CN111875791A - Preparation method of polyaryletherketone resin - Google Patents
Preparation method of polyaryletherketone resin Download PDFInfo
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- CN111875791A CN111875791A CN202010896413.8A CN202010896413A CN111875791A CN 111875791 A CN111875791 A CN 111875791A CN 202010896413 A CN202010896413 A CN 202010896413A CN 111875791 A CN111875791 A CN 111875791A
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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
- C08G65/4043—(I) or (II) containing oxygen other than as phenol or carbonyl group
- C08G65/405—(I) or (II) containing oxygen other than as phenol or carbonyl group in ring structure, e.g. phenolphtalein
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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
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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
- C08G65/48—Polymers modified by chemical after-treatment
Abstract
The invention belongs to the field of high polymer materials, and particularly relates to a preparation method of polyaryletherketone resin, which comprises the following steps: a) carrying out nucleophilic polycondensation on a dihalo monomer with a structure shown in a formula (I), a ketal diphenol monomer with a structure shown in a formula (ii) and a copolymerized aromatic diphenol monomer with a structure shown in a formula (iii) in an organic solvent under the action of an alkali catalyst to obtain a ketal polymer with a structure shown in a formula (I); b) and acidifying the ketal polymer in acid liquor to obtain the polyaryletherketone resin with the structure shown in the formula (II). The preparation method provided by the invention has the advantages of mild preparation conditions, low energy consumption, strong controllability and easy characterization of molecular weight. X-Q-X is of formula (i);
HO‑R3-OH formula (iii);
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to a preparation method of polyaryletherketone resin.
Background
The polyaryletherketone serving as a semi-crystalline polymer material has the advantages of good strength, high modulus, high-temperature steam resistance, solvent resistance, acid and alkali resistance, flame retardance and the like. Therefore, as special engineering plastics, the polyaryletherketone has wide application prospect and extremely high commercial value in the fields of medical sanitation, electronic devices, aerospace, automobile manufacturing, petroleum industry, nuclear energy and the like.
The polyaryletherketone polymer contains benzene rings, ether groups and ketone groups in the main chain of the molecule, and can be classified into Polyetherketone (PEK), Polyetherketoneketone (PEKK), Polyetheretherketone (PEEK), Polyetherketoneetherketoneketone (PEKEKK), and the like according to the number and sequence of the ether groups and ketone groups in the repeating units in the main chain of the molecule.
The synthesis method of the polyaryletherketone polymer can be divided into an electrophilic substitution method and a nucleophilic substitution method, the electrophilic polymerization method is to carry out Friedel-crafts acylation polymerization on a diacyl chloride monomer and an aromatic monomer, and the nucleophilic substitution method is to carry out nucleophilic substitution reaction on a bisphenol monomer and an aromatic dihalide under the action of an alkali carbonate to form ether bonds to realize polymerization.
Although the electrophilic substitution method has simple process and low monomer cost, the method has more side reactions in the synthesis and the catalyst remained in the product is difficult to remove, thereby influencing the product performance. The polyaryletherketone prepared by the nucleophilic substitution method has fewer side reactions, so the product has higher purity and better performance, and the existing production route of the polyaryletherketone mainly adopts a nucleophilic polycondensation method. However, the existing nucleophilic polycondensation processes generally have the following disadvantages: 1) in order to avoid the crystallization of the polymer, the polymerization reaction is generally carried out in a high-boiling-point solvent at a higher temperature, and the energy consumption is higher; 2) the reaction rate is fast at high temperature, the control of the process conditions is difficult, 3) the molecular weight of the polymer is difficult to characterize due to the fact that the polyaryletherketone is difficult to dissolve in the conventional solvent because of the tendency of crystallinity, and the viscosity is mostly used as the distinction between batches.
Disclosure of Invention
In view of the above, the present invention provides a method for preparing polyaryletherketone resin, and the preparation method provided by the present invention has the advantages of mild preparation conditions, low energy consumption, strong controllability, and easy characterization of molecular weight.
The invention provides a preparation method of polyaryletherketone resin, which comprises the following steps:
a) carrying out nucleophilic polycondensation on a dihalo monomer with a structure shown in a formula (I), a ketal diphenol monomer with a structure shown in a formula (ii) and a copolymerized aromatic diphenol monomer with a structure shown in a formula (iii) in an organic solvent under the action of an alkali catalyst to obtain a ketal polymer with a structure shown in a formula (I);
b) acidifying the ketal polymer in acid liquor to obtain polyaryletherketone resin with a structure shown in a formula (II);
X-Q-X is of formula (i);
HO-R3-OH formula (iii);
wherein Q is selected from one or more of the following substituents:
x represents a halogen;
R1one or more substituents selected from the group consisting of:
R2is selected from-CH3、-C2H5-tBu and-CH2OCH3One or more of;
R3one or more substituents selected from the group consisting of:
1≤m≤4，0.5≤z≤1，n≥10。
preferably, the step a) specifically comprises:
mixing a dihalo monomer with a structure shown in a formula (i), a ketal diphenol monomer with a structure shown in a formula (ii), a copolymerized aromatic diphenol monomer with a structure shown in a formula (iii), an alkali catalyst, a water-carrying agent and an organic solvent, and heating and refluxing to carry out water carrying; and then evaporating the water-carrying agent, heating to carry out nucleophilic polycondensation reaction to obtain the ketal polymer with the structure shown in the formula (I).
Preferably, the step a) specifically comprises:
mixing a ketal diphenol monomer with a structure shown in a formula (ii), a copolymerized aromatic diphenol monomer with a structure shown in a formula (iii), an alkali catalyst, a water-carrying agent and an organic solvent, and heating and refluxing to carry out water carrying; and (3) evaporating the water-carrying agent, mixing the residual component with a dihalo monomer with the structure shown in the formula (I), and heating to perform nucleophilic polycondensation reaction to obtain the ketal polymer with the structure shown in the formula (I).
Preferably, the step a) specifically comprises:
mixing a carbonyl diphenol monomer with a structure shown in a formula (ii'), a copolymerized aromatic diphenol monomer with a structure shown in a formula (iii), an acid catalyst and alcohol, and reacting the carbonyl diphenol monomer and the alcohol in a mixed system under the action of the acid catalyst to generate a ketal diphenol monomer with a structure shown in a formula (ii); then mixing the reacted mixed system with a dihalogen monomer with a structure shown in formula (i), an alkali catalyst, a water-carrying agent and an organic solvent, and heating and refluxing to carry out water carrying; then evaporating the water-carrying agent, heating to carry out nucleophilic polycondensation reaction to obtain a ketal polymer with the structure shown in the formula (I);
preferably, in step a), the molar ratio of the ketal diphenol monomer to the copolymerized aromatic diphenol monomer is 1: (0-1);
the total molar weight of the ketal diphenol monomer and the copolymerized aromatic diphenol monomer, the molar ratio of the dihalogen monomer to the base catalyst is 1: (0.95-1.05): (1.05-2.5).
Preferably, in step a), the base catalyst comprises an alkali metal hydroxide and/or an alkali metal carbonate;
the organic solvent comprises one or more of N, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone, diphenyl sulfone and sulfolane.
Preferably, in the step a), the temperature of the nucleophilic polycondensation is 140-280 ℃; the time of nucleophilic polycondensation is 0.2-48 h.
Preferably, the water-carrying agent comprises one or more of cyclohexane, benzene, toluene, xylene and chlorobenzene;
the temperature of the charged water is 120-190 ℃; the time for carrying water is 1-12 h.
Preferably, in step b), the acid in the acid solution comprises one or more of hydrochloric acid, sulfuric acid, nitric acid, hydrobromic acid, boric acid, phosphoric acid, formic acid, acetic acid, oxalic acid, succinic acid, salicylic acid, trifluoromethanesulfonic acid, trifluoroacetic acid, benzenesulfonic acid, p-toluenesulfonic acid and methanesulfonic acid;
the solvent in the acid liquor is water or a mixture of an organic solvent which can be mutually soluble with water and water;
the acid concentration in the acid solution is 0.1-10 mol/L.
Preferably, in the step b), the acidification temperature is 20-acid liquor boiling point; the acidification time is 1-48 h.
Compared with the prior art, the invention provides a preparation method of polyaryletherketone resin. The preparation method provided by the invention comprises the following steps: a) carrying out nucleophilic polycondensation on a dihalo monomer with a structure shown in a formula (I), a ketal diphenol monomer with a structure shown in a formula (ii) and a copolymerized aromatic diphenol monomer with a structure shown in a formula (iii) in an organic solvent under the action of an alkali catalyst to obtain a ketal polymer with a structure shown in a formula (I); b) and acidifying the ketal polymer in acid liquor to obtain the polyaryletherketone resin with the structure shown in the formula (II). The preparation method provided by the invention firstly adopts ketal protected and modified monomers to carry out nucleophilic polycondensation to prepare ketal polymers, and then prepares the polyaryletherketone resin by acidification and deprotection. Because the ketal polymer has better solubility, the ketal polymer can adopt a conventional polar aprotic solvent as a reaction solvent in the preparation process and complete the nucleophilic polycondensation reaction at a lower temperature. The preparation method provided by the invention solves the problem that the polymer with higher molecular weight is difficult to obtain due to precipitation in the nucleophilic polycondensation process of the polyaryletherketone under mild conditions, and reduces the polymerization temperature of the nucleophilic polycondensation route, thereby reducing the reaction energy consumption and improving the reaction controllability. In addition, the polymer precursor (ketal polymer) prepared by the method has better solubility, so the molecular weight can be characterized by conventional means (such as Gel Permeation Chromatography (GPC)), thereby reducing the difficulty of the characterization of the molecular weight of the polyaryletherketone. The preparation method provided by the invention has the advantages of mild preparation conditions, low energy consumption, strong controllability, easy molecular weight characterization and the like, and can be used for stably preparing the high-purity, high-strength, heat-resistant and corrosion-resistant polyaryletherketone resin. In addition, the invention can also utilize the characteristic of better solubility of the ketal polymer to firstly carry out solution processing on the ketal polymer and then directly prepare the polyaryletherketone device by acidification, thereby improving the processability of the polyaryletherketone resin.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is a NMR chart of a ketal polymer provided in example 1 of the invention;
FIG. 2 is a NMR spectrum of a ketal polymer provided in example 1 of the invention;
FIG. 3 is a nuclear magnetic resonance carbon spectrum of polyaryletherketone resin provided in example 1 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a preparation method of polyaryletherketone resin, which comprises the following steps:
a) carrying out nucleophilic polycondensation on a dihalo monomer with a structure shown in a formula (I), a ketal diphenol monomer with a structure shown in a formula (ii) and a copolymerized aromatic diphenol monomer with a structure shown in a formula (iii) in an organic solvent under the action of an alkali catalyst to obtain a ketal polymer with a structure shown in a formula (I);
b) acidifying the ketal polymer in acid liquor to obtain polyaryletherketone resin with a structure shown in a formula (II);
X-Q-X is of formula (i);
HO-R3-OH formula (iii);
wherein Q is selected from one or more of the following substituents:
x represents halogen, preferably-F or-Cl;
R1one or more substituents selected from the group consisting of:
R2is selected from-CH3、-C2H5-tBu (tert-butyl) and-CH2OCH3One or more of;
R3one or more substituents selected from the group consisting of:
m is more than or equal to 1 and less than or equal to 4, and can be 1, 2, 3 and 4; z is more than or equal to 0.5 and less than or equal to 1, and can be more than or equal to 0.5, 0.6, 0.7, 0.8, 0.9 and 1; n is not less than 10, specifically 70 to 110, more specifically 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 105, 106, 107, 108, 109 or 110.
In the preparation method provided by the invention, firstly, under the action of an alkali catalyst, a dihalo monomer with a structure shown in a formula (I), a ketal diphenol monomer with a structure shown in a formula (ii) and a copolymerized aromatic diphenol monomer with a structure shown in a formula (iii) are subjected to nucleophilic polycondensation in an organic solvent to prepare the ketal polymer with a structure shown in a formula (I). The present invention is not particularly limited to the specific preparation process of the ketal polymer, and any one of the following three modes may be preferably selected:
the first method is as follows: mixing a dihalo monomer with a structure shown in a formula (i), a ketal diphenol monomer with a structure shown in a formula (ii), a copolymerized aromatic diphenol monomer with a structure shown in a formula (iii), an alkali catalyst, a water-carrying agent and an organic solvent, and heating and refluxing to carry out water carrying; and then evaporating the water-carrying agent, heating to carry out nucleophilic polycondensation reaction to obtain the ketal polymer with the structure shown in the formula (I).
The second method comprises the following steps: mixing a ketal diphenol monomer with a structure shown in a formula (ii), a copolymerized aromatic diphenol monomer with a structure shown in a formula (iii), an alkali catalyst, a water-carrying agent and an organic solvent, and heating and refluxing to carry out water carrying (during the process, the ketal diphenol monomer is converted into phenolate); and (3) evaporating the water-carrying agent, mixing the residual component with a dihalo monomer with the structure shown in the formula (I), and heating to perform nucleophilic polycondensation reaction to obtain the ketal polymer with the structure shown in the formula (I).
The third method comprises the following steps: mixing a carbonyl diphenol monomer with a structure shown in a formula (ii'), a copolymerized aromatic diphenol monomer with a structure shown in a formula (iii), an acid catalyst and alcohol, and reacting the carbonyl diphenol monomer and the alcohol in a mixed system under the action of the acid catalyst to generate a ketal diphenol monomer with a structure shown in a formula (ii); then mixing the reacted mixed system with a dihalogen monomer with a structure shown in formula (i), an alkali catalyst, a water-carrying agent and an organic solvent, and heating and refluxing to carry out water carrying; then evaporating the water-carrying agent, heating to carry out nucleophilic polycondensation reaction to obtain a ketal polymer with the structure shown in the formula (I);
in the above ketal polymer production method provided by the present invention, in the third method, the acid catalyst is preferably a protonic acid or a lewis acid, and specifically may be p-toluenesulfonic acid; the specific type of the alcohol is determined according to the structure of the ketal diphenol monomer to be prepared, and ethylene glycol, propylene glycol, glycerol and the like can be specifically selected; the molar ratio of the carbonyldiphenol monomer to the corresponding alcohol is preferably 1: (0.5-20), specifically 1:0.5, 1:0.7, 1:1, 1:1.2, 1:1.4, 1:1.6, 1:1.8, 1:2, 1:2.5, 1:3, 1:4, 1:5, 1:10, 1:15 or 1: 20; during the mixing of the carbonyl diphenol monomer, the copolymerized aromatic diphenol monomer, the acid catalyst and the alcohol, a certain amount of reaction solvent is preferably added, wherein the reaction solvent comprises but is not limited to trimethyl orthoformate; the reaction temperature under the action of the acid catalyst is preferably 80-120 ℃, specifically 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃, 105 ℃, 110 ℃, 115 ℃ or 120 ℃, and the reaction time is preferably 6-12 h, specifically 6h, 7h, 8h, 9h, 10h, 11h or 12 h.
In the preparation method provided by the invention, in the process of preparing the ketal polymer with the structure shown in the formula (I), the molar ratio of the ketal diphenol monomer to the copolymerized aromatic diphenol monomer is preferably 1: (0-1), specifically 1:0, 1:0.1, 1:0.2, 1:0.3, 1:0.4, 1:0.5, 1:0.6, 1:0.7, 1:0.8, 1:0.9 or 1: 1; the combined molar amount of the ketal diphenol monomer and the copolymerized aromatic diphenol monomer and the molar ratio of the dihalo monomer are preferably 1: (0.95-1.05), specifically 1:0.95, 1:0.96, 1:0.97, 1:0.98, 1:0.99, 1:1, 1:1.01, 1:1.02, 1:1.03, 1:1.04, or 1: 1.05.
In the preparation method provided by the invention, in the process of preparing the ketal polymer with the structure shown in the formula (I), the base catalyst preferably comprises alkali metal hydroxide and/or alkali metal carbonate, more preferably alkali metal carbonate, and most preferably one or more of sodium carbonate, potassium carbonate and cesium carbonate; the combined molar amount of the ketal diphenol monomer and the copolymerized aromatic diphenol monomer and the molar ratio of the base catalyst are preferably 1: (1.05-2.5), specifically 1:1.05, 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1:1.5, 1:1.6, 1:1.7, 1:1.8, 1:1.9, 1:2, 1:2.1, 1:2.2, 1:2.3, 1:2.4 or 1: 2.5.
In the preparation method provided by the invention, in the process of preparing the ketal polymer with the structure shown in the formula (I), the organic solvent is a polar aprotic solvent, including but not limited to one or more of N, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone, diphenyl sulfone and sulfolane; the dosage ratio of the organic solvent to the dihalogen monomer is preferably 100mL: (5 to 50) g, specifically, 100mL:5g, 100mL:10g, 100mL:15g, 100mL:20g, 100mL:21g, 100mL:22g, 100mL:25g, 100mL:30g, 100mL:35g, 100mL:40g, 100mL:45g or 100mL:50 g.
In the preparation method provided by the invention, in the process of preparing the ketal polymer with the structure shown in the formula (I), the water-carrying agent is a solvent which can be subjected to azeotropic distillation with water, and comprises but is not limited to one or more of cyclohexane, benzene, toluene, xylene and chlorobenzene, and toluene and/or xylene are preferred; the dosage ratio of the water-carrying agent to the dihalogen monomer is preferably 50mL: (5-50) g, specifically 50mL:5g, 50mL:10g, 50mL:15g, 50mL:20g, 50mL:21g, 50mL:22g, 50mL:25g, 50mL:30g, 50mL:35g, 100mL:40g, 50mL:45g or 50mL:50 g; the temperature of the charged water is preferably 120-190 ℃, more preferably 140-180 ℃, and specifically can be 140 ℃, 145 ℃, 150 ℃, 155 ℃, 160 ℃, 165 ℃, 170 ℃, 175 ℃ or 180 ℃; the water carrying time is preferably 1-12 h, and specifically can be 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h or 12 h.
In the preparation method provided by the invention, in the process of preparing the ketal polymer with the structure shown in the formula (I), the nucleophilic polycondensation is preferably carried out under the protection of nitrogen; the temperature of the nucleophilic polycondensation is preferably 140 to 280 ℃, more preferably 150 to 240 ℃, most preferably 160 to 220 ℃, and specifically can be 160 ℃, 165 ℃, 170 ℃, 175 ℃, 180 ℃, 185 ℃, 190 ℃, 195 ℃, 200 ℃, 205 ℃, 210 ℃, 215 ℃ or 220 ℃; the time for nucleophilic polycondensation is preferably 0.2-48 h, more preferably 0.5-24 h, most preferably 1-12 h, and specifically may be 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h or 12 h.
In the preparation method provided by the invention, in the process of preparing the ketal polymer with the structure shown in the formula (I), after the nucleophilic polycondensation reaction is finished, the obtained reaction product material liquid is subjected to post-treatment to obtain the ketal polymer with the structure shown in the formula (I). Wherein, the specific process of the post-treatment preferably comprises the following steps: diluting the reaction product liquid by using an organic solvent, then carrying out solid-liquid separation on the diluent (aiming at filtering out an alkali catalyst), and settling the obtained clear liquid into a coagulating bath to obtain a ketal polymer (crude product) with the structure shown in the formula (I); the solid content of the diluent is preferably 5-25 wt%, and specifically can be 5 wt%, 10 wt%, 15 wt%, 20 wt% or 25 wt%; the coagulation bath includes, but is not limited to, one or more of water, methanol and ethanol, preferably water or ethanol.
In the preparation method provided by the invention, after the ketal polymer with the structure shown in the formula (I) is prepared, the ketal polymer is acidified in acid solution. Wherein the ketal polymer is preferably comminuted prior to acidification; the acid solution consists of acid and a solvent; the acid includes, but is not limited to, one or more of hydrochloric acid, sulfuric acid, nitric acid, hydrobromic acid, boric acid, phosphoric acid, formic acid, acetic acid, oxalic acid, succinic acid, salicylic acid, trifluoromethanesulfonic acid, trifluoroacetic acid, benzenesulfonic acid, p-toluenesulfonic acid, and methanesulfonic acid; the solvent is water, or a mixture of water and a water-miscible organic solvent, including but not limited to one or more of methanol, ethanol, isopropanol, Dimethylformamide (DMF), dimethylacetamide (DMAc), Tetrahydrofuran (THF), and acetone; the concentration of the acid in the acid solution is preferably 0.1-10 mol/L, more preferably 1-5 mol/L, and specifically can be 1mol/L, 1.5mol/L, 2mol/L, 2.5mol/L, 3mol/L, 3.5mol/L, 4mol/L, 4.5mol/L or 5 mol/L; the acidification is preferably carried out under the protection of nitrogen; the acidification temperature is preferably 20-acid liquor boiling point; the acidification time is preferably 1-48 h, more preferably 2-24 h, and specifically can be 2h, 4h, 6h, 8h, 10h, 12h, 14h, 16h, 18h, 20h, 22h or 24 h.
In the preparation method provided by the invention, after acidification is finished, a crude product of the polyaryletherketone with the structure shown in the formula (II) is obtained, and then the crude product is refined to obtain the refined polyaryletherketone with the structure shown in the formula (II). Wherein, the specific process of the refining preferably comprises the following steps: boiling the crude product in deionized water, filtering, and repeating for several times; boiling in organic solvent, filtering, and repeating for several times; and finally drying to obtain the refined polyaryletherketone with the structure shown in the formula (II).
The preparation method provided by the invention firstly adopts ketal protected and modified monomers to carry out nucleophilic polycondensation to prepare ketal polymers, and then prepares the polyaryletherketone resin by acidification and deprotection. Because the ketal polymer has better solubility, the ketal polymer can adopt a conventional polar aprotic solvent as a reaction solvent in the preparation process and complete the nucleophilic polycondensation reaction at a lower temperature. The preparation method provided by the invention solves the problem that the polymer with higher molecular weight is difficult to obtain due to precipitation in the nucleophilic polycondensation process of the polyaryletherketone under mild conditions, and reduces the polymerization temperature of the nucleophilic polycondensation route, thereby reducing the reaction energy consumption and improving the reaction controllability. In addition, the polymer precursor (ketal polymer) prepared by the method has better solubility, so the molecular weight can be characterized by conventional means (such as Gel Permeation Chromatography (GPC)), thereby reducing the difficulty of the characterization of the molecular weight of the polyaryletherketone. The preparation method provided by the invention has the advantages of mild preparation conditions, low energy consumption, strong controllability, easy molecular weight characterization and the like, and can be used for stably preparing the high-purity, high-strength, heat-resistant and corrosion-resistant polyaryletherketone resin. In addition, the invention can also utilize the characteristic of better solubility of the ketal polymer to firstly carry out solution processing on the ketal polymer and then directly prepare the polyaryletherketone device by acidification, thereby improving the processability of the polyaryletherketone resin.
For the sake of clarity, the following examples are given in detail.
Example 1
Choose to use
The ketal bisphenol monomer (2, 2-bis (4-hydroxyphenyl) -1, 3-dioxolane) with m ═ 1 is condensed with 4, 4' -difluorobenzophenone to prepare the polyaryletherketone resin, and the specific method is as follows:
25.83g (0.1mol) of 2, 2-bis (4-hydroxyphenyl) -1, 3-dioxolane, 21.82g (0.1mol) of 4, 4' -difluorobenzophenone and 28.9g (0.21mol) of potassium carbonate are added into a three-neck flask with nitrogen protection, mechanical stirring, a water separator and a condenser tube, then 100mL of dimethyl sulfoxide and 50mL of toluene are added, the mixture is heated to 150 ℃, toluene is refluxed with water for 6h, the toluene is evaporated and heated to 180 ℃ for nucleophilic polycondensation, 300mL of dimethyl sulfoxide is added for dilution after 2h of polycondensation, the supernatant is settled into deionized water after centrifugation, and a crude ketal polymer product is obtained, wherein the hydrogen spectrum and the carbon spectrum of nuclear magnetic resonance of the crude ketal polymer are shown in figures 1-2.
And (3) crushing the prepared ketal polymer crude product, boiling and acidifying in 2mol/L hydrochloric acid for 12h, boiling and washing with ionized water for 5 times, boiling and washing with ethanol for 3 times to obtain the refined polyaryletherketone resin, wherein the nuclear magnetic resonance carbon spectrum of the refined polyaryletherketone resin is shown in figure 3.
The polyaryletherketone resin prepared in this example has a structure represented by formula (II-1):
GPC testing of the polyaryletherketone resin prepared in this example showed that the polymer had a weight average molecular weight of about 32000 (corresponding to n 81). As can be seen, the polyaryletherketone resin prepared in this example has a higher molecular weight.
Example 2
Referring to the preparation method of example 1, except that the polycondensation time was extended from "2 h" to "4 h", a polyaryletherketone resin was prepared.
GPC testing of the polyaryletherketone resin prepared in this example showed that the polymer had a weight average molecular weight of about 38000 (corresponding to n: 96).
Example 3
Referring to the preparation method of example 1, except that the polar aprotic solvent was replaced with "N-methylpyrrolidone" from "dimethyl sulfoxide", and the polycondensation time was extended from "2 h" to "8 h", a polyaryletherketone resin was prepared and a polyaryletherketone resin was prepared.
GPC testing of the polyaryletherketone resin prepared in this example showed that the polymer had a weight average molecular weight of about 41000 (corresponding to n being 104).
Example 4
Choose to use
The ketal bisphenol monomer (2, 2-bis (4-hydroxyphenyl) -1, 3-dioxolane) with m ═ 1, 4 '-biphenol and 4, 4' -difluorobenzophenone are subjected to polycondensation to prepare the polyaryletherketone resin, and the specific method is as follows:
adding 20.66g (0.08mol) of 2, 2-bis (4-hydroxyphenyl) -1, 3-dioxolane, 3.72g (0.02mol) of 4,4 '-biphenol, 21.82g (0.1mol) of 4, 4' -difluorobenzophenone and 28.9g (0.21mol) of anhydrous potassium carbonate into a three-neck flask with nitrogen protection, mechanical stirring, a water separator and a condenser pipe, then adding 100mL of dimethyl sulfoxide and 50mL of toluene, heating to 150 ℃, refluxing the toluene with water for 6h, evaporating the toluene, heating to 180 ℃ for nucleophilic polycondensation, adding 300mL of dimethyl sulfoxide for dilution after 2h of polycondensation, centrifuging, and settling supernatant into deionized water to obtain a crude ketal polymer.
And (3) crushing the prepared ketal polymer crude product, boiling and acidifying in 2mol/L hydrochloric acid for 12h, boiling and washing with ionic water for 5 times, and boiling and washing with ethanol for 3 times to obtain the refined polyaryletherketone resin.
The polyaryletherketone resin prepared in this example has a structure represented by formula (II-2):
GPC testing of the polyaryletherketone resin prepared in this example showed that the polymer had a weight average molecular weight of about 35000 (corresponding to n being 90).
Example 5
21.422g (0.1mol) of 4,4 '-dihydroxy benzophenone, 12.04g (0.2mol) of ethylene glycol, 0.38g (0.002mol) of p-toluenesulfonic acid monohydrate and 28mL of trimethyl orthoformate are added into a three-neck flask with nitrogen protection, mechanical stirring, a water separator and a condenser tube to react for 8 hours at 100 ℃, then 100mL of dimethyl sulfoxide, 21.82g (0.1mol) of 4, 4' -difluorobenzophenone, 28.9g (0.21mol) of potassium carbonate and 50mL of toluene are added into the system, the system is heated to 150 ℃, toluene is refluxed with water for 6 hours, the toluene is evaporated and heated to 180 ℃ for nucleophilic polycondensation, 300mL of dimethyl sulfoxide is added for dilution after 4 hours of polycondensation, and supernatant after centrifugation is settled into deionized water to obtain a crude ketal polymer.
And (3) crushing the prepared ketal polymer crude product, boiling and acidifying in 2mol/L hydrochloric acid for 12h, boiling and washing with ionic water for 5 times, and boiling and washing with ethanol for 3 times to obtain the refined polyaryletherketone resin.
The polyaryletherketone resin prepared in this example has a structure represented by formula (II-1):
GPC testing of the polyaryletherketone resin prepared in this example showed that the polymer had a weight average molecular weight of about 35000 (corresponding to n: 89).
Example 6
17.138g (0.08mol) of 4,4 ' -dihydroxybenzophenone, 3.72g (0.02mol) of 4,4 ' -biphenol, 9.71g (0.16mol) of ethylene glycol, 0.38g (0.002mol) of p-toluenesulfonic acid monohydrate and 28mL of trimethyl orthoformate are added into a three-neck flask with nitrogen protection, mechanical stirring, a water separator and a condenser tube to react for 8 hours at 100 ℃, then 100mL of dimethyl sulfoxide, 21.82g (0.1mol) of 4,4 ' -difluorobenzophenone, 28.9g (0.21mol) of potassium carbonate and 50mL of toluene are added into the system, the system is heated to 150 ℃, the toluene is refluxed with water for 6 hours, the toluene is evaporated and heated to 180 ℃ to carry out nucleophilic polycondensation, 300mL of dimethyl sulfoxide is added to dilute after 4 hours of polycondensation, and supernatant is settled into deionized water after centrifugation to obtain a crude polymer.
And (3) crushing the prepared ketal polymer crude product, boiling and acidifying in 2mol/L hydrochloric acid for 12h, boiling and washing with ionic water for 5 times, and boiling and washing with ethanol for 3 times to obtain the refined polyaryletherketone resin.
The polyaryletherketone resin prepared in this example has a structure represented by formula (II-1):
GPC testing of the polyaryletherketone resin prepared in this example showed that the polymer had a weight average molecular weight of about 38000 (corresponding to n-98).
Example 7
Referring to the production method of example 5, except for replacing "12.04 g (0.2mol) of ethylene glycol" with "18.42 g (0.2mol) of glycerin", a polyaryletherketone resin was produced.
GPC testing of the polyaryletherketone resin prepared in this example showed that the polymer had a weight average molecular weight of about 31000 (corresponding to n 79).
Example 8
Referring to the preparation method of example 6, except for replacing "9.71 g (0.16mol) of ethylene glycol" with "14.74 g (0.16mol) of glycerin", a polyaryletherketone resin was prepared.
GPC testing of the polyaryletherketone resin prepared in this example showed that the polymer had a weight average molecular weight of about 32000 (corresponding to n being 82).
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A preparation method of polyaryletherketone resin comprises the following steps:
a) carrying out nucleophilic polycondensation on a dihalo monomer with a structure shown in a formula (I), a ketal diphenol monomer with a structure shown in a formula (ii) and a copolymerized aromatic diphenol monomer with a structure shown in a formula (iii) in an organic solvent under the action of an alkali catalyst to obtain a ketal polymer with a structure shown in a formula (I);
b) acidifying the ketal polymer in acid liquor to obtain polyaryletherketone resin with a structure shown in a formula (II);
X-Q-X is of formula (i);
HO-R3-OH formula (iii);
wherein Q is selected from one or more of the following substituents:
x represents a halogen;
R1one or more substituents selected from the group consisting of:
R2is selected from-CH3、-C2H5-tBu and-CH2OCH3One or more of;
R3one or more substituents selected from the group consisting of:
1≤m≤4，0.5≤z≤1，n≥10。
2. the method according to claim 1, wherein step a) comprises in particular:
mixing a dihalo monomer with a structure shown in a formula (i), a ketal diphenol monomer with a structure shown in a formula (ii), a copolymerized aromatic diphenol monomer with a structure shown in a formula (iii), an alkali catalyst, a water-carrying agent and an organic solvent, and heating and refluxing to carry out water carrying; and then evaporating the water-carrying agent, heating to carry out nucleophilic polycondensation reaction to obtain the ketal polymer with the structure shown in the formula (I).
3. The method according to claim 1, wherein step a) comprises in particular:
mixing a ketal diphenol monomer with a structure shown in a formula (ii), a copolymerized aromatic diphenol monomer with a structure shown in a formula (iii), an alkali catalyst, a water-carrying agent and an organic solvent, and heating and refluxing to carry out water carrying; and (3) evaporating the water-carrying agent, mixing the residual component with a dihalo monomer with the structure shown in the formula (I), and heating to perform nucleophilic polycondensation reaction to obtain the ketal polymer with the structure shown in the formula (I).
4. The method according to claim 1, wherein step a) comprises in particular:
mixing a carbonyl diphenol monomer with a structure shown in a formula (ii'), a copolymerized aromatic diphenol monomer with a structure shown in a formula (iii), an acid catalyst and alcohol, and reacting the carbonyl diphenol monomer and the alcohol in a mixed system under the action of the acid catalyst to generate a ketal diphenol monomer with a structure shown in a formula (ii); then mixing the reacted mixed system with a dihalogen monomer with a structure shown in formula (i), an alkali catalyst, a water-carrying agent and an organic solvent, and heating and refluxing to carry out water carrying; then evaporating the water-carrying agent, heating to carry out nucleophilic polycondensation reaction to obtain a ketal polymer with the structure shown in the formula (I);
5. the method of claim 1, wherein in step a), the molar ratio of the ketal diphenol monomer to the copolymerized aromatic diphenol monomer is 1: (0-1);
the total molar weight of the ketal diphenol monomer and the copolymerized aromatic diphenol monomer, the molar ratio of the dihalogen monomer to the base catalyst is 1: (0.95-1.05): (1.05-2.5).
6. The process according to claim 1, wherein in step a), the base catalyst comprises an alkali metal hydroxide and/or an alkali metal carbonate;
the organic solvent comprises one or more of N, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone, diphenyl sulfone and sulfolane.
7. The method according to claim 1, wherein the temperature of the nucleophilic polycondensation in step a) is 140 to 280 ℃; the time of nucleophilic polycondensation is 0.2-48 h.
8. The preparation method according to any one of claims 2 to 4, wherein the water-carrying agent comprises one or more of cyclohexane, benzene, toluene, xylene and chlorobenzene;
the temperature of the charged water is 120-190 ℃; the time for carrying water is 1-12 h.
9. The method according to claim 1, wherein in step b), the acid in the acid solution comprises one or more of hydrochloric acid, sulfuric acid, nitric acid, hydrobromic acid, boric acid, phosphoric acid, formic acid, acetic acid, oxalic acid, succinic acid, salicylic acid, trifluoromethanesulfonic acid, trifluoroacetic acid, benzenesulfonic acid, p-toluenesulfonic acid and methanesulfonic acid;
the solvent in the acid liquor is water or a mixture of an organic solvent which can be mutually soluble with water and water;
the acid concentration in the acid solution is 0.1-10 mol/L.
10. The preparation method according to claim 1, wherein in the step b), the acidification temperature is 20 ℃ to the acid liquor boiling point; the acidification time is 1-48 h.
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