A carboxyl-containing polyaryletherketone resin, preparation method thereof, and preparation method and application of cross-linked network structure polyaryletherketone

Abstract

This application discloses a carboxyl-containing polyaryletherketone resin, a preparation method, and a preparation method and application of a cross-linked network structure polyaryletherketone. By reacting the polyaryletherketone containing side carboxyl groups with multivalent (divalent or higher) metal ions, a dicarboxyl or polycarboxyl ion structure centered on the metal ion is formed. The degree of reaction is controlled, the heat resistance of the material is greatly improved, and the separation factor of the plate-type membrane material for gases is improved. The polyaryletherketone resin in this application has a cross-linked structure centered on the metal ion, has a higher glass transition temperature than carboxyl polymers, and has the advantages of being easily regulated. It has a wide range of applications in the fields of sensors, separation membranes, etc.

Description

Technical Field

[0001] The present application relates to a carboxyl-containing polyaryletherketone resin, a preparation method, and a preparation method and application of a cross-linked network structure polyaryletherketone, belonging to the field of polymer technology synthesis. Background Art

[0002] Polyaryletherketone (PEK) has excellent heat resistance, mechanical properties, and electrical insulation, and is widely used in aerospace, electronics, machinery manufacturing, and other fields. In applications, it was found that PEEK resins lack polar groups, have poor interaction with other carbon, metal, or polymer materials, and have weak interfaces. This has limited their applications in composite reinforcement, toughening, adhesives, and separation membranes. Since polymer water treatment membranes without polar side groups have poor antifouling properties, researchers have introduced carboxylic acid structures to improve their pollution resistance. However, the introduction of carboxyl groups often results in low temperature resistance in polymers. By using ionic polymers centered around metal ions, the interaction between molecular chains can be enhanced, thereby increasing their glass transition temperature.

[0003] Li Chenghui from Nanjing University reported a method for preparing a carboxyl-containing polymer centered on divalent zinc ions (NATURE COMMUNICATIONS, (2018) 9:2725). Since the polymer used is polydimethylsiloxane with pendant carboxyl groups and the main chain is a flexible structure, the mechanical properties of the polymer are insufficient. Summary of the Invention

[0004] This application combines the molecular design of polyaryletherketone resins with the application requirements of separation membranes and high-performance functional materials, and introduces divalent or higher metal ions as cross-linking centers in carboxyl-containing polymer chains. This structure has a more stable topological structure, making the polymer chain more stable when heated and having a higher glass transition temperature. For amorphous polymers, this means that the operating temperature will be greatly increased. At the same time, the cross-linking center can free the carboxyl groups and metal ions of the polymer under acidic conditions, and the high temperature resistance and stability of polyaryletherketone under acidic conditions make the carboxyl-containing polyaryletherketone reusable.

[0005] According to the first aspect of the present application, there is provided a carboxyl-containing polyaryletherketone resin having a structure as described in Formula I;

[0006]

[0007] 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 m+n=1; the carboxyl content of the carboxyl-containing polyaryletherketone resin is 10 wt% to 90 wt%.

[0008] According to a second aspect of the present application, a method for preparing the above-mentioned carboxyl-containing polyaryletherketone resin is provided, the preparation method comprising:

[0009] A mixture containing 3,3-bis(4-hydroxyphenyl)-2-benzisoisoindolin-1-one, phenolphthalein, dihalogenated dibenzophenone, alkali metal carbonate, solvent I, and water-carrying agent is reacted to obtain a carboxyl-containing polyaryletherketone resin.

[0010] Optionally, the dihalogenated benzophenone is at least one selected from 4,4'-difluorobenzophenone, 4,4'-dichlorobenzophenone, 1,4-bis(4-fluorobenzoyl)benzene, and 1,3-bis(4-fluorobenzoyl)benzene.

[0011] Optionally, the molar ratio of the 3,3-bis(4-hydroxyphenyl)-2-benzisoisoindolin-1-one to the dihalogenated benzophenone is 1:10 to 9:10.

[0012] Optionally, the molar ratio of the 3,3-bis(4-hydroxyphenyl)-2-benzisoisoindolin-1-one to the phenolphthalein is 1:9 to 9:1.

[0013] Optionally, the solvent I is selected from at least one of sulfolane, dimethyl sulfoxide, N-methylpyrrolidone, and N,N-dimethylacetamide.

[0014] Optionally, the mass of the solvent I is 2 to 8 times the theoretical mass yield of the carboxyl-containing polyaryletherketone resin.

[0015] Optionally, the water-carrying agent is selected from at least one of toluene and xylene.

[0016] Optionally, the mass of the water-carrying agent is 5% to 70% of the mass of the solvent.

[0017] Optionally, the alkali metal carbonate is selected from at least one of potassium carbonate, sodium carbonate, lithium carbonate, cesium carbonate, sodium bicarbonate, and potassium bicarbonate.

[0018] Optionally, the molar ratio of the dihalobenzophenone to the alkali metal carbonate is 1:1.05 to 1:1.5.

[0019] Optionally, the temperature of the reaction I is 120° C. to 210° C., and the time of the reaction I is 0.5 to 14 h.

[0020] Optionally, the temperature of the reaction I is selected from any value of 120°C, 150°C, 180°C, 190°C, 200°C, 210°C, or a range between any two of the above points.

[0021] Optionally, the reaction time I is selected from any value of 0.5, 1 h, 5 h, 8 h, 10 h, 12 h, 14 h, or a range between any two of the above points.

[0022] According to a third aspect of the present application, a method for preparing a cross-linked network structured polyaryletherketone is provided, the method comprising:

[0023] The mixture of carboxyl-containing polyaryletherketone resin, metal salt, solvent II and catalyst is reacted in step II to obtain the cross-linked network structure polyaryletherketone;

[0024] The carboxyl-containing polyaryletherketone resin is selected from the carboxyl-containing polyaryletherketone resin described above and the carboxyl-containing polyaryletherketone resin prepared by the preparation method described above.

[0025] Optionally, the metal salt is selected from Zn 2+ , Ca 2+ 、Ba 2+ Mg 2+ 、Fe 2+ 、Cu 2+ 、Ni 2+ 、Hg 2+ 、Al 3+ 、Fe 3+ 、Co 3 + 、Au 3+ 、Ce 3+ 、Ce 4+ 、Ti 4+ 、Zr 4+ 、Mn 4+ At least one of chlorides, sulfates, and nitrates of metal ions.

[0026] Optionally, the molar ratio of the carboxyl-containing polyaryletherketone resin to the metal salt is 10:0.1 to 10:1.

[0027] Optionally, the catalyst is selected from at least one of triethylamine, dimethyl sulfoxide, N,N-dimethylaniline, and diethylmethylamine.

[0028] Optionally, the molar ratio of the carboxyl-containing polyaryletherketone resin to the catalyst is 0.5:1 to 5:1.

[0029] Optionally, the solvent II is selected from at least one of N-methylpyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, and dimethyl sulfoxide.

[0030] Optionally, the mass of the solvent II is 0.5 to 8 times the theoretical mass yield of the cross-linked network structure polyaryletherketone.

[0031] Optionally, the temperature of the reaction II is 50 to 220° C., and the time of the reaction II is 0.5 to 24 hours.

[0032] Optionally, the temperature of the reaction II is selected from any value of 50°C, 80°C, 100°C, 120°C, 150°C, 180°C, 200°C, 220°C, or a range between any two of the above points.

[0033] Optionally, the time of reaction II is selected from any value of 0.5, 1 h, 5 h, 10 h, 12 h, 18 h, 24 h, or a range between any two of the above points.

[0034] According to a fourth aspect of the present application, there is provided a cross-linked network structure polyaryletherketone prepared by the above-mentioned preparation method, wherein the cross-linked network structure polyaryletherketone uses metal ions as cross-linking centers;

[0035] The glass transition temperature of the cross-linked network structure polyaryletherketone can be increased by 20 to 70°C.

[0036] According to the fifth aspect of the present application, there are provided a cross-linked network structure polyaryletherketone prepared by the above-mentioned preparation method, and the use of the above-mentioned cross-linked network structure polyaryletherketone in sensors and separation membranes.

[0037] According to the sixth aspect of the present application, a multivalent ion crosslinking method for carboxyl-containing polyaryletherketone is provided. Divalent and above metal ions, including divalent ions such as Zn 2+ , Ca 2+ 、Ba 2+ Mg 2+ 、Fe 2 + 、Cu 2+ 、Ni 2+ 、Hg 2+ etc., trivalent ions such as Al 3+ 、Fe 3+ 、Co 3+ 、Au 3+ 、Ce 3+ etc., tetravalent ions such as Ce 4+ 、Ti 4+ 、Zr 4+ 、Mn 4+ The polyvalent metal-centered carboxyl-containing polyaryletherketone resin has poor molecular chain mobility and greater chain rigidity due to the formation of metal ion bonds, which significantly increases the glass transition temperature, resulting in a carboxyl-containing polyaryletherketone resin with higher heat resistance. Since the carboxyl content can be adjusted, the cost of the polymer is greatly reduced.

[0038] In the present application, the cross-linking method of carboxyl-containing polyaryletherketone refers to a method of introducing metal ion bonds on the main chain of carboxyl-containing polyaryletherketone to form polyaryletherketone with a cross-linked network structure.

[0039] In the present application, a cross-linking method for carboxyl-containing polyaryletherketone resin is characterized by forming a dicarboxyl or polycarboxyl ion structure centered on the metal ion through the reaction of the side carboxyl-containing polyaryletherketone with multivalent (divalent and above) metal ions, controlling the degree of reaction, greatly improving the heat resistance of the material, and improving the separation factor of the plate membrane material for gas.

[0040] In the present application, the cross-linked network structure polyaryletherketone has a metal ion-centered cross-linked structure, has a higher glass transition temperature than carboxyl polymers, and has the advantages of easy structure regulation. It is widely used in sensors, separation membranes and other fields.

[0041] The beneficial effects of this application include:

[0042] 1) The present application provides a cross-linking method for a carboxyl-containing polyaryletherketone resin, which has high main chain rigidity, provides a controllable metal ion center, and achieves different cross-linking degrees and temperature resistance levels.

[0043] 2) The carboxyl-containing polyaryletherketone cross-linked resin provided in this application has readily available raw materials and has certain cost advantages.

[0044] 3) The cross-linking method of the carboxyl-containing polyaryletherketone resin provided in this application can adjust the free volume of the polymer, change the interchain structure, and improve the selective permeability to gases. BRIEF DESCRIPTION OF THE DRAWINGS

[0045] Figure 1 This is the secondary temperature rise curve of differential scanning calorimetry analysis in Example 1 of the present application.

[0046] Figure 2 This is the NMR spectrum in Example 1 of the present application. DETAILED DESCRIPTION

[0047] The present application is described in detail below with reference to embodiments, but the present application is not limited to these embodiments.

[0048] Unless otherwise specified, the raw materials in the examples of this application were purchased through commercial channels.

[0049] Room temperature in this application refers to 25°C.

[0050] The glass transition temperature was measured by differential scanning calorimetry (DSC25, TA Instruments) in the range of 30-300° C. The H NMR spectra were measured using a Bruker 400M NMR spectrometer.

[0051] A carboxyl-containing polyaryletherketone resin is mixed with a polyvalent metal halide / sulfate or nitrate in a specific proportion, an organic solvent and a catalyst are added, and the mixture is stirred at room temperature for 0-2 hours. The mixture is heated to 50-220°C and reacted for 0.5-24 hours. After purification, a polyaryletherketone resin with a certain degree of crosslinking centered around the polyvalent metal ion is obtained. The glass transition temperature can be increased by 20-70°C.

[0052] Example 1

[0053] 15.74 g of 3,3-bis(4-hydroxyphenyl)-2-benzisoisoindolin-1-one, 12.82 g of phenolphthalein, and 17.46 g of 4,4'-difluorobenzophenone were mixed in a ratio of 1:1. 19.07 g of potassium carbonate and 85.0 g of sulfolane were added as solvents, and 40 ml of toluene was used as a water carrier. The mixture was heated to 120°C for 3 h. The toluene was then removed and the reaction temperature was controlled at 210°C for 5 h. The reaction mixture was cooled and diluted with DMAc. The reaction mixture was precipitated in hydrochloric acid-acidified water / ethanol (hydrochloric acid:water:ethanol = 1:15:120, volume ratio). The mixture was washed repeatedly with water and purified to obtain a white flocculent polymer with a m:n ratio of 1:1.

[0054] Figure 1 It can be seen that the glass transition temperature of the cross-linked polyaryletherketone resin is 232°C.

[0055] Figure 2 The successful polymerization of the copolymer was confirmed by the H-NMR spectrum of the carboxyl-containing polyaryletherketone resin (m:n=1:1).

[0056] The glass transition temperature of the polymer is 232°C, the carboxyl content is 50%, and the plate-type membrane has a high permeability coefficient and separation factor for nitrogen.

[0057]

[0058] 5.56g of carboxyl-containing polyaryletherketone (PEK) and 0.34g of zinc chloride (ZnCl) were mixed in a 10:0.25 molar ratio. 50ml of DMAc was added as a solvent. 0.42ml of triethylamine was used as a catalyst. The mixture was stirred at room temperature for 10 minutes and heated to 120°C for 24 hours. After dilution, precipitation, and purification, a polyaryletherketone resin with a certain degree of crosslinking centered around divalent zinc ions was obtained. The glass transition temperature was increased by 60°C.

[0059] Example 2

[0060] This example still uses the carboxyl-containing polyaryletherketone described in Example 1, but replaces zinc chloride with ferric sulfate (ferric ion). 5.56g of the carboxyl-containing polyaryletherketone and 0.40g of ferric sulfate are mixed in a ratio of 10:0.1. 60ml of NMP and 0.6ml of triethylamine are added. The mixture is stirred at room temperature for 80 minutes, heated to 150°C for 4 hours, and then diluted, precipitated, and purified to obtain a polyaryletherketone resin with a certain degree of crosslinking centered around the ferric ion. The glass transition temperature is increased by 45°C.

[0061] Example 3

[0062] 5.56g of carboxyl-containing polyaryletherketone (PEK) and 0.878g of copper sulfate were mixed in a 10:0.55 molar ratio. 50ml of NMP was added as a solvent. 0.3ml of triethylamine was used as a catalyst. The mixture was stirred at room temperature for 200 minutes and heated to 160°C for 8 hours. After dilution, precipitation, and purification, a polyaryletherketone resin with a certain degree of crosslinking centered around divalent copper ions was obtained. The glass transition temperature was increased by 35°C.

[0063] Example 4

[0064] 5.56g of carboxyl-containing polyaryletherketone (PEK) and 1.04g of titanium tetrachloride (TiCl) were mixed in a 10:0.55 molar ratio. 50ml of NMP was added as the solvent, and nitrogen was introduced at a constant flow rate. 0.55ml of triethylamine was used as a catalyst. The mixture was stirred at room temperature for 200 minutes and heated to 160°C for 48 hours. After dilution, precipitation, and purification, a polyaryletherketone resin with a certain degree of crosslinking centered around tetravalent titanium ions was obtained. The glass transition temperature was increased by 70°C.

[0065] The above descriptions are merely a few embodiments of the present application and do not constitute any form of limitation to the present application. Although the present application discloses the preferred embodiments as above, they are not intended to limit the present application. Any technical personnel familiar with the present profession, without departing from the scope of the technical solution of the present application, using the technical content disclosed above to make slight changes or modifications are equivalent to equivalent implementation cases and fall within the scope of the technical solution.

Claims

1. A method for preparing a cross-linked network structure polyaryletherketone, characterized in that: The preparation method comprises: The mixture of carboxyl-containing polyaryletherketone resin, metal salt, solvent II and catalyst is reacted in step II to obtain the cross-linked network structure polyaryletherketone; The carboxyl-containing polyaryletherketone resin has the structure described in Formula I; Formula I; In formula I, the value range of n is 0.1~0.9, the value range of m is 0.1~0.9, and m+n=1; The carboxyl content of the carboxyl polyaryletherketone resin is 10 wt% to 90 wt%; The metal salt is selected from the group consisting of Zn 2+ , Ca 2+ 、Ba 2+ Mg 2+ 、Fe 2+ 、Cu 2+ 、Ni 2+ 、Hg 2+ 、Al 3+ 、Fe 3+ 、Co 3+ 、Au 3+ 、Ce 3+ 、Ce 4+ 、Ti 4+ 、Zr 4+ 、Mn 4+ At least one of chloride, sulfate, and nitrate of a metal ion; The catalyst is triethylamine; The solvent II is selected from at least one of N-methylpyrrolidone, N,N-dimethylacetamide, and N,N-dimethylformamide.

2. The preparation method according to claim 1, characterized in that The molar ratio of the carboxyl-containing polyaryletherketone resin to the metal salt is 10:0.1 to 10:1; The molar ratio of the carboxyl-containing polyaryletherketone resin to the catalyst is 0.5:1 to 5:

1.

3. The preparation method according to claim 1, characterized in that The mass of the solvent II is 0.5 to 8 times the theoretical mass yield of the cross-linked network structure polyaryletherketone; The temperature of the reaction II is 50-220° C., and the time of the reaction II is 0.5-24 h.

4. The preparation method according to claim 1, characterized in that The preparation method of the carboxyl-containing polyaryletherketone resin comprises: A mixture containing 3,3-bis(4-hydroxyphenyl)-2-benzisoisoindolin-1-one, phenolphthalein, dihalogenated dibenzophenone, alkali metal carbonate, solvent I, and water-carrying agent is subjected to reaction I to obtain a carboxyl-containing polyaryletherketone resin.

5. The preparation method according to claim 4, characterized in that The dihalogenated benzophenone is selected from at least one of 4,4'-difluorobenzophenone and 4,4'-dichlorobenzophenone; The molar ratio of the 3,3-bis(4-hydroxyphenyl)-2-benzisoisoindolin-1-one to the dihalogenated benzophenone is 1:10 to 9:10; The molar ratio of the 3,3-bis(4-hydroxyphenyl)-2-benzisoisoindolin-1-one to the phenolphthalein is 1:9 to 9:

1.

6. The preparation method according to claim 4, characterized in that The solvent I is selected from at least one of sulfolane, dimethyl sulfoxide, N-methylpyrrolidone, and N, N-dimethylacetamide; The mass of the solvent I is 2 to 8 times the theoretical mass yield of the carboxyl-containing polyaryletherketone resin; The water-carrying agent is selected from at least one of toluene and xylene; The mass of the water-carrying agent is 5% to 70% of the mass of the solvent; The alkali metal carbonate is selected from at least one of potassium carbonate, sodium carbonate, lithium carbonate, cesium carbonate, potassium bicarbonate, and sodium bicarbonate; The molar ratio of the dihalogenated benzophenone to the alkali metal carbonate is 1:1.05 to 1:1.

5.

7. The preparation method according to claim 4, characterized in that The temperature of the reaction I is 120° C. to 210° C., and the time of the reaction I is 0.5 to 14 h.

8. The cross-linked network structure polyaryletherketone prepared by the preparation method according to any one of claims 1 to 7, characterized in that: The cross-linked network structure polyaryletherketone uses metal ions as cross-linking centers; The glass transition temperature of the cross-linked network structure polyaryletherketone can be increased by 20-70°C.

9. Use of the cross-linked network structure polyaryletherketone prepared by the preparation method according to any one of claims 1 to 7, or the cross-linked network structure polyaryletherketone according to claim 8 in a sensor or a separation membrane.

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