CN112979940A - All-biphenyl polyaryletherketone precursor as well as preparation method and application thereof - Google Patents

All-biphenyl polyaryletherketone precursor as well as preparation method and application thereof Download PDF

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CN112979940A
CN112979940A CN202110204494.5A CN202110204494A CN112979940A CN 112979940 A CN112979940 A CN 112979940A CN 202110204494 A CN202110204494 A CN 202110204494A CN 112979940 A CN112979940 A CN 112979940A
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biphenyl
polyaryletherketone
precursor
full
acid
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杨砚超
王晟道
王贵宾
庞金辉
王岩
张淑玲
张梅
栾加双
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Jilin University
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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
    • C08G65/4062—(I) or (II) containing sulfur in ring structure
    • 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
    • C08G65/4081—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 forming cyclic polymers or oligomers
    • 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
    • C08G65/4093—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 characterised by the process or apparatus used

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Abstract

The invention provides a full biphenyl polyaryletherketone precursor, a preparation method and application thereof, and belongs to the technical field of high polymer materials. The full-biphenyl polyaryletherketone precursor is obtained by carrying out polymerization reaction on a difluoride monomer and biphenyl diphenol at the temperature of 170-210 ℃, and then carrying out acidification hydrolysis or one-step reaction or two-step reaction on the full-biphenyl polyaryletherketone precursor to obtain the full-biphenyl polyaryletherketone. The invention has the advantages that the homogeneous polymerization is carried out at lower reaction temperature, the obtained polymers are all in an all-biphenyl structure, so the rigidity of the molecular chain of the polymer, the regularity and the molecular weight of the molecular chain are obviously improved, and the prepared polymer has higher TmThe intrinsic viscosity reaches more than 416 ℃, and the intrinsic viscosity reaches more than 2.09 dL/g.

Description

All-biphenyl polyaryletherketone precursor as well as preparation method and application thereof
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a full biphenyl polyaryletherketone precursor, and a preparation method and application thereof.
Background
Resin-based composite materials are widely used in various fields because of their light weight, excellent mechanical properties, designability, and the like. With the development of the aviation field, the flight speed of the next generation of fighter aircraft is further improved, and higher requirements are put forward on the heat resistance of the composite material. The traditional resin matrix is difficult to meet the use requirements of long-term use at 350 ℃, short-term use at 400 ℃ or high-temperature corrosion environment, and even the polyether ether ketone (PEEK) as special engineering plastic is gradually difficult to meet the national strategic demands. Meanwhile, the development of composite materials based on Polyetherketoneketone (PEKK) resin has been started abroad, but since the synthetic route is electrophilic substitution reaction, domestic related research and production processes are not mature, and thus the development of high temperature resistant thermoplastic resin matrix with independent intellectual property rights is urgently needed.
Because the domestic method has a strong foundation for producing the polyaryletherketone through nucleophilic substitution, the polyaryletherketone resin matrix with higher heat resistance produced through nucleophilic substitution reaction can realize the shortcut of curve overtaking. Total biphenyl polyether ether ketone (PEDEK), total biphenyl polyether ether ketone (PEDEKK) and total biphenyl polyether ether ketone biphenyl ketone (PEDEKDK) are three resins with heat resistance far higher than that of PEEK, and the crystallization melting temperature (T) of the resins is higher than that of the PEEKm) 416.8 deg.C, 430.5 deg.C and 475.3 deg.C, respectively. But PEDEK and PEDEKK are too high in TmAlso brings about the problem that it is difficult to prepare high molecular weight polymers by directly polymerizing bisphenol monomers and difluorobenzophenone monomers: because the monomer molecular chain has high rigidity and can be regularly discharged into crystal lattices, oligomers can be crystallized and separated out in the polymerization process, and the polymerization reaction can not be carried out continuously in a homogeneous phase, only when the monomer molecular chain is close to the polymer TmThe polymerization at a higher temperature makes it possible to obtain products of higher molecular weight. The solvent for polymerization of conventional crystalline polyaryletherketones, represented by Polyetheretherketone (PEEK), is diphenyl sulfone, which has a boiling point of 360 ℃ and is much lower than the T of PEDEK, PEDEKK and PEDEKDKmTherefore, the use of diphenyl sulfone as a solvent has not been able to obtain a resin having a high molecular weight (as shown by the low intrinsic viscosity of the polymer in the prior scientific papers and patents), and thus has been studied in the pastThe medium biphenyl structural unit can only be used as a copolymerization component and is used for improving the mechanical property and the heat resistance of the resin. Therefore, PEDEK, PEDEKK and PEDEKDK of the all-biphenyl type having excellent heat resistance and mechanical properties cannot be industrially produced and commercially used.
Patents EP0327984(AZ), EP0266132(AZ), US4687833(a), JP62172020(a) and the like all use diphenyl sulfone as a solvent and biphenyl diphenol is directly polymerized with 4,4 '-difluorobenzophenone or 4, 4' -difluorotriphenyldione, but studies in patent CN1161975 show that the polymers obtained by the above technical route have low intrinsic viscosity. Furthermore, the examples of patents EP0327984(A2) and EP0266132 show that polymers having a higher intrinsic viscosity (i.e.a higher molecular weight) cannot be obtained according to the process disclosed therein.
Patent CN1884330 uses sulfolane as solvent, uses a mixed system of 4, 4' -difluorobenzophenone, hydroquinone and biphenol for polymerization, the content of biphenol is only 40% at most (claim 4, lines 4-5, original text: the molar fraction of biphenol is 1% -40% of the sum of the molar fractions of hydroquinone and biphenol), and the preparation of full-biphenyl polyether ether ketone (ped) cannot be realized; patent US4687833 uses a two-step process for the production of polymers structurally similar to patent CN1884330, by first using hydroquinone to produce oligomers and then using biphenol to couple to obtain the final product, but the theoretical upper limit of the content of biphenyl structure in the polymer obtained by this process is only 50% (oligomers are all dimers), and the preparation of all-biphenyl PEDEK has not been achieved. In addition, no literature report on the synthesis of the all-biphenyl polyetheretherketone biphenyl ketone (PEDEKDK) exists at present.
How to prepare the all-biphenyl PEDEK, PEDEKK and PEDEKDK resin with high molecular weight and high melting point, which is convenient for industrialization, at a relatively low polymerization temperature and avoid the problem of crystallization and precipitation of oligomers is a technical problem which needs to be solved at present.
Disclosure of Invention
In order to solve the technical problems, the invention provides a method for performing noncrystalline polymerization and then performing crystalline transformation, solves the problem of crystallization precipitation of oligomers, and successfully prepares full biphenyl PEDEK, PEDEKK and PEDEKDK resins with high molecular weight and high melting point at relatively low polymerization temperature.
The invention provides a preparation method of a full biphenyl polyaryletherketone precursor, which comprises the following steps: sequentially adding a solvent, a water-carrying agent, a salt forming agent, a difluoride monomer and a diphenol monomer in a nitrogen atmosphere, heating to 130-plus-200 ℃, carrying out azeotropic reflux on the water-carrying agent and water, then carrying out fractionation to remove water generated in the reaction process, carrying out azeotropic reflux for 2-6h, removing the water-carrying agent in the reaction system by distillation, heating to 170-plus-210 ℃, reacting for 5-10h, crushing, washing and drying to obtain a full-biphenyl polyaryletherketone precursor;
further, the molar ratio of the difluoride monomer to the diphenol monomer is 1-1.5: 1-1.5;
further, the solvent is sulfolane or diphenyl sulfone; the water-carrying agent is toluene or xylene; the salt forming agent is K2CO3Or Na2CO3Or K in a molar ratio of 19:12CO3And Cs2CO3In a mixture or in a molar ratio of 19:1 of Na2CO3And Cs2CO3A mixture of (a); the molar ratio of the salt forming agent to the diphenol is 1.5: 1;
further, the difluoride monomer is any one of the following structural formulas:
Figure BDA0002948953580000021
Figure BDA0002948953580000022
wherein R is
Figure BDA0002948953580000023
The invention also provides a full biphenyl polyaryletherketone precursor, which has the structural formula as follows:
Figure BDA0002948953580000024
Figure BDA0002948953580000025
wherein R is
Figure BDA0002948953580000026
n is a positive integer of 21 or more and 178 or less.
The invention also provides an application of the all-biphenyl polyaryletherketone precursor in preparing the all-biphenyl polyaryletherketone, which comprises the following steps: it comprises the following steps: dissolving a full-biphenyl polyaryletherketone precursor in an organic solvent, adding an acid solution with the pH value of 0.1-1, refluxing for 24-48h, washing with ethanol and water, and drying to obtain the full-biphenyl polyaryletherketone; the organic solvent is one of tetrahydrofuran, N-methylpyrrolidone, N '-dimethylformamide or N, N' -dimethylacetamide, and the acid solution is one of aqueous solutions of hydrochloric acid, sulfuric acid, methanesulfonic acid, benzenesulfonic acid, trifluoroacetic acid or trifluorobenzene sulfonic acid; the volume ratio of the organic solvent to the acid solution is 1: 2-8;
the application of the all-biphenyl polyaryletherketone precursor in preparing the all-biphenyl polyaryletherketone comprises the following steps: it comprises the following steps: dissolving a full-biphenyl polyaryletherketone precursor in chloroform, adding dimethyl sulfoxide and 2-iodine-2-methylpropane, reacting at 70-100 ℃ for 48-70h, and washing with water and methanol to obtain the full-biphenyl polyaryletherketone;
the application of the all-biphenyl polyaryletherketone precursor in preparing the all-biphenyl polyaryletherketone comprises the following steps: it comprises the following steps: dissolving a full-biphenyl polyaryletherketone precursor in dichloromethane, adding 1, 2-ethylene glycol and N-bromosuccinimide, reacting for 5-30min, adding an acid solution with the pH value of 0.1-1, refluxing for 24-48h, washing with ethanol and water, and drying to obtain the full-biphenyl polyaryletherketone; the acid solution is one of aqueous solutions of hydrochloric acid, sulfuric acid, methanesulfonic acid, benzenesulfonic acid, trifluoroacetic acid or trifluorobenzene sulfonic acid;
further, the structural formula of the total biphenyl polyaryletherketone is as follows:
Figure BDA0002948953580000027
Figure BDA0002948953580000028
wherein n is a positive integer of 21 or more and 178 or less;
further, the structural formula of the total biphenyl polyaryletherketone is as follows:
Figure BDA0002948953580000031
wherein n is a positive integer of 21 or more and a positive integer of 178 or less.
Compared with the prior art, the technical scheme of the invention is characterized in that:
1. a series of PEDEK, PEDEKK and PEDEKDK precursors which do not have crystallinity, but have good solubility and can be converted into crystalline holobiphenyl types are obtained through polymerization reaction by adopting a difluoride monomer different from the traditional difluoride monomer.
2. The invention obtains the polymer with the full-biphenyl structure without using the comonomer hydroquinone, and the polymer prepared by the invention has higher T compared with other prior art because the existence of the hydroquinone structural unit can reduce the rigidity of the molecular chain of the polymer and destroy the regularity of the molecular chainm；
3. The precursor prepared by the prior polymerization has no crystallinity, so that the phenomenon of oligomer crystallization separation can not be generated in the polymerization process, the polymerization temperature is obviously reduced from more than 320 ℃ to 210 ℃ at 190 ℃ and the problem that the diphenyl sulfone can not realize higher-temperature polymerization to keep homogeneous polymerization is solved. The reduction of the polymerization temperature not only allows the reduction of the energy consumption for polymerization, but also allows the polymerization under homogeneous phase and the significant increase of the molecular weight of the polymer as well as the reduction of side reactions and gel content at high temperatures. The intrinsic viscosity of the prepared PEDEK was 2.09dL/g, Tm416.8 ℃ is adopted; the intrinsic viscosity of PEDEKK is 2.13dL/g, TmIs 430.5 ℃; intrinsic viscosity of PEDEKDKIs 2.32dL/g, TmThe performance index is 475.3 ℃, the performance indexes exceed the performance of corresponding polymers prepared by the prior art, and the performance index is the highest value of the performance index of the like products which can realize industrial production at present.
4. The invention solves the problem of crystallization and precipitation of oligomers in the polymerization process of PEDEK, PEDEKK and PEDEKDK, not only successfully realizes low-temperature homogeneous polymerization, but also further improves the intrinsic viscosity of the polymer, thereby improving the molecular weight of the product.
Drawings
FIG. 1 is a DSC test curve of PEDEK finally obtained in example 1;
FIG. 2 is a DSC test curve of PEDEKK finally obtained in example 4;
FIG. 3 is a DSC test curve of the PEDEKDK finally obtained in example 7;
FIG. 4 is a NMR spectrum of difluoride monomer 3;
FIG. 5 is a NMR spectrum of difluoride monomer 6.
Detailed Description
The structures of the bis-fluoromonomers 1-9 employed in examples 1-9 are shown below:
Figure BDA0002948953580000041
example 1:
under the protection of nitrogen atmosphere, 4248g of sulfolane (solid content is 10 wt%), 1010mL of toluene, 207g of potassium carbonate, 286g of bifluoride monomer 1 and 186g of biphenyl diphenol are sequentially added into a polymerization reaction system, the temperature is raised to 140 ℃, azeotropic dehydration and reflux are carried out for 2h, toluene in the reaction system is removed through distillation, the temperature is raised to 190-mThe temperature was 416.8 ℃.
Example 2:
under the protection of nitrogen atmosphere, 976g of diphenyl sulfone (solid content: 30 wt%), 419mL of xylene, 158.8g of sodium carbonate, 294g of difluoride monomer 2 and 204.6g of biphenyl diphenol are sequentially added into a polymerization reaction system, the temperature is increased to 180 ℃, azeotropic dehydration and reflux are carried out for 2 hours, removing dimethylbenzene in a reaction system by distillation, heating to 180-210 ℃ for reaction for 2h, pouring a reaction product into anhydrous methanol for washing, crushing and drying to obtain a precursor, dissolving the precursor in 4586ml of trichloromethane, after the precursor is dissolved, 179g of dimethyl sulfoxide and 211g of 2-iodo-2-methylpropane are sequentially added, the mixture reacts for 48 hours at 70 ℃, the reaction product is poured into anhydrous methanol, and washing with anhydrous methanol and drying to obtain crystalline full biphenyl polyether ether ketone (PEDEK) with intrinsic viscosity of 2.09dL/g and T.mThe temperature was 416.8 ℃.
Example 3:
under the protection of nitrogen atmosphere, 4575g of sulfolane (solid content: 10 wt%), 1088mL of toluene, 196.7g of potassium carbonate, 24.4g of cesium carbonate, 322.3g of difluoride monomer 3 and 186g of biphenyl diphenol are sequentially added into a polymerization reaction system, the temperature is raised to 140 ℃, azeotropic dehydration and reflux are carried out for 2h, the toluene in the reaction system is removed through distillation, the temperature is raised to 190 ℃ -210 ℃, the reaction system is reacted for 6h, a reaction product is poured into absolute methanol for washing, crushing and drying to obtain a precursor, the precursor is dissolved in 4683mL of DMF, 585mL of methanesulfonic acid solution with pH of 0.1 is added into the solution after the precursor is completely dissolved, reflux is carried out for 24h, ethanol and water are used for washing and drying to obtain crystalline holobiphenyl polyether ether ketone (PEDEK), the intrinsic viscosity of the PEDEK is 2.09dL/g, T is TmThe temperature was 416.8 ℃.
Example 4:
under the protection of nitrogen atmosphere, sequentially adding 5495g of sulfolane (with the solid content of 10 wt%), 1649mL of toluene, 150.8g of potassium carbonate, 24.4g of cesium carbonate, 406g of difluoride monomer 4 and 204.6g of biphenyl diphenol into a polymerization reaction system, heating to 140 ℃, azeotropically removing water, refluxing for 2h, removing the toluene in the reaction system through distillation, heating to 190-210 ℃ for reaction for 10h, pouring a reaction product into anhydrous methanol for washing, crushing and drying to obtain a precursor, dissolving the precursor into 5706mL of DMAC, and carrying out heat exchange treatment on the obtained product until the previous reaction is finishedAdding 713mL sulfuric acid solution with pH of 0.1 into the solution after the flooding body is completely dissolved, refluxing for 24h, washing with ethanol and water, and drying to obtain crystalline holobiphenyl polyether ether ketone (PEDEKK), wherein the intrinsic viscosity of the PEDEKK is 2.13dL/g, and the T is TmThe temperature was 430.5 ℃.
Example 5:
under the protection of nitrogen atmosphere, adding 6107g sulfolane (solid content is 10wt percent), 1452mL toluene, 227.7g potassium carbonate, 474g difluoride monomer 5 and 204.6g biphenyl diphenol into a polymerization reaction system in sequence, heating to 140 ℃, removing water by azeotropy, refluxing for 2h, removing toluene in the reaction system by distillation, heating to 190 ℃ and 210 ℃ for reaction for 10h, pouring a reaction product into absolute methanol for washing, crushing and drying to obtain a precursor, dissolving the precursor into 9579mL dichloromethane, adding 40g 1, 2-ethylene glycol and 40g NBS in sequence after the precursor is dissolved for reaction for 5min, adding 1197mL hydrochloric acid solution with pH of 0.1 into the solution, refluxing for 24h, washing with ethanol and water, and drying to obtain the all-biphenyl polyether ether ketone (PEDEKK), wherein the intrinsic viscosity of the PEDEKK is 2.13dL/g, and the T is T.7 mLmThe temperature was 430.5 ℃.
Example 6:
under the protection of nitrogen atmosphere, 6089g of sulfolane (solid content is 10wt percent), 1448mL of methylbenzene, 227.7g of potassium carbonate, 472g of difluoride monomer 6 and 204.6g of biphenyl diphenol are sequentially added into a polymerization reaction system, the temperature is raised to 140 ℃, azeotropic dehydration and reflux are carried out for 2h, the methylbenzene in the reaction system is removed through distillation, the temperature is raised to 190-210 ℃, the reaction product is reacted for 10h, poured into absolute methanol for washing, crushed and dried to obtain a precursor, the precursor is dissolved in 6386mL of DMAC, after the precursor is completely dissolved, 798mL of benzenesulfonic acid solution with pH of 0.1 is added into the solution, the solution is refluxed for 24h, washed by ethanol and water, and dried to obtain crystalline holobiphenyl polyether ether ketone (PEDEKK), the intrinsic viscosity of the PEDEKK is 2.13dL/g, and T is TmThe temperature was 430.5 ℃.
Example 7:
under the protection of nitrogen atmosphere, 6179g of sulfolane (solid content: 10 wt%), 1470mL of toluene, 227.7g of potassium carbonate, 482g of difluoride monomer 7 and 204.6g of biphenol are sequentially added into a polymerization reaction system, and the temperature is raised to 14 gRemoving toluene in a reaction system by distillation at 0 ℃, carrying out azeotropic dehydration and reflux for 2h, heating to 190 ℃ and 210 ℃ for reaction for 10h, pouring a reaction product into absolute methanol for washing, crushing and drying to obtain a precursor, dissolving the precursor in 6466mL of DMAC, adding 808mL of trifluoroacetic acid solution with the pH value of 0.1 into the solution after the precursor is completely dissolved, refluxing for 24h, washing with ethanol and water, and drying to obtain the total biphenyl polyetheretherketone biphenyl (EKDK), wherein the intrinsic viscosity of the PEDEKDK is 2.32dL/g, and the T is 2.32dL/gmThe temperature was 475.3 ℃.
Example 8:
under the protection of nitrogen atmosphere, 6791.4g of sulfolane (solid content is 10 wt%), 1615mL of xylene, 227.7g of potassium carbonate, 550g of difluoride monomer 8 and 204.6g of biphenyl diphenol are sequentially added into a polymerization reaction system, the temperature is raised to 140 ℃, azeotropic dehydration and reflux are carried out for 2h, toluene in the reaction system is removed through distillation, the temperature is raised to 180 ℃ and 210 ℃ for reaction for 6h, the reaction product is poured into absolute methanol for washing, crushing and drying to obtain a precursor, the precursor is dissolved in 7146g of trichloromethane, 279g of dimethyl sulfoxide and 329g of 2-iodine-2-methylpropane are sequentially added after the precursor is dissolved, after the reaction is carried out for 48h at 70 ℃, methanol and water are used for washing and drying to obtain crystalline holobenzene type polyether ether ketone biphenyl (PEDEK), the intrinsic viscosity of the PEDEK is 2.32dL/g, and the T EK is obtainedmThe temperature was 475.3 ℃.
Example 9:
under the protection of nitrogen atmosphere, 6782g of sulfolane (solid content: 10 wt%), 1613mL of toluene, 227.7g of potassium carbonate, 549g of difluoride monomer 9 and 204.6g of biphenyl diphenol are sequentially added into a polymerization reaction system, the temperature is raised to 140 ℃, azeotropic dehydration and reflux are carried out for 2h, the toluene in the reaction system is removed through distillation, the temperature is raised to 190-210 ℃, the reaction product is reacted for 10h, poured into absolute methanol for washing, crushed and dried to obtain a precursor, the precursor is dissolved in 3536 mL of DMAC, after the precursor is completely dissolved, 68mL of trifluoro benzene sulfonic acid solution with the pH value of 0.1 is added into the solution, and after reflux is carried out for 24h, ethanol and water are used for washing and drying, the DK (PEDEK) is obtained, the intrinsic viscosity of the PEDEK is 2.32dL/g, the T is T3568.1, and the DKEK is obtainedmThe temperature was 475.3 ℃.
To sum up:
the general reaction formula of the preparation method of the total biphenyl polyether ether ketone (PEDEK), the total biphenyl polyether ether ketone (PEDEKK) and the total biphenyl polyether ether ketone biphenyl ketone (PEDEKDK) is as follows:
Figure BDA0002948953580000061
wherein:
Figure BDA0002948953580000062
nAis the molar number of reaction of biphenol, nBIs the reaction mole number of the bifluoro monomer, nAAnd nBThe molar ratio of (1-1.5: 1-1.5); dissolving the precursor of the full-biphenyl polyaryletherketone in an organic solvent, adding an acid solution with the pH value of 0.1-1, refluxing for 24-48h, washing with ethanol and water, and drying to obtain the full-biphenyl polyaryletherketone; dissolving the full-biphenyl polyaryletherketone precursor in chloroform, adding dimethyl sulfoxide and 2-iodine-2-methylpropane, reacting at 70-100 ℃ for 48-70h, and washing with water and methanol to obtain the full-biphenyl polyaryletherketone; dissolving a full-biphenyl polyaryletherketone precursor in dichloromethane, adding 1, 2-ethylene glycol and N-bromosuccinimide, reacting for 5-30min, adding an acidic solution with the pH value of 0.1-1, refluxing for 24-48h, washing with ethanol and water, and drying to obtain the full-biphenyl polyaryletherketone; wherein n is a positive integer of 21 or more and 178 or less; the finally obtained full biphenyl polyaryletherketone is a homopolymer with single repeating unit, high molecular weight and high intrinsic viscosity, and does not have an ether bond structure except for biphenyl ether; the intrinsic viscosity of the polymer is more than 2.0 dL/g; t of PEDEKmT of PEDEKK at 416.8 DEG CmT of PEDEKDK at 430.5 DEG CmThe temperature was 475.3 ℃.
The structural formulas of the total biphenyl PEDEK, the PEDEKK and the PEDEKDK are respectively as follows in sequence:
Figure BDA0002948953580000063
Figure BDA0002948953580000071
wherein n is a positive integer of 21 or more and a positive integer of 178 or less.
When the difluoride monomer is a monomer 1, a monomer 3, a monomer 4, a monomer 6, a monomer 7 or a monomer 9, converting the precursor into crystalline holobiphenyl PEDEK, PEDEKK and PEDEKDK through hydrolysis reaction; when the difluoride monomer is a monomer 2, a monomer 5 or a monomer 8, two reaction routes are adopted to convert a precursor polymer into crystalline holobiphenyl PEDEK, PEDEKK and PEDEKDK, wherein one method is an oxidation reaction of 2-iodine-2-methyl propane activated dimethyl sulfoxide (DMSO), the reaction has the advantage that the crystalline holobiphenyl PEDEK, PEDEKK and PEDEKDK are obtained through one-step chemical reaction, and the specific reaction method is as follows: dissolving a precursor in trichloromethane, adding dimethyl sulfoxide and 2-iodine-2-methylpropane in sequence after the precursor is dissolved, reacting for 48h at 70 ℃, crushing, washing and drying to obtain crystalline full biphenyl polyether ether ketone (PEDEK), full biphenyl polyether ether ketone (PEDEKK) or full biphenyl polyether ether ketone biphenyl (PEDEKDK), dissolving the precursor in dichloromethane, catalyzing by N-bromosuccinimide (NBS), adding ethylene glycol, and performing an acid hydrolysis process to obtain the crystalline full biphenyl polyether ether ketone (PEDEK), the full biphenyl polyether ether ketone (PEDEKK) or the full biphenyl polyether ether ketone biphenyl (PEDEKDK).

Claims (10)

1. A preparation method of a full biphenyl polyaryletherketone precursor is characterized by comprising the following steps: it includes: sequentially adding a solvent, a water-carrying agent, a salt-forming agent, a difluoride monomer and a diphenol monomer in a nitrogen atmosphere, heating to 130-plus-200 ℃, carrying out azeotropic reflux on the water-carrying agent and water, then carrying out fractionation to remove water generated in the reaction process, carrying out azeotropic reflux for 2-6h, removing the water-carrying agent in the reaction system by distillation, heating to 170-plus-210 ℃, reacting for 5-10h, crushing, washing and drying to obtain the full-biphenyl polyaryletherketone precursor.
2. The method for preparing the all-biphenyl polyaryletherketone precursor as claimed in claim 1, wherein the method comprises the following steps: the molar ratio of the difluoride monomer to the diphenol monomer is 1-1.5: 1-1.5.
3. The method for preparing the all-biphenyl polyaryletherketone precursor as claimed in claim 1, wherein the method comprises the following steps: the solvent is sulfolane or diphenyl sulfone; the water-carrying agent is toluene or xylene; the salt forming agent is K2CO3Or Na2CO3Or K in a molar ratio of 19:12CO3And Cs2CO3In a mixture or in a molar ratio of 19:1 of Na2CO3And Cs2CO3A mixture of (a); the molar ratio of the salt forming agent to the diphenol is 1.5: 1.
4. The method for preparing the all-biphenyl polyaryletherketone precursor as claimed in claim 1, wherein the method comprises the following steps: the difluoride monomer is any one of the following structural formulas:
Figure FDA0002948953570000011
Figure FDA0002948953570000012
wherein R is
Figure FDA0002948953570000013
5. The method for preparing the all-biphenyl polyaryletherketone precursor of claim 4, wherein the method comprises the following steps: the structural formula of the full biphenyl polyaryletherketone precursor is as follows:
Figure FDA0002948953570000014
Figure FDA0002948953570000015
wherein R is
Figure FDA0002948953570000016
n is a positive integer of 21 or more and 178 or less.
6. The application of the precursor of the total biphenyl polyaryletherketone in preparing the total biphenyl polyaryletherketone according to claim 5 is characterized in that: it comprises the following steps: dissolving a full-biphenyl polyaryletherketone precursor in an organic solvent, adding an acid solution with the pH value of 0.1-1, refluxing for 24-48h, washing with ethanol and water, and drying to obtain the full-biphenyl polyaryletherketone; the organic solvent is one of tetrahydrofuran, N-methylpyrrolidone, N '-dimethylformamide or N, N' -dimethylacetamide, and the acid solution is one of aqueous solutions of hydrochloric acid, sulfuric acid, methanesulfonic acid, benzenesulfonic acid, trifluoroacetic acid or trifluorobenzene sulfonic acid; the volume ratio of the organic solvent to the acid solution is 1: 2-8.
7. The application of the precursor of the total biphenyl polyaryletherketone in preparing the total biphenyl polyaryletherketone according to claim 5 is characterized in that: it comprises the following steps: dissolving the full-biphenyl polyaryletherketone precursor in chloroform, adding dimethyl sulfoxide and 2-iodine-2-methylpropane, reacting at 70-100 ℃ for 48-70h, and washing with water and methanol to obtain the full-biphenyl polyaryletherketone.
8. The application of the precursor of the total biphenyl polyaryletherketone in preparing the total biphenyl polyaryletherketone according to claim 5 is characterized in that: it comprises the following steps: dissolving a full-biphenyl polyaryletherketone precursor in dichloromethane, adding 1, 2-ethylene glycol and N-bromosuccinimide, reacting for 5-30min, adding an acid solution with the pH value of 0.1-1, refluxing for 24-48h, washing with ethanol and water, and drying to obtain the full-biphenyl polyaryletherketone; the acid solution is one of aqueous solutions of hydrochloric acid, sulfuric acid, methanesulfonic acid, benzenesulfonic acid, trifluoroacetic acid or trifluorobenzene sulfonic acid.
9. The use of the all-biphenyl polyaryletherketone precursor according to any one of claims 6 to 8 for preparing all-biphenyl polyaryletherketones, wherein: the structural formula of the total biphenyl polyaryletherketone is as follows:
Figure FDA0002948953570000021
Figure FDA0002948953570000022
wherein n is a positive integer of 21 or more and a positive integer of 178 or less.
10. The use of the all-biphenyl polyaryletherketone precursor of claim 9 in the preparation of all-biphenyl polyaryletherketones, wherein: the structural formula of the total biphenyl polyaryletherketone is as follows:
Figure FDA0002948953570000023
wherein n is a positive integer of 21 or more and a positive integer of 178 or less.
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