Preparation method of polyaryletherketone resin with amino side groups, polyaryletherketone resin with amino side groups and application

Abstract

The present application discloses a preparation method of a polyaryletherketone resin containing an amino side group, a polyaryletherketone resin containing an amino side group and an application. Starting from the molecular design of the polyaryletherketone resin and the gas separation membrane structure, the present application introduces a polar group with an amino group into the polymer main chain through a copolymerization reaction to form a polyaryletherketone resin with a polar amino structure, which is an amorphous structure. By adjusting the steric hindrance of the polymer side chain, the stacking of the polymer main chain is hindered, the molecular spatial volume is increased, so as to achieve the purpose of increasing the gas flux while intercepting gas molecules with a larger kinetic diameter. The gas separation membrane has a higher hydrogen permeability coefficient, shortens the gas separation time and improves the operating efficiency of the module.

Description

Technical Field

[0001] The present application relates to a preparation method of a polyaryletherketone resin with amino side groups, a polyaryletherketone resin with amino side groups and applications thereof, belonging to the technical field of polymer synthesis. Background Art

[0002] The temperature of the membrane separation process of gases is generally lower than 100 °C, and the driving force is the pressure difference on both sides of the gas separation membrane. Since the mixed gas source itself has pressure to provide power, membrane separation has the trend of gradually replacing other traditional processes and has the outstanding advantages of low energy consumption and low cost. The membrane materials mainly include inorganic membranes, polymer membranes, polymer-inorganic hybrid membranes, etc. Since polymer materials do not have a phase change at the separation temperature, no energy consumption or low process energy consumption is generated. At present, high-performance membrane materials, which are the core materials for modulating syngas components by membrane method, are controlled by foreign companies such as Ube in Japan and Air Products in the United States. Polyimide is the separation membrane material with the best performance and the most extensive use. However, due to its strong main chain rigidity and poor solubility, the preparation process of hollow fiber membranes is complex and the price is extremely expensive. Since the 1990s, polyarylethers have been used in China to prepare hydrogen separation membranes. Due to the huge gap in performance with foreign products, polysulfone membrane separators are only applicable to the synthetic ammonia industry, and the membrane separators for hydrogen recovery in the syngas-to-methanol and oil refining industries are completely monopolized by foreign countries. Breaking through the bottleneck of the core materials, membrane module design and preparation technology of membrane separators for modulating syngas components and realizing their low cost and localization have extremely important practical significance and economic value. The gas separation membrane special resin is mainly linear in structure. By adjusting large side groups, the chain spacing of the molecular chain can be appropriately increased to improve the gas permeability coefficient. Introducing a small amount of branched structure can further improve the stability of the gas separation membrane. Summary of the Invention

[0003] The present application provides a polyaryletherketone resin with an amino structure and its synthesis method, obtaining a polyaryletherketone resin with a polar amino structure, a larger free volume fraction, higher heat resistance and a faster permeability coefficient, and using it to prepare a separation membrane material to obtain a high-temperature resistant film with a higher permeability coefficient and better dimensional stability.

[0004] According to one aspect of the present application, a preparation method of a polyaryletherketone resin with amino side groups is provided. The preparation method includes:

[0005] Reacting a mixture of a bisphenol monomer, a dihalogen monomer, an amino-containing compound and a catalyst in an inert atmosphere to obtain the polyaryletherketone resin with amino side groups;

[0006] The amino-containing compound is selected from a bisphenol monomer containing an amino group or a dihalogen monomer containing an amino group.

[0007] Optionally, the bisphenol monomer is selected from at least one of at least one of bisphenol fluorene, o-methyl bisphenol fluorene, phenolphthalein, o-methyl phenolphthalein, thymolphthalein, bisisopropyl phenolphthalein, 3,3-bis(4-hydroxyphenyl)-2-phenylisoindolin-1-one, and 4,4'-dihydroxybenzophenone.

[0008] Optionally, the dihalogen monomer is selected from at least one of at least one of 4,4'-difluorobenzophenone, 4,4'-dichlorobenzophenone, and 1,4-bis(4'-fluorobenzoyl)benzene difluorotriphenyl dione.

[0009] Optionally, the amino-containing bisphenol monomer is selected from at least one of 9,9-bis(3-amino-4-hydroxyphenyl)fluorene, 9,9-bis(3-amino-4-hydroxyphenyl) isopropane, and 3,3'-diamino-4,4'-dihydroxy diphenyl sulfone.

[0010] Optionally, the amino-containing dihalogen monomer is bis(3-amino-4-hydroxyphenyl) sulfone.

[0011] Optionally, the molar ratio of the bisphenol monomer to the dihalogen monomer is 1:0.9 to 1.1.

[0012] Optionally, the molar ratio of the bisphenol monomer to the amino-containing compound is 0.05:1 to 1:0.05.

[0013] Optionally, the catalyst is selected from at least one of potassium carbonate, sodium carbonate, lithium carbonate, and cesium carbonate.

[0014] Optionally, the molar ratio of the bisphenol monomer to the catalyst is 1:1.05 to 1:3.

[0015] Optionally, the mixture further includes a solvent, and the solvent is selected from at least one of N,N-dimethylacetamide, N,N-dimethylformamide, N-methylpyrrolidone, diphenyl sulfone, sulfolane, and N,N-dimethyl-4-aminopyridine.

[0016] Optionally, the molar volume ratio of the bisphenol monomer to the solvent is 1 mol:800 to 3000 ml.

[0017] Optionally, the mixture further includes a water-carrying agent, and the water-carrying agent is selected from at least one of n-hexane, cyclohexane, benzene, toluene, xylene, and cumene.

[0018] Optionally, the molar volume ratio of the bisphenol monomer to the water-carrying agent is 1 mol:100 to 1200 ml.

[0019] Optionally, the inert atmosphere is selected from a nitrogen atmosphere and / or an argon atmosphere.

[0020] Optionally, the temperature of the reaction is 80 to 230 °C, and the reaction time is 0.5 to 24 h.

[0021] Optionally, the temperature of the reaction is selected from any value among 80 °C, 100 °C, 120 °C, 150 °C, 200 °C, 230 °C or the range value between any two of the above.

[0022] Optionally, the reaction time is selected from any value among 0.5 h, 1 h, 2 h, 4 h, 5 h, 12 h, 18 h, 24 h or the range value between any two of the above.

[0023] According to another aspect of the present application, a polyaryletherketone resin with an amino side group is provided, and the polyaryletherketone resin with an amino side group is prepared by the preparation method described above.

[0024] Optionally, the inherent viscosity of the polyaryletherketone resin with an amino side group is 0.25 dL / g to 1.2 dL / g.

[0025] Optionally, the glass transition temperature of the polyaryletherketone resin with an amino side group is 190 to 280 °C.

[0026] Optionally, the polyaryletherketone resin with an amino side group is selected from one of the structures shown in Formula I and Formula II;

[0027]

[0028] In Formula I, the value range of n is 0.1 to 0.9, the value range of m is 0.1 to 0.9, and n + m = 1;

[0029]

[0030] In Formula II, the value range of n is 0.1 to 0.9, the value range of m is 0.1 to 0.9, and n + m = 1.

[0031] According to still another aspect of the present application, there is provided an application of the polyaryletherketone resin with an amino side group prepared by the above-mentioned preparation method and the polyaryletherketone resin with an amino side group in a gas separation membrane.

[0032] Optionally, the hydrogen permeation coefficient is 7.5 to 25 Barrer; the nitrogen permeation coefficient is 0.03 to 0.50 Barrer.

[0033] Specifically, the present application is achieved through the following technical solutions:

[0034] An isatinone bisphenol monomer, a dihalo monomer, and a bisphenol or dihalo monomer with 1 to 2 amino groups are added into a reaction flask equipped with mechanical stirring, an air inlet, and a water separator in a certain proportion. Solvents, water-carrying agents, catalysts, etc. are added. Under the protection of an inert gas stream, it is heated to 80 - 170 °C and refluxed for 0.5 - 4 h. The water-carrying agent is removed, the temperature is continued to be raised, the water-carrying agent is discharged, and the water-carrying agent is removed from the reaction system. The temperature is continued to be raised to 140 - 230 °C and reacted for 0.5 - 24 h. After the viscosity of the system no longer increases, a certain amount of diluent is added after cooling, and the polymer is purified to obtain a polyarylether resin for a separation membrane.

[0035] The beneficial effects that this application can produce include:

[0036] 1) A polyaryletherketone resin with an amino structure provided by this application has high heat resistance, a high permeability coefficient, dimensional stability, and can separate gases with different hydrodynamic diameters.

[0037] 2) A polyaryletherketone resin provided by this application has easily available raw materials and has a certain cost advantage.

[0038] 3) The polyaryletherketone resin with an amino side group provided by this application has certain re-modification reaction sites and can be extended to the synthesis of related polyarylether resins and the development field of membrane materials.

[0039] 4) Starting from the molecular design of combining a polyaryletherketone resin and a gas separation membrane structure, a polar group with an amino group is introduced into the polymer main chain through a copolymerization reaction to form a polyaryletherketone resin with a polar amino structure, adjusting the steric hindrance of the polymer side chain, hindering the stacking of the polymer main chain, increasing the molecular spatial volume, and achieving the purpose of improving the gas flux while intercepting gas molecules with a larger kinetic diameter. This gas separation membrane has a higher hydrogen permeability coefficient, shortening the gas separation time and improving the component operation efficiency. Detailed Embodiments

[0040] The following details this application in combination with embodiments, but this application is not limited to these embodiments.

[0041] Unless otherwise specified, the raw materials in the embodiments of this application are all purchased through commercial channels.

[0042] Add isatinone bisphenol monomer, dihalo monomer, and bisphenol or dihalo monomer with 1-2 amino groups into a reaction flask equipped with mechanical stirring, an air inlet, and a water separator in a certain proportion. Add a solvent, a water-carrying agent, a catalyst, etc. Under the protection of an inert gas stream, heat to 80-170 °C and reflux for 0.5-4 h. Remove the water-carrying agent, continue to raise the temperature, release the water-carrying agent, transfer the water-carrying agent out of the reaction system, continue to raise the temperature to 140-230 °C, and react for 0.5-24 h. Wait until the viscosity of the system no longer increases. After cooling, add a certain amount of diluent, purify the polymer, and obtain a polyarylether resin for a separation membrane.

[0043] Gas permeability coefficient test: At 25 °C and a pressure of 0.2 MPa, test the single gas permeability coefficient.

[0044] In this application, the reduced viscosity is detected using an Ubbelohde viscometer;

[0045] The glass transition temperature is detected using DSC.

[0046] Example 1

[0047] Assemble the experimental device, add 11.213 g of bisphenol fluorene, 8.728 g of difluorobenzophenone, and 3.044 g of 9,9-bis(3-amino-4-hydroxyphenyl)fluorene. Pass nitrogen and cooling water, add 7.28 g of potassium carbonate, 25 ml of xylene, and 68 g of sulfolane. Heat to 155 °C. The water separator becomes turbid and droplets form. The water-carrying starts. Time for 2 h; raise the temperature to 165 °C, hold for 0.5-1 h, raise the temperature to 200 °C, and time for 1.5 h. When the reaction ends, the reaction solution is relatively viscous. Add N,N-dimethylacetamide for dilution; precipitate the diluted and uniform reaction solution in ethanol:water = 1000 ml:350 ml, and filter the precipitate; after crushing the solid, wash it with deionized water 8 times, dry it at 130 °C with blowing for 8 h, and dry it under vacuum to obtain polyaryletherketone powder with a reduced viscosity of 0.45 dl / g and Tg = 223 °C. Dissolve this polymer in DMAc and make a flat membrane for gas separation testing. The hydrogen permeability coefficient is 32 Barrer, and the nitrogen permeability coefficient is 0.8 Barrer; in the following formula, the value of m is 0.8 and the value of n is 0.2.

[0048]

[0049] Example 2

[0050] Assemble the experimental device, add 6.367 g of phenolphthalein, 12.892 g of 4,4-difluorotriphenyl diketone, and 5.6066 g of bis(3-amino-4-hydroxyphenyl) sulfone. Pass nitrogen and condensed water, add 7.0 g of potassium carbonate, 60 ml of xylene, and 69.5 g of sulfolane. Heat to 145 °C to remove water, time for 1 h; raise the temperature to 155 °C, hold for 50 min, then raise the temperature to 205 °C, time for 8 h. At the end of the reaction, the reaction solution is relatively viscous, add NMP for dilution; precipitate the diluted and uniform reaction solution in ethanol:water = 400 ml:800 ml, and filter the precipitate; after crushing the solid, wash it with deionized water, dry it at 100 °C with blowing for 10 h, and dry it in vacuum to obtain polyarylether powder with an inherent viscosity of 0.42 dl / g and Tg = 235 °C. Dissolve this polymer in NMP to make a flat membrane for gas separation testing. The hydrogen permeability coefficient is 21 Barrer, and the nitrogen permeability coefficient is 0.52 Barrer; in the following formula, the value of m is 0.5 and the value of n is 0.5.

[0051]

[0052] The above are only several embodiments of the present application and do not impose any form of limitation on the present application. Although the present application is disclosed above with preferred embodiments, it is not intended to limit the present application. Any person skilled in the art, without departing from the technical solution of the present application, making some changes or modifications using the disclosed technical content is equivalent to equivalent implementation cases and all fall within the scope of the technical solution.

Claims

1. A preparation method of an amino-group-containing polyaryletherketone resin, characterized in that, The preparation method includes: Under an inert atmosphere, reacting a mixture of a bisphenol monomer, a dihalo monomer, an amino-containing compound, and a catalyst to obtain the amino-group-containing side-chain polyaryletherketone resin; The amino-group-containing side-chain polyaryletherketone resin is selected from those having the structure shown in Formula II: Formula II; In Formula II, the value range of n is 0.1 to 0.9, the value range of m is 0.1 to 0.9, and n + m = 1; The amino-containing compound is bis(3-amino-4-hydroxyphenyl)sulfone; The bisphenol monomer is phenolphthalein; The dihalo monomer is 4,4-difluorotriphenyl dione; 2. The preparation method according to claim 1, characterized in that, The catalyst is selected from at least one of potassium carbonate, sodium carbonate, lithium carbonate, cesium carbonate, potassium bicarbonate, and sodium bicarbonate; 3. The preparation method according to claim 1, characterized in that, The molar ratio of the bisphenol monomer to the catalyst is 1:1.05 to 1:3; 4. The preparation method according to claim 1, wherein The mixture further includes a solvent, and the solvent is selected from at least one of N,N-dimethylacetamide, N,N-dimethylformamide, N-methylpyrrolidone, diphenyl sulfone, sulfolane, and N,N-dimethyl-4-aminopyridine; 5. The preparation method according to claim 4, characterized in that, The molar volume ratio of the bisphenol monomer to the solvent is 1 mol:800 to 3000 ml; 6. The preparation method according to claim 1, wherein The mixture further includes a water-carrying agent, and the water-carrying agent is selected from at least one of n-hexane, cyclohexane, benzene, toluene, xylene, and cumene; 7. The preparation method according to claim 6, characterized in that, The molar volume ratio of the bisphenol monomer to the water-carrying agent is 1 mol:100 to 1200 ml; 8. The preparation method according to claim 1, characterized in that, The inert atmosphere is selected from a nitrogen atmosphere and / or an argon atmosphere; 9. The preparation method according to claim 1, wherein, The temperature of the reaction is 80 to 230 °C, and the reaction time is 0.5 to 24 h; 10. The preparation method according to claim 1, characterized in that, The specific viscosity of the amino-group-containing side-chain polyaryletherketone resin is 0.25 dL / g to 1.2 dL / g; 11. According to the preparation method described in claim 1, wherein, The glass transition temperature of the amino-group-containing side-chain polyaryletherketone resin is 190 to 280 °C; 12. Use of the amino-group-containing side-chain polyaryletherketone resin prepared by the preparation method according to any one of claims 1 to 11 in a gas separation membrane.

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