキサゴナルに積層された積層体を得る、
（式２中、Ｘはアルカリ金属陽イオン、アルカリ土類金属陽イオン、アンモニウム陽イオン、又はイミダゾリウム陽イオン、Ｒ１は炭素数１〜６のアルキレン基、ｎは正の実数を表す。）
ことを特徴とする。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 represents an alkali metal cation, an alkaline earth metal cation, an ammonium cation, or an imidazolium cation, R 1 represents an alkylene group having 1 to 6 carbon atoms, and n represents a positive real number.)
It is characterized by that.
本発明では、より耐熱性に優れるホスホン酸基或いは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を提供できる。 In the present invention, it is possible to provide a ladder type polysilsesquioxane having a phosphonic acid group or a phosphonate group having a more excellent heat resistance in the side chain.
（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）
本実施の形態に係るラダー型ポリシルセスキオキサンは、式１又は式２で表される。式１及び式２中、Ｒ１は炭素数１〜６のアルキレン基、ｎは正の実数を表す。また、式２中Ｘはアルカリ陽イオン、アルカリ土類金属陽イオン、アンモニウム陽イオン、又はイミダゾリウム陽イオンを表す。(Ladder type polysilsesquioxane, ladder type polysilsesquioxane laminate)
The ladder-type polysilsesquioxane according to the present embodiment 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, and n represents a positive real number. In Formula 2, X represents an alkali cation, an alkaline earth metal cation, an ammonium cation, or an imidazolium cation.
式１及び式２で表されるラダー型ポリシルセスキオキサンは、ポリマー主鎖のＳｉにそれぞれ側鎖としてホスホン酸基或いはホスホネート基が結合している。即ち、ポリマー主鎖の一つのＳｉに対して一つのホスホン酸基或いはホスホネート基が結合している。この側鎖同士の電荷の反発により、式１及び式２で表されるラダー型ポリシルセスキオキサンは、図１に示すように、ポリマー主鎖が一次元的に延びるとともに、主鎖がねじれたロッド構造となっている。 In the ladder-type polysilsesquioxane represented by Formula 1 and Formula 2, 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.
そして、式１で表されるラダー型ポリシルセスキオキサンでは、側鎖のホスホン酸基が連続的なプロトン伝達経路を形成し、高いプロトン伝導性を発揮する。 In the ladder-type polysilsesquioxane represented by the formula 1, the side chain phosphonic acid groups form a continuous proton transfer path and exhibit high proton conductivity.
また、本実施の形態に係るラダー型ポリシルセスキオキサンは、主鎖のＳｉ−Ｏ−Ｓｉ結合に由来する優れた耐熱性、耐久性、並びに、二重鎖構造の剛直な主鎖に由来する高いガラス転移点を備える。このため、ラダー型ポリシルセスキオキサンは、１００℃を超える高温下（例えば、１５０℃〜２００℃）での固体高分子形燃料電池の固体電解質として好適に利用され得る。 Further, 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. For this reason, ladder-type polysilsesquioxane can be suitably used as a solid electrolyte of a polymer electrolyte fuel cell under a high temperature exceeding 100 ° C. (for example, 150 ° C. to 200 ° C.).
更には、本実施の形態に係るラダー型ポリシルセスキオキサンは、ホスホン酸基或いはホスホネート基に由来する難燃性も備える。このため、本実施の形態に係るラダー型ポリシルセスキオキサンは、難燃性材料としても好適に利用され得る。そして、ラダー型ポリシルセスキオキサンは、水性溶媒や極性の高い有機溶媒に対する相溶性に優れ、可溶である。例えば、ラダー型ポリシルセスキオキサンを溶媒に溶解した溶液を種々の素材にコーティングして製膜することが可能であり、難燃性のコーティング材料としても利用可能である。 Furthermore, 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.
また、式２で表されるホスホネート基を有するラダー型ポリシルセスキオキサンでは、図２に示すように、ロッド構造が規則的に配列してヘキサゴナルに積層された構造が構築される。 Further, in the ladder-type polysilsesquioxane having a phosphonate group represented by Formula 2, as shown in FIG. 2, a structure in which rod structures are regularly arranged and stacked in hexagonal is constructed.
（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の製造方法）
上述した式１で表されるラダー型ポリシルセスキオキサンは、式３で表される化合物の加水分解、重縮合により得られる。(Ladder type polysilsesquioxane, method for producing ladder type polysilsesquioxane laminate)
The ladder-type polysilsesquioxane represented by the above formula 1 is obtained by hydrolysis and polycondensation of the compound represented by the formula 3.
式３中、Ｒ１は炭素数１〜６のアルキレン基である。アルキレン基がこれより長い場合、規則的な立体配位が困難になり、ラダー構造の形成を妨げるおそれがある。更に、得られるラダー型ポリシルセスキオキサンの耐熱性、耐久性が低くなるおそれがある。In Formula 3, R 1 is an alkylene group having 1 to 6 carbon atoms. When 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.
また、Ｒ２は炭素数１〜４のアルキル基である。アルキル鎖が長いと後述の加水分解が生じにくくなるおそれがある。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.
式３で表される化合物として、２−ジエチルホスフェートエチルトリエトキシシラン、２−ジエチルホスフェートブチルトリエチルシラン、２−ジエチルホスフェートヘキシルトリエチルシラン、２−ジメチルホスフェートメチルトリメトキシシラン、２−ジプロピルホスフェートプロピルトリプロピルシラン、２−ジブチルホスフェートブチルトリブチルシランなど種々の化合物が挙げられる。 As the compound represented by Formula 3, 2-diethyl phosphate ethyl triethoxysilane, 2-diethyl phosphate butyl triethyl silane, 2-diethyl phosphate hexyl triethyl silane, 2-dimethyl phosphate methyl trimethoxy silane, 2-dipropyl phosphate propyl tri Various compounds such as propylsilane and 2-dibutylphosphate butyltributylsilane are exemplified.
式３で表される化合物の加水分解、重縮合は、式３で表される化合物を濃塩酸等の強酸性水溶液と混合し、還流攪拌することで行うことができる。また、その温度は１００℃程度、反応時間は１２時間程度とすればよい。なお、濃塩酸は式３で表される化合物に対し、過剰量（例えば、モル比で１２０倍）加えることが好ましい。濃塩酸が少ない場合、リンに結合しているアルコキシ基の水酸基化が進行し難くなるためである。 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 the mixture at 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.
そして、反応させた後、開放系で加熱（５０〜６０℃程度）し、溶媒を蒸発させて除去することで、式１で表されるラダー型ポリシルセスキオキサンが得られる。 And after making it react, the ladder type polysilsesquioxane represented by Formula 1 is obtained by heating (about 50-60 degreeC) by an open system, and evaporating and removing a solvent.
以下に、式３で表される化合物として、２−ジエチルホスフェートエチルトリエトキシシラン（ＤＰＥＴＥＳ）を用いて式１で表されるラダー型ポリシルセスキオキサンの合成例を示す。 Below, the synthesis example of the ladder type polysilsesquioxane represented by Formula 1 using 2-diethyl phosphate ethyltriethoxysilane (DPETES) as a compound represented by Formula 3 is shown.
更に、式１で表されるラダー型ポリシルセスキオキサンを、塩基で中和することで、下記の合成例に示すように、水酸基のＨが種々の陽イオンに置換され、ホスホン酸基がホスホネート基になった式２で表されるラダー型ポリシルセスキオキサンが得られる。そして、式２で表されるラダー型ポリシルセスキオキサンは、図２に示したように、ポリマー主鎖が規則的に配列したヘキサゴナルな積層体を構築する。 Furthermore, 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.
以下に、式１で表されるラダー型ポリシルセスキオキサンをＫＯＨで処理し、式２で表されるラダー型ポリシルセスキオキサンの合成例を示す。 Below, the ladder type polysilsesquioxane represented by Formula 1 is treated with KOH, and a synthesis example of the ladder type polysilsesquioxane represented by Formula 2 is shown.
以下の実施例により、本発明をさらに具体的に説明するが、本発明は実施例によって限定されるものではない。 The following examples further illustrate the present invention, but the present invention is not limited to the examples.
１．０ｍｍｏｌのＤＰＥＴＥＳに１０ｍＬの濃塩酸（１２０ｍｍｏｌ）を加え、１００℃で１２時間還流攪拌した。その後、この溶液を開放系で加熱（約５０〜６０℃、２〜３時間）し、溶媒を蒸発させて除去し、生成物を得た（収率９３％）。 10 mL of concentrated hydrochloric acid (120 mmol) was added to 1.0 mmol of DPETES, and the mixture was refluxed and stirred at 100 ° C. for 12 hours. The solution was then heated in an open system (about 50-60 ° C., 2-3 hours) and the solvent was removed by evaporation to give the product (93% yield).
得られた生成物が各種溶媒に溶解するか否か試みた。その結果を表１に示す。生成物は、水及びジメチルスルホキシド（ＤＭＳＯ）に可溶であった。 It was attempted whether or not the obtained product was dissolved in various solvents. The results are shown in Table 1. The product was soluble in water and dimethyl sulfoxide (DMSO).
得られた生成物を重水に溶解させ、１Ｈ ＮＭＲスペクトルを測定した。また、生成物のＩＲスペクトル、２９Ｓｉ ＮＭＲスペクトルを測定した。１Ｈ ＮＭＲスペクトル、ＩＲスペクトル、２９Ｓｉ ＮＭＲスペクトルをそれぞれ図３、図４、図５に示す。The obtained product was dissolved in heavy water, and a 1 H NMR spectrum was measured. In addition, 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.
図３の１Ｈ ＮＭＲスペクトルを見ると、ホスホン酸エステルに由来するピークは観測されず、エチル基由来の２本のブロードなピークのみが観測された。When the 1 H NMR spectrum of FIG. 3 was observed, no peak derived from the phosphonate ester was observed, and only two broad peaks derived from the ethyl group were observed.
図４のＩＲスペクトルを見ると、９３８ｃｍ−１、１０１０ｃｍ−１、及び、１１８７ｃｍ−１に、ホスホン酸基のＰ−ＯＨ、Ｐ（＝Ｏ）Ｏ−およびＰ＝Ｏに由来する吸収ピークがそれぞれ観測された。Looking at the IR spectrum of Figure 4, 938cm -1, 1010cm -1 and, in 1187cm -1, P-OH phosphonic acid group, P (= O) O - and P = absorption peaks originating from O, respectively Observed.
これらの結果から、ホスホン酸エステル基の加水分解反応が進行したことにより、生成物がホスホン酸基を有することを確認した。 From these results, it was confirmed that the product had a phosphonic acid group by proceeding with the hydrolysis reaction of the phosphonic acid ester group.
また、図４のＩＲスペクトルを見ると、１０４１ｃｍ−１および１１３５ｃｍ−１にＳｉ−Ｏ−Ｓｉ結合由来の吸収ピークが観測された。また、図５の２９Ｓｉ ＮＭＲスペクトルを見ると、３つのＳｉ−Ｏ−Ｓｉ結合を有するＳｉ原子に由来するブロードなＴ３ピークが主に観測された。これらのことから、ＤＰＥＴＥＳの加水分解／縮合反応が進行し、Ｓｉ−Ｏ−Ｓｉ結合が形成されたことが確認できる。Moreover, when the IR spectrum of FIG. 4 was observed, absorption peaks derived from Si—O—Si bonds were observed at 1041 cm −1 and 1135 cm −1 . Further, when the 29 Si NMR spectrum of FIG. 5 was observed, a broad T 3 peak derived from Si atoms having three Si—O—Si bonds was mainly observed. From these facts, it can be confirmed that the hydrolysis / condensation reaction of DPETES has progressed and Si—O—Si bonds have been formed.
これらの結果から、生成物は式４で示される側鎖にホスホン酸基を有するラダー型ポリシルセスキオキサン（以下、ＰＳＱ−ＰＯ（ＯＨ）２）であることを確認した。From these results, it was confirmed that the product was a ladder-type polysilsesquioxane (hereinafter, PSQ-PO (OH) 2 ) having a phosphonic acid group in the side chain represented by Formula 4.
また、ＰＳＱ−ＰＯ（ＯＨ）２について、酸素雰囲気下、及び、窒素雰囲気下にて、ＴＧＡ（Thermogravimetric Analysis）測定を行った。その結果を図６、図７に示す。PSQ-PO (OH) 2 was subjected to TGA (Thermogravimetric Analysis) measurement in an oxygen atmosphere and a nitrogen atmosphere. The results are shown in FIGS.
図６、図７のいずれにおいても、２１０℃付近から若干の重量減少が見られる。これは、以下のように、考えられる。図８のＰＳＱ−ＰＯ（ＯＨ）２の２５０℃での加熱後のＩＲスペクトルを見ると、１２７９ｃｍ−１にＰ−Ｏ−Ｐ＝Ｏ結合のＰ＝Ｏ結合に由来するピークが生じている。即ち、側鎖のホスホン酸基の脱水縮合が起こったため、重量が減少したものである。In both FIG. 6 and FIG. 7, a slight weight reduction is seen from around 210.degree. This is considered as follows. When the IR spectrum after heating at 250 ° C. of PSQ-PO (OH) 2 in FIG. 8 is observed, a peak derived from the P═O bond of the P—O—P═O bond is generated at 1279 cm −1 . That is, the weight is reduced because dehydration condensation of the phosphonic acid group in the side chain occurred.
また、図６、図７のいずれにおいても、４６０℃付近から大幅な重量減少が見られるが、これは主鎖に結合する側鎖のエチレン基が分解したためと考えられる。 Further, in both FIG. 6 and FIG. 7, a significant weight reduction is observed from around 460 ° C., which is considered to be due to the decomposition of the ethylene group in the side chain bonded to the main chain.
以上のことから、ＰＳＱ−ＰＯ（ＯＨ）２は２００℃付近まで熱的に安定であり、固体電解質として利用した場合、１００℃を超える温度条件下での使用にも耐え得ることがわかる。From the above, it can be seen that PSQ-PO (OH) 2 is thermally stable up to around 200 ° C., and can be used even under temperature conditions exceeding 100 ° C. when used as a solid electrolyte.
続いて、ＰＳＱ−ＰＯ（ＯＨ）２のＸＲＤ測定を行った。その測定結果を図９に示す。ＰＳＱ−ＰＯ（ＯＨ）２のスペクトルでは、ブロードな回折ピークが観測され、規則的な積層構造に由来するピークは観測されなかった。Subsequently, XRD measurement of PSQ-PO (OH) 2 was performed. The measurement results are shown in FIG. In the spectrum of PSQ-PO (OH) 2 , a broad diffraction peak was observed, and no peak derived from a regular laminated structure was observed.
続いて、ＰＳＱ−ＰＯ（ＯＨ）２にＫＯＨメタノール溶液（０．２ｍｏｌ／Ｌ）を加えて室温で攪拌（１時間）した。これにより、ホスホン酸基の−ＯＨを−ＯＫに変換した式５に示す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（以下、ＰＳＱ−ＰＯ（ＯＫ）２）を得た。Subsequently, KOH methanol solution (0.2 mol / L) was added to PSQ-PO (OH) 2 and stirred at room temperature (1 hour). As a result, a ladder-type polysilsesquioxane (hereinafter referred to as PSQ-PO (OK) 2 ) 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.
合成したＰＳＱ−ＰＯ（ＯＫ）２について、ＸＲＤ測定を行った。その測定結果を図９に示す。ＰＳＱ−ＰＯ（ＯＫ）２のスペクトルでは、ｄ値の比が低角度側から１：１／√３：１／２：１／√７：１／３である回折ピークが観測された。これは典型的なヘキサゴナル相の回折パターンであり、ロッド状ＰＳＱ−ＰＯ（ＯＫ）２が規則的に積層した構造を形成したことを示している。The synthesized PSQ-PO (OK) 2 was subjected to XRD measurement. The measurement results are shown in FIG. In the spectrum of PSQ-PO (OK) 2 , a diffraction peak having a d value ratio 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, indicating that a rod-shaped PSQ-PO (OK) 2 has a regularly laminated structure.
ＸＲＤパターンから計算されたロッド状ＰＳＱ−ＰＯ（ＯＫ）２の直径は２ｎｍ以下であり、また、図５の２９Ｓｉ ＮＭＲスペクトルよりＴ３ピークが主に観測されたことから、非常に限られた空間の中でＳｉ−Ｏ−Ｓｉ結合からなるネットワーク構造が形成されていると考えられる。すなわち、合成されたＰＳＱ−ＰＯ（ＯＫ）２は、Ｓｉ−Ｏ−Ｓｉ結合から構成される８員環が一次元方向につながったラダー状構造を有することが示唆された。さらに、ラダー状構造を有するＰＳＱ−ＰＯ（ＯＫ）２が側鎖のアニオン同士の電荷の反発により、側鎖間距離が最も離れたコンフォメーションと考えられるねじれた構造（ロッド構造）を形成し、ヘキサゴナル積層体を構築していると考えられる。The diameter of the rod-like 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. Furthermore, PSQ-PO (OK) 2 having a ladder-like structure forms a twisted structure (rod structure) that is considered to be a conformation in which the distance between side chains is farthest due to repulsion of charges between side chain anions, It is thought that a hexagonal laminate is constructed.
また、ＰＳＱ−ＰＯ（ＯＫ）２のＴＥＭ（Transmission Electron Microscope）写真を図１０に示す。ＴＥＭ写真からも、ＰＳＱ−ＰＯ（ＯＫ）２がヘキサゴナル積層体になっていることがわかる。Further, 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.
上述した実施の形態は、本発明を説明するためのものであり、本発明の範囲を限定するものではない。すなわち、本発明の範囲は、実施の形態ではなく、特許請求の範囲によって示される。そして、特許請求の範囲内およびそれと同等の発明の意義の範囲内で施される様々な変形が、本発明の範囲内とみなされる。 The above-described embodiments are for explaining the present invention and do not limit the scope of the present invention. In other words, the scope of the present invention is shown not by the embodiments but by the claims. Various modifications within the scope of the claims and within the scope of the equivalent invention are considered to be within the scope of the present invention.
本出願は、２０１６年２月２６日に出願された日本国特許出願２０１６−３５９０３号に基づく。本明細書中に、日本国特許出願２０１６−３５９０３号の明細書、特許請求の範囲、図面全体を参照として取り込むものとする。 This application is based on Japanese Patent Application No. 2016-35903 filed on February 26, 2016. In the present specification, the specification, claims, and entire drawings of Japanese Patent Application No. 2016-35903 are incorporated as references.
本発明に係るラダー型ポリシルセスキオキサンは、側鎖のホスホン酸基が連続的なプロトン伝達経路を形成し、高いプロトン伝導性を示すことから、燃料電池の電解質等への利用が期待される。また、主鎖のＳｉ−Ｏ−Ｓｉ結合に由来する耐熱性、耐久性に加え、ホスホン酸基或いはホスホネート基由来の難燃性から、難燃性材料としての利用が期待される。 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 In addition to the heat resistance and durability derived from the Si—O—Si bond of the main chain, the use as a flame retardant material is expected from the flame retardancy derived from the phosphonic acid group or phosphonate group.
Claims (5)
（式１及び式２中、Ｒ１は炭素数１〜６のアルキレン基、ｎは正の実数を表し、式２中、Ｘはアルカリ金属陽イオン、アルカリ土類金属陽イオン、アンモニウム陽イオン、又はイミダゾリウム陽イオンを表す。）
ことを特徴とするラダー型ポリシルセスキオキサン。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.)
Ladder type polysilsesquioxane characterized by the above.
ことを特徴とする請求項１に記載のラダー型ポリシルセスキオキサン。The main chain has a twisted rod structure,
The ladder-type polysilsesquioxane according to claim 1.
（式２中、Ｘはアルカリ金属陽イオン、アルカリ土類金属陽イオン、アンモニウム陽イオン、又はイミダゾリウム陽イオン、Ｒ１は炭素数１〜６のアルキレン基、ｎは正の実数を表す。）
ことを特徴とするラダー型ポリシルセスキオキサン積層体。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,
(In Formula 2, X represents an alkali metal cation, an alkaline earth metal cation, an ammonium cation, or an imidazolium cation, R 1 represents an alkylene group having 1 to 6 carbon atoms, and n represents a positive real number.)
A ladder-type polysilsesquioxane laminate characterized by the above.
（式３中、Ｒ１は炭素数１〜６のアルキレン基、Ｒ２は炭素数１〜４のアルキル基を表す。）
（式１中、Ｒ１は炭素数１〜６のアルキレン基、ｎは正の実数を表す。）
ことを特徴とするラダー型ポリシルセスキオキサンの製造方法。The compound represented by Formula 3 is hydrolyzed and condensed to obtain a ladder-type polysilsesquioxane represented by Formula 1.
(In Formula 3, R 1 represents an alkylene group having 1 to 6 carbon atoms, and R 2 represents an alkyl group having 1 to 4 carbon atoms.)
(In Formula 1, R 1 represents an alkylene group having 1 to 6 carbon atoms, and n represents a positive real number.)
A method for producing a ladder-type polysilsesquioxane, characterized in that:
式２で表され、主鎖がねじれたロッド構造になっている複数のラダー型ポリシルセスキオキサンがヘキサゴナルに積層された積層体を得る、
（式２中、Ｘはアルカリ金属陽イオン、アルカリ土類金属陽イオン、アンモニウム陽イオン、又はイミダゾリウム陽イオン、Ｒ１は炭素数１〜６のアルキレン基、ｎは正の実数を表す。）
ことを特徴とするラダー型ポリシルセスキオキサン積層体の製造方法。The ladder-type polysilsesquioxane obtained by the method for producing a ladder-type polysilsesquioxane according to claim 4 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 represents an alkali metal cation, an alkaline earth metal cation, an ammonium cation, or an imidazolium cation, R 1 represents an alkylene group having 1 to 6 carbon atoms, and n represents a positive real number.)
A method for producing a ladder-type polysilsesquioxane laminate, wherein:
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016035903 | 2016-02-26 | ||
| JP2016035903 | 2016-02-26 | ||
| PCT/JP2017/003756 WO2017145690A1 (en) | 2016-02-26 | 2017-02-02 | Ladder-type polysilsesquioxane having phosphonic acid group and phosphonate group in side chains thereof, ladder-type polysilsesquioxane laminate, method for producing ladder-type polysilsesquioxane, and method for producing ladder-type polysilsesquioxane laminate |
Publications (2)
| Publication Number | Publication Date |
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| JPWO2017145690A1 true JPWO2017145690A1 (en) | 2018-12-13 |
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