TWI577736B - Polyimide/zro2 hybrid material, its use and preparation thereof - Google Patents

Description

Polyimine/zirconium dioxide mixed material, use thereof and preparation method

This invention relates to a novel polyamidiene/zirconia hybrid material. In particular, it relates to a polyimine/zirconium oxide mixed material having a refractive index and an Abbe's number which can be adjusted by increasing the content of zirconium dioxide, and the use thereof and a preparation method thereof.

Many polymers having a high refractive index have been widely proposed in recent years to promote advancement in photovoltaic applications. In addition to the basic parameters of the refractive index, other characteristics such as birefringence, Abbe number, optical transparency, processability, thermal stability, etc. are also important, and they need to be considered in practical optical applications. Therefore, achieving the above needs is an important and persistent issue. Polyimine (PIs), due to its excellent thermal stability, chemical resistance and superior mechanical properties, make it the most promising candidate for applications in optical devices. In addition, by designing and synthesizing the molecular structure, it is possible to simultaneously obtain a polyimine with excellent processability and optical properties, making the polyimide optical material a research field worthy of further investigation. When incorporated into the polymer backbone, ruthenium and its derivatives have a bulky and rigid structure, which is a well-known candidate for optical materials, and can reduce the interaction between the PI chain molecules and the bulk density to increase Correspondence and processability of the corresponding PIs.

Recently, polymer-inorganic hybrid materials have attracted a great deal of attention because of their excellent mechanical, thermal, magnetic, optical, electronic, and optoelectronic properties compared to the single polymer or inorganic component. In optical material applications, the inorganic domains of the inorganic material are controlled to have a diameter of less than 40 nm to reduce scattering losses and maintain their optical clarity. By sol-gel method, the chemical bonding can overcome the agglomeration of nanoparticle by operating organic/inorganic interactions at various molecular and nanometer scales. In previous studies, the content of titanium dioxide can be increased. To achieve a mixture of polythenimine/titanium dioxide (TiO ₂ ) having a high refractive index, however, because the low energy gap (3.2 electron volts) of titanium dioxide causes its optical transparency to be significantly reduced in the wavelength range of approximately 400 nm, resulting in the obtained poly The quinone imine/titanium dioxide mixed film exhibited a pale yellow color. In addition, the Abbe number of the PI/titanium dioxide hybrid material also decreases as the titanium dioxide content decreases. Therefore, it is an important issue to increase the refractive index by selecting the kind of inorganic material in the mixture without sacrificing the optical transparency in the Abbe number and the visible wavelength range.

In order to solve the above problems, the applicant unexpectedly discovered that zirconium dioxide (ZrO ₂ ) has superior combined optical properties due to its large band gap in the range of 5.0 to 5.85 eV, such as high refractive index, Bayesian and transparency over a wide spectral range. Accordingly, the present invention provides a simple in situ sol-gel process for the preparation of optically clear polyimine/zirconium dioxide (PI/ZrO2) blends. The pendent hydroxyl groups of the PI chain provide an organic-inorganic bonding site bonded to zirconium n-butoxide (Zr(OBu) ₄ ). Therefore, a PI/ZrO ₂ mixed film containing different ZrO ₂ contents can be successfully prepared for use in advanced optical applications.

Accordingly, it is a primary object of the present invention to provide a polyimine/zirconium dioxide mixed material represented by the following formula (I). Wherein n represents a value from 10 to 250; wherein, in the plurality of repeating units, the A may be para and/or meta position relative to the hydroxyl group, and represents a naphthalenedioxy group or a straight chain which may be substituted by a halogen atom or Branch chain C1-4 alkyl group, or , where, the Can be or , the It may be the same or different in each of the repeating units, and the at least one functional group is selected from the group consisting of the following formulas (II) to (VIII): And B represents a covalent bond, a straight or branched chain C _1-4 alkyl group which may be substituted by a halogen atom, -O-, -CO-, -S- or -SO ₂ -.

In a preferred embodiment, the zirconium dioxide is bonded to the polyimine by a hydroxyl group of the polyimine, and wherein the weight of the zirconium dioxide accounts for the polyimine/two The total weight of the zirconia mixed material is at most 60%.

In another preferred embodiment, the weight percentage of the zirconium dioxide is from 10% to 50% by weight based on the total weight of the polyamidene/zirconia mixed material.

In another preferred embodiment, it has a refractive index ranging from 1.673 to 1.804 at a wavelength of 633 nm.

In another preferred embodiment, it has an Abbe's number between 20.65 and 32.18.

In another preferred embodiment, it has a birefringence between 0.0071 and 0.0118.

Another main object of the present invention is to provide a method for preparing a polyamidene/zirconia mixed material comprising a polyimine of the following formula (IX), Wherein n represents a value from 10 to 250, which may be para and/or meta position relative to a hydroxyl group, and represents a naphthalenedioxy group or a straight or branched chain C1-4 alkyl group which may be substituted by a halogen atom, or , where, the Can be or , wherein, in the plurality of repeating units, the It may be the same or different in each of the repeating units, and the at least one functional group is selected from the group consisting of the following formulas (II) to (VIII): And B represents a covalent bond, a straight or branched chain C _1-4 alkyl group which may be substituted by a halogen atom, -O-, -CO-, -S- or -SO ₂ -.

In a preferred embodiment, the method comprises the steps of: (a) reacting a hydroxyl group-containing aromatic diamine with an aromatic dianhydride at a temperature ranging from room temperature to 250 ° C to prepare a hydroxyl group in the main chain. a soluble aromatic polyimine wherein the equivalent ratio of the aromatic diamine to the aromatic dianhydride (aromatic diamine/aromatic dianhydride) is in the range of 0.5 to 2.0; (b) subsequently step (a) a hydroxyl-containing soluble aromatic polyimine on the obtained main chain and an alkoxy zirconium oxide of the formula Zr(OR) ₄ (wherein R is the same or different and represents a C1-6 linear or branched alkyl group) in an acid catalyst Hydrolysis-condensation is carried out in the presence of water to obtain a homogeneous solution of an aromatic or semi-aromatic polyimine-nano-zirconia mixed material, wherein the zirconium alkoxide is soluble in a hydroxyl group-containing soluble aromatic group in the main chain. Or a semi-aromatic polyimine containing a molar ratio of hydroxyl groups (zirconium oxide/hydroxyl) in the range of 1 to 10; and (c) the aromatic or semi-aromatic polyimine-nano The zirconia mixed material is uniformly coated into a film to obtain the aromatic or semi-aromatic polymerization of the present invention. a quinone imine-nano zirconia mixed film; wherein the aromatic diamine having a hydroxyl group is at least one compound selected from the group consisting of 1,2-bis(4-amino-3-hydroxyphenoxy) Naphthalene, 1,3-bis(4-amino-3-hydroxyphenoxy)naphthalene, 1,4-bis(4-amino-3-hydroxyphenoxy)naphthalene, 1,5-bis (4) -amino-3-hydroxyphenoxy)naphthalene, 1,6-bis(4-amino-3-hydroxyphenoxy)naphthalene, 1,7-bis(4-amino-3-hydroxyphenoxy) Naphthalene, 1,8-bis(4-amino-3-hydroxyphenoxy)naphthalene, 2,3-bis(4-amino-3-hydroxyphenoxy)naphthalene, 2,6-bis (4) -amino-3-hydroxyphenoxy)naphthalene, 2,7-bis(4-amino-3-hydroxyphenoxy)naphthalene, bis(3-amino-4-hydroxyphenyl)isoperfluoropropane Wherein the aromatic dianhydride is at least one compound selected from the group consisting of 4,4'-oxydiphthalic anhydride, 3,3',4,4'-biphenyltetracarboxylic acid Anhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 2,2',3,3'-benzophenonetetracarboxylic dianhydride, 2,2',3,3 '-biphenyltetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2, 2-bis(3,4-dicarboxyphenyl)hexafluoroisopropane dianhydride, double (3,4-dicarboxyphenyl)ether dianhydride, bis(3,4-dicarboxyphenyl)ruthenium anhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, double (2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride; wherein the aliphatic dianhydride is at least one compound selected from the group consisting of: 1 , 2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, bicyclo[2.2 .1] heptane-2,3,5,6-tetra-2,3:5,6-dianhydride (Bicyclo[2.2.1]heptane-2,3,5,6-tetracarboxylic 2,3:5,6 -dianhydrides), bicyclo[2.2.2]octane-2,3-:5,6-tetracarboxylic dianhydride (Bicyclo[2.2.2]octane-2,3:5,6-tetracarboxylic dianhydride), bicyclo[2.2 .2] Oct-7-ene-2,3,5,6-tetracarboxylic dianhydride (Bicyclo[2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride).

In a preferred embodiment, wherein the zirconium dioxide precursor is Zr(OY) ₄ , wherein the Y is a C _1-4 alkyl group.

Another main object of the present invention is to provide a use of a polyamidene/zirconia hybrid material for use as an optical film.

According to the present invention, the colorless and flexible polyimine can be easily prepared from a diamine containing hydrazine and a commercial dianhydride 6FDA and CHDA. In the sol-gel reaction, the hydroxyl group of the polyamidene chain provides an organic-inorganic bonding site bonded to zirconium n-butoxide (Zr(OBu) ₄ ). The refractive index and Abbe number of the obtained PI/ZrO ₂ mixed material can be adjusted by increasing the content of zirconium dioxide, and can be increased to 1.804 and 32.18, respectively. In addition, these PI/ZrO ₂ mixed films have higher optical transparency than the corresponding PI-TiO ₂ system due to the large energy gap of ZrO ₂ . Moreover, the three-layer anti-reflective coating on the hybrid film can have a reflectance of less than 0.5% in the visible light range, so the novel PI/ZrO ₂ mixed film has great potential for application in advanced optics. .

Figure 1 shows a representative flexible and highly transparent PI film FOH-6FPI and mixed films sF-6FZr30 and F-6FZr50 (thickness 19 ± 3 μm).

2 is a representative flexible and highly transparent PI film FOH-CHPI and a mixed film F-CHZr50 (thickness 19±3 μm).

3 is a FTIR spectrum of PI and mixed films (a) FOH-6FPI, (b) FOH-CHPI, (c) F-6FZr50, and (d) F-CHZr50.

Figure 4 shows FOH-6FPI and the mixed film in (a) nitrogen, (b) air TGA temperature record.

Fig. 5 is a TMA curve of a FOH-6FPI mixed film at a heating rate of 10 ° C/min.

Fig. 6 is an optical transmission spectrum of a thick film (a), (b) (thickness: 19 ± 3 μm), and a film (c), (d) (thickness: 500 to 600 nm) of F-6FTiX and F-6FZrX, respectively.

Figure 7 is a (a) UV-visible absorption spectrum of ZrO ₂ and TiO ₂ (thickness: 200 to 300 nm), and (b) optical transmission spectrum of ZrO ₂ and TiO ₂ film (thickness: 100 ± 15 nm) (100 wt% of ZrO2) And the TiO2 system is formed by heating Zr(OBu) ₄ and Ti(OBu) ₄ by a sol-gel reaction to 300 ° C, respectively.

Figure 8 is an optical transmission spectrum of F-CHZrX mixed (a) thick film (thickness: 19 ± 3 μm), (b) film (thickness: 500 - 600 nm).

Figure 9 is a graph showing the difference in refractive index of (a) F-6FTiX and (b) F-6FZrX mixed films at different wavelengths. The insertion is shown in the case where the refractive index changes with the titanium dioxide content at a wavelength of 633 nm.

Figure 10 is a TEM image of a mixed film of F-6FZr50.

Figure 11 is a graph showing the change in reflectance of a glass sheet having a three-layer anti-reflective coating at various wavelengths.

Polyimine/zirconium dioxide mixed material of the invention

A main object of the present invention is to provide a polyimine/zirconium dioxide mixed material represented by the following formula (I). Wherein n represents a value from 10 to 250; wherein, in the plurality of repeating units, the A may be para and/or meta position relative to the hydroxyl group, and represents a naphthalenedioxy group or a straight chain which may be substituted by a halogen atom or Branch chain C1-4 alkyl group, or , where, the Can be or , the It may be the same or different in each of the repeating units, and the at least one functional group is selected from the group consisting of the following formulas (II) to (VIII): And B represents a covalent bond, a straight or branched chain C _1-4 alkyl group which may be substituted by a halogen atom, -O-, -CO-, -S- or -SO ₂ -. According to the content of the present invention, the zirconium dioxide is bonded to the polyimine by a hydroxyl group of polyimine, and wherein the weight of the zirconium dioxide accounts for the polyimine/zirconium dioxide mixture. The total weight of the material is up to 60%.

The refractive index and Abbe number of the polyamidene/zirconia mixed material of the present invention can be adjusted by increasing the content of zirconium dioxide therein, and can be increased to 1.804 and 32.18, respectively.

Method for preparing polyimine/zirconium oxide mixed material of the invention

Another main object of the present invention is to provide a method for preparing a polyamidene/zirconia mixed material comprising a polyimine of the following formula (IX), Wherein n represents a value from 10 to 250, which may be para and/or meta position relative to a hydroxyl group, and represents a naphthalenedioxy group or a straight or branched chain C1-4 alkyl group which may be substituted by a halogen atom, or , where, the Can be or , wherein, in the plurality of repeating units, the It may be the same or different in each of the repeating units, and the at least one functional group is selected from the group consisting of the following formulas (II) to (VIII): And B represents a covalent bond, a straight or branched chain C _1-4 alkyl group which may be substituted by a halogen atom, -O-, -CO-, -S- or -SO ₂ -.

In a preferred embodiment, wherein the zirconium dioxide precursor is Zr(OY) ₄ , wherein the Y is C _1-4 alkyl, and each of the plurality Y may be the same or different. Examples of the ZrO ₂ precursor may include, but are not limited to, tetramethyl zirconia, tetraethylene zirconia, tetrapropoxide zirconia, tetraisopropoxide zirconia, tetrabutyl zirconia, and tetraisobutyl zirconia. However, each Y is preferably the same based on the viewpoint of easy availability. In order to avoid the transesterification reaction, Zr(OY) _{4 is} preferably dissolved in an alcohol corresponding to the carbon number of Y as a solvent, for example, when R is a methyl group, methanol is used as a solvent; and if R is a butyl group, Butanol was used as a solvent.

In the preparation method of the mixed material of the present invention, the acidic condition which can carry out the hydrolysis-condensation reaction means a pH in the range of 4 to 7, and can be adjusted by adding an acid such as acetic acid or HCl.

Use of the polyamidene/zirconia mixed material of the present invention

Another main object of the present invention is to provide a use of a polyamidene/zirconia hybrid material for use as an optical film. The polyimine/ZrO ₂ mixed film has high transparency due to the large energy gap of ZrO ₂ . In addition, the polyimine/ZrO ₂ mixed film can be used as a multilayer anti-reflective coating having a reflectance of less than 0.5% in the visible range. Therefore, the polyimine/ZrO ₂ mixed film has great potential for use in advanced optics applications.

To prepare a polyimine/ZrO ₂ mixed film from a polyimine/zirconium oxide mixed material, the sol-gel method can be used for stepwise heating under vacuum. The term "stage heating" means a process for curing the mixed material at two or more temperatures and for a period of time (for example, heating to 300 ° C). For example, the mixed material is subjected to a first prebaking stage of 1 to 8 hours at 60 ° C, followed by baking at 150 ° C for 60 to 180 minutes, followed by baking at 250 ° C for 60 to 120 minutes. Finally, bake at 300 ° C for 60 to 120 minutes. The solidified hybrid material obtained may optionally be subjected to a hydrothermal process in water at 100 ° C depending on the type of the inorganic nanoparticle precursor. Finally, the obtained material was dried in a vacuum oven at 100 ° C for 5 to 8 hours.

Further, the polyimine/zirconium oxide mixed material of the present invention is soluble in various solvents such as a polar aprotic solvent such as N-methyl-2-pyrrolidone (NMP). )), dimethylacetamide (DMAc), N,N-dimethylformamide (DMF) and dimethyl sulfoxide (DMSO), Further, the polyimine/zirconium oxide mixed film can be produced by various methods, such as spin coating or ink jet.

The following examples are not to be construed as limiting the invention in any way. Modifications and variations of the embodiments discussed herein may be made without departing from the spirit and scope of the invention, and still fall within the scope of the invention.

Example

material

9,9-bis(4-(4-amino-3-benzyloxyphenoxy)phenyl)indole is prepared by the method disclosed in the prior art (Chern, YTUSPatent 20060241187, 2006). 2,2-bis(3,4-dicarboxyphenyl)hexafluoroisopropylidene dicarboxylic anhydride (6FDA) (Chriskev) was purified by vacuum sublimation. Other sources of reagents used are commercial products. Poly( o -hydroxy-indenine)s, FOH-6FPI and FOH-CHPI are prepared by the methods disclosed in the prior art (Yen, HJ; Tsai, CL; Wang, PH; Lin, JJ; Liou, GS RSC Adv ., 2013, 3 , 17048-17056; Tsai, CL; Chen, CJ; Wang, PH; Lin, JJ; Liou, GS Polym. Chem. , 2013, 4 , 4570-4573), the flow is as follows Shown as follows:

The general procedure for the preparation of polyimine is illustrated using synthetic FOH-6FPI as an example (Scheme 1). A chemical dose mixture of the diamine F-DA (1.12 g, 2.00 mmol), dianhydride 6FDA (0.89 g, 2.00 mmol) and a few drops of isoquinoline (7 mL) of m-cresol The mixture was stirred at room temperature for 5 hours under a nitrogen atmosphere, and then the mixture was heated to 170 to 180 ° C and maintained at this temperature for 16 hours. During this period, the water produced during the imidization can be removed together with m-cresol. After the solution was cooled to room temperature, the viscous solution was slowly poured into 300 mL of a methanol solution while stirring. The precipitated polymer was collected by filtration, washed thoroughly with hot methanol, and dried at 150 ° C for 15 hours under vacuum. The intrinsic viscosity of the obtained polyimine FOH-6FPI was 0.71 dL/g (measured at 30 ° C and the concentration of DMAc was 0.5 g/dL). The infrared spectrum of FOH-6FPI (thin film state) has a broad absorption band at 3000 to 3700 cm ^-1 (OH stretching), and the characteristic absorption peak of quinone imine is 1782 (asymmetric C=O), 1718 (symmetric C) =O), 1388 (CN), 1357 (CF) and 747 cm ^-1 (rhodium imine ring); Yield: 98%.

Example 1: Preparation of PI/ZrO ₂ mixed material

A PI/ZrO ₂ mixed material was prepared, and a general synthetic route for preparing the mixed material F-6FZrX was described using F-6FZr ₅₀ as an example (Scheme 2).

First, 0.05 g (0.050 mmole) of FOH-6FPI was dissolved in 3 ml of DMAc, and then 0.10 ml of acetic acid was added to the PI solution very slowly, and further stirred at room temperature for 30 minutes. Next, 0.21 ml (0.62 mmole) of Zr(OBu) _{4 was} dissolved in butanol and added dropwise to the above solution with a syringe, and stirred at room temperature for 30 minutes. Finally, the obtained F-6FZr50 precursor solution was filtered through 0.45 mm of PTFE and poured into a 6 cm glass petri dish.

Experimental Example 1: Preparation of PI/ZrO ₂ mixed film

The PI/ZrO ₂ mixed material prepared in Example 1 was further processed into a process PI/ZrO ₂ mixed film. The mixed film having a thickness of 19 ± 3 μm can be obtained by subjecting to a subsequent heating procedure at room temperature for 6 hours, 60 ° C for 6 hours, 150 ° C for 3 hours, 250 ° C for 1 hour, and 300 ° C for 1 hour. . Flexible and transparent PI/ZrO ₂ hybrid optical films with different zirconium oxide contents can be successfully prepared. Further, the thin mixed film (thickness: 500-600 nm) can also be applied to a glass plate or a tantalum wafer by spin coating at 1000-3000 rpm for 30 seconds, and is prepared by the above-described subsequent heating procedure.

Comparative Example 1: Preparation of 100 wt% zirconium dioxide and titanium dioxide film

A pure zirconium dioxide film was prepared by the following procedure: 7.7 g (0.02 mole) of Zr(OBu) ₄ and 15 ml of butanol were placed in a 50 ml round bottom flask. Next, acetic acid was slowly added to the above Zr(OBu) ₄ solution and stirred at room temperature for 1 hour. To prepare a zirconium dioxide film, the precursor solution was first filtered through a 0.2 mm PTFE filter, and then coated on a glass plate or a tantalum wafer by spin coating at 1000 rpm for 30 seconds. Finally, the coated film was further processed by a multi-step heating process at 60 ° C for 30 minutes, 150 ° C for 30 minutes, 250 ° C for 30 minutes, and 300 ° C for 60 minutes to obtain an inorganic film. Further, the titanium dioxide film was prepared using the method disclosed in the prior art (Su, HW; Chen, WC J Mater. Chem., 2008, 18, 1139-1145), but in this case only heated to 300 °C.

Measure

Fourier transform infrared spectroscopy (FT-IR) was recorded on a PerkinElmer Spectrometer 100 spectrometer. The ¹ H spectrum of DMSO- d ₆ was measured using a JEOL JNM-AL 300 MHz spectrometer using tetramethyl decane as an internal reference, and the multiplicity of peaks was expressed in the following manner: d, double; m, multiple. The intrinsic viscosity was tested using a Tamson TV-2000 viscometer at a concentration of 0.5 g/dl at 30 °C. Thermogravimetric analysis (TGA) was performed with TA device Q50. The experiment was carried out by heating about 6 to 8 mg of the film sample in flowing nitrogen or air (flow rate 20 cm ³ /min) at a heating rate of 20 ° C/min. The coefficient of thermal expansion (CTE) and the glass transition temperature (Tg) were measured by a dilatometer (TA Instruments TMA Q400EM). The TMA experiment was carried out at a constant loading of 50 mN on a stretchable probe at 50 to 450 °C at a scan rate of 10 °C/min. Tg is the onset temperature of the probe displacement in the TMA trace. The CTE data is obtained from a tensile probe in a tensile mode at a temperature range of 50 to 200 °C. The ultraviolet-visible (UV-Vis) spectrum of the polymer film was recorded on a Hitachi U4100 UV-Vis-NIR spectrophotometer. The refractive index (n) of the prepared film was measured with an ellipsometer (SOPRA, GES-5E) at a wavelength range of 300 to 800 nm. The thickness (h) of the prepared film was also determined at the same time. The in-plane ( n _TE ) and out-of-plane ( n _TM ) refractive indices of the film formed on the ceria substrate were measured using a prism coupler (Metricon, PC-2000) at a wavelength of 632.8 nm at room temperature. The in-plane/out-of-plane birefringence (? n ) is calculated as Δ n = n _TE - n _TM . Wide-angle X-ray diffraction (WAXD) was measured at room temperature (25 ° C) using graphite-monochromated Cu-Kα ray and measured with a PANalytical-X'Pert PRO MPD X-ray diffractometer (40 kV, 20 mA). The microstructure of the prepared film was examined using a JOEL JEM-1230 transmission electron microscope (TEM).

result

Basic Features

The synthesis of FOH-6FPI is carried out in a single-step process by using a hydroxy-substituted diamine monomer F-DA and an aromatic tetracarboxylic dianhydride 6FDA and using isoquinoline as a catalyst in the presence of 170-180 ° C, such as Flow chart 1 is shown. The formation of FOH-6FPI was confirmed by FTIR and NMR. The FTIR spectrum of FOH-6FPI film shows that it has a broad absorption band at 3000 to 3700 cm ^-1 (OH stretching), and the characteristic absorption peak of quinone imine is 1782 (asymmetric C=O), 1718 (symmetric C=O), 1388 (CN), 1357 (CF), and 747 cm ^-1 (deuterium ring deformation) are shown in Fig. 3(a). Further, the IR spectrum of the mixed film F-6FZr50 (Fig. 3(c)) showed an additional absorption band (Zr-O-Zr) at 600 to 650 cm ^-1 . The result of the 1H NMR (DMSO- d ₆ , δ, ppm): FOH-6FPI 6.51 (d, 4H), 7.01 (d, 4H), 7.20 (m, 6H), 7.40 (m, 6H), 7.73 (S) , 2H), 7.93 (d, 4H), 8.12 (d, 2H), 10.03 (s, 2H, OH). The intrinsic viscosity and solubility properties of the obtained polyimine are summarized in Table 1. FOH-6FPI has been shown to have good solubility in common organic solvents. Therefore, FOH-6FPI can be cast as a solvent to form a flexible, transparent and strong film (Fig. 1).

The hybrid film is depicted in Flowchart 2 by the manufacturing process of PI and zirconia precursors. A flexible, transparent and homogeneous PI-nano-zirconia (F-6FZrX) hybrid optical film having different zirconium oxide contents can be successfully prepared. The appearance of the F-6FZr50 thick optical hybrid film is shown in Figure 1.

In addition, the flexible, transparent and homogeneous PI/ZrO ₂ (F-CHZrX) hybrid optical film having different zirconium oxide contents can be successfully prepared, and the appearance of the F-CHZr50 thick optical hybrid film is also shown in the figure. 2. The FTIR spectra of the FOH-CHPI and F-CHZr50 films (Fig. 3(b), 3(d)) show that they have a broad absorption band of 3000-3700 cm ^-1 (OH functional group), and the quinone imine characteristics. absorption peaks at 1779cm ^-1 (C = O asymmetric functional group), 1719cm ^-1 (C = O functional group ^{symmetry), 1388cm -1 (CN),} 748cm -1 ( deformation ring (PEI)). The PI/ZrO ₂ film, the absorption peak of F-CHZr50 at 2750-3700 cm ^-1 may be contributed by the hydroxyl group of zirconium dioxide. In addition, inorganic Zr-O-Zr linkages can also be observed at 600-650 cm ^-1 , as reported in previous studies (Lo ' pez, EF; Escribano, VS; Panizza, M.; Carnascialic, MM; Busca, G J. Mater. Chem. , 2001, 11, 1891-1897; Bansal, V.; Rautaray, D.; Ahmad, A.; Sastry, M. J. Mater. Chem. , 2004, 14, 3303-3305 .).

Thermal performance

The results of evaluation of polyimine-zirconium oxide mixture ((F-6FZrX, F-CHZrX) and polyamidino-titanium dioxide (F-6FTiX) by TGA and TMA are shown in Table 2. In nitrogen and air, The typical TGA curve of F-6FZrX (Fig. 4) shows excellent thermal stability and the amount of carbonized residue (coke yield) also increases with the increase of the content of zirconium dioxide. The content of zirconium dioxide in the mixed material can be The coke yield in the air stream is estimated to be consistent with the theory and successfully ensured the incorporation of the zirconium dioxide. On the other hand, these PI/ZrO ₂ blends do not have an initial weight reduction before 400 ° C. The case further provides evidence of organic-inorganic complete bonding. A typical TMA temperature record of FOH-6FPI and the corresponding hybrid material show that the glass transition temperature increases from 257 ° C to 358 ° C with the zirconium dioxide content. (Fig. 5). At the same time, the coefficient of thermal expansion (CTE) is an important index for the application of polymer films in the field of microelectronics. The CTE of pure PI film and PI/ZrO ₂ or PI/TiO ₂ mixed film is measured and summarized. In Table 2. In general, the inorganic reinforcing component is more phase-separated than the organic matrix, often The lower CTE value, which suppresses the CTE value of the obtained mixed material. Therefore, the CTE value of the organic-inorganic hybrid decreases as the volume ratio of the inorganic reinforcement increases. Further, in this experiment, when the same The polyimine mixed film is added with the same amount of different kinds of inorganic nanoparticles, and the mixed film also has similar thermal characteristics.

Optical properties

The UV-visible (UV-Vis) spectrum of the mixed thick film (thickness: 19±3 μm) and film (thickness: 500 nm to 600 nm) of the mixed TiO ₂ and ZrO _{2 was} also measured, and the results are summarized in FIG. 6 and Table 3. These hybrid films exhibit a sufficiently high optical transparency and a low cutoff wavelength in the UV wavelength region, indicating that a highly uniform dispersed PI/TiO ₂ hybrid material has been obtained. The cutoff wavelength and the corresponding band edge also cause red shift as the titanium dioxide content increases. Such a phenomenon can usually also be observed when the titanium dioxide is less than 10 nm.

According to the optical transmission spectrum of the TiO ₂ hybrid system, the transparency of the mixed film is remarkably lowered as the TiO ₂ content increases at a wavelength of 400 nm. In the ZrO ₂ mixing system, the transparency of the mixed film was slightly lowered at 400 nm. Fig. 7(a) shows different absorption wavelengths of TiO ₂ and ZrO ₂ . The on-set absorption peak of TiO ₂ is close to the wavelength of 400 nm, and thus the optical transparency of the mixed polymer can be significantly affected. In the ZrO ₂ absorption spectrum, the absorption peak of the set absorption peak is about 230 nm. According to Fig. 7(b), the ZrO ₂ mixed film has a superior optical transparency (96%) at a wavelength of 450 nm as compared with the TiO ₂ system (88%). The main reason is that the transparency of the polyimide is not significantly affected by the ZrO ₂ mixing system. Therefore, the FOH-CHPI mixed film containing zirconia (F-CHZrX) exhibited higher transparency than the other mixed systems, and the results are summarized in Fig. 8 and Table 3.

The refractive index profile of the obtained film at a wavelength of 350 to 800 nm is shown in Fig. 9, wherein the intercalation chart shows the difference in refractive index between the titanium dioxide and the zirconium dioxide content at a wavelength of 633 nm, respectively. The refractive index increases linearly with the content of zirconium dioxide, suggesting that the Zr-OH group of the hydrolyzed precursor gradually condenses to form the Zr-O-Zr structure and increases the refractive index. In addition, the ZrO ₂ hybrid system not only increases the refractive index, but also increases the Abbe number more efficiently than the TiO ₂ hybrid system. The results are summarized in Table 3.

Combining thickness, flexibility, and optical transparency, the Pi/ZrO ₂ mixed optical thick film F-6FZr50 (19 ± 3 μm in thickness) exhibits a higher degree of optical transparency than the PI/TiO ₂ mixed film.

Morphological analysis

The TEM image of the F-6FZr50 film is shown in Figure 10. Wherein the black spot is ZrO ₂ particles. Since the polyimine contains a hydroxyl group, it is organic-inorganic bonded to the inorganic material, and exhibits a uniform dispersion state in the mixed film. The zirconium dioxide had an average particle size of 6 nm.

Multi-layer anti-reflective coating

Figure 11 shows the three-layer anti-reflective coating structure on the glass substrate and its reflection spectrum. The glass substrate had a refractive index higher than air (n = 1.0) (n = 1.52) and an average reflectance of 4.5% in the visible range. The reflectance is significantly reduced by the three-layer anti-reflective coating comprising the first layer of colloidal SiO ₂ , the second layer of F-6Zr50 and the third layer of F-69FZr10, respectively. In order to reduce the reflection by the phase adjustment of the light, the thicknesses of the obtained colloidal SiO ₂ , F-6FZr50 and F-6FZr10 films respectively should be controlled at 38 nm (1.29), 92 nm (1.80) and 70 nm (1.69) in the three-layer structure, respectively. ). As shown in Figure 11, the reflectance prepared from the antireflective coating was less than 0.5% in the visible range (400 nm to 700 nm), a significant decrease and much less than 4.5% of the glass. The PI/ZrO ₂ hybrid film prepared by the present invention has considerable potential for use in optical device applications.

Claims (10)

A polyimine/zirconium dioxide mixed material represented by the following formula (I), Wherein n represents a value from 10 to 250; wherein, in the plurality of repeating units, the A may be para and/or meta position relative to the hydroxyl group, and represents a naphthalenedioxy group or a straight chain which may be substituted by a halogen atom or Branch chain C1-4 alkyl group, , Among them, the Can be or , the It may be the same or different in each of the repeating units, and the at least one functional group is selected from the group consisting of the following formulas (II) to (VIII): And B represents a covalent bond, a straight or branched chain C _1-4 alkyl group which may be substituted by a halogen atom, -O-, -CO-, -S- or -SO ₂ -. The polyamidene/zirconia mixed material of claim 1, wherein the zirconium dioxide is bonded to the polyimine by a hydroxyl group of a polyimine, and wherein the weight of the zirconium dioxide is It accounts for up to 60% of the total weight of the polyamidene/zirconia mixed material. The polyamidene/zirconia mixed material of claim 2, wherein the weight percentage of the zirconium dioxide is from 10% to 50% by weight based on the total weight of the polyamidene/zirconia mixed material. The polyamidene/zirconia hybrid material of claim 1, which has a refractive index ranging from 1.673 to 1.804 at a wavelength of 633 nm. The polyamidene/zirconia hybrid material of claim 1, which has an Abbe's number between 20.65 and 32.18. The polyamidene/zirconia hybrid material of claim 1, which has a birefringence of from 0.0071 to 0.0118. A method for preparing a polyamidene/zirconia mixed material according to claim 1, which comprises a polyimine of the following formula (IX), Wherein n represents a value from 10 to 250, and the A may be para and/or meta position relative to the hydroxyl group, and represents a naphthalenedioxy group or a straight or branched chain C1-4 alkyl group which may be substituted by a halogen atom, , Among them, the Can be or , wherein, in the plurality of repeating units, the It may be the same or different in each of the repeating units, and the at least one functional group is selected from the group consisting of the following formulas (II) to (VIII): , And B represents a covalent bond, a straight or branched chain C _1-4 alkyl group which may be substituted by a halogen atom, -O-, -CO-, -S- or -SO ₂ -. The method of claim 7, the method comprising the steps of: (a) reacting a hydroxyl group-containing aromatic diamine with an aromatic dianhydride at a temperature ranging from room temperature to 250 ° C to prepare a hydroxyl group-containing solubility in the main chain. An aromatic polyimine wherein the equivalent ratio of the aromatic diamine to the aromatic dianhydride (aromatic diamine/aromatic dianhydride) is in the range of 0.5 to 2.0; (b) the step (a) is subsequently obtained a hydroxyl-containing soluble aromatic polyimine on the main chain and an alkoxy zirconium oxide of the formula Zr(OR) ₄ (wherein R is the same or different and represents a C1-6 straight or branched alkyl group) in an acid catalyst and Performing hydrolysis-condensation in the presence of water to obtain a homogeneous solution of an aromatic or semi-aromatic polyimine-nano-zirconia mixture, wherein the zirconium alkoxide is soluble in a hydroxyl group-containing soluble aromatic or The molar ratio of hydroxyl groups (zirconium oxide/hydroxyl groups) contained in the semi-aromatic polyimine in the range of 1 to 10; and (c) oxidation of the aromatic or semi-aromatic polyimine-nano The zirconium mixed material is uniformly coated into a film to obtain the aromatic or semi-aromatic polymerization of the present invention. An imine-nano zirconia mixed film; wherein the aromatic diamine having a hydroxyl group is at least one compound selected from the group consisting of 1,2-bis(4-amino-3-hydroxyphenoxy) Naphthalene, 1,3-bis(4-amino-3-hydroxyphenoxy)naphthalene, 1,4-bis(4-amino-3-hydroxyphenoxy)naphthalene, 1,5-bis(4- Amino-3-hydroxyphenoxy)naphthalene, 1,6-bis(4-amino-3-hydroxyphenoxy)naphthalene, 1,7-bis(4-amino-3-hydroxyphenoxy) Naphthalene, 1,8-bis(4-amino-3-hydroxyphenoxy)naphthalene, 2,3-bis(4-amino-3-hydroxyphenoxy)naphthalene, 2,6-bis(4- Amino-3-hydroxyphenoxy)naphthalene, 2,7-bis(4-amino-3-hydroxyphenoxy)naphthalene, bis(3-amino-4-hydroxyphenyl)isoperfluoropropane; Wherein the aromatic dianhydride is at least one compound selected from the group consisting of 4,4'-oxydiphthalic anhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride , 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,2',3,3'-benzophenone tetracarboxylic dianhydride, 2,2',3,3' -biphenyltetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2 - bis(3,4-dicarboxyphenyl)hexafluoroisopropane dianhydride, double (3 , 4-dicarboxyphenyl)ether dianhydride, bis(3,4-dicarboxyphenyl)ruthenium anhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, double (2 , 3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride; wherein the aliphatic dianhydride is at least one compound selected from the group consisting of: 1, 2 , 3,4-cyclobutane tetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, bicyclo [2.2.1 Heptane-2,3,5,6-tetra-2,3:5,6-dianhydride (Bicyclo[2.2.1]heptane-2,3,5,6-tetracarboxylic 2,3:5,6-dianhydrides , bicyclo [2.2.2] octane-2,3-:5,6-tetracarboxylic dianhydride (Bicyclo [2.2.2] octane-2, 3:5, 6-tetracarboxylic dianhydride), bicyclo [2.2.2 ] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride (Bicyclo[2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride). The method of claim 7, wherein the zirconium dioxide precursor is Zr(OY) ₄ , wherein the Y is a C _1-4 alkyl group. A use of the polyamidene/zirconia hybrid material of claim 1 for use as an optical film.