CN116332781A - Diamine compound, process for producing the same, polymer formed from the diamine compound, and use thereof - Google Patents

Diamine compound, process for producing the same, polymer formed from the diamine compound, and use thereof Download PDF

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CN116332781A
CN116332781A CN202211658489.2A CN202211658489A CN116332781A CN 116332781 A CN116332781 A CN 116332781A CN 202211658489 A CN202211658489 A CN 202211658489A CN 116332781 A CN116332781 A CN 116332781A
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diamine compound
compound
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刘光舜
杨凭勲
张财源
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LEE CHANG YUNG CHEMICAL INDUSTRY Corp
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LEE CHANG YUNG CHEMICAL INDUSTRY Corp
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C229/52—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
    • C07C229/54—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton with amino and carboxyl groups bound to carbon atoms of the same non-condensed six-membered aromatic ring
    • C07C229/60—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton with amino and carboxyl groups bound to carbon atoms of the same non-condensed six-membered aromatic ring with amino and carboxyl groups bound in meta- or para- positions
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C227/04—Formation of amino groups in compounds containing carboxyl groups
    • 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
    • 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
    • C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
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    • 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
    • C08G73/1075—Partially aromatic polyimides
    • C08G73/1078—Partially aromatic polyimides wholly aromatic in the diamino moiety
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2602/00—Systems containing two condensed rings
    • C07C2602/36—Systems containing two condensed rings the rings having more than two atoms in common
    • C07C2602/42—Systems containing two condensed rings the rings having more than two atoms in common the bicyclo ring system containing seven carbon atoms
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/56—Ring systems containing bridged rings
    • C07C2603/90—Ring systems containing bridged rings containing more than four rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors

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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Polyamides (AREA)
  • Epoxy Resins (AREA)

Abstract

The invention provides a diamine compound represented by formula I.

Description

Diamine compound, process for producing the same, polymer formed from the diamine compound, and use thereof
Technical Field
The present invention relates to a diamine compound, and more particularly, to a diamine compound containing a norbornane ring.
Background
Diamine compounds are useful for synthesizing a variety of polymers, such as polyimide (polyimide), polyamide acid (polyamic acid), epoxy resin (epoxy s in), polyamide (polyimide), polyurea a, and polyimide (polyimide); and is used for various purposes such as an insulating tape, a wire paint, a protective coating, an alignment film, a transparent substrate, or a film.
Generally, diamine compounds with rod-like structures have a preferred packing factor, which reduces the coefficient of thermal expansion of the material from which they are formed. However, most rod-like diamine compounds contain aromatic groups, for example, 4-aminophenyl-4-aminobenzoate, which has a conjugated system, resulting in the possibility of yellowing of the formed material when applied for a long period of time or subjected to a high temperature process. Thus, there is a need for diamine compounds that impart good optical properties and lower coefficients of thermal expansion to materials.
Disclosure of Invention
According to an embodiment of the present invention, there is provided a diamine compound represented by formula I.
Figure BDA0004012624320000011
In formula I, a is an alicyclic hydrocarbon group (ali cycli C hydro C arbon group) containing a norbornane ring and having 7 to 30 carbon atoms, and Y is-co-or-conh-.
According to an embodiment of the present invention, there is provided a method for producing a diamine compound, including: the compound of formula III is subjected to a hydrogenation reaction to form a diamine compound of formula I.
Figure BDA0004012624320000021
In formulas I and ii, a is an alicyclic hydrocarbon group containing a norbornane ring and having 7 to 30 carbon atoms, B is an alicyclic hydrocarbon group containing a norbornane ring or a norbornene ring and having 7 to 30 carbon atoms, and Y is-co-or-conh-.
According to an embodiment of the present invention, there is provided a polymer derived from a diamine compound represented by formula I.
Figure BDA0004012624320000022
In formula I, a is an alicyclic hydrocarbon group containing a norbornane ring and having 7 to 30 carbon atoms, and Y is-co O-, or-C ON H-.
According to an embodiment of the present invention, there is provided a use of the polymer as described above for an insulating tape, an electric wire paint, a protective coating, an alignment film, a transparent substrate, or a film.
In order to make the features of the present invention comprehensible, embodiments accompanied with figures are described in detail below, and other remarks are made in the technical field.
Detailed Description
The diamine compound and the polymer formed therefrom are described in detail below. It is to be understood that the following description provides many different embodiments, or examples, for implementing different aspects of some embodiments of the invention. The specific components and arrangements described below are only for simplicity and clarity in describing some embodiments of the present invention. These are, of course, merely examples and are not intended to be limiting.
As used herein, the terms "about", "substantially" and "substantially" generally mean within 5%, preferably within 3%, more preferably within 1%, or within 2%, or within 1%, or within 0.5% of a given value or range. Where a given quantity is about, i.e., where "about", and "substantially" are not specifically recited, the meaning of "about", and "substantially" may be implied.
The diamine compound (di amine compound) of the present invention and a process for producing the same will be described in detail below.
[ diamine Compound ]
According to an embodiment of the present invention, there is provided a diamine compound represented by formula I.
Figure BDA0004012624320000031
In formula I, a is an alicyclic hydrocarbon group (ali cycli C hydro C arbon group) containing a norbornane ring and having 7 to 30 carbon atoms, and Y is-co-or-conh-.
In some embodiments, the diamine compounds of the present invention may be represented by formula II.
Figure BDA0004012624320000041
In formula II, B is absent or-C H 2 Y is-C O-or-C ONH-, and n and m represent 0 or an integer from 1 to 2. Wherein in formula II, at least one B is-C H 2 Whereby the diamine compound contains a norbornane ring group.
In some embodiments, the diamine compound of the present invention may have the structure shown below, for example, but is not limited thereto:
Figure BDA0004012624320000042
Figure BDA0004012624320000051
in some embodiments, the diamine compound of the present invention may have the structure shown below, for example, but is not limited thereto:
Figure BDA0004012624320000052
Figure BDA0004012624320000061
[ preparation of diamine Compound ]
According to an embodiment of the present invention, there is provided a method for producing a diamine compound, including: the compound of formula III is subjected to a hydrogenation reaction to form a diamine compound of formula I.
Figure BDA0004012624320000062
In formulas I and ii, a is an alicyclic hydrocarbon group containing a norbornane ring and having 7 to 30 carbon atoms, B is an alicyclic hydrocarbon group containing a norbornane ring or a norbornene ring and having 7 to 30 carbon atoms, and Y is-co-or-conh-.
In some embodiments, the compound of formula III may be formed by reacting a bis-alcohol compound of formula IV with nitrobenzoyl chloride.
B-(O H) 2 (IV)
In formula IV, B is an alicyclic hydrocarbon group containing a norbornane ring or a norbornene ring and having 7 to 30 carbon atoms.
In some embodiments, the compound of formula III may be formed by reacting a diamine compound of formula V with nitrobenzoyl chloride.
B-(NH 2 ) 2 (V)
In formula V, B is an alicyclic hydrocarbon group containing a norbornane ring or a norbornene ring and having 7 to 30 carbon atoms.
The following table lists specific examples of the diamine compounds of the present invention and the corresponding chemical names.
Figure BDA0004012624320000071
Figure BDA0004012624320000081
As described above, various polymers (for example, polyimide, polyamic acid, epoxy resin, polyamide, polyurea, and polyimide) can be formed using the diamine compound of the present invention, and these polymers can be used for various applications. The polymers and the preparation method thereof are described below by way of example, but it should be noted that the types and preparation methods of the polymers are not limited thereto.
According to an embodiment of the present invention, there is provided a polymer formed of a diamine compound represented by formula I.
Figure BDA0004012624320000091
In formula I, a is an alicyclic hydrocarbon group containing a norbornane ring and having 7 to 30 carbon atoms, and Y is-co O-, or-conh-.
Polyamic acid
In some embodiments, the polymer of the present invention may be a polyamic acid comprising a repeating unit of the formula.
Figure BDA0004012624320000092
In the above formula, X is a 4-valent organic group derived from a tetracarboxylic dianhydride compound. In some embodiments, the tetracarboxylic dianhydride compound may be 1,2,3, 4-cyclobutane tetracarboxylic dianhydride (CB DA), bicyclo [3, 0]Octane-2, 4,6, 8-tetracarboxylic dianhydride (B ODA), pyromellitic dianhydride (PMDA) or 2,3, 5-tricarboxycyclopentanyl acetic dianhydride (TCA), but is not limited thereto. In addition, one kind of tetracarboxylic dianhydride compound may be used alone, or two or more kinds of tetracarboxylic dianhydride compounds may be used in combination to react with the diamine compound represented by formula I of the present invention to form polyamic acid. In the above formula, Y 1 Are residues derived from the diamine compounds of formula I of the present invention.
[ method for producing Polyamic acid ]
In some embodiments, the polyamic acid of the present invention is formed by the following process: the tetracarboxylic dianhydride compound is mixed with the diamine compound shown in the formula I of the invention to perform condensation polymerization in a solvent to form polyamide acid. In some embodiments, the condensation polymerization reaction may be stirred at 200 to 400rpm for 3 to 12 hours at room temperature under nitrogen atmosphere, for example at 300rpm for 4 hours at room temperature. After the reaction is completed, it is cooled to obtain polyamic acid.
[ polyimide ]
In some embodiments, the polymer of the present invention may be a polyimide comprising repeating units of the general formula.
Figure BDA0004012624320000101
In the above formula, X is a 4-valent organic group derived from a tetracarboxylic dianhydride compound, and Y 1 Are residues derived from the diamine compounds of formula I of the present invention. The types of the tetracarboxylic dianhydride compound are as described above, and will not be described in detail. In addition, one kind of tetracarboxylic dianhydride compound may be used alone, or two or more kinds of tetracarboxylic dianhydride compounds may be used in combination to react with the diamine compound represented by formula I of the present invention to form polyimide.
[ method for producing polyimide ]
In some embodiments, the polyimide of the present invention is formed by the following process: the tetracarboxylic dianhydride compound and the diamine compound represented by formula I of the present invention are polymerized (polymizati on) in a solvent to obtain polyamic acid, and then the polyamic acid is imidized (imidization) to form polyimide. The synthesis method for imidizing the polyamic acid is exemplified by the following two methods, but is not limited thereto. The first method is carried out in two stages, first, a tetracarboxylic dianhydride compound and a diamine compound represented by formula I of the present invention are reacted in a polar solvent to form a precursor (pre cursor) polyamic acid of polyimide. Then imidization reaction is carried out by a high temperature method (300-500 ℃) or a chemical method, so that polyamide acid is dehydrated and closed to form polyimide. In some embodiments, the high temperature process is conducted at a temperature of 300 to 500 ℃ for 4 to 8 hours, for example, at 400 ℃ for 6 hours. In some embodiments, the chemical process is at room temperature
Acetic anhydride and catalyst are added at a temperature of about 120 ℃ for reaction for 3 to 24 hours, for example, at a temperature of 90 ℃ for 16 hours. The second method is to synthesize polyimide in one stage, react tetracarboxylic dianhydride compound with diamine compound shown in formula I in the invention in polar aprotic solvent, and heat to reflux temperature to react, thus forming polyimide. After the reaction is completed, the polyimide solid can be obtained by cooling and recrystallizing, purifying and drying the polyimide solid.
[ epoxy resin ]
In some embodiments, the polymer of the present invention may be an epoxy resin comprising structural units of the following formula.
Figure BDA0004012624320000111
In the above formula, Y 1 R is a residue derived from the diamine compound of formula I of the present invention 1 Is a 2-valent organic group, and n and m represent integers of 2 to 1000.
[ method for producing epoxy resin ]
In some embodiments, the epoxy resins of the present invention are formed by the following process: reacting an epoxy compound of the general formula with a diamine compound of formula I of the present invention to form an epoxy resin:
Figure BDA0004012624320000121
in the above formula, R 1 P is a p-valent organic radical, and p represents an integer from 2 to 6, for example 3,4 or 5. It should be understood that the epoxy compound may be any epoxy compound having two or more epoxy groups known in the art, and is not exemplified herein. In addition, one kind of epoxy compound may be used alone, or two or more kinds of epoxy compounds may be used in combination to react with the diamine compound represented by formula I of the present invention to form an epoxy resin.
[ Polyamide ]
In some embodiments, the polymer of the present invention may be a polyamide comprising repeat units of the general formula.
Figure BDA0004012624320000122
In the above formula, R 2 Is a 2-valent organic group derived from a diacid compound or a diacyl halide compound, and Y 1 Are residues derived from the diamine compounds of formula I of the present invention. The diacid compound(s) and diacid halide compound(s) may be any diacid compound(s) and diacid halide compound(s) known in the art, and are not recited herein. In addition, one diacid compound or diacid halide compound may be used alone, or two or more diacid compounds and/or diacid halide compounds may be used in combination to react with the diamine compound represented by the formula I of the present invention to form a polyamide.
[ Process for producing Polyamide ]
In some embodiments, the polyamide of the present invention is formed by the following process: the diacid compound(s) and/or the diacid halide compound(s) are reacted with the diamine compound(s) of formula I of the present invention to form a polyamide.
Polyurea
In some embodiments, the polymer of the present invention may be a polyurea comprising repeating units of the general formula.
Figure BDA0004012624320000131
In the above formula, R 4 Is a 2-valent organic group derived from a diisocyanate compound, and Y 1 Are residues derived from the diamine compounds of formula I of the present invention. The diisocyanate compound may be any diisocyanate compound known in the art and is not exemplified herein. In addition, one kind of diisocyanate compound may be used alone, or two or more kinds of diisocyanate compounds may be used in combination to react with the diamine compound represented by formula I of the present invention to form polyurea.
[ Process for producing polyurea ]
In some embodiments, the polyureas of the present invention are formed by the following process: the diisocyanate compound is reacted with the diamine compound represented by formula I of the present invention to form a polyurea.
[ Polyimine ]
In some embodiments, the polymer of the present invention may be a polyimide comprising repeating units of the general formula.
Figure BDA0004012624320000141
In the above formula, R 3 Is a 2-valent organic radical derived from a dialdehyde compound, and Y 1 Are residues derived from the diamine compounds of formula I of the present invention. The dialdehyde compound may be any dialdehyde compound known in the art and is not recited herein. In addition, one dialdehyde compound may be used alone, or two or more dialdehyde compounds may be used in combination to react with the diamine compound represented by formula I of the present invention to form a polyimide.
[ method for producing Polyimine ]
In some embodiments, the polyimide of the present invention is formed by the following process: the dialdehyde compound is reacted with the diamine compound of formula I of the present invention to form a polyimide.
[ optical Properties of Polymer of the invention ]
In some embodiments, the polymers of the invention have a total light transmittance (T.T) of greater than 80%, e.g., 82%, 85%, 88%, 91%, 94%, 97%, or 99%.
In some embodiments, the polymers of the present invention have a Yellowness Index (YI) of less than 5, preferably less than 3, and more preferably less than 2. For example, 4.5, 4, 3.5, 3, 2.5, 2, 1.5, 1 or 0.5.
In some embodiments, the polymer of the present invention has b of less than 3, preferably less than 2, more preferably less than 1.5. For example, 2.8, 2.5, 2.3, 1.8, 1.4, 1 or 0.5.
In some embodiments, the polymers of the present invention have a haze of less than 2.5%, preferably less than 2%, more preferably less than 1%, for example, 2.2%, 1.8%, 1.5%, 1.2%, 0.8%, 0.5%, 0.3%, 0.2%, or 0.1%.
[ physical and chemical Properties of Polymer of the invention ]
In some embodiments, the glass transition temperature (Tg) of the polymer of the present invention is greater than 200 ℃, preferably greater than 230 ℃, and more preferably greater than 250 ℃. For example 210 ℃, 215 ℃, 220 ℃, 225 ℃, 235 ℃, 240 ℃, 245 ℃, 255 ℃, 260 ℃, 265 ℃, 270 ℃, 275 ℃ or 280 ℃.
In some embodiments, the polymers of the present invention have a Coefficient of Thermal Expansion (CTE) of less than 55 ppm/. Degree.C, preferably less than 50 ppm/. Degree.C, more preferably less than 45 ppm/. Degree.C, for example, 53 ppm/. Degree.C, 48 ppm/. Degree.C, 46 ppm/. Degree.C, 43 ppm/. Degree.C, 41 ppm/. Degree.C, 39 ppm/. Degree.C, 36 ppm/. Degree.C, or 33 ppm/. Degree.C.
[ use of Polymer of the invention ]
According to an embodiment of the present invention, there is provided a use of a polymer containing a diamine compound for an insulating tape, an electric wire paint, a protective coating, an alignment film, a transparent substrate, or a film, but not limited thereto.
In some embodiments, the diamine compound-containing polymers of the present invention are useful in components of electronic devices. In some embodiments, the "component" may be an optical component, such as, but not limited to, a transparent film, a transparent substrate, a transparent plate (sheet), a transparent layer, or the like. In some embodiments, the "device" may also be a non-optical device, such as a semiconductor device, but is not limited thereto.
In the present invention, the term "electronic device" is intended to include devices of one or more organic semiconductor layers or materials. In some embodiments, the electronic device includes, but is not limited to:
(1) means for converting electrical energy into radiation (e.g., a light emitting diode display, a diode laser, or an illumination panel), (2) means for processing detection signals using electrons (e.g., a photodetector, a photoconductive cell, a photoresistor, a photoswitch, a phototransistor, a photocell, an Infrared (IR) detector, or a biosensor), (3) means for converting radiation into electrical energy (e.g., a photovoltaic device or a solar cell), (4) means (e.g., a transistor or a diode) comprising one or more electronic components comprising one or more organic semiconductor layers, or any combination of the means in (1) through (4).
In some embodiments, the polymers of the present invention are useful in components of liquid crystal displays (L CD). In some embodiments, the polymers of the present invention may be used in alignment layers in display devices. In some embodiments, the polymers of the present invention may be applied to components in organic electronic devices, such as organic light emitting diodes (O LEDs). In some embodiments, the polymer of the present invention may be applied to a transparent protective filter for a camera.
The present disclosure provides several examples to more specifically illustrate the effects that can be achieved by the polymers according to the embodiments of the present disclosure, and the characteristics of the polymers obtained by applying the present disclosure. However, the following examples are illustrative only and should not be construed as limiting the practice of this disclosure.
[ PREPARATION EXAMPLE 1] diamine Compound (tetradecahydro-1, 4:5, 8-dimethylanthracene-9, 10-diyl-bis (4-aminobenzoate))
Figure BDA0004012624320000171
For the synthesis of the diol compound 4, see the relevant synthesis procedure disclosed in patent document (WO 2017209199 A1), the diol compound 4 is synthesized from the compound 1 (1, 4-benzoquinone (b-benzoquinone)) and the compound 2 (dicyclopentadiene (di cyclop entadi ene)).
Step 3
Figure BDA0004012624320000172
4-nitrobenzoyl chloride (1.5 g,8.2 mmol) was added to a solution of bis-alcohol compound 4 (0.5 g,2.0 mmol) and 21mL of pyridine. The solution was stirred at room temperature. After 16 hours, the white solid was filtered and washed with methanol (20 mL) to give the product as a white solid (0.7 g, 63.1%) as diester compound 5. NMR spectrum data for diester compound 5 is as follows: 1 H NMR(400MHz,CD Cl 3 ,298K):δ＝1.18(d,J＝8.4Hz,1H),1.30(d,J＝8.4Hz,1H),1.49-1.56(m,2H),2.19-2.30(m,2H),2.69-2.78(m,2H),2.89-2.98(m,4H),4.73-4.85(m,2H),6.29-6.32(m,2H),6.33-6.37(m,2H),8.21-8.27(m,4H),8.28-8.34(m,4H).M S:c ald for C 30 H 27 N 2 O 8 :m/z 543.2；found:543.2[M+H] + 。
step 4
Figure BDA0004012624320000181
Diester compound 5 (0.6 g,1.10 mmol) was dissolved in 24mL of methanol and 72mL of methylene chloride, and 5% Pd/C (0.06 g) was added. The mixture was stirred at room temperature under a hydrogen atmosphere for 16 hours. The solution was filtered and concentrated to give the product as a white solid (0.5 g, 93.2%) as diamine compound 6 (tetradecahydro-1, 4:5, 8-dimethylanthracene-9, 10-diyl-bis (4-aminobenzoate)). NMR spectrum data of diamine compound 6 are as follows: 1 H NMR(400MHz,CD Cl 3 ,298K):δ＝1.20-1.42(m,6H),1.46-1.54(m,2H),1.63-1.75(m,2H),1.98-2.09(m,2H),2.17-2.24(m,2H),2.31-2.38(m,2H),2.67-2.81(m,4H),4.02(brs,4H),5.32-5.50(m,2H),6.59-6.66(m,4H),7.80-7.89(m,4H).M S:c ald for C 30 H 34 N 2 O 4 N a:m/z 509.2；found:509.6[M+N a] + 。
[ PREPARATION EXAMPLE 2] diamine Compound (tetradecahydro-1, 4:5, 8-dimethylanthracene-9, 10-diyl-bis (3-aminobenzoate))
Figure BDA0004012624320000191
For the synthesis of the diol compound 4, see the relevant synthesis procedure disclosed in patent document (WO 2017209199A 1), the diol compound 4 was synthesized from 1, 4-benzoquinone (b-benzoquinone) and dicyclopentadiene (di cyclop entadi ene).
3-nitrobenzoyl chloride (1.86 g,10.0 mmol) was added to a solution of the diol compound 4 (1.0 g,4.0 mmol), 4-dimethylaminopyridine (4-DMAP) (0.05 g,0.04 mmol) and 40mL of pyridine. The solution was stirred at room temperature. After 16 hours, 200mL of water was added to the reaction mixture. The white solid was filtered and washed with methanol to give the product as a white solid (1.5 g, 69%) as diester compound 5'.
Diester compound 5' (0.5 g,1.0 mmol) was dissolved in 7.5mL of methanol and 15mL of methylene chloride, and 10% Pd/C (0.05 g) was added. The mixture was stirred at room temperature under a hydrogen atmosphere for 24 hours. The solution was filtered and concentrated to give the product as a white solid (0.5 g, 92%) as diamine compound 6' (tetradecahydro-1, 4:5, 8-dimethylanthracene-9, 10-diyl-bis (3-aminobenzoate)). NMR spectrum data of diamine compound 6' are as follows: 1 H NMR(400MHz,CD Cl 3 ,298K):δ＝1.26-1.45(m,6H),1.49-1.59(m,2H),1.64-1.72(m,2H),2.01-2.09(m,2H),2.18-2.28(m,2H),2.32-2.42(m,2H),2.71-2.85(m,4H),3.80(brs,4H),5.39-5.51(m,2H),6.82-6.90(m,2H),7.18-7.25(m,2H),7.32-7.37(m,2H),7.40-7.49(m,2H).M S:c ald for C 30 H 35 N 2 O 4 :m/z 487.3；found:487.3
[M+H] + 。
[ PREPARATION EXAMPLE 3] diamine Compound (bicyclo [2.2.1] heptane-2, 5-diyl-bis (4-aminobenzoate))
Figure BDA0004012624320000201
Step 1
Figure BDA0004012624320000202
In a 1L round bottom flask, compound 7 (2, 5-norbornadiene) (100 g,1.08 mol) and 97% formic acid (600 mL) were added under argon. The reaction was refluxed at 120℃for 24 hours, after which the formic acid was distilled off and distilled under vacuum (120-130 ℃,10mmHg/13.3 mbar) to give a clear liquid of the diformate. The crude diformate (198.7 g,1.07 mol) was placed in a 3L round bottom flask and dissolved in THF (1.5L). The solution was cooled to 0deg.C and a solution containing NaO H (424 g) and water (600 mL) was added in a dropping funnel over 30 minutes. The reaction mixture was stirred at room temperatureAfter 10 hours, extraction was performed with ethyl acetate. The aqueous layer was saturated with sodium chloride, and then extracted with ethyl acetate. The combined organics were dried over magnesium sulfate and concentrated to give the product as a colourless solid (100 g), i.e. bis-alcohol compound 8. NMR spectrum data for the diol compound 8 is as follows: 1 H NMR(400MHz,CD Cl 3 ,298K):δ＝0.93-1.09(m,1H),1.17-1.25(m,1H),1.44-1.85(m,4H),1.96-2.29(m,4H),3.63-4.52(m,4H).GC/M S:[M-H]＝127。
step 2
Figure BDA0004012624320000211
In a 100mL round bottom flask, the diol compound 8 (1.0 g,5.43 mmol) was dissolved in dichloromethane (10 mL) and trimethylamine (1.65 g,16.29 mmol) at 0-10deg.C. Compound 9 (4-nitrobenzoyl chloride) (2.22 g,11.94 mmol) was added dropwise under nitrogen atmosphere for 1 hour and left at room temperature. The solution was stirred at room temperature for 16 hours. After the reaction is completed, the solution is washed 3 times with 100mL of water and the organic layer is dried by rotary evaporation to give a yellow solid (1.5 g, 69%) as dinitro compound 10. NMR spectrum data of dinitro compound 10 are as follows: 1 H NMR(400MHz,d6-DM S O,298K):δ＝1.03-1.25(m,1H),1.32-1.44(m,1H),1.55-1.88(m,4H),1.93-2.61(m,4H),4.66-5.02(m,2H),8.14-8.37(m,8H)；LC/M S:[M+Na]＝449。
step 3
Figure BDA0004012624320000221
Dinitro compound 10 (1.0 g,5.43 mmol) was dissolved in 6mL of methanol and 24mL of methylene chloride and 10% P d/C (0.1 g) was added. The mixture was stirred at room temperature under a hydrogen atmosphere for 24 hours. The solution was filtered and concentrated to give the product as a white solid (0.73 g, 85%) as diamine compound 11 (bicyclo [ 2.2.1)]Heptane-2, 5-diyl-bis (4-aminobenzoate)). NMR spectrum data of diamine compound 11 were as follows: 1 H NMR(400MHz,d6-DM S O,298K):δ＝1.29-1.35(m,1H),1.47-1.54(m,1H),1.58-1.98(m,4H),2.01-2.54(m,4H),4.53-4.82(m,2H),5.95-6.00(NH 2 ,m,4H),6.53-6.58(m,4H),7.59-7.66(m,4H)；LC/M S:[M+H]＝367。
PREPARATION EXAMPLE 4 polyimide
In a 100mL three-necked flask containing 5g GB L was placed diamine compound 6 of the aforementioned preparation 1 (1.0852 g,0.0022 mole) and TFMB (0.7143g,0.0022mol e) while maintaining a slow nitrogen flow. Tca (1.0000g,0.0044mol e) was added to the solution, after which 5g GB L was added again. The mixture was mechanically stirred at room temperature under a nitrogen stream for 24 hours to give a clear viscous solution. 5g GB L was added to the viscous solution for dilution. 3.6434g (0.03571 mol e) acetic anhydride (Ac) 2 O) and 3.8371g (0.02678 mole) TPA were slowly added dropwise to the solution and heated to 60℃for 12 hours. After the completion of the reaction, the solution was dropped into methanol and washed 3 times with methanol. Thereafter, the solid was filtered and dried in a vacuum oven to obtain pure polyimide powder.
The above components represent the following compounds:
GB L: gamma-butyrolactone (from Shengshi chemical Co., ltd.)
TFMB:2,2' -bis (trifluoromethyl) -4,4' -diaminobiphenyl (2, 2' -bs (tri fluorometrics) b enzidine) (available from Shifeng technologies Co., ltd.)
T CA:2,3, 5-Tricarboxycyclopentanylacetic acid dianhydride (3- (c carboxymethyl) -1,2,4-cyclop entanetri c arboxyli c acid 1,4:2,3-di anhydride) (Li Changrong manufactured by chemical industries Co., ltd.)
TPA: triphenylamine (from T C I)
PREPARATION EXAMPLE 5 polyimide varnish
The white polyimide powder prepared in preparation example 4 was dissolved in GB L (15 wt%) and degassed under vacuum to form a varnish.
PREPARATION EXAMPLE 6 polyimide film
The polyimide varnish was coated on a glass substrate by a blade coater to form a wet film. The wet film was dried in an oven with heating at 50 ℃ for 1 hour, 150 ℃ for 1 hour, and 200 ℃ for 2 hours to remove the solvent to form a polyimide film. Thereafter, the polyimide film was peeled from the substrate by immersing in deionized water. The various properties of the polyimide film were measured separately in the following test methods.
EXAMPLE 1 glass transition temperature test
Glass transition temperature (glas s trans ition temp erature, tg) analysis was performed using a TA Instruments thermo-mechanical analyzer "TMA/Q400" using a tensile thin film clamp. Cutting the sample into 16mm X5 mm, clamping and fixing the two ends of the test piece in TMA by using a clamp, introducing nitrogen with the flow rate of 100ml/min as a protective atmosphere, applying a fixed load of 0.05N, heating from 50 ℃ to 350 ℃ at the heating rate of 10 ℃/min, cooling to 50 ℃ by adopting a natural cooling mode, and heating to 500 ℃ at the heating rate of 10 ℃/min. The slope change turning point in the TMA measurement data is the glass transition temperature (Tg).
EXAMPLE 2 CTE test
Thermal expansion coefficient (co e ffi ci ent o f thermal exp ansion, CTE) analysis was performed using a TA Instruments thermo-mechanical analyzer "TMA/Q400" using a tensile film fixture. Cutting the sample into 16mm X5 mm, clamping and fixing the two ends of the test piece in TMA by using a clamp, introducing nitrogen with the flow rate of 100ml/min as a protective atmosphere, applying a fixed load of 0.05N, heating from 50 ℃ to 350 ℃ at the heating rate of 10 ℃/min, cooling to 50 ℃ by adopting a natural cooling mode, and heating to 500 ℃ at the heating rate of 10 ℃/min. Coefficient of Thermal Expansion (CTE) values are obtained from TMA measurement data by extracting the slope of 50-200 ℃.
EXAMPLE 3 full light transmittance test
The total light transmittance (total transmittanc e, T.T) was measured by using a chromaticity turbidity simultaneous measuring instrument "C SP-001" manufactured by the electric color industry (Co., ltd.) of Japan in accordance with A S TM D1003.
EXAMPLE 4 yellow index test
The yellow index (yellownes S index, YI) was measured by using a chromaticity turbidity simultaneous measuring instrument "C SP-001" manufactured by the electric color industry (Co., ltd.) of Japan in accordance with A S TM D1925.
Example 5]b value (b) test
CIE LabXcoordinate measurement was performed using a chromaticity turbidity simultaneous analyzer "C SP-001" manufactured by Nippon electric color industry (Co., ltd.) in accordance with A S TM D1925.
EXAMPLE 6 haze test
Haze (haze) was measured by using a chromaticity turbidity simultaneous measuring instrument "C SP-001" manufactured by the electric color industry (Co., ltd.) in accordance with A S TM D1003.
The polyimide film prepared in preparation example 6 was subjected to physical and chemical properties test by the above test method. The test results were as follows: the glass transition temperature was 283 ℃, the coefficient of thermal expansion was 35ppm/°c, the total light transmittance was 90.4%, the haze was 0.2%, the yellowness index was 1.65, and the b value (b x) was 0.85.
The present invention provides a novel diamine (di-amine) compound comprising a norbornane ring (norbonan) structure of a non-conjugated system. Since the novel diamine compound has a norbornane ring structure of a non-conjugated system, the optical properties (e.g., total light transmittance, yellow index, b value, and haze) of the synthesized polymer can be improved. In addition, the compound molecule can be more rigid and the structure is not easy to turn over by a huge cyclic structure such as the condensed cyclohexyl and the norbornyl, so that the dimensional stability of the high polymer material is further improved, and the Coefficient of Thermal Expansion (CTE) is reduced. Therefore, the diamine compound containing alicyclic hydrocarbon group can be used as the key composition of soft materials in electronic devices, so that the synthesized polymer has good heat resistance and optical characteristics. In addition, since the diamine compound of the present invention can synthesize a wide variety of polymer materials, for example, polyimide, polyamic acid, epoxy resin, polyamide, polyurea or polyimide, the present invention can be widely applied to various industrial fields where, for example, heat resistance or optical characteristics of materials are required.
The foregoing outlines several embodiments so that those skilled in the art to which the invention pertains may better understand the aspects of the embodiments of the present invention. Those skilled in the art will appreciate that they may readily use other processes and structures as a basis for designing or modifying other processes and structures for carrying out the same purposes and/or achieving the same advantages of the embodiments introduced herein. Those skilled in the art should also realize that such equivalent processes and structures do not depart from the spirit and scope of the present invention, and that they may make various changes, substitutions, and alterations herein without departing from the spirit and scope of the present invention.

Claims (15)

1. A diamine compound represented by formula I:
Figure FDA0004012624310000011
wherein A is an alicyclic hydrocarbon group containing a norbornane ring (norbornane ring) and having 7 to 30 carbon atoms, and Y is-COO-or-CONH-.
2. The diamine compound of claim 1, wherein the diamine compound is represented by formula II:
Figure FDA0004012624310000012
wherein B is absent or-CH 2 -*，
Y is-COO-or-CONH-, and
n and m represent 0 or an integer of 1 to 2.
3. The diamine compound of claim 1, wherein the diamine compound is:
Figure FDA0004012624310000021
4. the diamine compound of claim 1, wherein the diamine compound is:
Figure FDA0004012624310000031
5. a process for producing a diamine compound, comprising:
subjecting the compound of formula III to hydrogenation reaction to form a diamine compound of formula I,
Figure FDA0004012624310000041
wherein A is an alicyclic hydrocarbon group having a norbornane ring and a carbon number of 7 to 30,
b is alicyclic hydrocarbon group containing norbornane ring or norbornene ring and having 7 to 30 carbon atoms, and
y is-COO-or-CONH-.
6. The process for producing a diamine compound as described in claim 5, wherein the compound represented by the formula III is formed by reacting a diol compound represented by the formula IV with nitrobenzoyl chloride,
B-(OH) 2 (IV)
wherein B is an alicyclic hydrocarbon group having a norbornane ring or norbornene ring and having a carbon number of 7 to 30.
7. The process for producing a diamine compound according to claim 5, wherein the compound represented by formula III is formed by reacting a diamine compound represented by formula V with nitrobenzoyl chloride,
B-(NH 2 ) 2 (V)
wherein B is an alicyclic hydrocarbon group having a norbornane ring or norbornene ring and having a carbon number of 7 to 30.
8. A macromolecule derived from a diamine compound of formula I:
Figure FDA0004012624310000051
wherein A is an alicyclic hydrocarbon group containing a norbornane ring and having 7 to 30 carbon atoms, and Y is-COO-or-CONH-.
9. The polymer of claim 8, wherein the polymer comprises a repeating unit of the formula:
Figure FDA0004012624310000052
wherein X is a 4-valent organic group
Y 1 Is a residue derived from a diamine compound of formula I.
10. The polymer of claim 8, wherein the polymer comprises a repeating unit of the formula:
Figure FDA0004012624310000053
wherein X is a 4-valent organic group
Y 1 Is a residue derived from a diamine compound of formula I.
11. The polymer of claim 8, wherein the polymer comprises structural units of the formula:
Figure FDA0004012624310000061
wherein Y is 1 R is a residue derived from a diamine compound of formula I 1 Is a 2-valent organic group
n and m represent an integer of 2 to 1000.
12. The polymer of claim 8, wherein the polymer comprises a repeating unit of the formula:
Figure FDA0004012624310000062
wherein R is 2 Is a 2-valent organic group
Y 1 Is a residue derived from a diamine compound of formula I.
13. The polymer of claim 8, wherein the polymer comprises a repeating unit of the formula:
Figure FDA0004012624310000063
wherein R is 4 Is a 2-valent organic group
Y 1 Is a residue derived from a diamine compound of formula I.
14. The polymer of claim 8, wherein the polymer comprises a repeating unit of the formula:
Figure FDA0004012624310000071
wherein R is 3 Is a 2-valent organic group
Y 1 Is a residue derived from a diamine compound of formula I.
15. The use of the polymer according to claim 8 for an insulating tape, a wire paint, a protective coating, an alignment film, a transparent substrate, or a film.
CN202211658489.2A 2021-12-23 2022-12-22 Diamine compound, process for producing the same, polymer formed from the diamine compound, and use thereof Pending CN116332781A (en)

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