CN110938004B - Preparation method of C14 side chain substituted fluorine-containing diamine monomer - Google Patents
Preparation method of C14 side chain substituted fluorine-containing diamine monomer Download PDFInfo
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- 150000004985 diamines Chemical class 0.000 title claims abstract description 34
- 239000000178 monomer Substances 0.000 title claims abstract description 33
- 229910052731 fluorine Inorganic materials 0.000 title claims description 22
- 239000011737 fluorine Substances 0.000 title claims description 22
- 238000002360 preparation method Methods 0.000 title claims description 14
- 125000001153 fluoro group Chemical class F* 0.000 title claims 11
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 claims abstract description 12
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 50
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 19
- 239000012065 filter cake Substances 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 14
- 239000012295 chemical reaction liquid Substances 0.000 claims description 13
- 238000001914 filtration Methods 0.000 claims description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- 238000010791 quenching Methods 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 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 11
- 239000000047 product Substances 0.000 claims description 11
- 239000000706 filtrate Substances 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 239000002904 solvent Substances 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
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 8
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- 230000000171 quenching effect Effects 0.000 claims description 7
- 238000005406 washing 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
- 238000001816 cooling Methods 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 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
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- 125000005036 alkoxyphenyl group Chemical group 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
- 238000004537 pulping Methods 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- BWWHTIHDQBHTHP-UHFFFAOYSA-N 2-nitrobenzoyl chloride Chemical compound [O-][N+](=O)C1=CC=CC=C1C(Cl)=O BWWHTIHDQBHTHP-UHFFFAOYSA-N 0.000 claims 1
- 239000007795 chemical reaction product Substances 0.000 claims 1
- 229920001721 polyimide Polymers 0.000 abstract description 22
- 239000004642 Polyimide Substances 0.000 abstract description 21
- 229920000642 polymer Polymers 0.000 abstract description 8
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 abstract description 4
- 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
- 230000003287 optical effect Effects 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 10
- 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
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 6
- 239000011521 glass Substances 0.000 description 5
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 4
- 229910052763 palladium Inorganic materials 0.000 description 4
- 239000010408 film Substances 0.000 description 3
- 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 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
- 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
- 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
- 238000001035 drying Methods 0.000 description 1
- 150000002221 fluorine Chemical class 0.000 description 1
- 230000002401 inhibitory effect 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
- 239000012788 optical film Substances 0.000 description 1
- 238000013086 organic photovoltaic Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
Classifications
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- 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
- C07C213/06—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton from hydroxy amines by reactions involving the etherification or esterification of hydroxy groups
-
- 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
- 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
- C07C237/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups
- C07C237/28—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atom of at least one of the carboxamide groups bound to a carbon atom of a non-condensed six-membered aromatic ring of the carbon skeleton
- C07C237/40—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atom of at least one of the carboxamide groups bound to a carbon atom of a non-condensed six-membered aromatic ring of the carbon skeleton having the nitrogen atom of the carboxamide group bound to a carbon atom of a six-membered aromatic ring
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- 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 C14-FBDA with an innovative structure, which realizes simultaneous introduction of C14 side chain alkyl, trifluoromethyl, imide groups and a plurality of benzene ring structures in the molecular structure, breaks the regularity and crystallinity of polymer molecular chains, improves the free volume of the polymer, reduces the interaction between the molecular chains, and further greatly improves the film forming property and optical transparency of polyimide. In the synthesis of C14-FBDA, the invention develops a production process of industrially applicable C14-FBDA, the process has the advantages of short synthesis route, high yield, low-cost and easily available raw materials, low production cost, simple and convenient operation, environmental friendliness, capability of realizing large-scale mass production and great industrial application value.
Description
Technical Field
The invention relates to the fields of fine chemistry and high polymer chemistry, in particular to the field of polyimide polymer preparation.
Background
In recent years, with development of photoelectric devices, the requirement of flexible devices cannot be met by the traditional transparent glass substrate, and colorless and transparent high-molecular polymers are increasingly valued in the fields of patterned display devices, liquid crystal alignment films, optical films, organic photovoltaic solar panels, flexible printed circuit boards, touch panels and the like due to the advantages of transparency, light weight, impact resistance and the like. Polyimide has excellent high temperature resistance, dielectric property and machining property, and is the first choice for replacing a glass substrate. But for conventional polyimide, it is critical to improve its light transmission properties.
Traditional polyimide is generally brown or brown transparent material, because of strong electron donor (diamine) and electron acceptor (dianhydride) in the molecular structure of polyimide, strong charge transfer complex is formed in polyimide molecular chains or among the molecular chains, so that the molecular chains are closely accumulated, and polyimide has strong absorption in the visible light range; and the more electron donating and withdrawing capabilities the diamine and dianhydride residual groups, the greater the extent of charge transfer complex formation, the more readily light absorbing, and the darker the polyimide color (Yuanhong et al, doi:10.14133/j. Cnki.1008-9357.20190705001).
The trifluoromethyl with larger free volume, long side chain groups and a plurality of benzene ring structures are introduced into the polyimide structure, so that the charge transfer complex in and among polyimide molecular chains can be effectively reduced, the light transmittance of polyimide is further improved, and the high-transparency fluorine-containing polyimide film material is finally prepared. Polyimide is generally formed by polycondensation of diamine and dianhydride, and the polyimide performance can be optimized by modifying the molecular structure of the diamine or the dianhydride. Currently, there are 8 dianhydride monomers that have been commercially used, including cyclohexane tetracarboxylic dianhydride (HPMDA), pyromellitic dianhydride (PMDA), cyclobutane tetracarboxylic dianhydride (CBDA), hexafluoroisopropyl phthalic anhydride (6 FDA), 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, di (trifluoromethyl) diaminobiphenyl (TFMB) and diaminodiphenyl ether (ODA), respectively. The reason is mainly because the diamine monomer with an innovative structure has larger general molecular weight, the reduction of nitro group 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 of the diamine monomer is realized, and the development of the polyimide industry is promoted.
Based on the above, the invention designs a diamine monomer with an innovative structure (the chemical structural formula is shown in figure 1, abbreviated as C14-FBDA), and develops a synthesis process which can be applied to industry, and the high-efficiency production of C14-FBDA is realized by optimizing a reaction route.
Disclosure of Invention
The purpose of the invention is that: (1) Through innovation of molecular structure, more functionality is given to diamine monomer, specifically, C14 side chain alkyl, trifluoromethyl, imide group and a plurality of benzene ring structures are simultaneously introduced in the C14-FBDA molecular structure, the regularity and crystallinity of polymer molecular chains are broken, the free volume of the polymer is improved, the interaction among the molecular chains is reduced, and further the film forming property and optical transparency of polyimide are greatly improved. (2) A production process of the industrially applicable C14-FBDA is developed, and the efficient synthesis of the C14-FBDA is realized by optimizing a reaction route. (3) Enriches the variety of diamine monomer and promotes the development of polyimide industry to a certain extent.
The invention comprises the following steps:
The synthesis of C14-FBDA is divided into three steps.
The first step: adding 2, 2-bis (3-amino-4-sodium phenolate) hexafluoropropane, bromoC 14 alkane and solvent N, N-dimethylacetamide (abbreviated as DMAC) into a reaction kettle, stirring and heating, filtering while the reaction is hot after a period of heat preservation, removing sodium bromide as a byproduct generated by the reaction, cooling the filtrate to room temperature, adding water for quenching, and carrying out suction filtration again, wherein a great amount of solids appear at the moment, and the filter cake is sequentially subjected to water washing and vacuum drying treatment to obtain a pure 2, 2-bis (3-amino-4-C14 alkoxyphenyl) hexafluoropropane (abbreviated as C14-FN) product, wherein the chemical structural formula of the pure 2, 2-bis (3-amino-4-C14 alkoxyphenyl) hexafluoropropane (abbreviated as C14-FN) is shown in figure 2.
And a second step of: adding C14-FN and N-methylpyrrolidone (abbreviated as NMP) as solvents into a reaction kettle, starting stirring and cooling a jacket, slowly dripping a mixed solution of m-nitrobenzoyl chloride and NMP into the reaction kettle, continuing to react until the raw materials react completely, slowly adding the reaction solution into methanol to quench, wherein a large amount of solids appear, filtering, washing a filter cake with methanol and water in sequence, and then carrying out vacuum drying treatment to obtain a C14-FBDN pure product, wherein the chemical structural formula of the pure product is shown in figure 3.
And a third step of: under the protection of nitrogen, adding C14-FBDN, a palladium-carbon catalyst and a solvent N, N-dimethylformamide (abbreviated as DMF) into a reaction kettle, starting stirring and heating, slowly dripping a hydrazine hydrate solution into the reaction kettle, after dripping, performing heat preservation reaction until the C14-FBDN is completely reacted, then closing heating, filtering the reaction liquid while the reaction liquid is hot, slowly dripping the filtrate into water for quenching, wherein a large amount of solids appear at the moment, filtering again, pulping and purifying the filter cake by ethanol, and performing vacuum drying treatment to obtain a pure product of C14-FBDA.
The overall synthetic route for C14-FBDA is shown in FIG. 4.
The preparation method of the fluorine-containing diamine monomer with the substituted C14 side chain is characterized in that in the first step of synthesis reaction, the molar charge ratio of bromoC 14 alkane to 2, 2-bis (3-amino-4-sodium phenolate) hexafluoropropane is 2:1-10:1, and the preferable molar charge ratio is 2:1-3:1.
The preparation method of the fluorine-containing diamine monomer with the substituted C14 side chain is characterized in that in the first step of synthesis reaction, the concentration of 2, 2-bis (3-amino-4-sodium phenolate) hexafluoropropane in solvent DMAC is 0.1-2.0mol/L, and the preferable concentration is 1.1-1.6mol/L.
The preparation method of the fluorine-containing diamine monomer with the substituted C14 side chain is characterized in that in the first step of synthesis reaction, the reaction temperature is controlled between 80 ℃ and 166 ℃, and preferably between 120 ℃ and 130 ℃.
The preparation method of the fluorine-containing diamine monomer with the substituted C14 side chain is characterized in that in the second step of synthesis reaction, the molar charge ratio of m-nitrobenzoyl chloride to C14-FN is 2:1-10:1, and the preferable molar charge ratio is 2:1-3:1.
The preparation method of the fluorine-containing diamine monomer with the substituted C14 side chain is characterized in that in the second step of synthesis reaction, the concentration of C14-FN in solvent NMP is 0.1-2.0mol/L, and the preferable concentration is 0.5-1.5mol/L.
The preparation method of the fluorine-containing diamine monomer with the substituted C14 side chain is characterized in that in the second step of synthesis reaction, the temperature of a reaction solution is controlled between 0 and 50 ℃ and preferably between 20 and 30 ℃ when mixed solution of C14-FN and NMP is added dropwise.
The preparation method of the fluorine-containing diamine monomer with the substituted C14 side chain is characterized in that in the third step of synthesis reaction, the weight ratio of palladium to carbon to C14-FBDN is 0.05:1-0.1:1, and the preferable weight ratio of palladium to carbon to C14-FBDN is 0.05:1-0.08:1.
The preparation method of the fluorine-containing diamine monomer with the substituted C14 side chain is characterized in that in the third step of synthesis reaction, the feeding mole ratio of hydrazine hydrate to C14-FBDN is 30:1-50:1, and the preferable feeding mole ratio is 30:1-35:1.
The preparation method of the fluorine-containing diamine monomer with the substituted C14 side chain is characterized in that in the third step of synthesis reaction, the temperature of reaction liquid is controlled between 65 ℃ and 95 ℃ and preferably between 75 ℃ and 90 ℃ when hydrazine hydrate is added dropwise.
The beneficial effects are that: the invention focuses on the design and preparation of diamine monomer with innovative structure, specifically, in the design of C14-FBDA molecular structure, trifluoromethyl group with strong electronegativity, long-chain C14 alkyl substituent and rigid nonplanar structure are simultaneously introduced, thereby effectively reducing the order and symmetry of molecular chains, reducing the accumulation of polyimide polymer molecular chains, increasing the space free volume of molecular chains to a certain extent, disturbing the conjugation between chains, further inhibiting or reducing the formation of charge transfer complex between molecules and in molecules, finally reducing the absorption of polyimide in the visible light region, and greatly improving the light transmittance of the film. In the synthesis of C14-FBDA, the invention optimizes a shorter synthesis route, has higher synthesis yield, uses cheap and easily available raw materials, has lower production cost, is simple and convenient to operate and environment-friendly, can completely realize large-scale mass production, and has great industrial application value.
Drawings
Fig. 1: C14-FBDA structural formula.
Fig. 2: C14-FN structural formula.
Fig. 3: C14-FBDN structural formula.
Fig. 4: the total synthetic process route of C14-FBDA.
Detailed Description
Example 1
The first step: adding 1.2L DMAC, 1000g 2, 2-bis (3-amino-4-sodium phenolate) hexafluoropropane and 1347g bromoC 14 alkane into a four-port reaction bottle in sequence, starting stirring and heating, maintaining the temperature at 80 ℃ for reacting for 2-3h, after the reaction of the raw materials is finished, closing heating, pouring out the reaction liquid, filtering while the reaction liquid is hot, collecting and preserving an upper filter cake which is a byproduct sodium bromide, naturally cooling the filtrate to room temperature, adding the filtrate into 2.4L water for quenching, filtering, washing the filter cake with 3.5L water, and drying the filter cake in vacuum to obtain 1665g of pure C14-FN.
And a second step of: to a 10L four-port reaction flask, 1665g of C14-FN and 550mL of NMP were added, stirring was started, and then a mixture of 812g of m-nitrobenzoyl chloride and 550mL of NMP was slowly added dropwise thereto, and the temperature of the reaction solution was controlled to about 50 ℃. After the dripping is finished, 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 solution into 2200mL of methanol for quenching, wherein a large amount of solids appear at the moment, 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 2087g of C14-FBDN pure product.
And a third step of: under the protection of nitrogen, 3500mL of DMF, 2087g of C14-FBDN and 104.4g of palladium-carbon catalyst (palladium content 10%) are added into a four-necked flask, stirring and heating are started, 3500mL of hydrazine hydrate solution (concentration: about 17 mol/L) is slowly added dropwise into the reaction flask after the temperature of the reaction solution is raised to 65 ℃, the temperature of the reaction solution is controlled to be about 65 ℃, after the dropwise addition, the reaction is continued at 65 ℃ for 2-3h, and the temperature is kept at 65 ℃. After the reaction of the raw material C14-FBDN is finished, the heating is turned off, the reaction solution is filtered while the reaction solution is hot, the filtrate is slowly dripped into 7000mL of water to quench, a large amount of solids appear at the moment, the mixture is filtered again, the filter cake is pulped and purified by 3500mL of ethanol, and then the mixture is dried in vacuum, so that 1772g of pure C14-FBDA can be obtained.
Example 2
The first step: adding 24.3L DMAC, 1000g of 2, 2-bis (3-amino-4-sodium phenolate) hexafluoropropane and 6735g of bromoC 14 alkane into a 30L double-layer glass reaction kettle in sequence, starting stirring and heating, maintaining the temperature at 166 ℃ for reacting for 2-3h, closing heating after the reaction of the raw materials is finished, discharging reaction liquid, filtering while the reaction liquid is hot, collecting and preserving the upper filter cake as a byproduct sodium bromide, naturally cooling the filtrate to room temperature, adding the filtrate into 48.6L water for quenching, filtering, washing the filter cake with 3.5L of water, and vacuum drying the filter cake to obtain 1757g of C14-FN pure product.
And a second step of: 1757g of C14-FN and 11.5LNMP were added to a 30L double glass reaction vessel, stirring was started and the jacket was cooled, and after the temperature of the reaction solution was lowered to 0 ℃, a mixed solution of 4286g of m-nitrobenzoyl chloride and 11.5L of NMP was slowly added dropwise thereto, and the temperature of the reaction solution was controlled to about 0 ℃. After the dripping is finished, the temperature is kept at 0 ℃ to continue the reaction for 2 to 3 hours. After the raw materials are reacted completely, the reaction solution is slowly poured into 46L of methanol to quench, a large amount of solids appear at the moment, the mixture is filtered, a filter cake is washed by 1000mL of methanol and 1000mL of water in sequence, and the obtained filter cake is dried in vacuum, so that 2325g of pure C14-FBDN can be obtained.
And a third step of: 6500mL of DMF, 2325g of C14-FBDN and 232.5g of palladium-carbon catalyst (palladium content 10%) are added into a 30L double-layer glass reaction kettle under the protection of nitrogen, stirring and heating are started, 6500mL of hydrazine hydrate solution (concentration: about 17 mol/L) is slowly dripped into a reaction bottle after the temperature of the reaction liquid is raised to 95 ℃, the temperature of the reaction liquid is controlled to be about 95 ℃ after dripping, and the reaction is continued for 2-3h at the temperature of 95 ℃ after dripping. After the reaction of the raw material C14-FBDN is finished, the heating is closed, the reaction liquid is filtered while the reaction liquid is hot, the filtrate is slowly dripped into 13L of water to quench, a large amount of solids appear at the moment, the mixture is filtered again, a filter cake is pulped and purified by 6500mL of ethanol, and then the mixture is dried in vacuum, so that 2084g of pure C14-FBDA can be obtained.
Claims (9)
1. A preparation method of a C14 side chain substituted fluorine-containing diamine monomer, wherein the chemical structure of the C14 side chain substituted fluorine-containing diamine monomer C14-FBDA is shown as a formula 1, and the synthesis of the monomer is divided into three steps;
step one: adding 2, 2-bis (3-amino-4-sodium phenolate) hexafluoropropane, bromoC 14 alkane and solvent N, N-dimethylacetamide into a reaction kettle, starting stirring and heating, carrying out heat preservation reaction for a period of time, filtering while the reaction product is hot, removing sodium bromide as a byproduct generated by the reaction, cooling the filtrate to room temperature, adding water for quenching, and carrying out suction filtration again, wherein a large amount of solids appear at the moment, and sequentially carrying out water washing and vacuum drying treatment on a filter cake to obtain a pure product of 2, 2-bis (3-amino-4-C14 alkoxyphenyl) hexafluoropropane C14-FN, wherein the chemical structural formula of the pure product is shown as formula 2;
Step two: adding C14-FN and N-methylpyrrolidone as solvent into a reaction kettle, starting stirring and cooling a jacket, slowly dripping a mixed solution of m-nitrobenzoyl chloride and N-methylpyrrolidone into the reaction kettle, continuing to react until the raw materials react completely, slowly adding the reaction solution into methanol to quench, wherein a large amount of solids appear at the moment, filtering, washing a filter cake with methanol and water in sequence, and then carrying out vacuum drying treatment to obtain a C14-FBDN pure product, wherein the chemical structural formula of the pure product is shown as formula 3;
Step three: adding C14-FBDN, a palladium-carbon catalyst and a solvent N, N-dimethylformamide into a reaction kettle under the protection of nitrogen, starting stirring and heating, slowly dripping a hydrazine hydrate solution into the reaction kettle, keeping the temperature for reaction until the C14-FBDN is completely reacted, then closing heating, filtering the reaction liquid while the reaction liquid is hot, slowly dripping the filtrate into water for quenching, wherein a large amount of solids appear, filtering again, pulping and purifying the filter cake by ethanol, and carrying out vacuum drying treatment to obtain a C14-FBDA pure product;
in the first step, the molar feed ratio of the bromoC 14 alkane to the 2, 2-bis (3-amino-4-sodium phenolate) hexafluoropropane is 2:1-10:1.
2. A process for producing a C14 side chain-substituted fluorine-containing diamine monomer as described in claim 1, wherein in the step one, the concentration of 2, 2-bis (3-amino-4-sodium phenolate) hexafluoropropane in the solvent N, N-dimethylacetamide is 0.1 to 2.0mol/L.
3. A process for preparing a C14 side chain substituted fluorine-containing diamine monomer as described in claim 1, wherein the reaction temperature in the first step is controlled between 80 and 166 ℃.
4. A process for preparing a C14 side chain substituted fluorine-containing diamine monomer as described in claim 1, wherein the molar feed ratio of the intermediate nitrobenzoyl chloride to the C14-FN in the step (a) is 2:1 to 10:1.
5. A process for producing a C14 side chain-substituted fluorine-containing diamine monomer as described in claim 1, wherein the concentration of C14-FN in the solvent N-methylpyrrolidone in the second step is 0.1 to 2.0mol/L.
6. A process for producing a C14 side chain-substituted fluorine-containing diamine monomer as described in claim 1, wherein the temperature of the reaction solution is controlled to be 0 to 50 ℃ when a mixed solution of m-nitrobenzoyl chloride and N-methylpyrrolidone is added dropwise in the second step.
7. The process for producing a C14 side chain-substituted fluorine-containing diamine monomer as described in claim 1, wherein the weight ratio of palladium carbon to C14-FBDN in the third step is 0.05:1 to 0.1:1.
8. A process for preparing a C14 side chain substituted fluorine-containing diamine monomer as described in claim 1, wherein the molar charge ratio of hydrazine hydrate to C14-FBDN in the step three is 30:1 to 50:1.
9. A process for producing a C14 side chain-substituted fluorine-containing diamine monomer as described in claim 1, wherein the reaction solution temperature is controlled to be 65 to 95 ℃ when hydrazine hydrate is added dropwise in the step three.
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