CN108503831B - Composition for forming polyimide, polyimide and polyimide film - Google Patents
Composition for forming polyimide, polyimide and polyimide film Download PDFInfo
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- CN108503831B CN108503831B CN201710105902.5A CN201710105902A CN108503831B CN 108503831 B CN108503831 B CN 108503831B CN 201710105902 A CN201710105902 A CN 201710105902A CN 108503831 B CN108503831 B CN 108503831B
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- 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
- C08G73/1075—Partially aromatic polyimides
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- 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
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
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- 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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- 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
- C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
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- 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
- C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
- C08G73/106—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing silicon
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- 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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- 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
Abstract
The invention provides a composition for forming polyimide, polyimide and a polyimide film. The diamine monomer component includes 20 to 65 mole parts of 4,4' -diaminodiphenyl ether, 30 to 70 mole parts of a compound represented by formula (I), and 1 to 10 mole parts of melamine:
Description
Technical Field
The present invention relates to a composition, and more particularly, to a composition for forming polyimide, polyimide prepared from the composition, and a polyimide film prepared from the polyimide.
Background
Generally, Polyimide (PI) is a polymer material obtained by a polycondensation reaction of a diamine monomer and a dianhydride monomer. Currently, polyimide has been widely used in various industries, such as semiconductor industry, photoelectric industry, aviation material, biomedical material, textile industry, construction field, automobile industry, communication material, mechanical industry, and film industry, due to its chemical stability, electrical property, thermal stability, etc., and is an indispensable material in life. In order to further enhance the applicability of polyimides, the development of novel polyimides by those skilled in the art is still under development.
Disclosure of Invention
The invention provides a composition for forming polyimide, which can prepare polyimide or a polyimide film with heat resistance and elasticity.
The composition for forming polyimide of the present invention comprises a tetracarboxylic dianhydride monomer component, a diamine monomer component, and a solvent. The diamine monomer component includes 20 to 65 parts by mole of 4,4 '-diaminodiphenyl ether (ODA; 4,4' -diaminodiphenyl ether), 30 to 70 parts by mole of a compound represented by formula (I), and 1 to 10 parts by mole of melamine (melamine):
wherein the sum of x and z is from 1 to 20 and y is from 4 to 50.
In one embodiment of the present invention, the tetracarboxylic dianhydride monomer component includes a tetracarboxylic dianhydride containing an aromatic group.
In one embodiment of the present invention, the diamine monomer component includes 25 to 65 mole parts of 4,4' -diaminodiphenyl ether, 30 to 70 mole parts of the compound represented by formula (I), and 1 to 10 mole parts of melamine.
In one embodiment of the present invention, the tetracarboxylic dianhydride monomer component is 3,3',4,4' -diphenyl ether tetracarboxylic dianhydride (ODPA; 3,3',4,4' -oxydiphatic anhydride).
In one embodiment of the present invention, the diamine monomer component includes 20 to 45 mole parts of 4,4' -diaminodiphenyl ether, 50 to 70 mole parts of the compound represented by formula (I), and 5 to 10 mole parts of melamine.
In one embodiment of the present invention, the tetracarboxylic dianhydride monomer component is pyromellitic dianhydride (PMDA).
In one embodiment of the present invention, the diamine monomer component includes 25 to 45 mole parts of 4,4' -diaminodiphenyl ether, 50 to 70 mole parts of the compound represented by formula (I), and 5 to 10 mole parts of melamine.
In one embodiment of the present invention, the tetracarboxylic dianhydride monomer component is 3,3',4,4' -biphenyltetracarboxylic dianhydride (BPDA; 3,3',4,4' -biphenyltetracarboxylic dianhydride).
In an embodiment of the present invention, the diamine monomer component further includes siloxane diamine.
In one embodiment of the present invention, the siloxane diamine includes a compound represented by the formula (II):
In one embodiment of the present invention, the diamine monomer component includes 35 to 45 parts by mole of 4,4' -diaminodiphenyl ether, 40 to 50 parts by mole of the compound represented by formula (I), 5 to 10 parts by mole of melamine, and 5 to 10 parts by mole of siloxane diamine.
The polyimide of the present invention is prepared from the composition for forming polyimide as described above.
The polyimide film of the present invention is made of the polyimide as described above.
In view of the above, the composition for forming polyimide of the present invention can have good film-forming properties by including a tetracarboxylic dianhydride monomer component, a diamine monomer component, and a solvent, wherein the diamine monomer component includes 4,4' -diaminodiphenyl ether, a compound represented by formula (I), and melamine in amounts respectively within specific ranges. Thus, a polyimide film having excellent material properties can be obtained from the composition for forming polyimide of the present invention. In addition, the composition for forming polyimide according to the present invention includes a tetracarboxylic dianhydride monomer component, a diamine monomer component, and a solvent, wherein the diamine monomer component includes 4,4' -diaminodiphenyl ether, a compound represented by formula (I), and melamine in amounts respectively within specific ranges, whereby a polyimide or a polyimide film having heat resistance and elasticity can be prepared. In addition, the composition for forming polyimide of the present invention may further include siloxane diamine in a specific range to have good film forming property, thereby forming a polyimide film having heat resistance and elasticity.
In order to make the aforementioned and other features and advantages of the invention more comprehensible, embodiments accompanied with figures are described in detail below.
Detailed Description
In this context, a range denoted by "a numerical value to another numerical value" is a general expression avoiding a recitation of all numerical values in the range in the specification. Thus, recitation of a range of values herein is intended to encompass any value within the range and any smaller range defined by any value within the range, as if the range and smaller range were explicitly recited in the specification.
One embodiment of the present invention provides a composition for forming polyimide, which includes a tetracarboxylic dianhydride monomer component, a diamine monomer component, and a solvent. In the present embodiment, the ratio of the total mole percentage of the diamine monomer component to the total mole percentage of the tetracarboxylic dianhydride monomer component is 1: 0.95 to 1: 1.05.
In the present embodiment, the diamine monomer component includes 4,4 '-diaminodiphenyl ether (ODA; 4,4' -diaminodiphenyl ether), a compound represented by formula (I), and melamine (melamine):
wherein the sum of x and z is from 1 to 20 and y is from 4 to 50. That is, in the present embodiment, the diamine monomer component includes three kinds of diamine monomers. In addition, the amine hydrogen equivalent weight of the compound represented by formula (I) is between 250 and 270, and the number average molecular weight is about 1000.
In addition, in the present embodiment, the diamine monomer component includes 20 to 65 parts by mole of 4,4' -diaminodiphenyl ether, 30 to 70 parts by mole of the compound represented by formula (I), and 1 to 10 parts by mole of melamine. If the molar part of at least one of 4,4' -diaminodiphenyl ether, the compound represented by the formula (I), and melamine does not fall within the foregoing range, the composition for forming polyimide has no film-forming property.
In the present embodiment, the tetracarboxylic dianhydride monomer component includes a tetracarboxylic dianhydride containing an aromatic group. Specifically, examples of the aromatic-containing tetracarboxylic dianhydride include, but are not limited to: 3,3',4,4' -diphenylether tetracarboxylic dianhydride (ODPA; 3,3',4,4' -oxydiphthalic anhydride), pyromellitic dianhydride (PMDA; pyromelitic dianhydride), 3,3',4,4' -biphenyltetracarboxylic dianhydride (BPDA; 3,3',4,4' -biphenyltetracarboxylic dianhydride), 2 ', 3,3' -biphenyltetracarboxylic dianhydride, 3,3',4,4' -benzophenonetetracarboxylic dianhydride, 2 ', 3,3' -benzophenonetetracarboxylic dianhydride, 2-bis (2, 3-dicarboxyphenyl) hexafluoropropane dianhydride, 2-bis (3, 4-dicarboxyphenyl) hexafluoropropane dianhydride (FDA), bis (2, 3-dicarboxyphenyl) methane dianhydride, bis (3, 4-dicarboxyphenyl) methane dianhydride, 3,3',3, 4,4' -diphenylsulfone tetracarboxylic dianhydride (DSDA; 3,3',4,4' -diphenylsulfone tetracarboxylic dianhydride), 2-bis [4- (3, 4-dicarboxyphenoxy) phenyl ] propane dianhydride (BPADA; 2, 2-bis [4- (3, 4-dicarboxyphenoxy) phenyl ] propane dianhydride), bis (2, 3-dicarboxyphenyl) sulfone dianhydride, bis (3, 4-dicarboxyphenyl) sulfone dianhydride or ethylene glycol bistrimellitic dianhydride (TMEG; ethylene glycol bis (4-trimetallite anhydride)), and is preferably 3,3',4,4' -biphenyltetracarboxylic dianhydride, 3',4,4' -diphenylether tetracarboxylic dianhydride, pyromellitic dianhydride or 2, 2-bis (3, 4-dicarboxyphenyl) hexafluoropropane dianhydride (6 FDA).
On the other hand, in the present embodiment, the tetracarboxylic dianhydride monomer component includes one tetracarboxylic dianhydride monomer. For example, in one embodiment, the tetracarboxylic dianhydride monomer component is 3,3',4,4' -diphenyl ether tetracarboxylic dianhydride (ODPA), and in this case, the diamine monomer component includes 25 to 65 parts by mole of 4,4' -diaminodiphenyl ether, 30 to 70 parts by mole of the compound represented by formula (I), and 1 to 10 parts by mole of melamine, and the composition for forming polyimide has good film-forming properties. As another example, in an embodiment, the tetracarboxylic dianhydride monomer component is pyromellitic dianhydride (PMDA), and in this case, the diamine monomer component includes 20 to 45 parts by mole of 4,4' -diaminodiphenyl ether, 50 to 70 parts by mole of the compound represented by formula (I), and 5 to 10 parts by mole of melamine, and the composition for forming polyimide has good film-forming properties. As another example, in one embodiment, the tetracarboxylic dianhydride monomer component is 3,3',4,4' -biphenyltetracarboxylic dianhydride (BPDA), and in this case, the diamine monomer component includes 25 to 45 parts by mole of 4,4' -diaminodiphenyl ether, 50 to 70 parts by mole of the compound represented by formula (I), and 5 to 10 parts by mole of melamine, and the composition for forming polyimide has good film-forming properties.
In addition, from the viewpoint of enhancing the elasticity of the polyimide, the diamine monomer component may further include a siloxane diamine. Specifically, examples of siloxane diamines include (but are not limited to): a compound represented by the following formula (II),
wherein n is 8 to 11. In one embodiment, the diamine monomer component includes 35 to 45 mole parts of 4,4' -diaminodiphenyl ether, 40 to 50 mole parts of a compound represented by formula (I), 5 to 10 mole parts of melamine, and 5 to 10 mole parts of siloxane diamine.
In the present embodiment, the solvent is not particularly limited as long as it can dissolve the tetracarboxylic dianhydride monomer component and the diamine monomer component. Specifically, examples of the solvent include, but are not limited to: amide solvents such as N, N-dimethylacetamide (DMAc), N-Dimethylformamide (DMF), N' -diethylacetamide, N-methyl-2-pyrrolidone (NMP), γ -butyrolactone, and hexamethylphosphoric triamide; urea solvents such as tetramethylurea and N, N-dimethylethylurea; sulfoxide or sulfone solvents such as dimethyl sulfoxide, diphenyl sulfone and tetramethyl sulfone; halogenated alkyl solvents such as chloroform and dichloromethane; aromatic hydrocarbon solvents such as benzene and toluene; phenol solvents such as phenol and cresol; or ether solvents such as tetrahydrofuran, 1, 3-dioxolane, dimethyl ether, diethyl ether, and p-cresol methyl ether. The above solvents may be used alone or in combination of plural kinds. In order to improve the solubility and reactivity of the tetracarboxylic dianhydride monomer component and the diamine monomer component, the solvent is preferably an amide solvent such as DMAc, DMF, NMP, or the like.
It is to be noted that, as described above, in the present embodiment, by including the tetracarboxylic dianhydride monomer component, the diamine monomer component including 4,4' -diaminodiphenyl ether, the compound represented by the formula (I), and melamine in amounts respectively within specific ranges, and the solvent, the composition for forming polyimide can have good film-forming properties.
Another embodiment of the present invention provides a polyimide prepared from the composition for forming a polyimide according to any one of the above embodiments. The description of the diamine monomer component, the tetracarboxylic dianhydride monomer component, and the solvent in the composition for forming polyimide is described in detail in the foregoing embodiments, and thus will not be repeated herein.
Specifically, in the present embodiment, the polyimide is prepared by a condensation polymerization reaction of a diamine monomer component and a tetracarboxylic dianhydride monomer component in a solvent. In one embodiment, the polyimide may be prepared using three diamine monomers and one tetracarboxylic dianhydride monomer. In another embodiment, the polyimide may be prepared using four diamine monomers and one tetracarboxylic dianhydride monomer. Since the diamine monomer and the tetracarboxylic dianhydride monomer react to produce polyimide, the ratio of the total number of moles of amino groups in the diamine monomer to the total number of moles of acid anhydride groups in the tetracarboxylic dianhydride monomer is about 1: 1. In more detail, the ratio may be between 1: 0.95 and 1: 1.05.
In the present embodiment, the polyimide is prepared by, for example, a thermal cyclization method or a chemical cyclization method. The thermal and chemical cyclization processes, respectively, can be carried out using any procedure known to those of ordinary skill in the art. For example, the preparation of polyimide by the thermal cyclization process comprises the following steps: after a polymerization reaction is performed using a composition for forming polyimide to form a polyamic acid solution, the polyamic acid solution is heated to perform an imidization reaction (i.e., a dehydrative cyclization reaction) to form polyimide. Specifically, the composition for forming polyimide is prepared, for example, by uniformly mixing a diamine monomer component and a tetracarboxylic dianhydride monomer component in a solvent at a temperature ranging from 5 ℃ to 40 ℃. The method of mixing is not particularly limited as long as the diamine monomer component and the tetracarboxylic dianhydride monomer component can be uniformly mixed in the solvent. In one embodiment, in the step of forming the polyamic acid solution, the reaction temperature is, for example, between 5 ℃ and 40 ℃; the reaction time is, for example, between 3 hours and 12 hours. In one embodiment, the imidization is carried out, for example, under the temperature environments of 100 ℃, 150 ℃ and 220 ℃ for 1 to 2 hours.
By way of another example, the preparation of polyimide by chemical cyclization comprises the steps of: after a polymerization reaction is performed using a composition for forming polyimide to form a polyamic acid solution, a dehydrating agent and an imidizing agent are added to the polyamic acid solution to perform an imidization reaction (i.e., a dehydrative cyclization reaction) to form polyimide. Specifically, the composition for forming polyimide is prepared, for example, by uniformly mixing a diamine monomer component and a tetracarboxylic dianhydride monomer component in a solvent at a temperature ranging from 5 ℃ to 40 ℃. The method of mixing is not particularly limited as long as the diamine monomer component and the tetracarboxylic dianhydride monomer component can be uniformly mixed in the solvent. In one embodiment, in the step of forming the polyamic acid solution, the reaction temperature is, for example, between 5 ℃ and 40 ℃; the reaction time is, for example, between 3 hours and 12 hours. In one embodiment, the imidization is performed under conditions of, for example, 120 ℃ for 2 to 5 hours, preferably 3 hours. In one embodiment, examples of dehydrating agents include, but are not limited to: acetic anhydride, propionic anhydride, n-butyric anhydride, benzoic anhydride or trifluoroacetic anhydride; examples of imidizing agents include, but are not limited to: pyridine, picoline, quinoline or isoquinoline. In one embodiment, the addition amount of the dehydrating agent is, for example, 0.5 to 10.0 times the molar equivalent, and the addition amount of the imidizing agent is, for example, 0.5 to 5.0 times the molar equivalent, with respect to the amide group of the polyamic acid.
It is to be noted that, as described above, in the present embodiment, since the composition for forming polyimide can have good film forming property by including the tetracarboxylic dianhydride monomer component, the diamine monomer component including 4,4' -diaminodiphenyl ether, the compound represented by the formula (I), and melamine in the respective contents within specific ranges, and the solvent, the polyimide produced from the composition for forming polyimide can form a thin film having excellent material properties.
On the other hand, by using a composition for forming a polyimide comprising a tetracarboxylic dianhydride monomer component, a diamine monomer component comprising 4,4' -diaminodiphenyl ether, a compound represented by formula (I) and melamine in respective contents within specific ranges, and a solvent, the polyimide has not only excellent film-forming properties but also a film formed therefrom is more heat-resistant and elastic. Therefore, the applicability and commercial value of the polyimide disclosed by the invention in various industries are greatly improved.
In addition, the polyimide may be blended with additives as required within a range not to impair the essential effects of the polyimide of the present invention, to further increase the applicability and commercial value of the polyimide. The additives include, for example, conductive materials, flame retardants, colorants, fillers, or combinations thereof. For example, in order to impart conductivity to polyimide to meet the industry demand for conductivity, polyimide may be blended with conductive materials, such as graphene, carbon nanotubes, silver nanoparticles, silver nanowires, or conductive polymers; methods of blending include, for example, directly mixing the polyimide with the conductive material, or the composition used to form the polyimide further includes the conductive material.
In addition, as described above, although the composition for forming polyimide can have good film-forming properties so that the polyimide obtained therefrom can form a thin film, the polyimide of the present invention may be present in the form of powder, solution, or the like.
Another embodiment of the present invention provides a polyimide film made from the polyimide of any of the previous embodiments. The description of the polyimide is given in detail in the foregoing embodiments, and thus is not repeated herein. In the present embodiment, the thickness of the polyimide film varies depending on the application, and generally ranges from about 15 μm to about 200 μm, preferably from about 15 μm to about 100 μm.
In addition, in the present embodiment, the polyimide film may be prepared by any method known to those having ordinary skill in the art. For example, in one embodiment, a polyimide film may be formed by subjecting polyimide to a solution casting method. For example, in one embodiment, referring to the method for preparing polyimide, the method for preparing a polyimide film may include coating a polyamic acid solution onto a substrate through a coating process after the polyamic acid solution is formed, and then performing imidization. In detail, the coating process can be performed by any coating method known to those skilled in the art, such as blade coating, spin coating, pneumatic blade coating, slot coating, extrusion coating, or roller coating; the substrate may be any suitable substrate, such as a fabric, copper foil, glass, teflon or plastic substrate, depending on the application.
It is to be noted that, as described above, in the present embodiment, by the composition for forming the polyimide including the tetracarboxylic dianhydride monomer component, the diamine monomer component including the 4,4' -diaminodiphenyl ether, the compound represented by the formula (I), and the melamine in the respective contents within the specific ranges, and the solvent, the polyimide film can have excellent heat resistance and elasticity. Therefore, the applicability and commercial value of the polyimide film in various industries are greatly improved.
In addition, as described above, the polyimide of the present invention may be blended with a conductive material so that the polyimide film formed may have conductivity, within the range that does not impair the essential effects of the polyimide of the present invention, in order to meet the requirement of conductivity. In one embodiment, the conductive polyimide film can be formed, for example, by mixing polyimide with a conductive material and then performing a solution casting method. In another embodiment, the polyimide film having conductivity may be formed, for example, by: adding the conductive material into the polyamic acid solution, uniformly mixing, coating the mixed solution on a substrate by a coating process, and then carrying out imidization reaction. It is worth mentioning that the polyimide film with conductivity has excellent film quality, heat resistance and elasticity, and thus can be applied to smart wearable devices such as smart fabrics (e.g. jumping belt, smart glove), stretch display devices, body surface electronic patch systems, or electronic skin.
The features of the present invention will be described more specifically below with reference to examples 1 to 25. Although the following examples 1 to 25 are described, the materials used, the amounts and ratios thereof, the details of the treatment, the flow of the treatment, and the like may be appropriately changed without departing from the scope of the present invention. Therefore, the present invention should not be construed restrictively by the examples described below. In particular, since the diamine monomer and the tetracarboxylic dianhydride monomer will react to produce polyimide and the ratio of the total number of moles of amino groups in the diamine monomer component to the total number of moles of anhydride groups in the tetracarboxylic dianhydride monomer component is about 1: 1, it can be seen that the molar fraction of the tetracarboxylic dianhydride monomer should be the result of equilibrium calculation of the total molar fraction of amino groups in the diamine monomer component and the ratio can be between 0.95: 1 and 1.05: 1.
Information on the main materials used for preparing the polyimide films of examples 1 to 25 is shown below.
Diamine monomer component:
4,4' -diaminodiphenyl ether (hereinafter abbreviated as ODA): purchased from Sigma-Aldrich (Sigma-Aldrich); a compound represented by formula (I): product name RT-1000, available from Huntsman corporation (Huntsman Ltd.); melamine: purchased from sigma-orniths; siloxane diamine: from Scientific Polymer Products, Inc.
The tetracarboxylic dianhydride monomer component:
3,3',4,4' -diphenylether tetracarboxylic dianhydride (hereinafter abbreviated as ODPA): purchased from sigma-orniths; pyromellitic dianhydride (hereinafter abbreviated as PMDA): purchased from sigma-orniths; 3,3',4,4' -biphenyltetracarboxylic dianhydride (hereinafter abbreviated as BPDA): from sigma-orniths.
Dehydrating agent:
acetic anhydride: from sigma-orniths.
Imidizing agent:
pyridine: from sigma-orniths.
Conductive material:
graphene: obtained from the institute for textile industry integration (TTRI).
Example 1
First, high purity nitrogen gas was passed into a 150mL three-necked flask to maintain the inside of the flask dry. Next, 49 molar parts ODA, 50 molar parts RT-1000, 1 molar part melamine, and 25mL DMAc (as solvent) were added to a three-necked flask at room temperature and mixed well. Thereafter, 100.5 molar parts of ODPA was added to the aforementioned mixed solution at room temperature, and the reaction was continued under nitrogen for 12 hours to form a polyamic acid solution having a solid content of 35%. Subsequently, 20mL of acetic anhydride and 10mL of pyridine were added to the polyamic acid solution, and imidization was performed at 120 ℃ for 3 hours. After the reaction was completed, the resulting mixed solution was cooled to room temperature. Then, the resulting mixed solution was slowly poured into a large amount of methanol under stirring, and then filtered to obtain a solid portion. Thereafter, the resulting solid was washed with methanol and dried at 120 ℃ for 2 hours to obtain polyimide of example 1. Next, the polyimide of example 1 was dissolved in an appropriate amount of DMAc to form a polyimide solution. Thereafter, the polyimide solution was cast on a glass plate and baked at 80 ℃ for 3 hours to prepare a polyimide film of example 1.
Examples 2 to 14
Polyimide films of examples 2-14 were prepared following a similar procedure to example 1, and following the ingredients and their molar parts as shown in table 1.
Example 15
The polyimide film of example 15 was prepared according to the similar preparation procedure as example 1, and according to the components and their addition ratios shown in table 1, but the difference was mainly in the following steps: after the polyimide of example 15 was prepared, the polyimide of example 15 was dissolved in 15mL of NMP together with 5 wt% of graphene and then cast on a glass plate.
Examples 16 to 19
Polyimide films of examples 16 to 19 were prepared according to a similar preparation procedure to that of example 15, and according to the components and their addition ratios shown in table 1.
Example 20
The polyimide film of example 20 was prepared according to the similar preparation procedure as in example 1, and according to the components and their addition ratios shown in table 1, but the difference was mainly in the following steps: in example 20, ODA, RT-1000, melamine, and siloxane diamine were added together in DMAc; in example 1, however, no siloxane diamine was used.
Examples 21 to 22
Polyimide films of examples 21 to 22 were prepared according to a similar preparation procedure to that of example 20, and according to the components and their addition ratios shown in table 1.
Example 23
A polyimide film of example 23 was prepared following a similar preparation procedure to that of example 20, and following the ingredients and their addition ratios shown in table 1, but differing mainly in the following steps: after the polyimide of example 23 was prepared, the polyimide of example 23 was dissolved in 15mL of NMP together with 16.7 wt% of graphene and then cast on a glass plate. The thickness of the polyimide film of example 23 was 100 μm.
Examples 24 to 25
Polyimide films of examples 24 to 25 were prepared according to a similar preparation procedure to that of example 23, with the components and their addition ratios shown in Table 1, wherein the thickness of the polyimide film of example 24 was 25 μm and the thickness of the polyimide film of example 25 was 100 μm.
Thereafter, the film forming properties of the polyimide films of examples 1 to 25 were evaluated, and the polyimide films of examples 1 to 6, 9 to 14, 20 and 22 were subjected to a 5% thermogravimetric loss temperature (T)d5％) 10% thermal weight loss temperature (T)d10％) The polyimide films of examples 1 to 6 and 9 to 14 were measured for residual weight ratio (R) at 800 deg.Cw800) The polyimide films of examples 3, 10, 12, 20 to 22 were subjected to glass transition temperature (glass transition temperature; tg), tensile strength (tensile strength) and elongation at break (elongation) of the polyimide films of examples 3, 10, 12, 20-21, storage modulus (storage modulus) of the polyimide films of examples 10, 20, and surface resistivity of the polyimide films of examples 15-19, 23-25, respectively. The above-mentioned measurement items are described below, and the evaluation or measurement results are shown in table 2.
< evaluation of film Forming Property >
The polyimide films of examples 1 to 25 were observed with a naked eye and an optical microscope, respectively, and were classified into three types, i.e., intact, broken and unmoldable, according to the actual conditions.
<Td5％、Td10％And Rw800Measurement of>
T of the polyimides of examples 1 to 6, 9 to 14, 20 and 22 were measured by thermogravimetric analysis (TGA)d5％、Td10％And R of the polyimides of examples 1 to 6 and 9 to 14 was measured by thermogravimetric analysis (TGA)w800. The thermogravimetric analysis conditions were that the sample was heated at a constant speed (heating rate of 10 ℃/min) under a nitrogen atmosphere (gas flow rate of 60cm3/min) and the weight change of the material was recorded, and the measuring apparatus was a thermogravimetric analyzer (model Q50, manufactured by TA Instruments).
Td5％Means a temperature at which the weight loss reaches 5% by weight, where Td5％Higher indicates better heat resistance of the sample. T isd10％Means a temperature at which the weight loss reaches 10% by weight, where Td10％Higher indicates better heat resistance of the sample. Rw800Refers to the residual weight ratio of the material when the heating temperature reaches 800 ℃.
<TgMeasurement of>
T of the polyimide films of examples 3, 10, 12, 20 to 22 were measured by Differential Scanning Calorimetry (DSC), respectivelygThe analysis conditions were such that a sample was heated at a constant rate (heating rate of 10 ℃/min) and the change in enthalpy of the material was recorded, wherein the measuring apparatus was a differential scanning thermal analyzer (model: Q10, manufactured by TA Instruments).
< measurement of tensile Strength and elongation at Break >
The tensile strength and elongation at break of the polyimide films of examples 3, 10, 12, 20-21 were measured using a universal material tester (model: HT-8336-S, manufactured by Hung Daorks Instruments, Inc. (HUNG TA Instruments)), respectively, wherein the samples were dumbbell-shaped test pieces and the tensile rate was 3 mm/min.
< measurement of storage modulus >
The storage modulus of the polyimide films of examples 10 and 20 was measured by Dynamic Mechanical Analysis (DMA). The storage modulus analysis conditions were to heat the sample at a constant rate (heating rate: 5 ℃/min, frequency: 1Hz) and record the change in the storage modulus of the material, wherein the measuring apparatus was a dynamic mechanical analyzer (model: Q800, manufactured by TA Instruments, Inc.).
< measurement of surface resistivity >
The surface resistivity of the polyimide films of examples 15 to 19 and 23 to 25 was measured by a four-point probe method, respectively, using a four-point probe low resistivity meter (model: LORESTA-GP MCP-T600, manufactured by MITSUHI CHEMICAL Co., Ltd.). The standard of conductivity was evaluated using the rating standard specified in FTTS-FA-009; wherein, when the surface resistivity is more than 1 x 1012Ω, then represents an insulating material; when the surface resistivity is between 1X 105Omega and 1X 1012Between Ω, it represents a static dissipative material; when the surface resistivity is less than 1 x 104Ω represents a conductive material, and the lower the surface resistivity, the more excellent the conductivity.
As is clear from Table 2 above, the polyimide films of examples 1 to 14 all exhibited good film formability. This shows that the composition for forming polyimide of the present invention comprises a tetracarboxylic dianhydride monomer component, a diamine monomer component comprising 4,4' -diaminodiphenyl ether, a compound represented by formula (I) and melamine in amounts respectively within specific ranges, and a solvent, whereby the composition for forming polyimide can have good film-forming properties and a polyimide film excellent in material properties can be obtained therefrom.
Further, as is clear from the above Table 2, the polyimide films of examples 20 to 22 all exhibited good film formability. This shows that, by making the composition for forming polyimide of the present invention include a tetracarboxylic dianhydride monomer component, a diamine monomer component including 4,4' -diaminodiphenyl ether, a compound represented by formula (I), and melamine in amounts respectively within specific ranges, and a solvent, the composition for forming polyimide can have good film-forming properties even if the diamine monomer component further includes siloxane diamine, and a polyimide film excellent in material properties can be obtained therefrom.
Further, as is clear from the above table 2, the polyimide films of examples 15 to 19 all exhibited good performance in evaluation of film formability, and also all exhibited electrical conductivity. This shows that, by including the tetracarboxylic dianhydride monomer component, the 4,4' -diaminodiphenyl ether, the compound represented by formula (I), and the diamine monomer component of melamine in specific amounts, and the solvent in the composition for forming polyimide of the present invention, not only can a polyimide film excellent in material properties be obtained, but also additional characteristics such as electrical conductivity can be imparted to the polyimide film by blending the polyimide with additives without impairing essential effects, thereby increasing the applicability and commercial value of the polyimide film.
Further, as is clear from the above table 2, the polyimide films of examples 23 to 25 all exhibited good performance in evaluation of film formability and also all exhibited electrical conductivity. This shows that, by including the tetracarboxylic dianhydride monomer component, the diamine monomer component including 4,4' -diaminodiphenyl ether, the compound represented by formula (I), and melamine in specific amounts, respectively, and the solvent in the composition for forming a polyimide of the present invention, not only can a polyimide film excellent in material properties be obtained, but also an additive can be blended with the polyimide to impart additional characteristics, such as conductivity, to the polyimide film without impairing the essential effects, thereby increasing the applicability and commercial value of the polyimide film.
In addition, the results are shown in Table 2 above with respect to Td5％、Td10％、Rw800、TgAs a result of the results of the present invention, the group for forming polyimide according to the present invention was found to have high tensile strength and elongation at breakThe composition comprises a tetracarboxylic dianhydride monomer component, a diamine monomer component comprising 4,4' -diaminodiphenyl ether, a compound represented by formula (I) and melamine in respective contents within specific ranges, and a solvent, whereby the polyimide film can have heat resistance and elasticity.
In addition, as is clear from table 2 above, the polyimide films of examples 20 to 21 exhibited good tensile strength and elongation at break. This shows that the polyimide film prepared by the composition for forming polyimide of the present invention comprising a tetracarboxylic dianhydride monomer component, a diamine monomer component comprising 4,4' -diaminodiphenyl ether, a compound represented by formula (I), melamine and siloxane diamine in amounts respectively within specific ranges, and a solvent can have ductility or elasticity.
Although the present invention has been described with reference to the above embodiments, it should be understood that various changes and modifications can be made by those skilled in the art without departing from the spirit and scope of the invention.
Claims (13)
1. A composition for forming a polyimide, comprising:
a tetracarboxylic dianhydride monomer component;
a diamine monomer component comprising 20 to 65 mole parts of 4,4' -diaminodiphenyl ether, 30 to 70 mole parts of a compound represented by formula (I), and 1 to 10 mole parts of melamine:
wherein the sum of x and z is from 1 to 20 and y is from 4 to 50; and
a solvent.
2. The composition for forming polyimide according to claim 1, wherein the tetracarboxylic dianhydride monomer component comprises a tetracarboxylic dianhydride containing an aromatic group.
3. The composition for forming polyimide according to claim 1, wherein the diamine monomer component comprises 25 to 65 parts by mole of 4,4' -diaminodiphenyl ether, 30 to 70 parts by mole of the compound represented by formula (I), and 1 to 10 parts by mole of melamine.
4. The composition for forming polyimide according to claim 3, wherein the tetracarboxylic dianhydride monomer component is 3,3',4,4' -diphenylether tetracarboxylic dianhydride.
5. The composition for forming polyimide according to claim 1, wherein the diamine monomer component comprises 20 to 45 mole parts of 4,4' -diaminodiphenyl ether, 50 to 70 mole parts of the compound represented by formula (I), and 5 to 10 mole parts of melamine.
6. The composition for forming polyimide according to claim 5, wherein the tetracarboxylic dianhydride monomer component is pyromellitic dianhydride.
7. The composition for forming polyimide according to claim 1, wherein the diamine monomer component comprises 25 to 45 mole parts of 4,4' -diaminodiphenyl ether, 50 to 70 mole parts of the compound represented by formula (I), and 5 to 10 mole parts of melamine.
8. The composition for forming polyimide according to claim 7, wherein the tetracarboxylic dianhydride monomer component is 3,3',4,4' -biphenyltetracarboxylic dianhydride.
9. The composition for forming polyimide according to claim 1, wherein the diamine monomer component further comprises a siloxane diamine.
10. The composition for forming polyimide according to claim 9, wherein the siloxane diamine comprises a compound represented by formula (II):
11. The composition for forming polyimide according to claim 9, wherein the diamine monomer component comprises 35 to 45 mole parts of 4,4' -diaminodiphenyl ether, 40 to 50 mole parts of the compound represented by formula (I), 5 to 10 mole parts of melamine, and 5 to 10 mole parts of siloxane diamine.
12. A polyimide obtained from the composition for forming a polyimide according to any one of claims 1 to 11.
13. A polyimide film obtained from the polyimide according to claim 12.
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| CN101472975A (en) * | 2006-06-16 | 2009-07-01 | 宇部兴产株式会社 | Polyether polyamide elastomer |
| WO2012048888A1 (en) * | 2010-10-14 | 2012-04-19 | Tata Steel Nederland Technology B.V. | Preparation of a polyetherimide intermediate and its application on metal substrates |
| KR20150037572A (en) * | 2013-09-30 | 2015-04-08 | 주식회사 엘지화학 | Thermoplastic Resin comprising Polyamide |
| CN105745265A (en) * | 2013-09-23 | 2016-07-06 | 沙特基础全球技术有限公司 | Nitrogen containing polymer compositions having reduced combustion toxicity |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101472975A (en) * | 2006-06-16 | 2009-07-01 | 宇部兴产株式会社 | Polyether polyamide elastomer |
| WO2012048888A1 (en) * | 2010-10-14 | 2012-04-19 | Tata Steel Nederland Technology B.V. | Preparation of a polyetherimide intermediate and its application on metal substrates |
| CN105745265A (en) * | 2013-09-23 | 2016-07-06 | 沙特基础全球技术有限公司 | Nitrogen containing polymer compositions having reduced combustion toxicity |
| KR20150037572A (en) * | 2013-09-30 | 2015-04-08 | 주식회사 엘지화학 | Thermoplastic Resin comprising Polyamide |
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