CN116120539A - Polyarylether polymer containing ketimine structure and preparation method thereof - Google Patents

Polyarylether polymer containing ketimine structure and preparation method thereof Download PDF

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CN116120539A
CN116120539A CN202310190536.3A CN202310190536A CN116120539A CN 116120539 A CN116120539 A CN 116120539A CN 202310190536 A CN202310190536 A CN 202310190536A CN 116120539 A CN116120539 A CN 116120539A
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ketimine
substituted
monomer
polyarylether polymer
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张所波
喻会婷
孙宇轩
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Changchun Institute of Applied Chemistry of CAS
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
    • C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
    • C08G65/4012—Other compound (II) containing a ketone group, e.g. X-Ar-C(=O)-Ar-X for polyetherketones
    • C08G65/4031—(I) or (II) containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
    • C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
    • C08G65/4012—Other compound (II) containing a ketone group, e.g. X-Ar-C(=O)-Ar-X for polyetherketones
    • C08G65/4056—(I) or (II) containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
    • C08G2650/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing oxygen in addition to the ether group
    • C08G2650/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing oxygen in addition to the ether group containing ketone groups, e.g. polyarylethylketones, PEEK or PEK
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
    • C08G2650/50—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing nitrogen, e.g. polyetheramines or Jeffamines(r)

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Abstract

The invention relates to the technical field of polymer synthesis, in particular to a polyarylether polymer containing ketimine structures and a preparation method thereof. The invention provides a polyarylether polymer containing ketimine structure, which has a structure shown in formula (I); in the formula (I), n is more than or equal to 10; ar is selected from aromatic groups; r is R 1 Selected from a substituted or unsubstituted aryl group, or a substituted or unsubstituted alkyl group. According to the invention, bisphenol monomer containing benzophenone structure is modified to prepare bisphenol monomer containing ketimine structure, the activity of the modified bisphenol monomer participating in polymerization is increased, and then the modified bisphenol monomer is polymerized with dihalogen monomer, so that the soluble polyarylether polymer with high molecular weight and ketimine structure can be obtained. Meanwhile, the polyarylether polymer containing ketimine structure obtained by the preparation method provided by the invention has higher yield.

Description

Polyarylether polymer containing ketimine structure and preparation method thereof
Technical Field
The invention relates to the technical field of polymer synthesis, in particular to a polyarylether polymer containing ketimine structures and a preparation method thereof.
Background
The polyarylether has the advantages of good heat resistance, excellent mechanical property, good dimensional stability, simple material synthesis, high cost performance and the like, and is widely applied to the industrial fields of electronics, food, machinery, medical treatment, automobiles, aerospace and the like. The representative products mainly comprise polyarylether, polyarylether sulfone, polyarylether ketone, polyarylether nitrile and the like.
Among them, polyarylether polymers containing ketocarbonyl groups tend to have poor solubility in organic solvents due to the strong rigidity of benzophenone structural units and pi-pi stacking effect. Polymers such as Polyetherketone (PEK), polyetheretherketone (PEEK), polyetherketoneketone (PEKK), polyetherketoneketone (PEKEEK), polyetherketoneketone (PEKEKK) are generally insoluble in conventional organic solvents, making such polymers ideal solvent-resistant specialty polymeric materials. However, poor solubility limits the use of such polymers in many fields, especially in devices of nanoscale precision that are difficult to achieve by melt processing, such as nanofibers, nanofiltration membranes, and the like. A common solution processing method for such polymers is to dissolve them in strong acids such as concentrated sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid, etc., but this method usually brings about degradation of the main chain, and the use of a large amount of strong acid brings about great difficulty in mass production.
In order to improve the solubility of polyarylether polymers containing benzophenone structures, researchers have developed a method for preparing polyarylether polymers containing ketimine structures by converting ketcarbonyl groups into ketimine groups. The polymer prepared by the method has good solubility, can be processed by solution, and can be converted into carbonyl-containing polyarylether polymers such as polyether-ether-ketone and the like after being processed into devices by acid treatment.
The prior art is to modify carbonyl group-containing dihalogen monomer to obtain ketimine structure-containing dihalogen monomer, and then polymerize (see patent CN 106633034 a). The technical route has the limitation that the monomer preparation conversion speed is low, side reactions occur in the monomer preparation process due to the existence of halogen atoms, the crude product needs more times of recrystallization and other complex purification processes, and finally the yield of the dihalogen monomer containing ketimine structure is lower, so that the manufacturing cost of the polymer is greatly increased. In addition, the electron withdrawing ability is reduced after the carbonyl group is converted into ketimine, so that the polymerization activity of the dihalogen monomer is reduced.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a soluble polyarylether polymer containing ketimine structure and a preparation method thereof.
The invention provides a polyarylether polymer containing ketimine structure, which has a structure shown in formula (I);
Figure BDA0004105250280000021
in the formula (I), n is more than or equal to 10;
ar is selected from aromatic groups;
R 1 selected from a substituted or unsubstituted aryl group, or a substituted or unsubstituted alkyl group.
Preferably, n is more than or equal to 20;
ar is selected from structures shown in formulas A-1 to A-3:
Figure BDA0004105250280000022
in formula a-2, a=1, 2 or 3;
R 1 selected from phenyl, substituted phenyl, biphenyl, naphthyl, substituted naphthyl or alkyl with 1-12 carbon atoms; the alkyl is selected from linear alkyl, branched alkyl or cycloalkyl.
Preferably, R 1 Selected from the structures represented by the formulas R-1 to R-7:
Figure BDA0004105250280000023
R 2 selected from the group consisting of-H, -F, -Cl, -Br, -COOH, -SO 3 H、-NH 2 、-NO 3 、-CN、-OCH 3 、-CH 3 、-C 2 H 5 or-tBu;
in the formula R-7, m is more than or equal to 1 and less than or equal to 12.
The invention also provides a preparation method of the polyarylether polymer containing ketimine structure, which comprises the following steps:
under the action of a first catalyst, carrying out polymerization reaction on a diphenol monomer with a ketimine structure and an aromatic dihalide monomer with a structure shown in a formula (II) in a first solvent to obtain a polyarylether polymer with a ketimine structure and a structure shown in a formula (I);
Figure BDA0004105250280000031
wherein n is more than or equal to 10;
ar is selected from aromatic groups;
R 1 selected from a substituted or unsubstituted aryl group, or a substituted or unsubstituted alkyl group.
Preferably, the preparation method of the ketimine structure-containing diphenol monomer with the structure shown in the formula (II) comprises the following steps:
4,4' -dihydroxybenzophenone, R 1 -NH 2 Mixing the second catalyst with a second solvent, and then reacting to obtain a diphenol monomer containing a ketimine structure and having a structure shown in a formula (II);
R 1 selected from a substituted or unsubstituted aryl group, or a substituted or unsubstituted alkyl group.
Preferably, the second catalyst comprises one or more of hydrochloric acid, acetic acid, sulfuric acid, oxalic acid, p-toluenesulfonic acid monohydrate, methanesulfonic acid, aluminum chloride, titanium chloride and tin chloride;
the 4,4' -dihydroxybenzophenone, R 1 -NH 2 And the molar ratio of the second catalyst is 1:1 to 10:0.01 to 0.5;
the second solvent comprises one or more of N-methylpyrrolidone, dimethyl sulfoxide, N-dimethylformamide and N, N-dimethylacetamide.
Preferably, the temperature of the reaction is 60-200 ℃ and the time is 6-48 h.
Preferably, the first catalyst comprises one or more of sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate;
the molar ratio of the 4,4' -dihydroxybenzophenone, the aromatic dihalogen monomer and the first catalyst is 1:0.95 to 1.05:1.05 to 2.5.
Preferably, the aromatic dihalogen monomer is selected from structures represented by formulas F-1 to F-3:
Figure BDA0004105250280000032
wherein X is 1 And X 2 Independently selected from halogen;
in formula F-2, a=1, 2 or 3.
Preferably, the first solvent comprises one or more of N, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone, diphenyl sulfone and sulfolane;
the temperature of the polymerization reaction is 150-250 ℃ and the time is 0.5-48 h.
The invention provides a polyarylether polymer containing ketimine structure, which has a structure shown in formula (I); in the formula (I), n is more than or equal to 10; ar is selected from aromatic groups; r is R 1 Selected from a substituted or unsubstituted aryl group, or a substituted or unsubstituted alkyl group. The polyarylether polymer containing ketimine structure provided by the invention can be dissolved in polar aprotic solvents such as tetrahydrofuran, N-methylpyrrolidone, N-dimethylacetamide and the like, and high molecular weight polyarylether polymer containing ketimine structure in halogenated hydrocarbons such as dichloromethane, chloroform and the like.
The invention also provides a preparation method of the polyarylether polymer containing ketimine structure, which comprises the following steps: under the action of a first catalyst, carrying out polymerization reaction on a diphenol monomer with a ketimine structure and an aromatic dihalide monomer with a structure shown in a formula (II) in a first solvent to obtain a polyarylether polymer with a ketimine structure and a structure shown in a formula (I); wherein n is more than or equal to 10; ar is selected from aromatic groups; r is R 1 Selected from a substituted or unsubstituted aryl group, or a substituted or unsubstituted alkyl group. The invention develops a new technical route, namely, bisphenol monomer containing benzophenone structure is modified to prepare bisphenol monomer containing ketimine structure, the activity of the modified bisphenol monomer participating in polymerization is increased, and then the bisphenol monomer is polymerized with dihalogen monomer, thus obtaining polyarylether polymer containing ketimine structure with high molecular weight, which is soluble in polar aprotic solvents such as tetrahydrofuran, N-methylpyrrolidone, N-dimethylacetamide and the like, and halogenated hydrocarbons such as methylene dichloride, chloroform and the like. The invention provides a preparation methodThe yield of the polyarylether polymer containing ketimine structure obtained by the method is higher.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of N-phenyl-4, 4' -dihydroxybenzophenone imine according to example 1 of the present invention.
FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of polyaryletherketone containing ketimine structure according to example 3 of the present invention.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a polyarylether polymer containing ketimine structure, which has a structure shown in formula (I);
Figure BDA0004105250280000051
in the formula (I), n is more than or equal to 10;
ar is selected from aromatic groups;
R 1 selected from a substituted or unsubstituted aryl group, or a substituted or unsubstituted alkyl group.
In certain embodiments of the invention, n.gtoreq.20.
In certain embodiments of the invention, ar is selected from structures represented by formulas A-1 through A-3:
Figure BDA0004105250280000052
in formula a-2, a=1, 2 or 3.
In certain embodiments of the invention, R 1 Selected from phenyl, substituted phenyl, biphenyl, naphthyl, substituted naphthyl or alkyl with 1-12 carbon atoms; the alkyl group is selected from straight chainAlkyl, branched alkyl or cycloalkyl; specifically, it may be cyclohexyl, cyclopentyl or tert-butyl. The substituents include hydrogen, halogen, carboxyl, sulfonic, amino, nitro, cyano, alkoxy, straight chain alkyl or branched alkyl.
In certain embodiments of the invention, R 1 Selected from the structures represented by the formulas R-1 to R-7:
Figure BDA0004105250280000053
R 2 selected from the group consisting of-H, -F, -Cl, -Br, -COOH, -SO 3 H、-NH 2 、-NO 3 、-CN、-OCH 3 、-CH 3 、-C 2 H 5 or-tBu.
In the formula R-7, m is more than or equal to 1 and less than or equal to 12.
In certain embodiments of the present invention, the polyarylether polymer comprising ketimine structures has a number average molecular weight of 30 to 60kDa, a weight average molecular weight of 50 to 100kDa, and a molecular weight distribution index of 1.5 to 2.5.
In certain embodiments of the present invention, the polyarylether polymer having a ketimine structure is prepared from a raw material including a ketimine structure-containing diphenol monomer having a structure represented by formula (II), an aromatic dihalogen monomer, a first catalyst, and a first solvent.
The invention also provides a preparation method of the polyarylether polymer containing ketimine structure, which comprises the following steps:
under the action of a first catalyst, carrying out polymerization reaction on a diphenol monomer with a ketimine structure and an aromatic dihalide monomer with a structure shown in a formula (II) in a first solvent to obtain a polyarylether polymer with a ketimine structure and a structure shown in a formula (I);
Figure BDA0004105250280000061
wherein n is more than or equal to 10;
ar is selected from aromatic groups;
R 1 selected from a substituted or unsubstituted aryl group, or a substituted or unsubstituted alkyl group.
In the preparation method, R 1 The selection of (c) is the same as above and will not be described in detail herein.
In certain embodiments of the present invention, the ketimine structure-containing diphenol monomer having the structure of formula (II) is selected from the group consisting of 4,4' -dihydroxybenzophenone, R 1 -NH 2 The raw materials of the second catalyst and the second solvent are prepared.
In some embodiments of the present invention, the preparation method of the ketimine structure-containing diphenol monomer having the structure represented by formula (ii) includes the steps of:
4,4' -dihydroxybenzophenone, R 1 -NH 2 And mixing the second catalyst with a second solvent, and then reacting to obtain the diphenol monomer containing the ketimine structure and having the structure shown in the formula (II).
The R is 1 The selection of (c) is the same as above and will not be described in detail herein. In certain embodiments of the invention, the R 1 Phenyl, formula R-4 or formula R-5; r is R 1 -NH 2 Is aniline, cyclohexane or cyclopentylamine.
The second catalyst is a protic or Lewis acid well known to those skilled in the art, including, but not limited to, one or more of hydrochloric acid, acetic acid, sulfuric acid, oxalic acid, p-toluenesulfonic acid monohydrate, methanesulfonic acid, aluminum chloride, titanium chloride, and tin chloride.
The 4,4' -dihydroxybenzophenone, R 1 -NH 2 And the molar ratio of the second catalyst is 1:1 to 10:0.01 to 0.5; the method specifically comprises the following steps of 1:3:0.02.
the second solvent is any organic solvent known to those skilled in the art that can dissolve 4,4' -dihydroxybenzophenone or directly R 1 -NH 2 As a reaction solvent. The second solvent comprises one or more of N-methylpyrrolidone, dimethyl sulfoxide, N-dimethylformamide and N, N-dimethylacetamide. The dosage ratio of the 4,4' -dihydroxybenzophenone to the second solvent is 1mol: 100-500 mL; specifically 1mol:300mL。
Optionally, a water-carrying agent known to those skilled in the art, preferably toluene, xylene, chlorobenzene or cyclohexane, may be added during the reaction. Specifically, the water distributor is filled with a water carrying agent, and the volume ratio of the water carrying agent added into the reaction system to the second solvent is 0.2-2: 1 to 2; the method specifically comprises the following steps of 1:1.5.
the reaction temperature is 60-200 ℃, specifically 180 ℃, 150 ℃, 130 ℃ and 100 ℃; the time is 6-48 h, specifically 18h, 10h, 12h and 16h.
In certain embodiments of the present invention, after the reacting, further comprising: settling the product solution after the reaction to NaHCO 3 Obtaining white solid in the aqueous solution, and recrystallizing with ethanol to obtain the diphenol monomer containing ketimine structure with the structure shown in formula (II).
In certain embodiments of the present invention, after the reacting, further comprising: removing the water carrying agent.
In certain embodiments, after removing the water-carrying agent, further comprising: settling the product solution after the reaction to NaHCO 3 Obtaining white solid in the aqueous solution, and recrystallizing with ethanol to obtain the diphenol monomer containing ketimine structure with the structure shown in formula (II). The method of removing the water-carrying agent may be to distill out the water-carrying agent.
In certain embodiments of the present invention, after the reacting, further comprising: removing the remaining R 1 -NH 2 The method comprises the steps of carrying out a first treatment on the surface of the The specific method comprises the following steps: heating and steaming.
After obtaining a diphenol monomer containing ketimine structure and having a structure shown in formula (II), under the action of a first catalyst, carrying out polymerization reaction on the diphenol monomer containing ketimine structure and having a structure shown in formula (II) and an aromatic dihalogen monomer in a first solvent to obtain a polyarylether polymer containing ketimine structure and having a structure shown in formula (I).
Specifically, the method comprises the following steps:
the method comprises the following steps: mixing a diphenol monomer containing a ketimine structure and having a structure shown in a formula (II), an aromatic dihalogen monomer, a first catalyst and a first solvent, and then carrying out polymerization reaction to obtain a polyarylether polymer containing a ketimine structure and having a structure shown in a formula (I);
or (b)
The second method is as follows: directly after the above reaction (i.e., the reaction for preparing the ketimine structure-containing diphenol monomer having the structure represented by formula (II)), the remaining R is removed 1 -NH 2 In the system (i.e. after the reaction has ended, only the residual R is removed 1 -NH 2 The system of the step (a) or the system of removing the water-carrying agent after the reaction (i.e. the system of only removing the water-carrying agent after the reaction is finished), adding an aromatic dihalogen monomer, a first catalyst and a first solvent for polymerization reaction to obtain the polyarylether polymer containing ketimine structure and having the structure shown in the formula (I) (the second method is a one-pot method).
In certain embodiments of the present invention, the aromatic dihalogen monomer is selected from structures represented by formulas F-1 through F-3:
Figure BDA0004105250280000081
wherein X is 1 And X 2 Independently selected from halogen, in particular, X 1 And X 2 Independently selected from F or Cl. The source of the aromatic dihalogen monomer may be generally commercially available.
In formula F-2, a=1, 2 or 3.
In certain embodiments of the invention, the first catalyst is a base catalyst. The first catalyst includes, but is not limited to, an alkali metal hydroxide and/or an alkali metal carbonate; preferably one or more of sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate.
In certain embodiments of the invention, the molar ratio of 4,4' -dihydroxybenzophenone, aromatic dihalogen monomer, and first catalyst is 1:0.95 to 1.05:1.05 to 2.5; the method specifically comprises the following steps of 1:1:2.05 or 1:1:1.5.
in certain embodiments of the invention, the first solvent is a polar aprotic solvent; comprises one or more of N, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone, diphenyl sulfone and sulfolane. In certain embodiments, the mass ratio of the aromatic dihalogen monomer to the first solvent is 50 to 100g: 80-500 mL; specifically 21.82g:200mL or 21.82g:90mL.
In the course of the polymerization, water-carrying agents known to those skilled in the art, preferably toluene, xylene, chlorobenzene or cyclohexane, may optionally be added. Specifically, the water distributor is filled with a water-carrying agent, and the volume ratio of the water-carrying agent added into the polymerization reaction system to the first solvent is 0.2-2: 1, a step of; specifically, 0.5:1.
the temperature of the polymerization reaction is 150-250 ℃, specifically 170-230 ℃, more specifically 180 ℃ and 200 ℃; the time is 0.5 to 48 hours, specifically 1 to 12 hours, more specifically 3 hours, 1.2 hours, 1.5 hours or 4 hours.
In certain embodiments of the invention, the polymerization is carried out under conditions of a shielding gas, which is an inert gas; specifically nitrogen. In certain embodiments of the invention, the polymerization reaction is carried out with agitation.
The polymerization reaction is carried out in a reaction vessel containing mechanical agitation, a water separator and a condenser.
In certain embodiments of the present invention, after the polymerization reaction, further comprising:
and pouring the product solution obtained by the polymerization reaction into deionized water or ethanol, and washing and drying the obtained solid.
In certain embodiments of the present invention, before pouring the product solution obtained by the polymerization reaction into deionized water or ethanol, the method further comprises: dilution with the first solvent. The molar amount of the aromatic dihalogen monomer to the amount of the first solvent used for dilution was 0.1mol: 100-300 mL; specifically 0.1mol:200mL.
In the one-pot method for preparing the polyarylether polymer containing the ketimine structure, complex purification processes such as recrystallization and the like are not needed. After the ketimine structure-containing diphenol monomer with the structure shown in the formula (II) is obtained, the complex purification processes such as recrystallization and the like are not needed in the preparation of the ketimine structure-containing polyarylether polymer with the structure shown in the formula (I).
The source of the raw materials used in the present invention is not particularly limited, and may be generally commercially available.
The bisphenol monomer containing ketimine structure and having the structure shown in the formula (II) can participate in preparing the polyarylether polymer containing ketimine structure, and the yield of the polyarylether polymer containing ketimine structure is higher.
The yield and purity of the ketimine structure-containing diphenol monomer obtained by the preparation method of the ketimine structure-containing diphenol monomer are high.
The polyarylether polymer containing ketimine structure provided by the invention can be dissolved in polar aprotic solvents such as tetrahydrofuran, N-methylpyrrolidone, N-dimethylacetamide and the like, and high molecular weight polyarylether polymer containing ketimine structure in halogenated hydrocarbons such as dichloromethane, chloroform and the like.
The invention develops a new technical route, namely, bisphenol monomer containing benzophenone structure is modified to prepare bisphenol monomer containing ketimine structure, the activity of the modified bisphenol monomer participating in polymerization is increased, and then the bisphenol monomer is polymerized with dihalogen monomer, thus obtaining polyarylether polymer containing ketimine structure with high molecular weight, which is soluble in polar aprotic solvents such as tetrahydrofuran, N-methylpyrrolidone, N-dimethylacetamide and the like, and halogenated hydrocarbons such as methylene dichloride, chloroform and the like. The polyarylether polymer containing ketimine structure obtained by the preparation method provided by the invention has higher yield. In addition, the preparation method provided by the invention is simple to operate, does not need a complex purification process, has fewer side reactions in the preparation process, can be used for polymerization by a one-pot method, and can greatly shorten the production period.
In order to further illustrate the present invention, the following examples are provided to describe in detail a polyarylether polymer containing ketimine structure and a preparation method thereof, but the present invention is not to be construed as being limited to the scope of the present invention.
Example 1
Preparation of N-phenyl-4, 4' -dihydroxybenzophenone imine having a structure represented by formula (II) (wherein R 1 Phenyl):
21.42g (0.1 mol) of 4,4' -dihydroxybenzophenone, 27.99g (0.3 mol) of aniline, 0.38g (0.002 mol) of p-toluenesulfonic acid monohydrate and 30 mLN-methylpyrrolidone are added into a three-neck flask with a stirrer, a water separator and a condenser tube, reacted for 18h at 180 ℃, and the product solution after the reaction is settled to NaHCO 3 Obtaining white solid from the aqueous solution, recrystallizing with ethanol to obtain N-phenyl-4, 4' -dihydroxybenzophenone imine (R in the formula) 1 Is phenyl); the reaction equation is shown as a formula (1);
Figure BDA0004105250280000101
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of N-phenyl-4, 4' -dihydroxybenzophenone imine according to example 1 of the present invention.
The detection shows that the yield of the N-phenyl-4, 4' -dihydroxybenzophenone imine is 85 percent and the purity is 99 percent.
Example 2
Preparation of N-phenyl-4, 4' -dihydroxybenzophenone imine having a structure represented by formula (II) (wherein R 1 Phenyl):
21.42g (0.1 mol) of 4,4' -dihydroxybenzophenone, 27.99g (0.3 mol) of aniline, 0.38g (0.002 mol) of p-toluenesulfonic acid monohydrate, 30 mLN-methylpyrrolidone and 20mL of toluene with water agent are added into a three-necked flask with a stirrer, a water separator (the water separator is filled with toluene with water agent) and a condenser tube, reflux reaction is carried out at 150 ℃ for 10h, toluene is distilled off after the reaction is finished, and the product solution after the reaction is settled to NaHCO 3 Obtaining white solid from the aqueous solution, recrystallizing with ethanol to obtain N-phenyl-4, 4' -dihydroxybenzophenone imine (R in the formula) 1 Is phenyl); the reaction equation is shown in formula (1).
The detection shows that the yield of the N-phenyl-4, 4' -dihydroxybenzophenone imine is 87 percent and the purity is 99 percent.
Example 3
Polyarylether polymer containing ketimine structure (in formula I, R 1 Of formula R-1)Preparation:
n-phenyl-4, 4 '-dihydroxybenzophenone imine prepared in example 1, 21.82g (0.1 mol) 4,4' -difluorobenzophenone (having the structure of formula F-2 wherein X 1 And X 2 F, a=1), 28.33g (0.205 mol) potassium carbonate, 200mL dimethyl sulfoxide and 100mL toluene are added into a three-port bottle provided with mechanical stirring, a nitrogen inlet, a water separator (water-carrying agent toluene is filled in the water separator) and a condensing tube, toluene is distilled out after water is recycled for 6 hours at 150 ℃ under the nitrogen atmosphere, the temperature is raised to 180 ℃ for reaction for 3 hours, the product solution obtained by the reaction is poured into deionized water, and the obtained solid is washed and dried to obtain the polyaryletherketone containing the ketimine structure shown in the formula (2).
Figure BDA0004105250280000111
FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of polyaryletherketone containing ketimine structure according to example 3 of the present invention; wherein the solvent is CDCl 3 . FIG. 2 demonstrates that the ketimine structure-containing polyaryletherketone of example 3 of the present invention has a structure represented by formula (2).
The detection shows that the yield of the polyaryletherketone containing ketimine structure is 97%.
Example 4
Polyarylether polymer containing ketimine structure (in formula I, R 1 For the preparation of the formula R-1):
n-phenyl-4, 4 '-dihydroxybenzophenone imine prepared in example 1, 21.82g (0.1 mol) 4,4' -difluorobenzophenone (having the structure of formula F-2 wherein X 1 And X 2 F, a=1), 20.73g (0.15 mol) of potassium carbonate and 90 mLN-methyl pyrrolidone are added into a three-mouth bottle provided with a mechanical stirrer, a nitrogen inlet, a water separator and a condenser tube, and react for 1.5 hours at 200 ℃ under the nitrogen atmosphere to obtain a viscous polymer solution, 200 mLN-methyl pyrrolidone is added for dilution, and then the viscous polymer solution is poured into deionized water, and the obtained solid is washed and dried to obtain the polyaryletherketone containing ketimine structure shown in the formula (2).
The detection shows that the yield of the polyaryletherketone containing ketimine structure is 97%.
Example 5
One-pot method for preparing polyaryletherketone polymer containing ketimine structure (R in formula I 1 Is of formula R-1):
21.42g (0.1 mol) of 4,4 '-dihydroxybenzophenone, 27.99g (0.3 mol) of aniline, 0.38g (0.002 mol) of p-toluenesulfonic acid monohydrate, 30 mLN-methylpyrrolidone and 20mL of toluene with water agent are added into a three-necked flask with mechanical stirring, nitrogen inlet, water separator (water-carrying toluene is filled in the water separator) and a condenser tube, reflux reaction is carried out at 150 ℃ for 10 hours, toluene is distilled out after the reaction is finished, 21.82g (0.1 mol) of 4,4' -difluorobenzophenone (having a structure represented by formula F-2) is added into the system, wherein X 1 And X 2 F, a=1), 20.73g (0.15 mol) of potassium carbonate and 90 mLN-methyl pyrrolidone, reacting for 1.2h at 200 ℃ under nitrogen atmosphere to obtain a viscous polymer solution, adding 200mL of N-methyl pyrrolidone for dilution, pouring the product into deionized water, washing and drying the solid to obtain the polyaryletherketone containing ketimine structure shown in the formula (2).
The detection shows that the yield of the polyaryletherketone containing ketimine structure is 97%.
Example 6
One-pot method for preparing polyaryletherketone polymer containing ketimine structure (R in formula I 1 Formula R-4):
21.42g (0.1 mol) of 4,4 '-dihydroxybenzophenone, 29.75g (0.3 mol) of cyclohexylamine, 0.38g (0.002 mol) of p-toluenesulfonic acid monohydrate and 30. 30 mLN-methylpyrrolidone are added into a three-necked flask with mechanical stirring, nitrogen inlet, water separator and condenser tube, reacted at 130℃for 12 hours, after the reaction is finished, heated to 150℃to distill off the remaining cyclohexylamine, 21.82g (0.1 mol) of 4,4' -difluorobenzophenone (having a structure represented by the formula F-2 wherein X 1 And X 2 F, a=1), 20.73g (0.15 mol) potassium carbonate and 90 mLN-methyl pyrrolidone, reacting for 1.2h at 200 ℃ under nitrogen atmosphere to obtain a viscous polymer solution, adding 200 mLN-methyl pyrrolidone for dilution, pouring the product into deionized water, washing and drying the solid to obtain the structurePolyaryletherketone containing ketimine structure as shown in formula (3).
The detection shows that the yield of the polyaryletherketone containing ketimine structure is 97%.
Figure BDA0004105250280000121
Example 7
One-pot method for preparing polyaryletherketone polymer containing ketimine structure (R in formula I 1 Formula R-5):
21.42g (0.1 mol) of 4,4 '-dihydroxybenzophenone, 25.54g (0.3 mol) of cyclopentylamine, 0.38g (0.002 mol) of p-toluenesulfonic acid monohydrate, 30 mLN-methylpyrrolidone and 20mL of toluene as a water-carrying agent are added into a three-necked flask with a mechanical stirring, a nitrogen inlet, a water separator (water-carrying agent toluene is filled in the water separator) and a condenser tube, reacted at 100 ℃ for 16 hours, heated to 130 ℃ after the reaction is finished, excess cyclopentylamine is distilled off, 21.82g (0.1 mol) of 4,4' -difluorobenzophenone (having a structure represented by formula F-2) is added into the system, wherein X 1 And X 2 F, a=1), 20.73g (0.15 mol) of potassium carbonate and 90mL of N-methyl pyrrolidone, reacting for 1.2h at 200 ℃ under the nitrogen atmosphere to obtain a viscous polymer solution, adding 200 mLN-methyl pyrrolidone to dilute, pouring the product into deionized water, washing and drying the solid to obtain the polyaryletherketone containing ketimine structure shown in the formula (4).
The detection shows that the yield of the polyaryletherketone containing ketimine structure is 97%.
Figure BDA0004105250280000131
Example 8
One-pot method for preparing polyarylethersulfone polymer containing ketimine structure (R in formula I 1 Is of formula R-1):
21.42g (0.1 mol) of 4,4' -dihydroxybenzophenone, 27.99g (0.3 mol) of aniline, 0.38g (0.002 mol) of p-toluenesulfonic acid monohydrate, 30 mLN-methylpyrrolidone and 20mL of toluene as a water-carrying agent were added to the beltIn a three-necked flask having a mechanical stirring, a nitrogen inlet, a water separator (water-carrying toluene is charged in the water separator) and a condenser tube, reflux-reacting at 150℃for 10 hours, distilling off toluene after the reaction is completed, and adding 21.82g (0.1 mol) of 4,4' -dichlorodiphenyl sulfone (having a structure represented by formula F-1 wherein X 1 And X 2 Cl), 20.73g (0.15 mol) of potassium carbonate and 90 mLN-methyl pyrrolidone, reacting for 4 hours at 200 ℃ under the nitrogen atmosphere to obtain a viscous polymer solution, adding 200 mLN-methyl pyrrolidone for dilution, pouring the product into deionized water, washing and drying the solid to obtain the polyarylethersulfone containing ketimine structure shown in the formula (5).
The yield of the polyarylethersulfone containing ketimine structure is 96 percent through detection.
Figure BDA0004105250280000132
Comparative example 1
Modifying dihalogen monomer strategy to prepare ketimine structure-containing polyaryletherketone:
21.82g (0.1 mol) of 4,4 '-fluorobenzophenone, 27.99g (0.3 mol) of aniline, 0.38g (0.002 mol) of p-toluenesulfonic acid monohydrate and 50mL of toluene are added into a three-necked flask with a stirrer, a water separator (the water separator is filled with toluene with water-carrying agent) and a condenser tube, reflux reaction is carried out for 18h at 150 ℃, the product solution after the reaction is concentrated to half volume and then left for 24h, a large amount of yellow solid is precipitated, the obtained solid is recrystallized by toluene for 2 times, and N-phenyl-4, 4' -difluorobenzophenone imine is obtained with the yield of about 60%.
14.67g (0.05 mol) of N-phenyl-4, 4' -difluorobenzophenone imine, 5.51g (0.05 mol) of hydroquinone, 10.365g (0.075 mol) of potassium carbonate and 40 mLN-methylpyrrolidone are added into a three-mouth bottle provided with a mechanical stirring device, a nitrogen inlet, a water separator and a condenser tube, reacted for 4 hours under the nitrogen atmosphere to obtain a viscous polymer solution, 100 mLN-methylpyrrolidone is added for dilution, and then poured into deionized water, and the obtained solid is washed and dried to obtain the polyaryletherketone containing the ketimine structure shown in the formula (6). The yield was 95%.
Figure BDA0004105250280000141
As is evident from the test, the polymers obtained in examples 3 to 8 and comparative example 1 were all soluble in polar aprotic solvents such as tetrahydrofuran, N-methylpyrrolidone and N, N-dimethylacetamide and halogenated hydrocarbons such as methylene chloride and chloroform.
The permeation gel chromatography (GPC) tests of the polymers obtained in examples 3 to 8 and comparative example 1 are shown in Table 1, wherein the solvent and the eluent were tetrahydrofuran, and the sample concentration was 2mg/mL.
TABLE 1 permeation gel chromatography test results for the polymers obtained in examples 3 to 8 and comparative example 1
M n (KDa) 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
In Table 1, M n 、M w And PDI represents the number average molecular weight, weight average molecular weight and molecular weight distribution index, respectively.
As is clear from the above examples, either the preparation of bisphenol monomer containing ketimine structure followed by purification and polymerization (examples 1 to 4) or the preparation of bisphenol monomer containing ketimine structure followed by polymerization by one pot method without purification (examples 5 to 8) can obtain polyarylether polymer containing ketimine structure.
In combination with the monomer yield, the total yield in comparative example 1 is 50% -60%, the total yield in examples 1-4 in the invention is 80% -90% by the separate preparation process, and in addition, the invention also comprises a polymer prepared by a one-pot method, the process does not need to purify the monomer, and the total yield can reach more than 90%.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the 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 (10)

1. A polyarylether polymer containing ketimine structure has a structure shown in formula (I);
Figure FDA0004105250270000011
in the formula (I), n is more than or equal to 10;
ar is selected from aromatic groups;
R 1 selected from a substituted or unsubstituted aryl group, or a substituted or unsubstituted alkyl group.
2. The polyarylether polymer containing ketimine structures according to claim 1, wherein n is not less than 20;
ar is selected from structures shown in formulas A-1 to A-3:
Figure FDA0004105250270000012
in formula a-2, a=1, 2 or 3;
R 1 selected from phenyl, substituted phenyl, biphenyl, naphthyl, substituted naphthyl or alkyl with 1-12 carbon atoms; the alkyl is selected from linear alkyl, branched alkyl or cycloalkyl.
3. The polyarylether polymer containing ketimine structures according to claim 1, wherein R 1 Selected from the structures represented by the formulas R-1 to R-7:
Figure FDA0004105250270000013
R 2 selected from the group consisting of-H, -F, -Cl, -Br, -COOH, -SO 3 H、-NH 2 、-NO 3 、-CN、-OCH 3 、-CH 3 、-C 2 H 5 or-tBu;
in the formula R-7, m is more than or equal to 1 and less than or equal to 12.
4. A preparation method of polyarylether polymer containing ketimine structure comprises the following steps:
under the action of a first catalyst, carrying out polymerization reaction on a diphenol monomer with a ketimine structure and an aromatic dihalide monomer with a structure shown in a formula (II) in a first solvent to obtain a polyarylether polymer with a ketimine structure and a structure shown in a formula (I);
Figure FDA0004105250270000021
wherein n is more than or equal to 10;
ar is selected from aromatic groups;
R 1 selected from a substituted or unsubstituted aryl group, or a substituted or unsubstituted alkyl group.
5. The method according to claim 4, wherein the method for producing the ketimine structure-containing diphenol monomer having the structure represented by formula (II) comprises the steps of:
4,4' -dihydroxybenzophenone, R 1 -NH 2 Mixing the second catalyst with a second solvent, and then reacting to obtain a diphenol monomer containing a ketimine structure and having a structure shown in a formula (II);
R 1 selected from a substituted or unsubstituted aryl group, or a substituted or unsubstituted alkyl group.
6. The preparation method according to claim 5, wherein the second catalyst comprises one or more of hydrochloric acid, acetic acid, sulfuric acid, oxalic acid, p-toluenesulfonic acid monohydrate, methanesulfonic acid, aluminum chloride, titanium chloride and tin chloride;
the 4,4' -dihydroxybenzophenone, R 1 -NH 2 And the molar ratio of the second catalyst is 1:1 to 10:0.01 to 0.5;
the second solvent comprises one or more of N-methylpyrrolidone, dimethyl sulfoxide, N-dimethylformamide and N, N-dimethylacetamide.
7. The method according to claim 5, wherein the reaction is carried out at a temperature of 60 to 200℃for a period of 6 to 48 hours.
8. The method according to claim 5, wherein the first catalyst comprises one or more of sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate;
the molar ratio of the 4,4' -dihydroxybenzophenone, the aromatic dihalogen monomer and the first catalyst is 1:0.95 to 1.05:1.05 to 2.5.
9. The process of claim 4, wherein the aromatic dihalogen monomer is selected from the structures represented by formulas F-1 to F-3:
Figure FDA0004105250270000022
wherein X is 1 And X 2 Independently selected from halogen;
in formula F-2, a=1, 2 or 3.
10. The method according to claim 4, wherein the first solvent comprises one or more of N, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone, diphenylsulfone and sulfolane;
the temperature of the polymerization reaction is 150-250 ℃ and the time is 0.5-48 h.
CN202310190536.3A 2023-03-02 2023-03-02 Polyarylether polymer containing ketimine structure and preparation method thereof Pending CN116120539A (en)

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