CN100360584C - Method of synthesizing fluorine containing superbranched light wave conductive material based on A2+B3 type monomer reaction - Google Patents

Abstract

The method for synthesizing a fluorine-containing hyperbranched optical waveguide material based on the reaction of A ₂ +B ₃ type monomers of the invention belongs to the field of polymer materials and their preparation. With 1,3,5-tris[4-(4-fluorobenzoyl)phenoxy]benzene and (3-trifluoromethylbenzene)hydroquinone or (3,5-bistrifluoromethylbenzene) Hydroquinone or 6F-bisphenol A is used as the raw material; the raw material, salt forming agent, water-carrying agent and solvent are mixed according to the ratio and stirred with nitrogen, the temperature is raised to reflux to release toluene, and then the temperature is raised to 210-220°C for 5-6 hours; The material is discharged into deionized water and treated to obtain a fluorine-containing hyperbranched optical waveguide material. The near-infrared spectrum of the polymer thin film prepared by the method of the present invention shows that there is less absorption in the communication band, so it has a relatively ideal performance suitable for making low-loss optical waveguide devices; it also enhances the thermal stability and hydrophobicity of the polymer. Multiple effects of oil repellency, chemical resistance and low cohesive energy.

Description

Method for Synthesizing Fluorine-Containing Hyperbranched Optical Waveguide Materials Based on A2+B3 Type Monomer Reaction

technical field

The invention belongs to the field of polymer materials and their preparation, and in particular relates to a method for synthesizing hyperbranched polyaryletherketone optical waveguide materials by using _A2 + _B3 type monomers to react.

Background technique

As a special engineering plastic, polyaryletherketone has excellent heat resistance, chemical corrosion resistance and good mechanical properties, but it is almost insoluble in conventional solvents and cannot be spin-coated into a film by solution, so it is used as a film material It is greatly restricted, especially in the research and application of optical properties. In the past ten years, hyperbranched polymers, as a new class of polymers, have good solubility, low melt and solution viscosity due to their unique highly branched structure, which indicates that this new type of polymer will open the traditional linear Features that polymers don't have.

The introduction of fluorine atoms into the hyperbranched polymer framework as an optical waveguide material has attracted widespread attention. The introduction of fluorine atoms can enhance the polymer's thermal stability, hydrophobicity, oil repellency, chemical properties and low cohesion energy. , while substituting with fluorine can reduce the loss of absorbed light at 1.3 μm and 1.55 μm.

For the background technology related to the present invention, refer to the article "Synthesis and Characterization of Hyperbranched Polyaryletherketone Based on A ₂ +B ₃ Type Reaction" published in Polymer Preprints 2004, 45(1), 1130. The author of this article uses 1,3,5-tris[4-(4-fluorobenzoyl)phenoxy]benzene as the B _3- type monomer and bisphenol A-type monomer as raw materials, using sulfolane as the solvent, after mixing, Salt formation, prepolymerization, and reaction at 220°C for 4 hours to synthesize hyperbranched polyaryletherketone. Hyperbranched polyaryletherketones with different end groups were prepared by changing the ratio of A ₂ and B ₃ , and the effect of end group polarity on the thermal properties of polymers was studied. The hyperbranched polymer containing bisphenol A structure does not show certain functionality because the whole polymer does not contain functional groups.

Contents of the invention

The technical problem to be solved in the present invention is to replace the bisphenol A type monomer with a fluorine-containing functional bisphenol monomer on the basis of the background technology, introduce fluorine element through the main chain and side groups, and use fluorine substitution to reduce the absorption of light in the Optical loss at 1.3μm and 1.55μm wavelengths.

The present invention uses the B ₃ type high-activity fluorine-terminated monomer disclosed in the background technology to react with the A ₂ type fluorine-containing bisphenol monomer, and introduces fluorine atoms into the hyperbranched polyaryletherketone skeleton by an inlay method, and the utilization is easy to change The structure of the _A2 monomer, the characteristics of the chain length, and the dual method of changing the ratio of _A2 : _B3 to control the fluorine content of the entire polymer can reduce the near-infrared region at 1.3μm and 1.55μm wavelength. light loss.

The B _3- type monomer used in the present invention is 1,3,5-tris[4-(4-fluorobenzoyl)phenoxy]benzene; the A _2- type monomer is (3-trifluoromethylbenzene) p- Hydroquinone (3F-PH) or (3,5-ditrifluoromethylbenzene) hydroquinone (6F-PH) or 6F-bisphenol A (6F-DA), the structures are as follows:

The method for synthesizing fluorine-containing hyperbranched optical waveguide material of the present invention is, with B ₃ type monomer and A ₂ type monomer as reactant, with potassium carbonate as salt-forming agent, with sulfolane or dimethyl sulfoxide or N-methyl sulfoxide Base pyrrolidone is used as a solvent, and toluene is used as a water-carrying agent. Said B type ₃ monomer is 1,3,5-tris[4-(4-fluorobenzoyl)phenoxy]benzene, said A ₂ type monomer is (3-trifluoromethylbenzene ) hydroquinone or (3,5-ditrifluoromethylbenzene) hydroquinone or 6F-bisphenol A, the molar ratio of raw materials is B ₃ type monomer: _{A 2} type monomer: potassium carbonate= 1: 0.5～0.74: 0.5～1 or 1:3～4:3～4.4, the amount of solvent and water-carrying agent is 3.5-5.5L of solvent and 2.5-3.5L of water-carrying agent per mole of _B3 type monomer; The raw materials are mixed in proportion, nitrogen gas is passed, stirred, the temperature is raised to 130°C-140°C, refluxed for 1.5-2 hours, toluene is released, the temperature is raised to 210-220°C, and the reaction is carried out for 5-6 hours. Discharge into deionized water with a pH value of 6.5-7, pulverize, boil in boiling water for 2-4 times to remove solvent, suction filter, and dry; then wash with methanol for 2-3 times under reflux, and heat filter to remove small molecular weight hyperbranched polymers and drying to obtain a higher molecular weight fluorine-containing hyperbranched optical waveguide material.

When the molar ratio of raw materials is B ₃ type monomer: A ₂ type monomer: potassium carbonate=1: 0.5～0.74: 0.5～1, what is synthesized is a fluorine-terminated hyperbranched polyetheretherketone optical waveguide material; when When the molar ratio of raw materials is _B3 type monomer: _A2 type monomer: potassium carbonate = 1:3-4:3-4.4, the synthesized is a hydroxyl-terminated hyperbranched polyether ether ketone optical waveguide material.

The glass transition temperature (Tg) of the fluorine-containing hyperbranched optical waveguide material is measured by DSC, and it is in the range of 94-142°C (see Figures 1-6). It can be seen that the end groups play a decisive role in the glass transition temperature (Tg) of hyperbranched polymers.

The near-infrared absorption spectra of 3FHPEEK-F, 6FHPEEK-F, 6FAHPEEK-F and 6FAHPEEK-OH thin films prepared by the method of the present invention are shown in Figs. 7-10 respectively. It can be seen that there is only one obvious absorption peak around 1.38 μm in the four polymers in the optical communication band. The absorption peak here is caused by the coupling of the double frequency of the stretching vibration of the CH bond and the deformation vibration (2 v ^φ CH+δ ^φ CH), in addition, the stretching vibration of the OH bond in the moisture also appears here (2 v ^φ OH(H ₂ O)). Another stronger peak (1.66 μm) is due to the 2-fold frequency of the CH bond stretching vibration. However, in the optical communication band (1.3 μm and 1.55 μm), the near-infrared spectra of the four polymer films all have lower absorption “windows”, that is, there is less absorption in the communication band. Therefore, this type of hyperbranched polyaryletherketone has ideal properties suitable for making low-loss optical waveguide devices. At the same time, it also enhances the thermal stability, hydrophobicity, oil repellency, chemical resistance and multiple effects of low cohesive energy of the polymer. The advantage compared with linear polymers is that this type of polymer has unique properties such as low chain entanglement, low solution viscosity, and high solubility, and can be used to prepare ultra-thin films by solution spin coating. Such materials will have broad application prospects in the field of optical waveguide materials.

Description of drawings

Fig. 1 is the DSC curve of the 3FHPEEK-F material of the present invention.

Fig. 2 is the DSC curve of the 3FHPEEK-OH material of the present invention.

Fig. 3 is the DSC curve of the 6FHPEEK-F material of the present invention.

Fig. 4 is the DSC curve of the 6FHPEEK-OH material of the present invention.

Fig. 5 is the DSC curve of the 6FAHPEEK-F material of the present invention.

Fig. 6 is a DSC curve of the 6FAHPEEK-OH material of the present invention.

Fig. 7 is a near-infrared spectrogram of the 3FHPEEK-F film of the present invention.

Fig. 8 is a near-infrared spectrogram of the 6FHPEEK-F film of the present invention.

Fig. 9 is a near-infrared spectrogram of the 6FAHPEEK-F film of the present invention.

Fig. 10 is a near-infrared spectrogram of the 6FAHPEEK-OH thin film of the present invention.

Detailed ways

Example 1: Synthesis of fluorine-terminated hyperbranched polyetheretherketone (3FHPEEK-F) containing 3-trifluoromethylbenzene side group structure

721g (0.01mol) of B _3- type monomer 1,3.5-tris[4-(4-fluorobenzoyl)phenoxy]benzene, A _2- type monomer (3-trifluoromethylbenzene)hydroquinone 1.83g (0.0072mol), 1.04g (0.0076mol) of anhydrous potassium carbonate, 40ml sulfolane, and 30ml toluene (different azeotropic water dehydrating agents have no effect on the reaction result) are put into a 100ml three-necked bottle with a water device, and nitrogen is ventilated. Stir, heat up to 130°C, reflux for 1.5-2 hours, release toluene, heat up to 220°C for 6 hours. The material is discharged into acidic deionized water, pulverized, boiled in boiling water for 3 times to remove sulfolane, filtered with suction, dried, then washed twice with methanol under reflux, hot filtered to remove small molecular weight hyperbranched polymers, and dried to obtain sulfolane containing 3- 6.42 g of fluorine-terminated hyperbranched polyetheretherketone (3FHPEEK-F) with trifluoromethylbenzene side group structure, the yield is 71%, and its glass transition temperature is 103° C. as measured by DSC. The DSC curve of polymer 3FHPEEK-F obtained by this ratio is shown in Figure 1, and the near-infrared spectrum is shown in Figure 7.

B _3- type monomer 1,3,5-tris[4-(4-fluorobenzoyl)phenoxy]benzene 0.01mol, A _2- type monomer (3-trifluoromethylbenzene)hydroquinone 0.00675mol, when 0.01mol of anhydrous potassium carbonate is used, according to the above-mentioned treatment process, it is also possible to synthesize fluorine-terminated hyperbranched polyether ether ketone (3FHPEEK-F) containing 3-trifluoromethylbenzene side group structure, but the product The degree of branching, glass transition temperature, and molecular weight are slightly different compared with the first ratio.

B _3- type monomer 1,3,5-tris[4-(4-fluorobenzoyl)phenoxy]benzene 0.01mol, A _2- type monomer (3-trifluoromethylbenzene)hydroquinone 0.006mol, when using 0.006mol of anhydrous potassium carbonate, according to the above-mentioned treatment process, it is also possible to synthesize fluorine-terminated hyperbranched polyether ether ketone (3FHPEEK-F) containing 3-trifluoromethylbenzene side group structure, but the The degree of branching of the obtained polymer is higher than the above two ratios, and the glass transition temperature and molecular weight are lower than the above two ratios.

Example 2: Synthesis of hydroxyl-terminated hyperbranched polyetheretherketone (3FHPEEK-OH) containing 3-trifluoromethylbenzene side group structure

7.21g (0.01mol) of B type ₃ monomer 1,3,5-tris[4-(4-fluorobenzoyl)phenoxy]benzene, A type ₂ monomer (3-trifluoromethylbenzene) Hydroquinone 7.735g (0.03045mol), anhydrous potassium carbonate 4.2g (0.03045mol), 50ml cyclosulfone, 30ml toluene (different azeotropic water dehydrating agents have no effect on the reaction result) are put into 100ml water-carrying device The three-necked round-bottomed flask was ventilated with nitrogen, stirred, heated to 140°C, refluxed for 1.5-2 hours, released toluene, and heated to 210°C for 5 hours. Discharge into acidic deionized water, pulverize, boil in boiling water for 3 times to remove sulfolane, suction filter, dry, then wash with methanol for 2 times, heat filter to remove small molecular weight hyperbranched polymer, and dry to obtain 3FHPEEK-OH 10.2g, the yield is 68%, and its glass transition temperature measured by DSC is 123°C. This ratio obtains the DSC curve of the polymer 3FHPEEK-OH as shown in Figure 2.

B type ₃ monomer 1.3.5-x tris[4-(4-fluorobenzoyl)phenoxy]benzene uses 0.01mol, A type ₂ monomer (3-trifluoromethylbenzene)hydroquinone uses 0.0309 mol, when 0.0318mol of anhydrous potassium carbonate is used, 3FHPEEK-OH material can also be synthesized according to the above-mentioned treatment process, but the branching degree, glass transition temperature, molecular weight and end group content of the product are different from the former.

B _3- type monomer 1,3,5-tris[4-(4-fluorobenzoyl)phenoxy]benzene 0.01mol, A _2- type monomer (3-trifluoromethylbenzene)hydroquinone 0.04mol, and when 0.042mol of anhydrous potassium carbonate is used, the 3FHPEEK-OH material can also be synthesized according to the above-mentioned treatment process, but the material has a higher degree of branching and a lower molecular weight.

Example 3: Synthesis of fluorine-terminated hyperbranched polyether ether ketone (6FHPEEK-F) containing 3,5-bistrifluoromethylbenzene side group structure

The synthesis method and treatment process are the same as in Example 1, except that the A2 _- type monomer is changed to (3,5-ditrifluoromethylbenzene) hydroquinone. The yield of 6FHPEEK-F was 75%. The Tg of 6FHPEEK-F is 108°C (see Figure 3 for the DSC curve). The near-infrared spectrum of the 6FHPEEK-F film is shown in Figure 8.

Example 4: Synthesis of 3,5-bistrifluoromethylbenzene side group structure hydroxyl-terminated hyperbranched polyetheretherketone (6FHPEEK-OH)

The synthesis method and treatment process are the same as in Example 2, except that the A2 _- type monomer is changed to (3,5-bistrifluoromethylbenzene) hydroquinone. The yield of 6FHPEEK-OH was 73%. The Tg of 6FHPEEK-OH is 124.5°C (see Figure 4 for the DSC curve).

Example 5 Synthesis of fluorine-terminated hyperbranched polyether ether ketone (6FAHPEEK-F) containing 6F-bisphenol A structure

The synthesis method and treatment process are the same as in Example 1, except that the type A ₂ monomer is changed to 6F-bisphenol A. The yield of 6FAHPEEK-F was 65%, and the Tg of 6FAHPEEK-F was 94°C (see Figure 5 for the DSC curve). The near-infrared spectrum of the 6FAHPEEK-F film is shown in Figure 9.

Example 6: Synthesis of hydroxyl-terminated hyperbranched polyether ether ketone (6FAHPEEK-OH) containing 6F-bisphenol A structure

The synthesis method and treatment process are the same as in Example 2, except that the type A ₂ monomer is changed to 6F-bisphenol A. 6FAHPEEK-OH was obtained with a yield of 68%, and the Tg of 6FAHPEEK-OH was 142°C (see Figure 6 for the DSC curve). The near-infrared spectrum of the 6FAHPEEK-OH film is shown in Figure 10.

Example 7 uses different solvents

The solvent sulfolane in Examples 1-6 is changed to dimethyl sulfoxide or N-methylpyrrolidone, and the synthesis effect is the same.

Claims (2)

1. A method for synthesizing fluorine-containing hyperbranched optical waveguide materials based on the reaction of A ₂ +B ₃ type monomers, using B ₃ type monomers and A ₂ type monomers as reactants, said B ₃ type monomers It is 1,3,5-three [4-(4-fluorobenzoyl)phenoxy]benzene, with potassium carbonate as salt-forming agent and toluene as water-carrying agent, characterized in that, sulfolane or dimethyl Sulfone or N-methylpyrrolidone is a solvent, and said _A2 type monomer is (3-trifluoromethylbenzene) hydroquinone or (3,5-ditrifluoromethylbenzene) hydroquinone or 6F-bisphenol A, the structural formula of 6F-bisphenol A is

The molar ratio of raw materials is B ₃ type monomer: A ₂ type monomer: potassium carbonate = 1: 0.5～0.74: 0.5～1 or 1: 3～4: 3～4.4, the amount of solvent and water-carrying agent is per mole Add 3.5-5.5L of solvent and 2.5-3.5L of water-carrying agent for type B ₃ monomer; mix the raw materials in proportion, pass nitrogen gas, stir, heat up to 130°C-140°C, reflux for 1.5-2 hours, release toluene, and then heat up React at 210-220°C for 5-6 hours; discharge into deionized water with a pH value of 6.5-7, pulverize, boil in boiling water for 2-4 times to remove solvent, extract and dry; then wash with methanol for 2-3 times , and dried to obtain a fluorine-containing hyperbranched optical waveguide material. 2. The method for synthesizing fluorine-containing hyperbranched optical waveguide materials based on the reaction of A ₂ +B ₃ type monomers according to claim 1, characterized in that when the molar ratio of raw materials is B ₃ type monomer: _{A 2} type Monomer: Potassium Carbonate = 1:0.5～0.74:0.5～1, the fluorine-terminated hyperbranched polyetheretherketone optical waveguide material will be synthesized; when the molar ratio of raw materials is _B3 type monomer: _A2 type monomer : Potassium carbonate = 1: 3 ~ 4: 3 ~ 4.4, when the hydroxyl-terminated hyperbranched polyether ether ketone optical waveguide material will be synthesized.

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