WO2022257351A1 - 一种具有优异光学性能的聚二硫化物材料及其制备方法 - Google Patents

一种具有优异光学性能的聚二硫化物材料及其制备方法 Download PDF

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WO2022257351A1
WO2022257351A1 PCT/CN2021/129202 CN2021129202W WO2022257351A1 WO 2022257351 A1 WO2022257351 A1 WO 2022257351A1 CN 2021129202 W CN2021129202 W CN 2021129202W WO 2022257351 A1 WO2022257351 A1 WO 2022257351A1
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polydisulfide
polymer
metal complex
excellent optical
optical properties
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PCT/CN2021/129202
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French (fr)
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任伟民
巢济岩
乐天俊
吕小兵
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大连理工大学
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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
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/14—Polysulfides
    • C08G75/16—Polysulfides by polycondensation of organic compounds with inorganic polysulfides

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  • the invention belongs to the field of polymer materials, and in particular relates to a polydisulfide polymer material with excellent optical properties and a preparation method thereof.
  • Polydisulfide refers to a polymer material containing disulfide bonds in the main polymer chain.
  • the sulfur atoms introduced in the main chain endow the polymer with excellent optical properties, electrical properties, mechanical properties and self-healing ability.
  • polydisulfides can be prepared by condensation of dihaloalkanes with inorganic persulfides or ring-opening polymerization of cyclic disulfides.
  • the former involves the use of halogenated alkanes and has the problem of high waste emission, which is a non-"green chemistry"approach; while the latter is relatively simple in the structure of the synthesized polydisulfide due to the limitation of monomer types.
  • Penczek realized the copolymerization of epithiopropane and S8 for the first time through anionic polymerization, and synthesized polymers with high sulfur content.
  • the sulfur anion at the end of the chain will undergo a "bite back" reaction, removing an uncertain number of sulfur atoms, resulting in an uncertain number of sulfur atoms in the polymer and an unclear structure.
  • the Penczek research group continued to study the reaction by using sodium benzyl thiolate, and determined that the structure of the polymer was epithioalkane and short-chain polysulfide (such as: disulfide, trisulfide, tetrasulfide) by Raman infrared spectroscopy. etc.) copolymerized structure.
  • Wreczycki et al. used potassium benzyl thiolate as the initiator to realize the copolymerization reaction of phenylephrine and S8 , synthesized the corresponding polysulfide, and studied its thermodynamic properties.
  • the synthesized polymer structure is still an alternating structure of epithioalkanes and short-chain polysulfides.
  • the present invention provides a kind of catalytic system that is made up of metal complex and organic base, the epithioalkane of catalysis and S Copolymerization reaction synthetic polydisulfide method, the obtained polymer has excellent optical performance, Its refractive index is 1.60-1.78, Abbe's number is 26-40, and glass transition temperature is -30-150°C.
  • the polydisulfide material is obtained after solution polymerization, the content of disulfide segments in the polymer main chain is 95-99%, the number-average molecular weight is 1000-5000000g/mol, and the molecular weight distribution is 1.1-2.6.
  • the structure of the metal complex in the adopted catalytic system is as follows:
  • M is Al 3+ , Fe 3+ , Co 3+ , Ni 3+ , Cr 3+ , Mn 3+ or Ru 3+ trivalent metal ion or Mg 2+ , Fe 2+ , Co 2+ , Ni 2+ or Cu 2+ divalent metal ion;
  • X is F -1 , Cl -1 , Br -1 , I -1 , NO 3 -1 , CH 3 COO -1 , CCl 3 COO -1 , CF 3 COO -1 , ClO 4 -1 , BF 4 -1 , BPh 4 -1 , N 3 -1 , PF 6 -1 , SbF 6 -1 , p-toluate, p-toluenesulfonate, o-nitrophenol oxygen, p-nitrophenol oxide, m-nitrophenol oxide, 2,4-dinitrophenol oxide, 3,5-dinitrophenol oxide, 2,4,6-trinitrophenol oxide, 3,5- Dichlorophenoloxy, 3,5-difluor
  • the organic base is selected from triethylamine, tri-n-butylamine, phosphazene base P1, phosphazene base P2, phosphazene base P3, phosphazene base P4, pyridine, piperidine, morpholine, 4-dimethylaminopyridine (DMAP), 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) or 7 -Methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene (MTBD).
  • DMAP 1,8-diazabicyclo[5.4.0]undec-7-ene
  • DBU 1,8-diazabicyclo[5.4.0]undec-7-ene
  • TBD 1,5,7-triazabicyclo[4.4.0]dec-5-ene
  • MTBD 7 -Methyl-1,5,7-triazabic
  • the chain initiator is selected from ethanethiol, propanethiol, n-butanethiol, benzylmercaptan, ethanedithiol, thiophenol, 1,2-propanedithiol, 1,3-propanedithiol, p-dithiol Benzylmercaptan, p-dithiol, cyclohexanedithiol, 2-hydroxyethanethiol, 2-hydroxy-1-propanethiol, 3-hydroxy-1-propanethiol or 2-hydroxy-1-cyclo Hexanol.
  • the molar ratio of the metal complex to the organic base is 1:0.5-10, preferably 1:1.
  • the episulfide alkane that adopts is epithiopropane, epithioethane, epithiobutane, epithiohexane, isopropoxyphenyl epithiopropane, phenyl thiophene, benzyl thioethane, cyclosulfide Thiocyclohexane, thiocyclopentane, thiocycloheptane, 2,3-thiobutane, 3,4-thiotetrahydrofuran, 3,5-dioxathione, 2,3-cyclo One of sulfur-1,2,3,4-tetralin.
  • the molar ratio of the epithioalkane to the elemental sulfur S8 is 1-12:1; the molar ratio of the epithioalkane to the metal complex is 100-100000:1.
  • the molar ratio of the chain initiator to the metal complex is 0-100:1, preferably 1:10.
  • the polymerization reaction is carried out at -20-120° C. for 0.1-24 hours.
  • the polymerization reaction is carried out as in a solution, and the solvent used is selected from toluene, trichlorobenzene, tetrahydrofuran, xylene, diglyme, diglyme, and 1,4-dioxane any kind.
  • the polydisulfide obtained in the present invention is obtained through the polymerization of elemental sulfur (S 8 ) and epithioalkane, and epithioalkane has a wide range of sources, so various polydisulfides can be prepared;
  • the obtained polydisulfide has no polyether chain segment
  • the optical performance of the polymer is greatly improved compared with similar products.
  • FIG. 1 is the 1 H NMR chart of the polymer product obtained in Example 1.
  • Fig. 2 is the Raman infrared spectrogram of the polymerization product obtained in Example 1.
  • Example 3 is a differential scanning calorimetry diagram of the polymer product obtained in Example 1.
  • Fig. 4 is the thermogravimetric analysis curve of polymer obtained in embodiment 1.
  • FIG. 5 is a curve of the refractive index of the polymer product obtained in Example 1 as a function of wavelength.
  • the epithioalkane used and the serial number of the catalyst are shown in the following formula.
  • R groups in the complexes used are named as follows:
  • a 10mL Schlenk bar bottle equipped with a magnet was dried at 130°C for more than 12 hours, vacuumized and cooled to room temperature, and filled with nitrogen for use. Under the protection of nitrogen, weigh a certain amount of metal complex catalyst 2a and co-catalyst organic base MTBD into the bottle at room temperature, and the molar ratio of metal complex catalyst to co-catalyst is 1/1. Add S8 and episulfide alkane 1a again, the mol ratio of episulfide alkane and S8 and metal complex catalyst is 100/100/1. After sealing the strip bottle, place it in an oil bath preheated to 25° C., and start stirring. Reaction to the appointed time, stop stirring.
  • the polydisulfide segment content is 99%, the molecular weight M n of the obtained polymer is 9.3 kg/mol, and the molecular weight distribution is 1.16.
  • the differential scanning calorimetry and thermogravimetric analysis curves of the polymer are shown in Figure 3 and Figure 4, respectively. It can be seen from the figure that the glass transition temperature of the polymer is –14°C, and the thermal decomposition temperature of 50% weight loss is 194.5°C.
  • the curve of the refractive index of the polymer as a function of light wavelength is shown in Figure 5, and its refractive index at a wavelength of 589.6 nm is 1.712. After calculation, the Abbe number of this polymer is 32.
  • a 10mL Schlenk bar bottle equipped with a magnet was dried at 130°C for more than 12 hours, vacuumized and cooled to room temperature, and filled with nitrogen for use. Under nitrogen protection, weigh a certain amount of metal complex catalyst 2b and cocatalyst organic base MTBD and benzyl mercaptan at room temperature and add them to the bottle. The molar ratio of metal complex catalyst to organic base and benzyl mercaptan is 1/1/1 . Then add S 8 and episulfide alkane 1a, the mol ratio of episulfide alkane to S 8 and metal complex catalyst is 500/500/1. After sealing the strip bottle, place it in an oil bath preheated to 25° C., and start stirring.
  • reaction polymer Reaction to the appointed time, stop stirring. A very small amount of the reaction mixture was taken out for 1 H NMR and GPC testing, and the remaining reaction polymer was purified. Purification of the polymer: first dissolve the crude product in a small amount of dichloromethane, then add a large amount of methanol, and stir vigorously to precipitate the polymer. Repeat this process repeatedly to obtain a yellow polymer, which is vacuum-dried before use.
  • the polydisulfide segment content is 96%
  • the molecular weight M n of the obtained polymer is 48.9 kg/mol
  • the molecular weight distribution is 1.28.
  • the polymer has a refractive index of 1.703. After calculation, its Abbe number is 33.
  • a 10mL Schlenk bar bottle equipped with a magnet was dried at 130°C for more than 12 hours, vacuumized and cooled to room temperature, and filled with nitrogen for use. Under the protection of nitrogen, weigh a certain amount of metal complex catalyst 2c and cocatalyst organic base MTBD and ethanethiol at room temperature and add them to the bottle. The molar ratio of metal complex catalyst to organic base and ethanethiol is 1/1/10 . Then add S 8 and episulfide alkane 1a, the mol ratio of episulfide alkane to S 8 and metal complex catalyst is 1000/250/1. After sealing the strip bottle, place it in an oil bath preheated to 25° C., and start stirring. Reaction to the appointed time, stop stirring.
  • reaction mixture A very small amount of the reaction mixture was taken out for 1 H NMR and GPC testing, and the remaining reaction polymer was purified. Purification of the polymer: first dissolve the crude product in a small amount of dichloromethane, then add a large amount of methanol, and stir vigorously to precipitate the polymer. Repeat this process repeatedly to obtain a yellow polymer, which is vacuum-dried before use.
  • the polydisulfide segment content is 99%, the molecular weight M n of the obtained polymer is 10.3 kg/mol, and the molecular weight distribution is 1.10.
  • the polymer has a refractive index of 1.698. After calculation, its Abbe number is 34.
  • a 10mL Schlenk bar bottle equipped with a magnet was dried at 130°C for more than 12 hours, vacuumized and cooled to room temperature, and filled with nitrogen for use. Under nitrogen protection, weigh a certain amount of metal complex catalyst 2a and cocatalyst organic base MTBD and ethanedithiol at room temperature and add them to the bottle. The molar ratio of metal complex catalyst to organic base and ethanedithiol is 1/2 /50. Add S 8 and episulfide alkane 1b again, the mol ratio of episulfide alkane to S 8 and metal complex catalyst is 5000/1250/1. After sealing the strip bottle, place it in an oil bath preheated to 25° C., and start stirring. Reaction to the appointed time, stop stirring.
  • reaction mixture A very small amount of the reaction mixture was taken out for 1 H NMR and GPC testing, and the remaining reaction polymer was purified. Purification of the polymer: first dissolve the crude product in a small amount of dichloromethane, then add a large amount of methanol, and stir vigorously to precipitate the polymer. Repeat this process repeatedly to obtain a yellow polymer, which is vacuum-dried before use.
  • the polydisulfide segment content is 99%, the molecular weight M n of the obtained polymer is 9.3 kg/mol, and the molecular weight distribution is 1.18.
  • the polymer has a refractive index of 1.693. After calculation, its Abbe number is 37.
  • a 10mL Schlenk bar bottle equipped with a magnet was dried at 130°C for more than 12 hours, vacuumized and cooled to room temperature, and filled with nitrogen for use. Under the protection of nitrogen, weigh a certain amount of metal complex catalyst 2e and cocatalyst organic base MTBD and propanethiol at room temperature and add them into the bottle. The molar ratio of metal complex catalyst to organic base and benzyl mercaptan is 1/4/ 100. Add S 8 and episulfide alkane 1c again, the mol ratio of episulfide alkane to S 8 and metal complex catalyst is 10000/1250/1. After sealing the strip bottle, place it in an oil bath preheated to 25° C., and start stirring. Reaction to the appointed time, stop stirring.
  • reaction mixture A very small amount of the reaction mixture was taken out for 1 H NMR and GPC testing, and the remaining reaction polymer was purified. Purification of the polymer: first dissolve the crude product in a small amount of dichloromethane, then add a large amount of methanol, and stir vigorously to precipitate the polymer. Repeat this process repeatedly to obtain a yellow polymer, which is vacuum-dried before use.
  • the polydisulfide segment content is 99%, the molecular weight M n of the obtained polymer is 9.3 kg/mol, and the molecular weight distribution is 2.01.
  • the polymer has a refractive index of 1.709. After calculation, its Abbe number is 33.
  • a 10mL Schlenk bar bottle equipped with a magnet was dried at 130°C for more than 12 hours, vacuumized and cooled to room temperature, and filled with nitrogen for use. Under nitrogen protection, weigh a certain amount of metal complex catalyst 2f and cocatalyst organic base triethylamine and n-butanethiol at room temperature and add it to the bottle.
  • the molar ratio of metal complex catalyst to organic base and n-butanethiol is 1/ 10/1.
  • S8 and episulfide alkane 1d the molar ratio of episulfide alkane to S8 and metal complex catalyst is 10000/1250/1. After sealing the strip bottle, place it in an oil bath preheated to 25° C., and start stirring.
  • reaction polymer Reaction to the appointed time, stop stirring. A very small amount of the reaction mixture was taken out for 1 H NMR and GPC testing, and the remaining reaction polymer was purified. Purification of the polymer: first dissolve the crude product in a small amount of dichloromethane, then add a large amount of methanol, and stir vigorously to precipitate the polymer. Repeat this process repeatedly to obtain a yellow polymer, which is vacuum-dried before use.
  • the polydisulfide segment content is 99%, the molecular weight M n of the obtained polymer is 90.3 kg/mol, and the molecular weight distribution is 1.91.
  • the polymer has a refractive index of 1.68. After calculation, its Abbe number is 35.
  • a 10mL Schlenk bar bottle equipped with a magnet was dried at 130°C for more than 12 hours, vacuumized and cooled to room temperature, and filled with nitrogen for use. Under the protection of nitrogen, weigh a certain amount of metal complex catalyst 2g and co-catalyst organic base MTBD and 1,2-propanedithiol at room temperature and add them to the bottle, the metal complex catalyst and organic base and 1,2-propanedithiol
  • the molar ratio of alcohol is 0.5/1/10.
  • Add S8 and episulfide alkane 1e again, the mol ratio of episulfide alkane to S8 and metal complex catalyst is 10000/1250/1. After sealing the strip bottle, place it in an oil bath preheated to 25° C., and start stirring.
  • reaction polymer Reaction to the appointed time, stop stirring. A very small amount of the reaction mixture was taken out for 1 H NMR and GPC testing, and the remaining reaction polymer was purified. Purification of the polymer: first dissolve the crude product in a small amount of dichloromethane, then add a large amount of methanol, and stir vigorously to precipitate the polymer. Repeat this process repeatedly to obtain a yellow polymer, which is vacuum-dried before use.
  • the polydisulfide segment content was 97%
  • the molecular weight M n of the obtained polymer was 889.3 kg/mol
  • the molecular weight distribution was 1.27.
  • the polymer has a refractive index of 1.64. After calculation, its Abbe number is 40.
  • a 10mL Schlenk bar bottle equipped with a magnet was dried at 130°C for more than 12 hours, vacuumized and cooled to room temperature, and filled with nitrogen for use. Under the protection of nitrogen, weigh a certain amount of metal complex catalyst at room temperature for 2h and cocatalyst organic base triethylamine and thiophenol into the bottle, the molar ratio of metal complex catalyst to organic base and thiophenol is 1/1 /50.
  • Add S8 and episulfide alkane 1f again, the mol ratio of episulfide alkane and S8 and catalyst is 60000/5000/1. After sealing the strip bottle, place it in an oil bath preheated to 25° C., and start stirring. Reaction to the appointed time, stop stirring.
  • reaction mixture A very small amount of the reaction mixture was taken out for 1 H NMR and GPC testing, and the remaining reaction polymer was purified. Purification of the polymer: first dissolve the crude product in a small amount of dichloromethane, then add a large amount of methanol, and stir vigorously to precipitate the polymer. Repeat this process repeatedly to obtain a yellow polymer, which is vacuum-dried before use.
  • the polydisulfide segment content is 95%
  • the molecular weight M n of the obtained polymer is 5000.3 kg/mol
  • the molecular weight distribution is 2.6.
  • the polymer has a refractive index of 1.66. After calculation, its Abbe number is 38.
  • a 10mL Schlenk bar bottle equipped with a magnet was dried at 130°C for more than 12 hours, vacuumized and cooled to room temperature, and filled with nitrogen for use. Under the protection of nitrogen, weigh a certain amount of metal complex catalyst 2i and cocatalyst organic base morpholine and p-dibenzyl mercaptan at room temperature and add them to the bottle.
  • the molar ratio of metal complex catalyst to organic base and p-dibenzyl mercaptan is 1/1/10.
  • Add S8 and episulfide alkane 1g again, the mol ratio of episulfide alkane and S8 and metal complex catalyst is 10000/1250/1.
  • reaction polymer After sealing the strip bottle, place it in an oil bath preheated to 25° C., and start stirring. Reaction to the appointed time, stop stirring. A very small amount of the reaction mixture was taken out for 1 H NMR and GPC testing, and the remaining reaction polymer was purified. Purification of the polymer: first dissolve the crude product in a small amount of dichloromethane, then add a large amount of methanol, and stir vigorously to precipitate the polymer. Repeat this process repeatedly to obtain a yellow polymer, which is vacuum-dried before use. The polydisulfide segment content is 99%, the molecular weight M n of the obtained polymer is 96.3 kg/mol, and the molecular weight distribution is 1.10. The polymer has a refractive index of 1.71. After calculation, its Abbe number is 32.
  • a 10mL Schlenk bar bottle equipped with a magnet was dried at 130°C for more than 12 hours, vacuumized and cooled to room temperature, and filled with nitrogen for use. Under nitrogen protection, weigh a certain amount of metal complex catalyst 2j and cocatalyst organic base triethylamine and 2-hydroxyethanethiol at room temperature and add them to the bottle.
  • the molar ratio of metal complex catalyst to organic base and benzyl mercaptan is 1/1/1.
  • S 8 and episulfide alkane for 1 h the molar ratio of episulfide alkane to S 8 and the metal complex catalyst is 10000/1250/1.
  • the strip bottle was sealed, placed in an oil bath preheated to 25° C., and started stirring. Reaction to the appointed time, stop stirring. A very small amount of the reaction mixture was taken out for 1 H NMR and GPC testing, and the remaining reaction polymer was purified. Purification of the polymer: first dissolve the crude product in a small amount of dichloromethane, then add a large amount of methanol, and stir vigorously to precipitate the polymer. Repeat this process repeatedly to obtain a yellow polymer, which is vacuum-dried before use.
  • the polydisulfide segment content is 99%, the molecular weight M n of the obtained polymer is 963.2 kg/mol, and the molecular weight distribution is 1.18.
  • the polymer has a refractive index of 1.712. After calculation, its Abbe number is 37.
  • a 10mL Schlenk bar bottle equipped with a magnet was dried at 130°C for more than 12 hours, vacuumized and cooled to room temperature, and filled with nitrogen for use. Under nitrogen protection, take a certain amount of metal complex catalyst 2k and cocatalyst organic base triethylamine and 2-hydroxyethanethiol at room temperature and add in the bottle, the mixture of metal complex catalyst and organic base and 2-hydroxypropanethiol The molar ratio is 1/1/10. Then add S 8 and episulfide alkane 1i, the molar ratio of episulfide alkane to S 8 and metal complex catalyst is 10000/1250/1.
  • the strip bottle was sealed, placed in an oil bath preheated to 50° C., and started stirring. Reaction to the appointed time, stop stirring. A very small amount of the reaction mixture was taken out for 1 H NMR and GPC testing, and the remaining reaction polymer was purified. Purification of the polymer: first dissolve the crude product in a small amount of dichloromethane, then add a large amount of methanol, and stir vigorously to precipitate the polymer. Repeat this process repeatedly to obtain a yellow polymer, which is vacuum-dried before use.
  • the polydisulfide segment content is 99%, the molecular weight M n of the obtained polymer is 93.2 kg/mol, and the molecular weight distribution is 1.28.
  • the polymer has a refractive index of 1.68. After calculation, its Abbe number is 35.
  • a 10mL Schlenk bar bottle equipped with a magnet was dried at 130°C for more than 12 hours, vacuumized and cooled to room temperature, and filled with nitrogen for use. Under the protection of nitrogen, weigh a certain amount of metal complex catalyst 2l and cocatalyst organic base tri-n-butylamine and 2-hydroxypropanethiol at room temperature and add them to the bottle, and the metal complex catalyst and organic base and 2-hydroxypropanethiol The molar ratio is 1/1/50. Then add S 8 and episulfide alkane 1j, the molar ratio of episulfide alkane to S 8 and metal complex catalyst is 500/500/1.
  • the strip bottle was sealed, placed in an oil bath preheated to 80° C., and started stirring. Reaction to the appointed time, stop stirring. A very small amount of the reaction mixture was taken out for 1 H NMR and GPC testing, and the remaining reaction polymer was purified. Purification of the polymer: first dissolve the crude product in a small amount of dichloromethane, then add a large amount of methanol, and stir vigorously to precipitate the polymer. Repeat this process repeatedly to obtain a yellow polymer, which is vacuum-dried before use.
  • the polydisulfide segment content is 97%, the molecular weight M n of the obtained polymer is 1.0 kg/mol, and the molecular weight distribution is 1.38.
  • the polymer has a refractive index of 1.763. After calculation, its Abbe number is 41.
  • a 10mL Schlenk bar bottle equipped with a magnet was dried at 130°C for more than 12 hours, vacuumized and cooled to room temperature, and filled with nitrogen for use. Under the protection of nitrogen, weigh a certain amount of metal complex catalyst 2a and cocatalyst organic base pyridine and 3-hydroxyl-1-propanethiol at room temperature and add them to the bottle, the metal complex catalyst and organic base and 3-hydroxyl-1-
  • the molar ratio of propanethiol is 1/1/50.
  • S8 and episulfide alkane 1k the molar ratio of episulfide alkane to S8 and metal complex catalyst is 500/500/1.
  • the polydisulfide segment content is 98%, the molecular weight M n of the obtained polymer is 1.1 kg/mol, and the molecular weight distribution is 1.8.
  • the polymer has a refractive index of 1.779. After calculation, its Abbe number is 31.
  • a 10mL Schlenk bar bottle equipped with a magnet was dried at 130°C for more than 12 hours, vacuumized and cooled to room temperature, and filled with nitrogen for use. Under the protection of nitrogen, weigh a certain amount of metal complex catalyst 2c and co-catalyst organic base piperidine into the bottle at room temperature, and the molar ratio of metal complex catalyst to co-catalyst is 1/1. Then add S 8 and episulfide alkane 1l, the molar ratio of episulfide alkane to S 8 and metal complex catalyst is 500/500/1.
  • the strip bottle was sealed, placed in an oil bath preheated to 120° C., and started stirring. Reaction to the appointed time, stop stirring. A very small amount of the reaction mixture was taken out for 1 H NMR and GPC testing, and the remaining reaction polymer was purified. Purification of the polymer: first dissolve the crude product in a small amount of dichloromethane, then add a large amount of methanol, and stir vigorously to precipitate the polymer. Repeat this process repeatedly to obtain a yellow polymer, which is vacuum-dried before use.
  • the polydisulfide segment content is 95%, the molecular weight M n of the obtained polymer is 48.0 kg/mol, and the molecular weight distribution is 2.59.
  • the polymer has a refractive index of 1.743. After calculation, its Abbe number is 46.
  • a 10mL Schlenk bar bottle equipped with a magnet was dried at 130°C for more than 12 hours, vacuumized and cooled to room temperature, and filled with nitrogen for use. Under the protection of nitrogen, weigh a certain amount of metal complex catalyst 2c and cocatalyst organic base DMAP into the bottle at room temperature, and the molar ratio of metal complex catalyst to cocatalyst is 1/1. Then add S 8 and episulfide alkane 1a, the mol ratio of episulfide alkane to S 8 and metal complex catalyst is 500/500/1. Finally, after adding xylene equal to the volume of epithioalkane as a solvent, the strip bottle was sealed, placed in an oil bath cooled to 0° C., and started stirring.
  • reaction polymer Reaction to the appointed time, stop stirring. A very small amount of the reaction mixture was taken out for 1 H NMR and GPC testing, and the remaining reaction polymer was purified. Purification of the polymer: first dissolve the crude product in a small amount of dichloromethane, then add a large amount of methanol, and stir vigorously to precipitate the polymer. Repeat this process repeatedly to obtain a yellow polymer, which is vacuum-dried before use.
  • the polydisulfide segment content is 99%, the molecular weight M n of the obtained polymer is 46.6 kg/mol, and the molecular weight distribution is 1.12.
  • the polymer has a refractive index of 1.710. After calculation, its Abbe number is 32.
  • a 10mL Schlenk bar bottle equipped with a magnet was dried at 130°C for more than 12 hours, vacuumized and cooled to room temperature, and filled with nitrogen for use. Under the protection of nitrogen, weigh a certain amount of metal complex catalyst 2a and co-catalyst organic base DBU into the bottle at room temperature, and the molar ratio of metal complex catalyst to co-catalyst is 1/1. Then add S 8 and episulfide alkane 1a, the mol ratio of episulfide alkane to S 8 and metal complex catalyst is 500/500/1.
  • the strip bottle was sealed, placed in an oil bath preheated to -10°C, and started stirring. Reaction to the appointed time, stop stirring. A very small amount of the reaction mixture was taken out for 1 H NMR and GPC testing, and the remaining reaction polymer was purified. Purification of the polymer: first dissolve the crude product in a small amount of dichloromethane, then add a large amount of methanol, and stir vigorously to precipitate the polymer. Repeat this process repeatedly to obtain a yellow polymer, which is vacuum-dried before use.
  • a 10mL Schlenk bar bottle equipped with a magnet was dried at 130°C for more than 12 hours, vacuumized and cooled to room temperature, and filled with nitrogen for use. Under the protection of nitrogen, weigh a certain amount of metal complex catalyst 2a and cocatalyst organic phosphazene base tBu -P1 into the bottle at room temperature, and the molar ratio of metal complex catalyst to cocatalyst is 1/1. Add S 8 and episulfide alkane 1a again, the mol ratio of episulfide alkane to S 8 and metal complex catalyst is 4000/500/1.
  • the polydisulfide segment content is 99%, the molecular weight M n of the obtained polymer is 50.6 kg/mol, and the molecular weight distribution is 1.10.
  • the polymer has a refractive index of 1.708. After calculation, its Abbe number is 33.
  • reaction mixture A very small amount of the reaction mixture was taken out for 1 H NMR and GPC testing, and the remaining reaction polymer was purified. Purification of the polymer: first dissolve the crude product in a small amount of dichloromethane, then add a large amount of methanol, and stir vigorously to precipitate the polymer. Repeat this process repeatedly to obtain a yellow polymer, which is vacuum-dried before use.
  • the polydisulfide segment content is 99%, the molecular weight M n of the obtained polymer is 416.6 kg/mol, and the molecular weight distribution is 1.12.
  • the polymer has a refractive index of 1.7011. After calculation, its Abbe number is 33.
  • a 10mL Schlenk bar bottle equipped with a magnet was dried at 130°C for more than 12 hours, vacuumized and cooled to room temperature, and filled with nitrogen for use. Under the protection of nitrogen, weigh a certain amount of metal complex catalyst 2a and cocatalyst organic phosphazene base tBu -P3 into the bottle at room temperature, and the molar ratio of metal complex catalyst to cocatalyst is 1/1. Add S 8 and episulfide alkane 1a again, the mol ratio of episulfide alkane to S 8 and metal complex catalyst is 4000/500/1. After sealing the strip bottle, place it in an oil bath preheated to 25° C., and start stirring. Reaction to the appointed time, stop stirring.
  • reaction mixture A very small amount of the reaction mixture was taken out for 1 H NMR and GPC testing, and the remaining reaction polymer was purified. Purification of the polymer: first dissolve the crude product in a small amount of dichloromethane, then add a large amount of methanol, and stir vigorously to precipitate the polymer. Repeat this process repeatedly to obtain a yellow polymer, which is vacuum-dried before use.
  • the polydisulfide segment content is 99%, the molecular weight M n of the obtained polymer is 40.9 kg/mol, and the molecular weight distribution is 1.23.
  • the polymer has a refractive index of 1.69. After calculation, its Abbe number is 38.
  • a 10mL Schlenk bar bottle equipped with a magnet was dried at 130°C for more than 12 hours, vacuumized and cooled to room temperature, and filled with nitrogen for use. Under the protection of nitrogen, weigh a certain amount of metal complex catalyst 2a and cocatalyst organic phosphazene base tBu -P4 into the bottle at room temperature, and the molar ratio of metal complex catalyst to cocatalyst is 1/1. Add S 8 and episulfide alkane 1a again, the mol ratio of episulfide alkane to S 8 and metal complex catalyst is 4000/500/1. After sealing the strip bottle, place it in an oil bath preheated to 25° C., and start stirring. Reaction to the appointed time, stop stirring.
  • reaction mixture A very small amount of the reaction mixture was taken out for 1 H NMR and GPC testing, and the remaining reaction polymer was purified. Purification of the polymer: first dissolve the crude product in a small amount of dichloromethane, then add a large amount of methanol, and stir vigorously to precipitate the polymer. Repeat this process repeatedly to obtain a yellow polymer, which can be used after vacuum drying.
  • the content of the sulfide segment is 99%, the molecular weight M n of the obtained polymer is 39.9 kg/mol, and the molecular weight distribution is 1.26. .
  • the polymer has a refractive index of 1.708. After calculation, its Abbe number is 32.
  • a 10mL Schlenk bar bottle equipped with a magnet was dried at 130°C for more than 12 hours, vacuumized and cooled to room temperature, and filled with nitrogen for use. Under the protection of nitrogen, weigh a certain amount of metal complex catalyst 2a and cocatalyst organic base TBD into the bottle at room temperature, and the molar ratio of metal complex catalyst to cocatalyst is 1/1. Add S 8 and episulfide alkane 1a again, the mol ratio of episulfide alkane to S 8 and metal complex catalyst is 4000/500/1. After sealing the strip bottle, place it in an oil bath preheated to 25° C., and start stirring. Reaction to the appointed time, stop stirring.

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Abstract

本发明公开了一种具有优异光学性能的聚二硫化物材料及其制备方法，属于高分子材料领域。所述的聚二硫化物是环硫烷烃与单质硫在催化剂的作用下共聚形成聚二硫化物。该聚二硫化物主链中二硫链段含量为95～99％。本发明提出的聚二硫化物材料具有高折射率、高阿贝数以及高透光性等优点。

Description

一种具有优异光学性能的聚二硫化物材料及其制备方法 技术领域
本发明属于高分子材料领域，具体涉及一种具有优异光学性能的聚二硫化物高分子材料及其制备方法。
背景技术
石油、煤等非再生资源的开发利用为人类生产生活带来方便的同时，其使用过程中的脱硫处理造成了硫在人类生活圈的大量富集。因此，开发利用丰富的硫资源对于促进硫循环以及人类生产生活具有重要的意义。硫元素的一种重要的利用形式是将其引入到聚合物主链中。硫原子的引入往往会赋予材料优异的光学性能、电性能、机械性能、自修复性能以及对重金属的吸附能力。在众多含硫聚合物中、聚二硫化物以其优异的光学性能、生物性能以及自修复能力引起了越来越多的关注。
聚二硫化物是指聚合物主链中含有二硫键的高分子材料。主链中引入的硫原子使得聚合物具有优异的光学性能、电性能、机械性能以及自修复能力等。最初，聚二硫化物可以通过双卤代烷烃与无机过硫化盐缩合反应或者环状二硫化物的开环聚合反应制备。前者涉及卤代烷烃的使用且存在高排废问题，是一个非“绿色化学”途径；而后者由于单体种类的局限性，所合成的聚二硫化物的结构比较单一。1978年，Penczek通过阴离子聚合的方式首次实现了环硫丙烷与S 8的共聚反应，合成出高硫含量的聚合物。但是，由于硫硫键具有较低的键能，因此链末端的硫负离子会发生“回咬”反应，脱去不确定数目的硫原子，导致聚合物中硫原子数目不确定，结构不明确。随后，Penczek课题组采用苄硫醇钠继续对该反应继续研究，并通过拉曼红外光谱确定了聚合物的结构为环硫烷烃与短链多硫化物(如：二硫、三硫、四硫等)共聚的结构。2020年，Wreczycki等以 苄硫醇钾为引发剂，实现了苯基环硫乙烷与S 8的共聚反应，合成出相应的聚多硫化物，并对其热力学性能进行了研究。然而，经过结构表征，所合成的聚合物结构仍然是环硫烷烃与的短链多硫化物交替的结构。
上述表明，环硫烷烃与S 8共聚反应是构建聚多硫化物的有效方法。结构种类丰富的环硫烷烃为构建结构多样化的聚二硫化物提供了有力保障。然而，由于缺乏对反应的控制，所合成的聚合物结构混乱，无法合成结构明确的聚二硫聚合物。
发明内容
针对上述问题，本发明提供了一种由金属配合物和有机碱组成的催化体系，催化的环硫烷烃与S 8共聚反应合成聚二硫化物的方法，所得聚合物的具有优异的光学性能，其折射率为1.60～1.78，阿贝数为：26～40，玻璃化温度为：–30～150℃。
上述路线是在基于发明人对配位聚合机理以及酸解协同催化机理的理解，并结合前期关于含硫聚合物的研究基础下提出的。
为了实现上述目的，本发明采用的技术方案如下，
一种具有优异光学性能的聚二硫化物材料，以单质硫与环硫烷烃为原料，采用由金属配合物和有机碱组成的催化体系，在有或者无链引发剂存在下，经本体聚合或者溶液聚合后得到所述的聚二硫化物材料，聚合物主链中二硫链段含量为95～99％，数均分子量为1000～5000000g/mol，分子量分布为1.1～2.6。
所采用的催化体系中金属配合物的结构如下：
Figure PCTCN2021129202-appb-000001
Figure PCTCN2021129202-appb-000002
式中：
Figure PCTCN2021129202-appb-000003
M为Al 3+、Fe 3+、Co 3+、Ni 3+、Cr 3+、Mn 3+或Ru 3+三价金属离子或Mg 2+、Fe 2+、 Co 2+、Ni 2+或Cu 2+二价金属离子；X为F -1、Cl -1、Br -1、I -1、NO 3 -1、CH 3COO -1、CCl 3COO -1、CF 3COO -1、ClO 4 -1、BF 4 -1、BPh 4 -1、N 3 -1、PF 6 -1、SbF 6 -1、对甲基苯甲酸根、对甲基苯磺酸根、邻-硝基苯酚氧、对-硝基苯酚氧、间-硝基苯酚氧、2,4-二硝基苯酚氧、3,5-二硝基苯酚氧、2,4,6-三硝基苯酚氧、3,5-二氯苯酚氧、3,5-二氟苯酚氧、3,5-二-三氟甲基苯酚氧或五氟酚氧负离子；R 1是H、C 1～C 6烷基、C 1～C 6烷氧基、Cl、Br或NO 2基团。
有机碱选用三乙胺、三正丁胺、磷腈碱P1、磷腈碱P2、磷腈碱P3、磷腈碱P4、吡啶、哌啶、吗啉、4-二甲氨基吡啶(DMAP)、1,8-二氮杂二环[5.4.0]十一碳-7-烯(DBU)、1,5,7-三氮杂双环[4.4.0]癸-5-烯(TBD)或7-甲基-1,5,7-三氮杂双环[4.4.0]癸-5-烯(MTBD)。
链引发剂选用乙硫醇、丙硫醇、正丁硫醇、苄硫醇、乙二硫醇、苯硫酚、1,2-丙二硫醇、1,3-丙二硫醇、对二苄硫醇、对二苯硫酚、环己二硫醇、2-羟基乙硫醇、2-羟基-1-丙硫醇、3-羟基-1-丙硫醇或2-羟基-1-环己醇。
进一步地，金属配合物与有机碱的摩尔比为1:0.5～10，优选1:1。
所采用的环硫烷烃为环硫丙烷、环硫乙烷、环硫丁烷、环硫己烷、异丙氧基苯环硫丙烷、苯基环硫乙烷、苄基环硫乙烷、环硫环己烷、环硫环戊烷、环硫环庚烷、2,3-环硫丁烷、3,4-环硫四氢呋喃、3,5-二氧杂环硫烷烃、2,3-环硫-1,2,3,4-四氢化萘中的一种。
所述环硫烷烃与单质硫S 8的摩尔比例为1～12:1；环硫烷烃与金属配合物的摩尔比为100～100000:1。
所述链引发剂与金属配合物的摩尔比为0～100:1，优选比例1:10。
所述聚合反应在–20～120℃下进行0.1～24h。
所述聚合反应如在溶液下进行，所采用的溶剂选自甲苯、三氯苯、四氢呋 喃、二甲苯、二乙醇二甲醚、二乙二醇二甲醚、1,4-二氧六环中任意一种。
相比于现有技术，本发明显著的有益效果：
1、本发明所得到的聚二硫化物，是通过单质硫(S 8)与环硫烷烃聚合而来，环硫烷烃来源广泛，因此可制备多种聚二硫化物；
2、反应条件温和，催化剂活性高，聚合物选择性高；
3、所得聚二硫化物无聚醚链段；
4、聚合物光学性能比同类产品有较大提高。
附图说明
图1为实施例1中所得聚合产物的 1H NMR图。
图2为实施例1中所得聚合产物的拉曼红外光谱图。
图3为实施例1中所得聚合产物的差示扫描量热图。
图4为实施例1中所得聚合物的热失重分析曲线。
图5为实施例1中所得聚合产物的折射率随波长变化曲线。
具体实施方式
为了具体地描述本发明，下面结合附图及具体实施方式对本发明的技术方案进行详细说明。
本发明中，所使用的环硫烷烃和催化剂序号如下式中所示。
Figure PCTCN2021129202-appb-000004
Figure PCTCN2021129202-appb-000005
所使用的配合物中R基团命名如下：
Figure PCTCN2021129202-appb-000006
实施例1
配有磁子的10mL Schlenk条形瓶在130℃干燥12h以上，抽真空待其冷却至室温，充入氮气准备使用。在氮气保护下，室温称取一定量的金属配合物催化剂2a和助催化剂有机碱MTBD加入瓶中，金属配合物催化剂与助催化剂 的摩尔比为1/1。再加入S 8和环硫烷烃1a，环硫烷烃与S 8及金属配合物催化剂的摩尔比为100/100/1。将条形瓶密封后，置于事先预热至25℃的油浴中，并开启搅拌。反应到约定时间，停止搅拌。取出极少量的反应混合物，用于进行 1H NMR和GPC测试，将剩余的反应聚合物进行提纯。聚合物的提纯：先将粗品溶于少量的二氯甲烷，再加入大量甲醇，并剧烈搅拌，使聚合物沉淀出来，反复重复此过程，可得到黄色聚合物，经真空干燥后待用。本实施例制备的聚二硫化物的 1H NMR和 13C NMR谱分别如图1、图2所示，从图中可知聚合物链段中没有聚硫醚单元，表明具有完全的交替结构。聚二硫化物链段含量为99％，所得聚合物分子量M n为9.3kg/mol，分子量分布为1.16。该聚合物的差示扫描量热图和热失重分析曲线分别如图3和图4所示。从图中可知，聚合物的玻璃化温度为–14℃，失重50％质量的热分解温度为194.5℃。此聚合物折射率随光波长变化曲线如图5所示，其在波长为589.6nm处的折射率为1.712。经过计算，此聚合物的阿贝数位32。
实施例2
配有磁子的10mL Schlenk条形瓶在130℃干燥12h以上，抽真空待其冷却至室温，充入氮气准备使用。在氮气保护下，室温称取一定量的金属配合物催化剂2b和助催化剂有机碱MTBD和苄硫醇加入瓶中，金属配合物催化剂与有机碱以及苄硫醇的摩尔比为1/1/1。再加入S 8和环硫烷烃1a，环硫烷烃与S 8及金属配合物催化剂的摩尔比为500/500/1。将条形瓶密封后，置于事先预热至25℃的油浴中，并开启搅拌。反应到约定时间，停止搅拌。取出极少量的反应混合物，用于进行 1H NMR和GPC测试，将剩余的反应聚合物进行提纯。聚合物的提纯：先将粗品溶于少量的二氯甲烷，再加入大量甲醇，并剧烈搅拌，使聚合物沉淀出来，反复重复此过程，可得到黄色聚合物，经真空干燥后待用。 聚二硫化物链段含量为96％，所得聚合物分子量M n为48.9kg/mol，分子量分布为1.28。此聚合物的折射率为1.703。经过计算，其阿贝数位33。
实施例3
配有磁子的10mL Schlenk条形瓶在130℃干燥12h以上，抽真空待其冷却至室温，充入氮气准备使用。在氮气保护下，室温称取一定量的金属配合物催化剂2c和助催化剂有机碱MTBD和乙硫醇加入瓶中，金属配合物催化剂与有机碱以及乙硫醇的摩尔比为1/1/10。再加入S 8和环硫烷烃1a，环硫烷烃与S 8及金属配合物催化剂的摩尔比为1000/250/1。将条形瓶密封后，置于事先预热至25℃的油浴中，并开启搅拌。反应到约定时间，停止搅拌。取出极少量的反应混合物，用于进行 1H NMR和GPC测试，将剩余的反应聚合物进行提纯。聚合物的提纯：先将粗品溶于少量的二氯甲烷，再加入大量甲醇，并剧烈搅拌，使聚合物沉淀出来，反复重复此过程，可得到黄色聚合物，经真空干燥后待用。聚二硫化物链段含量为99％，所得聚合物分子量M n为10.3kg/mol，分子量分布为1.10。此聚合物的折射率为1.698。经过计算，其阿贝数位34。
实施例4
配有磁子的10mL Schlenk条形瓶在130℃干燥12h以上，抽真空待其冷却至室温，充入氮气准备使用。在氮气保护下，室温称取一定量的金属配合物催化剂2a和助催化剂有机碱MTBD和乙二硫醇加入瓶中，金属配合物催化剂与有机碱以及乙二硫醇的摩尔比为1/2/50。再加入S 8和环硫烷烃1b，环硫烷烃与S 8及金属配合物催化剂的摩尔比为5000/1250/1。将条形瓶密封后，置于事先预热至25℃的油浴中，并开启搅拌。反应到约定时间，停止搅拌。取出极少量的反应混合物，用于进行 1H NMR和GPC测试，将剩余的反应聚合物进行提纯。聚合物的提纯：先将粗品溶于少量的二氯甲烷，再加入大量甲醇，并剧烈 搅拌，使聚合物沉淀出来，反复重复此过程，可得到黄色聚合物，经真空干燥后待用。聚二硫化物链段含量为99％，所得聚合物分子量M n为9.3kg/mol，分子量分布为1.18。此聚合物的折射率为1.693。经过计算，其阿贝数位37。
实施例5
配有磁子的10mL Schlenk条形瓶在130℃干燥12h以上，抽真空待其冷却至室温，充入氮气准备使用。在氮气保护下，室温称取一定量的金属配合物催化剂2e和助催化剂有机碱MTBD和丙硫醇加瓶入中，金属配合物催化剂与有机碱以及苄硫醇的摩尔比为1/4/100。再加入S 8和环硫烷烃1c，环硫烷烃与S 8及金属配合物催化剂的摩尔比为10000/1250/1。将条形瓶密封后，置于事先预热至25℃的油浴中，并开启搅拌。反应到约定时间，停止搅拌。取出极少量的反应混合物，用于进行 1H NMR和GPC测试，将剩余的反应聚合物进行提纯。聚合物的提纯：先将粗品溶于少量的二氯甲烷，再加入大量甲醇，并剧烈搅拌，使聚合物沉淀出来，反复重复此过程，可得到黄色聚合物，经真空干燥后待用。聚二硫化物链段含量为99％，所得聚合物分子量M n为9.3kg/mol，分子量分布为2.01。此聚合物的折射率为1.709。经过计算，其阿贝数位33。
实施例6
配有磁子的10mL Schlenk条形瓶在130℃干燥12h以上，抽真空待其冷却至室温，充入氮气准备使用。在氮气保护下，室温称取一定量的金属配合物催化剂2f和助催化剂有机碱三乙胺和正丁硫醇加入瓶中，金属配合物催化剂与有机碱以及正丁硫醇的摩尔比为1/10/1。再加入S 8和环硫烷烃1d，环硫烷烃与S 8及金属配合物催化剂的摩尔比为10000/1250/1。将条形瓶密封后，置于事先预热至25℃的油浴中，并开启搅拌。反应到约定时间，停止搅拌。取出极少量的反应混合物，用于进行 1H NMR和GPC测试，将剩余的反应聚合物进行提纯。 聚合物的提纯：先将粗品溶于少量的二氯甲烷，再加入大量甲醇，并剧烈搅拌，使聚合物沉淀出来，反复重复此过程，可得到黄色聚合物，经真空干燥后待用。聚二硫化物链段含量为99％，所得聚合物分子量M n为90.3kg/mol，分子量分布为1.91。此聚合物的折射率为1.68。经过计算，其阿贝数位35。
实施例7
配有磁子的10mL Schlenk条形瓶在130℃干燥12h以上，抽真空待其冷却至室温，充入氮气准备使用。在氮气保护下，室温称取一定量的金属配合物催化剂2g和助催化剂有机碱MTBD和1,2-丙二硫醇加入瓶中，金属配合物催化剂与有机碱以及1,2-丙二硫醇的摩尔比为0.5/1/10。再加入S 8和环硫烷烃1e，环硫烷烃与S 8及金属配合物催化剂的摩尔比为10000/1250/1。将条形瓶密封后，置于事先预热至25℃的油浴中，并开启搅拌。反应到约定时间，停止搅拌。取出极少量的反应混合物，用于进行 1H NMR和GPC测试，将剩余的反应聚合物进行提纯。聚合物的提纯：先将粗品溶于少量的二氯甲烷，再加入大量甲醇，并剧烈搅拌，使聚合物沉淀出来，反复重复此过程，可得到黄色聚合物，经真空干燥后待用。聚二硫化物链段含量为97％，所得聚合物分子量M n为889.3kg/mol，分子量分布为1.27。此聚合物的折射率为1.64。经过计算，其阿贝数位40。
实施例8
配有磁子的10mL Schlenk条形瓶在130℃干燥12h以上，抽真空待其冷却至室温，充入氮气准备使用。在氮气保护下，室温称取一定量的金属配合物催化剂2h和助催化剂有机碱三乙胺和苯硫酚加入瓶中，金属配合物催化剂与有机碱以及苯硫酚的摩尔比为1/1/50。再加入S 8和环硫烷烃1f，环硫烷烃与S 8及催化剂的摩尔比为60000/5000/1。将条形瓶密封后，置于事先预热至25℃的 油浴中，并开启搅拌。反应到约定时间，停止搅拌。取出极少量的反应混合物，用于进行 1H NMR和GPC测试，将剩余的反应聚合物进行提纯。聚合物的提纯：先将粗品溶于少量的二氯甲烷，再加入大量甲醇，并剧烈搅拌，使聚合物沉淀出来，反复重复此过程，可得到黄色聚合物，经真空干燥后待用。聚二硫化物链段含量为95％，所得聚合物分子量M n为5000.3kg/mol，分子量分布为2.6。此聚合物的折射率为1.66。经过计算，其阿贝数位38。
实施例9
配有磁子的10mL Schlenk条形瓶在130℃干燥12h以上，抽真空待其冷却至室温，充入氮气准备使用。在氮气保护下，室温称取一定量的金属配合物催化剂2i和助催化剂有机碱吗啉和对二苄硫醇加入瓶中，金属配合物催化剂与有机碱以及对二苄硫醇的摩尔比为1/1/10。再加入S 8和环硫烷烃1g，环硫烷烃与S 8及金属配合物催化剂的摩尔比为10000/1250/1。将条形瓶密封后，置于事先预热至25℃的油浴中，并开启搅拌。反应到约定时间，停止搅拌。取出极少量的反应混合物，用于进行 1H NMR和GPC测试，将剩余的反应聚合物进行提纯。聚合物的提纯：先将粗品溶于少量的二氯甲烷，再加入大量甲醇，并剧烈搅拌，使聚合物沉淀出来，反复重复此过程，可得到黄色聚合物，经真空干燥后待用。聚二硫化物链段含量为99％，所得聚合物分子量M n为96.3kg/mol，分子量分布为1.10。此聚合物的折射率为1.71。经过计算，其阿贝数位32。
实施例10
配有磁子的10mL Schlenk条形瓶在130℃干燥12h以上，抽真空待其冷却至室温，充入氮气准备使用。在氮气保护下，室温称取一定量的金属配合物催化剂2j和助催化剂有机碱三乙胺和2-羟基乙硫醇加入瓶中，金属配合物催化剂与有机碱以及苄硫醇的摩尔比为1/1/1。再加入S 8和环硫烷烃1h，环硫烷烃 与S 8及金属配合物催化剂的摩尔比为10000/1250/1。最后加入与环硫烷烃等体积的甲苯作为溶剂后，将条形瓶密封后，置于事先预热至25℃的油浴中，并开启搅拌。反应到约定时间，停止搅拌。取出极少量的反应混合物，用于进行 1H NMR和GPC测试，将剩余的反应聚合物进行提纯。聚合物的提纯：先将粗品溶于少量的二氯甲烷，再加入大量甲醇，并剧烈搅拌，使聚合物沉淀出来，反复重复此过程，可得到黄色聚合物，经真空干燥后待用。聚二硫化物链段含量为99％，所得聚合物分子量M n为963.2kg/mol，分子量分布为1.18。此聚合物的折射率为1.712。经过计算，其阿贝数位37。
实施例11
配有磁子的10mL Schlenk条形瓶在130℃干燥12h以上，抽真空待其冷却至室温，充入氮气准备使用。在氮气保护下，室温称取一定量的金属配合物催化剂2k和助催化剂有机碱三乙胺和2-羟基乙硫醇加入瓶中，金属配合物催化剂与有机碱以及2-羟基丙硫醇的摩尔比为1/1/10。再加入S 8和环硫烷烃1i，环硫烷烃与S 8及金属配合物催化剂的摩尔比为10000/1250/1。最后加入与环硫烷烃等体积的甲苯作为溶剂后，将条形瓶密封后，置于事先预热至50℃的油浴中，并开启搅拌。反应到约定时间，停止搅拌。取出极少量的反应混合物，用于进行 1H NMR和GPC测试，将剩余的反应聚合物进行提纯。聚合物的提纯：先将粗品溶于少量的二氯甲烷，再加入大量甲醇，并剧烈搅拌，使聚合物沉淀出来，反复重复此过程，可得到黄色聚合物，经真空干燥后待用。聚二硫化物链段含量为99％，所得聚合物分子量M n为93.2kg/mol，分子量分布为1.28。此聚合物的折射率为1.68。经过计算，其阿贝数位35。
实施例12
配有磁子的10mL Schlenk条形瓶在130℃干燥12h以上，抽真空待其冷 却至室温，充入氮气准备使用。在氮气保护下，室温称取一定量的金属配合物催化剂2l和助催化剂有机碱三正丁胺和2-羟基丙硫醇加入瓶中，金属配合物催化剂与有机碱以及2-羟基丙硫醇的摩尔比为1/1/50。再加入S 8和环硫烷烃1j，环硫烷烃与S 8及金属配合物催化剂的摩尔比为500/500/1。最后加入与环硫烷烃等体积的1,4-二氧六环作为溶剂后，将条形瓶密封后，置于事先预热至80℃的油浴中，并开启搅拌。反应到约定时间，停止搅拌。取出极少量的反应混合物，用于进行 1H NMR和GPC测试，将剩余的反应聚合物进行提纯。聚合物的提纯：先将粗品溶于少量的二氯甲烷，再加入大量甲醇，并剧烈搅拌，使聚合物沉淀出来，反复重复此过程，可得到黄色聚合物，经真空干燥后待用。聚二硫化物链段含量为97％，所得聚合物分子量M n为1.0kg/mol，分子量分布为1.38。此聚合物的折射率为1.763。经过计算，其阿贝数位41。
实施例13
配有磁子的10mL Schlenk条形瓶在130℃干燥12h以上，抽真空待其冷却至室温，充入氮气准备使用。在氮气保护下，室温称取一定量的金属配合物催化剂2a和助催化剂有机碱吡啶和3-羟基-1-丙硫醇加入瓶中，金属配合物催化剂与有机碱以及3-羟基-1-丙硫醇的摩尔比为1/1/50。再加入S 8和环硫烷烃1k，环硫烷烃与S 8及金属配合物催化剂的摩尔比为500/500/1。最后加入与环硫烷烃等体积的四氢呋喃作为溶剂后，将条形瓶密封后，置于事先预热至100℃的油浴中，并开启搅拌。反应到约定时间，停止搅拌。取出极少量的反应混合物，用于进行 1H NMR和GPC测试，将剩余的反应聚合物进行提纯。聚合物的提纯：先将粗品溶于少量的二氯甲烷，再加入大量甲醇，并剧烈搅拌，使聚合物沉淀出来，反复重复此过程，可得到黄色聚合物，经真空干燥后待用。聚二硫化物链段含量为98％，所得聚合物分子量M n为1.1kg/mol，分子量分布为1.8。 此聚合物的折射率为1.779。经过计算，其阿贝数位31。
实施例14
配有磁子的10mL Schlenk条形瓶在130℃干燥12h以上，抽真空待其冷却至室温，充入氮气准备使用。在氮气保护下，室温称取一定量的金属配合物催化剂2c和助催化剂有机碱哌啶加入瓶中，金属配合物催化剂与助催化剂的摩尔比为1/1。再加入S 8和环硫烷烃1l，环硫烷烃与S 8及金属配合物催化剂的摩尔比为500/500/1。最后加入与环硫烷烃等体积的三氯苯作为溶剂后，将条形瓶密封后，置于事先预热至120℃的油浴中，并开启搅拌。反应到约定时间，停止搅拌。取出极少量的反应混合物，用于进行 1H NMR和GPC测试，将剩余的反应聚合物进行提纯。聚合物的提纯：先将粗品溶于少量的二氯甲烷，再加入大量甲醇，并剧烈搅拌，使聚合物沉淀出来，反复重复此过程，可得到黄色聚合物，经真空干燥后待用。聚二硫化物链段含量为95％，所得聚合物分子量M n为48.0kg/mol，分子量分布为2.59。此聚合物的折射率为1.743。经过计算，其阿贝数位46。
实施例15
配有磁子的10mL Schlenk条形瓶在130℃干燥12h以上，抽真空待其冷却至室温，充入氮气准备使用。在氮气保护下，室温称取一定量的金属配合物催化剂2c和助催化剂有机碱DMAP加入瓶中，金属配合物催化剂与助催化剂的摩尔比为1/1。再加入S 8和环硫烷烃1a，环硫烷烃与S 8及金属配合物催化剂的摩尔比为500/500/1。最后加入与环硫烷烃等体积的二甲苯作为溶剂后，将条形瓶密封后，置于事先冷却至0℃的油浴中，并开启搅拌。反应到约定时间，停止搅拌。取出极少量的反应混合物，用于进行 1H NMR和GPC测试，将剩余的反应聚合物进行提纯。聚合物的提纯：先将粗品溶于少量的二氯甲烷，再加 入大量甲醇，并剧烈搅拌，使聚合物沉淀出来，反复重复此过程，可得到黄色聚合物，经真空干燥后待用。聚二硫化物链段含量为99％，所得聚合物分子量M n为46.6kg/mol，分子量分布为1.12。此聚合物的折射率为1.710。经过计算，其阿贝数位32。
实施例16
配有磁子的10mL Schlenk条形瓶在130℃干燥12h以上，抽真空待其冷却至室温，充入氮气准备使用。在氮气保护下，室温称取一定量的金属配合物催化剂2a和助催化剂有机碱DBU加入瓶中，金属配合物催化剂与助催化剂的摩尔比为1/1。再加入S 8和环硫烷烃1a，环硫烷烃与S 8及金属配合物催化剂的摩尔比为500/500/1。最后加入与环硫烷烃等体积的乙二醇二甲醚作为溶剂后，将条形瓶密封后，置于事先预热至–10℃的油浴中，并开启搅拌。反应到约定时间，停止搅拌。取出极少量的反应混合物，用于进行 1H NMR和GPC测试，将剩余的反应聚合物进行提纯。聚合物的提纯：先将粗品溶于少量的二氯甲烷，再加入大量甲醇，并剧烈搅拌，使聚合物沉淀出来，反复重复此过程，可得到黄色聚合物，经真空干燥后待用。聚二硫化物链段含量为99％，所得聚合物分子量M n为46.6kg/mol，分子量分布为1.12。此聚合物的折射率为1.708。经过计算，其阿贝数位33。
实施例17
配有磁子的10mL Schlenk条形瓶在130℃干燥12h以上，抽真空待其冷却至室温，充入氮气准备使用。在氮气保护下，室温称取一定量的金属配合物催化剂2a和助催化剂有机磷腈碱 tBu-P1加入瓶中，金属配合物催化剂与助催化剂的摩尔比为1/1。再加入S 8和环硫烷烃1a，环硫烷烃与S 8及金属配合物催化剂的摩尔比为4000/500/1。最后加入与环硫烷烃等体积的二乙二醇二甲醚作 为溶剂后，将条形瓶密封后，置于事先预热至–20℃的油浴中，并开启搅拌。反应到约定时间，停止搅拌。取出极少量的反应混合物，用于进行 1H NMR和GPC测试，将剩余的反应聚合物进行提纯。聚合物的提纯：先将粗品溶于少量的二氯甲烷，再加入大量甲醇，并剧烈搅拌，使聚合物沉淀出来，反复重复此过程，可得到黄色聚合物，经真空干燥后待用。聚二硫化物链段含量为99％，所得聚合物分子量M n为50.6kg/mol，分子量分布为1.10。此聚合物的折射率为1.708。经过计算，其阿贝数位33。
实施例18
配有磁子的10mL Schlenk条形瓶在130℃干燥12h以上，抽真空待其冷却至室温，充入氮气准备使用。在氮气保护下，室温称取一定量的金属配合物催化剂2a和助催化剂有机磷腈碱 tBu-P2加入瓶中，金属配合物催化剂与助催化剂的摩尔比为1/1。再加入S 8和环硫烷烃1a，环硫烷烃与S 8及金属配合物催化剂的摩尔比为4000/500/1。将条形瓶密封后，置于事先预热至25℃的油浴中，并开启搅拌。反应到约定时间，停止搅拌。取出极少量的反应混合物，用于进行 1H NMR和GPC测试，将剩余的反应聚合物进行提纯。聚合物的提纯：先将粗品溶于少量的二氯甲烷，再加入大量甲醇，并剧烈搅拌，使聚合物沉淀出来，反复重复此过程，可得到黄色聚合物，经真空干燥后待用。聚二硫化物链段含量为99％，所得聚合物分子量M n为416.6kg/mol，分子量分布为1.12。此聚合物的折射率为1.7011。经过计算，其阿贝数位33。
实施例19
配有磁子的10mL Schlenk条形瓶在130℃干燥12h以上，抽真空待其冷却至室温，充入氮气准备使用。在氮气保护下，室温称取一定量的金属配合物催化剂2a和助催化剂有机磷腈碱 tBu-P3加入瓶中，金属配合物催化剂与助催 化剂的摩尔比为1/1。再加入S 8和环硫烷烃1a，环硫烷烃与S 8及金属配合物催化剂的摩尔比为4000/500/1。将条形瓶密封后，置于事先预热至25℃的油浴中，并开启搅拌。反应到约定时间，停止搅拌。取出极少量的反应混合物，用于进行 1H NMR和GPC测试，将剩余的反应聚合物进行提纯。聚合物的提纯：先将粗品溶于少量的二氯甲烷，再加入大量甲醇，并剧烈搅拌，使聚合物沉淀出来，反复重复此过程，可得到黄色聚合物，经真空干燥后待用。聚二硫化物链段含量为99％，所得聚合物分子量M n为40.9kg/mol，分子量分布为1.23。此聚合物的折射率为1.69。经过计算，其阿贝数位38。
实施例20
配有磁子的10mL Schlenk条形瓶在130℃干燥12h以上，抽真空待其冷却至室温，充入氮气准备使用。在氮气保护下，室温称取一定量的金属配合物催化剂2a和助催化剂有机磷腈碱 tBu-P4加入瓶中，金属配合物催化剂与助催化剂的摩尔比为1/1。再加入S 8和环硫烷烃1a，环硫烷烃与S 8及金属配合物催化剂的摩尔比为4000/500/1。将条形瓶密封后，置于事先预热至25℃的油浴中，并开启搅拌。反应到约定时间，停止搅拌。取出极少量的反应混合物，用于进行 1H NMR和GPC测试，将剩余的反应聚合物进行提纯。聚合物的提纯：先将粗品溶于少量的二氯甲烷，再加入大量甲醇，并剧烈搅拌，使聚合物沉淀出来，反复重复此过程，可得到黄色聚合物，经真空干燥后待用聚二硫化物链段含量为99％，所得聚合物分子量M n为39.9kg/mol，分子量分布为1.26。。此聚合物的折射率为1.708。经过计算，其阿贝数位32。
实施例21
配有磁子的10mL Schlenk条形瓶在130℃干燥12h以上，抽真空待其冷却至室温，充入氮气准备使用。在氮气保护下，室温称取一定量的金属配合物 催化剂2a和助催化剂有机碱TBD加入瓶中，金属配合物催化剂与助催化剂的摩尔比为1/1。再加入S 8和环硫烷烃1a，环硫烷烃与S 8及金属配合物催化剂的摩尔比为4000/500/1。将条形瓶密封后，置于事先预热至25℃的油浴中，并开启搅拌。反应到约定时间，停止搅拌。取出极少量的反应混合物，用于进行 1H NMR和GPC测试，将剩余的反应聚合物进行提纯。聚合物的提纯：先将粗品溶于少量的二氯甲烷，再加入大量甲醇，并剧烈搅拌，使聚合物沉淀出来，反复重复此过程，可得到黄色聚合物，经真空干燥后待用。聚二硫化物链段含量为99％，所得聚合物分子量M n为411.6kg/mol，分子量分布为1.29。此聚合物的折射率为1.71。经过计算，其阿贝数位33。

Claims (10)

  1. 一种具有优异光学性能的聚二硫化物材料，其特征在于，以单质硫与环硫烷烃为原料，采用由金属配合物和有机碱组成的催化体系，在有或者无链引发剂存在下，经本体聚合或者溶液聚合后得到所述的聚二硫化物材料，聚合物主链中二硫链段含量为95～99％，数均分子量为1000～5000000g/mol，分子量分布为1.1～2.6。
  2. 根据权利要求1所述的一种具有优异光学性能的聚二硫化物材料，其特征在于，所采用的催化体系中金属配合物的结构如下：
    Figure PCTCN2021129202-appb-100001
    Figure PCTCN2021129202-appb-100002
    式中：
    Figure PCTCN2021129202-appb-100003
    Figure PCTCN2021129202-appb-100004
    表示连接位置
    M为Al 3+、Fe 3+、Co 3+、Ni 3+、Cr 3+、Mn 3+、Ru 3+、Mg 2+、Fe 2+、Co 2+、Ni 2+或Cu 2+；X为F -1、Cl -1、Br -1、I -1、NO 3 -1、CH 3COO -1、CCl 3COO -1、CF 3COO -1、ClO 4 -1、BF 4 -1、BPh 4 -1、N 3 -1、PF 6 -1、SbF 6 -1、对甲基苯甲酸根、对甲基苯磺酸根、邻-硝基苯酚氧、对-硝基苯酚氧、间-硝基苯酚氧、2,4-二硝基苯酚氧、3,5-二硝基苯酚氧、2,4,6-三硝基苯酚氧、3,5-二氯苯酚氧、3,5-二氟苯酚氧、3,5-二-三氟甲基苯酚氧或五氟酚氧负离子；R 1是H、C 1～C 6烷基、C 1～C 6烷氧基、Cl、Br或NO 2基团；
    有机碱选用三乙胺、三正丁胺、磷腈碱P1、磷腈碱P2、磷腈碱P3、磷腈碱P4、吡啶、哌啶、吗啉、4-二甲氨基吡啶DMAP、1,8-二氮杂二环[5.4.0]十一碳-7-烯DBU、1,5,7-三氮杂双环[4.4.0]癸-5-烯TBD或7-甲基-1,5,7-三氮杂双环[4.4.0]癸-5-烯MTBD；
    链引发剂选用乙硫醇、丙硫醇、正丁硫醇、苄硫醇、乙二硫醇、苯硫酚、1,2-丙二硫醇、1,3-丙二硫醇、对二苄硫醇、对二苯硫酚、环己二硫醇、2-羟基乙硫醇、2-羟基-1-丙硫醇、3-羟基-1-丙硫醇或2-羟基-1-环己醇。
  3. 根据权利要求1所述的一种具有优异光学性能的聚二硫化物材料，其特征在于，金属配合物与有机碱的摩尔比为1:0.5～10。
  4. 根据权利要求1所述的一种具有优异光学性能的聚二硫化物材料，其特征在于，所采用的环硫烷烃为环硫丙烷、环硫乙烷、环硫丁烷、环硫己烷、异丙氧基环硫丙烷、苯基环硫乙烷、苄基环硫乙烷、环硫环己烷、环硫环戊烷、环氧环庚烷、2,3-环氧丁烷、3,4-环硫四氢呋喃、3,5-二氧杂环硫烷烃、2,3-环硫-1,2,3,4-四氢化萘中的一种。
  5. 根据权利要求1所述的一种具有优异光学性能的聚二硫化物材料，其特征在于，所述环硫烷烃与单质硫的摩尔比例为1～12:1；环硫烷烃与金属配合物的摩尔比为100～100000:1。
  6. 根据权利要求书1所述的一种具有优异光学性能的聚二硫化物材料，其特征在于，所述链引发剂与金属配合物的摩尔比为0～100:1。
  7. 根据权利要求1-5任一所述的一种具有优异光学性能的聚二硫化物材料，其特征在于，金属配合物与有机碱的摩尔比为1:1。
  8. 根据权利要求书1-5任一所述的一种具有优异光学性能的聚二硫化物材料，其特征在于，所述链引发剂与金属配合物的摩尔比为1:10。
  9. 权利要求1-8任一所述的一种具有优异光学性能的聚二硫化物材料的制备方法，其特征在于，以单质硫与环硫烷烃为原料，采用由金属配合物和有机碱组成的催化体系，在有或者无链引发剂存在下，经本体聚合或者溶液聚合后得到所述的聚二硫化物材料，所述聚合反应在–20～120℃下进行0.1～24h。
  10. 根据权利要求9所述的一种具有优异光学性能的聚二硫化物材料的制备方法，其特征在于，所述聚合反应如在溶液下进行，所采用的溶剂选自甲苯、三氯苯、四氢呋喃、二甲苯、乙二醇二甲醚、二乙二醇二甲醚、1,4-二氧六环中任意一种。
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