CN115819752A - Carboxylated fluorine-containing polyfluorene ether ketone compound for toughening epoxy resin and preparation method thereof - Google Patents
Carboxylated fluorine-containing polyfluorene ether ketone compound for toughening epoxy resin and preparation method thereof Download PDFInfo
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- -1 ether ketone compound Chemical class 0.000 title claims abstract description 56
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 44
- 239000011737 fluorine Substances 0.000 title claims abstract description 44
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 41
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 41
- 229920002098 polyfluorene Polymers 0.000 title claims abstract description 33
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 claims abstract description 15
- SNPPMOSOWNHABX-UHFFFAOYSA-N 4-[9-(4-hydroxy-3,5-dimethylphenyl)fluoren-9-yl]-2,6-dimethylphenol Chemical compound CC1=C(O)C(C)=CC(C2(C3=CC=CC=C3C3=CC=CC=C32)C=2C=C(C)C(O)=C(C)C=2)=C1 SNPPMOSOWNHABX-UHFFFAOYSA-N 0.000 claims abstract description 9
- 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 claims abstract description 8
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 claims abstract description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- 150000002576 ketones Chemical class 0.000 claims description 25
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 20
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 18
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000001914 filtration Methods 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 13
- 239000000047 product Substances 0.000 claims description 13
- 239000012265 solid product Substances 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 10
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 10
- 229910052786 argon Inorganic materials 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 150000002221 fluorine Chemical class 0.000 claims description 8
- 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 7
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 6
- FKBMTBAXDISZGN-UHFFFAOYSA-N 5-methyl-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1C(C)CCC2C(=O)OC(=O)C12 FKBMTBAXDISZGN-UHFFFAOYSA-N 0.000 claims description 6
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 6
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 6
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 5
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 3
- 238000000034 method Methods 0.000 claims 6
- 238000004519 manufacturing process Methods 0.000 claims 1
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 7
- 239000002131 composite material Substances 0.000 abstract description 6
- 239000011159 matrix material Substances 0.000 abstract description 3
- 230000021523 carboxylation Effects 0.000 abstract description 2
- 238000006473 carboxylation reaction Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 abstract 2
- 150000008065 acid anhydrides Chemical class 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 abstract 1
- 238000006116 polymerization reaction Methods 0.000 abstract 1
- 238000005452 bending Methods 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 4
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- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000012745 toughening agent Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004697 Polyetherimide Substances 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 125000005997 bromomethyl group Chemical group 0.000 description 2
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229920002492 poly(sulfone) Polymers 0.000 description 2
- 229920006260 polyaryletherketone Polymers 0.000 description 2
- 229920001601 polyetherimide Polymers 0.000 description 2
- 229920006380 polyphenylene oxide Polymers 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
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- 238000001291 vacuum drying Methods 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920012266 Poly(ether sulfone) PES Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
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- 239000004841 bisphenol A epoxy resin Substances 0.000 description 1
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- 125000000524 functional group Chemical group 0.000 description 1
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- 239000001257 hydrogen Substances 0.000 description 1
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- 238000002329 infrared spectrum Methods 0.000 description 1
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- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
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Abstract
The invention relates to a carboxylated fluorine-containing polyfluorene ether ketone compound for toughening epoxy resin and a preparation method thereof. The invention takes 9, 9-bis (3, 5-dimethyl-4-hydroxyphenyl) fluorene, 4' -difluorobenzophenone and hexafluorobisphenol A as raw materials, the fluorine-containing polyfluorene ether ketone with high molecular weight is obtained by polymerization, then the fluorine-containing polyfluorene ether ketone reacts with N-bromosuccinimide to brominate benzyl, and finally the fluorine-containing polyfluorene ether ketone compound with carboxylation is obtained by reacting the benzyl with p-hydroxyphenylpropionic acid. The carboxyl of the compound is at the tail end of a side chain, the content is easy to adjust, and the interface performance with an epoxy resin matrix can be improved. Introducing the carboxylated fluorine-containing polyfluorene ether ketone compound into an epoxy resin/acid anhydride system for curing to obtain the composite material with good toughness and thermal stability.
Description
Technical Field
The invention belongs to the technical field of materials, and particularly relates to a carboxylated fluorine-containing polyfluorene ether ketone compound and a preparation method thereof.
Background
Epoxy resins are one of the most commonly used thermosetting materials due to their excellent mechanical properties, good processability and low cost, and are now widely used in the fields of coatings, adhesives, structural composites and electronic materials. However, the low toughness resulting from its high degree of chemical crosslinking severely limits the use of epoxy resins. Therefore, toughening of epoxy resins has been a focus of attention in both academic and industrial circles.
In order to solve the problem, scholars at home and abroad adopt thermoplastic resin to toughen and modify the epoxy resin from the eighties of the last century, and the thermoplastic polymer has the characteristics of good toughness, high modulus, high heat resistance and the like, so that the thermoplastic polymer is used for modifying the epoxy resin, the toughness can be improved, the modulus and the heat resistance are not reduced, and the modified resin is used for a high-performance composite material substrate, can improve the fatigue resistance, the impact toughness, the transverse tensile strength and the interlaminar shear strength of the composite material, and can improve the service temperature of the composite material. The thermoplastic resin used for toughening the epoxy resin mainly comprises Polysulfone (PSF), polyethersulfone (PES), polyetherimide (PEI), polycarbonate (PC), polyaryletherketone (PAEK), polyphenylene oxide (PPO) and the like. Luo (RSC Advances,2022,7 (32): 20471-20480) et al investigated the effect of CTPBA modification on the adhesion and room temperature mechanical properties of epoxy adhesives by preparing carboxyl terminated polybutylene adipate succinate. The CTPBA modification obviously improves the bonding strength and the elongation at break, but also reduces the tensile strength, the glass transition temperature and the thermal stability, in addition, the content of carboxyl functional groups of the CTPBA is low, the CTPBA is only distributed at two ends of the polymer, and the modification effect is limited.
Disclosure of Invention
The invention aims to provide a carboxylated fluorine-containing polyfluorene ether ketone compound serving as a toughening agent of epoxy resin, wherein the interface performance of the toughening agent and a matrix is improved by utilizing the reaction of a carboxyl side chain of the carboxylated fluorine-containing polyfluorene ether ketone compound and an epoxy group in the epoxy resin, so that a composite material with good toughness and thermal stability is obtained.
The invention also aims to provide a preparation method of the carboxylated fluorine-containing polyfluoreneether ketone compound.
A carboxylated fluorine-containing polyfluorene ether ketone compound has the following structural formula:
wherein m =10 to 20, n =20 to 100.
The preparation method of the carboxylated fluorine-containing polyfluoreneether ketone compound comprises the following steps:
(1) Adding 9, 9-bis (3, 5-dimethyl-4-hydroxyphenyl) fluorene (CAS: 80850-00-6), hexafluorobisphenol A, 4' -difluorobenzophenone and N, N-dimethylacetamide into a round-bottom flask provided with a water separator, magnetically stirring under the protection of argon to completely dissolve solids, adding toluene and anhydrous potassium carbonate, heating to 140-150 ℃ for reaction for 2-4 h, removing water generated in the reaction through the water separator, evaporating the toluene in the system, heating to 160-170 ℃ for continuous reaction for 3-20 h, naturally cooling the system to room temperature, slowly pouring deionized water into the system to separate out white solids, filtering to collect solid products, vacuum drying at 60-80 ℃ for 12-24 h, re-dissolving the solid products in dichloromethane, pouring the solution into methanol to separate out, filtering to collect solids, and drying in a vacuum oven at 60-80 ℃ for 12-24 h to obtain the fluorine-containing polyfluorene. The reaction formula is shown as follows:
(2) Dissolving fluorine-containing polyfluoreneether ketone in 1, 2-dichloroethane, adding N-bromosuccinimide and dibenzoyl peroxide, heating the reaction system to 75 to 85 ℃ under the protection of argon, reacting for 5 to 7 hours, naturally cooling the system to room temperature, slowly pouring the system into methanol to separate out solid, filtering and collecting a solid product, drying in vacuum at 60 to 80 ℃ for 12 to 24 hours, dissolving in dichloromethane again, pouring the solution into methanol to separate out and filtering and collecting the solid, and drying in a vacuum oven at 60 to 80 ℃ for 12 to 24 hours to obtain bromomethylated fluorine-containing polyfluoreneether ketone. The reaction formula is shown as follows:
(3) Dissolving bromomethylated fluorine-containing polyfluorene ether ketone and p-hydroxyphenylpropionic acid in N-methyl pyrrolidone. Adding anhydrous potassium carbonate, heating the system to 75-85 ℃ under the protection of argon, and reacting for 6-8 h. And naturally cooling the system to room temperature, slowly pouring the cooled system into deionized water to precipitate, filtering and collecting a solid product, and drying in a vacuum oven at 60-80 ℃ for 12-24 h to obtain the carboxylated fluorine-containing polyfluorene ether ketone compound. The reaction process is as follows:
in order to better implement the invention, in the step (1), the sum of the molar amounts of 9, 9-bis (3, 5-dimethyl-4-hydroxyphenyl) fluorene and hexafluorobisphenol A is equal to the molar amount of 4,4 '-difluorobenzophenone, and the molar amount of anhydrous potassium carbonate is 1 to 5 times of the molar amount of 4,4' -difluorobenzophenone. The molar ratio of 9, 9-bis (3, 5-dimethyl-4-hydroxyphenyl) fluorene to hexafluorobisphenol a was 1:1 to 100.
In the step (1), the ratio of the volume of N, N-dimethylacetamide to the mass of 4,4' -difluorobenzophenone is 10 to 30:1mL/g; the volume ratio of N, N-dimethylacetamide to toluene to deionized water =10: 1: 4: 50: 500.
In the step (2), the molar weight of N-bromosuccinimide (NBS) is 3 to 5 times of that of fluorenyl in the fluorine-containing polyfluoreneether ketone, and the molar weight of dibenzoyl peroxide is 1 to 10 percent of that of NBS.
In the step (2), the ratio of the volume of the 1, 2-dichloroethane to the mass of the polyfluoreneether ketone containing fluorine is 10 to 30:1mL/g, and the volume of the methanol is 5 to 50 times of the volume of the 1, 2-dichloroethane.
In the step (3), the molar weight of fluorenyl in bromomethylated fluorine-containing polyfluorene ether ketone is as follows: the molar weight of the p-hydroxyphenylpropionic acid is that the molar weight of the anhydrous potassium carbonate is =1 to 6.
In the step (3), the volume ratio of NMP to the mass ratio of bromomethylated fluorine-containing polyfluoreneether ketone is 10 to 30:1mL/g.
A carboxylated fluorine-containing polyfluorene ether ketone compound modified epoxy resin cured product mainly comprises a carboxylated fluorine-containing polyfluorene ether ketone compound, epoxy resin, a curing agent 4-methyl-1, 2-cyclohexane dicarboxylic anhydride and a curing accelerator 2-ethyl-4-methylimidazole, wherein the mass ratio of the epoxy resin to the carboxylated fluorine-containing polyfluorene ether ketone compound is 1:0.05 to 0.8, wherein the mass ratio of the epoxy resin to the curing agent is 1:0.5 to 1, wherein the mass ratio of the epoxy resin to the curing accelerator is 1:0.001 to 0.05. The preparation method comprises the following steps:
(1) Dissolving a carboxylated fluorine-containing polyfluoreneether ketone compound in a tetrahydrofuran solvent to obtain a solution with the mass percent of more than or equal to 5%, then adding epoxy resin, a curing agent 4-methyl-1, 2-cyclohexanedicarboxylic anhydride and a curing accelerator 2-ethyl-4-methylimidazole, and stirring for 1-2 h at 50-70 ℃.
(2) Removing the solvent from the mixed solution obtained in the step (1) through an oil pump in vacuum, curing for 2-4 h at 130-140 ℃ under the vacuum degree of 0.01-0.1MPa, then curing for 2-4 h at 155-165 ℃, and then curing for 2-4 h at 185-190 ℃ to obtain the carboxylated fluorine-containing polyfluoreneether ketone compound modified epoxy resin cured product.
Compared with the prior art, the invention has the following advantages:
(1) The adopted raw materials are easy to obtain, the synthesis steps are simple, the yield is high, and the byproducts are few.
(2) The carboxyl of the carboxylated polyfluorene ether ketone compound containing fluorine is at the tail end of a side chain, and the content of the carboxyl is easy to adjust.
(3) The carboxylated fluorine-containing polyfluorene ether ketone compound has good thermal stability.
(4) The carboxyl side chain of the carboxylated fluorine-containing polyfluorene ether ketone compound reacts with the epoxy group of the epoxy resin, so that the interface performance of the toughening agent and the matrix can be improved.
(5) The carboxylated polyfluorene ether ketone containing fluorine can improve the mechanical properties of the epoxy resin, such as bending fracture strain, notch impact strength, critical stress intensity factor and the like, and can improve the thermal decomposition temperature of the epoxy resin.
Drawings
FIG. 1 shows NMR hydrogen spectra of fluorinated polyfluoreneether ketone (PFEK) of example 1, bromomethylated fluorinated polyfluoreneether ketone (Br-PFEK) of example 2, and carboxylated fluorinated polyfluoreneether ketone (C-PFEK) of example 3.
FIG. 2 shows IR spectra of fluorinated polyfluoreneether ketone (PFEK) of example 1, bromomethylated fluorinated polyfluoreneether ketone (Br-PFEK) of example 2 and carboxylated fluorinated polyfluoreneether ketone (C-PFEK) of example 3.
FIG. 3 is a differential scanning calorimetry curve of fluorinated polyfluoreneether ketone (PFEK) of example 1 and carboxylated fluorinated polyfluoreneether ketone (C-PFEK) of the present invention.
FIG. 4 shows the thermogravimetric curves of fluorinated polyfluoreneether ketone (PFEK) of example 1 and carboxylated fluorinated polyfluoreneether ketone (C-PFEK) of the present invention.
Detailed Description
The present invention will be further described with reference to the following examples, but the present invention is not limited to these examples.
Example 1 Synthesis of fluorine-containing Polyfluoreneetherketone (PFEK)
0.2439g (0.6 mmol) of 9, 9-bis (3, 5-dimethyl-4-hydroxyphenyl) fluorene, 1.8156g (5.4 mmol) of hexafluorobisphenol A, 1.3092g (6 mmol) of 4,4' -difluorobenzophenone and 30 mL of N, N-dimethylacetamide were placed in a 100 mL round-bottomed flask equipped with a water separator, and under the protection of argon, magnetic stirring was carried out to completely dissolve the solid, and 7mL of toluene and 1.2438g (9 mmol) of anhydrous potassium carbonate were added. The temperature was raised to 145 ℃ for 2h and the water produced in the reaction was removed by a water trap. Then, evaporating toluene in the system, heating to 165 ℃ for continuous reaction for 20h, naturally cooling the system to normal temperature, slowly pouring the mixture into deionized water to separate out white solid, filtering and collecting a solid product, drying in vacuum at 60 ℃ for 12h, dissolving the product in dichloromethane again, pouring the solution into methanol to separate out, filtering and collecting the solid, and drying in a vacuum oven at 60 ℃ for 24h to obtain the fluorine-containing polyfluorene ether ketone PFEK with the yield of 96%. Of PFEK 1 H NMR is shown in FIG. 1The peak at the 2.04ppm position in the figure is the resonance peak of the proton on the methyl group.
Example 2 Synthesis of bromomethylated fluorinated polyfluoreneetherketone (Br-PFEK)
Dissolving 1g (the molar weight of fluorenyl is 0.19 mmol) of fluorine-containing polyfluorene ether ketone (the average molecular weight of a repeating unit of the fluorine-containing polyfluorene ether ketone is 521.45 g/mol) in 25 ml of 1, 2-dichloroethane, then adding 0.13g (0.72 mmol) of N-bromosuccinimide and 0.01g (0.04 mmol) of dibenzoyl peroxide, raising the temperature of a reaction system to 80 ℃ under the protection of argon gas for reaction for 5h, naturally cooling the system to room temperature, slowly pouring the system into methanol to separate out a solid, filtering and collecting a solid product, vacuum drying at 60 ℃ for 12h, re-dissolving the solid product in dichloromethane, then pouring the solution into methanol to separate out and filtering and collecting the solid, drying in a vacuum oven at 80 ℃ for 24h to obtain bromomethylated fluorine-containing polyfluorene ether ketone Br-PFEK with the yield of 95%. Of Br-PFEK 1 H NMR is shown in fig. 1, in which the peak at the 4.32ppm position is the peak of the proton on the bromomethyl group, and the bromination degree of Br-PFEK is calculated to be 50% from the integrated area ratio of the peak of the proton on the bromomethyl group to the peak of the proton on the unreacted methyl group, i.e., 50% of the methyl groups are successfully bromomethylated.
Example 3 Synthesis of carboxylated fluorinated polyfluoreneetherketone (C-PFEK)
Dissolving 0.9g (the molar weight of fluorenyl is 0.17 mmol) of bromomethylated fluorine-containing polyfluoreneether ketone (the average molecular weight of a repeating unit of the fluorine-containing polyfluoreneether ketone is 537.23 g/mol) and 0.11g (0.67 mmol) of p-hydroxyphenylpropionic acid in 20 mL of N-methylpyrrolidone, adding 0.14 g (1.00 mmol) of anhydrous potassium carbonate, heating the system to 80 ℃ under the protection of argon, reacting for 6 h, naturally cooling the system to room temperature, slowly pouring the cooled system into deionized water to precipitate, filtering and collecting a solid product, and drying for 24h in a vacuum oven at 80 ℃ to obtain a carboxylated fluorine-containing polyfluoreneether ketone compound C-PFEK with the yield of 93%. Of C-PFEK 1 H NMR is shown in FIG. 1, in which peaks at 4.95, 2.65 and 2.30ppm are peaks of protons in propionic acid. FT-IR spectrum of C-PFEK at 1733cm is shown in FIG. 2 -1 The absorption peak is a characteristic peak of C = O on the introduced p-hydroxyphenylpropionic acid, which indicates the success of carboxylation.
The differential scanning calorimetry curves of PFEK and C-PFEK are shown in FIG. 3, the glass transition temperature T of PFEK g T of 179 ℃ and C-PFEK g The temperature was 169 ℃. As can be seen from FIG. 4, the 5% thermogravimetric temperatures of PFEK and C-PFEK are 500 ℃ and 420 ℃ respectively. At 800 ℃, the carbon residue rate of PFEK is 51 percent, while the carbon residue rate of C-PFEK reaches 55 percent. It can be seen that both PFEK and C-PFEK are thermally stable.
Example 4 preparation of unmodified epoxy resin cured product
5g of bisphenol A epoxy resin E51,4.2 g of a curing agent 4-methyl-1, 2-cyclohexanedicarboxylic anhydride, 0.04 g of a curing accelerator 2-ethyl-4-methylimidazole and 4mL of a tetrahydrofuran solvent are put into a round-bottom flask, stirred for 1h at 60 ℃ to obtain a mixed solution, the obtained mixed solution is vacuumized by an oil pump to remove the solvent, cured for 2h at 130 ℃ under the vacuum degree of 0.02MPa, cured for 2h at 160 ℃, and cured for 2h at 190 ℃. As shown in Table 1, the glass transition temperature (T) of the obtained unmodified epoxy resin cured product g ) At 130 ℃ and 5% temperature of thermal weight loss (T) d5% ) 319 ℃, bending strength of 90.01MPa, bending modulus of 3.12MPa, bending strain at break of 3.07%, critical stress intensity factor (K) IC ) Is 1.53 MN/m 3/2 Critical strain energy release rate (G) IC ) Is 0.59 KJ/m 2 Notched impact strength of 2.56 KJ/m 2 。
Example 5 preparation of carboxylated fluorinated polyfluoreneether ketone Compound-modified epoxy resin cured product
Dissolving 0.5g of carboxylated fluorine-containing polyfluoreneether ketone compound in 4mL of tetrahydrofuran solvent, adding 5g of bisphenol A type epoxy resin E51,4.2 g of curing agent 4-methyl-1, 2-cyclohexanedicarboxylic anhydride and 0.04 g of curing accelerator 2-ethyl-4-methylimidazole to prepare a resin solution, stirring for 2 hours at the temperature of 60 ℃, vacuumizing the obtained mixed solution through an oil pump to remove the solvent, curing for 2 hours at the temperature of 130 ℃ under the vacuum degree of 0.02MPa, then curing for 2 hours at the temperature of 160 ℃, and curing for 2 hours at the temperature of 190 ℃. As shown in Table 1, the glass transition temperature (T) of the resulting modified epoxy resin cured product g ) At 128 ℃ and a 5% temperature of thermal weight loss (T) d5% ) At 340 ℃, a bending strength of 98.58 MPa, a bending modulus of 2.99MPa, and a bending strain at break5.22%, critical stress intensity factor (K) IC ) Is 2.12MN/m 3/2 Critical strain energy release rate (G) IC ) Is 0.97 KJ/m 2 Notched impact strength of 3.34 KJ/m 2 . The modified epoxy resin cured product showed an improvement in flexural strength of 9.5%, a reduction in flexural modulus of 4.2%, an improvement in flexural strain at break of 70%, and a critical stress intensity factor (K) over the unmodified epoxy resin cured product of example 4 IC ) The critical strain energy release rate (G) is improved by 38.6 percent IC ) The improvement is 64.4 percent, and the notch impact strength is improved by 30.5 percent.
Table 1 properties of the unmodified epoxy resin cured product and the carboxylated fluorinated polyfluorene ether ketone compound-modified epoxy resin cured product.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (10)
1. The carboxylated fluorine-containing polyfluorene ether ketone compound for toughening the epoxy resin is characterized in that the structural formula of the carboxylated fluorine-containing polyfluorene ether ketone compound is as follows:
wherein m =10 to 20, n =20 to 100.
2. The preparation method of the carboxylated fluorinated polyfluoroethylene ketone compound as claimed in claim 1, which is characterized by comprising the following steps:
(1) Adding 9, 9-bis (3, 5-dimethyl-4-hydroxyphenyl) fluorene, hexafluorobisphenol A, 4' -difluorobenzophenone and N, N-dimethylacetamide into a round-bottom flask provided with a water separator, magnetically stirring under the protection of argon to completely dissolve solids, adding toluene and anhydrous potassium carbonate, heating to 140-150 ℃ for reaction for 2-4 h, removing water generated in the reaction through the water separator, evaporating the toluene in the system, heating to 160-170 ℃ for continuous reaction for 3-20 h, naturally cooling the system to room temperature, slowly pouring the system into deionized water to separate out white solids, filtering and collecting solid products, drying at 60-80 ℃ for 12-24 h in vacuum, re-dissolving in dichloromethane, pouring the solution into methanol to separate out and filtering and collecting solids, and drying at 60-80 ℃ for 12-24 h in a vacuum oven to obtain fluorine-containing polyfluorene ether ketone;
(2) Dissolving fluorine-containing polyfluoreneether ketone in 1, 2-dichloroethane, adding N-bromosuccinimide and dibenzoyl peroxide, heating the reaction system to 75 to 85 ℃ under the protection of argon, reacting for 5 to 7 hours, naturally cooling the system to room temperature, slowly pouring the system into methanol to separate out solid, filtering and collecting a solid product, drying in vacuum at 60 to 80 ℃ for 12 to 24 hours, dissolving in dichloromethane again, pouring the solution into methanol to separate out and filtering and collecting the solid, and drying in a vacuum oven at 60 to 80 ℃ for 12 to 24 hours to obtain bromomethylated fluorine-containing polyfluoreneether ketone;
(3) Dissolving bromomethylated fluorine-containing polyfluorene ether ketone and p-hydroxyphenylpropionic acid in N-methylpyrrolidone, adding anhydrous potassium carbonate, heating the system to 75-85 ℃ under the protection of argon, reacting for 6-8 h, naturally cooling the system to room temperature, slowly pouring the system into deionized water to precipitate, filtering and collecting a solid product, and drying in a vacuum oven at 60-80 ℃ for 12-24 h to obtain the carboxylated fluorine-containing polyfluorene ether ketone compound.
3. The method for producing a carboxylated fluorinated polyfluoroethylene ketone compound according to claim 2, wherein in the step (1), the sum of the molar amounts of 9, 9-bis (3, 5-dimethyl-4-hydroxyphenyl) fluorene and hexafluorobisphenol a is equal to the molar amount of 4,4 '-difluorobenzophenone, the molar amount of anhydrous potassium carbonate is 1 to 5 times the molar amount of 4,4' -difluorobenzophenone, and the molar ratio of 9, 9-bis (3, 5-dimethyl-4-hydroxyphenyl) fluorene to hexafluorobisphenol a is 1:1 to 100.
4. The method for preparing a carboxylated fluorinated polyfluoroethylene ketone compound according to claim 2, wherein in the step (1), the ratio of the volume of N, N-dimethylacetamide to the mass of 4,4' -difluorobenzophenone is 10 to 30:1mL/g; according to the volume ratio, the ratio of N, N-dimethylacetamide to toluene = 10.
5. The method for preparing a carboxylated polyfluoreneether ketone compound according to claim 2, wherein in the step (2), the molar amount of N-bromosuccinimide is 3 to 5 times that of the fluorenyl in the polyfluoreneether ketone, and the molar amount of dibenzoyl peroxide is 1 to 10% that of N-bromosuccinimide.
6. The method for preparing a carboxylated fluorinated polyfluoreneether ketone compound according to claim 2, wherein in the step (2), the ratio of the volume of 1, 2-dichloroethane to the mass of the fluorinated polyfluoreneether ketone is from 10 to 30:1mL/g.
7. The method for preparing a carboxylated fluorinated polyfluoroethylene ketone compound according to claim 2, wherein in the step (3), the molar weight of the fluorenyl group in the bromomethylated fluorinated polyfluoroethylene ketone is as follows: the molar weight of the p-hydroxyphenylpropionic acid is that the molar weight of the anhydrous potassium carbonate is =1 to 6.
8. The method for preparing a carboxylated fluorinated polyfluoreneether ketone compound according to claim 2, wherein in the step (3), the ratio of the volume of N-methylpyrrolidone to the mass of bromomethylated fluorinated polyfluoreneether ketone is 10 to 30:1mL/g.
9. The cured product of the epoxy resin modified by the carboxylated fluorine-containing polyfluoreneether ketone compound according to claim 1, which is characterized by mainly comprising the carboxylated fluorine-containing polyfluoreneether ketone compound, the epoxy resin, a curing agent 4-methyl-1, 2-cyclohexanedicarboxylic anhydride and a curing accelerator 2-ethyl-4-methylimidazole, wherein the mass ratio of the epoxy resin to the carboxylated fluorine-containing polyfluoreneether ketone compound is 1:0.05 to 0.8, wherein the mass ratio of the epoxy resin to the curing agent is 1:0.5 to 1, wherein the mass ratio of the epoxy resin to the curing accelerator is 1:0.001 to 0.05.
10. The method for preparing the cured carboxylated fluorinated polyfluoroethylene ketone compound-modified epoxy resin as claimed in claim 9, comprising the steps of:
1) Dissolving a carboxylated fluorine-containing polyfluorene ether ketone compound in a tetrahydrofuran solvent to obtain a solution with the mass percent of more than or equal to 5%, then adding epoxy resin, a curing agent 4-methyl-1, 2-cyclohexanedicarboxylic anhydride and a curing accelerator 2-ethyl-4-methylimidazole, and stirring for 1 to 2 hours at the temperature of 50 to 70 ℃;
2) Removing the solvent from the mixed solution obtained in the step 1) through oil pump vacuum pumping, curing for 2-4 h at 130-140 ℃ under the vacuum degree of 0.01-0.1MPa, then curing for 2-4 h at 155-165 ℃, and then curing for 2-4 h at 185-190 ℃ to obtain the carboxylated fluorine-containing polyfluoreneether ketone compound modified epoxy resin cured product.
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| CN108530660A (en) * | 2018-04-17 | 2018-09-14 | 福州大学 | A kind of quaternized polyfluorene ether ketone compound of local dense and preparation method thereof |
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| US20200062888A1 (en) * | 2016-12-03 | 2020-02-27 | Soochow University | Biomass-based epoxy resin and preparation method thereof |
| CN114133555A (en) * | 2021-12-09 | 2022-03-04 | 福州大学 | Preparation method of cross-linked fluorine-containing polyfluorene ether anion exchange membrane |
| CN115304764A (en) * | 2022-09-20 | 2022-11-08 | 福州大学 | Epoxidized fluorine-containing polyarylether compound and preparation method thereof |
| CN115403764A (en) * | 2022-09-26 | 2022-11-29 | 福州大学 | Epoxy group-containing polyaryletherketone compound and preparation method thereof |
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| US20200062888A1 (en) * | 2016-12-03 | 2020-02-27 | Soochow University | Biomass-based epoxy resin and preparation method thereof |
| CN108530660A (en) * | 2018-04-17 | 2018-09-14 | 福州大学 | A kind of quaternized polyfluorene ether ketone compound of local dense and preparation method thereof |
| CN110387036A (en) * | 2019-07-25 | 2019-10-29 | 福州大学 | A kind of random polyarylether electrode active material and preparation method thereof containing purpurine side chain |
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