JP3722850B2 - Organic-inorganic polymer and method for producing the same - Google Patents

Description

表１にはＨＥＭＡ重合体中に配合した積層構造体の割合とガラス転移温度との関係を示した。表１に示すように積層構造体に０．０５重量％ＨＥＭＡに加え重合した珪素系重合体は、ＨＥＭＡ単独の重合体に比べてガラス転移温度が約４℃高くなる。さらにＨＥＭＡに配合する積層構造体の量が増えるにしたがい有機珪素系重合体のガラス転移温度も上昇し、積層構造体の添加量が５０重量％の場合はＨＥＭＡ単独の重合体に比べてガラス転移温度が１５℃高くなっている。さらに積層構造体の添加割合が７５重量％以上では有機−無機重合体のガラス転移温度を示さなくなる。したがって、無機性の強い有機−無機重合体になっている。
【００３１】
図１は表１のデータを線グラフとして描いたもので、少量の積層構造体の添加でガラス転移温度が急激に上昇することを示している。さらにこの有機−無機重合体のガラス転移温度ｙと積層構造体ｘの含有率との間にはｙ＝９６．７５２＋５．３７５５ｌｏｇｘの関係があることが判明した。
このことは光重合時に積層構造体とＨＥＭＡが反応し結合していることを示す。また０．０５重量％といった極少量の積層構造体の添加でＨＥＭＡ重合体の耐熱性を高めるのに寄与することが判明した。
【００３２】
【発明の効果】
この有機−無機重合体は、有機重合体層を形成する共重合性の有機化合物の種類により色、表面の親水性／疎水性、比誘電率などの特性を付与することができる。
また、有機−無機重合体は、有機化合物の積層構造体との比率を変えることにより有機性、無機性を変化させることができ、有機重合体のフィラーやコート材などの用途に利用できる。
【図面の簡単な説明】
【図１】 この図は、積層構造体の含有％による重合体のガラス転移温度の変化の様子を示す線グラフである。[0001]
[Industrial application fields]
The present invention relates to an organic-inorganic polymer that can be used as a coating material, a filler for a resin, various functional materials, and the like, and a method for producing the same.
[0002]
[Prior art]
In general, the main component materials such as coating materials and molded bodies or inorganic materials as fillers have characteristics such as high hardness and heat resistance, but heating and firing are required to quickly form a dense solid phase from a liquid phase or solution. And
Moreover, these inorganic materials do not have good affinity with organic solvents or organic phases. On the other hand, the organic material has characteristics such as flexibility and rapid film forming property at room temperature, but has a drawback of poor hardness and heat resistance. For this reason, the inorganic-organic hybrid material having the above-mentioned characteristics of the inorganic material and the organic material and limiting the above disadvantages as much as possible and such a material are conventionally used under easy conditions such as a temperature around room temperature. It is desired to develop an effective manufacturing method that can be quickly manufactured below.
[0003]
As a technique for responding to such a request, Japanese Patent Application Laid-Open No. 1-108272 discloses an inorganic-organic hybrid paint. This paint is an abrasion resistant coating material comprising a partial hydrolyzate of epoxy silane, a reaction product of a carbonyl group-containing compound and a non-silane based aliphatic polyamine.
In this case, however, the inorganic structure in the coating film is limited to one part introduced into the organic polymer, and the inorganic structure part may grow or form a film in the coating film due to an organic reaction near room temperature. Therefore, the characteristics of the inorganic material cannot be fully exhibited, and a dramatic improvement cannot be expected as compared with the organic polymer.
[0004]
Next, Japanese Patent Application Laid-Open No. 62-74957 related to the applicant's application discloses that the field of application does not match that of the present invention, but an organized clay (layered clay mineral between layers) that is an inorganic-organic hybrid material. An intercalation compound in which an organic compound is introduced by an ion exchange reaction) is disclosed. Such an organoclay is extremely effective in achieving the object of the invention according to the above application, but is not necessarily sufficient for application in the field to which the present invention is intended.
[0005]
In the above-mentioned organic clay, organic substances are introduced between the layers of the clay mineral by an ion exchange reaction. Therefore, organic substances that are difficult to ionize, such as those containing an epoxy moiety and those having an amino group at the terminal cannot be introduced. Moreover, organic substances can be introduced only up to the ion exchange capacity inherent to clay minerals. Furthermore, since the clay mineral and the organic substance are bonded by an ionic bond, there is a possibility that the ionic bond is broken and the organic substance is liberated by a practical operation or the like.
[0006]
[Problems to be solved by the invention]
The present invention relates to a polymer in which an inorganic part and an organic part are firmly bonded to form a solid and dense solid phase, and a polymer in which the ratio between the inorganic part and the organic part can be easily controlled and a method for producing the same. The purpose is to provide.
[0007]
[Means for Solving the Problems]
The inventors previously filed a novel silicon-based layered polymer having a polymerizable organic side chain on the surface. When the organic side chain of the silicon-based novel layered polymer has the same kind of reactive group such as acryl, epoxy, and vinyl group, a polymer that can be shaped by the polymerization reaction of the reactive group can be obtained. This polymer is superior in heat resistance and hardness to those not containing an inorganic component, and has flexibility that is not found in inorganic materials. However, depending on the application, it may be required to have higher flexibility. The present invention has been completed by finding that necessary physical properties can be imparted by controlling the ratio of the inorganic part to the organic part by bonding organic molecules to the above-mentioned polymer.
[0008]
The first organic-inorganic polymer of the present invention comprises at least one atom selected from silicon and Ge, or an atom obtained by substituting a part of the atom with at least one atom selected from Al, Fe and P. A tetrahedral structure layer composed of a tetrahedral surface structure as a central atom and an octahedral surface having at least one metal selected from Mg, Al, Ni, Co, Cu, Mn, Fe, Li, V, and Zr as a central atom A crystalline layered structure having a layered structure of a phyllosilicate mineral type composed of a layered structure of 2: 1 type or 1: 1 type with an octahedral structure layer constituting the body surface structure, and forming the layered structure An organic polymer layer having an organic substance that is covalently bonded to at least a part of atoms of silicon and Ge that are central atoms of the tetrahedral plane structure, and the organic substance of the organic polymer layer includes: Less of silicon and Ge Also, an organic group having one bonded methacryloxy group as a polymerizable reactive group per one silicon or Ge1 covalently bound to some of the atoms, methyl methacrylate together by a reactive group copolymerizable with the organic group and / Or 2-hydroxyethyl methacrylate.
[0009]
The second method for producing an organic-inorganic polymer of the present invention comprises a compound having silicon having three alkoxy groups and covalently bonded to an organic group having a polymerizable reactive group and three alkoxy groups. And at least one compound selected from compounds having Ge covalently bonded to an organic group having a polymerizable reactive group, and Mg, Al, Ni, Co, Cu, Mn, Fe, Li, V, A mixing step in which an inorganic salt, organic salt or alkoxide of at least one metal selected from Zr and a polar solvent in which one or more of inorganic or organic are mixed are mixed to form a mixed solution;
An alkali is added to the mixed solution to adjust the pH of the mixed solution to be alkaline, or at least one atom selected from silicon and Ge, or a part of the atom is selected from Al and Fe by aging. A tetrahedral structure layer comprising a tetrahedral plane structure having an atom substituted by at least one kind of atom as a central atom, and at least selected from Mg, Al, Ni, Co, Cu, Mn, Fe, Li, V, and Zr A stacked structure forming step in which an octahedral structure layer formed by an octahedral surface structure having one kind of metal as a central atom forms a crystalline stacked structure;
The laminated structure and an organic compound that can be polymerized with a reactive group of an organic group of the laminated structure and can form a polymer alone are mixed to copolymerize the organic group and the organic compound. And a polymer forming step of forming a polymer layer of the organic compound on the laminated structure.
In the second method for producing an organic-inorganic polymer of the present invention, the mixed solution contains a compound having P, and includes at least one kind of atom selected from silicon and Ge that are central atoms of the tetrahedral plane structure. Preference is given to partial replacement by P.
Furthermore, the mixed solution contains at least one compound selected from silicon alkoxide having three alkoxy groups, germanium alkoxide having three alkoxy groups, and germanium, and silicon, Ge, which is a central atom of the tetrahedral plane structure. It is desirable that a part of at least one atom selected from is an atom that is not covalently bonded to the organic group having a polymerizable reactive group.
[0010]
The first aspect of the present invention is a four-plane structure having at least one atom selected from silicon and Ge, or an atom obtained by substituting a part of the atom with at least one atom selected from Al, Fe and P as a central atom. A tetrahedral structure layer formed by the body surface structure and an octahedral surface structure having at least one metal selected from Mg, Al, Ni, Co, Cu, Mn, Fe, Li, V, and Zr as a central atom are formed. The octahedral structure layer forms a crystalline laminated structure having a phyllosilicate mineral type layered structure . This laminated structure has a so-called 2: 1 type structure in which a tetrahedral structure layer is formed on both sides of an octahedral structure layer, and a so-called 1: 1 type in which a tetrahedral structure layer is formed on one side of the octahedral structure layer. There is a thing of structure. When it is desired to include a large amount of organic groups or to improve the bond strength between organic groups, a 2: 1 type structure is more desirable.
[0011]
The 2: 1 type or 1: To form a type structure can be formed by preparing a fraction of the atoms that constitute atoms and octahedral surface structure forming the tetrahedral surface structure.
A part of at least one of silicon and Ge, which are the central atoms of the tetrahedral structure , can be substituted with one or more atoms selected from Al, Fe and P. These Al, Fe, and P can be easily introduced by central atom substitution with silicon or Ge.
[0012]
A part or all of the atoms forming the tetrahedral plane structure are covalently bonded to an organic group having a polymerizable reactive group. The maximum possible introduction amount of the organic group is 1 to 3 per one central atom of the tetrahedron.
This organic group has a polymerizable reactive group and is itself copolymerized with an organic compound that can form a polymer to form an organic-inorganic polymer organic polymer layer . For this reason, the organic property and inorganic property of an organic-inorganic polymer can be changed by adjusting a compounding ratio with the laminated structure of an organic compound.
[0013]
Therefore, when this organic-inorganic polymer is used as, for example, a coating material, the organic property can be enhanced to ensure the characteristics of the organic material such as flexibility and rapid film forming property at room temperature. Affinity with an organic solvent or an organic phase when used as a filler can be ensured.
Further, in this organic-inorganic polymer, the organic group is covalently bonded to the atoms constituting the tetrahedral plane structure, so that both the inorganic part composed of the laminated structure and the organic part composed of the organic polymer layer are used. The bond is robust, and even when mixed with other composition components when used as a coating material or a filler and subjected to various operations in practical use, the bond between the two is not impaired.
[0014]
In addition, since this organic-inorganic polymer has more surface organic groups than conventional clay hybrid composite materials, the physical properties such as heat resistance of organic compound polymers can be achieved by adding a very small amount of laminated structure. Can be improved. In principle, the addition amount of the laminated structure is more than 0% and less than 100%, and a useful polymer molded product can be obtained, but 0.05 to 85% by weight is desirable.
[0015]
Among the organic-inorganic polymers of the present invention, the following can be easily synthesized from inexpensive organoalkoxysilanes used as silane coupling agents, and desirably have highly reactive organic side chains. This has an organic side chain having an amino, epoxy, mercapto, acrylic, methacrylic or vinyl group, and a tetrahedral structure layer having a structure in which oxygen is tetrahedrally coordinated around Si covalently bonded thereto , This is an organosilicon polymer having a crystalline laminated structure in which Mg or the like is a central atom and an octahedral structural layer having a structure in which oxygen is octahedrally coordinated is laminated around the central atom.
[0016]
The manufacturing method of the second invention of the present application includes a mixing step of mixing each component, a laminated structure forming step of adjusting the pH of the mixture to form a crystalline laminated structure of an inorganic part, and an organic compound in the laminated structure. And a polymer forming step for polymerizing.
In the mixing step, a compound having a central atom of tetrahedral surface structure, a compound having a central atom of octahedral surface structure, compounds having a P as needed or silicon alkoxide, germanium alkoxide or a germanium halide compound, and the polarity solvent solution and mixture. And a compound having a central atom of tetrahedral surface structure, for example, organosilicon compounds such as organoalkoxysilane having an alkoxy group and a polymerizable functional group, such as an organic germanium compound such as organo germanium and the like. 8 is a compound having a central atom of tetrahedral surface structure, Mg, Al, Ni, Co , Cu, Mn, Fe, Li, V, inorganic salts of at least one metal atom selected from Zr, organic salts , Alkoxide or the like is used. Among these, Al and Fe become the central atoms of the octahedral plane structure, and some of them become atoms that replace a part of the central atoms (silicon, Ge 2 ) of the tetrahedral plane structure . Is a polar Solvent available water, alcohol, acetone, organic acids, one or more of the mixed polar solution of an inorganic acid. A compound having a tetrahedral surface structure central atom and a compound having an octahedral surface structure central atom are not necessarily completely dissolved, and the object can be achieved even in a certain degree of dispersion.
[0017]
Incidentally, it is possible to add a compound having a P at the time of mixing. P in this compound is an atom that substitutes a part of the central atom (silicon, Ge) of the tetrahedral plane structure . Is in this compound, is phosphoric acid or a derivative thereof, an inorganic salt of P, organic salts, such as P,.
Also during mixing, silicon Arco key Sid, germanium alkoxide or germanium halide compound, can be added. The compounds of these are also then integrated into the laminated structure in the same manner as the compound having a central atom of tetrahedral surface structure. In this application, the alkoxy group is not particularly defined as an organic group. And atom not covalently bound to the organic group having a polymerizable reactive group a part of the silicon or Ge is the central atom of the tetrahedral surface structure by the addition of these compounds. The these compounds can be adjusted ratio of the inorganic portion in the stack structure by combination at a predetermined ratio for a compound having a central atom of tetrahedral surface structure.
[0018]
In the laminated structure forming step, the pH of the prepared mixed solution is made alkaline to promote the growth of the laminated structure. The pH value at which the mixed solution becomes alkaline cannot be uniformly defined due to factors such as the selection of the raw material system. For example, the pH value is about 8 to 10, but the crystal of the laminated structure grows and the gel of the mixed solution is desired. It is sufficient that the pH is not so strong that the organic group to be bonded is damaged at a pH that proceeds at a rate higher than the above-described rate. This laminated structure forming step proceeds sufficiently even at room temperature, but can also be performed under a temperature condition of a certain level that does not damage the organic group. This laminated structure forming step may be completed immediately depending on the selection of raw materials and reaction conditions. In some cases, for example, aging for about 1 to 2 days may be required. The obtained gel-like laminated structure is preferably isolated as a dry powder once the solvent is removed.
[0019]
Mechanisms laminated structure of a laminated structure forming step of the present invention is formed is not necessarily clear, when the pH of the mixed-solution is adjusted to alkaline, preceded the crystal structure of the octahedral surface whose central atom of the metal silicosis elements of Oruganoa Turkey Kishishiran binds to octahedral structural layer by dehydration condensation after hydrolysis of the alkoxy groups to follow to growing, the crystal structure of tetrahedral surface around this silicofluoride-containing grows 4 layered structure of the tetrahedral structure layer and the octahedral structural layer is estimated that will be formed. This is considered to be the same when the central atom is Ge. Thus, tetrahedral structural layer also of silicon or Ge in a state in which an organic group is bonded directly to a portion of the silicon or Ge of tetrahedral surface structures 8 are formed following the tetrahedral structure layer eventually stacked structure of the inorganic is formed I think.
[0020]
In the polymer forming step, an organic compound is mixed with the laminated structure, and an organic group of the laminated structure is copolymerized with the organic compound by an ordinary polymerization method. In this case, the polymerization is allowed to proceed with an initiator or heating as necessary. As the polymerization method, so-called cast polymerization, bulk polymerization, suspension polymerization and the like can be applied. It can also be photopolymerized by irradiation with light. This organic compound needs to be liquid at room temperature or heating or soluble in a solvent in order to be uniformly mixed with the laminated structure as a powder. It can be used as long as these conditions are satisfied. For example, if the organic group is an acrylic group, an acrylic organic compound or an organic compound having a vinyl group is suitable. If the organic group is an epoxy group, an organic molecule having an epoxy group is suitable. Alternatively, an organic compound that forms a polymer whose polymerization terminal is an amino group is suitable. The organic compound here does not necessarily have a low molecular weight, and may be a polymer or an oligomer. By adjusting the amount of the organic compound, the ratio of the organic part to the inorganic part can be controlled.
[0021]
If the organic compound to be added is liquid, it may be added and mixed with the laminated structure as it is. In the case of an organic compound that becomes liquid upon heating, addition and mixing in a heat bath are required. When mixing both in a solvent, it is necessary to use a common solvent in which the laminated structure swells and the organic compound dissolves.
Depending on the organic compound or solvent to be added, the laminated structure may not be instantly dispersed and time may be required. In this case, the organic compound or solvent is dispersed by, for example, forced stirring with a mixer or applying ultrasonic waves. Can be promoted.
[0022]
Depending on the organic compound to be added, a catalyst necessary for polymerization or an initiator is required. In addition to the above organic compounds, components such as pigments and plasticizers can be added.
In the organic-inorganic polymer of the present invention, the organic part and the inorganic part are bonded by a covalent bond, and the organic part on the surface and the inorganic part inside are formed. For this reason, the organic-inorganic polymer of the present invention is different from a conventional composite material such as FPR in which there is no chemical bond between the synthetic resin and the inorganic substance dispersed therein and it is simply mixed. There is also a clay-hybrid composite material that is bonded to a resin containing organic ions on the clay surface. However, the bond between the clay and the organic ion is an ionic bond, so that the bonding force is weak and easily cut. However, in the present invention, the organic part and the inorganic part of the resin layer are connected by a covalent bond to form a stronger bond than other bonds.
[0023]
[Action]
In the organic-inorganic polymer of the present invention, a crystalline inorganic structure portion is formed in a structure in which a tetrahedral surface and an octahedral surface are laminated, and the central atom constituting the tetrahedral surface is polymerized. Organic groups are bonded by a covalent bond, and the organic group is copolymerized with another polymerizable organic compound to form an organic part. Therefore, the organic part and the inorganic part are laminated, and when the organic part is mainly used, the inorganic part can impart high hardness and high heat resistance to the organic part. On the contrary, when the inorganic part is mainly used, it can be used as a filler or a coating material as an inorganic material covered with an organic substance.
[0024]
For this reason, it can be set as a flexible filler and coating material with high affinity with another organic substance. Further, in this method for producing an organic-inorganic polymer, the ratio between the organic part and the inorganic part can be easily controlled during the process. That is, the ratio of the organic part and the inorganic part in the organic-inorganic polymer can be controlled by the amount of the organic compound to be copolymerized and the amount of alkoxysilane added in the mixing step.
[0025]
In this organic-inorganic polymer, the central atom constituting the tetrahedral surface of the inorganic structure and the organic group are covalently bonded, and this organic group is copolymerized with the organic compound constituting the organic layer portion. To form a polymer. For this reason, the inorganic part and the organic part are strongly bonded as compared with the case where the organic part is bonded to the inorganic part by the conventional ionic bond, and the bond between the inorganic part and the organic part during operation and use is reduced. It is possible to prevent them from being cut and peeled off.
[0026]
In the production of the organic-inorganic polymer, a laminated structure can be easily formed by dissolving a predetermined raw material in a polar solution and making the pH of the solution weakly alkaline. An organic compound can be added to and mixed with this laminated structure and produced by a normal polymerization method. And the ratio of an inorganic part and an organic part can be easily performed only by changing the mixing preparation ratio in a mixing process and a polymerization process.
[0027]
【Example】
Hereinafter, the present invention will be described specifically by way of examples.
(Example 1)
(Mixing process)
A sodium hydroxide aqueous solution (solution A) diluted by adding 4000 ml of water to 200 ml of 1N aqueous sodium hydroxide solution was prepared. Separately, 49.6 g of 3-methacryloxypropyltrimethoxysilane (MPTS) and 20.4 g of magnesium chloride hexahydrate were added to 1000 ml of methanol, and the mixture was stirred well to prepare solution B.
(Laminated structure forming process)
Crystalline laminated structure in which liquid A is added and mixed while stirring liquid B, and the mixed liquid is gelled to form a tetrahedral structure centered on silicon atoms and an octahedral surface structure centered on magnesium atoms. A laminated structure having was synthesized. The gelled product was isolated by filtration, washing with water, and vacuum drying. In this laminated structure, an organic group is formed by forming a covalent bond with silicon as a central atom and methacrylic acid of an organic group as an active group through silicon and a propyl group.
(Polymerization process)
To 1 g of the laminated structure product, 2 g of 2-hydroxyethyl methacrylate (HEMA) and 0.03 g of benzoyl isopropyl ether as a photopolymerization initiator were added and mixed with stirring. This mixed solution was applied to an acrylic plate (with a film thickness of about 100 μm and 500 μm (0.5 mm)), and photopolymerized by irradiating ultraviolet rays with a high-pressure ultraviolet lamp for 1 hour. As a result, the organic having the organic polymer layer and HEMA and methacrylic Le residues are copolymerized onto the acrylic plate - coating film of an inorganic polymer is formed. When the surface hardness of this coat film was measured by the pencil method, both were 6H, which was more improved than the surface hardness 6B or less of the HEMA homopolymer. This indicates that the organic-inorganic polymer can improve the surface hardness of the organic polymer. In addition, 0.5 mm is thicker than conventional VV hard coat materials (50 μm or less).
(Example 2)
To 12 g of the laminated structure produced in Example 1, 5 g of methyl methacrylate (MMA) and 0.07 g of benzoin isopropyl ether as a photopolymerization initiator were added and mixed with stirring. This mixed solution was applied to an acrylic plate with a film thickness of about 100 μm and photopolymerized by irradiating with ultraviolet rays with a high-pressure ultraviolet lamp for 1 hour. As a result, the organic having the organic polymer layer and a methacrylic Le residues of MMA and the laminated structure obtained by copolymerization - coating film of an inorganic polymer is formed. When the surface hardness of this coat film was measured by the pencil method, it was 9H, which was markedly improved compared to the surface hardness 6B of the MMA polymer.
[0028]
(Example 3)
The HEMA was prepared such that the laminated structure manufactured in Example 1 had a ratio of 0.05, 0.5, 1, 3, 6.5, 12.5, 25, 50, 75, and 85% by weight with respect to HEMA. A sample mixed with was prepared. 1% by weight of a photopolymerization initiator benzoyl isopropyl ether was added to each sample and mixed. This was poured into a 20 mm × 10 mm × 1 mm mold and irradiated with ultraviolet rays for 1 hour with a high-pressure ultraviolet lamp to effect photopolymerization to obtain a plate-like product. DMA (dynamic viscoelasticity) was measured for each plate-like material obtained above. The glass transition point of each plate-like polymer was determined from the peak of the loss modulus E ″ obtained from the DMA measurement. The results are shown in FIG.
[0029]
[Table 1]

Table 1 shows the relationship between the ratio of the laminated structure blended in the HEMA polymer and the glass transition temperature. As shown in Table 1, the silicon polymer polymerized in addition to 0.05% by weight of HEMA on the laminated structure has a glass transition temperature of about 4 ° C. higher than that of the polymer of HEMA alone. Further risen glass transition temperature of the organic silicofluoride Motokei polymer according increases the amount of the laminated structure be incorporated into the HEMA, if the added amount is 50 wt.% Of the laminate structure as compared to the polymer of HEMA alone glass The transition temperature is increased by 15 ° C. Further, when the addition ratio of the laminated structure is 75% by weight or more, the glass transition temperature of the organic-inorganic polymer is not exhibited. Therefore, it is a highly inorganic organic-inorganic polymer.
[0031]
FIG. 1 shows the data of Table 1 as a line graph, and shows that the glass transition temperature rises sharply with the addition of a small amount of laminated structure. Furthermore, it has been found that there is a relationship of y = 96.752 + 5.3755 logx between the glass transition temperature y of this organic-inorganic polymer and the content of the laminated structure x.
This indicates that the laminated structure and HEMA are reacted and bonded during photopolymerization. It was also found that the addition of a very small amount of laminated structure such as 0.05% by weight contributes to enhancing the heat resistance of the HEMA polymer.
[0032]
【The invention's effect】
This organic-inorganic polymer can impart properties such as color, surface hydrophilicity / hydrophobicity, and dielectric constant depending on the type of copolymerizable organic compound forming the organic polymer layer .
In addition, the organic-inorganic polymer can change the organicity and the inorganicity by changing the ratio of the organic compound to the laminated structure, and can be used for applications such as a filler or a coating material of the organic polymer.
[Brief description of the drawings]
FIG. 1 is a line graph showing a change in glass transition temperature of a polymer depending on the content percentage of a laminated structure.

Claims (4)

A tetrahedron having a tetrahedral structure having a central atom composed of at least one atom selected from silicon and Ge, or an atom obtained by substituting a part of the atom with at least one atom selected from Al, Fe and P 2: a structure layer and an octahedral structure layer constituted by an octahedral structure having at least one metal selected from Mg, Al, Ni, Co, Cu, Mn, Fe, Li, V, and Zr as a central atom; A crystalline laminated structure having a layered structure of a phyllosilicate mineral type comprising a laminate of type 1 or 1: 1, and silicon, Ge, which is a central atom of the tetrahedral plane structure forming the laminated structure An organic polymer layer having an organic substance that is covalently bonded to at least some of the atoms, and
The organic substance of the organic polymer layer includes an organic group having a methacryloxy group as a reactive group capable of being bonded to one or more silicon or Ge by a covalent bond with at least a part of atoms of silicon and Ge; An organic-inorganic polymer comprising methyl methacrylate and / or 2-hydroxyethyl methacrylate bonded to a reactive group of an organic group by copolymerization. A silicon-containing compound covalently bonded to an organic group having three alkoxy groups and having a polymerizable reactive group, and a covalent bond to an organic group having three alkoxy groups and having a polymerizable reactive group At least one compound selected from compounds having Ge,
Inorganic salt, organic salt or alkoxide of at least one metal selected from Mg, Al, Ni, Co, Cu, Mn, Fe, Li, V, Zr;
A polar solvent in which one or more of inorganic or organic are mixed,
Mixing step to make a mixed solution,
An alkali is added to the mixed solution to adjust the pH of the mixed solution to be alkaline, or at least one atom selected from silicon and Ge, or a part of the atom is selected from Al and Fe by aging. A tetrahedral structure layer comprising a tetrahedral plane structure having an atom substituted by at least one kind of atom as a central atom, and at least selected from Mg, Al, Ni, Co, Cu, Mn, Fe, Li, V, and Zr A stacked structure forming step in which an octahedral structure layer formed by an octahedral surface structure having one kind of metal as a central atom forms a crystalline stacked structure;
The laminated structure and an organic compound that can be polymerized with a reactive group of an organic group of the laminated structure and can form a polymer alone are mixed to copolymerize the organic group and the organic compound. A polymer forming step of forming a polymer layer of the organic compound on the laminated structure;
A process for producing an organic-inorganic polymer comprising:   3. The mixed solution contains a compound having P, and at least one atom selected from silicon and Ge, which is a central atom of the tetrahedral structure, is substituted with P. A method for producing an organic-inorganic polymer. The mixed solution contains at least one compound selected from silicon alkoxides having three alkoxy groups and germanium alkoxides having three alkoxy groups, and at least selected from silicon and Ge which are the central atoms of the tetrahedral plane structure. one part of the atoms, the organic claim 2 or 3 further characterized in that the organic groups covalently bonded non atoms having a polymerizable reactive group - method of producing an inorganic polymer.

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