WO2018072291A1 - 含硒聚酰亚胺聚合物及其制备方法和应用 - Google Patents

含硒聚酰亚胺聚合物及其制备方法和应用 Download PDF

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WO2018072291A1
WO2018072291A1 PCT/CN2016/110235 CN2016110235W WO2018072291A1 WO 2018072291 A1 WO2018072291 A1 WO 2018072291A1 CN 2016110235 W CN2016110235 W CN 2016110235W WO 2018072291 A1 WO2018072291 A1 WO 2018072291A1
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selenium
formula
preparation
refractive index
selenoether
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French (fr)
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朱健
李琪龙
丁春来
姜慧楠
朱秀林
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Suzhou University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors

Definitions

  • the invention relates to a polymer material, in particular to a selenium-containing polyimide polymer material and a preparation method and application thereof.
  • High refractive index materials have important applications in the fields of optical materials, lenses, and displays.
  • the refractive index of common materials is relatively low. Between 1.3-1.70, materials with a refractive index greater than 1.70 are generally referred to as high refractive index materials.
  • High refractive index materials mainly include polymer-based materials and inorganic hybrid materials, while polymer-based materials are mainly polymer resin materials and polymer-nanoparticle blending materials, and inorganic hybrid materials are mainly ordinary inorganic glass materials.
  • Etc.; polymer-based high refractive index materials are lighter, more resistant to fracture and higher refractive index than inorganic hybrid materials.
  • inorganic hybrid materials used in optical devices have been slowly The replacement of polymer-based materials has become the focus of research in this field.
  • High refractive index polymers are generally used as optical materials such as prisms, plastic lenses, LED sealing materials, and anti-refractive coatings.
  • polyimide-titanium dioxide nanocrystal nanocomposites can be used as anti-refractive coatings.
  • Polyphenylene sulfide is used as an image sensor microscope head, phenylsiloxane is used as an LED sealing material, and the like.
  • the main high refractive index polymer materials that have been reported so far are: halogen-containing high refractive index polymers, phosphorus-containing high refractive index polymers, high refractive index polymers with large conjugated groups in the side chain, and selenium.
  • Hyperbranched polystyrene and sulfur-containing polyimide materials were reviewed.
  • Richard A. Minns et al. reported a halogen-containing high refractive index polymer with a refractive index of 1.67-1.77. They found that as the halogen content in the side chain increases, the refractive index value also increases, and the effect of iodine is better than bromine because the polarization of iodine is stronger than bromine.
  • halogen-containing polymers have a high refractive index, they are unstable under light or other conditions, and halogens are potentially contaminated by the environment, so there is still room for improvement. Allcock et al. reported a high refractive index of phosphorus-containing Number of polymers.
  • the phosphorus-containing polymer such as polyphosphazene, polyphosphate, or the like has a high refractive index.
  • Some polyphosphazene materials have a refractive index of 1.664-1.755 and a good transparency.
  • the chemical structure of polyphosphate is similar to that of polyphosphazene. Its refractive index is between 1.60-1.64, and its thermal stability and melt processing performance are better.
  • Tu Yingfeng et al. reported a high refractive index polymer containing a fullerene structure in the side chain.
  • fullerene is an all-carbon structure with excellent optical and electrical properties, it is a good optoelectronic material, but it is difficult to obtain a structure-controlled fullerene-containing polymer by radical or anionic polymerization, and they use polycondensation through advance
  • the side chain fullerene structure was designed, and the polymer with different structure was prepared by changing the intermediate structure of the dicarbonyl chloride.
  • the obtained fullerene side chain polymer material has a refractive index of 1.80 or more.
  • the inventors' research group reported the preparation of a selenium-containing hyperbranched polymer by copolymerization of styrene and styrene containing a selenoether structure.
  • the selenium-containing group has a high refractive index (>1.7) in the polymer side chain. However, its thermal stability is poor and its film forming performance is not good.
  • Polyimide material was first synthesized in the laboratory by Marston Bogert in 1908 by melt-polycondensation of 4-aminophthalic anhydride. In 1955, Du Pont applied for the world's first book on polyamido. The amine was applied to the material patent, and the polyimide film with the trade name kapton was developed in 1961. In 1968, Amoco Company of the United States developed the "gel film forming method" based on the chemical amination method. Good polyimide film, more than 20 major types of polyimides have been commercialized in the 21st century. Polyimide materials have great applications in high-tech fields such as defense and military industry because of their excellent performance in terms of heat, force, light and electricity.
  • the inventor's research team found through literature research that the key to increasing the refractive index of polymers It is introduced into a group having a high molar refractive index, a low molar volume, and a high polarity.
  • a commonly used method for increasing the refractive index of a polymer material, particularly a polyimide material is to introduce a sulfur element.
  • the obtained polyimide material has a limited increase in the refractive index and a low Abbe number, which limits the application of the material to some extent.
  • the presenter actively researches and innovates in order to create a preparation method of selenium-containing polyimide and its application, so as to make it more industrially valuable.
  • an object of the present invention is to provide a method for preparing a high refractive index selenium-containing polyimide and an application thereof, and to introduce selenium into a polyimide structure, thereby effectively improving the refractive index of the polymer material.
  • the index can significantly increase the Abbe number.
  • the present invention relates to a selenium-containing polyimide polymer having the following structural formula:
  • Ar is a selenoether group
  • R is one of an aromatic ring, an aromatic ring derivative, an aliphatic ring and an aliphatic ring derivative, 2 ⁇ n ⁇ 100.
  • R is one of the following structural formulas:
  • the structural formula of the selenoether group is: Ar 1 -Se-Ar 2 , Ar 3 -Se-Se-Ar 4 or Ar 5 -Se-Ar 6 -Se-Ar 7 -Se-Ar 8
  • Ar 1 -Ar 8 are independently selected from the group consisting of a phenyl group, a phenyl derivative, a naphthyl group, a naphthyl derivative, and an alkyl chain of C 2 -C 15 .
  • selenoether group is one of the following structural formulas:
  • the preparation method of a selenium-containing polyimide polymer of the invention comprises the following steps:
  • the solid content of the polyamic acid is about 13-17%, preferably 15%; the molar ratio of the selenoether diamine monomer to the dianhydride monomer is 1:0.8-1.2; the reaction is preferably carried out under inert gas protection,
  • the inert gas is preferably argon;
  • the organic solvent is one or more of N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc) and methylpyrrolidone (NMP).
  • Anhydrous DMF is preferred.
  • Ar is one of a selenoether group, an R aromatic ring, an aromatic ring derivative, an aliphatic ring and an aliphatic ring derivative, and 2 ⁇ n ⁇ 100.
  • the polymerization temperature is 20 to 40 ° C, preferably 28 to 32 ° C.
  • the thermal imidization temperature is from 60 ° C to 310 ° C, preferably from 70 ° C to 300 ° C, and more preferably, the thermal imidization is carried out under the conditions of a 70 ° C gradient to 300 ° C.
  • the thermal imidization is preferably carried out at 70-75 ° C for 40-80 min, 95-105 ° C for 40-80 min, 145-155 ° C for 40-80 min, 195-205 ° C for 70-100 min, and 215-255 ° C for heating 70. -100 min, heated at 295-300 ° C for 20-40 min.
  • the selenoether diamine monomer of the formula (II) is 4,4'-diaminodiphenyl selenide, 4,4'-diaminodinaphthyl selenide, 2, 2 '-Diaminodipropyl selenoether, 6,6'-diaminodihexyl selenide, 4,4'-diaminodiphenyl diselenide, 4,4'-diaminodinaphthyl diselenide, 2,2'-diaminodipropyl diselenide or 6,6'-diaminodihexyl diselenide.
  • the dianhydride monomer of the formula (III) is pyromellitic anhydride, 4,4'-oxydiphthalic anhydride, 4,4'-(hexafluoroisopropene) Anthracene anhydride or cyclobutane tetracarboxylic dianhydride.
  • the preparation of 4,4'-diaminodiphenyl selenoether comprises the steps of: reacting the p-aniline compound of the formula (I) with selenium at 105-135 ° C in an organic solvent, and tracking the reaction by TLC. After completion, a tan solid is obtained, and the solid is reduced by NaBH 4 to obtain a tan solid 4,4'-diaminodiphenyl selenide; wherein the reaction is preferably carried out in a catalyst, an activator, and protected from light.
  • the activator is a base, such as K 2 CO 3 , NaCO 3 , KOH or NaOH, preferably K 2 CO 3 , the molar ratio of base to p-aniline compound is 1:0.8-1.2;
  • the inert gas such as nitrogen, helium, argon, preferably argon;
  • the solvent is one or more of dimethyl sulfoxide (DMSO), N,N-dimethylformamide (DMF) and toluene , preferably DMSO;
  • X is I, Br or Cl
  • the corresponding catalysts are CuI, CuBr or CuCl, respectively.
  • the molar ratio of the p-aniline compound to selenium is: 9-11:4-5.
  • selenium-containing polyimide polymer of the present invention in an optical material, the selenium-containing polyimide polymer having a refractive index value of from 1.7 to 1.82.
  • the present invention has at least the following advantages:
  • the invention discloses for the first time a polyimide polymer material containing a selenoether structure, which introduces selenium into the polyimide structure, effectively improves the refractive index and ultraviolet absorption of the polymer material, and can significantly increase the Abbe number.
  • the selenium-containing polyimide polymer is obtained by synthesizing a selenoether diamine monomer and polymerizing with a dianhydride. It has been found that the introduction of selenium in the polyimide can increase the refractive index and greatly improve the existing poly-polymer. The defect that the refractive index of the imide material is not high makes it extended in the field of optics.
  • the present invention synthesizes 4,4'-diaminodiphenyl selenoether (BAPS) and structurally characterizes it with pyromellitic anhydride (PMDA) and 4,4'-oxybisphthalic acid, respectively.
  • the acid anhydride (ODPA) is subjected to polycondensation reaction, and after thermal imidization, two kinds of selenium-containing polyimide (PI) polymers (polymer form as a film) are obtained, and the two polyimide films are used.
  • Figure 1 is a nuclear magnetic resonance spectrum of 4,4' diaminodiphenyl selenide in Example 1 of the present invention
  • Example 2 is a nuclear magnetic resonance of 4,4'-diaminodiphenyl selenoether in Example 1 of the present invention. Carbon spectrum
  • Figure 3 is a nuclear magnetic resonance selenium spectrum of 4,4'-diaminodiphenylselenoether in Example 1 of the present invention
  • Figure 4 is an infrared spectrum diagram of a selenium-containing polyamic acid PAA1 obtained by polymerizing 4,4'-diaminodiphenyl selenoether and pyromellitic anhydride in Example 1 of the present invention;
  • Figure 5 is an infrared spectrum diagram of a selenium-containing polyimide film PI1 obtained by thermal imidization of a selenium-containing polyamic acid PAA1 in Example 1 of the present invention
  • Figure 6 is an infrared spectrum diagram of a selenium-containing polyamic acid PAA2 obtained by polymerizing 4,4'-diaminodiphenyl selenoether and 4,4'-oxydiphthalic anhydride in Example 2 of the present invention;
  • FIG. 7 is an infrared spectrum diagram of a selenium-containing polyimide film PI2 obtained by thermal imidization of a selenium-containing polyamic acid PAA2 in Example 2 of the present invention
  • Figure 8 is a graph showing dynamic thermomechanical analysis of four polyimide films obtained in Examples 1, 2, 3, and 4 of the present invention.
  • Figure 9 is a thermogravimetric analysis graph of four polyimide films obtained in Examples 1, 2, 3, and 4 of the present invention.
  • Figure 10 is a UV-Vis spectrum of four polyimide films obtained in Examples 1, 2, 3, and 4 of the present invention.
  • Figure 11 is a graph showing refractive index values of four polyimide films obtained in Examples 1, 2, 3, and 4 of the present invention at different wavelengths.
  • MS Small molecule mass spectrometry
  • FT-TR Fourier transform infrared spectroscopy
  • UV-vis spectroscopy (UV-vis) test was carried out by thermally imidizing a polyamic acid uniformly coated (15 ⁇ m) quartz plate into a film and inserting it into an integrating sphere using SHIMADZU UV-2600;
  • Dynamic thermomechanical analysis is to cut the polymer film into a strip having a width of about 5 mm, a thickness of about 0.10 mm, and a length of about 10 mm, which is tested by TA Instrument DMA Q800;
  • Thermogravimetric analysis was tested by shearing the PIs polymer film and using a PerkinElmer Pyris 1TGA in a N 2 atmosphere at a heating rate of 10 ° C/min.
  • the preparation of a selenium-containing polyimide polymer film comprises the following steps:
  • Figures 1, 2 and 3 are the nuclear magnetic resonance spectrum, the nuclear magnetic resonance carbon spectrum and the nuclear magnetic resonance selenium spectrum of the product 4,4'-diaminodiphenylselenoether, respectively.
  • Figure 4 is an infrared spectrum of the selenium-containing polyamic acid PAA1 obtained in the present step. It can be seen from Fig. 4 that there is a very broad absorption peak at 3480 cm -1 , which is attributed to the carboxyl group contained in the PAA (- COOH) of a hydroxyl group (-OH) absorption; at 1660cm -1, 1532cm -1, the absorption at 1253cm -1 attributable to three amide (-CONH-) characteristic absorption; 1721 cm -1 is the carbonyl group (-CO- Characteristic absorption of FIG. 5; FIG.
  • FIG. 5 is an infrared spectrum of the selenium-containing polyimide film PI1 (BASP/PDMA) obtained in the step, and it can be seen from FIG. 5 that the strong absorption peak at the original 3480 cm -1 disappears. This is illustrated by the thermal imidization, a carboxylic acid structure hydroxyl groups have reacted and formed a further 1720cm -1; 1370cm -1; wherein 720cm -1 three new absorption of an imide, the above described analysis can having a poly Imide structure.
  • BASP/PDMA selenium-containing polyimide film PI1
  • the steps of this example are basically the same as those of the first embodiment, except that the dianhydride monomer in the step (2) is 4,4'-oxydiphthalic anhydride (ODPA), and the selenium-containing polyamic acid PAA2 is obtained; (3) The selenium-containing polyamic acid PAA2 was thermally imidized to obtain a selenium-containing polyimide film PI2 (BASP/ODPA).
  • Figure 6 is an infrared spectrum of the selenium-containing polyamic acid PAA2 obtained in the present step. It can be seen from Fig.
  • FIG. 7 is a schematic selenium obtained in step The infrared spectrum of the polyimide film PI2 (BASP/ODPA) can be seen from Fig. 7: the strong absorption peak at the original 3450 cm -1 disappears, which indicates the hydroxyl group in the carboxylic acid structure by thermal imidization. It has been formed and further reacted 1720cm -1; 1370cm -1; 740cm -1 three new features imide absorption, the above analysis can be described by having a polyimide structure.
  • the preparation of the selenium-free polyimide polymer film comprises the following steps:
  • This embodiment is basically the same as the step of the third embodiment, except that the dianhydride monomer 4,4'-oxydiphthalic anhydride (ODPA) is added in the step (1) to obtain the polyamic acid PAA4; step (3) The polyamic acid PAA4 was thermally imidized to obtain a polyimide film PI4 (ODA/ODPA).
  • ODPA dianhydride monomer 4,4'-oxydiphthalic anhydride
  • PI can be dissolved in a common organic solvent, generally by two methods: (1) reducing the rigidity or regularity of the main chain, such as by polymerization of an aliphatic diamine and an aliphatic dianhydride. (2) reducing the density of the imide ring in the main chain, such as by reducing the molecular weight of PI.
  • the most common way is to introduce fluorine into the diamine or dianhydride monomer to improve the solubility of PI, and the optical properties of the fluorine-containing PI will change.
  • the thermal stability of the polyimide film was characterized by dynamic thermomechanical analysis (DMA) and thermogravimetric analysis (TGA) curves.
  • the DMA curves of the four polymer films are tested at a frequency of 1 Hz.
  • the PI1 curve is not measured because of the strong rigidity of the main chain of PI1 and the instability of selenium, so that PAA1 is in the thermal imine. A continuous film cannot be formed during the process, so there is no DMA test.
  • Tg glass transition temperature
  • Tg of PI2 is slightly lower than PI3 due to the instability of selenium at high temperature, but this does not affect the overall performance of PI2, which is obtained by polymerization of ODA and PMDA.
  • One of the most commonly used polyimides has a particularly large backbone, so its Tg is much higher than the other two PIs.
  • the TGA curves of the four polyimide films are in the range of 50-600 °C. It can be seen from Fig. 9 that the initial decomposition temperatures of the four films are all above 350 °C, indicating that the material can be used for a long time at high temperature, and the temperature at 5% weight loss is PI1450 °C, PI2478 °C, PI3520 °C, PI4530, respectively. °C.
  • PI1 and PI3 have similar structures
  • PI2 and PI4 have similar structures, but since PI1 and PI2 contain selenium, they are unstable at high temperatures and are easily decomposed to lower their decomposition temperature, but still do not affect their thermal stability.
  • the rigid structure in the PI backbone has a large effect on its glass transition temperature and decomposition temperature.
  • the optical transmittances of the four polyimides are different.
  • the reason for the color of the conventional polyimide is the charge transfer (CT) between the electron-donating diamine monomer and the electron-donating dianhydride monomer.
  • the ultraviolet-visible spectra of four polyimide films are shown in Fig. 10.
  • the transmittance of the four PIs at a wavelength of 600 nm or more is almost 100%, and the transmittances of PI1 and PI2 are shown in Fig. 10. Then, the rapid reduction is started.
  • the wavelength is 400 nm
  • the transmittance is almost zero, and the cutoff wavelength ( ⁇ 0 ) is 426 nm and 362 nm, respectively.
  • the transmittance of PI3 and PI4 up to the wavelength of 300 nm is 0, the cutoff wavelength.
  • the transmittances are 329 nm and 299 nm, respectively, and the transmittance in the visible light region (400-800 nm) is almost 100%. This shows that the optical transmittance of PI3 and PI4 in the visible region is much better than that of PI1 and PI2.
  • PI1 and PI2 have a transmittance of almost zero in the ultraviolet region, which can be used as an ultraviolet protection material.
  • transparent polyimide materials are required for a specific field, and a fluorine-containing group such as -CF 3 is usually introduced in the polyimide main chain to attenuate the charge transfer effect, thereby reducing the color depth of the PI.
  • T 400 (%) a in the table represents the transmittance at 400 nm
  • ⁇ 0 (nm) b represents the cutoff wavelength of UV-vis
  • the refractive index (n) c represents the refractive index at 589 nm
  • the in-plane refractive index (n TE ), out-of-plane refractive index (n TM ), average refractive index (n av ) and birefringence ( ⁇ n) of the four polyimide films are summarized.
  • the refractive index values of polyimide films at different wavelengths, the n TE and n TM values of the four polyimide films at 589 nm are between 1.724-1.829 and 1.655-1.796, respectively.
  • n TE values are slightly larger than the n TM values, indicating that the main chain is preferentially aligned parallel to the plane of the film.
  • the n av of PI1 and PI2 are 1.740 and 1.818, respectively, which are greater than the corresponding PI3 and PI4 of 1.714 and 1.712, respectively.
  • n av depends diamine monomers and dianhydride monomers characteristics, the PI1 n av is greater than the value of PI3 n av, the PI2 greater than the value of n av PI4, which is because, according to classical electromagnetic theory, the refractive index of the material
  • the refractive index has a great relationship with the molar refractive index of the material molecules.
  • the refractive index of the material with high molar refractive index structure is larger, while the diamine groups in PI1 and PI2 are higher.
  • the molar refractive index of -Se- so that the refractive index of PI1 and PI2 is greater than the corresponding PI3 and PI4.
  • V D values of PI1 and PI2 are 12.44 and 18.10, respectively, while the V D values of PI3 and PI4 are 15.83 and 18.07, respectively, indicating that the introduction of selenium has little effect on the V D value of PI.
  • the refractive index and the Abbe number are to be weighed because the optical absorption in the ultraviolet-visible region results in an increase in the refractive index at shorter visible wavelengths.
  • the Abbe number of the PI reported here is small, indicating that it has a large wavelength dispersion in the passage of the high refractive index.

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Abstract

一种高折光指数的含硒聚酰亚胺的制备方法及其应用，方法包括：(1)将硒醚二胺单体与二酸酐单体聚合得到含硒聚酰胺酸；(2)将步骤(1)中得到的含硒聚酰胺酸经热亚胺化得到含硒聚酰亚胺聚合物。聚酰亚胺中引入硒元素能够提高折光指数，折光指数值为1.7-1.82，极大的改善了现有聚酰亚胺材料折光指数不高的缺陷，使其在光学领域的应用得到延伸。

Description

含硒聚酰亚胺聚合物及其制备方法和应用 技术领域
本发明涉及一种聚合物材料，尤其涉及一种含硒聚酰亚胺聚合物材料及其制备方法和应用。
背景技术
高折光指数材料在光学材料、透镜以及显示等领域有着重要的应用，常见材料的折光指数相对较低，在1.3-1.70之间，一般将折光指数值大于1.70的材料称为高折光指数材料。高折光指数材料主要包括聚合物基材料和无机杂化材料两大类，而聚合物基材料主要是聚合物树脂材料和聚合物-纳米粒子共混材料，无机杂化材料主要是普通无机玻璃材料等；聚合物基的高折光指数材料比无机杂化材料具有更轻便，更好的抗断裂性的以及更高的折光指数等特性，近年来用于光学器件上的无机杂化材料慢慢被聚合物基材料所取代，成为该领域研究的重点。
高折光指数聚合物(n＞1.7)一般用作棱镜、塑料镜头、、LED密封材料、抗折光涂层等光学材料，例如聚酰亚胺一二氧化钛纳米晶体纳米复合材料可用作抗折光涂层，聚苯硫醚用作图像传感器显微镜头，苯基硅氧烷用作LED密封材料等等。目前已经报道的主要的高折光指数聚合物材料主要有：含卤素的高折光指数聚合物，含磷的高折光指数聚合物，侧链含大共轭基团的高折光指数聚合物，含硒的超支化聚苯乙烯以及含硫的聚酰亚胺材料等。Richard A.Minns等人报道了含卤素的高折光指数聚合物，其折光指数在1.67-1.77。他们发现，随着侧链上的卤素含量上升，折光指数值也随之增大，且碘元素的效果要比溴要好，这是因为碘元素的极化比溴要强。虽然含卤素的聚合物折光指数较高，但其在光或其他条件下不稳定，并且卤素对环境有潜在的污染，所以还有待改进。Allcock等人报道了含磷系的高折光指 数聚合物。由于磷元素具有高极化率，使得含磷聚合物如聚磷腈，聚磷酸酯等具有较高折光指数。一些聚磷腈材料的折光指数在1.664-1.755且透明度也较好。而聚磷酸酯的化学结构和聚磷腈相似，其折光指数在1.60-1.64之间，热稳定性和熔融加工性能较好。屠迎峰等人报道了侧链含有富勒烯结构的高折光指数聚合物。由于富勒烯是全碳结构具有优异的光学，电学特性，是很好的光电材料，但通过自由基或阴离子聚合难以得到结构可控的含富勒烯的聚合物，他们利用缩聚，通过预先设计好侧链富勒烯结构，并利用变化二羰基氯化物中间基团结构，制备得到了具有不同结构的聚合物。所得富勒烯侧链聚合物材料的折光指数在1.80以上。发明人研究小组报道了由含硒醚结构的苯乙烯与苯乙烯共聚，制备含硒的超支化聚合物，含硒基团在聚合物侧链，虽具有较高的折光指数(＞1.7)，但其热稳定性较差，成膜性能不好。
聚酰亚胺材料于1908年Marston Bogert通过4-氨基邻苯二甲酸酐熔融自缩聚首次在实验室中合成出聚酰亚胺，1955年Du Pont公司申请了世界上第一篇有关聚酰亚胺应用于材料方面的专利，并与1961年开发出了商品名为kapton的聚酰亚胺薄膜，1968年美国Amoco公司基于化学胺化法，发展了“凝胶成膜法”得到了性能更好的聚酰亚胺薄膜，21世纪已商品化的聚酰亚胺已有20多个大类。聚酰亚胺材料由于在热、力、光、电等方面表现出优益的性能，使其在国防军工等高尖端领域有着重大的应用。主要用作光学薄膜，气体分离膜，光刻胶，聚电解质材料以及电子器件柔性材料。Ueda等人报道了各种结构的含硫聚酰亚胺材料，其折光指数在1.680-1.769，影响折光指数值的因素主要是重复单元数量，芳基含量，分子体积。具有高折射率，优异的热性能，优异的物理性能，优异的机械性能，较低的介电常数。
发明人研究小组通过文献调研发现，提高聚合物的折光指数关键 在于引入高摩尔折射率、低摩尔体积以及高极性的基团。目前，常用的提高聚合物材料，特别是聚酰亚胺材料的折光指数的方法是引入硫元素。然而，所得聚酰亚胺材料的折光指数提高有限，其阿贝数也较低，一定程度上限制了该类材料的应用。
有鉴于上述的缺陷，本设计人，积极加以研究创新，以期创设一种含硒聚酰亚胺的制备方法及其应用，使其更具有产业上的利用价值。
发明内容
为解决上述技术问题，本发明的目的是提供一种高折光指数的含硒聚酰亚胺的制备方法及其应用，将硒元素引入聚酰亚胺结构中，有效提升了聚合物材料的折光指数，并可以显著提高阿贝数。
本发明一种含硒聚酰亚胺聚合物，所述聚合物的结构通式如下：
Figure PCTCN2016110235-appb-000001
其中，Ar为硒醚基团，R为芳香环、芳香环衍生物、脂肪环和脂肪环衍生物中的一种，2≤n≤100。
进一步的，R为如下结构式中的一种：
Figure PCTCN2016110235-appb-000002
进一步的，所述硒醚基团的结构通式为：Ar1-Se-Ar2、Ar3-Se-Se-Ar4或Ar5-Se-Ar6-Se-Ar7-Se-Ar8，其中，Ar1-Ar8独立地选自苯基、苯基衍生物、萘基、萘基衍生物和C2-C15的烷基链中的一种。
进一步的，硒醚基团为如下结构式中的一种：
Figure PCTCN2016110235-appb-000003
本发明的一种含硒聚酰亚胺聚合物的制备方法，包括以下步骤：
(1)将式(II)的硒醚二胺单体与式(III)的二酸酐单体在有机溶剂中发生聚合反应，得到式(IV)的含硒聚酰胺酸；其中，得到含硒聚酰胺酸的固含量约13-17％，优选15％；所述硒醚二胺单体与二酸酐单体的摩尔比为1∶0.8-1.2；所述反应优选在惰性气体保护下进行，惰性气体优选氩气；所述有机溶剂为N，N-二甲基甲酰胺(DMF)、N，N-二甲基乙酰胺(DMAc)和甲基吡咯烷酮(NMP)的一种或几种，优选无水的DMF。
(2)将步骤(1)中得到的式(IV)的含硒聚酰胺酸经热亚胺化得到式(V)含硒聚酰亚胺聚合物。
反应式如下：
Figure PCTCN2016110235-appb-000004
其中，Ar为硒醚基团，R芳香环、芳香环衍生物、脂肪环和脂肪环衍生物中的一种，2≤n≤100。
进一步的，步骤(1)中，聚合反应温度为20-40℃，优选28-32℃。
进一步的，热亚胺化温度为60℃-310℃，优选70℃-300℃，更优选地，热亚胺化在70℃梯度升温至300℃的条件下进行。
进一步，热亚胺化优选在70-75℃加热40-80min，95-105℃加热40-80min，145-155℃加热40-80min，195-205℃加热70-100min，215-255℃加热70-100min，295-300℃加热20-40min。
进一步的，步骤(1)中，式(II)的硒醚二胺单体为4，4′-二氨基二苯基硒醚、4，4′-二氨基二萘基硒醚、2，2′-二氨基二丙基硒醚、6，6′-二氨基二己基硒醚、4，4′-二氨基二苯基二硒醚、4，4′-二氨基二萘基二硒醚、2，2′-二氨基二丙基二硒醚或6，6′-二氨基二己基二硒醚等。
进一步的，步骤(2)中，式(III)的二酸酐单体为均苯四甲酸酐、4，4′-氧双邻苯二甲酸酐、4，4′-(六氟异丙烯)二酞酸酐或环丁烷四甲酸二酐。
进一步的，4，4′-二氨基二苯基硒醚的制备包括以下步骤：在有机溶剂中，式(I)的对苯胺化合物与硒在105-135℃下反应，通过TLC跟踪反应，反应完毕后得到棕褐色的固体，将所述固体通过NaBH4还原，再次得到棕褐色固体4，4′-二氨基二苯基硒醚；其中，所述反应优选在催化剂、活化剂、避光、惰性气体保护的条件下进行，所述活化剂为碱，如K2CO3、NaCO3、KOH或NaOH，优选K2CO3，碱与对苯胺类化合物的摩尔比为1∶0.8-1.2；所述惰性气体如氮气、氦气，氩气，优选氩气；所述溶剂为二甲亚砜(DMSO)、N，N-二甲基甲酰胺(DMF)和甲苯中的一种或几种，优选DMSO；
反应式如下：
Figure PCTCN2016110235-appb-000005
其中，X为I、Br或Cl，与其相对应的催化剂分别为CuI、CuBr或CuCl。
进一步的，所述对苯胺化合物与硒的摩尔比为∶9-11∶4-5。
本发明的含硒聚酰亚胺聚合物在光学材料中的应用，所述含硒聚酰亚胺聚合物的折光指数值为1.7-1.82。
借由上述方案，本发明至少具有以下优点：
本发明首次公开了含硒醚结构的聚酰亚胺聚合物材料，将硒元素引入聚酰亚胺结构中，有效提升了聚合物材料的折光指数以及紫外吸收，并可以显著提高阿贝数，通过合成硒醚二胺单体，并与二酸酐聚合得到含硒聚酰亚胺聚合物，经过测试发现，在聚酰亚胺中引入硒元素能够提高折光指数，极大的改善了现有聚酰亚胺材料折光指数不高的缺陷，使其在光学领域的应用得到延伸。
本发明通过合成4，4′-二氨基二苯基硒醚(BAPS)并对其进行结构表征，将其分别与均苯四甲酸酐(PMDA)和4，4′-氧双邻苯二甲酸酐(ODPA)进行缩聚反应，再经过热亚胺化后，得到两种含硒聚酰亚胺(PI)聚合物(聚合物形态为薄膜)，将这两种聚酰亚胺薄膜与两种普通不含硒的聚酰亚胺薄膜进行比较，通过傅里叶红外变换光谱(FTIR)、紫外-可见吸收光谱(UV-vis)、动态热机械分析仪(DMA)、热重分析仪(TGA)以及光谱型椭偏仪对得到的聚酰亚胺薄膜的结构和性能的表征，发现新型的含硒聚酰亚胺的热稳定性没有较大的改变，其折光指数得到提高以及对紫外光的吸收也提高，折光指数值从1.712-1.818。这些初步探索能够说明引入硒元素能够提高聚酰亚胺的折光指数并且对紫外吸收得以增强。
上述说明仅是本发明技术方案的概述，为了能够更清楚了解本发明的技术手段，并可依照说明书的内容予以实施，以下以本发明的较佳实施例并配合附图详细说明如后。
附图说明
图1是本发明的实施例1中4，4′二氨基二苯基硒醚的核磁共振氢谱；
图2是本发明的实施例1中4，4′-二氨基二苯基硒醚的核磁共振 碳谱；
图3是本发明的实施例1中4，4′-二氨基二苯基硒醚的核磁共振硒谱；
图4是本发明的实施例1中4，4′-二氨基二苯基硒醚和均苯四甲酸酐聚合后得到的含硒聚酰胺酸PAA1的红外光谱图；
图5是本发明的实施例1中由含硒聚酰胺酸PAA1热亚胺化后得到含硒聚酰亚胺薄膜PI1的红外光谱图；
图6是本发明的实施例2中4，4′-二氨基二苯基硒醚和4，4′-氧双邻苯二甲酸酐聚合后得到的含硒聚酰胺酸PAA2的红外光谱图；
图7是本发明的实施例2中由含硒聚酰胺酸PAA2热亚胺化后得到含硒聚酰亚胺薄膜PI2的红外光谱图；
图8是本发明的实施例1、2、3、4中得到的四种聚酰亚胺薄膜动态热机械分析曲线图；
图9是本发明的实施例1、2、3、4中得到的四种聚酰亚胺薄膜热重分析曲线图；
图10是本发明的实施例1、2、3、4中得到的四种聚酰亚胺薄膜的紫外-可见光谱图；
图11图示了本发明的实施例1、2、3、4中得到的四种聚酰亚胺薄膜在不同波长下的折光指数值。
具体实施方式
下面结合附图和实施例，对本发明的具体实施方式作进一步详细描述。以下实施例用于说明本发明，但不用来限制本发明的范围。
具体实施例中性能测试方法如下：
1、核磁氢谱(1HNMR)和碳谱(13C NMR)是通过Bruker 300MHz核磁仪，将待测小分析试样以DMSO-d6为溶剂，四甲基硅烷(TMS)为内标溶解后进行测试；
2、核磁硒谱(77Se NMR)是通过Agilent 400MHz核磁仪测试；
3、元素分析是通过PerkinElmer 2400CNH元素分析仪来测试；
4、小分子质谱(MS)是通过以乙腈做溶剂，过滤头后通过Bruker microTOF-QIII质谱仪测试；
5、傅里叶红外变换光谱(FT-TR)测试是通过将聚酰亚胺酸旋涂在KBr压片上进过热亚胺化后用Bruker TENSOR 27FT-IR测试；
6、紫外-可见光谱(UV-vis)测试是通过将聚酰胺酸均匀平涂(15μm)石英片上热亚胺化成膜后插入积分球中用SHIMADZU UV-2600进行测试；
7、折光指数(RI)的测量是通过将聚酰胺酸旋涂在硅片上后热亚胺化成膜后用M2000，J.A.Woollam Co.光谱型椭偏仪进行测量，测出nTE和nTM值，其中平均折射率(nav)通过方程nav 2＝(2nTE 2+nTM 2)/3计算得到，双折射(Δn)通过方程Δn＝nTE-nTM计算得到；
8、动态热机械分析(DMA)是将聚合物薄膜裁剪成宽5mm左右，厚度0.10mm左右，长度10mm左右的长条通过TA Instrument DMA Q800来测试；
9、热重分析(TGA)是通过将PIs聚合物薄膜剪碎后用PerkinElmer Pyris 1TGA在N2氛围下，升温速率为10℃/min来测试。
实施例1
含硒聚酰亚胺聚合物薄膜的制备，包括以下步骤：
(1)合成硒醚二胺单体4，4′-二氨基二苯基硒醚(BASP)：先将50mL三口烧瓶通氩气两个小时，排除空气，然后将对碘苯胺(10mmol)、CuI(1mmol)、K2CO3(10mmol)、DMSO(20mL)加入三口烧瓶中，搅拌使对碘苯胺溶解，再将干燥的硒粉(6mmol)加入反应体系中，预先设定反应温度为120℃；将反应装置避光，并一直通氩气，反应过程通过TLC跟踪，约12h，对碘苯胺基本可以反应完。自然冷却后，避光抽滤，水洗后乙酸乙酯萃取(40mL×3)，有机相用无水硫酸钠干燥，再次抽滤，旋转蒸发剥离溶剂后硅胶柱层析 分离(洗脱液PE∶EA＝2∶1)，得到棕褐色的固体，然后将该固体通过NaBH4还原后，再次得到的棕褐色固体为所要的产物4，4′-二氨基二苯基硒醚(BASP)。
附图1、2和3分别是产物4，4′-二氨基二苯基硒醚的核磁共振氢谱、核磁共振碳谱以及核磁共振硒谱。
元素分析(％)：理论值：C，55.54；N，10.61；H，4.591；测量值：C，55.16；N，10.55；H，4.502。
质谱(MS)m/z：[M+H]+理论值：265.02，测量值：265.0236。
(2)制备含硒聚酰胺酸：称取BASP(0.2640g，1mmol)溶解于3mL无水的DMF中，在氩气氛围下搅拌至BASP完全溶解，继续通氩气半小时，再加入二酸酐单体均苯四甲酸酐(PMDA)(0.2189g，1mmol)，维持反应温度为30℃，搅拌反应3h后得到含硒聚酰胺酸PAA1，固含量为15％。
(3)制备含硒聚酰亚胺(PI)薄膜：将含硒聚酰胺酸PAA1快速涂抹在玻璃板上进行热亚胺化，经过下面的升温程序：70℃加热1h，100℃加热1h，150℃加热1h，200℃加热1.5h，250℃加热1.5h，300℃加热0.5h，自然降温至室温后，将玻璃板浸没于蒸馏水中，使得到的含硒聚酰亚胺薄膜PI1(BASP/PDMA)从玻璃板表面自然脱落。
附图4为本步骤得到的含硒聚酰胺酸PAA1的红外光谱图，从图4中可以看出在3480cm-1处有很明显很宽的吸收峰，这归属于PAA所含的羧基(-COOH)中的羟基(-OH)吸收；在1660cm-1，1532cm-1，1253cm-1三处吸收归属于酰胺结构(-CONH-)的特征吸收；在1721cm-1处是羰基(-CO-)的特征吸收；附图5为本步骤得到的含硒聚酰亚胺薄膜PI1(BASP/PDMA)的红外光谱图，从图5中可以看出在原来3480cm-1处的强吸收峰消失，这说明通过热亚胺化，羧酸结构中的羟基已经参与反应并且还形成了1720cm-1；1370cm-1；720cm-1 三处新的酰亚胺的特征吸收，通过以上分析能够说明具有聚酰亚胺结构。
实施例2
本实施例步骤与实施例1基本相同，其区别在于：步骤(2)中二酸酐单体为4，4′-氧双邻苯二甲酸酐(ODPA)，得到含硒聚酰胺酸PAA2；步骤(3)中将含硒聚酰胺酸PAA2进行热亚胺化，得到含硒聚酰亚胺薄膜PI2(BASP/ODPA)。附图6为本步骤得到的含硒聚酰胺酸PAA2的红外光谱图，从图6中可以看出：在3450cm-1处有很明显很宽的吸收峰，这归属于PAA所含的羧基(-COOH)中的羟基(-OH)吸收；在1660cm-1，1532cm-1，1260cm-1三处吸收归属于酰胺结构(-CONH-)的特征吸收；附图7为本步骤得到的含硒聚酰亚胺薄膜PI2(BASP/ODPA)的红外光谱图，从图7中可以看出：在原来3450cm-1处的强吸收峰消失，这说明通过热亚胺化，羧酸结构中的羟基已经参与反应并且还形成了1720cm-1；1370cm-1；740cm-1三处新的酰亚胺的特征吸收，通过以上分析能够说明具有聚酰亚胺结构。
以下为对比实施例，不含硒聚酰亚胺聚合物薄膜的制备：
实施例3
不含硒聚酰亚胺聚合物薄膜的制备，包括以下步骤：
(1)制备聚酰胺酸：称取4，4′-二氨基二苯醚(ODA)(0.2640g，1mmol)溶解于3mL无水的DMF中，在氩气氛围下搅拌至ODA完全溶解，继续通氩气半小时，再加入二酸酐单体均苯四甲酸酐(PMDA)(0.2189g，1mmol)，维持反应温度为30℃，搅拌反应3h后得到聚酰胺酸PAA3，控制投料比，使其固含量在15％。
(2)制备聚酰亚胺(PI)薄膜：将聚酰胺酸PAA3快速涂抹在玻璃板上进行热亚胺化，经过下面的升温程序：70℃加热1h，100℃加热1h，150℃加热1h，200℃加热1.5h，250℃加热1.5h，300℃ 加热0.5h，自然降温至室温后，将玻璃板浸没于蒸馏水中，使得到的聚酰亚胺薄膜PI3(ODA/PDMA)从玻璃板表面自然脱落。
实施例4
本实施与实施例3步骤基本相同，其区别在于：步骤(1)中加入二酸酐单体4，4′-氧双邻苯二甲酸酐(ODPA)，得到聚酰胺酸PAA4；步骤(3)中将聚酰胺酸PAA4进行热亚胺化，得到聚酰亚胺薄膜PI4(ODA/ODPA)。
对上述得到的四种聚合物薄膜PI1(BASP/PDMA)、PI2(BASP/ODPA)PI3(ODA/PDMA)、PI4(ODA/ODPA)做性能测试如下：
1、聚合物薄膜的溶解性：
表1.四种聚酰亚胺薄膜在常用有机溶剂中的溶解性
Figure PCTCN2016110235-appb-000006
如上述表1中(“-”代表常温下不溶；“+”代表常温下可溶)所示的每10mg样品在1mL溶剂中的相对溶解性，以测试聚合物薄膜(PI)在DMSO中的溶解性为例，将所得到的四种聚酰亚胺薄膜(厚度在20μm左右)各称取2mg后剪成小碎屑，常温下各自装进含有2mLDMSO的小瓶中，常温下搅拌2小时后发现四种PI在DMSO都不溶，以同样的方法来测试四种PI在表1中所列出的有机溶剂中的溶解性，发现在常温下也都不溶，这是因为这四种PI的主链分子刚性较强，使其链柔性较差，主链结构在有机有机溶剂中舒展不开，从而导致其不溶。这就使得这四种PI具有耐溶剂性，可以长期在上 述的有机溶剂环境下使用而不影响PI的性能。但是在一些其他领域需要PI常能够溶解于常用有机溶剂中，一般通过两种方式来实现：(1)降低主链的刚性或规整度，如通过脂肪族二胺和脂肪族二酐的聚合得到的PI；(2)降低主链中酰亚胺环的密度，如通过降低PI的分子量等方式。而最常用的方式就是在二胺或二酐单体中引入氟元素，来提高PI的溶解性，而且含氟的PI的光学性能会有多改变。
2、聚合物薄膜的热稳定性：
通过动态热机械分析(DMA)和热重分析(TGA)曲线来表征聚酰亚胺薄膜的热稳定性。
如图8所示，是四种聚合物薄膜的DMA曲线，测试频率为1Hz，没有测出PI1的曲线是因为PI1的主链刚性较强以及含硒的不稳定性，使PAA1在热亚胺化过程中不能形成连续的薄膜，所以没有能够进行DMA的测试。从PI2，PI3以及PI4的DMA曲线可以看出其玻璃化转变温度(Tg)在264℃、274℃、382℃，比较PI2和PI4发现，这两者只有二胺单体中含硒和含氧的不同，其他结构相同，但是由于硒元素在高温下的不稳定性使PI2的Tg略低于PI3，但这并不影响PI2的整体的性能，而PI3是由ODA和PMDA聚合得到的，是最常用的一种聚酰亚胺，其主链刚性特别大，所以其Tg远高于另外两种PI。
如图9所示，是四种聚酰亚胺薄膜的TGA曲线，升温范围在50-600℃。从图9中可以看出四种薄膜的初始分解温度都在350℃以上，说明该材料可在高温下的长期使用，而失重5％时的温度分别为PI1450℃、PI2478℃、PI3520℃、PI4530℃。虽然PI1和PI3具有类似的结构，PI2和PI4有类似的结构，但由于PI1和PI2含有硒元素，在高温下不稳定易分解使其的分解温度降低，但还是不影响其热稳定性能，并且PI主链中的刚性结构对其玻璃化转变温度和分解温度有很大的影响。
3、聚合物薄膜的光学性能：
通过对得到四种PI薄膜的观察，发现其都有颜色，并且颜色深度不同，也就是说四种聚酰亚胺的光学透过性是不同的。造成普通聚酰亚胺带有颜色的原因是供电子的二胺单体和得电子的二酸酐单体之间的电荷转移(CT)。
如图10所示是四种聚酰亚胺薄膜的紫外-可见光谱，从图10中可以看出四种PI在波长600nm以上时透过率几乎为100％，而PI1和PI2的透过率随后就开始快速降低，到波长400nm时就透过率就几乎为0了，截止波长(λ0)分别为426nm和362nm；而PI3和PI4的直至波长300nm左右才透过率为0，截止波长分别为329nm和299nm，且在可见光区域(400-800nm)的透过率几乎为100％。这说明PI3和PI4在可见光区域的光学透过率要比PI1和PI2要好很多。但是我们发现，PI1和PI2在紫外光区域的透过率几乎为0，这样可以用作防紫外材料。有时，透明性聚酰亚胺材料需要用于特定的领域，通常在聚酰亚胺主链引入含氟的基团如-CF3来减弱电荷转移效应，从而降低PI的颜色深度。
表2.四种聚酰亚胺的光学性能
Figure PCTCN2016110235-appb-000007
如表2所示(表中T400(％)a表示400nm处的透过率，λ0(nm)b表示UV-vis的截止波长，折光指数(n)c表示589nm处的折射率)，总结了这四种聚酰亚胺薄膜的面内折光指数(nTE)，面外折光指数(nTM)，平均折光指数(nav)以及双折射(Δn)；如图11所示是四种聚酰亚胺 薄膜在不同波长下的折光指数值，这四种聚酰亚胺薄膜在589nm处的nTE和nTM值分别在1.724-1.829和1.655-1.796之间。从四种PI中可以看出nTE值都比nTM值要稍微大点，这说明主链平行于膜的平面择优排列。PI1和PI2的nav分别为1.740和1.818都大于与之对应的PI3和PI4分别为1.714和1.712。nav取决于二胺单体和二酐单体的特性，PI1的nav值大于PI3的nav值，PI2的nav值大于PI4的值，这是因为根据经典电磁理论，材料的折射率折光指数和材料分子的摩尔折射率有很大的关系，在分子结构类似的情况下，含有高摩尔折射率结构的材料折光指数较大，而PI1和PI2中的二胺基团都含有较高摩尔折射率的-Se-，所以使PI1和PI2的折光指数大于与之对应的PI3和PI4。
折光指数的各向异性被认为是双折射，这是材料应用于棱镜以及光导设备上很重要的一个参数，大的双折射会带来像差。通过比较PI1和PI3，PI2和PI4，发现引入含硒基团还可以减小双折射。阿贝数(VD)通过方程VD＝(nD-1)/(nF-nC)来计算得到，其中nD，nF，nC分别代表D线(589nm)，F线(486nm)和C线(563nm)。VD值越小代表波长色散越高，VD值越大说明波长色散越低。PI1和PI2的VD值分别为12.44和18.10，而PI3和PI4的VD值分别为15.83和18.07，说明引入硒元素对PI的VD值影响并不大。折光指数和阿贝数是要权衡考虑的，因为在紫外-可见区域的光学吸收导致在较短可见光波长下的折光指数的提高。这里报道的PI的阿贝数较小，说明其在高折光指数的通过有大的波长色散。
以上所述仅是本发明的优选实施方式，并不用于限制本发明，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明技术原理的前提下，还可以做出若干改进和变型，这些改进和变型也应视为本发明的保护范围。

Claims (10)

  1. 一种含硒聚酰亚胺聚合物，其特征在于，所述聚合物结构通式如下：
    Figure PCTCN2016110235-appb-100001
    其中，Ar为硒醚基团，R为芳香环、芳香环衍生物、脂肪环和脂肪环衍生物中的一种，2≤n≤100。
  2. 根据权利要求1所述的含硒聚酰亚胺聚合物，其特征在于，所述硒醚基团的结构通式为：Ar1-Se-Ar2、Ar3-Se-Se-Ar4或Ar5-Se-Ar6-Se-Ar7-Se-Ar8，其中，Ar1-Ar8独立地选自苯基、苯基衍生物、萘基、萘基衍生物和C2-C15的烷基链中的一种。
  3. 一种如权利要求1或2所述的含硒聚酰亚胺聚合物的制备方法，其特征在于，包括以下步骤：
    (1)将式(II)的硒醚二胺单体与式(III)的二酸酐单体在有机溶剂中发生聚合反应，得到式(IV)的含硒聚酰胺酸；
    (2)将步骤(1)中得到的式(IV)的含硒聚酰胺酸经热亚胺化得到式(V)含硒聚酰亚胺聚合物；
    反应式如下：
    Figure PCTCN2016110235-appb-100002
    其中，2≤n≤100；R为芳香环、芳香环衍生物、脂肪环和脂肪环衍生物中的一种；Ar为硒醚基团。
  4. 根据权利要求3所述的制备方法，其特征在于：步骤(1)中，聚 合反应温度为20-40℃。
  5. 根据权利要求3所述的制备方法，其特征在于：步骤(2)中，热亚胺化温度为60℃-310℃。
  6. 根据权利要求3所述的制备方法，其特征在于：步骤(1)中，式(II)的硒醚二胺单体为4，4′-二氨基二苯基硒醚、4，4′-二氨基二萘基硒醚、2，2′-二氨基二丙基硒醚、6，6′-二氨基二己基硒醚、4，4′-二氨基二苯基二硒醚、4，4′-二氨基二萘基二硒醚、2，2′-二氨基二丙基二硒醚或6，6′-二氨基二己基二硒醚等。
  7. 根据权利要求3所述的制备方法，其特征在于：步骤(2)中，式(III)的二酸酐单体为均苯四甲酸酐、4，4′-氧双邻苯二甲酸酐、4，4′-(六氟异丙烯)二酞酸酐或环丁烷四甲酸二酐。
  8. 根据权利要求6所述的制备方法，其特征在于，4，4′-二氨基二苯基硒醚的制备包括以下步骤：在有机溶剂中，式(I)的对苯胺化合物与硒在105-135℃下反应，反应结束后经还原，得到4，4′-二氨基二苯基硒醚。
    反应式如下：
    Figure PCTCN2016110235-appb-100003
    其中，X为I、Br或Cl。
  9. 根据权利要求8所述的制备方法，其特征在于：所述对苯胺化合物与硒的摩尔比为：9-11∶4-5。
  10. 如权利要求1所述的含硒聚酰亚胺聚合物在制备光学材料中的应用，其特征在于：所述含硒聚酰亚胺聚合物的折光指数值为1.7-1.82。
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KR102103552B1 (ko) * 2018-10-04 2020-04-23 한국과학기술연구원 칼코겐계 디아민, 이로부터 형성된 폴리아믹산과 폴리이미드, 상기 폴리이미드를 포함한 폴리이미드 필름
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CN111808286B (zh) * 2020-07-30 2022-05-03 浙江道明光电科技有限公司 一种分别盛装二胺和二酐的聚酰亚胺胶囊体的制备方法

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