A polyarylether polymer containing a ketimine structure and its preparation method

Abstract

The present invention relates to the technical field of polymer synthesis, and particularly relates to a polyarylether polymer containing a ketimine structure and a preparation method thereof. The present invention provides a polyarylether polymer containing a ketimine structure, having the structure shown in formula (I); in formula (I), n≥10; Ar is selected from aromatic groups; R1 is selected from substituted or unsubstituted aromatic groups, or substituted or unsubstituted alkyl groups. The present invention modifies a bisphenol monomer containing a benzophenone structure to prepare a bisphenol monomer containing a ketimine structure. The reactivity of the modified bisphenol monomer in the polymerization reaction increases, and then polymerization with a dihalogen monomer can obtain a soluble high-molecular-weight polyarylether polymer containing a ketimine structure. At the same time, the yield of the polyarylether polymer containing a ketimine structure obtained by the preparation method provided by the present invention is relatively high.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer synthesis, and particularly relates to a polyarylether polymer containing a ketimine structure and a preparation method thereof. Background Art

[0002] Polyarylethers have advantages such as good heat resistance, excellent mechanical properties, good dimensional stability, simple material synthesis, and high cost performance, and are widely used in industrial fields such as electronics, food, machinery, medical treatment, automobiles, and aerospace. Its representative products mainly include polyarylethers, polyarylether sulfones, polyarylether ketones, polyarylether nitriles, etc.

[0003] Among them, polyarylether polymers containing a ketone carbonyl group often have poor solubility in organic solvents due to the strong rigidity of the diphenyl ketone structural unit and the π-π stacking effect. Polymers such as polyether ketone (PEK), polyether ether ketone (PEEK), polyether ketone ketone (PEKK), polyether ketone ether ether ketone (PEKEEK), and polyether ketone ether ketone ketone (PEKEKK) are usually insoluble in conventional organic solvents, which makes such polymers ideal solvent-resistant special high molecular materials. However, the poor solubility limits the application of such polymers in many fields, especially in devices with nanoscale precision that are difficult to achieve by melt processing, such as nanofibers, nanofiltration membranes, etc. Common methods for solution processing of such polymers are to dissolve them in strong acids such as concentrated sulfuric acid, methanesulfonic acid, and trifluoromethanesulfonic acid, but this method usually causes degradation of the main chain, and the use of a large amount of strong acids brings great difficulties to large-scale production.

[0004] In order to improve the solubility of polyarylether polymers containing a diphenyl ketone structure, researchers have developed a method for preparing polyarylether polymers containing a ketimine structure by converting a ketone carbonyl group into a ketimine group. The polymers prepared by this method have good solubility, can be processed by solution, and can be converted into polyarylether polymers containing a carbonyl group such as polyether ether ketone after acid treatment after being processed into devices.

[0005] The existing technical solution is to modify a carbonyl-containing dihalogen monomer to obtain a dihalogen monomer containing a ketimine structure, and then carry out polymerization (see Patent CN 106633034A). The limitation of this technical route is that the conversion speed of monomer preparation is slow, the presence of halogen atoms leads to side reactions during monomer preparation, and the crude product requires complex purification processes such as multiple recrystallizations, resulting in a low yield of the dihalogen monomer containing a ketimine structure, greatly increasing the manufacturing cost of the polymer. In addition, after converting the carbonyl group into a ketimine, the electron-withdrawing ability is weakened, resulting in a decrease in the polymerization activity of the dihalogen monomer. Summary of the Invention

[0006] In view of this, the technical problem to be solved by the present invention is to provide a soluble polyarylether polymer containing a ketimine structure and a preparation method thereof.

[0007] The present invention provides a polyarylether polymer containing a ketimine structure, having the structure shown in formula (I);

[0008]

[0009] In formula (I), n≥10;

[0010] Ar is selected from aromatic groups;

[0011] R1 is selected from substituted or unsubstituted aromatic groups, or substituted or unsubstituted alkyl groups.

[0012] Preferably, n≥20;

[0013] Ar is selected from the structures shown in formula A-1 to formula A-3:

[0014]

[0015] In formula A-2, a = 1, 2 or 3;

[0016] R1 is selected from phenyl, substituted phenyl, biphenyl, naphthyl, substituted naphthyl or an alkyl group with 1 to 12 carbon atoms; the alkyl group is selected from straight-chain alkyl groups, branched-chain alkyl groups or cycloalkyl groups.

[0017] Preferably, R1 is selected from the structures shown in formula R-1 to formula R-7:

[0018]

[0019] R2 is selected from -H, -F, -Cl, -Br, -COOH, -SO3H, -NH2, -NO3, -CN, -OCH3, -CH3, -C2H5 or -tBU;

[0020] In formula R-7, 1≤m≤12.

[0021] The present invention also provides a preparation method of the polyarylether polymer containing a ketimine structure described above, including the following steps:

[0022] Under the action of a first catalyst, a diphenol monomer containing a ketimine structure with the structure shown in formula (II) and an aromatic dihalide monomer are subjected to a polymerization reaction in a first solvent to obtain a polyarylether polymer containing a ketimine structure with the structure shown in formula (I);

[0023]

[0024] Among them, n≥10;

[0025] Ar is selected from aromatic groups;

[0026] R1 is selected from substituted or unsubstituted aromatic groups, or substituted or unsubstituted alkyl groups.

[0027] Preferably, the preparation method of the ketimine structure-containing diphenol monomer having the structure shown in formula (II) includes the following steps:

[0028] Mix 4,4'-dihydroxybenzophenone, R1-NH2, a second catalyst and a second solvent, and then carry out a reaction to obtain a ketimine structure-containing diphenol monomer having the structure shown in formula (II);

[0029] R1 is selected from substituted or unsubstituted aromatic groups, or substituted or unsubstituted alkyl groups.

[0030] Preferably, the second catalyst includes one or more of hydrochloric acid, acetic acid, sulfuric acid, oxalic acid, p-toluenesulfonic acid, p-toluenesulfonic acid monohydrate, methanesulfonic acid, aluminum chloride, titanium chloride, and tin chloride;

[0031] The molar ratio of the 4,4'-dihydroxybenzophenone, R1-NH2 and the second catalyst is 1:1 to 10:0.01 to 0.5;

[0032] The second solvent includes one or more of N-methylpyrrolidone, dimethyl sulfoxide, N,N-dimethylformamide, and N,N-dimethylacetamide.

[0033] Preferably, the temperature of the reaction is 60 to 200 °C, and the time is 6 to 48 h.

[0034] Preferably, the first catalyst includes one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate;

[0035] The molar ratio of 4,4'-dihydroxybenzophenone, aromatic dihalide monomer and the first catalyst is 1:0.95 to 1.05:1.05 to 2.5.

[0036] Preferably, the aromatic dihalide monomer is selected from the structures shown in formula F-1 to formula F-3:

[0037]

[0038] Among them, X1 and X2 are independently selected from halogens;

[0039] In formula F-2, a = 1, 2 or 3.

[0040] Preferably, the first solvent includes one or more of N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone, diphenyl sulfone, and sulfolane;

[0041] The temperature of the polymerization reaction is 150 - 250 °C, and the time is 0.5 - 48 h.

[0042] The present invention provides a polyarylether polymer containing a ketimine structure, having the structure shown in formula (I); in formula (I), n ≥ 10; Ar is selected from aromatic groups; R1 is selected from substituted or unsubstituted aromatic groups, or substituted or unsubstituted alkyl groups. The polyarylether polymer containing a ketimine structure provided by the present invention is a high-molecular-weight polyarylether polymer containing a ketimine structure that is soluble in polar aprotic solvents such as tetrahydrofuran, N-methylpyrrolidone, N,N-dimethylacetamide, and halogenated hydrocarbons such as dichloromethane and chloroform.

[0043] The present invention also provides a preparation method of the above-mentioned polyarylether polymer containing a ketimine structure, comprising the following steps: under the action of a first catalyst, a diphenol monomer containing a ketimine structure shown in formula (II) and an aromatic dihalide monomer are subjected to a polymerization reaction in a first solvent to obtain a polyarylether polymer containing a ketimine structure shown in formula (I); wherein, n ≥ 10; Ar is selected from aromatic groups; R1 is selected from substituted or unsubstituted aromatic groups, or substituted or unsubstituted alkyl groups. The present invention develops a new technical route, that is, a bisphenol monomer containing a benzophenone structure is modified to prepare a bisphenol monomer containing a ketimine structure. The reactivity of the modified bisphenol monomer in the polymerization reaction increases, and then it is polymerized with a dihalide monomer to obtain a high-molecular-weight polyarylether polymer containing a ketimine structure that is soluble in polar aprotic solvents such as tetrahydrofuran, N-methylpyrrolidone, N,N-dimethylacetamide, and halogenated hydrocarbons such as dichloromethane and chloroform. The polyarylether polymer containing a ketimine structure obtained by the preparation method provided by the present invention has a high yield. Description of the Drawings

[0044] Figure 1 1H NMR spectrum of N-phenyl-4,4'-dihydroxybenzophenone imine in Example 1 of the present invention.

[0045] Figure 2 1H NMR spectrum of the polyarylether ketone containing a ketimine structure in Example 3 of the present invention. Detailed Description of the Invention

[0046] The technical solutions of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention.

[0047] The present invention provides a polyarylether polymer containing a ketimine structure, having the structure shown in formula (I);

[0048]

[0049] In formula (I), n ≥ 10;

[0050] Ar is selected from aromatic groups;

[0051] R1 is selected from substituted or unsubstituted aromatic groups, or substituted or unsubstituted alkyl groups.

[0052] In certain embodiments of the present invention, n ≥ 20.

[0053] In certain embodiments of the present invention, Ar is selected from the structures shown in Formula A-1 to Formula A-3:

[0054]

[0055] In Formula A-2, a = 1, 2 or 3.

[0056] In certain embodiments of the present invention, R1 is selected from phenyl, substituted phenyl, biphenyl, naphthyl, substituted naphthyl or alkyl groups having 1 to 12 carbon atoms; the alkyl groups are selected from linear alkyl groups, branched alkyl groups or cycloalkyl groups; specifically, they can be cyclohexyl, cyclopentyl or tert-butyl. The substituents include hydrogen, halogen, carboxyl, sulfonic acid group, amino group, nitro group, cyano group, alkoxy group, linear alkyl group or branched alkyl group.

[0057] In certain embodiments of the present invention, R1 is selected from the structures shown in Formula R-1 to Formula R-7:

[0058]

[0059] R2 is selected from -H, -F, -Cl, -Br, -COOH, -SO3H, -NH2, -NO3, -CN, -OCH3, -CH3, -C2H5 or -tBU.

[0060] In Formula R-7, 1 ≤ m ≤ 12.

[0061] In certain embodiments of the present invention, the number average molecular weight of the polyarylether polymer containing a ketimine structure is 30 to 60 KDa, the weight average molecular weight is 50 to 100 KDa, and the molecular weight distribution index is 1.5 to 2.5.

[0062] In certain embodiments of the present invention, the polyarylether polymer containing a ketimine structure is prepared from raw materials including a ketimine structure diphenol monomer having the structure shown in Formula (II), an aromatic dihalide monomer, a first catalyst and a first solvent.

[0063] The present invention also provides a method for preparing the polyarylether polymer containing a ketimine structure as described above, comprising the following steps:

[0064] Under the action of a first catalyst, a diphenol monomer containing a ketimine structure with the structure shown in formula (II) and an aromatic dihalide monomer are subjected to a polymerization reaction in a first solvent to obtain a polyarylether polymer containing a ketimine structure with the structure shown in formula (I);

[0065]

[0066] wherein, n ≥ 10;

[0067] Ar is selected from aromatic groups;

[0068] R1 is selected from substituted or unsubstituted aromatic groups, or substituted or unsubstituted alkyl groups.

[0069] In the said preparation method, the selection of R1 is the same as above and will not be elaborated herein specially.

[0070] In certain embodiments of the present invention, the diphenol monomer containing a ketimine structure with the structure shown in formula (II) is prepared from raw materials including 4,4'-dihydroxybenzophenone, R1-NH2, a second catalyst and a second solvent.

[0071] In certain embodiments of the present invention, the preparation method of the diphenol monomer containing a ketimine structure with the structure shown in formula (II) comprises the following steps:

[0072] After mixing 4,4'-dihydroxybenzophenone, R1-NH2, a second catalyst and a second solvent, a reaction is carried out to obtain a diphenol monomer containing a ketimine structure with the structure shown in formula (II).

[0073] The selection of the said R1 is the same as above and will not be elaborated herein specially. In certain embodiments of the present invention, the R1 is phenyl, formula R-4 or formula R-5; R1-NH2 is aniline, cyclohexylamine or cyclopentylamine.

[0074] The said second catalyst is a protonic acid or a Lewis acid well-known to those skilled in the art, including but not limited to one or several of hydrochloric acid, acetic acid, sulfuric acid, oxalic acid, p-toluenesulfonic acid, p-toluenesulfonic acid monohydrate, methanesulfonic acid, aluminum chloride, titanium chloride and stannous chloride.

[0075] The molar ratio of 4,4'-dihydroxybenzophenone, R1-NH2 and the second catalyst is 1:1 to 10:0.01 to 0.5; specifically 1:3:0.02.

[0076] The second solvent is any organic solvent well-known to those skilled in the art that can dissolve 4,4'-dihydroxybenzophenone, or directly use R1-NH2 as the reaction solvent. The second solvent includes one or more of N-methylpyrrolidone, dimethyl sulfoxide, N,N-dimethylformamide, and N,N-dimethylacetamide. The dosage ratio of 4,4'-dihydroxybenzophenone to the second solvent is 1 mol: 100 - 500 mL; specifically 1 mol: 300 mL.

[0077] During the reaction process, a water-carrying agent well-known to those skilled in the art can be optionally added, preferably toluene, xylene, chlorobenzene, or cyclohexane. Specifically, the water-separator is filled with the water-carrying agent, and the volume ratio of the water-carrying agent added to the reaction system to the second solvent is 0.2 - 2: 1 - 2; specifically 1: 1.5.

[0078] The temperature of the reaction is 60 - 200 °C, specifically 180 °C, 150 °C, 130 °C, 100 °C; the time is 6 - 48 h, specifically 18 h, 10 h, 12 h, 16 h.

[0079] In some embodiments of the present invention, after the reaction, it further includes: settling the reaction product solution in an aqueous NaHCO3 solution to obtain a white solid, and recrystallizing with ethanol to obtain a ketimine-structured diphenol monomer having the structure shown in formula (II).

[0080] In some embodiments of the present invention, after the reaction, it further includes: removing the water-carrying agent.

[0081] In some embodiments, after removing the water-carrying agent, it further includes: settling the reaction product solution in an aqueous NaHCO3 solution to obtain a white solid, and recrystallizing with ethanol to obtain a ketimine-structured diphenol monomer having the structure shown in formula (II). The method for removing the water-carrying agent can be distilling out the water-carrying agent.

[0082] In some embodiments of the present invention, after the reaction, it further includes: removing the remaining R1-NH2; the specific method is: heating and evaporating.

[0083] After obtaining the ketimine-structured diphenol monomer having the structure shown in formula (II), under the action of a first catalyst, the ketimine-structured diphenol monomer having the structure shown in formula (II) and an aromatic dihalide monomer are subjected to a polymerization reaction in a first solvent to obtain a ketimine-structured polyarylether polymer having the structure shown in formula (I).

[0084] Specifically, it includes:

[0085] Method 1: A ketimine structure diphenol monomer having the structure shown in formula (II), an aromatic dihalide monomer, a first catalyst, and a first solvent are mixed and then subjected to a polymerization reaction to obtain a polyarylether polymer having a ketimine structure shown in formula (I);

[0086] Or

[0087] Method 2: Directly in the system after removing the remaining R1-NH2 in the above reaction (i.e., the reaction for preparing the ketimine structure diphenol monomer having the structure shown in formula (II)) (i.e., the system that only performs the step of removing the remaining R1-NH2 after the reaction) or in the system after removing the water-carrying agent in the above reaction (i.e., the system that only performs the step of removing the water-carrying agent after the reaction), an aromatic dihalide monomer, a first catalyst, and a first solvent are added, and a polymerization reaction is carried out to obtain a polyarylether polymer having a ketimine structure shown in formula (I) (this second method is a one-pot preparation).

[0088] In certain embodiments of the present invention, the aromatic dihalide monomer is selected from the structures shown in formula F-1 to formula F-3:

[0089]

[0090] Among them, X1 and X2 are independently selected from halogens. Specifically, X1 and X2 are independently selected from F or Cl. The source of the aromatic dihalide monomer can be commercially available generally.

[0091] In formula F-2, a = 1, 2, or 3.

[0092] In certain embodiments of the present invention, the first catalyst is a base catalyst. The first catalyst includes but is not limited to alkali metal hydroxides and / or alkali metal carbonates; preferably one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate.

[0093] In certain embodiments of the present invention, the molar ratio of 4,4'-dihydroxybenzophenone, the aromatic dihalide monomer, and the first catalyst is 1:0.95 - 1.05:1.05 - 2.5; specifically 1:1:2.05 or 1:1:1.5.

[0094] In certain embodiments of the present invention, the first solvent is a polar aprotic solvent; including one or more of N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone, diphenyl sulfone, and sulfolane. In certain embodiments, the mass ratio of the aromatic dihalide monomer to the amount of the first solvent used is 50 - 100 g:80 - 500 mL; specifically 21.82 g:200 mL or 21.82 g:90 mL.

[0095] During the polymerization reaction, a water-carrying agent well-known to those skilled in the art can be optionally added, preferably toluene, xylene, chlorobenzene or cyclohexane. Specifically, the water-carrying agent fills the water separator, and the volume ratio of the water-carrying agent added to the polymerization reaction system to the first solvent is 0.2-2:1; specifically 0.5:1.

[0096] The temperature of the polymerization reaction is 150-250°C, specifically 170-230°C, more specifically 180°C, 200°C; the time is 0.5-48 h, specifically 1-12 h, more specifically 3 h, 1.2 h, 1.5 h or 4 h.

[0097] In some embodiments of the present invention, the polymerization reaction is carried out under the condition of a protective gas, and the protective gas is an inert gas; specifically nitrogen. In some embodiments of the present invention, the polymerization reaction is carried out under stirring conditions.

[0098] The polymerization reaction is carried out in a reaction vessel equipped with a mechanical stirrer, a water separator and a condenser.

[0099] In some embodiments of the present invention, after the polymerization reaction, it further includes:

[0100] Pour the product solution obtained from the polymerization reaction into deionized water or ethanol, and wash and dry the obtained solid.

[0101] In some embodiments of the present invention, before pouring the product solution obtained from the polymerization reaction into deionized water or ethanol, it further includes: diluting with a first solvent. The molar amount of the aromatic dihalide monomer to the amount of the first solvent used for dilution is 0.1 mol: 100-300 mL; specifically 0.1 mol: 200 mL.

[0102] In the one-pot preparation method of the polyarylether polymer containing a ketimine structure provided by the present invention, there is no need for complex purification processes such as recrystallization. After obtaining the ketimine structure diphenol monomer with the structure shown in formula (II), there is also no need for complex purification processes such as recrystallization in the preparation of the polyarylether polymer containing a ketimine structure with the structure shown in formula (I).

[0103] The present invention has no special restrictions on the sources of the raw materials used above, and they can be generally commercially available.

[0104] The ketimine structure diphenol monomer provided by the present invention can participate in the preparation of polyarylether polymers containing a ketimine structure, and the yield of the obtained polyarylether polymers containing a ketimine structure is relatively high.

[0105] The yield and purity of the ketimine structure diphenol monomer obtained by the preparation method of the ketimine structure diphenol monomer are both relatively high.

[0106] The polyarylether polymer containing a ketimine structure provided by the present invention is a high-molecular-weight polyarylether polymer containing a ketimine structure that is soluble in polar aprotic solvents such as tetrahydrofuran, N-methylpyrrolidone, and N,N-dimethylacetamide, as well as halogenated hydrocarbons such as dichloromethane and chloroform.

[0107] The present invention has developed a new technical route, that is, modifying a bisphenol monomer containing a benzophenone structure to prepare a bisphenol monomer containing a ketimine structure. The reactivity of the modified bisphenol monomer in the polymerization reaction increases, and then it is polymerized with a dihalogen monomer to obtain a high-molecular-weight polyarylether polymer containing a ketimine structure that is soluble in polar aprotic solvents such as tetrahydrofuran, N-methylpyrrolidone, and N,N-dimethylacetamide, as well as halogenated hydrocarbons such as dichloromethane and chloroform. The polyarylether polymer containing a ketimine structure obtained by the preparation method provided by the present invention has a high yield. In addition, the preparation method provided by the present invention is simple to operate, does not require a complex purification process, has fewer side reactions during the preparation process, and can be polymerized by a one-pot method, which can greatly shorten the production cycle.

[0108] In order to further illustrate the present invention, the following describes in detail a polyarylether polymer containing a ketimine structure and its preparation method provided by the present invention in conjunction with examples, but it should not be construed as a limitation on the protection scope of the present invention.

[0109] Example 1

[0110] Preparation of N-phenyl-4,4'-dihydroxybenzophenone imine having the structure shown in formula (Ⅱ) (wherein, R1 is a phenyl group):

[0111] 21.42 g (0.1 mol) of 4,4'-dihydroxybenzophenone, 27.99 g (0.3 mol) of aniline, 0.38 g (0.002 mol) of p-toluenesulfonic acid monohydrate, and 30 mL of N-methylpyrrolidone were added to a three-necked flask equipped with a stirrer, a water separator, and a condenser, and reacted at 180 °C for 18 h. The reaction product solution was sedimented into an aqueous NaHCO3 solution to obtain a white solid, which was recrystallized from ethanol to obtain N-phenyl-4,4'-dihydroxybenzophenone imine having the structure shown in formula (Ⅱ) (wherein, R1 is a phenyl group); the reaction equation is shown in formula (1);

[0112]

[0113] Figure 1 This is the 1H NMR spectrum of N-phenyl-4,4'-dihydroxybenzophenone imine of Example 1 of the present invention.

[0114] After detection, the yield of N-phenyl-4,4'-dihydroxybenzophenone imine was 85%, and the purity was 99%.

[0115] Example 2

[0116] Preparation of N-phenyl-4,4'-dihydroxybenzophenone imine with the structure shown in formula (II) (wherein, R1 is a phenyl group):

[0117] Add 21.42 g (0.1 mol) of 4,4'-dihydroxybenzophenone, 27.99 g (0.3 mol) of aniline, 0.38 g (0.002 mol) of p-toluenesulfonic acid monohydrate, 30 mL of N-methylpyrrolidone, and 20 mL of water-carrying agent toluene into a three-necked flask equipped with a stirrer, a water separator (the water separator is filled with the water-carrying agent toluene), and a condenser. React under reflux at 150 °C for 10 h. After the reaction is completed, distill out the toluene. Settle the reaction product solution into an aqueous NaHCO3 solution to obtain a white solid. Recrystallize with ethanol to obtain N-phenyl-4,4'-dihydroxybenzophenone imine with the structure shown in formula (II) (wherein, R1 is a phenyl group); the reaction equation is as shown in formula (1).

[0118] Upon detection, the yield of N-phenyl-4,4'-dihydroxybenzophenone imine is 87%, and the purity is 99%.

[0119] Example 3

[0120] Preparation of polyarylether-based polymer containing a ketimine structure (in formula I, R1 is formula R-1):

[0121] Add the N-phenyl-4,4'-dihydroxybenzophenone imine prepared in Example 1, 21.82 g (0.1 mol) of 4,4'-difluorobenzophenone (with the structure shown in formula F-2, wherein X1 and X2 are both F, a = 1), 28.33 g (0.205 mol) of potassium carbonate, 200 mL of dimethyl sulfoxide, and 100 mL of toluene into a three-necked flask equipped with mechanical stirring, a nitrogen inlet, a water separator (the water separator is filled with the water-carrying agent toluene), and a condenser. Under a nitrogen atmosphere, reflux with water removal at 150 °C for 6 h, then distill out the toluene. Raise the temperature to 180 °C and react for 3 h. Pour the reaction product solution into deionized water. The obtained solid is washed and dried to obtain a polyarylether ketone containing a ketimine structure with the structure shown in formula (2).

[0122]

[0123] Figure 2 1H NMR spectrum of the polyarylether ketone containing a ketimine structure in Example 3 of the present invention; wherein, the solvent is CDCl3. Figure 2 It is confirmed that the polyarylether ketone containing a ketimine structure in Example 3 of the present invention has the structure shown in formula (2).

[0124] Upon detection, the yield of the polyarylether ketone containing a ketimine structure is 97%.

[0125] Example 4

[0126] Preparation of polyarylether polymers containing a ketimine structure (in formula I, R1 is formula R-1):

[0127] Add N-phenyl-4,4'-dihydroxybenzophenone imine prepared in Example 1, 21.82 g (0.1 mol) of 4,4'-difluorobenzophenone (having the structure shown in formula F-2, where X1 and X2 are both F, a = 1), 20.73 g (0.15 mol) of potassium carbonate, and 90 mL of N-methylpyrrolidone into a three-necked flask equipped with a mechanical stirrer, a nitrogen inlet, a water separator, and a condenser. Under a nitrogen atmosphere, react at 200 °C for 1.5 h to obtain a viscous polymer solution. After diluting with 200 mL of N-methylpyrrolidone, pour it into deionized water. The obtained solid is washed and dried to obtain a polyarylether ketone containing a ketimine structure as shown in formula (2).

[0128] After detection, the yield of the polyarylether ketone containing a ketimine structure is 97%.

[0129] Example 5

[0130] One-pot preparation of polyarylether ketone polymers containing a ketimine structure (in formula I, R1 is formula R-1):

[0131] Add 21.42 g (0.1 mol) of 4,4'-dihydroxybenzophenone, 27.99 g (0.3 mol) of aniline, 0.38 g (0.002 mol) of p-toluenesulfonic acid monohydrate, 30 mL of N-methylpyrrolidone, and 20 mL of a water-carrying agent toluene into a three-necked flask equipped with a mechanical stirrer, a nitrogen inlet, a water separator (the water separator is filled with the water-carrying agent toluene), and a condenser. Reflux and react at 150 °C for 10 h. After the reaction, distill out the toluene. Add 21.82 g (0.1 mol) of 4,4'-difluorobenzophenone (having the structure shown in formula F-2, where X1 and X2 are both F, a = 1), 20.73 g (0.15 mol) of potassium carbonate, and 90 mL of N-methylpyrrolidone into the system. Under a nitrogen atmosphere, react at 200 °C for 1.2 h to obtain a viscous polymer solution. After diluting with 200 mL of N-methylpyrrolidone, pour the product into deionized water. The solid is washed and dried to obtain a polyarylether ketone containing a ketimine structure as shown in formula (2).

[0132] After detection, the yield of the polyarylether ketone containing a ketimine structure is 97%.

[0133] Example 6

[0134] One-pot preparation of polyarylether ketone polymers containing a ketimine structure (in formula I, R1 is formula R-4):

[0135] 21.42 g (0.1 mol) of 4,4'-dihydroxybenzophenone, 29.75 g (0.3 mol) of cyclohexylamine, 0.38 g (0.002 mol) of p-toluenesulfonic acid monohydrate, and 30 mL of N-methylpyrrolidone were added to a three-necked flask equipped with a mechanical stirrer, a nitrogen inlet, a water separator, and a condenser. The reaction was carried out at 130 °C for 12 h. After the reaction was completed, the remaining cyclohexylamine was distilled off by heating to 150 °C. Then, 21.82 g (0.1 mol) of 4,4'-difluorobenzophenone (having the structure shown in Formula F-2, wherein X1 and X2 are both F, and a = 1), 20.73 g (0.15 mol) of potassium carbonate, and 90 mL of N-methylpyrrolidone were added to the system. The reaction was carried out at 200 °C for 1.2 h in a nitrogen atmosphere to obtain a viscous polymer solution. After dilution with 200 mL of N-methylpyrrolidone, the product was poured into deionized water. The solid was washed and dried to obtain a polyaryletherketone containing a ketimine structure as shown in Formula (3).

[0136] The yield of the polyaryletherketone containing a ketimine structure was detected to be 97%.

[0137]

[0138] Example 7

[0139] One-pot preparation of polyaryletherketone polymers containing a ketimine structure (in Formula I, R1 is Formula R-5):

[0140] 21.42 g (0.1 mol) of 4,4'-dihydroxybenzophenone, 25.54 g (0.3 mol) of cyclopentylamine, 0.38 g (0.002 mol) of p-toluenesulfonic acid monohydrate, 30 mL of N-methylpyrrolidone, and 20 mL of a water-carrying agent toluene were added to a three-necked flask equipped with a mechanical stirrer, a nitrogen inlet, a water separator (the water separator was filled with the water-carrying agent toluene), and a condenser. The reaction was carried out at 100 °C for 16 h. After the reaction was completed, the excess cyclopentylamine was distilled off by heating to 130 °C. Then, 21.82 g (0.1 mol) of 4,4'-difluorobenzophenone (having the structure shown in Formula F-2, wherein X1 and X2 are both F, and a = 1), 20.73 g (0.15 mol) of potassium carbonate, and 90 mL of N-methylpyrrolidone were added to the system. The reaction was carried out at 200 °C for 1.2 h in a nitrogen atmosphere to obtain a viscous polymer solution. After dilution with 200 mL of N-methylpyrrolidone, the product was poured into deionized water. The solid was washed and dried to obtain a polyaryletherketone containing a ketimine structure as shown in Formula (4).

[0141] The yield of the polyaryletherketone containing a ketimine structure was detected to be 97%.

[0142]

[0143] Example 8

[0144] One-pot preparation of polyarylethersulfone polymers containing ketimine structures (in formula I, R1 is of formula R-1):

[0145] Add 21.42 g (0.1 mol) of 4,4'-dihydroxybenzophenone, 27.99 g (0.3 mol) of aniline, 0.38 g (0.002 mol) of p-toluenesulfonic acid monohydrate, 30 mL of N-methylpyrrolidone, and 20 mL of a water-carrying agent toluene into a three-necked flask equipped with a mechanical stirrer, a nitrogen inlet, a water separator (filled with the water-carrying agent toluene), and a condenser. React under reflux at 150 °C for 10 h. After the reaction is completed, distill out the toluene. Add 21.82 g (0.1 mol) of 4,4'-dichlorodiphenyl sulfone (having the structure shown in formula F-1, where X1 and X2 are both Cl), 20.73 g (0.15 mol) of potassium carbonate, and 90 mL of N-methylpyrrolidone to the system. React at 200 °C for 4 h under a nitrogen atmosphere to obtain a viscous polymer solution. Dilute with 200 mL of N-methylpyrrolidone and pour the product into deionized water. The solid is washed and dried to obtain a polyarylethersulfone containing a ketimine structure as shown in formula (5).

[0146] It was detected that the yield of the polyarylethersulfone containing a ketimine structure was 96%.

[0147]

[0148] Comparative Example 1

[0149] Preparation of polyaryletherketone containing ketimine structure by modifying the dihalogen monomer strategy:

[0150] Add 21.82 g (0.1 mol) of 4,4'-fluorobenzophenone, 27.99 g (0.3 mol) of aniline, 0.38 g (0.002 mol) of p-toluenesulfonic acid monohydrate, and 50 mL of toluene into a three-necked flask equipped with a stirrer, a water separator (filled with the water-carrying agent toluene), and a condenser. React under reflux at 150 °C for 18 h. Concentrate the reaction product solution to half its volume and let it stand for 24 h to precipitate a large amount of yellow solid. The obtained solid is recrystallized twice with toluene to obtain N-phenyl-4,4'-difluorobenzophenone imine, with a yield of about 60%.

[0151] 14.67 g (0.05 mol) of N-phenyl-4,4'-difluorobenzophenone imine, 5.51 g (0.05 mol) of hydroquinone, 10.365 g (0.075 mol) of potassium carbonate and 40 mL of N-methylpyrrolidone were added to a three-necked flask equipped with a mechanical stirrer, a nitrogen inlet, a water separator and a condenser. Under a nitrogen atmosphere, the reaction was carried out at 220 °C for 4 h to obtain a viscous polymer solution. After dilution with 100 mL of N-methylpyrrolidone, it was poured into deionized water. The obtained solid was washed and dried to obtain a polyaryletherketone containing a ketimine structure as shown in formula (6). The yield was 95%.

[0152]

[0153] It can be known through testing that the polymers obtained in Examples 3-8 and Comparative Example 1 are all soluble in polar aprotic solvents such as tetrahydrofuran, N-methylpyrrolidone, N,N-dimethylacetamide, and halogenated hydrocarbons such as dichloromethane and chloroform.

[0154] The gel permeation chromatography (GPC) tests of the polymers obtained in Examples 3-8 and Comparative Example 1 are shown in Table 1, where the solvent and eluent are tetrahydrofuran and the injection concentration is 2 mg / mL.

[0155] Table 1 Gel permeation chromatography test results of the polymers obtained in Examples 3-8 and Comparative Example 1

[0156] <![CDATA[M n (KDa)]]> <![CDATA[M w (KDa)]]> PDI Example 3 40.3 65.4 1.62 Example 4 54.8 86.2 1.57 Example 5 56.6 87.6 1.55 Example 6 49.2 80.2 1.63 Example 7 53.5 88.8 1.66 Example 8 44.1 68.3 1.55 Comparative Example 1 40.2 64.3 1.60

[0157] In Table 1, M n , M w and PDI represent the number average molecular weight, weight average molecular weight and molecular weight distribution index, respectively.

[0158] It can be seen from the above examples that whether the bisphenol monomer containing a ketimine structure is first prepared and purified and then polymerized (Examples 1-4), or the bisphenol monomer containing a ketimine structure is polymerized by a one-pot method without purification (Examples 5-8), a polyarylether polymer containing a ketimine structure can be obtained.

[0159] Combined with the monomer yield, the total yield in Comparative Example 1 is 50%-60%. In Examples 1-4 of the present invention, the total yield of the separate preparation process is 80%-90%. In addition, the present invention also includes the preparation of polymers by a one-pot method. This process does not require monomer purification and the total yield can reach more than 90%.

[0160] The foregoing description of the disclosed embodiments enables those skilled in the art to practice or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the present invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A method for preparing a polyarylether polymer containing a ketimine structure, comprising the following steps: Under the action of a first catalyst, a diphenol monomer containing a ketimine structure with the structure shown in formula (Ⅱ) and an aromatic dihalide monomer are subjected to a polymerization reaction in a first solvent to obtain a polyarylether polymer containing a ketimine structure with the structure shown in formula (Ⅰ); wherein, n≥10; Ar is selected from aromatic groups; R1 is selected from substituted or unsubstituted aromatic groups, or substituted or unsubstituted alkyl groups.

2. The preparation method according to claim 1, wherein n≥20； Ar is selected from the structures shown in formula A-1 to formula A-3: In formula A-2, a = 1, 2 or 3; R1 is selected from phenyl, substituted phenyl, biphenyl, naphthyl, substituted naphthyl or an alkyl group with 1 to 12 carbon atoms; the alkyl group is selected from straight-chain alkyl groups, branched-chain alkyl groups or cycloalkyl groups.

3. The preparation method according to claim 1, wherein R1 is selected from the structures shown in formula R-1 to formula R-7: R2 is selected from -H, -F, -Cl, -Br, -COOH, -SO3H, -NH2, -NO3, -CN, -OCH3, -CH3, -C2H5 or -tBU; In formula R-7, 1≤m≤12.

4. The preparation method according to claim 1, characterized in that, The method for preparing the diphenol monomer containing a ketimine structure with the structure shown in formula (Ⅱ) comprises the following steps: 4,4'-Dihydroxybenzophenone, R1-NH2, a second catalyst and a second solvent are mixed and then reacted to obtain a diphenol monomer containing a ketimine structure with the structure shown in formula (Ⅱ); R1 is selected from substituted or unsubstituted aromatic groups, or substituted or unsubstituted alkyl groups.

5. The preparation method according to claim 4, characterized in that, The second catalyst includes one or more of hydrochloric acid, acetic acid, sulfuric acid, oxalic acid, p-toluenesulfonic acid, p-toluenesulfonic acid monohydrate, methanesulfonic acid, aluminum chloride, titanium chloride and tin chloride; The molar ratio of 4,4'-dihydroxybenzophenone, R1-NH2 and the second catalyst is 1:1 to 10:0.01 to 0.5; The second solvent includes one or more of N-methylpyrrolidone, dimethyl sulfoxide, N,N-dimethylformamide and N,N-dimethylacetamide.

6. The preparation method according to claim 4, wherein The temperature of the reaction is 60 to 200 °C, and the time is 6 to 48 h.

7. The preparation method according to claim 4, characterized in that, The first catalyst includes one or more of sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate; The molar ratio of 4,4'-dihydroxybenzophenone, the aromatic dihalide monomer and the first catalyst is 1:0.95 to 1.05:1.05 to 2.

5.

8. The preparation method according to claim 1, wherein, The aromatic dihalide monomer is selected from the structures shown in formula F-1 to formula F-3: wherein, X1 and X2 are independently selected from halogens; In formula F-2, a = 1, 2 or 3.

9. The preparation method according to claim 1, characterized in that, The first solvent includes one or more of N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone, diphenyl sulfone and sulfolane; The temperature of the polymerization reaction is 150 to 250 °C, and the time is 0.5 to 48 h.

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