CN111116401A - Preparation method of C7 side chain substituted fluorine-containing diamine monomer - Google Patents
Preparation method of C7 side chain substituted fluorine-containing diamine monomer Download PDFInfo
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- CN111116401A CN111116401A CN201911333086.9A CN201911333086A CN111116401A CN 111116401 A CN111116401 A CN 111116401A CN 201911333086 A CN201911333086 A CN 201911333086A CN 111116401 A CN111116401 A CN 111116401A
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- 150000004985 diamines Chemical class 0.000 title claims abstract description 38
- 239000000178 monomer Substances 0.000 title claims abstract description 37
- 229910052731 fluorine Inorganic materials 0.000 title claims description 25
- 239000011737 fluorine Substances 0.000 title claims description 25
- 238000002360 preparation method Methods 0.000 title claims description 14
- 125000001153 fluoro group Chemical class F* 0.000 title claims 14
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 15
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims description 47
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- 239000012065 filter cake Substances 0.000 claims description 18
- 238000001914 filtration Methods 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 16
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- NSGXIBWMJZWTPY-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropane Chemical compound FC(F)(F)CC(F)(F)F NSGXIBWMJZWTPY-UHFFFAOYSA-N 0.000 claims description 13
- 238000010791 quenching Methods 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 10
- 239000000706 filtrate Substances 0.000 claims description 10
- 230000000171 quenching effect Effects 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- 238000001291 vacuum drying Methods 0.000 claims description 10
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-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 8
- 239000012295 chemical reaction liquid Substances 0.000 claims description 8
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 8
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- NXTNASSYJUXJDV-UHFFFAOYSA-N 3-nitrobenzoyl chloride Chemical compound [O-][N+](=O)C1=CC=CC(C(Cl)=O)=C1 NXTNASSYJUXJDV-UHFFFAOYSA-N 0.000 claims description 6
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 6
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 239000006227 byproduct Substances 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 238000004537 pulping Methods 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- 125000005036 alkoxyphenyl group Chemical group 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims 1
- 229920001721 polyimide Polymers 0.000 abstract description 23
- 239000004642 Polyimide Substances 0.000 abstract description 22
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 229920000642 polymer Polymers 0.000 abstract description 8
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 abstract description 4
- 230000003287 optical effect Effects 0.000 abstract description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 3
- 125000000217 alkyl group Chemical group 0.000 abstract description 2
- 125000005462 imide group Chemical group 0.000 abstract description 2
- 230000003993 interaction Effects 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract 1
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 10
- 150000002221 fluorine Chemical class 0.000 description 10
- 239000011521 glass Substances 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 2
- YGYCECQIOXZODZ-UHFFFAOYSA-N 4415-87-6 Chemical compound O=C1OC(=O)C2C1C1C(=O)OC(=O)C12 YGYCECQIOXZODZ-UHFFFAOYSA-N 0.000 description 2
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 125000001246 bromo group Chemical group Br* 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- LJMPOXUWPWEILS-UHFFFAOYSA-N 3a,4,4a,7a,8,8a-hexahydrofuro[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1C2C(=O)OC(=O)C2CC2C(=O)OC(=O)C21 LJMPOXUWPWEILS-UHFFFAOYSA-N 0.000 description 1
- PQHCQWFFYWTDHE-UHFFFAOYSA-N 4-(1,1,1,3,3,3-hexafluoropropan-2-yl)-2-benzofuran-1,3-dione Chemical compound FC(C(C(F)(F)F)C1=C2C(C(=O)OC2=O)=CC=C1)(F)F PQHCQWFFYWTDHE-UHFFFAOYSA-N 0.000 description 1
- DHRKBGDIJSRWIP-UHFFFAOYSA-N 4-(4-aminophenyl)-2,3-bis(trifluoromethyl)aniline Chemical group C1=CC(N)=CC=C1C1=CC=C(N)C(C(F)(F)F)=C1C(F)(F)F DHRKBGDIJSRWIP-UHFFFAOYSA-N 0.000 description 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- QQGYZOYWNCKGEK-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)oxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC=2C=C3C(=O)OC(C3=CC=2)=O)=C1 QQGYZOYWNCKGEK-UHFFFAOYSA-N 0.000 description 1
- JVERADGGGBYHNP-UHFFFAOYSA-N 5-phenylbenzene-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C=2C=CC=CC=2)=C1C(O)=O JVERADGGGBYHNP-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000009918 complex formation Effects 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- RZIPTXDCNDIINL-UHFFFAOYSA-N cyclohexane-1,1,2,2-tetracarboxylic acid Chemical compound OC(=O)C1(C(O)=O)CCCCC1(C(O)=O)C(O)=O RZIPTXDCNDIINL-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000013086 organic photovoltaic Methods 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/12—Preparation of carboxylic acid amides by reactions not involving the formation of carboxamide groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
-
- 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention designs a polyimide diamine monomer C7-FBDA with an innovative structure, which realizes the simultaneous introduction of C7 side chain alkyl, trifluoromethyl, imide groups and a plurality of benzene ring structures in the molecular structure of the polyimide diamine monomer, breaks the regularity and crystallinity of polymer molecular chains, improves the free volume of a polymer, reduces the interaction among the molecular chains, and further greatly improves the film forming property and the optical transparency of polyimide. In the synthesis of the C7-FBDA, the invention develops an industrially applicable production process of the C7-FBDA, and the process has the advantages of short synthetic route, high yield, cheap and easily available raw materials, low production cost, simple and convenient operation, environmental friendliness, complete large-scale mass production and great industrial application value.
Description
Technical Field
The invention relates to the fields of fine chemistry and high molecular chemistry, in particular to the field of preparation of polyimide polymers.
Background
In recent years, with the development of photoelectric devices, the conventional transparent glass substrate cannot meet the requirements of flexible devices, and colorless and transparent high molecular polymers have the advantages of transparency, light weight, impact resistance and the like, so that the colorless and transparent high molecular polymers are increasingly emphasized in the fields of patterned display equipment, liquid crystal orientation films, optical thin films, organic photovoltaic solar panels, flexible printed circuit boards, touch panels and the like. Polyimide has excellent high temperature resistance, dielectric property and machining property, and is the first choice for replacing glass substrates. However, it is critical for conventional polyimides to improve their light transmission properties.
The traditional polyimide is generally a brown or brown yellow transparent material, which is because the polyimide molecular structure has stronger electron donor (diamine) and electron acceptor (dianhydride), and a strong charge transfer complex effect is formed in the polyimide molecular chain or among the molecular chains, so that the molecular chains are tightly stacked, and the polyimide has strong absorption in the visible light range; and the stronger the electron donating and withdrawing ability of the diamine and dianhydride residual groups, the greater the extent of charge transfer complex formation and the easier it is to absorb light, the darker the polyimide color (Asahi et al, Doi: 10.14133/j. cnki.1008-9357.20190705001, in the blue).
The trifluoromethyl with larger free volume, the long side chain group and a plurality of benzene ring structures are introduced into the polyimide structure, so that the charge transfer complex function in the polyimide molecular chain and among the molecular chains can be effectively reduced, the light transmittance of the polyimide is further improved, and the high-transparency fluorine-containing polyimide film material is finally prepared. Polyimide is generally prepared by condensation polymerization of diamine and dianhydride, and the optimization of the polyimide performance can be realized by modifying the molecular structure of the diamine or the dianhydride. Currently, 8 kinds of dianhydride monomers have been commercially used, including cyclohexane tetracarboxylic dianhydride (HPMDA), pyromellitic dianhydride (PMDA), cyclobutane tetracarboxylic dianhydride (CBDA), hexafluoroisopropyl phthalic anhydride (6FDA), diphenyl ether tetracarboxylic dianhydride (ODPA), Benzophenone Tetracarboxylic Dianhydride (BTDA), biphenyl tetracarboxylic dianhydride (BPDA), and bisphenol a type diether dianhydride (BPADA). Diamine monomers are relatively few compared to dianhydride monomers, and only two are currently commercially available, bis (trifluoromethyl) diaminobiphenyl (TFMB) and diaminodiphenyl ether (ODA), respectively. The reason is mainly because diamine monomers with innovative structures generally have large molecular weights, the reduction of nitro groups is difficult, and the production cost is relatively high, which limits the development of polyimide to a certain extent. Therefore, the diamine monomer with an innovative structure is designed, the production process is innovated, the large-scale production is realized, and the method is very beneficial to promoting the development of the polyimide industry.
Based on the technical scheme, the invention designs a diamine monomer (chemical structural formula is shown in figure 1 and is abbreviated as C7-FBDA) with an innovative structure, develops an industrially applicable synthesis process, and realizes the efficient production of C7-FBDA by optimizing a reaction route.
Disclosure of Invention
The purpose of the invention is as follows: (1) through the innovation of a molecular structure, more functionality is endowed to a diamine monomer, and particularly, the simultaneous introduction of C7 side chain alkyl, trifluoromethyl, imide groups and a plurality of benzene ring structures is realized in a C7-FBDA molecular structure, the regularity and crystallinity of a polymer molecular chain are broken, the free volume of a polymer is improved, the interaction among the molecular chains is reduced, and the film-forming property and the optical transparency of polyimide are greatly improved. (2) Develops a production process of C7-FBDA which can be applied industrially, and realizes the high-efficiency synthesis of C7-FBDA by optimizing a reaction route. (3) Enriches the varieties of diamine monomers and promotes the development of the polyimide industry to a certain extent.
The invention content is as follows:
the synthesis of C7-FBDA is divided into three steps.
The first step is as follows: adding 2, 2-bis (3-amino-4-sodium phenolate) hexafluoropropane, bromo-C7 alkane and solvent N, N-Dimethylacetamide (DMAC) into a reaction kettle, stirring and heating, keeping the temperature for reaction for a period of time, filtering while the mixture is hot, removing a by-product sodium bromide generated in the reaction, cooling the filtrate to room temperature, adding water for quenching, wherein a large amount of solid appears, performing suction filtration again, and sequentially washing and vacuum-drying a filter cake to obtain a pure 2, 2-bis (3-amino-4-C7 alkoxyphenyl) hexafluoropropane (C7-FN) product, wherein the chemical structural formula of the pure 2, 2-bis (3-amino-4-C7 alkoxyphenyl) hexafluoropropane is shown in figure 2.
The second step is that: adding C7-FN and solvent N-methyl pyrrolidone (NMP), stirring and cooling with a jacket, slowly dropwise adding mixed solution of m-nitrobenzoyl chloride and NMP into the reaction kettle, continuously reacting until the raw materials react completely, slowly adding the reaction solution into methanol to quench, wherein a large amount of solid appears, filtering, washing the filter cake with methanol and water in sequence, and then carrying out vacuum drying treatment to obtain the pure C7-FBDN, wherein the chemical structural formula of the pure C7-FBDN is shown in figure 3.
The third step: adding C7-FBDN, palladium carbon catalyst and solvent N, N-Dimethylformamide (DMF) into a reaction kettle under the protection of nitrogen, starting stirring and heating, then slowly dropwise adding hydrazine hydrate solution into the reaction kettle, after dropwise adding, keeping the temperature for reaction until the C7-FBDN completely reacts, then closing heating, filtering the reaction liquid while hot, slowly dropwise adding filtrate into water for quenching, wherein a large amount of solids appear at the moment, filtering again, and sequentially pulping and purifying a filter cake by ethanol and drying in vacuum to obtain the pure C7-FBDA.
The general synthetic route of C7-FBDA is shown in FIG. 4.
The preparation method of the C7 side chain substituted fluorine-containing diamine monomer is characterized in that in the first step of synthesis reaction, the molar feeding ratio of bromo-C7 alkane and 2, 2-bis (3-amino-4-sodium phenolate) hexafluoropropane is 2: 1-10: 1, and the preferable molar feeding ratio is 2: 1-3: 1.
The preparation method of the C7 side chain substituted fluorine-containing diamine monomer is characterized in that in the first step of synthesis reaction, the concentration of 2, 2-bis (3-amino-4-sodium phenolate) hexafluoropropane in a solvent DMAC is 0.1-2.0mol/L, and the preferable concentration is 1.1-1.6 mol/L.
The preparation method of the C7 side chain substituted fluorine-containing diamine monomer is characterized in that in the first step of the synthesis reaction, the reaction temperature is controlled between 80 and 166 ℃, preferably between 120 and 130 ℃.
The preparation method of the C7 side chain substituted fluorine-containing diamine monomer is characterized in that in the second step of synthesis reaction, the molar charge ratio of m-nitrobenzoyl chloride to C7-FN is 2: 1-10: 1, and the preferred molar charge ratio is 2: 1-3: 1.
The preparation method of the C7 side chain substituted fluorine-containing diamine monomer is characterized in that in the second step of synthesis reaction, the concentration of C7-FN in NMP solvent is 0.1-2.0mol/L, and the preferable concentration is 0.5-1.5 mol/L.
The preparation method of the C7 side chain substituted fluorine-containing diamine monomer is characterized in that in the second step of synthesis reaction, the temperature of reaction liquid is controlled between 0 and 50 ℃, preferably between 20 and 30 ℃ when the mixed solution of C7-FN and NMP is dripped.
The preparation method of the C7 side chain-substituted fluorine-containing diamine monomer is characterized in that in the third step of synthesis reaction, the feeding weight ratio of palladium carbon to C7-FBDN is 0.05: 1-0.1: 1, and the preferable feeding weight ratio is 0.05: 1-0.08: 1.
The preparation method of the C7 side chain-substituted fluorine-containing diamine monomer is characterized in that in the third step of synthesis reaction, the feeding molar ratio of hydrazine hydrate to C7-FBDN is 30: 1-50: 1, and the preferable feeding molar ratio is 30: 1-35: 1.
The preparation method of the C7 side chain substituted fluorine-containing diamine monomer is characterized in that in the third step of synthesis reaction, the temperature of reaction liquid is controlled between 65 and 95 ℃, preferably between 75 and 90 ℃ when hydrazine hydrate is dripped.
Has the advantages that: the invention focuses on the design and preparation of diamine monomers with innovative structures, and particularly introduces a trifluoromethyl group with strong electronegativity, a long-chain C7 alkyl substituent and a rigid non-planar structure when designing a C7-FBDA molecular structure, so that the orderliness and symmetry of a molecular chain are effectively reduced, the accumulation of the molecular chain of a polyimide polymer is reduced, the space free volume of the molecular chain is increased to a certain extent, the conjugation among chains is disturbed, the formation of charge transfer complexes among molecules and in molecules is further inhibited or reduced, the absorption of polyimide in a visible light region is finally reduced, and the light transmittance of a film is greatly improved. In the synthesis of C7-FBDA, the invention selects a shorter synthetic route, has higher synthesis yield, uses cheap and easily available raw materials, has lower production cost, is simple and convenient to operate, is environment-friendly, can completely realize large-scale mass production and has great industrial application value.
Description of the drawings:
FIG. 1: C7-FBDA structural formula.
FIG. 2: C7-FN structural formula.
FIG. 3: C7-FBDN structural formula.
FIG. 4: C7-FBDA general synthetic route.
Detailed Description
Example 1
The first step is as follows: sequentially adding 1.2L of DMAC, 1000g of 2, 2-bis (3-amino-4-sodium phenolate) hexafluoropropane and 868g of bromo C7 alkane into a 10L four-mouth reaction bottle, starting stirring and heating, maintaining at 80 ℃ for reaction for 2-3h, closing heating after the reaction of raw materials is finished, pouring out reaction liquid, filtering while hot, collecting and storing an upper layer of filter cake which is a byproduct sodium bromide, naturally cooling the filtrate to room temperature, adding the filtrate into 2.4L of water for quenching, wherein a large amount of solid appears, performing suction filtration, washing the filter cake with 3.5L of water, draining, and performing vacuum drying on the filter cake to obtain a pure 1234g C7-FN product.
The second step is that: A10L four-necked reaction flask was charged with 1234g C7-FN and 550mL of NMP, and after stirring was started, a mixture of 812g of m-nitrobenzoyl chloride and 550mL of NMP was slowly added dropwise thereto while controlling the temperature of the reaction mixture at about 50 ℃. After dripping, the reaction is continued for 2 to 3 hours at the temperature of 50 ℃. After the reaction of the raw materials is finished, slowly pouring the reaction liquid into 2200mL of methanol for quenching, wherein a large amount of solid appears, filtering, washing a filter cake with 1000mL of methanol and 1000mL of water in sequence, and performing vacuum drying treatment on the obtained filter cake to obtain a 169 1699g C7-FBDN pure product.
The third step: under the protection of nitrogen, 3500mL of DMF, 169 1699g C7-FBDN and 85g of palladium carbon catalyst (palladium content is 10%) are added into a 10L four-neck flask, stirring and heating are started, 3500mL of hydrazine hydrate solution (concentration: about 17mol/L) is slowly dripped into the reaction flask when the temperature of the reaction solution rises to 65 ℃, the temperature of the reaction solution is controlled to be about 65 ℃ when dripping is finished, and the temperature is kept at 65 ℃ for continuous reaction for 2-3 h. And after the reaction of the raw material C7-FBDN is finished, turning off heating, filtering the hot reaction solution, slowly dropwise adding the filtrate into 7000mL of water for quenching, wherein a large amount of solid appears, filtering again, pulping and purifying the filter cake by 3500mL of ethanol, and then carrying out vacuum drying treatment to obtain the pure 1423g C7-FBDA product.
Example 2
The first step is as follows: adding 24.3L of DMAC, 1000g of 2, 2-bis (3-amino-4-sodium phenolate) hexafluoropropane and 4342g of bromo C7 alkane into a 30L double-layer glass reaction kettle in sequence, starting stirring and heating, keeping at 166 ℃ for reacting for 2-3h, closing heating after the reaction of raw materials is finished, discharging reaction liquid, filtering while hot, collecting and storing an upper layer of filter cake which is a byproduct sodium bromide, naturally cooling the filtrate to room temperature, adding the filtrate into 48.6L of water for quenching, wherein a large amount of solid appears at the moment, performing suction filtration, washing the filter cake with 3.5L of water, draining, and performing vacuum drying on the filter cake to obtain a 1303g C7-FN pure product.
The second step is that: 1303g C7-FN and 11.5L NMP were added into a 30L double-layer glass reaction kettle, stirring and jacket cooling were started, and after the temperature of the reaction solution was lowered to 0 deg.C, a mixture of 4286g of m-nitrobenzoyl chloride and 11.5L NMP was slowly added dropwise thereto while controlling the temperature of the reaction solution at about 0 deg.C. After the dripping is finished, the temperature is kept at 0 ℃ for continuous reaction for 2 to 3 hours. After the raw materials are completely reacted, slowly pouring the reaction liquid into 46L of methanol for quenching, wherein a large amount of solid appears, filtering, washing a filter cake with 1000mL of methanol and 1000mL of water in sequence, and carrying out vacuum drying treatment on the obtained filter cake to obtain a pure product 1894g C7-FBDN.
The third step: under the protection of nitrogen, 6500mL of DMF, 1894g C7-FBDN and 189.4g of palladium-carbon catalyst (palladium content is 10%) are added into a 30L double-layer glass reaction kettle, stirring and heating are started, 6500mL of hydrazine hydrate solution (concentration: about 17mol/L) is slowly dripped into a reaction bottle when the temperature of the reaction solution rises to 95 ℃, the temperature of the reaction solution is controlled to be about 95 ℃ when dripping is finished, and the reaction is continued for 2-3h after the temperature is kept at 95 ℃. And after the reaction of the raw material C7-FBDN is finished, closing and heating, filtering the hot reaction solution, slowly dropwise adding the filtrate into 13L of water for quenching, wherein a large amount of solid appears, filtering again, pulping and purifying the filter cake by 6500mL of ethanol, and then carrying out vacuum drying treatment to obtain a 1674g C7-FBDA pure product.
Claims (13)
1. A preparation method of a C7 side chain substituted fluorine-containing diamine monomer is disclosed, wherein the chemical structure of the C7 side chain substituted fluorine-containing diamine monomer is shown as a formula 1 (abbreviated as C7-FBDA), and the synthesis of the monomer is divided into three steps.
2. A method for preparing C7 side chain substituted fluorine-containing diamine monomer is characterized in that the first operation step of the C7-FBDA synthesis is described as follows: adding 2, 2-bis (3-amino-4-sodium phenolate) hexafluoropropane, bromo-C7 alkane and solvent N, N-Dimethylacetamide (DMAC) into a reaction kettle, stirring and heating, filtering while the mixture is hot after the mixture is subjected to heat preservation reaction for a period of time, removing a by-product sodium bromide generated in the reaction, cooling the filtrate to room temperature, adding water for quenching, wherein a large amount of solid appears, performing suction filtration again, and sequentially washing and vacuum-drying filter cakes to obtain a pure 2, 2-bis (3-amino-4-C7 alkoxyphenyl) hexafluoropropane (C7-FN) product with a chemical structural formula shown in formula 2.
3. A method for preparing C7 side chain substituted fluorine-containing diamine monomer is characterized in that the second operation step of the C7-FBDA synthesis is described as follows: adding C7-FN and solvent N-methyl pyrrolidone (NMP), stirring and cooling by a jacket, slowly dropwise adding mixed solution of m-nitrobenzoyl chloride and NMP into the reaction kettle, continuously reacting until the raw materials react completely, slowly adding the reaction solution into methanol to quench, filtering, washing the filter cake with methanol and water in sequence, and vacuum drying to obtain the pure C7-FBDN with the chemical structural formula shown in formula 3.
4. A method for preparing C7 side chain substituted fluorine-containing diamine monomer is characterized in that the third operation step of the C7-FBDA synthesis is described as follows: adding C7-FBDN, palladium carbon catalyst and solvent N, N-Dimethylformamide (DMF) into a reaction kettle under the protection of nitrogen, starting stirring and heating, then slowly dropwise adding hydrazine hydrate solution into the reaction kettle, after dropwise adding, keeping the temperature for reaction until the C7-FBDN completely reacts, then closing heating, filtering the reaction liquid while hot, slowly dropwise adding filtrate into water for quenching, wherein a large amount of solids appear at the moment, filtering again, and sequentially pulping and purifying a filter cake by ethanol and drying in vacuum to obtain the pure C7-FBDA.
5. The method for preparing the C7 side chain substituted fluorine-containing diamine monomer as claimed in claim 1 and claim 2, wherein the molar charge ratio of the bromo-C7 alkane to the 2, 2-bis (3-amino-4-sodium phenoxide) hexafluoropropane is 2: 1-10: 1, preferably 2: 1-3: 1.
6. The method for preparing C7 side chain-substituted fluorine-containing diamine monomer according to claim 1 and claim 2, wherein the concentration of 2, 2-bis (3-amino-4-sodium phenoxide) hexafluoropropane in solvent DMAC is 0.1-2.0mol/L, preferably 1.1-1.6 mol/L.
7. The method for preparing C7 side chain substituted fluorine-containing diamine monomer as claimed in claim 1 and claim 2, wherein the reaction temperature is controlled between 80-166 ℃, preferably between 120-130 ℃.
8. The method for preparing C7 side-chain-substituted fluorine-containing diamine monomer as claimed in claim 1 and claim 3, wherein the molar charge ratio of m-nitrobenzoyl chloride to C7-FN is 2: 1-10: 1, preferably 2: 1-3: 1.
9. The method for preparing a C7 side-chain substituted fluorine-containing diamine monomer as claimed in claim 1 and claim 3, wherein the concentration of C7-FN in NMP solvent is 0.1-2.0mol/L, preferably 0.5-1.5 mol/L.
10. The method for preparing a fluorinated diamine monomer having a side chain substituted with C7 according to claims 1 and 3, wherein the temperature of the reaction solution is controlled to be between 0-50 ℃, preferably between 20-30 ℃ when a mixture of C7-FN and NMP is added dropwise.
11. The method for preparing C7 side-chain-substituted fluorine-containing diamine monomer as claimed in claim 1 and claim 4, wherein the ratio of palladium carbon to C7-FBDN is 0.05: 1-0.1: 1, preferably 0.05: 1-0.08: 1.
12. The method for preparing C7 side-chain-substituted fluorine-containing diamine monomer as claimed in claim 1 and claim 4, wherein the feeding molar ratio of hydrazine hydrate to C7-FBDN is 30: 1-50: 1, preferably 30: 1-35: 1.
13. The method for preparing C7 side chain substituted fluorine-containing diamine monomer as claimed in claim 1 and claim 4, wherein the temperature of the reaction solution is controlled between 65-95 deg.C, preferably between 75-90 deg.C, when hydrazine hydrate is added dropwise.
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