Soluble polyimides and methods for making the same

Abstract

The present invention provides a polyimide having solubility in an organic solvent and including, as polymerization units, a dianhydride monomer including bisphenol A type diether dianhydride (BPADA) and a diamine monomer including 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (6-FAP).

Description

Technical Field

[0001] This disclosure relates to a soluble polyimide and a method for preparing the same. More specifically, this disclosure relates to a polyimide with excellent thermal properties and simultaneously soluble in organic solvents, and a method for preparing the same. Background Technology

[0002] Typically, polyimide (PI) is based on an imide ring with excellent chemical stability along with a rigid aromatic backbone. It is a polymer material with the highest levels of heat resistance, chemical resistance, electrical insulation, and weather resistance among organic materials, and is thus prepared in various forms such as films, fibers, and membranes. Due to these properties, polyimide is used as an advanced material and insulating coating agent in a wide range of fields, including electrical and electronic, semiconductor, display, automotive, aerospace, and aviation materials.

[0003] Polyimides can be prepared by dissolving an acid dianhydride with two anhydride groups and a diamine with two amino groups in a solvent to synthesize a polyimide precursor called polyamic acid (PAA), followed by applying and drying the polyimide precursor, and then heat-treating it at about 350°C to perform imidization. Previously, due to the high demand for handling polyimides in solution, extensive development has been undertaken on solvent-soluble polyimides.

[0004] However, conventional polyimides prepared by imidization via dehydration and ring-closing reactions using conventional chemical or high-temperature methods are insoluble in solvents, leading to processing difficulties. Furthermore, to prepare solvent-soluble polyimides, there is usually no choice but to use highly soluble monomers, but these monomers typically have low heat resistance, resulting in polyimides with low heat and chemical resistance. Meanwhile, to use polyimides in solution form that possess both heat and chemical resistance, there exists a method for preparing polyimides by forming a coating film using a polyamic acid solution as a polyimide precursor, followed by imidization.

[0005] However, polyamic acid solutions have disadvantages such as being susceptible to moisture, difficult to handle and store, and requiring a high-temperature heat treatment process to imidize the polyamic acid.

[0006] In this context, there is a need to develop a polyimide that can be readily soluble in organic solvents while maintaining its high heat resistance and insulation properties, and that can be used to manufacture polyimide-based products simply by solvent drying without the need for a high-temperature imidization process. Summary of the Invention

[0007] [Technical Issues] One object of this disclosure is to provide a polyimide (PI) that is soluble in organic solvents and also has excellent thermal and mechanical properties.

[0008] Another object of this disclosure is to provide a polyimide that is fully imidized and can be widely manufactured into films, fibers, etc. by solvent drying without an imidization process at high temperatures.

[0009] Furthermore, one object of this disclosure is to provide a polyimide solution comprising the polyimide.

[0010] Furthermore, one object of this disclosure is to provide a polyimide powder comprising the polyimide.

[0011] Furthermore, one object of this disclosure is to provide a polyimide film comprising the polyimide.

[0012] Furthermore, one object of this disclosure is to provide various forms of the polyimide, such as separators, adhesives, insulating coatings, and coating materials comprising the polyimide.

[0013] Furthermore, one object of this disclosure is to provide a method for preparing the polyimide.

[0014] [Technical Solution] This disclosure can be modified in various ways and can be implemented in various ways; therefore, specific embodiments will be illustrated and described in detail below. However, this is not intended to limit this disclosure to the specific embodiments, but rather to cover all modifications, equivalents, and alternatives that fall within the spirit and scope of this disclosure.

[0015] The terminology used in this disclosure is for the purpose of describing particular embodiments only and is not intended to be limiting of the disclosure. Singular expressions include plural expressions unless the context clearly indicates otherwise. In this disclosure, terms such as “comprising” or “having” are intended to indicate the presence of features, quantities, steps, operations, components, parts, or combinations thereof described in the specification, and should not be construed as excluding the possibility of the presence or addition of one or more other features, quantities, steps, operations, components, parts, or combinations thereof.

[0016] In this specification, when dosage, concentration or other values ​​or parameters are given as an enumeration of ranges, preferred ranges or preferred upper and lower limits, it should be understood that all ranges consisting of any pair of upper or preferred values ​​and lower or preferred values ​​are specifically disclosed, regardless of whether such range is disclosed individually.

[0017] When referring to a range of values ​​herein, unless otherwise stated, it is intended to include the endpoints of that range, and the scope of this disclosure is not intended to be limited to the specific numerical values ​​mentioned when the range is defined.

[0018] As used herein, “dianhydride” is intended to include its precursors or derivatives, and may also be referred to as “diacid anhydride,” “dianhydride,” or “acid dianhydride.” These precursors or derivatives may not technically be dianhydrides, but may still react with diamines to produce polyamic acid, which can then be converted back to polyimide.

[0019] As used herein, “diamine” is intended to include its precursors or derivatives, which may not technically be diamines but can still react with dianhydrides to form polyamic acid, and which can be converted back into polyimide.

[0020] Unless otherwise defined, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure pertains. Terms such as those defined in commonly used dictionaries should be interpreted as having a meaning consistent with their meaning in the context of the relevant art, and should not be interpreted as having an idealized or overly formal meaning unless expressly defined in this application. A detailed description of embodiments of this disclosure will follow.

[0021] This disclosure relates to a soluble polyimide and a method for preparing the same.

[0022] polyimide This disclosure provides a polyimide comprising a dianhydride monomer and a diamine monomer as polymerization units; the dianhydride monomer comprises bisphenol A diether dianhydride (BPADA); the diamine monomer comprises 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (6-FAP); and the polyimide is soluble in an organic solvent.

[0023] The polyimide may comprise a polymerization unit consisting of the bisphenol A diether dianhydride (BPADA) and the 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (6-FAP).

[0024] The polyimide exhibits solubility in organic solvents when its solid content is 15 wt% or more. Specifically, the polyimide exhibits excellent solubility in organic solvents for solid contents of 15 wt%, 16 wt%, 17 wt%, 18 wt%, 19 wt%, 20 wt%, 21 wt%, 22 wt%, 23 wt%, 24 wt%, 25 wt% or more, and according to one embodiment, the turbidity of the solution is visually confirmed after adding 20 wt% of the polyimide solid content at room temperature and stirring for 30 minutes.

[0025] The organic solvent may include at least one selected from the group consisting of: N,N'-dimethylformamide (DMF), N-methylpyrrolidone (NMP), N,N'-diethylformamide (DEF), N,N'-dimethylacetamide (DMAc), dimethylpropionamide (DMPA), N,N-diethylacetamide (DEAc), dimethyl sulfoxide (DMSO), 3-methoxy-N,N-dimethylpropionamide (KJCMPA), p-chlorophenol, o-chlorophenol, γ-butyrolactone (GBL), diethylene glycol dimethyl ether, and naphthalene, preferably at least one selected from the group consisting of: N,N'-dimethylformamide (DMF), N-methylpyrrolidone (NMP), and N,N'-dimethylacetamide (DMAc), and more preferably N,N'-dimethylformamide (DMF).

[0026] Based on the total amount of the dianhydride monomers, the content of the bisphenol A type diether dianhydride (BPADA) can be from 50 mol% to 100 mol%, preferably from 50 mol% to 90 mol%, 50 mol% to 80 mol%, 50 mol% to 70 mol%, 50 mol% to 60 mol%, and more preferably from 50 mol% to 55 mol%. If the content of the bisphenol A type diether dianhydride (BPADA) is less than 50 mol%, the polyimide cannot achieve both solubility and thermal properties, and is therefore not preferred.

[0027] Based on the total amount of the diamine monomer, the content of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (6-FAP) can be from 30 mol% to 100 mol%, preferably from 30 mol% to 90 mol%, 30 mol% to 80 mol%, 30 mol% to 70 mol%, 30 mol% to 60 mol%, 30 mol% to 50 mol%, and more preferably from 30 mol% to 40 mol%. If the content of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (6-FAP) is less than 30 mol%, the polyimide cannot achieve both solubility and thermal properties, and is therefore not preferred.

[0028] The dianhydride monomer further comprises at least one selected from the group consisting of: 3,3',4,4'-benzophenone tetracarboxylic dianhydride (BTDA), pyromellitic tetracarboxylic dianhydride (PMDA), biphenyl tetracarboxylic dianhydride (BPDA), oxidiphthalic dianhydride (ODPA), diphenyl sulfone-3,4,3',4'-tetracarboxylic dianhydride (DSDA), bis(3,4-dicarboxyphenyl)sulfidedianhydride, and 2,2-bis(3,4-dicarboxyphenyl)-1,1,1,3,3,3-hexafluoropropane dianhydride. dianhydride), 2,3,3',4'-benzophenone tetracarboxylic dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, p-phenylenebis(trimellitic monoester acid anhydride), p-biphenylenebis(trimellitic monoester acid anhydride), m-terphenyl-3,4,3',4'-tetracarboxylic dianhydride dianhydride), p-terphenyl-3,4,3',4'-tetracarboxylic dianhydride, 1,3-bis(3,4-dicarboxyphenoxy)phthalic anhydride, 1,4-bis(3,4-dicarboxyphenoxy)phthalic anhydride, 1,4-bis(3,4-dicarboxyphenoxy)biphenyl dianhydride, 2,2-bis[(3,4-dicarboxyphenoxy)phenyl]propane dianhydride (BPADA), 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride and 4,4'-(2,2-hexafluoroisopropylidene)bisphthalic anhydride (4,4'-(2,2-hexafluoroisopropylidene (diphthalic dianhydride), and preferably further comprising 3,3',4,4'-benzophenone tetracarboxylic dianhydride (BTDA).

[0029] The diamine monomer further comprises at least one selected from the group consisting of: m-phenylenediamine (MPD), 4,4'-diaminodiphenylmethane (MDA), 4,4'-diaminodiphenyl ether (ODA), 2,2-diaminophenoxyphenylpropane (BAPP), m-phenylenediamine, 3,3'-dimethylbenzidine, 2,2'-dimethylbenzidine, 2,4-diaminotoluene, 2,6-diaminotoluene, 3,5-diaminobenzoic acid (DABA), 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl (m-tolidine), 2,2 '-Di(trifluoromethyl)-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dicarboxy-4,4'-diaminodiphenylmethane, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 4,4'-diaminobenzidine, 3,3'-dimethoxybenzidine, 2,2'-dimethoxybenzidine, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfidesulfide), 3,3'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminobenzophenone, 4,4'-diaminobenzophenone, 3,3'-diamino-4,4'-dichlorobenzophenone, 3,3'-diamino-4,4'-dimethoxybenzophenone, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 2,2-bis(3-aminophenyl)propane (2,2-b 2,2-bis(3-aminophenyl)propane, 2,2-bis(3-aminophenyl)-1,1,1,3,3,3-hexafluoropropane, 2,2-bis(4-aminophenyl)-1,1,1,3,3,3-hexafluoropropane, 3,3'-diaminodiphenyl sulfoxide, 3,4'-diaminodiphenyl sulfoxide, 4,4'-diaminodiphenyl sulfoxidesulfoxide), 1,3-bis(3-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 1,4-bis(3-aminophenyl)benzene, 1,4-bis(4-aminophenyl)benzene, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene (TPE-R), 1,4-bis(3-aminophenyl)benzene (TPE-Q), 1,3-bis(3-aminophenyl)benzene (TPE-Q), 1,3-bis(3-aminophenyl)benzene (TPE-Q), 1,3-bis(4-aminophenyl)benzene (TPE-R), 1,4-bis(3-aminophenyl)benzene (TPE-Q), 1,3-bis(3-aminophenyl)benzene (TPE-Q), 1,3-bis(4-aminophenyl)benzene (TPE-R), 1,3-bis(4-aminophenyl)benzene (TPE-Q), 1,3-bis(3 ... 1,3-bis(3-aminophenoxy)-4-trifluoromethylbenzene, 3,3'-diamino-4-(4-phenyl)phenoxybenzophenone, 3,3'-diamino-4,4'-di(4-phenylphenoxy)benzophenone, 1,3-bis(3-aminophenyl)benzene 1,3-bis(4-aminophenyl sulfide)benzene, 1,4-bis(4-aminophenyl sulfide)benzene, 1,3-bis(3-aminophenyl sulfone)benzene, 1,3-bis(4-aminophenyl sulfone)benzene, 1,4-bis(4-aminophenyl sulfone)benzene, 1,4-bis(4-aminophenyl sulfone)benzenesulfone)benzene), 1,3-bis[2-(4-aminophenyl)isopropyl]benzene, 1,4-bis[2-(4-aminophenyl)isopropyl]benzene, 1,4-bis[2-(3-aminophenyl)isopropyl]benzene, 1,4-bis[2-(4-aminophenyl)isopropyl]benzene, 3,3'-bis(3-aminophenoxy)biphenyl (3, 3'-bis(3-aminophenoxy)biphenyl), 3,3'-bis(4-aminophenoxy)biphenyl, 4,4'-bis(3-aminophenoxy)biphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, bis[3-(3-aminophenoxy)phenyl]ether ether), bis[3-(4-aminophenoxy)phenyl] ether, bis[4-(3-aminophenoxy)phenyl] ether, bis[4-(3-aminophenoxy)phenyl] ether, bis[4-(4-aminophenoxy)phenyl] ether, bis[3-(3-aminophenoxy)phenyl] ketone, bis[3-(4-aminophenoxy)phenyl] ketone, bis[4-(3-aminophenoxy)phenyl] ketone, bis[4-(4-aminophenoxy)phenyl] ketone, bis[4-(4-aminophenoxy)phenyl] ketone ketone), bis[3-(3-aminophenoxy)phenyl] sulfide, bis[3-(3-aminophenoxy)phenyl] sulfidesulfide), bis[4-(3-aminophenoxy)phenyl]sulfide, bis[4-(4-aminophenoxy)phenyl]sulfide, bis[3-(3-aminophenoxy)phenyl]sulfone, bis[3-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[3-(3-aminophenoxy)phenyl]methane methane, bis[3-(4-aminophenoxy)phenyl]methane, bis[4-(3-aminophenoxy)phenyl]methane, bis[4-(3-aminophenoxy)phenyl]methanemethane), 2,2-bis[3-(3-aminophenoxy)phenyl]propane, 2,2-bis[3-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(3-aminophenoxy)phenyl]propane, 2,2-bis[4-(3-aminophenoxy)phenyl]propane, 2,2-bis[4-(3-aminophenoxy)phenyl]propane, 2,2-bis[3-(3-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 2,2-bis[3-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 2,2-bis[3-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 2,2-bis[3-(4-aminophenoxy)phenyl]-1,1,1,3,3 The compounds may include 2,2-bis[3-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 2,2-bis[4-(3-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, and 2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, and preferably may further include at least one selected from the group consisting of m-phenylenediamine (MPD) and 4,4'-diaminodiphenylmethane (MDA).

[0030] According to one embodiment, the polyimide may include a dianhydride monomer and a diamine monomer as polymerization units; the dianhydride monomer is bisphenol A diether dianhydride (BPADA) and 3,3',4,4'-benzophenone tetracarboxylic dianhydride (BTDA); the diamine monomer is 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (6-FAP) and m-phenylenediamine (MPD).

[0031] According to one embodiment, the polyimide may include a dianhydride monomer and a diamine monomer as polymerization units; the dianhydride monomer is bisphenol A diether dianhydride (BPADA) and 3,3',4,4'-benzophenone tetracarboxylic dianhydride (BTDA); the diamine monomer is 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (6-FAP) and 4,4'-diaminodiphenylmethane (MDA).

[0032] According to one embodiment, the polyimide may include dianhydride monomers and diamine monomers as polymerization units; the dianhydride monomers are bisphenol A type diether dianhydride (BPADA) and 3,3',4,4'-benzophenone tetracarboxylic dianhydride (BTDA); the diamine monomers are 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (6-FAP), m-phenylenediamine (MPD), and 4,4'-diaminodiphenylmethane (MDA).

[0033] The polyimide may comprise 90 mol% to 110 mol%, preferably 95 mol% to 105 mol%, and more preferably 100 mol% of the diamine monomer.

[0034] The polyimide may comprise 90 mol% to 110 mol%, preferably 95 mol% to 105 mol%, and more preferably 100 mol% of the dianhydride monomer.

[0035] The polyimide may include the dianhydride monomer and the diamine monomer in a molar ratio of 1:2 to 2:1, preferably 1:1.

[0036] In this disclosure, the thermal decomposition temperature (Td) is identified, which is primarily used as a standard for determining the thermal properties of the polyimide.

[0037] The 5wt% thermal decomposition temperature (Td) of the polyimide may be 385°C or higher, and for example, the lower limit of the thermal decomposition temperature of the polyimide may be 387±1°C, 390±1°C, 393±1°C, 395±1°C, 397±1°C, 400±1°C, 403±1°C, 405±1°C, 407±1°C, or 410±1°C or higher. The upper limit of the thermal decomposition temperature is not particularly limited, but may be 600°C or lower, 590°C or lower, or 580°C or lower.

[0038] The thermal decomposition temperature can be measured using a TA Instruments Q50 thermogravimetric analyzer. In a specific embodiment, the polyimide can be heated to 100°C at a rate of 10°C / min under a nitrogen atmosphere, and then held at that temperature for 1 hour to remove moisture. Subsequently, the temperature is increased to 600°C at a rate of 10°C / min to measure the temperature at which a 5% weight loss occurs.

[0039] The polyimide disclosed herein is characterized by excellent thermal properties while exhibiting excellent solubility in organic solvents.

[0040] On the other hand, a polyimide solution comprising the polyimide described herein and an organic solvent is also provided.

[0041] The polyimide disclosed herein has excellent solubility in organic solvents, and therefore has the advantage that it can be readily used in polyimide films, fibers or coatings by using polyimide in solution form dissolved in organic solvents.

[0042] In this disclosure, based on 100 parts by weight of the polyimide solution, the polyimide solution may have a polyimide solids content of 15 wt% to 50 wt%. The lower limit of the weight percentage of the solids content may be 16 wt%, 17 wt%, 18 wt%, 19 wt%, 20 wt% or more, and the upper limit of the weight percentage of the solids content may be 45 wt%, 40 wt%, 35 wt%, 30 wt%, 27 wt%, 25 wt% or less. By controlling the solids content of the polyimide solution, the increase in viscosity can be controlled and the curing time can be shortened.

[0043] In addition, on the other hand, a polyimide powder comprising the polyimide described in this disclosure is also provided.

[0044] In addition, on the other hand, a polyimide film comprising the polyimide described in this disclosure is also provided.

[0045] The thickness of the polyimide film can be appropriately selected considering the application, operating environment, and physical properties of the polyimide film. For example, the thickness of the polyimide film can be 1 μm to 100 μm, 5 μm to 50 μm, 10 μm to 40 μm, or 15 μm to 25 μm, but is not limited thereto.

[0046] Furthermore, on the other hand, a component comprising a molded article formed from said polyimide is provided.

[0047] Specifically, the components may be electronic circuit board elements, semiconductor devices, lithium-ion battery elements, solar cell elements, fuel cell elements, motor windings, engine peripheral equipment elements, coatings, optical components, heat insulation materials, electromagnetic shielding materials, surge components, dental materials, sliding coatings, and electrostatic chucks, but are not limited thereto.

[0048] Furthermore, this disclosure provides a separator comprising a polyimide as described above.

[0049] Furthermore, this disclosure provides a fiber comprising a polyimide as described above.

[0050] Furthermore, this disclosure provides an insulating layer comprising a polyimide as described above.

[0051] Furthermore, this disclosure provides a coating comprising a polyimide as described above.

[0052] Preparation method of polyimide This disclosure provides a method for preparing polyimide, comprising: preparing polyimide by polymerizing a dianhydride monomer including bisphenol A type diether dianhydride (BPADA) and a diamine monomer including 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (6-FAP).

[0053] The steps for preparing the polyimide may include: polymerizing bisphenol A diether dianhydride (BPADA) and 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (6-FAP) to form a polymeric unit consisting of the bisphenol A diether dianhydride (BPADA) and the 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (6-FAP).

[0054] The polyimide can be prepared in the presence of a solvent.

[0055] The solvent may be an aprotic polar organic solvent and may include at least one selected from the group consisting of: N,N'-dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), N,N'-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), N,N-diethylacetamide (DEAc), N-ethyl-2-pyrrolidone (NEP), N,N'-diethylformamide (DEF), dimethylpropionamide (DMPA), and γ-butyrolactone (GBL), and preferably N,N'-dimethylformamide (DMF).

[0056] Furthermore, in another aspect, a polyimide powder comprising the polyimide prepared by the method for preparing the polyimide described in this disclosure is also provided.

[0057] Furthermore, in another aspect, a polyimide film comprising the polyimide prepared by the method for preparing the polyimide described in this disclosure is also provided.

[0058] The thickness of the polyimide film can be appropriately selected considering the application, operating environment, and physical properties of the polyimide film. For example, the thickness of the polyimide film can be 1 μm to 100 μm, 5 μm to 50 μm, 10 μm to 40 μm, or 15 μm to 25 μm, but is not limited thereto.

[0059] Furthermore, in another aspect, a component comprising a molded article formed from the polyimide prepared by the method described in this disclosure is also provided.

[0060] Specifically, the components may be electronic circuit board elements, semiconductor devices, lithium-ion battery elements, solar cell elements, fuel cell elements, motor windings, engine peripheral equipment elements, coatings, optical components, heat insulation materials, electromagnetic shielding materials, surge components, dental materials, sliding coatings, and electrostatic chucks, but are not limited thereto.

[0061] Furthermore, this disclosure provides a separator comprising a polyimide prepared by the method for preparing the polyimide as described above.

[0062] Furthermore, this disclosure provides a fiber comprising the polyimide prepared according to the preparation method of the polyimide described above.

[0063] Furthermore, this disclosure provides an insulating layer comprising the polyimide prepared according to the preparation method of the polyimide described above.

[0064] Furthermore, this disclosure provides a coating comprising the polyimide prepared by the method for preparing the polyimide as described above.

[0065] [Beneficial Effects] The polyimide described in this disclosure has excellent solubility in organic solvents and also has excellent thermal properties.

[0066] The polyimide described in this disclosure is fully imidized and can be manufactured into films, fibers, etc. in a variety of ways by solvent drying without imidization at high temperatures, thereby improving the ease of processing.

[0067] Furthermore, the polyimide described in this disclosure has the effect of being applicable to various fields, such as films, adhesives, insulating coatings, coating materials, and fibers. Detailed Implementation

[0068] [Best way] To facilitate understanding of this disclosure, some embodiments are listed below. These embodiments are only used to facilitate a better understanding of this disclosure, and the content of this disclosure is not limited to these embodiments.

[0069] <Example> Example 1 Preparation of polyimide Example 1-1 Under a nitrogen / room temperature atmosphere, 50 mol% of bisphenol A diether dianhydride (BPADA) and 40 mol% of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (6-FAP) were added to a dimethylformamide (DMF) organic solvent to form polymerization units consisting of BPADA and 6-FAP. Subsequently, 50 mol% of 3,3',4,4'-benzophenone tetracarboxylic dianhydride (BTDA) and 60 mol% of m-phenylenediamine (MPD) were added, and polymerization was carried out to obtain a polyamic acid composition.

[0070] A tertiary catalyst (BP, β-methylpyridine) and a dehydrating agent (acetic anhydride, AA) were added to the obtained polyamic acid composition, and chemical imidization was carried out in a continuous process in a polymerization reactor at 60°C. Next, after the reaction was complete, the polymer was precipitated in an ethanol-free solvent to remove impurities (unreacted material, tertiary catalyst, AA, etc.) and dried in a vacuum oven at a temperature below 60°C for 24 hours to prepare polyimide powder (20 wt% solids).

[0071] Examples 1-2 to 1-5 Except for adjusting the ratio of dianhydride monomers and the type and ratio of diamine monomers as shown in Table 1 below, polyimide films were prepared in the same manner as in Example 1-1.

[0072] Comparative Examples 1-1 to 1-5 Except for adjusting the ratio of dianhydride monomers and the type and ratio of diamine monomers as shown in Table 1 below, polyimide films were prepared in the same manner as in Example 1-1.

[0073] Table 1 below summarizes the composition and content of dianhydride monomers and diamine monomers used in the preparation of polyimide films according to Examples 1-1 to 1-5 and Comparative Examples 1-1 to 1-5, as well as the presence or absence of steps including the formation of polymeric units consisting of BPADA and 6-FAP.

[0074] Table 1

[0075] The abbreviations for the materials used in Table 1 are as follows.

[0076] BTDA: 3,3',4,4'-benzophenone tetracarboxylic dianhydride BPADA: Bisphenol A type diether dianhydride 6-FAP: 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane MPD: m-phenylenediamine MDA: 4,4'-Diaminodiphenylmethane

[0077] Example 2 Preparation of polyimide film

[0078] Example 2-1 The polyimide powder prepared according to Example 1-1 was dissolved in an organic solvent (DMF) to obtain a solution with a solid content of 20 wt%. The resulting solution was coated onto a glass substrate with a thickness of 20 μm using a spin coater (MS-B200, Mikasa) and dried at 250°C for 20 minutes. The coating method used here is not particularly limited. Subsequently, after cooling at 25°C, it was peeled off from the glass substrate to prepare a polyimide film with a thickness of approximately 20 μm.

[0079] Examples 2-2 to 2-5 Except that the polyimide powder prepared according to Examples 1-2 to 1-5 was used instead of the polyimide powder prepared according to Example 1-1, the polyimide film was prepared in the same manner as in Example 2-1.

[0080] Comparative Examples 2-1 to 2-5 Except that the polyimide powder prepared according to Comparative Examples 1-1 to 1-5 was used instead of the polyimide powder prepared according to Example 1-1, the polyimide film was prepared in the same manner as in Example 2-1.

[0081] <Experimental Example> Experiment Example 1: Evaluation of Solubility The solubility of polyimide in organic solvents was evaluated by visually confirming the addition of 20 g of polyimide powder prepared according to Examples 1-1 to 1-5 and Comparative Examples 1-1 to 1-5 to 80 g of the organic solvent N,N'-dimethylformamide (DMF). Specifically, the turbidity of the solution was visually confirmed after adding 20 wt% of the polyimide solids at room temperature and stirring for 30 minutes. The results are shown in Table 2 below.

[0082] Table 2

[0083] As can be seen from Table 2, under the same preparation conditions, Examples 1-1 to 1-5, which include at least 50 mol% BPADA and at least 30 mol% 6-FAP (Comparative Example 1-1) or less than 50 mol% BPADA (Comparative Examples 1-2 to 1-5), exhibit superior solubility in DMF compared to those with less than 30 mol% 6-FAP (Comparative Example 1-1) or less than 50 mol% BPADA (Comparative Examples 1-2 to 1-5).

[0084] Experimental Example 2: Evaluation of the 5wt% thermal decomposition temperature (Td) Using a TA Instruments Q50 thermogravimetric analyzer, the polyimide films prepared according to Examples 2-1 to 2-5 and Comparative Examples 2-1 to 2-5 were heated to 100°C at a rate of 10°C / min under a nitrogen atmosphere, and then held at that temperature for 1 hour to remove moisture. Subsequently, the temperature was increased to 600°C at a rate of 10°C / min to measure the temperature at which 5% weight loss occurred. The results are shown in Table 3 below.

[0085] Table 3

[0086] As can be seen from Table 3, under the same preparation conditions, Examples 2-1 to 2-5, which include at least 50 mol% BPADA and at least 30 mol% 6-FAP (Comparative Example 2-1) or less than 50 mol% BPADA (Comparative Examples 2-2 to 2-5), exhibit superior thermal properties compared to those with less than 30 mol% 6-FAP (Comparative Example 2-1) or less than 50 mol% BPADA (Comparative Examples 2-2 to 2-5).

[0087] Detailed descriptions of content that can be fully understood and inferred by those skilled in the art have been omitted in this specification, and various modifications may be made without altering the technical concept or basic structure of this disclosure, apart from the specific examples described herein. Therefore, this disclosure can be practiced in ways different from those specifically described and illustrated herein, as will be apparent to those skilled in the art.

Claims

1. A polyimide comprising a dianhydride monomer and a diamine monomer as polymerization units; The dianhydride monomer includes bisphenol A type diether dianhydride (BPADA). The diamine monomer comprises 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (6-FAP); and The polyimide is soluble in organic solvents.

2. The polyimide according to claim 1, characterized in that, The polyimide comprises a polymerization unit consisting of the bisphenol A type diether dianhydride (BPADA) and the 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (6-FAP).

3. The polyimide according to claim 1, characterized in that, The polyimide exhibits solubility in organic solvents when its solid content is 15 wt% or more.

4. The polyimide according to claim 1, characterized in that, The organic solvent comprises at least one selected from the group consisting of: N,N'-dimethylformamide (DMF), N-methylpyrrolidone (NMP), N,N'-diethylformamide (DEF), N,N'-dimethylacetamide (DMAc), dimethylpropionamide (DMPA), N,N-diethylacetamide (DEAc), dimethyl sulfoxide (DMSO), 3-methoxy-N,N-dimethylpropionamide (KJCMPA), p-chlorophenol, o-chlorophenol, γ-butyrolactone (GBL), diethylene glycol dimethyl ether (Diglyme), and naphthalene.

5. The polyimide according to claim 1, characterized in that, Based on the total amount of the dianhydride monomer, the content of the bisphenol A type diether dianhydride (BPADA) is from 50 mol% to 100 mol%.

6. The polyimide according to claim 1, characterized in that, Based on the total amount of the diamine monomer, the content of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (6-FAP) is from 30 mol% to 100 mol%.

7. The polyimide according to claim 1, characterized in that, The dianhydride monomer further comprises at least one selected from the group consisting of: 3,3',4,4'-benzophenone tetracarboxylic dianhydride (BTDA), pyromellitic tetracarboxylic dianhydride (PMDA), biphenyl tetracarboxylic dianhydride (BPDA), oxydiphthalic dianhydride (ODPA), diphenyl sulfone-3,4,3',4'-tetracarboxylic dianhydride (DSDA), bis(3,4-dicarboxyphenyl)sulfide dianhydride, 2,2-bis(3,4-dicarboxyphenyl)-1,1,1,3,3,3-hexafluoropropane dianhydride, 2,3,3',4'-benzophenone tetracarboxylic dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, and 2,2-bis(3,4-dicarboxyphenyl) Propane dianhydride, p-phenylenebis(triphenyltriacrylic acid monoester anhydride), p-biphenylenebis(triphenyltriacrylic acid monoester anhydride), m-terphenyl-3,4,3',4'-tetracarboxylic dianhydride, p-terphenyl-3,4,3',4'-tetracarboxylic dianhydride, 1,3-bis(3,4-dicarboxyphenoxy)phthalic dianhydride, 1,4-bis(3,4-dicarboxyphenoxy)phthalic dianhydride, 1,4-bis(3,4-dicarboxyphenoxy)biphenyl dianhydride, 2,2-bis[(3,4-dicarboxyphenoxy)phenyl]propane dianhydride (BPADA), 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, and 4,4'-(2,2-hexafluoroisopropylidene)bisphthalic dianhydride.

8. The polyimide according to claim 7, characterized in that, The dianhydride monomer further comprises 3,3',4,4'-benzophenone tetracarboxylic dianhydride (BTDA).

9. The polyimide according to claim 1, characterized in that, The diamine monomer further comprises at least one selected from the group consisting of: m-phenylenediamine (MPD), 4,4'-diaminodiphenylmethane (MDA), 4,4'-diaminodiphenyl ether (ODA), 2,2-diaminophenoxyphenylpropane (BAPP), m-phenylenediamine, 3,3'-dimethylbenzidine, 2,2'-dimethylbenzidine, 2,4-diaminotoluene, 2,6-diaminotoluene, 3,5-diaminobenzoic acid (DABA), 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl (m-tolidine), 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 3,3'-dimethyl- 4,4'-Diaminodiphenylmethane, 3,3'-Dicarboxy-4,4'-Diaminodiphenylmethane, 3,3',5,5'-Tetramethyl-4,4'-Diaminodiphenylmethane, 4,4'-Diaminobenzoylaniline, 3,3'-Dimethoxybenzidine, 2,2'-Dimethoxybenzidine, 3,3'-Diaminodiphenyl ether, 3,4'-Diaminodiphenyl ether, 3,3'-Diaminodiphenyl sulfone, 3,4'-Diaminodiphenyl sulfone, 4,4'-Diaminodiphenyl sulfone, 3,3'-Diaminobenzophenone, 4,4'-Diaminobenzophenone, 3,3'-Diamino-4,4'-Dichlorodiphenyl ether Phenylacetone, 3,3'-diamino-4,4'-dimethoxydiphenyl ketone, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 2,2-bis(3-aminophenyl)propane, 2,2-bis(4-aminophenyl)propane, 2,2-bis(3-aminophenyl)-1,1,1,3,3,3-hexafluoropropane, 2,2-bis(4-aminophenyl)-1,1,1,3,3,3-hexafluoropropane, 3,3'-diaminodiphenyl sulfoxide, 3,4'-diaminodiphenyl sulfoxide, 4,4'-diaminodiphenyl sulfoxide, 1,3-bis(3-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 1,4-bis(3-aminophenyl)benzene, 1,4-bis(4-aminophenyl)benzene 1,3-Bis(4-aminophenoxy)benzene, 1,4-Bis(3-aminophenoxy)benzene (TPE-R), 1,3-Bis(3-aminophenoxy)-4-trifluoromethylbenzene, 3,3'-diamino-4-(4-phenyl)phenoxybenzophenone, 3,3'-diamino-4,4'-di(4-phenylphenoxy)benzophenone, 1,3-bis(3-aminophenyl sulfide)benzene, 1,3-bis(4-aminophenyl sulfide)benzene, 1,4-bis(4-aminophenyl sulfide)benzene, 1,3-bis(3-aminophenyl sulfone)benzene, 1,3-bis(4-aminophenyl sulfone)benzene, 1,4-bis(4-aminophenyl sulfone)benzene, 1,3-bis[2-(4-aminophenyl)isopropyl]benzene, 1,4-Bis[2-(3-aminophenyl)isopropyl]benzene, 1,4-bis[2-(4-aminophenyl)isopropyl]benzene, 3,3'-bis(3-aminophenoxy)biphenyl, 3,3'-bis(4-aminophenoxy)biphenyl, 4,4'-bis(3-aminophenoxy)biphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, bis[3-(3-aminophenoxy)phenyl]ether, bis[3-(4-aminophenoxy)phenyl]ether, bis[4-(3-aminophenoxy)phenyl]ether, bis[4-(4- [Aminophenoxy)phenyl] ether, bis[3-(3-aminophenoxy)phenyl] ketone, bis[3-(4-aminophenoxy)phenyl] ketone, bis[4-(3-aminophenoxy)phenyl] ketone, bis[4-(4-aminophenoxy)phenyl] ketone, bis[3-(3-aminophenoxy)phenyl] sulfide, bis[3-(4-aminophenoxy)phenyl] sulfide, bis[4-(3-aminophenoxy)phenyl] sulfide, bis[4-(4-aminophenoxy)phenyl] sulfide, bis[3-(3-aminophenoxy)phenyl] sulfone bis[3-(4-aminophenoxy)phenyl] sulfone, bis[4-(3-aminophenoxy)phenyl] sulfone, bis[4-(4-aminophenoxy)phenyl] sulfone, bis[3-(3-aminophenoxy)phenyl]methane, bis[3-(4-aminophenoxy)phenyl]methane, bis[4-(3-aminophenoxy)phenyl]methane, bis[4-(4-aminophenoxy)phenyl]methane, 2,2-bis[3-(3-aminophenoxy)phenyl]propane, 2,2-bis[3-(4-aminophenoxy)phenyl]propane 2,2-bis[4-(3-aminophenoxy)phenyl]propane, 2,2-bis[3-(3-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 2,2-bis[3-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 2,2-bis[4-(3-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane and 2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane.

10. The polyimide according to claim 9, characterized in that, The diamine monomer further comprises at least one selected from the group consisting of m-phenylenediamine (MPD) and 4,4'-diaminodiphenylmethane (MDA).

11. The polyimide according to claim 1, characterized in that, The 5wt% thermal decomposition temperature (Td) of the polyimide is 385°C or higher.

12. A polyimide solution comprising the polyimide according to any one of claims 1 to 11 and an organic solvent.

13. A polyimide film comprising the polyimide according to any one of claims 1 to 11.

14. A method for preparing polyimide, comprising: Polyimide was prepared by polymerizing a dianhydride monomer including bisphenol A diether dianhydride (BPADA) and a diamine monomer including 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (6-FAP).

15. The preparation method according to claim 14, characterized in that, The steps for preparing the polyimide include: A polymerization unit consisting of bisphenol A diether dianhydride (BPADA) and 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (6-FAP) is formed by polymerizing bisphenol A diether dianhydride (BPADA) and 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (6-FAP).

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