Patent Application
20240132669
The present disclosure relates to a polyimide compound and a monomer as the starting material and a precursor thereof.
Polyimides has excellent in the properties including the heat resistance, the mechanical properties, and the insulating properties. Accordingly, polyimides are widely used in various applications, and, for example, used for automobile components, aircraft components, and electrical and electronic components (for example, Patent Literature 1).
Patent Literature 1: Japanese Patent Laid-Open No. 2020-203981
Since polyimides are widely used in various applications, there are needs for polyimides having various structures.
The present disclosure includes the following aspects.
[1] A polyimide compound represented by formula (I):
wherein
wherein
wherein
[8] The polyimide compound according to any one of [1] to [5], wherein A2 is any one of the following groups:
[9] The polyimide compound according to [1], wherein formula (I) is formula (Id):
wherein
wherein
wherein
wherein
wherein
wherein
H2N-Ar1-A1-Ar2-NH2
wherein
H-Ar4-NH2
I-A1-I
The present invention can provide polyimides having various structures.
The present disclosure provides a polyimide compound represented by formula (I):
wherein
In one embodiment, Ar1 is a phenylene group substituted with one or more substituents each selected from a C1-6 alkyl group, a C1-6 alkoxy group, and a halogen atom.
In another embodiment, Ar1 is an indolylene group optionally substituted with one or more substituents each selected from a C1-6 alkyl group, a C1-6 alkoxy group, and a halogen atom.
In one embodiment, Ar2 is a phenylene group substituted with one or more substituents each selected from a C1-6 alkyl group, a C1-6 alkoxy group, and a halogen atom.
In another embodiment, Ar2 is an indolylene group optionally substituted with one or more substituents each selected from a C1-6 alkyl group, a C1-6 alkoxy group, and a halogen atom.
In one embodiment, Ar1 and Ar2 are each a phenylene group substituted with one or more substituents each selected from a C1-6 alkyl group, a C1-6 alkoxy group, and a halogen atom.
In one embodiment, Ar1 and Ar2 are each an indolylene group optionally substituted with one or more substituents each selected from a C1-6 alkyl group, a C1-6 alkoxy group, and a halogen atom.
In one embodiment, the indolylene group is not substituted.
In another embodiment, the indolylene group is substituted with one or more substituents each selected from a C1-6 alkyl group, a C1-6 alkoxy group, and a halogen atom.
The polyimide compound of the present disclosure has improved adhesiveness to a metal surface due to having an indole ring.
The polyimide compound of the present disclosure may have one or more substituents on its aromatic ring, for example, the benzene ring or the indole ring as Ar1 or Ar2. The polyimide compound of the present disclosure may have various properties due to having such a substituent.
The C1-6 alkyl group as a substituent on the phenylene group or indolylene group described above may be linear or branched, and is preferably a C1-3 alkyl group and more preferably a methyl group or an ethyl group.
The polyimide compound of the present disclosure may have excellent flexibility and/or solubility in a solvent due to having a C1-6 alkyl group as a substituent.
The C1-6 alkoxy group as a substituent on the phenylene group or indolylene group described above may be linear or branched, and is preferably a C1-3 alkoxy group, more preferably a methoxy group or an ethoxy group, and particularly preferably a methoxy group.
The polyimide compound of the present disclosure may have solubility in a solvent and/or excellent flexibility due to having a C1-6 alkoxy group as a substituent.
The halogen atom as a substituent on the phenylene group or indolylene group described above is a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and is preferably a fluorine atom or a chlorine atom.
In one embodiment, the halogen atom is a fluorine atom. The polyimide compound of the present disclosure may have excellent transparency, low dielectricity, and flame retardancy due to having a fluorine atom as a substituent.
In another embodiment, the halogen atom is a chlorine atom. The polyimide compound of the present disclosure may have great flame retardancy due to having a chlorine atom as a substituent.
In a preferable embodiment, the number of the substituents on the phenylene group or indolylene group described above may be two or more, for example, 2 to 4. When a plurality of such substituents are present, the substituents in Ar1 or Ar2 may be the same or different, and are preferably the same.
In a preferable embodiment, the substituent of the phenylene group or indolylene group is bonded to the atom adjacent to the atom bonding to A2. For example, in the case where Ar1 or Ar2 is a phenylene group, the C1-6 alkyl group, C1-6 alkoxy group, or halogen atom is located on the ortho-position to the atom bonding to A2.
In a more preferable embodiment, the phenylene group or indolylene group has the same C1-6 alkyl groups, preferably, methyl groups or ethyl groups, as the substituents, on the two atoms adjacent to the atom bonding to A2. The polyimide compound of the present disclosure may have a higher glass transition temperature, and the char production rate may be improved due to having the same C1-6 alkyl groups, preferably, methyl groups or ethyl groups.
A1 is a linear or branched C4-16 perfluoroalkylene group. The C4-16 perfluoroalkylene group is preferably a C4-12 perfluoroalkylene group, more preferably a C4-10 perfluoroalkylene group, and even more preferably a C4-8 perfluoroalkylene group. In one embodiment, the C4-16 perfluoroalkylene group is linear. In another embodiment, the C4-16 perfluoroalkylene group is branched. In a preferable embodiment, the C4-16 perfluoroalkylene group is a linear C4-8 perfluoroalkylene group.
The polyimide compound of the present disclosure can be improved in terms of transparency, flexibility, low dielectricity, and/or solubility in a solvent due to including C4-16 perfluoroalkylene group as A1.
A2 is an aliphatic or aromatic bisimide-N′,N-diyl, or in other words, is a group having two following structures:
A2 is typically derived from a tetracarboxylic acid as a starting material of the polyimide represented by formula (I).
n1 is any integer, and may preferably be 2 to 500, more preferably 2 to 100, even more preferably 5 to 100, and particularly preferably 5 to 50.
In a preferable embodiment, formula (I) is formula (Ia):
wherein
In a preferable embodiment, formula (I) is formula (Ia′):
wherein
In other words, Ar1 in formula (I) is a group represented by the following formula:
and Ar2 in formula (I) is a group represented by the following formula:
In another preferable embodiment, formula (I) is formula (Ia″):
wherein
The polyimide compound represented by formula (Ia″) may have improved flexibility and improved transparency, as compared to the polyimide compound represented by formula (Ia′).
In a more preferable embodiment, R11 and R12 are each a C1-6 alkyl group, a C1-6 alkoxy group, or a halogen atom; R15 and R16 are each a C1-6 alkyl group, a C1-6 alkoxy group, or a halogen atom; and R13, R14, R17, and R18 are each a hydrogen atom.
In a preferable embodiment, formula (I) is formula (Ib):
wherein
R20 is independently in each occurrence a C1-6 alkyl group, a C1-6 alkoxy group, or a halogen atom,
In a preferable embodiment, A1 is bonded to the indole ring at the 2- or 3-position. In one embodiment, A1 is bonded to the indole ring at the 3-position. In another embodiment, A1 is bonded to one indole ring at the 2-position and bonded to the other indole ring at the 3-position.
In a preferable embodiment, Ar2 is boned to the indole ring at any of the 4- to 7-positions, preferably the 5- or 6-position, and more preferably the 5-position.
In one embodiment, p1 and p2 are each 0.
In another embodiment, p1 and p2 are each an integer of 1 to 5, and preferably an integer of 2 to 4, for example, 2.
In one embodiment, formula (I) is formula (Ic):
wherein
In other words, A2 in formula (I) is a group represented by the following formula:
In a preferable embodiment, A3 is a single bond, a linear or branched C1-16 alkylene group optionally substituted with a fluorine atom, an oxygen atom, —CO—, —C≡C—, —SO2—,
The C1-16 alkylene group of the linear or branched C1-16 alkylene group optionally substituted with a fluorine atom, as A3, may be preferably a C1-10 alkylene group, and more preferably a C1-6 alkylene group.
In one embodiment, the C1-16 alkylene group is substituted with one or more fluorine atoms. In one embodiment, all hydrogen atoms in the C1-16 alkylene group may be replaced with fluorine atoms, or that is, the C1-16 alkylene group may be a perfluoroalkylene group.
In a preferable embodiment, A2 is a group selected from the following groups.
In a preferable embodiment, formula (I) is represented by formula (Id):
wherein
The present disclosure also provides an intermediate for producing the above-described polyimide compound.
The intermediate is a compound represented by formula (II) below:
wherein
In a preferable embodiment, formula (II) is a compound represented by formula (IIa):
wherein Ar1, Ar2, A1, A2, and n1 each have the same meaning as defined in formula (II).
The polyimide compound represented by formula (I) described above can be obtained by (1) reacting a tetracarboxylic acid or an anhydride thereof with a diamine compound represented by formula (IV):
H2N-Ar1-A1-Ar2-NH2
wherein
In one embodiment, Ar1 is a phenylene group substituted with one or more substituents each selected from a C1-6 alkyl group, a C1-6 alkoxy group, and a halogen atom, and Ar2 is a phenylene group substituted with one or more substituents each selected from a C1-6 alkyl group, a C1-6 alkoxy group, and a halogen atom.
In one embodiment, the compound represented by formula (IV) is a diamine compound represented by formula (IVa):
wherein
In one embodiment, the compound represented by formula (IV) is a diamine compound represented by formula (IVb):
In another embodiment, a compound represented by formula (IV) is a diamine compound represented by formula (IVc):
wherein
In a preferable embodiment, R11, R12, R15, and R16 are each independently a C1-6 alkyl group, a C1-6 alkoxy group, or a halogen atom, and R13, R14, R17, and R18 are each a hydrogen atom.
In a further preferable embodiment, R11, R12, R15, and R16 are each a C1-6 alkyl group, a C1-6 alkoxy group, or a halogen atom, and R13, R14, R17, and R18 are each a hydrogen atom.
In another embodiment, Art is an indolylene group optionally substituted with one or more substituents each selected from a C1-6 alkyl group, a C1-6 alkoxy group, and a halogen atom, and Are is an indolylene group optionally substituted with one or more substituents each selected from a C1-6 alkyl group, a C1-6 alkoxy group, and a halogen atom.
In another embodiment, the compound represented by formula (IV) is a diamine compound represented by formula (IVd):
wherein
In one embodiment, p1 and p2 are each 0.
In another embodiment, p1 and p2 are each an integer of 1 to 5, and preferably an integer of 2 to 4, for example, 2.
In a preferable embodiment, A1 is a C4-12 perfluoroalkylene group, more preferably a C4-10 perfluoroalkylene group, and even more preferably a C4-8 perfluoroalkylene group. In one embodiment, the C4-16 perfluoroalkylene group is linear. In another embodiment, the C4-16 perfluoroalkylene group is branched.
The diamine compound represented by formula (IV):
H2N-Ar1-A1-Ar2-NH2
wherein
H-Ar4-NH2
I-A1-I
In the above-described reaction, one compound represented by formula (VII) reacts with two compounds represented by formula (VIII). The two compounds represented by formula (VIII) may have the same structure or may have different structures. Preferably, the compounds represented by formula (VIII) are of a single type. That is, one compound represented by formula (VII) reacts with two compounds having the same structure represented by formula (VIII).
In one embodiment, Ar1 is a phenylene group substituted with one or more substituents each selected from a C1-6 alkyl group, a C1-6 alkoxy group, and a halogen atom, Ar2 is a phenylene group substituted with one or more substituents each selected from a C1-6 alkyl group, a C1-6 alkoxy group, and a halogen atom, and Ar4 is a phenylene group substituted with one or more substituents each selected from a C1-6 alkyl group, a C1-6 alkoxy group, and a halogen atom.
In another embodiment, Ar1 is an indolylene group optionally substituted with one or more substituents each selected from a C1-6 alkyl group, a C1-6 alkoxy group, and a halogen atom, Ar2 is an indolylene group optionally substituted with one or more substituents each selected from a C1-6 alkyl group, a C1-6 alkoxy group, and a halogen atom, and Ar4 is an indolylene group optionally substituted with one or more substituents each selected from a C1-6 alkyl group, a C1-6 alkoxy group, and a halogen atom.
The irradiation with light described above is preferably irradiation with ultraviolet rays, and is performed by irradiating with light having a wavelength of 300 to 400 nm, for example, a wavelength of 350 to 380 nm.
Examples of the light source used for the irradiation with light includes, but not particularly limited to, an LED, a mercury lamp, a xenon lamp, a UV lamp, and a halogen lamp, and an LED is preferably used.
The reaction described above can preferably be performed with a basic compound, a catalyst, a one-electron reductant, or a radical generator.
Examples of the basic compound include an inorganic base, such as Cs2CO3, K2CO3, Na2CO3, Li2CO3, CsF, CsHCO3, KHCO3, NaHCO3, and LiHCO3; an amine compound such as triethylamine, tributylamine, diisopropylethylamine, N,N,N′,N′-tetramethyleRediamine, N,N,N′,N′-tetraethylenediamine, pyrrolidine, pyridine, collidine, ammonia, dimethylamine, and DBU; tributylphosphine, triphenylphosphine, triarylphosphines, and disubstituted phosphines, and Cs2CO3 is preferably used.
Examples of the catalyst include a transition metal complex, an organic dye compound, and an enamine compound.
Examples of the central metal of the transition metal complex include cobalt, ruthenium, rhodium, rhenium, iridium, zinc, nickel, palladium, osmium, and platinum.
Examples of the organic dye compound include Rose Bengal, Erythrosine, Eosin (e.g., Eosin B, Eosin Y), Acriflavin, Lipoflavin, Thionin, Phenoxazine, and Phenothiazine.
The enamine compound has a structure represented by
and is a chemical species generated by a reaction between an aldehyde compound:
wherein R1 is a phenyl group or a benzyl group, and R2 is a hydrogen atom, a methyl group, or a phenyl group, and a pyrrolidine compound:
wherein R3 is a hydrogen atom or a bis(3,4-dimethoxyphenyl)methoxymethyl group. An enamine compound that has been synthesized beforehand may be added, or an aldehyde compound and a pyrrolidine compound may be directly added to generate the catalyst in the reaction system.
Examples of the aldehyde compound include 3-phenyl-2-methylpropanal, 2-phenylpropanal, diphenylacetaldehyde, and phenylacetaldehyde.
Examples of the pyrrolidine compound include pyrrolidine, and (S)-2-[3,4-bis(dimethoxyphenyl)methoxymethyl]pyrrolidine.
Examples of the one-electron reductant include sodium thiosulfate, lithium dithionite, sodium dithionite, potassium dithionite, cesium dithionite, copper(I) iodide, copper(I) bromide, copper(I) chloride, triethylamine, tributylamine, tetrabutylammonium iodide, tetrabutylphosphonium iodide, ascorbic acid, an ascorbate salt, zinc powder, indium powder, and magnesium powder. Preferred is sodium thiosulfate, sodium dithionite, copper(I) iodide, and copper(I) bromide, and sodium thiosulfate or sodium dithionite is particularly preferred.
Examples of the radical generator include an organic peroxide, an inorganic peroxide, and an organic azo compound, and an organic peroxide is preferably used. Examples include, but not limited to, benzoyl peroxide as the organic peroxide, potassium persulfite as the inorganic peroxide, and azobisisobutyronitrile (AIBN) as the organic azo compound.
The reaction described above is preferably carried out in a solvent. Examples of the solvent include, but not particularly limited to, dichloromethane, chloroform, carbon tetrachloride, dichloroethane, dichloropentafluoropropane (HCFC-225), C5-C12 perfluoroaliphatic hydrocarbons (e.g., perfluorohexane, perfluoromethylcyclohexane and perfluoro-1,3-dimethylcyclohexane); a polyfluoroaromatic hydrocarbon (e.g. bis(trifluoromethyl)benzene); a polyfluoroaliphatic hydrocarbon (e.g., C6F13CH2CH3 (ASAHIKLIN (registered trademark) AC-6000, manufactured by AGC Inc.)), 1,1,2,2,3,3,4-heptafluorocyclopentane (e.g., ZEORORA (registered trademark) H, manufactured by ZEON CORPORATION), a hydrofluoroether (HFE) such as an alkyl perfluoroalkyl ether (the perfluoroalkyl group and the alkyl group may be linear or branched), perfluoropropyl methyl ether (C3F7OCH3) (e.g., Novec (registered trademark) 7000, manufactured by 3M), perfluorobuthyl methyl ether (C4F9OCH3) (e.g., Novec (registered trademark) 7100, manufactured by 3M), perfluorobuthyl ethyl ether (C4F9OC2H5) (e.g., Novec (registered trademark) 7200, manufactured by 3M), perfluorohexyl methyl ether (C2F5CF(OCH3)C3F7 (e.g., Novec (registered trademark) 7300, manufactured by 3M), or CF3CH2OCF2CHF2 (e.g., ASAHIKLIN (registered trademark) AE-3000, manufactured by AGC Inc).
The reaction temperature in the reaction may be preferably 0 to 60° C., and more preferably 10 to 40° C., for example, room temperature.
The reaction time in the reaction may be, for example, 1 to 72 hours, and preferably 12 to 48 hours.
The tetracarboxylic acid or the anhydride thereof is not particularly limited as long as it can react with the diamine compound to form a polyimide compound, and may be an aliphatic or aromatic tetracarboxylic acid or an anhydride thereof.
In a preferable embodiment, the tetracarboxylic acid or the anhydride thereof is a tetracarboxylic acid anhydride.
Examples of the aliphatic tetracarboxylic acid anhydride include the following compounds.
Examples of the aromatic tetracarboxylic acid anhydride include the following compounds.
The present disclosure also provides a polyimide compound represented by formula (III):
wherein
The polyimide compound represented by formula (III) described above may have a large solubility since moieties derived from phthalic acid and aromatic moieties (Ar3) are present alternately to thereby generate polarization in the direction of the main chain of the molecular.
In one embodiment, Ar3 is an optionally substituted phenylene group.
In one embodiment, Ar3 is an optionally substituted indolylene group.
Examples of the substituent of the optionally substituted phenylene group or indolylene group as Ar3 include a C1-6 alkyl group, a C1-6 alkoxy group, and a halogen atom.
The C1-6 alkyl group may be linear or branched, and is preferably a C1-3 alkyl group, and more preferably a methyl group.
The C1-6 alkoxy group may be linear or branched, and is preferably a C1-3 alkoxy group, more preferably a methoxy group or a methyl group, and particularly preferably a methoxy group.
The halogen atom is a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and is preferably a fluorine atom or a chlorine atom, and more preferably a fluorine atom.
A4 is a linear or branched C4-16 perfluoroalkylene group. The C4-16 perfluoroalkylene group is preferably a C4-12 perfluoroalkylene group, more preferably a C4-10 perfluoroalkylene group, and even more preferably a C4-8 perfluoroalkylene group. In one embodiment, the C4-16 perfluoroalkylene group is linear. In another embodiment, the C4-16 perfluoroalkylene group is branched.
n2 is any integer, and may be preferably 2 to 500, more preferably 2 to 100, even more preferably 5 to 100, and particularly preferably 5 to 50.
In a preferable embodiment, the formula (III) described above is represented by formula (IIIa):
wherein
In a preferable embodiment, R31 and R32 are each independently a C1-6 alkyl group, a C1-6 alkoxy group, or a halogen atom, and R33 and R34 are each hydrogen atom.
In a more preferable embodiment, R31 and R32 are each a C1-6 alkyl group, a C1-6 alkoxy group, or a halogen atom, and R33 and R34 are each hydrogen atom.
The polyimide compound represented by formula (III) described above can be obtained by polymerizing a dicarboxylic acid having an amino group or an anhydride thereof.
For example, the compound represented by formula (IIIa) can be obtained by polymerizing a compound represented by formula (VI):
wherein
The compound represented by formula (VI) may have a large solubility since phthalic acid anhydride moieties and benzene ring moieties are present to thereby generate polarization in the direction of the main chain of the molecular.
In a preferable embodiment, R31 and R32 in formula (VI) are each independently a C1-6 alkyl group, a C1-6 alkoxy group, or a halogen atom, and R33 and R34 in formula (VI) are each a hydrogen atom.
In a more preferable embodiment, R31 and R32 in formula (VI) are each a C1-6 alkyl group, a C1-6 alkoxy group, or a halogen atom, and R33 and R34 in formula (VI) are each a hydrogen atom.
The polyimide compound represented by formula (I) and the polyimide compound represented by formula (III) of the present disclosure can be used for various applications.
Examples of the application include automobile components, aircraft components, and electrical and electronic components, coatings, and adhesives.
The polyimide of the present disclosure as well as the production method and the intermediate thereof have been described above in detail. The applications, the production method, etc. of the polyimide of the present disclosure are not limited to those illustrated above.
The polyimide of the present disclosure will be described more specifically by way of Examples below; however, the present invention is not limited to these Examples.
To a dodecafluoro-1,6-diiodohexane (0.3 mmol, 70 μL) solution in dichloromethane (2 mL), 10 equivalents of 2,6-xylidine (1), 5 equivalents of cesium carbonate, and 10 equivalents of sodium thiosulfate aqueous solution (1 mL) were added, and the mixture was irradiated with light using LED of a wavelength 365 nm in atmospheric air. As a result, the target diamine compound 2a and 2b were obtained with yields of 60% and 15%, respectively.
1H NMR (400 MHz, CDCl3) δ=7.13; (4H, s), 3.85; (4H, br s), 2.20; (12H, s).
19F NMR (376 MHz, CDCl3) δ=−109.6; (4F, s), −121.9; (4F, s), −122.3; (4F, s).
13C NMR (150 MHz, CDCl3) δ=145.9, 126.7, 121.0, 117.6; (t, J=24.0 Hz), 18.0.
1H NMR (400 MHz, CDCl3) δ=7.14; (2H, s), 7.03; (1H, d, J=8.2 Hz), 6.93; (1H, d, J=8.2 Hz), 3.86; (2H, br s), 3.74; (2H, br s), 2.22; (6H, s), 2.21; (6H, s).
19F NMR (376 MHz, CDCl3) δ=−104.5; (2F, s), −109.6; (2F, s), −121.0; (2F, s), −121.8; (2F, s), −122.1; (2F, s), −122.2; (2F, s).
13C NMR (150 MHz, CDCl3) δ=145.9, 144.0, 131.6, 127.6, 126.7, 121.0, 118.4-117.5; (m), 18.1, 17.6.
To a dodecafluoro-1,6-diiodohexane (0.3 mmol, 70 .1.1,) solution in dichloromethane (4 mL), 10 equivalents of 2,6-xylidine (1), 1.5 equivalents of cesium carbonate, and 5 equivalents of sodium thiosulfate aqueous solution (2 mL) were added, and the mixture was irradiated with light using LED of a wavelength 365 nm in atmospheric air. As a result, the target diamine compounds 2a and 2b were obtained with yields of 60% and 21%, respectively.
To a dodecafluoro-1,6-diiodohexane (0.6 mmol, 335.6 mg) solution in dichloromethane (5 mL), 5 equivalents of 2,6-xylidine (1), 1.5 equivalents of cesium carbonate, and 5 equivalents of sodium thiosulfate aqueous solution (4 mL) were added, and the mixture was irradiated with light for 48 hours using LED of a wavelength 365 nm in atmospheric air. As a result, the target diamine compounds 2a and 2b were obtained with yields of 56% and 20%, respectively.
To a 4,4′-oxydiphthalic anhydride (3) (0.13 mmol, 41.2 mg) solution in DMF (N,N-dimethylformamide) (20 wt %), an equimolar amount of diamine compound (2a) was added, and the mixture was stirred in an argon atmosphere at 50° C. for 50 hours, and then, 80° C. for 14 hours, 110° C. for 24 hours, and 140° C. for 24 hours, sequentially. As a result, polyimide 4a having a number average molecular weight of 13000 was obtained with a yield of 78%. In this process, production of the target PAA (polyamic acid) intermediate and PI (polyimide) was confirmed after each reaction time. The product was dissolved in DMF, and the resultant was applied to a quartz plate by spin-coating and heat-treated at 70° C. for 0.5 hours and 260° C. for 1.5 hours, to thereby obtain a light yellow transparent polyimide film.
1H NMR (400 MHz, CDCl3) δ=8.05; (2H, d, J=8.2 Hz), 7.59; (2H, s), 7.56; (2H, d, J=8.2 Hz), 7.44; (4H, s), 2.26; (12H, s).
19F NMR (376 MHz, CDCl3) δ=−111.2; (4F, s), −121.7; (8F, s).
To a 4,4′-oxydiphthalic anhydride (3) (0.19 mmol, 101.3 mg) solution in DMF (20 wt %), an equimolar amount of diamine compound (2b) was added, and the mixture was stirred in an argon atmosphere at 50° C. for 50 hours, and then, 80° C. for 14 hours, 110° C. for 24 hours, and 140° C. for 24 hours, sequentially. As a result, polyimide 4b having a number average molecular weight of 6400 was obtained with a yield of 56%. In this process, production of the target PAA (polyamic acid) intermediate and PI (polyimide) was confirmed after each reaction time.
1H NMR (500 MHz, CDCl3) δ=8.05; (2H, d, J=8.3 Hz), 7.61-7.55; (5H, m), 7.43; (2H, s), 7.34; (1H, d, J=7.7 Hz), 2.24-2.21; (12H, m).
19F NMR (471 MHz, CDCl3) δ=−105.3; (2F, s), −111.2; (2F, s), −120.9; (2F, s), −121.3-−121.6; (4F, m), −122.0; (2F, s).
To a 4,4′-oxydiphthalic anhydride (3) (0.25 mmol, 77.5 mg) solution in DMF (20 wt %), an equimolar amount of a mixture of diamine compounds (2a:2b=49:51) was added, and the mixture was stirred in an argon atmosphere at 50° C. for 50 hours, and then, 80° C. for 14 hours, 110° C. for 24 hours, and 140° C. for 24 hours, sequentially. As a result, polyimide 4ab having a number average molecular weight of 8400 was obtained with a yield of 62% (entry 2). In this process, production of the target PAA (polyamic acid) intermediate and PI (polyimide) was confirmed after each reaction time.
1H NMR (500 MHz, CDCl3) δ=8.05; (d, J=8.3 Hz), 7.61-7.55; (m), 7.43 (s), 7.34; (d, J=7.7 Hz), 2.24-2.21; (12H, m).
19F NMR (471 MHz, CDCl3) δ=−105.3; (s), −111.2; (s), −120.9; (s), −121.3-−121.6; (m), −122.0; (s).
To a perfluoro-1,8-diiodooctane (0.3 mmol, 191.4 mg) solution in dichloromethane (2.5 mL), 5 equivalents of 2,6-xylidine (1), 3 equivalents of cesium carbonate, and 5 equivalents of sodium thiosulfate aqueous solution (2 mL) were added, and the mixture was irradiated with light for 24 hours using LED of a wavelength 365 nm in atmospheric air.
As a result, the target diamine compound 5a and 5b were obtained with yields of 53% and 17%, respectively.
1H NMR (500 MHz, CDCl3) δ=7.13; (4H, s), 3.87; (4H, br s), 2.20; (12H, s). 19F NMR (471 MHz, CDCl3) δ=−109.7; (4F, s), −121.8; (4F, s), −122.3; (8F, s).
13C NMR (150 MHz, CDCl3) δ=146.0, 126.7, 121.0, 117.4; (t, J=24.0 Hz), 17.7.
1H NMR (500 MHz, CDCl3) δ=7.14; (2H, s), 7.04; (1H, d, J=8.0 Hz), 6.93; (1H, d, J=8.0 Hz), 3.81; (4H, br s), 2.22-2.21; (12H, m).
19F NMR (471 MHz, CDCl3) δ=−104.5; (2F, s), −109.7; (2F, s), −121.0; (2F, s), −121.8; (2F, s), −122.0; (2F, s), −122.3; (6F, s).
13C NMR (150 MHz, CDCl3) δ=146.0, 144.1, 127.6, 126.7, 125.5, 121.0, 117.9, 117.4; (t, J=24.0 Hz), 18.1, 17.7, 14.0.
To a dodecafluoro-1,6-diiodohexane (0.3 mmol) solution in dichloromethane (2.5 mL), 10 equivalents of 2,6-difluoroaniline (6), 3 equivalents of cesium carbonate, and 5 equivalents of sodium thiosulfate aqueous solution (2 mL) were added, and the mixture was irradiated with light using LED of a wavelength 365 nm for 72 hours in atmospheric air. As a result, the target diamine compound 7a and 7b were obtained with yields of 42% and 11%, respectively.
1H NMR (500 MHz, CDCl3) δ=7.07; (4H, dd, J=6.7, 1.9 Hz), 4.07; (4H, br s).
19F NMR (471 MHz, CDCl3) δ=−109.9; (4F, s), −121.9; (4F, s), −122.5; (4F, s), −131.8; (4F, s).
1H NMR (500 MHz, CDCl3) δ=7.07; (2H, dd, J=6.7, 1.9 Hz), 6.92; (1H, t, J=9.3 Hz), 6.86-6.84; (1H, m), 4.07; (2H, br s), 3.90; (2H, br s).
19F NMR (471 MHz, CDCl3) δ=−109.3; (2F, s), −109.9; (2F, s), −121.9; (2F, s), −122.2; (2F, s), −122.5; (2F, s), −122.5; (2F, s), −126.0; (1F, s), −131.0; (1F, s), −131.8; (2F, s).
To a perfluoro-1,8-diiodooctane (0.6 mmol, 163.3 mg) solution in dichloromethane (5 mL), 5 equivalents of 2,6-difluoroaniline (6X), 3 equivalents of cesium carbonate, and 5 equivalents of sodium thiosulfate aqueous solution (4 mL) were added, and the mixture was irradiated with light using LED of a wavelength 365 nm for 72 hours in atmospheric air. As a result, the target diamine compound 8a and 8b were obtained with yields of 26% and 12%, respectively.
1H NMR (500 MHz, CDCl3) δ=7.07; (4H, dd, J=6.6, 2.0 Hz), 4.08; (4H, br s).
19F NMR (471 MHz, CDCl3) δ=−109.9; (4F, s), −121.8; (4F, s), −122.4; (8F, s), −131.7; (4F, s).
1H NMR (500 MHz, CDCl3) δ=7.07; (2H, dd, J=6.6, 1.7 Hz), 6.93; (1H, t, J=9.6 Hz), 6.87-6.84; (1H, m), 4.08; (2H, br s), 3.91; (2H, br s).
19F NMR (471 MHz, CDCl3) 8 =−109.3; (2F, s), −109.9; (2F, s), −121.8; (2F, s), −122.1; (2F, s), −122.4; (12F, s), −125.9; (1F, s), −131.0; (1F, s), −131.7; (2F, s).
To a perfluoro-1,6-diiodohexane (0.3 mmol, 159.6 mg) solution in dichloromethane (2.5 mL), 5 equivalents of 5-aminoindole (9), 3 equivalents of cesium carbonate, and 5 equivalents of sodium thiosulfate aqueous solution (2 mL) were added, and the mixture was irradiated with light using LED of a wavelength 365 nm for 48 hours in atmospheric air. As a result, the target diamine compound was obtained with a yield of 26%.
19F NMR (471 MHz, CDCl3) δ=−106.1; (4H, s), −122.1; (4H, s), −122.4; (4H, s).
To a dodecafluoro-1,6-diiodohexane (0.3 mmol) solution in dichloromethane (2.5 mL), 5 equivalents of 2,6-diethylaniline (10), 1.5 equivalents of cesium carbonate, and 5 equivalents of sodium thiosulfate aqueous solution (2 mL) were added, and the mixture was irradiated with light using LED of a wavelength 365 nm for 24 hours in atmospheric air. As a result, the target diamine compound 11 was obtained with a yield of 50%.
1H NMR (500 MHz, CDCl3) δ=7.15; (4H, s, PhH), 3.93; (4H, br s, PhNH2), 2.54; (8H, q, J=7.5, PhCH2CH3), 1.27; (12H, t, J=7.6, PhCH2CH3).
19F NMR (471 MHz, CDCl3) δ=−109.7; (4F, s, PhCF2), −121.9; (4F, s, CF2), −122.3; (4F, s, CF2)
To a dodecafluoro-1,6-diiodohexane (0.3 mmol) solution in dichloromethane (2.5 mL), 5 equivalents of 2,6-dichloroaniline (12), 3 equivalents of cesium carbonate, and 5 equivalents of sodium thiosulfate aqueous solution (2 mL) were added, and the mixture was irradiated with light using LED of a wavelength 365 nm for 72 hours in atmospheric air. As a result, the target diamine compounds 13a:13b were obtained in a production ratio of 73:27.
1NMR (500 MHz, CDCl3) δ=7.39; (4H, s, PhH), 4.80; (4H, br s, PhNH2).
19F NMR (471 MHz, CDCl3) δ=−110.1; (4F, s, PhCF2), −121.8; (4F, s, CF2), −122.1; (4F, s, CF2)
1H NMR (500 MHz, CDCl3) δ=7.39; (2H, s, PhH), 7.29; (1H, d, J=8.6 Hz, PhH), 6.92; (1H, d, J=8.6 Hz, PhH), 4.80; (2H, br s, PhNH2), 4.74; (2H, br s, PhNH2).
19F NMR (471 MHz, CDCl3) δ=−107.2; (2F, s, PhCF2), −110.1; (2F, s, PhCF2), −120.5; (2F, s, CF2), −121.8; (2F, s, CF2), −122.1; (4F, s, CF2)
To a 4,4′-oxydiphthalic anhydride (3) (0.13 mmol, 41.2 mg) solution in DMF (20 wt %), an equimolar amount of diamine compound (7) was added, and the mixture was stirred in an argon atmosphere at 50° C. for 50 hours, and then, 80° C. for 14 hours, 110° C. for 24 hours, and 140° C. for 24 hours, sequentially. As a result, polyimide 14 having a number average molecular weight of 1.3×104 was obtained with a yield of 50%. The product was dissolved in DMF, and the resultant was applied to a quartz plate by spin-coating and heat-treated at 70° C. for 0.5 hours and 260° C. for 1.5 hours, to thereby obtain a light yellow transparent polyimide film.
19F NMR (471 MHz, CDCl3) δ=−111.4; (4F, s), −122.1; (8F, s), −132.0; (4F, s)
To a 4,4′-oxydiphthalic anhydride (3) (0.25 mmol, 76.7 mg) solution in DMF (20 wt %), an equimolar amount of diamine compound (11) was added, and the mixture was stirred in an argon atmosphere at 50° C. for 50 hours, and then, 80° C. for 14 hours, 110° C. for 24 hours, and 140° C. for 24 hours, sequentially. As a result, polyimide 15 having a number average molecular weight of 3.7×103 was obtained with a yield of 85%. The product was dissolved in DMF, and the resultant was applied to a quartz plate by spin-coating and heat-treated at 70° C. for 0.5 hours and at 260° C. for 1.5 hours, to thereby obtain a light yellow transparent polyimide film.
1H NMR (500 MHz, CDCl3) 8 =8.06; (2H, d, J=8.0), 7.59-7.56; (4H, m), 7.48; (4H, s), 2.57-52; (8H, m), 1.21-1.17; (12H, m).
19F NMR (471 MHz, CDCl3) δ=−111.2; (4F, s), −121.7; (8F, s).
To a 1,8-diiodoperfluorooctane (0.6 mmol, 784.2 mg) solution in dichloromethane (4 mL), 5 equivalents of 2,6-diethylaniline (897.0 mg), 5 equivalents of sodium thiosulfate aqueous solution (947.2 mg in 4 mL of water), and 1.5 equivalents of cesium carbonate (587.4 mg) were added, and the mixture was irradiated with light using LED of a wavelength 365 nm for 48 hours in atmospheric air. As a result, the target diamine compounds 16a and 16b were obtained with NMR yields of 71% and 5%, respectively.
1H NMR (500 MHz, CDCl3) δ=7.15; (4H, s), 3.94; (4H, s), 2.54; (8H, q, J=7.4), 1.28; (12H, t, J=7.6).
19F NMR (471 MHz, CDCl3) δ=−109.7; (4F, s), −121.8; (4F, s), −122.3; (4F, s), −122.3; (4F, s)
19F NMR (471 MHz, CDCl3) δ=−104.2; (2F, s), −109.7; (2F, s), −121.7; (2F, s), −121.8; (4F, s), −122.3; (6F, s)
To a 4,4′-oxydiphthalic anhydride (3) (0.23 mmol, 69.9 mg) solution in DMF (20 wt %), an equimolar amount of diamine compound (16a) was added, and the mixture was stirred in an argon atmosphere at 50° C. for 50 hours, and then, 80° C. for 14 hours, 110° C. for 24 hours, and 140° C. for 24 hours, sequentially. As a result, polyimide 17 having a number average molecular weight of 5.2×103 was obtained with a yield of 73%. The product was dissolved in DMF, and the resultant was applied to a quartz plate by spin-coating and heat-treated at 70° C. for 0.5 hours and 260° C. for 1.5 hours, to thereby obtain a light yellow transparent polyimide film.
1H NMR (500 MHz, CDCl3) δ=8.06; (2H, d, J=8.0), 7.59-7.57; (4H, m), 7.47 (4H, s), 2.57-52; (8H, m), 1.21-1.17; (12H, m).
19F NMR (471 MHz, CDCl3) δ=−111.0; (4F, s), −121.7; (8F, s).
To a 1,6-diiodoperfluorohexane (0.6 mmol, 140 μL) solution in dichloromethane (5 mL), 5 equivalents of 2-methoxy,6-methylaniline (411 mg), 5 equivalents of sodium thiosulfate aqueous solution (474 mg in 4 mL of water), and 1.5 equivalents of cesium carbonate (587.4 mg) were added, and the mixture was irradiated with light using LED of a wavelength 365 nm for 48 hours in atmospheric air. As a result, the target diamine compound 19a and a mixture of the target diamine compounds 19b and 19c were obtained with yields of 68% and 21%, respectively. Diamine compound 19a:
1H NMR (500 MHz, CDCl3) δ=6.94; (2H, s), 6.83; (2H, s), 4.04; (4H, br s), 3.87; (6H, s), 2.20; (6H, s).
19F NMR (471 MHz, CDCl3) δ=−109.4; (4F, s), −121.9; (4F, s), −122.3; (4F, s).
1H NMR (500 MHz, CDCl3) δ=6.98; (1H, d, J=9.2), 6.74; (1H, d, J=9.2), 4.04; (4H, br s), 3.89; (6H, s), 2.22; (6H, s).
19F NMR (471 MHz, CDCl3) δ=−104.0; (2F, s), −109.4; (2F, s), −121.0; (2F, s) −121.9; (2F, s), −122.3; (4F, s).
To a 4,4′-oxydiphthalic anhydride (3) (0.50 mmol, 155.1 mg) solution in DMF (20 wt %), an equimolar amount of diamine compound (19) was added, and the mixture was stirred in an argon atmosphere at 50° C. for 50 hours, and then, 80° C. for 14 hours, 110° C. for 24 hours, and 140° C. for 24 hours, sequentially. As a result, polyimide 20 having a number average molecular weight of 4.6×103 was obtained with a yield of 79%. The product was dissolved in DMF, and the resultant was applied to a quartz plate by spin-coating and heat-treated at 70° C. for 0.5 hours and 260° C. for 1.5 hours, to thereby obtain a light yellow transparent polyimide film.
1H NMR (500 MHz, CDCl3) δ=8.03; (2H, d, J=6.6), 7.57-7.52; (4H, m), 7.21; (2H, s), 7.05; (2H, s), 3.83-3.82; (6H, m), 2.29-2.27; (6H, m).
19F NMR (471 MHz, CDCl3) δ=−115.4; (4F, s), −127.6; (8F, s).
To a 4,4′-(hexafluoroisopropylidene)diphthalic anhydride 21 [common name: 6FDA] (0.27 mmol, 117.0 mg) solution in DMF (20 wt %), an equimolar amount of diamine compound (11) was added, and the mixture was stirred in an argon atmosphere at 50° C. for 50 hours, and then, 80° C. for 14 hours, 110° C. for 24 hours, and 140° C. for 24 hours, sequentially. As a result, polyimide 22 having a number average molecular weight of 2.5×103 was obtained with a yield of 60%. The product was dissolved in DMF, and the resultant was applied to a quartz plate by spin-coating and heat-treated at 70° C. for 0.5 hours and 260° C. for 1.5 hours, to thereby obtain a light yellow transparent polyimide film. The polyimide film was insoluble in AK-225 (1 mol/L).
1H NMR (500 MHz, CDCl3) δ=8.09; (2H, d, J=8.2), 7.99; (4H, m), 7.49; (4H, s), 2.54; (8H, m), 1.20; (12H, t, J=7.6).
19F NMR (471 MHz, CDCl3) δ=−63.6; (6F, s), −111.3; (4F, s), −121.8; (8F, s).
To a 4,4′-(hexafluoroisopropylidene)diphthalic anhydride 21 [common name: 6FDA] (0.199 mmol, 88.5 mg) solution in DMF (20 wt %), an equimolar amount of diamine compound (2a) was added, and the mixture was stirred in an argon atmosphere at 50° C. for 50 hours, and then, 80° C. for 14 hours, 110° C. for 24 hours, and 140° C. for 24 hours, sequentially. As a result, polyimide 23 having a number average molecular weight of 6.3×103 was obtained with a yield of 95%.
1H NMR (500 MHz, CDCl3) δ=8.09; (2H, d, J=7.8), 7.99; (4H, m), 7.45; (4H, s), 2.27; (12H, s).
19F NMR (471 MHz, CDCl3) δ=−63.6; (6F, s) , −111.3; (4F, s), −121.7; (8F, s).
To a dodecafluoro-1,6-diiodohexane (1.0 mmol) solution in a mixture of acetonitrile/water (25/5 mL), 6 equivalents of 2,6-diisopropylaniline (24), 10 mol % of eosin Y-2Na, 2.5 equivalents of cesium carbonate, and 4 equivalents of ascorbic acid (2 mL) were added, and the mixture was irradiated with light for 24 hours using white LED in an argon atmosphere. As a result, the target diamine compound 25 was obtained with a yield of 68%.
1H NMR (500 MHz, CDCl3) δ=7.19; (4H, s), 4.02; (4H, br s), 2.90; (2H, m), 1.28; (6H, d, J=6.9).
19F NMR (471 MHz, CDCl3) δ=−109.8; (4F, s), −121.9; (4F, s), −122.3; (4F, s).
To a 4,4′-oxydiphthalic anhydride (3) (0.50 mmol, 155.9 mg) solution in DMF (50 wt %), an equimolar amount of diamine compound (25) was added, and the mixture was stirred in an argon atmosphere at 50° C. for 50 hours, and then, 80° C. for 14 hours, 110° C. for 24 hours, and 140° C. for 24 hours, sequentially. As a result, polyimide 6 having a number average molecular weight of 2.3×104 was obtained. The product was dissolved in DMF, and the resultant was applied to a quartz plate by spin-coating and heat-treated at 70° C. for 0.5 hours and 260° C. for 1.5 hours, to thereby obtain a light yellow transparent polyimide film.
1H NMR (500 MHz, CDCl3) δ=8.07; (2H, d, J=9.2), 7.60; (4H, m), 7.51; (4H, s), 7.40; (4H, d, J=7.3), 2.79; (4H, m), 1.21; (24H, m).
19F NMR (471 MHz, CDCl3) δ=−111.5; (4F, s), −121.9; (8F, s).
To a 4,4′-oxydiphthalic anhydride (3) (0.50 mmol, 155.8 mg) solution in DMF (50 wt %), an equimolar amount of diamine compound (8) was added, and the mixture was stirred in an argon atmosphere at 50° C. for 50 hours, and then, 80° C. for 14 hours, 110° C. for 24 hours, and 140° C. for 24 hours, sequentially. As a result, polyimide 27 having a number average molecular weight of 5.3x10 3 was obtained. The product was dissolved in DMF, and the resultant was applied to a quartz plate by spin-coating and heat-treated at 70° C. for 0.5 hours and 260° C. for 1.5 hours, to thereby obtain a light yellow transparent polyimide film.
To a 4,4′-(hexafluoroisopropylidene)diphthalic anhydride 21 [common name: 6FDA] (0.51 mmol, 225.4 mg) solution in DMF (50 wt %), an equimolar amount of diamine compound (8) was added, and the mixture was stirred in an argon atmosphere at 50° C. for 50 hours, and then, 80° C. for 14 hours, 110° C. for 24 hours, and 140° C. for 24 hours, sequentially. As a result, polyimide 28 having a number average molecular weight of 6.7×103 was obtained with a yield. The product was dissolved in DMF, and the resultant was applied to a quartz plate by spin-coating and heat-treated at 70° C. for 0.5 hours and 260° C. for 1.5 hours, to thereby obtain a light yellow transparent polyimide film.
1H NMR (500 MHz, CDCl3) δ=8.11; (2H, d, J=8.2), 8.01; (2H, s), 7.93; (2H, d, J=8.2), 7.40; (4H, d, J=7.3).
19F NMR (471 MHz, CDCl3) δ=−63.6; (6F, s), −111.3; (4F, s), −112.3; (4F, s), −121.7; (6F, s), 122.2; (6F, s).
To a 4,4′-(hexafluoroisopropylidene)diphthalic anhydride 21 [common name: 6FDA] (0.50 mmol, 223.0 mg) solution in DMF (50 wt %), an equimolar amount of diamine compound (7) was added, and the mixture was stirred in an argon atmosphere at 50° C. for 50 hours, and then, 80° C. for 14 hours, 110° C. for 24 hours, and 140° C. for 24 hours, sequentially. As a result, polyimide 29 having a number average molecular weight of 6.1×103 was obtained. The product was dissolved in DMF, and the resultant was applied to a quartz plate by spin-coating and heat-treated at 70° C. for 0.5 hours and 260° C. for 1.5 hours, to thereby obtain a light yellow transparent polyimide film. The polyimide film was soluble completely in AK-225 (1 mol/L). It was considered that this solubility was exhibited due to fluorine atoms on aromatic rings, as compared with Example 19.
1H NMR (500 MHz, CDCl3) δ=8.11; (2H, d, J=7.8), 8.03; (2H, s), 7.93; (2H, d, J=7.8), 7.40; (4H, d, J=6.9).
19F NMR (471 MHz, CDCl3) δ=−63.7; (6F, s), −111.3; (4F, s), −112.4; (4F, s), −121.7; (8F, s).
Reference was made to Polymer Preprints, Japan vol. 69, No. 2 (2020) 3R05 for values of physical properties and characteristics of polyimide 30 described above.
To a 4,4′-oxydiphthalic anhydride (3) (0.300 mmol, 93.0 mg) solution in DMF (20 wt %), 2,2′-bis(4-aminophenylhexafluoropropane) 31 (0.300 mmol, 100.0 mg) was added, and the mixture was stirred in an argon atmosphere at 50° C. for 50 hours, and then, 80° C. for 14 hours, 110° C. for 24 hours, and 140° C. for 24 hours, sequentially. After the completion of the reaction, it was found by visual observation that there was a polymer that was insoluble in DMF as the reaction medium and thus deposited. The medium was distilled off from the resulting reaction mixture. When THF (tetrahydrofuran) was added, part of the polymer was dissolved. The component soluble in THF and that insoluble in THF were purified by reprecipitation and washing, respectively, so that polyimide 32 that was soluble in THF and polyimide 32 that was insoluble in THF were obtained with yields of 10% and 21%, respectively. The number average molecular weight of the component soluble in THF was measured by GPC and found to be 4.9×103.
The values of various physical properties of the compounds obtained in Examples are collectively shown in the table below.
The polyimide obtained in each Example was dissolved in DMF (1 mL). The resulting solution was dropped on a quartz plate and applied thereto using a spin coater, and then heat-treated was performed at 70° C. for 0.5 hours and 260° C. for 1.5 hours to thereby prepare a polyimide film.
On a thin film obtained by firing on a silicon substrate, the measurements of TE and TM were carried out at measurement wavelengths of 633, 850, 1550, and 3120 nm using a prism Coupler (METRICON PC-2010).
The dielectric constant was calculated using the following formula.
Dielectric Constant ε=1.1×[Refractive Index n (@ 588 nm)]2
The polyimide compound of the present disclosure can be used in a wide variety of applications including automobile components, aircraft components, and electrical and electronic components.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2021-018385 | Feb 2021 | JP | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/JP2022/004744 | 2/7/2022 | WO |
