CN113480716A - Polyaromatic hydrocarbon with main chain containing perfluoroarene and perfluoroalkane and preparation method thereof - Google Patents
Polyaromatic hydrocarbon with main chain containing perfluoroarene and perfluoroalkane and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 title description 3
- 229920000642 polymer Polymers 0.000 claims abstract description 27
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 19
- 239000000178 monomer Substances 0.000 claims abstract description 19
- VBZWSGALLODQNC-UHFFFAOYSA-N hexafluoroacetone Chemical compound FC(F)(F)C(=O)C(F)(F)F VBZWSGALLODQNC-UHFFFAOYSA-N 0.000 claims abstract description 16
- QJPLLYVRTUXAHZ-UHFFFAOYSA-N 1,1,1,3,3,4,4,4-octafluorobutan-2-one Chemical compound FC(F)(F)C(=O)C(F)(F)C(F)(F)F QJPLLYVRTUXAHZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 10
- 239000011737 fluorine Substances 0.000 claims abstract description 10
- 239000003960 organic solvent Substances 0.000 claims abstract description 9
- 239000003377 acid catalyst Substances 0.000 claims abstract description 8
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 15
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 14
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 13
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 10
- -1 perfluoroalkyl ketone Chemical class 0.000 claims description 8
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 8
- YFAAPDSUPCJZBM-UHFFFAOYSA-N 1,2,4,5-tetrafluoro-3-(2,3,5,6-tetrafluorophenoxy)benzene Chemical compound FC1=CC(F)=C(F)C(OC=2C(=C(F)C=C(F)C=2F)F)=C1F YFAAPDSUPCJZBM-UHFFFAOYSA-N 0.000 claims description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 6
- SDXUIOOHCIQXRP-UHFFFAOYSA-N 1,2,4,5-tetrafluorobenzene Chemical compound FC1=CC(F)=C(F)C=C1F SDXUIOOHCIQXRP-UHFFFAOYSA-N 0.000 claims description 5
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 5
- KULDEWSCRMZBQI-UHFFFAOYSA-N 1,2,3,4,5,6,7,8-octafluoroanthracene Chemical compound FC1=C(F)C(F)=C(F)C2=CC3=C(F)C(F)=C(F)C(F)=C3C=C21 KULDEWSCRMZBQI-UHFFFAOYSA-N 0.000 claims description 3
- UGHVWMVKWCJJPZ-UHFFFAOYSA-N 1,2,3,4,6,7-hexafluoronaphthalene Chemical compound FC1=C(F)C(F)=C2C=C(F)C(F)=CC2=C1F UGHVWMVKWCJJPZ-UHFFFAOYSA-N 0.000 claims description 3
- INYWUOKJBGAYRT-UHFFFAOYSA-N 1,2,3,5,6,7-hexafluoronaphthalene Chemical compound FC1=C(F)C=C2C(F)=C(F)C(F)=CC2=C1F INYWUOKJBGAYRT-UHFFFAOYSA-N 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000007334 copolymerization reaction Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000012716 precipitator Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 claims 3
- 238000005406 washing Methods 0.000 claims 1
- 229920005989 resin Polymers 0.000 abstract description 13
- 239000011347 resin Substances 0.000 abstract description 13
- 239000000463 material Substances 0.000 abstract description 7
- 230000009477 glass transition Effects 0.000 abstract description 4
- 125000000217 alkyl group Chemical group 0.000 abstract description 3
- 239000002131 composite material Substances 0.000 abstract description 2
- 239000011159 matrix material Substances 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- 238000005979 thermal decomposition reaction Methods 0.000 abstract description 2
- 230000004580 weight loss Effects 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 239000012065 filter cake Substances 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 17
- 239000000047 product Substances 0.000 description 15
- 239000003054 catalyst Substances 0.000 description 11
- 238000009835 boiling Methods 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 10
- 239000002244 precipitate Substances 0.000 description 10
- 230000001376 precipitating effect Effects 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 150000001335 aliphatic alkanes Chemical class 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 230000001012 protector Effects 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000002411 thermogravimetry Methods 0.000 description 3
- VKPSKYDESGTTFR-UHFFFAOYSA-N 2,2,4,6,6-pentamethylheptane Chemical compound CC(C)(C)CC(C)CC(C)(C)C VKPSKYDESGTTFR-UHFFFAOYSA-N 0.000 description 2
- ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 2,3-dimethylbutane Chemical compound CC(C)C(C)C ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 0.000 description 2
- WGECXQBGLLYSFP-UHFFFAOYSA-N 2,3-dimethylpentane Chemical compound CCC(C)C(C)C WGECXQBGLLYSFP-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- ZQBFAOFFOQMSGJ-UHFFFAOYSA-N hexafluorobenzene Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1F ZQBFAOFFOQMSGJ-UHFFFAOYSA-N 0.000 description 2
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical compound FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000012643 polycondensation polymerization Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 2
- FHUDAMLDXFJHJE-UHFFFAOYSA-N 1,1,1-trifluoropropan-2-one Chemical compound CC(=O)C(F)(F)F FHUDAMLDXFJHJE-UHFFFAOYSA-N 0.000 description 1
- MIZLGWKEZAPEFJ-UHFFFAOYSA-N 1,1,2-trifluoroethene Chemical group FC=C(F)F MIZLGWKEZAPEFJ-UHFFFAOYSA-N 0.000 description 1
- LERDAFCBKALCKT-UHFFFAOYSA-N 1,2,3,4,5-pentafluoro-6-(2,3,4-trifluorophenyl)benzene Chemical group FC1=C(F)C(F)=CC=C1C1=C(F)C(F)=C(F)C(F)=C1F LERDAFCBKALCKT-UHFFFAOYSA-N 0.000 description 1
- QWCHHUZAAGRHDB-UHFFFAOYSA-N 1,2,4,5-tetrafluoro-3-(2,3,5,6-tetrafluorophenyl)benzene Chemical group FC1=CC(F)=C(F)C(C=2C(=C(F)C=C(F)C=2F)F)=C1F QWCHHUZAAGRHDB-UHFFFAOYSA-N 0.000 description 1
- IQXYRXOYBYUMLV-UHFFFAOYSA-N 1-fluoro-2-(2-phenylphenyl)benzene Chemical group FC1=CC=CC=C1C1=CC=CC=C1C1=CC=CC=C1 IQXYRXOYBYUMLV-UHFFFAOYSA-N 0.000 description 1
- NOFQKTWPZFUCOO-UHFFFAOYSA-N 2,2,4,4,6-pentamethylheptane Chemical compound CC(C)CC(C)(C)CC(C)(C)C NOFQKTWPZFUCOO-UHFFFAOYSA-N 0.000 description 1
- BZHMBWZPUJHVEE-UHFFFAOYSA-N 2,3-dimethylpentane Natural products CC(C)CC(C)C BZHMBWZPUJHVEE-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- IYRWEQXVUNLMAY-UHFFFAOYSA-N carbonyl fluoride Chemical compound FC(F)=O IYRWEQXVUNLMAY-UHFFFAOYSA-N 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- KYKAJFCTULSVSH-UHFFFAOYSA-N chloro(fluoro)methane Chemical compound F[C]Cl KYKAJFCTULSVSH-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000009439 industrial construction Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 239000006174 pH buffer Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920005548 perfluoropolymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
Images
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
-
- 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
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/12—Copolymers
- C08G2261/122—Copolymers statistical
-
- 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
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/14—Side-groups
- C08G2261/146—Side-chains containing halogens
-
- 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
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/31—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
- C08G2261/312—Non-condensed aromatic systems, e.g. benzene
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a polymer with a main chain containing perfluorinated aromatic hydrocarbon and a perfluorinated alkyl chain and a preparation method thereof, belonging to the technical field of synthesis of high polymer materials. The structure of the polymer simultaneously has perfluoroarene and perfluoroalkyl chain, and has a structural formula shown in a formula I. The preparation method comprises the following steps: the polymer is prepared by taking a fluorine-containing aromatic hydrocarbon monomer, a hexafluoroacetone monomer and an octafluoro-2-butanone monomer as raw materials and carrying out nucleophilic substitution reaction in an organic solvent in the presence of an acid catalyst. The polymer has better solubility in common organic solvents, higher glass transition temperature (>300 ℃) and higher thermal decomposition temperature (5% thermal weight loss temperature >450 ℃), is suitable for being used as a high-performance structural material, and can also be used as a composite material matrix resin or a functional film material.
Description
Technical Field
The invention belongs to the technical field of polymers, and particularly relates to a perfluorinated polyaromatic hydrocarbon material and a preparation method thereof.
Background
Perfluoropolymers, because of their many unique structures, exhibit a number of special properties, such as: fluorine atoms have low polarizability, strong electronegativity, small van der waals radius and strong C-F bond energy (485kJ/mol), so that the fluorocarbon polymer with high fluorine content has high heat resistance, chemical corrosion resistance, durability and weather resistance, especially the inertness to many solvents, hydrocarbons and various acids and bases, low capacitance, low flammability, low refractive index, low surface energy (neither oleophilic nor hydrophilic) and moisture absorption performance. Moreover, the strong C-F bond enables such polymers to have very strong stability to redox. The polymer is widely applied to the fields of industrial construction (used as an inner and outer wall coating and used for preventing ultraviolet rays and noise), petrochemical and automobile industries, aerospace industries (used for gaskets and films in the form of elastomers and used on containers required for containing liquid hydrogen for space shuttles at extremely low temperature), chemical engineering (used for high-performance films), optics (used for inner cores and attached layers of optical fibers), treatment of textile articles, treatment of cultural stone tablets, microelectronics and the like.
Most of the currently used perfluoro resins are made of fluoroolefin, TFE (tetrafluoroethylene), HFP (hexafluoropropylene), trifluoroethylene and the like, the number of carbon atoms of which is between 2 and 4, and the dispersion medium is usually a chlorofluorocarbon organic solvent, but these substances have a certain effect of destroying the ozone layer, and recently, methyl branched hydrocarbons such as 2, 3-dimethylbutane, 2, 3-dimethylpentane, 2,2, 4-trimethylpentane, 2,2,4,6, 6-pentamethylheptane and 2,2,4,4, 6-pentamethylheptane are mainly used, but these methylated hydrocarbons are not expensive and are not feasible from the viewpoint of industrialization. Furthermore, the above reaction requires the use of an initiator, a pH buffer, a polymerization regulator, etc., and also requires many requirements for reaction temperature, reaction pressure, and stirring rate, for example: the initial reaction temperature is preferably 10 to 80 ℃. The reaction pressure is preferably 4 to 30 kg/cm. The stirring rate is preferably 50 to 700 rpm. The reaction time is preferably 1 to 20 hours.
In order to expand the processing means and application range of the perfluorinated high polymer material and improve the use temperature of the material, aiming at exploring a novel aromatic perfluorinated structure, it is necessary to explore amorphous poly-perfluorinated aromatic hydrocarbon and alkyl-containing resin obtained by condensation polymerization of fluorine-containing aromatic hydrocarbon and perfluorinated ketone, and develop resin with excellent performances such as chemical corrosion resistance, atmospheric aging resistance, excellent dielectric property, unique low surface energy, wide use temperature range and the like, so that the comprehensive performance of the resin can be comparable with that of polytetrafluoroethylene and polyvinylidene fluoride, and the resin has excellent dissolution processability and can greatly improve the application field of the resin.
Disclosure of Invention
The perfluoro polyaromatic hydrocarbon of the invention uses the resin which is obtained by condensation polymerization of fluorine-containing aromatic hydrocarbon and perfluoro-substituted ketone and contains amorphous perfluoro aromatic hydrocarbon and alkyl, can endow the polymer with good solubility and excellent heat resistance and hydrophobicity (super-large hydrophobic angle), and can widen the application of the polymer in the fields of films, separation membranes, coatings, insulating paints and the like.
The purpose of the invention is realized by the following technical scheme:
the main chain of the polyaromatic alkane contains a perfluorinated aromatic hydrocarbon and a perfluorinated methylene structure, and the structure of the polyaromatic alkane simultaneously has a perfluorinated alkane substituent.
Among the above-mentioned polyarylalkanes, as a preferred embodiment, said polyarylalkanes have the structural formula represented by formula I:
wherein m is more than or equal to 0 and less than or equal to 1, n is more than or equal to 0 and less than or equal to 1, and m + n is equal to 1; ar is any one of structures (a) to (h):
r is one or two of (i) or (j):
in the above perfluoroaromatic resin, as a preferred embodiment, the perfluoroaromatic resin has a number average molecular weight of 1 x 10 as measured by GPC4~6*104。
The preparation method of the polyaromatic resin with the main chain perfluorinated aromatic hydrocarbon and the perfluoroalkyl group structure takes a fluorine-containing aromatic hydrocarbon monomer and a perfluoroalkyl group ketone monomer as raw materials, and obtains the perfluorinated polyaromatic resin through homopolymerization or copolymerization reaction in the presence of a catalyst and a solvent.
In the above production method, as a preferred embodiment, the fluorine-containing aromatic hydrocarbon monomer is one of 1,2,4, 5-tetrafluorobenzene, 2',3,3',5,5',6,6' -octafluorobiphenyl, 3,3 '-oxybis (1,2,4, 5-tetrafluorobenzene), 2',2 ", 3,3', 3", 5,5',5 ", 6,6',6 ″ -dodecafluoroterphenyl, 3,3' - (perfluoro-1, 4-phenyl) bis (oxy) bis (1,2,4, 5-tetrafluorobenzene), 1,2,3,4,6, 7-hexafluoronaphthalene, 1,2,3,5,6, 7-hexafluoronaphthalene, 1,2,3,4,5,6,7, 8-octafluoroanthracene.
In the above production method, as a preferred embodiment, the perfluoroalkanone monomer is one or both of hexafluoroacetone and octafluoro-2-butanone.
The invention also provides a preparation method of the polymer containing the perfluorinated aromatic hydrocarbon and the perfluorinated alkane, which takes 1,2,4, 5-tetrafluorobenzene, hexafluoroacetone and octafluoro-2-butanone as raw materials as a preferred embodiment, and the reaction formula is as follows:
in the above preparation method, as a preferred embodiment, the preparation method is specifically as follows: mixing a mol of fluorine-containing aromatic hydrocarbon monomer, b mol of hexafluoroacetone monomer (dichloroethane solution of hexafluoroacetone) and c mol of octafluoro-2-butanone with an acid catalyst and an organic solvent, controlling the temperature to be-30-20 ℃ (such as-30 ℃, 20 ℃, 10 ℃, 0 ℃, 10 ℃ and 20 ℃), then reacting for 1-48 h (such as 1h, 5h, 10h, 15h, 24h, 35h and 48h), and adding a precipitator; then filtering, separating, cleaning and drying to obtain the perfluorinated polyaryl alkane copolymer; wherein a is b + c, a is more than 0, b is more than or equal to 0, and c is more than or equal to 0.
In the above preparation method, as a preferred embodiment, the acid catalyst is one or more of methanesulfonic acid, p-toluenesulfonic acid and trifluoromethanesulfonic acid, and the molar ratio of the fluorinated aromatic hydrocarbon monomer to the acid catalyst is 1:0.01 to 0.20 (for example: 1:0.01, 1:0.03, 1:0.08, 1:0.12, 1:0.16 and 1: 0.20).
In the above preparation method, as a preferred embodiment, the solvent is one of dichloromethane, chloroform and dichloroethane, and the amount of the solvent is 1.0-50.0 mL/1 g of the fluoroarene and perfluoroalkyl ketone monomer mixture (e.g., 1mL/g, 5mL/g, 10mL/g, 20mL/g, 30mL/g, 40mL/g, 50 mL/g).
In the above preparation method, as a preferred embodiment, the precipitant is one or both of ethanol and methanol.
The invention has the beneficial effects that:
1. the polymer structure of the invention has perfluorinated aromatic hydrocarbon group and perfluoroalkyl group at the same time, and the content of the two groups can be regulated and controlled; the polymer containing the two structures in the main chain has good solubility in common organic solvents, has high glass transition temperature (>300 ℃) and high thermal decomposition temperature (5% thermal weight loss temperature >450 ℃) and excellent hydrophobicity, is suitable for being used as a high-performance structural material, can also be used as a composite material matrix resin or a functional film material, and the like.
2. In the structure of the polymer, perfluorobenzene and perfluoroalkyl are connected through covalent bonds, but the solubility of the prepared polymer is also obviously improved because the two groups have larger free volumes; can be dissolved in common organic solvents such as chloroform, tetrahydrofuran, toluene and the like at normal temperature, and lays an important foundation for the application of the polymer in the aspects of membrane materials, epoxy toughening, coatings, high-temperature resistant coatings and the like.
3. In the preparation method, the temperature-resistant grade and the solubility of the polymer can be effectively regulated and controlled by regulating the proportion of hexafluoroacetone and octafluoro-2-butanone in the copolymer so as to adapt to the use requirements of different fields.
4. The polymer of the invention is a perfluoro-substituted polymer, so the polymer has the inertness of various acids and bases, low capacitance, low flammability, low refractive index, low surface energy (neither oleophilic nor hydrophilic) and moisture absorption performance. Moreover, the strong C-F bond enables such polymers to have very strong stability to redox.
Drawings
FIG. 1 is an IR spectrum of the product obtained in example 1;
FIG. 2 is a thermogravimetric analysis of the product obtained in example 1.
The specific implementation mode is as follows:
in order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
Adding 1,2,4, 5-tetrafluorobenzene (0.01mol, 1.50g), 0.005mol of hexafluoroacetone/dichloroethane solution and 0.005mol of octafluoro-2-butanone into a three-neck flask with a mechanical stirrer, a thermometer, a condenser and a nitrogen protection at-30 ℃, adding 0.0001mol of methanesulfonic acid as a catalyst and 1.5mL of dichloromethane as a solvent, heating to 0 ℃ for reaction for 1h, precipitating the reaction liquid in ethanol, filtering, and collecting a filter cake; the precipitate was boiled in boiling water and filtered several times, the filter cake was collected and vacuum dried at 110 ℃ for 24h to obtain a white product. The infrared spectrum of the product is shown in figure 1, and the thermogravimetric analysis (TGA) spectrum of the product is shown in figure 2.
Example 2
Adding 2,2',3,3',5,5',6,6' -octafluorobiphenyl (0.01mol, 29.81g), 0.01mol of hexafluoroacetone/dichloroethane solution into a three-neck flask provided with a mechanical stirrer, a thermometer, a condenser and a nitrogen protection device at-30 ℃, adding 14.9mL of chloroform as a solvent into 0.0003mol of trifluoromethanesulfonic acid as a catalyst, heating to 10 ℃, reacting for 15 hours, precipitating the reaction solution in methanol, filtering and collecting a filter cake; the precipitate was boiled in boiling water and filtered several times, the filter cake was collected and vacuum dried at 110 ℃ for 24h to obtain a white product.
Comparative example:
adding biphenyl (0.01mol, 1.54g) and 0.01mol of trifluoroacetone into a three-neck flask with a mechanical stirrer, a thermometer, a condenser tube and a nitrogen protection device at the temperature of minus 30 ℃, adding 14.9mL of chloroform as a solvent by taking 0.0003mol of trifluoromethanesulfonic acid as a catalyst, heating to 10 ℃, reacting for 15h, precipitating the reaction solution in methanol, filtering, and collecting a filter cake; the precipitate was boiled in boiling water and filtered several times, the filter cake was collected and vacuum dried at 110 ℃ for 24h to obtain a white product.
Example 3
Adding 3,3' -oxydi (1,2,4, 5-tetrafluorobenzene) (0.01mol and 3.14g) and 0.01mol of hexafluoroacetone/dichloroethane solution into a three-neck flask provided with a mechanical stirrer, a thermometer, a condenser and a nitrogen protection device at the temperature of-30 ℃, adding 31.41mL of dichloroethane as a solvent by taking 0.0008mol of trifluoromethanesulfonic acid as a catalyst, heating to 20 ℃, reacting for 10 hours, precipitating the reaction solution in methanol, filtering and collecting a filter cake; the precipitate was boiled in boiling water and filtered several times, the filter cake was collected and vacuum dried at 110 ℃ for 24h to obtain a white product.
Example 4
Adding 2,2',3,3',5,5',6,6' -dodecafluoroterphenyl (0.01mol, 4.46g), 0.008mol of hexafluoroacetone/dichloroethane solution and 0.002mol of octafluoro-2-butanone into a three-necked flask with a mechanical stirrer, a thermometer, a condenser and a nitrogen gas protector at-30 ℃, adding 89.24mL of dichloromethane serving as a solvent with 0.0012mol of methanesulfonic acid serving as a catalyst, heating to 30 ℃ for reaction for 15 hours, precipitating the reaction solution into ethanol, filtering, and collecting a filter cake; the precipitate was boiled in boiling water and filtered several times, the filter cake was collected and vacuum dried at 110 ℃ for 24h to obtain a white product.
Example 5
Adding 3,3' - ((perfluoro-1, 4-phenyl) di (oxy) di (1,2,4, 5-tetrafluorobenzene) (0.01mol, 4.78g) and 0.01mol of octafluoro-2-butanone into a three-neck flask provided with a mechanical stirrer, a thermometer, a condenser tube and a nitrogen gas protector at the temperature of-30 ℃, adding 143.46mL of chloroform as a solvent by taking 0.0016mol of p-toluenesulfonic acid as a catalyst, heating to 0 ℃ for reaction for 24 hours, precipitating the reaction liquid into methanol, filtering, collecting a filter cake, putting the precipitate into boiling water, filtering for several times, collecting the filter cake, and drying in vacuum at the temperature of 110 ℃ for 24 hours to obtain a white product.
Example 6
Adding 1,2,3,4,6, 7-hexafluoronaphthalene (0.01mol, 2.36g), 0.005mol of hexafluoroacetone/dichloroethane solution and 0.005mol of octafluoro-2-butanone into a three-necked flask provided with a mechanical stirrer, a thermometer, a condenser and a nitrogen gas protector at-30 ℃, taking 0.0020mol of trifluoromethanesulfonic acid as a catalyst, adding 9.44mL of dichloromethane as a solvent, heating to 10 ℃, reacting for 35 hours, precipitating the reaction solution in ethanol, filtering, and collecting a filter cake; the precipitate was boiled in boiling water and filtered several times, the filter cake was collected and vacuum dried at 110 ℃ for 24h to obtain a white product.
Example 7
Adding 1,2,3,5,6, 7-hexafluoronaphthalene (0.01mol, 2.36g) and 0.01mol of hexafluoroacetone/dichloroethane solution into a three-necked flask with a mechanical stirrer, a thermometer, a condenser and a nitrogen protection device at the temperature of-30 ℃, adding 11.81mL of dichloroethane as a solvent by taking 0.0001mol of methanesulfonic acid as a catalyst, heating to-20 ℃ for reaction for 48 hours, precipitating the reaction solution in ethanol, filtering and collecting a filter cake; the precipitate was boiled in boiling water and filtered several times, the filter cake was collected and vacuum dried at 110 ℃ for 24h to obtain a white product.
Example 8
Adding 1,2,3,4,5,6,7, 8-octafluoroanthracene (0.01mol, 3.22g), 0.007mol of hexafluoroacetone/dichloroethane solution and 0.003mol of octafluoro-2-butanone into a three-neck flask with a mechanical stirrer, a thermometer, a condenser and a nitrogen protection at-30 ℃, adding 0.0003mol of trifluoromethanesulfonic acid as a catalyst and 20mL of chloroform as a solvent, heating to 20 ℃, reacting for 5 hours, precipitating the reaction solution in methanol, filtering and collecting a filter cake; the precipitate was boiled in boiling water and filtered several times, the filter cake was collected and vacuum dried at 110 ℃ for 24h to obtain a white product.
Example 9
Adding 1,2,4, 5-tetrafluorobenzene (0.01mol, 1.50g), 0.003mol of hexafluoroacetone/dichloroethane solution and 0.007mol of octafluoro-2-butanone into a three-neck flask provided with a mechanical stirrer, a thermometer, a condenser and a nitrogen protection device at the temperature of-30 ℃, adding 0.002mol of trifluoromethanesulfonic acid as a catalyst and 75.0mL of dichloroethane as a solvent, heating to 10 ℃, reacting for 20 hours, precipitating the reaction solution in ethanol, filtering, and collecting a filter cake; the precipitate was boiled in boiling water and filtered several times, the filter cake was collected and vacuum dried at 110 ℃ for 24h to obtain a white product.
The products obtained in examples 1 to 9 were compared for overall performance, and the results were as follows:
as can be seen from the above table: when the fluoroterphenyl is adopted, the glass transition temperature is obviously improved by more than 400 ℃, but the solubility is obviously reduced. The optimal result is that octafluorobiphenyl is used for reacting with perfluoroketone, so that the glass transition temperature can be increased, and the solubility and the hydrophobicity can be improved.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be able to cover the technical solutions and the inventive concepts of the present invention within the technical scope of the present invention.
Claims (9)
1. A polymer with a main chain containing a perfluorinated aromatic hydrocarbon and perfluoroalkyl chain structure is characterized in that the polymer structure simultaneously contains perfluorinated aromatic hydrocarbon and perfluoroalkyl chain groups.
3. the polymer according to claim 1, characterized in that it has a number average molecular weight of 1 x 10 as determined by GPC4~6*104。
4. The method for preparing the polymer according to any one of claims 1 to 3, wherein a fluorine-containing aromatic hydrocarbon monomer and a perfluoroalkyl ketone monomer are used as raw materials, and the polymer with a main chain containing a perfluorinated aromatic hydrocarbon and a perfluoroalkyl chain structure is obtained by homopolymerization or copolymerization reaction in an organic solvent in the presence of an acid catalyst.
5. The method according to claim 4, wherein the fluorine-containing aromatic hydrocarbon monomer is one of 1,2,4, 5-tetrafluorobenzene, 2',3,3',5,5',6,6' -octafluorobiphenyl, 3,3 '-oxybis (1,2,4, 5-tetrafluorobenzene), 2',3,3',5,5',6,6 '-dodecafluoroterphenyl, 3,3' - (perfluoro-1, 4-phenyl) bis (oxy) bis (1,2,4, 5-tetrafluorobenzene), 1,2,3,4,6, 7-hexafluoronaphthalene, 1,2,3,5,6, 7-hexafluoronaphthalene, 1,2,3,4,5,6,7, 8-octafluoroanthracene.
6. The method according to claim 4, wherein the perfluoroalkanone monomer is one or both of hexafluoroacetone and octafluoro-2-butanone.
7. The preparation method according to claim 4, which is characterized by comprising the following steps: mixing a mol of fluorine-containing aromatic hydrocarbon monomer, b mol of hexafluoroacetone monomer and c mol of octafluoro-2-butanone with an acid catalyst and an organic solvent, controlling the temperature to be-30-20 ℃, reacting for 1-48 h, and adding a precipitator; filtering, separating, washing and drying to obtain the perfluoro polyaryl alkane copolymer; wherein a is b + c, a is more than 0, b is more than or equal to 0, and c is more than or equal to 0.
8. The preparation method of claim 7, wherein the acid catalyst is one or more of methanesulfonic acid, p-toluenesulfonic acid and trifluoromethanesulfonic acid, and the molar ratio of the fluorinated aromatic hydrocarbon monomer to the acid catalyst is 1: 0.01-0.20; the precipitant is one or two of ethanol and methanol.
9. The preparation method according to claim 4, wherein the organic solvent is one of dichloromethane, chloroform and dichloroethane, and the amount of the solvent is 1.0-50.0 mL/1 g of the monomer mixture of the fluoroarene and the perfluoroalkyl ketone.
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