CN116969877A - Monomer containing imide structure, fluorinated polyaryletherketone, preparation method and application thereof - Google Patents
Monomer containing imide structure, fluorinated polyaryletherketone, preparation method and application thereof Download PDFInfo
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- CN116969877A CN116969877A CN202310857359.XA CN202310857359A CN116969877A CN 116969877 A CN116969877 A CN 116969877A CN 202310857359 A CN202310857359 A CN 202310857359A CN 116969877 A CN116969877 A CN 116969877A
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- Prior art keywords
- imide structure
- monomer
- polyaryletherketone
- fluorinated
- fluorine
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- 125000005462 imide group Chemical group 0.000 title claims abstract description 72
- 229920006260 polyaryletherketone Polymers 0.000 title claims abstract description 65
- 239000000178 monomer Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 30
- 239000011737 fluorine Substances 0.000 claims abstract description 28
- 229920000642 polymer Polymers 0.000 claims abstract description 27
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical group C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims abstract description 17
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 6
- 238000004519 manufacturing process Methods 0.000 claims abstract description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 39
- 238000006243 chemical reaction Methods 0.000 claims description 35
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 24
- 238000006116 polymerization reaction Methods 0.000 claims description 23
- 239000012024 dehydrating agents Substances 0.000 claims description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 17
- LSQARZALBDFYQZ-UHFFFAOYSA-N 4,4'-difluorobenzophenone Chemical compound C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 LSQARZALBDFYQZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 15
- 229930185605 Bisphenol Natural products 0.000 claims description 14
- 150000008064 anhydrides Chemical class 0.000 claims description 13
- BBRLKRNNIMVXOD-UHFFFAOYSA-N bis[4-(3-aminophenoxy)phenyl]methanone Chemical compound NC1=CC=CC(OC=2C=CC(=CC=2)C(=O)C=2C=CC(OC=3C=C(N)C=CC=3)=CC=2)=C1 BBRLKRNNIMVXOD-UHFFFAOYSA-N 0.000 claims description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 10
- 230000018044 dehydration Effects 0.000 claims description 10
- 238000006297 dehydration reaction Methods 0.000 claims description 10
- 239000008096 xylene Substances 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 9
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 8
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 3
- CSDQQAQKBAQLLE-UHFFFAOYSA-N 4-(4-chlorophenyl)-4,5,6,7-tetrahydrothieno[3,2-c]pyridine Chemical compound C1=CC(Cl)=CC=C1C1C(C=CS2)=C2CCN1 CSDQQAQKBAQLLE-UHFFFAOYSA-N 0.000 claims description 2
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical group 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 239000011698 potassium fluoride Substances 0.000 claims description 2
- 235000003270 potassium fluoride Nutrition 0.000 claims description 2
- 239000011541 reaction mixture Substances 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 239000011347 resin Substances 0.000 abstract description 13
- 229920005989 resin Polymers 0.000 abstract description 13
- 239000011159 matrix material Substances 0.000 abstract description 5
- 238000004806 packaging method and process Methods 0.000 abstract description 4
- 239000003973 paint Substances 0.000 abstract description 4
- 229920006254 polymer film Polymers 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 20
- 230000009477 glass transition Effects 0.000 description 15
- 238000010521 absorption reaction Methods 0.000 description 14
- 239000000203 mixture Substances 0.000 description 13
- 239000000047 product Substances 0.000 description 11
- 238000001035 drying Methods 0.000 description 10
- 239000012299 nitrogen atmosphere Substances 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- -1 dichlorimide phenoxy benzophenone Chemical compound 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 238000010992 reflux Methods 0.000 description 8
- 239000002244 precipitate Substances 0.000 description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- ZFVMWEVVKGLCIJ-UHFFFAOYSA-N bisphenol AF Chemical compound C1=CC(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C=C1 ZFVMWEVVKGLCIJ-UHFFFAOYSA-N 0.000 description 6
- 239000004642 Polyimide Substances 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 210000003298 dental enamel Anatomy 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 229920001721 polyimide Polymers 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 239000004696 Poly ether ether ketone Substances 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 229920002530 polyetherether ketone Polymers 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- LERREUOVCXYKGR-UHFFFAOYSA-N (2-phenoxyphenyl)-phenylmethanone Chemical compound C=1C=CC=C(OC=2C=CC=CC=2)C=1C(=O)C1=CC=CC=C1 LERREUOVCXYKGR-UHFFFAOYSA-N 0.000 description 2
- BTTRMCQEPDPCPA-UHFFFAOYSA-N 4-chlorophthalic anhydride Chemical compound ClC1=CC=C2C(=O)OC(=O)C2=C1 BTTRMCQEPDPCPA-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 150000008378 aryl ethers Chemical class 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- LKFIWRPOVFNPKR-UHFFFAOYSA-N (2-fluorophenyl)-(4-fluorophenyl)methanone Chemical compound C1=CC(F)=CC=C1C(=O)C1=CC=CC=C1F LKFIWRPOVFNPKR-UHFFFAOYSA-N 0.000 description 1
- MOFZHBRFFAIMKM-UHFFFAOYSA-N 2,3,5,6-tetrafluoro-4-(2,3,5,6-tetrafluoro-4-hydroxyphenyl)phenol Chemical compound FC1=C(F)C(O)=C(F)C(F)=C1C1=C(F)C(F)=C(O)C(F)=C1F MOFZHBRFFAIMKM-UHFFFAOYSA-N 0.000 description 1
- ZSDAMBJDFDRLSS-UHFFFAOYSA-N 2,3,5,6-tetrafluorobenzene-1,4-diol Chemical compound OC1=C(F)C(F)=C(O)C(F)=C1F ZSDAMBJDFDRLSS-UHFFFAOYSA-N 0.000 description 1
- XVMKZAAFVWXIII-UHFFFAOYSA-N 5-fluoro-2-benzofuran-1,3-dione Chemical compound FC1=CC=C2C(=O)OC(=O)C2=C1 XVMKZAAFVWXIII-UHFFFAOYSA-N 0.000 description 1
- HJNTWZFZPOUDDG-UHFFFAOYSA-N [2-(3-aminophenoxy)phenyl]-phenylmethanone Chemical compound NC1=CC=CC(OC=2C(=CC=CC=2)C(=O)C=2C=CC=CC=2)=C1 HJNTWZFZPOUDDG-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000008365 aromatic ketones Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000010485 coping Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000007590 electrostatic spraying Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N phthalic anhydride Chemical class C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 229920005575 poly(amic acid) Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920006259 thermoplastic polyimide Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/44—Iso-indoles; Hydrogenated iso-indoles
- C07D209/48—Iso-indoles; Hydrogenated iso-indoles with oxygen atoms in positions 1 and 3, e.g. phthalimide
-
- 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
- C08G65/4018—(I) or (II) containing halogens other than as leaving group (X)
- C08G65/4025—(I) or (II) containing fluorine other than as leaving group (X)
-
- 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
- C08G65/4037—(I) or (II) containing nitrogen in ring structure, e.g. pyridine group
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Polyethers (AREA)
Abstract
The invention relates to the technical field of high polymer materials, and discloses monomer containing an imide structure, fluorinated polyaryletherketone, a preparation method and application thereof, wherein the fluorinated polyaryletherketone has a structure shown as follows, ar is fluorine-containing bisphenol residue, x+y=1, and x is more than 0 and less than 0.6. According to the invention, by introducing the imide structure, the internal rotation steric hindrance of the polymer chain is increased, the thermal stability of the polymer is effectively improved, and the prepared polymer film has the characteristics of excellent thermal stability and low dielectric constant, so that the application of the polyaryletherketone resin in the fields of insulating paint for manufacturing enameled wires in the electronic/electric industry, matrix resin of a printed circuit board, packaging resin of an integrated circuit die and the like can be further expanded.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to monomer containing an imide structure, fluorinated polyaryletherketone, a preparation method and application thereof.
Background
Polyaryletherketone (PAEK) is a special engineering plastic with good performances in the aspects of chemistry, physics, machinery and the like, and a composite material prepared by adopting PAEK as a resin matrix has a great effect in the fields of aerospace, communication, national defense, military industry, petrochemical industry and the like. The traditional polyaryletherketone has lower glass transition temperature and larger dielectric constant, is difficult to process in the preparation of composite materials, and limits the application of the traditional polyaryletherketone.
The unique property of fluorine atoms endows the fluorine-containing polymer with excellent characteristics, the radius of the fluorine atoms is small, the electronegativity is large (4.0), the bond energy of C-F bonds (440 kJ/mol) is much higher than that of C-H bonds (410 kJ/mol), C-C bonds (356 kJ/mol), C-O bonds (360 kJ/mol) and C-Cl bonds (356 kJ/mol), and the distance between the C-F bonds is short, so that the C-F bonds have strong stability. Therefore, the fluorine-containing polyaryletherketone has extremely wide application prospect in the fields of low dielectric constant microelectronics, low-loss optical waveguide devices and the like due to the unique performance. However, although the excellent solubility of the fluorine modified polyaryletherketone is favorable for improving the sample processability, the thermal stability of the fluorine modified polyaryletherketone is relatively poor, and the requirements of application scenes are difficult to meet.
Polyimide is a polymer with a full aromatic ring structure and an imide ring structure on a molecular main chain, has stronger intermolecular acting force between molecular chains, and can be used in a high-temperature environment for a long time. CN 105567076A discloses a high temperature resistant wire enamel composition based on fluorine-containing polyaryletherketone copolymerization modified polyimide and a preparation method thereof. The wire enamel composition comprises: 10-45% of fluorine-containing polyaryletherketone copolymerization modified polyamic acid, 30-70% of solvent, 10-60% of diluent, 1-10% of lubricant and 0.1-2.0% of flatting agent, wherein the sum of the weight percentages is 100%. The solid content of the wire enamel composition is 15-45%, the wire enamel composition has excellent heat resistance, and the national standard of 240-grade wire enamel is met. However, the hydroxyl-terminated fluorine-containing polyether-ether-ketone is prepared firstly, then the hydroxyl-terminated fluorine-containing polyether-ether-ketone and the acid anhydride are subjected to end-group grafting reaction, the thermal stability of the product is still weak, and the processability, dielectric constant and other properties of the product are not evaluated.
CN 102875819A discloses an aromatic block copolymer, a preparation method thereof and application thereof as a compatibilizer, wherein an amino-terminated polyether-ether-ketone oligomer and an anhydride-terminated polyimide oligomer are adopted for polycondensation to obtain the polyether-ether-ketone-polyimide block copolymer, and the product is mainly used for improving the compatibilization and modification of polyether-ether-ketone and thermoplastic polyimide alloy, but the thermal stability of the blend is not improved from the results of examples thereof.
And by adopting polyimide modified polyaryletherketone, the thermal stability of the polymer can be truly and effectively improved, and meanwhile, the good processability and excellent dielectric property of the fluorinated polyaryletherketone can be ensured, so that the fluorinated polyaryletherketone is worthy of further exploration.
Disclosure of Invention
Aiming at the problem that the thermal stability of the fluorinated polyaryletherketone is relatively poor, the invention provides the monomer containing the imide structure and the fluorinated polyaryletherketone containing the imide structure, and the fluorinated polyaryletherketone obtained based on the monomer has excellent thermal stability, can keep the original excellent processing performance and dielectric property of the fluorinated polyaryletherketone, and even can improve the solubility of the copolymer.
In order to achieve the above purpose, the invention adopts the following technical scheme:
an imide structure-containing monomer having a structure as shown in formula I:
wherein X is halogen, such as Cl, br, F.
The invention also provides a preparation method of the monomer containing the imide structure, which comprises the following steps: and (3) carrying out grafting reaction on the 4,4' -bis (3-aminophenoxy) benzophenone, the 4-halophthalic anhydride and the dehydrating agent in a solvent to obtain a monomer containing an imide structure shown in the formula I, namely a dichlorinated imide phenoxy benzophenone monomer.
Preferably X is Cl or F.
Preferably, the molar ratio of 4,4' bis (3-aminophenoxy) benzophenone to 4-halophthalic anhydride is 1 (2-2.4);
the 4-halophthalic anhydride comprises 4-chlorophthalic anhydride and 4-fluorophthalic anhydride.
Preferably, the grafting reaction temperature is 120-200 ℃ and the reaction time is 1-8h; preferably, the grafting reaction is carried out for dehydration at 120-160 ℃ for 1-6h, and then the temperature is further raised to 160-180 ℃ for 30-120min to evaporate the redundant dehydrating agent.
It is further preferred that the grafting reaction is carried out at 130-150℃for 3-5 hours to dehydrate and remove by-product water generated when 4,4' -bis (3-aminophenoxy) benzophenone is grafted with 4-halophenolic anhydride to facilitate forward movement of the reaction.
The solvent comprises one or more of dimethylformamide, dimethylacetamide, N-methylpyrrolidone, sulfolane or diphenyl sulfone;
the dehydrating agent comprises one or more of benzene, toluene or xylene.
4,4' -bis (3-aminophenoxy) benzophenone, 4-halophthalic anhydride, a dehydrating agent and a solvent are mixed to form a reaction liquid with a solid content of 15-35wt%.
The invention also provides fluorinated polyaryletherketone containing an imide structure, which has a structure shown in a formula II:
wherein Ar is a fluorine-containing bisphenol residue, x+y=1, and 0 < x < 0.6. Such as x is 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, or any value therebetween.
According to the invention, the imide structure modified fluorinated polyaryletherketone is selected, and the imide structure is introduced to increase internal rotation steric hindrance of the polymer chain, so that the polymer chain is difficult to move, and a higher temperature is required to provide enough energy for thermal movement of the polymer chain, so that the glass transition temperature is increased. The imide structure has strong polarity, and strong intermolecular force exists between molecular chains, so that the glass transition temperature is increased. Thereby effectively improving the thermal stability of the polymer.
Meanwhile, the excellent solubility and dielectric property of the fluorine-containing polyaryletherketone resin can be ensured, the duty ratio of the imide structure can be adjusted according to different requirements of practical application scenes, and the glass transition temperature of the polymer is gradually increased along with the increase of the mole fraction of the imide structure, so that the purpose of controllable glass transition temperature is achieved. The finally prepared polymer film has the characteristics of excellent thermal stability and low dielectric constant, and can further expand the application of the polyaryletherketone resin in the fields of insulating paint for manufacturing enameled wires in the electronic/electric industry, matrix resin of printed circuit boards, packaging resin of integrated circuit dies and the like.
Preferably, the larger the x is less than or equal to 0.5, the more the imide structure mole fraction is increased, the glass transition temperature of the polymer is gradually increased, and the more excellent the thermal stability of the fluorinated polyaryletherketone polymer is. However, the applicant found that further increasing the ratio of monomer containing imide structure makes the polymerization of the system difficult, the molecular weight of the product is very low, and it is difficult to obtain high molecular weight polymer, probably because the high volume group of the main chain of the dichlorimide phenoxy benzophenone monomer and the long main chain structure result in a larger polymerization reaction difficulty, so that the content of the dichlorimide phenoxy benzophenone monomer is increased, the difficulty of the polymerization system is also increased, and the performance effect is general. Further preferably 0.2.ltoreq.x.ltoreq.0.5, such as 0.25, 0.3, 0.35, 0.4, 0.45, or any value therebetween.
Preferably, ar comprises any one or more of the following structures:
the invention also provides a preparation method of the fluorinated polyaryletherketone containing the imide structure, which comprises the following steps:
step 1, carrying out grafting reaction on 4,4' -bis (3-aminophenoxy) benzophenone, 4-halophthalic anhydride and a dehydrating agent in a solvent to obtain a monomer containing an imide structure shown in a formula I;
step 2, the monomer containing the imide structure, the fluorine-containing bisphenol monomer, the 4,4' -difluorobenzophenone, the dehydrating agent and the catalyst are subjected to azeotropic dehydration in a solvent, and then a polymer is obtained through polymerization, and the polymer is crushed, washed and dried to obtain the fluorinated polyaryletherketone containing the imide structure.
According to the invention, first, halogenated phthalic anhydride and 4,4' -bis (3-aminophenoxy) benzophenone are subjected to grafting reaction to synthesize a chlorinated monomer with an imide structure, and the imide structure in the monomer has stronger intermolecular acting force and a large-volume group, so that the stability of a polymerization system is enhanced. And then, carrying out ternary polymerization on a fluorine-containing bisphenol monomer, 4 '-difluorobenzophenone and a dichlorimide phenoxy benzophenone monomer, mixing the 4,4' -difluorobenzophenone and the dichlorimide phenoxy benzophenone monomer in the polymerization system with a catalytic salifying agent, carrying out nucleophilic substitution reaction to generate an intermediate salt, and further carrying out polycondensation on the intermediate salt and the bisphenol monomer to obtain the fluorinated polyaryletherketone containing the imide structure. The polymerization system obtains a controllable glass transition temperature range of the copolymer by adjusting the mole ratio of the dichlorimide phenoxy benzophenone monomer and the 4,4' -difluorobenzophenone, thereby realizing the purpose of coping with various application conditions.
The fluorine-containing bisphenol monomer comprises any one or more of the following structures:
preferably, the fluorine-containing bisphenol monomer has the following structure:
the fluorine-containing bisphenol monomer with the structure has more fluorine atoms, and the obtained polymer has more excellent dielectric properties.
The solvent comprises one or more of dimethylformamide, dimethylacetamide, N-methylpyrrolidone, sulfolane or diphenyl sulfone;
the dehydrating agent comprises one or more of benzene, toluene or xylene;
the catalyst comprises one or more of calcium hydride, potassium fluoride, sodium carbonate, potassium carbonate and cesium carbonate.
In the step 1, the molar ratio of the 4,4' -bis (3-aminophenoxy) benzophenone to the 4-halophthalic anhydride is 1 (2-2.4);
the molar ratio of the monomer containing the imide structure to the 4,4' -difluorobenzophenone in the step 2 is x, y, x+y=1, and 0 < x < 0.6; the higher the x-ratio, the more excellent the copolymer thermal stability, but the more difficult the polymerization.
The molar ratio of the total molar amount of the monomer containing the imide structure and the 4,4' -difluorobenzophenone to the fluorine-containing bisphenol monomer in the step 2 is 1:0.9-1.2.
Preferably, the molar ratio of the total molar amount of the imide structure containing monomer and 4,4' -difluorobenzophenone to the fluorine containing bisphenol monomer is 1:1.
The grafting reaction temperature in the step 1 is 120-200 ℃ and the reaction time is 1-8h; preferably, the grafting reaction is carried out for dehydration at 120-160 ℃ for 1-6h, and then the temperature is further raised to 160-180 ℃ for 30-120min to evaporate the redundant dehydrating agent.
It is further preferred that the grafting reaction is carried out at 130-150℃for 3-5 hours to dehydrate and remove by-product water generated when 4,4' -bis (3-aminophenoxy) benzophenone is grafted with 4-halophenolic anhydride to facilitate forward movement of the reaction.
In the step 2, the azeotropic dehydration temperature is 120-180 ℃ and the dehydration time is 1-6h; removing by-product water generated in the reaction process by azeotropic reflux, and promoting the reaction to move forward; the byproduct water generated when the catalyst salifies with hexafluorobisphenol A is removed by azeotropic reflux, so as to facilitate the forward movement of the reaction.
Preferably, the azeotropic dehydration is carried out at a temperature of 130 to 160℃and for a dehydration time of 3 to 5 hours, more preferably 3.5 to 4.5 hours.
Further preferably, the azeotropic reaction is carried out at 120-150 ℃ for 1-5 hours, and then the temperature is further raised to 150-160 ℃ for 30-60 minutes to evaporate the redundant dehydrating agent.
In the step 2, the polymerization temperature is 180-220 ℃, and the polymerization time is 6-24h. Preferably, the polymerization temperature is 190-210℃and the polymerization time is 6-24 hours. The polymerization reaction is preferably carried out under stirring, and the stirring rate is not particularly limited in the present invention, and may be carried out according to a process well known in the art. In the polymerization reaction process, phenolic hydroxyl of a fluorine-containing bisphenol monomer is salified with a catalyst, and then para-fluorine of the dichlorimide phenoxy benzophenone and the 4,4' -difluoro benzophenone is attacked to generate nucleophilic substitution reaction, so that fluorinated polyaryletherketone containing imide structure is generated.
Preferably, in step 1 or step 2, the volume ratio of the dehydrating agent to the solvent is 15-50:100, and in this range, the dehydrating agent can remove water generated during the reaction well, thereby pushing the reaction to proceed forward and obtaining a polymer with a higher molecular weight.
In the step 2, the molar ratio of the catalyst to the fluorine-containing bisphenol monomer is (0.9-1.2): 1, and in the range, the catalyst can well reduce the reaction energy barrier of nucleophilic substitution polycondensation reaction, accelerate the reaction speed and improve the reaction efficiency and selectivity.
Preferably, in step 1 or step 2, the solid content of the reaction mixture formed by all the reaction raw materials is 15 to 35wt%. The solids content is preferably from 20 to 30% by weight.
And (3) separating out the product after the reaction in the step (1) or the step (2) in deionized water or ethanol, and obtaining a pure product through crushing, washing and drying. Washing with deionized water and/or ethanol;
drying the product in the step 1 at 40-80 ℃ for 8-36h; the product of step 2 is dried at 100-140 ℃ for 8-36h.
Preferably, step 1 or step 2 is carried out under an inert gas such as nitrogen, argon, etc.
The number average molecular weight of the fluorinated polyaryletherketone containing the imide structure prepared by the invention is 0.8 x 10 4 g/mol～2*10 4 g/mol, weight average molecular weight of 2 x 10 4 g/mol～6*10 4 g/molThe glass transition temperature is 160-220 ℃ and T 5％ The temperature is 500-620 ℃, and the dielectric constant is below 2.8.
The invention also provides application of the monomer containing the imide structure or the fluorinated polyaryletherketone containing the imide structure in the electronic/electric industry. Such as insulating paint for manufacturing enamelled wires, matrix resin of printed circuit boards, packaging resin of integrated circuit dies and the like;
the method of application comprises the following steps: the fluorinated polyaryletherketone containing the imide structure is dissolved in an organic solvent, and then is cast and solidified to form a film for application. And the processing and application can also be carried out by adopting electrostatic spraying, mould pressing or injection molding technology.
The organic solvent comprises one or more of chloroform, tetrahydrofuran, dimethylformamide or dimethylacetamide; the mass content of the fluorinated polyaryletherketone in the mixed solution of the fluorinated polyaryletherketone and the organic solvent is 5-20%.
The curing temperature is preferably 30-160 ℃, more preferably 50-140 ℃; in the present invention, the curing means is preferably gradient drying, and the temperature and time of the gradient drying are preferably 50 ℃ drying 2h, 60 ℃ drying 2h, 80 ℃ drying 2h, 100 ℃ drying 2h and 140 ℃ drying 2h in this order. In the invention, the gradient drying can ensure that the organic solvent is removed more thoroughly, and a large number of bubbles are avoided on the surface of the film.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the invention, the monomer containing the aromatic ring and the imide structure is introduced into the fluorine-containing polyaryletherketone, so that the internal rotation resistance of a molecular chain is increased, the effect of effectively improving the glass transition temperature and the thermal stability of the polymer is realized, meanwhile, the product keeps excellent solubility and dielectric properties of the fluorine-containing polyaryletherketone, and the application of the polyaryletherketone resin in the fields of insulating paint for manufacturing enameled wires, matrix resin of printed circuit boards, packaging resin of integrated circuit dies and the like in the electronic/electric industry is further expanded.
(2) The fluorinated polyaryletherketone product can regulate and control the proportion of the comonomer dichlorimide phenoxy benzophenone according to different environmental requirements in practical application, thereby realizing that the glass transition temperature of the polymer can be accurately regulated and controlled.
Drawings
FIG. 1 is an infrared spectrum of the bischloroimide phenoxy benzophenone monomer prepared in example 1.
FIG. 2 is an infrared spectrum of the preparation of fluorinated polyaryletherketone containing imide structure of example 1.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention. Modifications and equivalents will occur to those skilled in the art upon understanding the present teachings without departing from the spirit and scope of the present teachings.
The raw materials used in the following embodiments are all commercially available.
Example 1
Step 1, 4-chlorophthalic anhydride (20.08 g,0.11 mol), 4' -bis (3-aminophenoxy) benzophenone (19.82 g,0.05 mol), N, N-dimethylacetamide (100 mL) and toluene (20 mL) were mixed for 0.5h under nitrogen atmosphere, the resulting mixture was heated to 145 ℃ and maintained at azeotropic reflux for 4h, the reaction system was continuously heated to 170 ℃ and maintained for 1h, the resulting material was added to absolute ethanol to precipitate, the resulting powder was suction-filtered and washed 3 times with absolute ethanol and dried in a vacuum oven at 50 ℃ for 24h, to obtain a bischloroimidophenoxybenzophenone monomer having the structure shown below, the infrared spectrum of which is shown in FIG. 1.
Step 2, 4' -difluorobenzophenone (7.86 g,0.036 mol), hexafluorobisphenol A (13.45 g,0.04 mol), bischloroimidophenoxybenzophenone (2.17 g,0.04 mol), K under nitrogen atmosphere 2 CO 3 (5.80 g,0.042 mol), sulfolane (70 mL) and toluene (12 mL) are mixed for 0.5h, the obtained mixture is heated to 145 ℃ for azeotropic reflux for 4h, the reaction system is continuously heated to 160 ℃ for 0.5h, redundant toluene is distilled off, the system is continuously heated to 220 ℃ for polymerization for 20h, the obtained material is added into deionized water for precipitation, the obtained precipitate is crushed, and then is washed with water and ethanol for 3 times respectively, and is dried in a vacuum oven at 120 ℃ for overnight, so as to obtain fluorinated polyaryletherketone containing imide structures, the structure is shown as follows, wherein x: y=0.1:0.9, and the infrared spectrogram is shown as figure 2.
As can be seen from FIG. 1, 3060cm -1 Is C-H telescopic vibration absorption peak of aromatic ring, 1780cm -1 、1720cm -1 Carbonyl vibration absorption peak of imide ring, 1640cm -1 Is C-N vibration absorption peak, 1590cm -1 、1500cm -1 Is 1380cm as benzene ring skeleton absorption peak -1 Is characterized by the characteristic absorption peak of imide benzene ring, 1170cm -1 Is an asymmetric telescopic vibration absorption peak of aryl ether of 725cm -1 The absorption peak is replaced by an aromatic ring.
As can be seen from FIG. 2, the wavelength is 2970cm -1 Is the vibration absorption peak of saturated C-H, 1780cm -1 Carbonyl vibration absorption peak of imide ring, 1660cm -1 Is an aromatic ketone telescopic absorption peak; 1590cm -1 、1500cm -1 Is 1380cm as benzene ring skeleton absorption peak -1 Characteristic absorption peak of imide group, 1240cm -1 Is an asymmetric telescopic vibration absorption peak of the aromatic ether with 1170cm -1 Is a fluorocarbon bond absorption peak. All characteristic peaks are clearly attributed, and the synthesized dichlorimide phenoxy benzophenone monomer and the fluorinated polyaryletherketone containing the imide structure are proved to accord with the expected structure.
Example 2
4,4' -difluorobenzophenone (6.98 g,0.032 mol), hexafluorobisphenol A (13.45 g,0.04 mol) and the bischloroimidophenoxybenzophenone prepared in example 1 (4.34 g,0.008 mol) were reacted under nitrogen atmosphere),K 2 CO 3 (6.08 g,0.044 mol), N-methylpyrrolidone (70 mL) and toluene (12 mL) were mixed for 0.5h, the resulting mixture was heated to 150℃and azeotropically refluxed for 4h, the reaction system was continued to be heated to 160℃and kept for 0.5h, excess toluene was distilled off, the system was continued to be heated to 190℃and polymerized for 15h, the resulting material was added to deionized water to precipitate out, the resulting precipitate was crushed, washed with water and ethanol respectively for 3 times, and dried in a vacuum oven at 140℃overnight to give a fluorinated polyaryletherketone having an imide structure, wherein x: y=0.2:0.8.
Example 3
4,4' -difluorobenzophenone (6.11 g,0.028 mol), hexafluorobisphenol A (13.45 g,0.04 mol), the bischloroimidophenoxybenzophenone prepared in example 1 (6.52 g,0.012 mol), na 2 CO 3 (4.45 g,0.042 mol), sulfolane (70 mL) and xylene (12 mL) were mixed for 0.5h, the resulting mixture was heated to 150 ℃ for 4h at azeotropic reflux, the reaction system was continued to be heated to 160 ℃ for 0.5h, excess xylene was distilled off, the system was continued to be heated to 220 ℃ for polymerization for 24h, the resulting material was added to deionized water to precipitate out, the resulting precipitate was crushed, washed with water and ethanol respectively for 3 times, and dried in a vacuum oven at 120 ℃ overnight to give a fluorinated polyaryletherketone containing imide structure, wherein x: y=0.3:0.7.
Example 4
4,4' -difluorobenzophenone (5.24 g,0.024 mol), 2,3,5, 6-tetrafluorohydroquinone (7.28 g,0.04 mol), the bischloroimidophenoxybenzophenone prepared in example 1 (8.69 g,0.016 mol), na were reacted under nitrogen atmosphere 2 CO 3 (5.09 g,0.048 mol), sulfolane (70 mL) and xylene (12 mL) were mixed for 0.5h, the resulting mixture was heated to 150℃for 4h at azeotropic reflux, the reaction system was continued to be heated to 160℃for 0.5h, excess xylene was distilled off, the system was continued to be heated to 210℃for 24h of polymerization, the resulting material was added to deionized water to precipitate out, the resulting precipitate was crushed, washed with water and ethanol respectively for 3 times, and dried overnight at 120℃in a vacuum oven to give a fluorinated polyaryletherketone having an imide structure, wherein x: y=0.4:0.6.
Example 5
4,4 '-difluorobenzophenone (4.36 g,0.02 mol), octafluoro-4, 4' -biphenol (13.2 g,0.04 mol), the bischloroimidophenoxybenzophenone prepared in example 1 (10.86 g,0.02 mol), K under nitrogen atmosphere 2 CO 3 (5.80 g,0.042 mol), N-methylpyrrolidone (70 mL) and xylene (11 mL) were mixed for 0.5h, the resulting mixture was heated to 150℃and azeotropically refluxed for 3h, the reaction system was further heated to 160℃and maintained for 0.5h, the excess xylene was distilled off, the system was further heated to 190℃and polymerized for 24h, the resulting material was added to deionized water to precipitate out, the resulting precipitate was crushed, washed with water and ethanol respectively for 3 times, and dried in a vacuum oven at 120℃overnight to give fluorinated polyaryletherketone having imide structure, wherein x: y=0.5:0.5.
Comparative example 1
4,4' -difluorobenzophenone (8.73 g,0.04 mol), hexafluorobisphenol A (13.45 g,0.04 mol), K under nitrogen atmosphere 2 CO 3 (6.072 g,0.044 mol), sulfolane (80 mL) and toluene (20 mL) were mixed for 0.5h, the resulting mixture was heated to 150 ℃ and maintained at azeotropic reflux for 4h, the reaction system was continued to be heated to 160 ℃ and maintained for 0.5h, excess toluene was distilled off, the system was continued to be heated to 190 ℃ and polymerized for 6h, the obtained material was added into deionized water to precipitate out, the obtained precipitate was crushed, washed with water and ethanol respectively for 3 times, and dried in a vacuum oven at 120 ℃ overnight to obtain fluorinated polyaryletherketone free of imide structure, wherein x: y=0:1.
Comparative example 2
4,4' -difluorobenzophenone (3.49 g,0.016 mol), hexafluorobisphenol A (13.45 g,0.04 mol), the bischloroimidophenoxybenzophenone prepared in example 1 (13.03 g,0.024 mol), K were reacted under nitrogen atmosphere 2 CO 3 (6.072 g,0.044 mol), N-methylpyrrolidone (100 mL) and toluene (20 mL) were mixed for 0.5h, the resulting mixture was heated to 150℃and maintained at azeotropic reflux for 4h, the reaction system was continued to be heated to 160℃and maintained for 0.5h, excess toluene was distilled off, the system was continued to be heated to 200℃and polymerized for 24h, the polymerization system viscosity was still lower, the resulting material was added to deionized water,fine-grained, powdery precipitates (unable to form the harder bar polymers of examples 1-5) were obtained, washed 3 times with water and ethanol, respectively, and dried overnight in a vacuum oven at 140 ℃ to give fluorinated polyaryletherketones containing imide structures, where x: y=0.6:0.4. GPC test results show that the molecular weight of the product is low, and it is difficult to obtain a polymer with a high molecular weight when the x content is too high.
The fluorinated polyaryletherketone containing the imide structure prepared in the examples and the comparative examples is subjected to molecular weight, DSC and TGA tests, and the test methods are respectively as follows: the molecular weight was characterized by Gel Permeation Chromatography (GPC) with the following conditions: mobile phase THF, tested at room temperature at 25 ℃; DSC testing range is 50-400 ℃, and the speed is 10 ℃/min under nitrogen atmosphere; the TGA test range is 100-800 ℃, and the speed is 10 ℃/min under nitrogen atmosphere;
dielectric Property Using a dielectric analyzer at 100Hz -4 The dielectric properties were measured in the MHz range as a function of frequency. The sample was cut into a square of about 10mm by 10mm prior to testing and the thickness of the sample was accurately measured. The sample was then coated with conductive silver paste on both sides and dried in an oven to form a plate-like conductor. And accurately measuring the area coated with silver paste and then testing.
Solubility test: the prepared polymer was added to DMF, DMSO, DMAc, THF, chloroform and dichloromethane organic solvents respectively to test the dissolution properties, and if all the polymer was completely dissolved, the polymer was considered to be soluble.
The test results are summarized in Table 1, where Mn is the number average molecular weight, mw is the weight average molecular weight, PDI is the molecular weight distribution, T g T is the glass transition temperature 5％ The temperature corresponds to a thermal weight loss of 5%.
TABLE 1 Performance parameters of fluorinated polyaryletherketones containing imide structures prepared in examples and comparative examples
As can be seen from Table 1, the fluorinated polyaryletherketone containing imide structure synthesized by the invention has higher molecular weight and lower molecular weight distribution index; meanwhile, the fluorinated polyaryletherketone containing the imide structure has higher glass transition temperature, and the glass transition temperature is 167-183 ℃. In nitrogen atmosphere, the 5% thermal weight loss temperature of the fluorinated polyaryletherketone containing the imide structure is above 527 ℃, which indicates that the fluorinated polyaryletherketone containing the imide structure has excellent thermal stability.
Examples 1 to 5 show that as the ratio of the imide structure increases, the higher the glass transition temperature becomes, the higher the thermal stability becomes, but when the ratio of x reaches 0.6 (comparative example 2), it is difficult to obtain a polymer having a high molecular weight, the glass transition temperature decreases, the thermal stability thereof also decreases greatly, and it is possible that the steric hindrance of the polymer becomes large due to the imide structure having a strong intermolecular force and a large volume group, and the polymerization reaction becomes difficult.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. An imide structure-containing monomer, characterized by having a structure as shown in formula I:
(formula I) wherein X is halogen.
2. The method for producing an imide structure-containing monomer according to claim 1, comprising the steps of: and (3) carrying out grafting reaction on the 4,4' -bis (3-aminophenoxy) benzophenone, the 4-halophthalic anhydride and the dehydrating agent in a solvent to obtain the monomer containing the imide structure shown in the formula I.
3. The method for producing an imide structure containing monomer according to claim 2, wherein the molar ratio of 4,4' -bis (3-aminophenoxy) benzophenone to 4-halophenolic anhydride is 1 (2-2.4);
and/or the grafting reaction temperature is 120-200 ℃ and the reaction time is 1-8h;
and/or the solvent comprises one or more of dimethylformamide, dimethylacetamide, N-methylpyrrolidone, sulfolane or diphenyl sulfone;
and/or the dehydrating agent comprises one or more of benzene, toluene or xylene;
and/or mixing 4,4' -bis (3-aminophenoxy) benzophenone, 4-halophthalic anhydride, dehydrating agent and solvent to form a reaction liquid with a solid content of 15-35wt%.
4. A fluorinated polyaryletherketone containing an imide structure, wherein the fluorinated polyaryletherketone has a structure as shown in formula II:
wherein Ar is a fluorine-containing bisphenol residue, x+y=1, and 0 < x < 0.6.
5. The fluorinated polyaryletherketone comprising imide structure according to claim 4, wherein Ar comprises any one or more of the following structures:
6. the method for preparing fluorinated polyaryletherketone having imide structure according to claim 4, comprising the steps of:
step 1, carrying out grafting reaction on 4,4' -bis (3-aminophenoxy) benzophenone, 4-halophthalic anhydride and a dehydrating agent in a solvent to obtain a monomer containing an imide structure shown in a formula I;
step 2, the monomer containing the imide structure, the fluorine-containing bisphenol monomer, the 4,4' -difluorobenzophenone, the dehydrating agent and the catalyst are subjected to azeotropic dehydration in a solvent, and then a polymer is obtained through polymerization, and the polymer is crushed, washed and dried to obtain the fluorinated polyaryletherketone containing the imide structure.
7. The method for preparing fluorinated polyaryletherketone containing imide structure according to claim 6, wherein the fluorine-containing bisphenol monomer comprises any one or more of the following structures:
and/or the solvent comprises one or more of dimethylformamide, dimethylacetamide, N-methylpyrrolidone, sulfolane or diphenyl sulfone;
and/or the dehydrating agent comprises one or more of benzene, toluene or xylene;
and/or the catalyst comprises one or more of calcium hydride, potassium fluoride, sodium carbonate, potassium carbonate and cesium carbonate.
8. The method for preparing fluorinated polyaryletherketone containing imide structure according to claim 6, wherein the molar ratio of 4,4' bis (3-aminophenoxy) benzophenone to 4-halophenolic anhydride in step 1 is 1 (2-2.4);
and/or the molar ratio of the monomer containing the imide structure and the 4,4' -difluorobenzophenone in the step 2 is x, y, x+y=1, and 0 < x < 0.6;
and/or the molar ratio of the total molar amount of the imide structure-containing monomer and the 4,4' -difluorobenzophenone to the fluorine-containing bisphenol monomer in the step 2 is 1 (0.9-1.2).
9. The method for preparing fluorinated polyaryletherketone containing imide structure according to claim 6, wherein the grafting reaction temperature in step 1 is 120-200 ℃ and the reaction time is 1-8h;
and/or in the step 2, the azeotropic dehydration temperature is 120-180 ℃ and the dehydration time is 1-6h; the polymerization temperature is 180-220 ℃, and the polymerization time is 6-24h;
and/or in step 1 or step 2, the volume ratio of the dehydrating agent to the solvent is (15-50): 100;
and/or in step 2, the molar ratio of the catalyst to the fluorine-containing bisphenol monomer is (0.9-1.2): 1;
and/or in step 1 or step 2, the solid content of the reaction mixture formed by all the reaction raw materials is 15-35wt%.
10. Use of the imide structure containing monomer according to claim 1 or the imide structure containing fluorinated polyaryletherketone according to claim 4 in the electronics/electrical industry.
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