TWI491647B - Compounds with benzoxazine-bridged silsesquioxanes structure - Google Patents

Description

Bridged oxirane structure compound having oxonitrobenzo ring unit

This invention relates to a compound of a bridged oxane structure, and more particularly to a self-assembling bridged oxymethane structure having an oxonitrobenzoxazine unit.

The development of modern wafer technology continues to drive demand and research for new ultra-low dielectric constant ( k < 2.0) materials. The porous material can hold some air ( k = 1.01) in its solid networks, such that the porous material has a k value below 2.0. However, the introduction of porous materials in the application of dielectric materials will result in the sacrifice of mechanical properties of the dielectric materials and pose new challenges for subsequent wafer fabrication. Thus, the possibility of preparing organic-inorganic materials by sol-gel has been studied. Organic-inorganic hybrid materials can improve the mechanical properties of dielectric materials by enhancing film network connectivity. It is preferred in various studies of the art to use carbon-bridged alkoxysilane compounds as reaction precursors. The introduction of a dielectric material formed by an organic group in a sol-gel method can reduce the friability of the dielectric material. Special porogens can help control the size and distribution of the pores. The interconnected network structure and control of the closed nanopores will help maintain the mechanical properties of the dielectric material and reduce the k value of the dielectric material.

Bridged polysilsesquioxanes (bridged polysilsesquioxanes) can be obtained by using a carbon-bridged bis(alkoxysilane) compound as a synthetic reaction precursor. The chemical structure of the carbon bridge group plays an important role in the structure, morphology, and mechanical properties of the formed gel product. Using silsesquioxane as a reaction precursor and self-assembly, periodic mesoporous organic mesoporous can be prepared for the integration of bridging organic groups into channel walls. Organolica; PMO) material. The dielectric constant of hybrid films will gradually decrease as the organic portion of the structure increases. A dielectric material made of pure bridge polysilsesquioxanes (neat bridged polysilsesquioxanes) can exhibit a dielectric constant of about 2.9. During the course of the reaction, the heat treatment at about 400 °C causes bridging-to-thermal transformation of the bridge polysilsesquioxanes, resulting in a reduction in the k value of the resulting dielectric material to about 1.8. By more on the control of structural phases, there will be an opportunity to further improve the dielectric constant of the materials produced.

There are reports in the prior art on the structural control of bridged polysesquioxanes. The aforementioned structural control can control the shape of the formed material to different sizes and shapes. It is worth noting that the dielectric constant of a composite material depends not only on the composition of the inorganic filler, but also on the orientation of the filler. When the low-k (k LOW-) vertical phase filler in the layer structure when the applied electric field, such that the dielectric constant of the composite material closer to the low-k dielectric filler in the range of many of filler. Therefore, the phase of the low-k component in the organic/inorganic composite material can be a research method for efficiently preparing low- k materials. Therefore, self-assembled bridge polysesquioxanes having a layered structure perpendicular to the applied electric field are a notable way to prepare low- k materials.

In summary, in order to improve the shortcomings of the dielectric materials of the prior art, how to provide a dielectric material having a low dielectric constant and high mechanical strength and being clean and simple in the preparation process has been a research direction with high industrial development value.

In view of the inconvenience and absence of the above background, in order to meet the needs of certain interests in the industry, the present invention provides a bridged oxirane structure compound having an oxonitrobenzo ring unit, having oxonitrogen in accordance with the present invention. The compound of the bridged siloxane structure of the benzo ring unit has not only a low dielectric constant but also high mechanical strength.

It is an object of the present invention to provide a compound of a bridged oxirane structure having an oxonitrobenzo ring unit. By virtue of the teachings of the present invention, a compound of a bridged oxane structure having an oxonitrobenzo ring unit can be prepared via a clean and simple self-assembly reaction. For the industry, the effect of saving production costs can be achieved.

Another object of the present invention is to provide a compound of a bridged oxirane structure having an oxonitrobenzo ring unit. By increasing the porosity, the dielectric constant of the compound can be effectively reduced.

It is still another object of the present invention to provide a bridged oxirane structure compound having an oxonitrobenzo ring unit. The dielectric constant of the compound is effectively reduced by controlling the phase and ratio of the organic groups within the compound.

It is still another object of the present invention to provide a bridged oxirane structure compound having an oxonitrobenzo ring unit. The mechanical strength of the compound is effectively enhanced by forming a cross-linked network structure in the compound.

It is still another object of the present invention to provide a bridged oxirane structure compound having an oxonitrobenzo ring unit. By applying intermolecular and intramolecular hydrogen bonds, a self-assembly effect can be effectively induced and a cross-linked network structure can be formed, thereby effectively maintaining the flaky shape of the compound of the bridged oxirane structure having an oxo-nitrobenzobenzene unit. Architecture.

It is still another object of the present invention to provide a bridged oxirane structure compound having an oxonitrobenzo ring unit. By adding a suitable electroluminescent group to the organic bridging group, a compound having a bridged oxoxane structure having an oxonitrobenzo ring unit can be made to have electroluminescence characteristics.

In accordance with the above objects, the present invention discloses a bridged oxirane structure compound having an oxonitrobenzo ring unit, the bridged oxirane structure compound having an oxonitrobenzo ring unit It has a sheet mesh structure. According to the design of the present invention, the compound of the bridged oxime structure having an oxonitrobenzo ring unit can exhibit characteristics such as low dielectric constant, high mechanical strength, and electroluminescence.

In accordance with the above objects, the present invention discloses a bridged oxirane structure compound having an oxonitrobenzo ring unit. In order to thoroughly understand the present invention, detailed steps and compositions thereof will be set forth in the following description. Obviously, the practice of the present invention is not limited to the specific details in the field that are common to those skilled in the art. On the other hand, well-known components or steps are not described in detail to avoid unnecessarily limiting the invention. The preferred embodiments of the present invention will be described in detail below, but the present invention may be widely practiced in other embodiments, and the scope of the present invention is not limited by the following detailed description. Prevail.

According to one embodiment of the present specification, a compound of a bridged oxirane structure having an oxonitrobenzo ring unit is disclosed. The general structural formula of the above-mentioned bridged oxirane structure compound having an oxonitrobenzo ring unit is as follows:

Wherein X may be one selected from the group consisting of: a chemical bond, -O-, -CH ₂ -, , , , , R ¹ and R ³ may be the same or different, and R ¹ and R ³ may be an alkyl group selected from C ₁ to C ₈ , respectively, or an aryl group of C ₆ to C ₁₅ ; The m system can be an integer greater than zero.

In a preferred embodiment according to this embodiment, when m is equal to 1, the structural formula of the above-mentioned bridged oxirane structure compound having an oxonitrobenzo ring unit is as follows:

Wherein R ² and R ⁴ may be the same or different, and R ² and R ⁴ may be an alkyl group selected from C ¹ to C ⁸ , respectively.

In another preferred embodiment according to this embodiment, the structural formula of the above-mentioned bridged oxirane structure compound having an oxonitrobenzo ring unit is as follows:

Wherein m in the above structural formula may be an integer greater than zero.

In still another preferred embodiment according to this embodiment, the structural formula of the above-mentioned bridged oxirane structure compound having an oxonitrobenzo ring unit is as follows:

According to another embodiment of the present specification, there is disclosed a compound of a bridged oxirane structure having an oxonitrobenzo ring unit, the above-mentioned compound having a bridged oxoxane structure having an oxonitrobenzo ring unit The general structure is as follows:

Wherein X may be one selected from the group consisting of: a chemical bond, -O-, -CH ₂ -, , , , , R ¹ and R ³ may be the same or different, and R ¹ and R ³ may be an alkyl group selected from C ₁ to C ₈ , respectively, or an aryl group of C ₆ to C ₁₅ ; The m and n systems may each be selected from an integer greater than zero.

In a preferred embodiment according to this embodiment, the structural formula of the above-mentioned bridged oxirane structure compound having an oxonitrobenzo ring unit is as follows:

Hereinafter, the structures, synthetic forms, and physical properties of a plurality of compounds of a bridged oxirane structure having an oxonitrobenzo ring unit according to the present specification will be described. However, the scope of the present specification should be followed by The scope of patents shall prevail and shall not be limited to the following examples.

Synthetic method:

In the synthetic manners described in the following examples, the bisphenol-A (BPA) used was purchased from Showa Chemicals. Formaldehyde (37% in water) and 3-aminopropyltriethoxydecane were purchased from Aldrich Chemical Company. Tetrahydrofuran (THF) was purchased from Tedia Chemical Company and dried by molecular sieves prior to use.

First embodiment:

A method of preparing a oxoxane compound (Bz-BES) having an oxoazobenzo ring structure:

Referring to Reaction Scheme 1 , BPA (10 g, 43.8 mmol), formaldehyde (5.26 g, 175 mmol), and 3-aminopropyltriethoxydecane (19.4 g, 87.6 mmol) were mixed in chloroform (100 mL) In this, the mixed solution was allowed to react at 85 ° C for 24 hours. The results after the foregoing reaction were carried out without further purification. Direct concentration gave the expected product Bz-BES (yield: 75%). Elemental analysis calcd (%) for C ₃₇ H ₆₂ N ₂ O ₈ Si ₂ : C 61.83, H 9.63, N 3.89; found C 61.70, H 8.67, N 3.81.

Second embodiment:

Hydrolysis and condensation of a oxoxane compound (Bz-BES) having an oxoazobenzo ring structure:

Bz-BES was dissolved in tetrahydrofuran (THF) to prepare a 0.4 M solution in THF. The aforementioned Bz-BES THF solution was mixed with a 1.08 N aqueous NaOH solution to carry out the reaction as in Reaction Scheme 2. In the mixing ratio of the foregoing reaction, the water/Bz-BES has a molar ratio of about 6.2. The above mixed solution was subjected to a reaction at 30 ° C for 48 hours to obtain a gel product. The gel product was washed with THF and distilled water and then dried under vacuum at room temperature to obtain a dry gel (xerogel) product of Bz-BES (XG-Bz-BES).

Reaction formula 2

Third embodiment:

Preparation of a thermally cured polysesquioxane having a oxobenzobenzo ring structure (PBz-BPSSQ):

A 0.4 M solution of Bz-BES in tetrahydrofuran (THF) was mixed with a 1.08 N aqueous NaOH solution to carry out a reaction. After reacting at 30 ° C for 2 hours, the mixed solution was poured into a stainless mold. Subsequently, the foregoing mixed solution was subjected to heat treatment at 90 ° C for 1 hour, heat treatment at 150 ° C for 1 hour, heat treatment at 180 ° C for 3 hours, and heat treatment at 220 ° C for 2 hours, as shown in Reference Reaction Formula 3 . Thereafter , a poly sesquioxane (PBz-BPSSQ) product having an oxonitrobenzo ring structure after heat treatment is obtained.

Poly-oxo-N-substituted benzo ring / Poly Silicon sesqui siloxane (polybenzoxazine / PSSQ) of Nanocomposites (Nanocomposite) may be obtained via the above experiment the same operation flow. The difference was that the reaction initiators used were Bz-BES and BPA-FBz (50/50% by weight). The resulting heat treated product can be coded as PBz-BPSSQ/PBz.

Converted by the force FU leaf infrared (FTIR) spectroscopic analysis, refer to FIGS. A first, Bz-BES respectively 1231cm ^-1, 1021cm ^-1 [benzo ring stretching (stretching), oxo-substituted nitrogen COC], 1498cm ^-1 (trisubstituted benzene ring group) and 1100 cm ^-1 (Si-OC) exhibit characteristic absorption peaks. In the spectral analysis of ¹ H NMR spectroscopy ( ¹ H NMR), referring to the first b-graph, Bz-BES at δ = 4.83 ppm (OC H ₂ -N) and δ = 3.93 ppm (Ph-C H ₂ -O) The position of the ) exhibits characteristic resonance peaks. At the same time, in the spectral analysis of ¹ H NMR, it was also found that other characteristic resonance peaks of Bz-BES appeared at δ=0.67ppm (Si-C H ₂ -), δ=1.22ppm (Si-OCH ₂ C H ₃ ). , δ = 1.59 ppm (-C H ₃ in bisphenol A), δ = 1.68 ppm (Si-CH ₂ C H ₂ -), δ = 2.74 ppm (NC H ₂ -), δ = 3.82 ppm (Si- OC H ₂ CH ₃ ), and δ = 6.66 to 6.93 ppm [aromatic protons]. In addition to the aforementioned characteristic formants, the ¹ H NMR spectrum of Bz-BES did not show any formants at a chemical shift of about 3.0 to 3.5 ppm. That is, it can be seen from the spectral analysis that there is no ring-opened oxonitrobenzobenzo group present in the reaction product. Further, in the ²⁹ Si nuclear magnetic resonance spectrum ( ²⁹ Si NMR), referring to the first c-picture, Bz-BES showed only a resonance peak at a position of about δ = -51.3 ppm. Compared with the characteristic resonance peak exhibited by APTES at δ=-46.3 ppm, the resonance peak of the aforementioned Bz-BES apparently showed displacement. This also indicates that the chemical structure of Bz-BES and the reactant APTES are not the same. The spectral results of a single peak can also be used as a supporting result for high purity Bz-BES. Hydrolysis of Si-OEt did not occur during the preparation of Bz-BES. The molecular weight measurement of Bz-BES was 717.8 g mol ^-1 , which was in accordance with the calculated molecular weight of 718 g mol ^-1 (C ₃₇ H ₆₂ N ₂ O ₈ Si ₂ ).

In the reaction of hydrolysis and condensation of Bz-BES, a dry gel (xerogel) obtainable by sol-gel using Bz-BES as a starting material. The type and concentration of the catalyst has a great influence on the gel time. According to the understanding of the sol-gel method by the skilled artisan, in the reaction of the hydrolysis and condensation, an acid (HCl) or a basic (NaOH) catalyst can be selected for the reaction. When a 0.2 N aqueous NaOH solution was used to catalyze the foregoing reaction, the gel time required was about 96 hours. On the other hand, when a 0.2 N aqueous HCl solution was used to catalyze the above reaction, gelation did not occur even after one month. This result is similar to that reported in previous literatures on alkyl- and aryl-bridged polysilsesquioxanes, but with bisimide-bridge polypothala The related literature on bisimide-bridged polysilsesquioxane is reported to be the opposite. When the concentration of the NaOH catalyst is raised to 0.4 N, the gel time in the sol-gel system of Bz-BES can be shortened to about 3 hours. The gel product obtained after the reaction was washed with THF and distilled water, and vacuum-dried at room temperature to obtain a dry gel of Bz-BES (XG-Bz-BES). FTIR spectroscopic analysis of the, XG-Bz-BES broad absorption peak appears Si-O-Si of (broad absorption peak) at the position of about 1000-1100cm ^-1, and CH absorption intensity peak at a position of about 2900cm ^-1 Attenuation can be used to illustrate the sol-gel reaction of Bz-BES (as shown in Figure a).

Further heat treatment of XG-Bz-BES will form a cured polybenzoxazine-bridged polysilsesquioxanes (PBz-BPSSQ). During the aforementioned heat treatment, the oxo-nitrobenzo ring group will undergo ring-opening polymerization to form a cross-linked polybenzoxazine (cross-linked polybenzoxazine). Networks). Furthermore, condensation may occur between residual silanol groups, and the condensation degree with oxoazobenzene polysesquioxane is increased.

In the solid-state ²⁹ Si NMR spectrum, as shown in the second figure, both XG-Bz-BES and PBz-BPSSQ showed a major resonance peak at a position of about δ=-67.0 ppm, and the position of this resonance peak was completely concentrated.矽(T ₃ ) matches. The resonance peaks corresponding to the T ₂ and T ₁ structures also appear at positions of about δ = -58.5 ppm and δ = -54.2 ppm, respectively. Relative to PBz-BPSSQ, the aforementioned two resonance peaks of T ₂ and T ₁ appear to be relatively weaker, which also indicates that a condensation reaction of a sterol group occurs during thermal curing. The polymerization of the aforementioned oxonitrobenzo ring group also leads to the formation of a tetrasubstituted benzene ring group. The aforementioned tetrasubstituted benzene ring group has an absorption peak at a position of about 1485 cm ^-1 in the spectral analysis of FTIR. As a comparison, the trisubstituted benzene ring group of Bz-BES has an absorption peak at a position of about 1498 cm ^-1 in the spectral analysis of FTIR (as shown in the first a diagram).

The reaction state of the oxonitrobenzo ring group of Bz-BES can also be traced by DSC. Referring to the third figure, in the DSC analysis, Bz-BES exhibits an exothermic peak. The aforementioned exothermic effect is related to the thermo-induced ring-opening reaction of the oxoazobenzo ring group of Bz-BES. The center of the exothermic peak is at about 253 ° C, and the reaction enthalpy is about 170 J g ^-1 . The above reaction temperatures and enthalpy values are similar to those reported for other oxonitrobenzo compounds. XG-Bz-BES also has an exothermic peak due to the polymerization of the oxonitrobenzo ring. Compared to Bz-BES, the exothermic peak of XG-Bz-BES shifts to a higher temperature and has a lower reaction enthalpy. The difference between the aforementioned temperature shift and the reaction enthalpy can be attributed to the steric hindrance caused by the polysilsesquioxane network structure in XG-Bz-BES. After the heat treatment, the formed product PBz-BPSSQ did not exhibit any exothermic peak in the DSC thermogram. Therefore, during the heat treatment, the oxo-nitrobenzo ring group of XG-Bz-BES undergoes polymerization, and the degree of conversion of this reaction is quite high. At the same time, it is worth noting that PBz-BPSSQ has a glass transition temperature of about 295 ° C. This glass transition temperature also shows the formation of a highly crosslinked polyoxonitrobenzocyclonet network.

The fourth graph is a nitrogen adsorption/desorption isotherms of XG-Bz-BES and PBz-BPSSQ, in which gas adsorption/desorption is recorded. The surface area of XG-Bz-BES is 144.0 m ² g ^-1 . XG-Bz-BES is a porous material and has an average pore diameter of about 3.7 nm. The rigid oxo-nitrobenzo ring bridge structure helps prevent pore collapse and maintains the porous structure of XG-Bz-BES during gel reaction and drying. The polymerization of the oxonitrobenzo ring group forms a large amount of crosslinked structure in PBz-BPSSQ to induce pore collapse in the organic region of PBz-BPSSQ. Therefore, the surface area of PBz-BPSSQ was significantly reduced to 4.0 m ² g ^-1 . The low surface area of PBz-BPSSQ also indicates that the highly crosslinked polyoxonitrobenzo ring region is relatively dense.

The dielectric constant of PBz-BPSSQ at 1 megahertz (MHz) is about 1.57. PBz-BPSSQ clearly exhibits a lower dielectric constant than the dielectric constant of other bridged polysesquioxanes. As described above, PBz-BPSSQ has a low porosity in the range of the organopolyoxonitrobenzo ring, and this lower porosity may not contribute to a decrease in dielectric constant. It is well known to those skilled in the art that the dielectric constant of hybrid polysilsesquioxanes will decrease with the organic content. Therefore, the decrease in the dielectric constant of PBz-BPSSQ may be due to the structure of polysesquioxanes. However, the dielectric constant of PBz-BPSSQ is lower than that reported by the bridge polypotpenal oxide in the previous literature (~1.8) (1 MHz).

In addition, Bz-BES can be an effective crosslinking additive for the preparation of low k crosslinked resins. Polyoxobenzobenzo/polysesquioxanes (PBz-BPSSQ/PBz) nanoparticles can be prepared by mixing Bz-BES and BPA-FBZ (50/50% by weight) as reaction precursors. Composite material.

As shown in the fifth figure, the PBz-BPSSQ/PBz can also observe the self-assembled layered structure by transmission electron microscopy (TEM). The dark domain will decrease as the BPSSQ content in the corresponding PBz-BPSSQ/PBz decreases. Its knot As a result, the dielectric constant of PBz-BPSSQ/PBz is about 1.73. This value is higher than the dielectric constant of PBz/BPSSQ and relatively lower than the dielectric constant of the thermosetting resin.

Mechanical strength is also an important property for ultra-low k dielectric materials. For porous materials, increasing the porosity of the porous dielectric material will significantly reduce the dielectric constant of the porous material. However, high porosity will also greatly reduce the modulus of the dielectric material. It is worth noting that the Young's modulus of PBz-BPSSQ is about 3.1 GPa. Therefore, PBz-BPSSQ has superior mechanical strength compared to the methyl sesquiterpene oxide (MSSQ) film having a k value of about 1.85 and a Young's modulus of about 1.1 GPa in the prior art.

In summary, benzoxazine is a heterocyclic group that readily forms powerful intermolecular hydrogen bonds. Hydrogen bonding facilitates the formation of self-assembled bridge polysesquioxanes. Further, the oxonitrobenzo ring group can undergo ring-opening addition polymerization under heating reaction conditions. The polymerization of the bridging groups will help to control the arrangement of the organic fragments in the bridge polysesquioxane.

According to the design of the present specification, a benzoxazine-bridged bis(triethoxysilane) compound is synthesized first, and then passed through a sol-gel method (sol- Cross-linked polybenzoxazine-bridged polysilsesquioxane can be obtained by gel and thermal treatment. The phase of the polysesquioxane region in the layered structure can be found simultaneously when observing the oxo-nitrobenzo-bridged polyhaxaluminoxane material. Arrange mode.

In summary, the present invention discloses a bridged oxirane structure compound having an oxonitrobenzo ring unit. According to the disclosure of the present invention, the above-mentioned compound having a bridged oxoxane structure having an oxonitrobenzo ring unit has a sheet network structure. More preferably, the above-mentioned bridged oxirane structure compound having an oxonitrobenzo ring unit exhibits a low dielectric constant and high mechanical strength.

Obviously, many modifications and differences may be made to the invention in light of the above description. It is therefore to be understood that within the scope of the appended claims, the invention may be The above are only the preferred embodiments of the present invention, and are not intended to limit the scope of the claims of the present invention; all other equivalent changes or modifications which are not departing from the spirit of the present invention should be included in the following claims. Within the scope.

Figure 1a is a Bz-BESFTIR spectrum of a compound of a bridged oxirane structure having an oxonitrobenzo ring unit according to the present invention.

Figure 1b is a Bz-BES ¹ H NMR spectrum of a compound of a bridged oxoxane structure having an oxonitrobenzo ring unit according to the present invention.

The first c-graph is a Bz-BES ²⁹ Si NMR spectrum of a compound of a bridged oxirane structure having an oxonitrobenzo ring unit according to the present invention.

The second panel is a solid-state ²⁹ Si NMR spectrum of the compound XG-Bz-BES and PBz-BPSSQ of a bridged oxime structure having an oxoazobenzo ring unit according to the present invention.

The third figure is a bridge having an oxonitrobenzobenzene unit according to the present invention. The DSC thermogram of the compounds Bz-BES, XG-Bz-BES, and PBz-BPSSQ of the decane structure.

The fourth graph is a nitrogen adsorption/desorption isotherm diagram of the compound XG-Bz-BES and PBz-BPSSQ of a bridged oxirane structure having an oxoazobenzo ring unit according to the present invention.

Figure 5 is a TEM photomicrograph (x 50K) of the compound PBz-BPSSQ and PBz-BPSSQ/PBz of a bridged oxirane structure having an oxoazobenzo ring unit according to the present invention.

Claims (6)

A compound of a bridged oxoxane structure having an oxonitrobenzoxazine unit having a general structural formula of a bridged oxirane structure having an oxoazobenzo ring unit is as follows: Wherein X may be selected from a chemical bond, -O-, -CH ₂ -, R ¹ and R ³ may be the same or different, and R ¹ and R ³ are each selected from a C ₁ to C ₈ alkyl group, or a C ₆ to C ₁₅ aryl group; Is an integer, but at least 1. A compound of a bridged fluorinated alkane structure having an oxoazobenzo ring unit as described in claim 1, wherein the above-mentioned compound having a bridged oxoxane structure having an oxonitrobenzo ring unit The structure is as follows: Wherein R ² and R ⁴ may be the same or different, and R ² and R ⁴ may be an alkyl group selected from C ₁ to C ₈ , respectively. A compound of a bridged fluorinated alkane structure having an oxoazobenzo ring unit as described in claim 1, wherein the above-mentioned compound having a bridged oxoxane structure having an oxonitrobenzo ring unit The structure is as follows: Where m is an integer but at least 1. A compound of a bridged fluorinated alkane structure having an oxoazobenzo ring unit as described in claim 1, wherein the above-mentioned compound having a bridged oxoxane structure having an oxonitrobenzo ring unit The structure is as follows: A polysesquioxane having an oxonitrobenzoocyclic structure which is thermally treated, and the general structural formula of the polysesquioxanes which have been subjected to heat treatment with an oxonitrobenzo ring structure is as follows: Wherein X may be one selected from the group consisting of: a chemical bond, -O-, -CH ₂ -, , , , , R ¹ and R ³ may be the same or different, and R ¹ and R ³ may be an alkyl group selected from C ₁ to C ₈ , respectively, or an aryl group of C ₆ to C ₁₅ ; m and n are integers, but at least 1. The polysesquioxane having an oxo-nitrobenzo-benzo ring structure, as described in claim 5, wherein the above-mentioned heat treatment has a oxo-benzophenoline-structured polysesquioxane The structure is as follows: