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WO2023013573A1 - Corps de gel de faible densité et procédé de production d'un corps de gel de faible densité - Google Patents

Corps de gel de faible densité et procédé de production d'un corps de gel de faible densité Download PDF

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WO2023013573A1
WO2023013573A1 PCT/JP2022/029457 JP2022029457W WO2023013573A1 WO 2023013573 A1 WO2023013573 A1 WO 2023013573A1 JP 2022029457 W JP2022029457 W JP 2022029457W WO 2023013573 A1 WO2023013573 A1 WO 2023013573A1
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low
density
density gel
gel
organic polymer
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PCT/JP2022/029457
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Japanese (ja)
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俊明 木曽
主祥 金森
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宇部エクシモ株式会社
国立大学法人京都大学
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Publication of WO2023013573A1 publication Critical patent/WO2023013573A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F130/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F130/04—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
    • C08F130/08—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
    • 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
    • C08G77/48—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 in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum

Definitions

  • the present invention relates to a low-density gel body and a method for producing a low-density gel body.
  • low-density gel bodies such as those described above are required to have high strength when compressed and high visible light transmittance.
  • a low-density gel that solves the above problems is a low-density gel that contains polysiloxane chains and organic polymer chains, has a three-dimensional network structure, and has a density of 0.3 g/cm 3 or less.
  • the pore diameter is in the range of 10 nm or more and 40 nm or less
  • the skeleton diameter is in the range of 3 nm or more and 10 nm or less.
  • the low-density gel body may have a strength of 2 MPa or more when compressed by 50%.
  • the pore diameter may be 25 nm or less, and the skeleton diameter may be 7 nm or less.
  • the method for producing the low-density gel comprises an organic polymer preparation step, a hydrolysis step, a dispersion step, and a gel preparation step, wherein the organic polymer preparation step comprises a first alkoxide having a radically polymerizable group is a step of preparing an organic polymer having the organic polymer chain by radically polymerizing the above, and the hydrolysis step includes adding a mixture containing the organic polymer and a second alkoxide polymerizable only by siloxane bonds to It is a step of hydrolyzing the alkoxide by adding an acid, and the dispersing step includes mixing a surfactant made of an amphipathic substance other than alcohol with the mixed solution before the gel preparation step, so that the mixing It is a step of dispersing components in a liquid, and the gel preparation step is a step of preparing a gel by adding a base to the mixed liquid after the hydrolysis step.
  • the organic polymer preparation step comprises a first alkoxide having a radically polymerizable
  • the surfactant may contain a polyoxyethylene/polyoxypropylene block copolymer.
  • the organic polymer preparation step may be performed using a monomer liquid containing the first alkoxide and the second alkoxide.
  • FIG. 2 is a schematic diagram showing an example of the molecular structure of a low-density gel
  • the low-density gel of this embodiment contains polysiloxane chains and organic polymer chains and has a three-dimensional network structure.
  • the low-density gel body has a skeleton containing polysiloxane chains and organic polymer chains, and pores.
  • a polysiloxane chain is composed of two or more siloxane bonds (-Si-O-).
  • a hydrogen atom, a hydroxyl group, a methyl group, or the like may be bonded to the silicon atom of the polysiloxane chain.
  • Organic polymer chains are those obtained from radically polymerizable monomers.
  • the organic polymer chain is, for example, an acrylic chain obtained by polymerizing a methacrylic acid ester or an acrylic acid ester, and has an ester bond in its side chain.
  • the skeleton containing the polysiloxane chain and the organic polymer chain has a structure in which the polysiloxane chain and the organic polymer chain are covalently bonded using the silicon atom of the polysiloxane chain as the bonding point. More specifically, the skeleton containing the polysiloxane chain and the organic polymer chain is such that the polysiloxane chain and the organic polymer chain are bonded at multiple positions on both chains with the silicon atom of the polysiloxane chain as the bonding point. It has a structure that is bonded to each other by covalent bonds.
  • FIG. 1 schematically shows part of the molecular structure of a polymer obtained from methacryloxypropyltrimethoxysilane (MPTMS) and methyltrimethoxysilane (MTMS).
  • MPTMS is a radically polymerizable monomer having a methacrylic group as a radically polymerizable group.
  • the silicon atoms of the polymer produced from MPTMS and the silicon atoms of MTMS serve as bonding points, thereby forming a three-dimensional network structure of a low-density gel.
  • the density of the low-density gel body is within the range of 0.3 g/cm 3 or less. When the density of the low-density gel is 0.3 g/cm 3 or less, breakage of the low-density gel when compressively deformed can be suppressed.
  • the lower limit of the density of the low-density gel is not particularly limited. The lower limit of the density of the low-density gel may be, for example, 0.05 g/cm 3 or more, or 0.16 g/cm 3 or more.
  • the pore size of the low-density gel body is within the range of 10 nm or more and 40 nm or less.
  • the pore diameter of the low-density gel is 10 nm or more, breakage of the low-density gel when compressively deformed can be suppressed.
  • the pore size of the low-density gel is 40 nm or less, the visible light transmittance of the low-density gel can be increased.
  • the pore size of the low-density gel is preferably 25 nm or less.
  • the skeleton diameter of the low-density gel body is within the range of 3 nm or more and 10 nm or less.
  • the skeleton diameter of the low-density gel is 3 nm or more, the strength of the low-density gel can be increased when it is compressed and deformed.
  • the skeleton diameter of the low-density gel is 10 nm or less, the visible light transmittance of the low-density gel can be increased.
  • the skeleton diameter of the low-density gel is preferably 7 nm or less.
  • the strength of the low-density gel when compressed by 50% is preferably 2 MPa or more.
  • the visible light transmittance of the low-density gel is preferably 60% or more, more preferably 70% or more, as measured under conditions of a wavelength of 550 nm and a thickness of 10 mm.
  • the low-density gel Since the low-density gel has a finer pore structure than the mean free path of gas molecules, the contribution of gas heat conduction due to collisions between gas molecules is low, and the skeleton fraction is also low. Contribution is also low. Therefore, the thermal conductivity of the low-density gel body is kept low. Also, the low-density gel body has enhanced visible light transmittance and compression strength. Therefore, the low-density gel body of the present embodiment can be suitably used, for example, as a heat insulating layer of multi-layer glass.
  • a method for producing a low-density gel comprises an organic polymer preparation step, a hydrolysis step, a dispersion step, and a gel preparation step.
  • the organic polymer preparation step is a step of preparing an organic polymer having an organic polymer chain by radically polymerizing the first alkoxide (A1) having a radically polymerizable group.
  • the first alkoxide (A1) for example, methacryloxypropyltrimethoxysilane can be preferably used.
  • a polymerization solution containing the first alkoxide (A1) having a radically polymerizable group and water is used.
  • the content of the first alkoxide (A1) having a radically polymerizable group is preferably, for example, 1% by volume or more and 20% by volume or less.
  • azobisisobutyronitrile (AIBN) can be used as a radical polymerization initiator.
  • the radical polymerization initiator is preferably blended so as to be in the range of, for example, 0.01 mol or more and 0.1 mol or less per 1 mol of the first alkoxide (A1).
  • the hydrolysis step is a step of hydrolyzing the alkoxide by adding an acid to the mixed liquid containing the organic polymer and the second alkoxide (A2).
  • the second alkoxide (A2) unlike the first alkoxide (A1), is an alkoxide polymerizable only by siloxane bonding.
  • Examples of the second alkoxide (A2) include tetraethoxysilane (TEOS), methyltrimethoxysilane (MTMS), dimethyldimethoxysilane (DMDMS), and the like.
  • the second alkoxide (A2) preferably contains MTMS.
  • As the acid used in the hydrolysis step it is preferable to use a strong acid such as nitric acid.
  • the strong acid it is preferable to use a strong acid aqueous solution within a range of 5 mM or more and 10 mM or less, for example.
  • the amount of the strong acid aqueous solution to be added is, for example, about 1 mL per 1 mL of the mixed liquid.
  • the organic polymer preparation step is preferably carried out using a monomer liquid containing the first alkoxide (A1) and the second alkoxide (A2).
  • the content of the first alkoxide (A1) when the total amount of the first alkoxide (A1) and the second alkoxide (A2) is 100% by volume is, for example, 1% by volume or more and 30% by volume. It is preferably within the following range.
  • the content of the organic polymer in the mixed liquid is, for example, preferably within the range of 20% by volume or more and 50% by volume or less, and within the range of 30% by volume or more and 50% by volume or less. It is more preferable to have When the content of the organic polymer in the mixed liquid is 50% by volume or less, the density of the low-density gel body can be further reduced. On the other hand, when the content of the organic polymer in the mixed liquid is 20% by volume or more, it is possible to prevent the pore diameter from becoming excessively small.
  • the dispersing step is a step of dispersing the components in the mixed liquid by mixing a surfactant consisting of an amphipathic substance other than alcohol with the mixed liquid before the gel preparation process.
  • the dispersing step may be performed on the liquid mixture before the hydrolysis step, or may be performed on the liquid mixture after the hydrolysis step. By performing the dispersing step, it becomes easy to keep the skeleton diameter of the low-density gel body small.
  • the surfactant used in the dispersion process is composed of amphipathic substances other than alcohol.
  • surfactants include anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants.
  • nonionic surfactants are preferred.
  • the surfactant more preferably contains a polyoxyethylene/polyoxypropylene block copolymer, which is a type of nonionic surfactant.
  • a gel preparation process is a process of preparing a gel by adding a base to the liquid mixture after a hydrolysis process.
  • the silicon atoms of the organic polymer obtained from the first alkoxide (A1) are further condensed with the polysiloxane chain obtained by condensation of the second alkoxide (A2) to form a low-density gel. can get.
  • the base used in the gel preparation step is preferably a strong base, more preferably quaternary ammonium hydroxide, still more preferably tetramethylammonium hydroxide (TMAOH).
  • TMAOH tetramethylammonium hydroxide
  • the gel obtained in the gel preparation process is preferably aged for about 24 hours, and then the solvent is replaced with, for example, isopropanol.
  • a method for drying the gel is not particularly limited. Drying of the gel is preferably carried out by supercritical drying using a supercritical drying apparatus.
  • the low-density gel contains polysiloxane chains and organic polymer chains and has a three-dimensional network structure.
  • the density of the low-density gel body is within the range of 0.3 g/cm 3 or less.
  • the pore diameter of the low-density gel body is within the range of 10 nm or more and 40 nm or less.
  • the skeleton diameter of the low-density gel is in the range of 3 nm or more and 10 nm or less.
  • the strength during compression can be increased.
  • Visible light transmittance can be increased when the pore diameter of the low-density gel is 40 nm or less.
  • the skeleton diameter of the low-density gel is 3 nm or more, the strength during compression can be increased.
  • Visible light transmittance can be increased when the skeleton diameter of the low-density gel is 10 nm or less. Therefore, it is possible to increase the strength when compressed and to increase the visible light transmittance.
  • the pore diameter of the low-density gel is preferably 25 nm or less, and the skeleton diameter is preferably 7 nm or less.
  • the strength at 50% compression of the low-density gel can be maintained at 2 MPa or more, and the visible light transmittance measured under conditions of a wavelength of 550 nm and a thickness of 10 mm can be increased to 70% or more.
  • a method for producing a low-density gel comprises an organic polymer preparation step, a hydrolysis step, a dispersion step, and a gel preparation step.
  • the organic polymer preparation step is a step of preparing an organic polymer having an organic polymer chain by radically polymerizing a first alkoxide having a radically polymerizable group.
  • the hydrolysis step is a step of hydrolyzing the alkoxide by adding an acid to the mixed solution containing the organic polymer and the second alkoxide polymerizable only by the siloxane bond.
  • the dispersing step is a step of dispersing the components in the mixed liquid by mixing a surfactant composed of an amphipathic substance other than alcohol with the mixed liquid before the gel preparation step.
  • a gel preparation process is a process of preparing a gel by adding a base to the liquid mixture after a hydrolysis process.
  • the surfactant used in the dispersing step preferably contains a polyoxyethylene/polyoxypropylene block copolymer.
  • a low-density gel having the density, pore size, and skeleton diameter within the ranges described above can be more easily produced.
  • the organic polymer preparation step is preferably performed using a monomer liquid containing the first alkoxide (A1) and the second alkoxide (A2).
  • the second alkoxide (A2) becomes a reaction solvent for the radical polymerization reaction of the first alkoxide (A1), so that the organic polymer formed from the first alkoxide (A1) is dispersed and the organic polymer gels. It is thought that the reaction can be suppressed.
  • Example 1 Methacryloxypropyltrimethoxysilane (MPTMS) represented by the following structural formula (1) was prepared as the first alkoxide (A1). Moreover, methyltrimethoxysilane (MTMS) represented by the following structural formula (2) was prepared as the second alkoxide (A2).
  • MPTMS Methacryloxypropyltrimethoxysilane
  • MTMS methyltrimethoxysilane represented by the following structural formula (2) was prepared as the second alkoxide (A2).
  • An organic polymer having an organic polymer chain is represented by the following structural formula (3).
  • the column "Content of first alkoxide” in Table 1 shows the content of the first alkoxide (A1) when the total amount of the first alkoxide (A1) and the second alkoxide (A2) is 100% by volume. is shown.
  • ⁇ Hydrolysis step> 1.0 mL of the above mixed solution was put into a screw tube bottle together with a stirrer tip, and 1.0 mL of 5 mM nitric acid aqueous solution (HNO 3 aq) was added while stirring the mixed solution. At this time, 0.2 mL of HNO 3 aq was added every 2 minutes, and a uniform sol was prepared by stirring for 12 minutes from the start of addition of HNO 3 aq.
  • hydrolyzate of the organic polymer is represented by the following structural formula (4).
  • a hydrolyzate of MTMS is represented by the following structural formula (5).
  • the surfactant (B1) is a nonionic surfactant (manufactured by Sigma-Aldrich, trade name: Pluronic L-64, polyoxypropylene chain molecular weight: 1750, ethylene oxide content: 40% by mass).
  • This nonionic surfactant is a polyoxyethylene/polyoxypropylene block copolymer.
  • the mixed solvent in the wide-mouthed bottle was replaced with IPA, and after the bottle was sealed, the bottle was allowed to stand in an oven at 60° C. for 8 hours for solvent replacement.
  • IPA isopropanol
  • Example 2 As shown in Table 1, in Example 2, a low-density gel was obtained in the same manner as in Example 1, except that the blending amount of the surfactant (B1) in the dispersion step was changed.
  • Example 3 As shown in Table 1, in Example 3, a low-density gel was obtained in the same manner as in Example 1, except that the blending amount of MPTMS in the polymer solution preparation step was changed.
  • Example 4 As shown in Table 1, in Example 4, a low-density gel was obtained in the same manner as in Example 1, except that the amount of polymer solution used in the hydrolysis step was changed.
  • Example 5 As shown in Table 1, in Example 5, a low-density gel was obtained in the same manner as in Example 1 except that the surfactant (B1) used in the dispersion step was changed to surfactant (B2).
  • the surfactant (B2) is a nonionic surfactant (manufactured by Sigma-Aldrich, trade name: Pluronic L-44, polyoxypropylene chain molecular weight: 1200, ethylene oxide content: 40% by mass).
  • This nonionic surfactant is a polyoxyethylene/polyoxypropylene block copolymer.
  • Comparative example 1 As shown in Table 2, in Comparative Example 1, a low-density gel was obtained in the same manner as in Example 1, except that the amount of surfactant (B1) added in the dispersion step was changed.
  • Comparative example 2 As shown in Table 2, in Comparative Example 2, a low-density gel was obtained in the same manner as in Example 1, except that the polymer solution preparation step was omitted and the polymer solution was changed to MTMS.
  • Comparative Example 3 As shown in Table 2, in Comparative Example 3, a low-density gel was obtained in the same manner as in Example 1, except that the amount of polymer solution used in the hydrolysis step was changed.
  • Comparative Example 4 As shown in Table 2, in Comparative Example 4, a low-density gel was obtained in the same manner as in Example 1 except that 0.8 g of isopropanol (IPA) was blended without blending the surfactant (B1) used in the dispersion step. got a body
  • ⁇ Pore diameter> The peak pore size of the low-density gel was measured by nitrogen adsorption analysis. For this measurement, a nitrogen adsorption analyzer (manufactured by Microtrack Bell, trade name: BELSORP-mini) was used. The peak pore size was determined from the adsorption branch using the Barrett-Joyner-Halenda (BJH) method. The peak value of the pore diameter was measured three times and taken as the average value.
  • BJH Barrett-Joyner-Halenda
  • a sample for measurement of the low-density gel in each example was prepared as follows. First, the low-density gel was pulverized to a size of several millimeters to obtain gel powder. Next, about 30 mg of the resulting gel powder was collected in a cell and degassed under vacuum at 80° C. for 24 hours. The results are shown in the "pore size" column in Tables 3 and 4.
  • ⁇ Skeleton diameter> The skeleton diameter of the low-density gel was measured using a field emission transmission electron microscope (FE-TEM, manufactured by JEOL Ltd., trade name: JEM-2200FS). First, three images were obtained by imaging three different positions of the sample for measurement using the FE-TEM. For each image, the skeletal diameter of 3 isolated skeletal points was measured. The skeleton diameter can be obtained from the ratio to the scale bar in the image. An average value of skeletal diameters at a total of 9 points measured from each image was obtained. The results are shown in the "skeleton diameter" column in Tables 3 and 4.
  • the strength and elastic modulus of the low-density gel at 50% compression were measured using a compression/tensile tester (manufactured by Shimadzu Corporation, trade name: EZGraph). A sample for measurement was obtained by cutting a rod-shaped gel with a diameter of 9.5 mm into a length of 10 mm. The sample for this measurement was compressed in the longitudinal direction at a compression speed of 0.5 mm/s until the compression strain reached 50%, and the strength at this time was measured. At this time, the elastic modulus was determined from the strain in the test force range of 10 to 20N. The strength and elastic modulus of the low-density gel at 50% compression were measured for three measurement samples, and the average value was calculated.
  • visible light transmittance The visible light transmittance of the low-density gel was measured using an ultraviolet-visible-near-infrared spectrophotometer (manufactured by JASCO Corporation, trade name: V-670). The thickness of the sample for measurement is 10 mm, and the wavelength of visible light is 550 nm. The results are shown in the "visible light transmittance" column in Tables 3 and 4.
  • the strength at 50% compression of the low-density gel bodies of Examples 1 to 5 was 2 MPa or more. In contrast, the low-density gel bodies of Comparative Examples 1, 3, and 4 could not withstand 50% compressive strain and were destroyed. The strength at 50% compression of the low-density gel body of Comparative Example 2 was less than 2 MPa.
  • the visible light transmittance of the low-density gel bodies of Examples 1 to 5 is 60% or more, and the low-density gel bodies of Examples 1 to 5 have good visible light transmittance. I understand.
  • the visible light transmittance in Examples 1, 3 to 5 is 70% or more, and it can be seen that the low-density gel bodies of Examples 1, 3 to 5 are excellent in visible light transmittance.

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Abstract

La présente invention aborde le problème de la fourniture d'un corps de gel de faible densité qui permet d'avoir une résistance accrue lorsqu'il est comprimé et ayant une transmittance élevée de la lumière visible, et un procédé de production du corps de gel de faible densité. Le corps de gel de faible densité comprend une chaîne polysiloxane et une chaîne polymère organique, et a une structure maillée tridimensionnelle. La densité du corps de gel de faible densité n'est pas supérieure à 0,3 g/cm3. La taille des pores du corps de gel à faible densité se situe dans la plage de 10 à 40 nm. La taille du squelette du corps de gel à faible densité se situe dans la plage de 3 à 10 nm.
PCT/JP2022/029457 2021-08-04 2022-08-01 Corps de gel de faible densité et procédé de production d'un corps de gel de faible densité WO2023013573A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006070264A (ja) * 2004-08-31 2006-03-16 Ind Technol Res Inst 機械強度および反射防止性能を備えた三次元ナノポアフィルムとその製造方法
WO2007010949A1 (fr) * 2005-07-19 2007-01-25 Dynax Corporation Procédé de production d'un aérogel d'alkylsiloxane, aérogel d'alkylsiloxane, appareil permettant de le produire et procédé de fabrication d'un panneau qui en contient
JP2007519780A (ja) * 2004-01-06 2007-07-19 アスペン エアロゲルズ，インコーポレイティド ケイ素結合ポリメタクリレートを含有する有機変性シリカエアロゲル
WO2019039541A1 (fr) * 2017-08-25 2019-02-28 国立大学法人京都大学 Gel de faible densité et son procédé de production
WO2020261901A1 (fr) * 2019-06-28 2020-12-30 Ａｇｃ株式会社 Procédé de production de gel et appareil de production de gel

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007519780A (ja) * 2004-01-06 2007-07-19 アスペン エアロゲルズ，インコーポレイティド ケイ素結合ポリメタクリレートを含有する有機変性シリカエアロゲル
JP2006070264A (ja) * 2004-08-31 2006-03-16 Ind Technol Res Inst 機械強度および反射防止性能を備えた三次元ナノポアフィルムとその製造方法
WO2007010949A1 (fr) * 2005-07-19 2007-01-25 Dynax Corporation Procédé de production d'un aérogel d'alkylsiloxane, aérogel d'alkylsiloxane, appareil permettant de le produire et procédé de fabrication d'un panneau qui en contient
WO2019039541A1 (fr) * 2017-08-25 2019-02-28 国立大学法人京都大学 Gel de faible densité et son procédé de production
WO2020261901A1 (fr) * 2019-06-28 2020-12-30 Ａｇｃ株式会社 Procédé de production de gel et appareil de production de gel

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