Benzimidazole diamine, polybenzimidazole imide and preparation method and application thereof

Abstract

The invention relates to benzimidazole diamine, polybenzimidazole imide as well as a preparation method and application of the benzimidazole diamine and the polybenzimidazole imide. The structural formula of the benzimidazole diamine is as shown in a formula (I): # imgabs0 #; wherein R1 and R2 are respectively and independently selected from hydrogen and substituted or unsubstituted C1-C8 alkyl groups. The benzimidazole diamine with the specific structure contains biphenyl and an imidazole ring, and is used for preparing polyimide, so that the linear expansion coefficient of the polyimide is effectively reduced on the basis of ensuring relatively high glass transition temperature and thermal decomposition temperature of the polyimide, and the thermal decomposition temperature of the polyimide is reduced. Meanwhile, the Young modulus, the tensile strength and the elongation at break of the polyimide can be effectively improved, so that the polyimide has better thermal stability.

Description

Technical Field

[0001] The present application relates to the field of material technology, and in particular to a benzimidazole diamine, a polybenzimidazole imide, and a preparation method and application thereof. Background Art

[0002] Polybenzimidazole imide is a high-performance polymer material with good heat resistance, mechanical properties, chemical corrosion resistance, low dielectric constant and low dielectric loss. It can be used to manufacture high-temperature resistant structural components or insulating materials for use in the aerospace field, as an insulating material and electronic packaging material for use in the electronic and electrical fields, and for the manufacture of corrosion-resistant equipment and pipelines for use in the chemical industry.

[0003] However, the thermal stability of traditional polybenzimidazole imide needs to be further improved. Summary of the invention

[0004] Based on this, the present application provides a benzimidazole diamine, a polybenzimidazole imide, and a preparation method and application thereof. The benzimidazole diamine can be used as an intermediate for preparing polybenzimidazole imide, and the prepared polybenzimidazole imide has good thermal stability.

[0005] The technical solution of this application to solve the above technical problems is as follows.

[0006] In a first aspect, the present application provides a benzimidazole diamine, wherein the structural formula of the benzimidazole diamine is shown in formula (I):

[0007]

[0008] Wherein, R1 and R2 are independently selected from hydrogen, substituted or unsubstituted C1~C8 alkyl.

[0009] In some embodiments, in the benzimidazole diamine, R1 and R2 are independently selected from one of hydrogen and C1-C4 alkyl.

[0010] In some embodiments, in the benzimidazole diamine, the structural formula of the benzimidazole diamine is shown in formula (I-1):

[0011] .

[0012] The second aspect of the present application provides a method for preparing benzimidazole diamine, comprising the following steps:

[0013] Condensation reaction is performed between the compound of formula (II) and the compound of formula (III) to prepare the compound of formula (IV);

[0014] Subjecting the compound of formula (IV) to a ring-closing reaction to prepare a compound of formula (V);

[0015] The compound of formula (V) is subjected to hydrogenation reaction to prepare benzimidazole diamine, the structural formula of which is shown in formula (I):

[0016]

[0017]

[0018] Among them, in formula (I) to formula (V), R1 and R2 are independently selected from hydrogen, substituted or unsubstituted C1~C8 alkyl.

[0019] In some embodiments, in the method for preparing benzimidazole diamine, the condensation reaction satisfies at least one of the following characteristics:

[0020] (1) the condensation reaction is carried out in the presence of an acid-binding agent, wherein the acid-binding agent comprises at least one of triethylamine, diisopropylethylamine, pyridine, sodium carbonate, sodium bicarbonate and potassium carbonate;

[0021] (2) The solvent used in the condensation reaction includes at least one of dichloroethane, dichloromethane, benzene, toluene, chloroform, carbon tetrachloride and tetrahydrofuran;

[0022] (3) The condensation reaction temperature is 0°C to 10°C, and the reaction time is 5 h to 16 h.

[0023] In some embodiments, in the method for preparing benzimidazole diamine, the ring-closing reaction satisfies at least one of the following characteristics:

[0024] (1) The ring-closing reaction is carried out in the presence of an acidic catalyst, wherein the acidic catalyst comprises at least one of acetic acid, sulfuric acid, hydrochloric acid and p-toluenesulfonic acid;

[0025] (2) the solvent used in the ring-closure reaction includes at least one of N-methylpyrrolidone, butyrolactone, sulfolane and dichlorobenzene;

[0026] (3) The temperature of the ring-closure reaction is 180°C to 220°C, and the time is 8 h to 16 h.

[0027] In some embodiments, in the method for preparing benzimidazole diamine, the hydrogenation reaction satisfies at least one of the following characteristics:

[0028] (1) The hydrogenation reaction is carried out in the presence of a metal catalyst, wherein the metal catalyst comprises at least one of palladium carbon, platinum carbon, activated nickel and rhodium carbon;

[0029] (2) The solvent used in the hydrogenation reaction includes at least one of tetrahydrofuran, ethanol, methanol, isopropanol, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dioxane, ethyl acetate, benzene, toluene and xylene;

[0030] (3) The temperature of the hydrogenation reaction is 40°C to 100°C, the pressure is 0.5MPa to 3MPa, and the time is 4 h to 10 h.

[0031] In some embodiments, in the method for preparing benzimidazole diamine, the preparation of the compound of formula (III) comprises the following steps:

[0032] The compound of formula (III) is prepared by subjecting 4'-nitrobiphenyl-4-carboxylic acid to an acyl chlorination reaction with an acyl chlorination agent.

[0033] In some embodiments, in the method for preparing benzimidazole diamine, the chlorination reaction satisfies at least one of the following characteristics:

[0034] (1) The acyl chlorination agent comprises at least one of phosphorus trichloride and thionyl chloride;

[0035] (2) The temperature of the acyl chlorination reaction is 50°C to 90°C and the time is 4 h to 10 h;

[0036] (3) The solvent used in the acyl chlorination reaction includes N,N-dimethylformyl.

[0037] The third aspect of the present application provides a polybenzimidazole imide, wherein the polybenzimidazole imide comprises a structure shown in formula (VI):

[0038]

[0039] Wherein, R1 and R2 are independently selected from hydrogen, substituted or unsubstituted C1~C8 alkyl, and R3 is selected from C4~C 20 wherein n is an integer of 40 to 60.

[0040] In some embodiments, in the polybenzimidazole imide, R3 is selected from one of cyclobutyl, phenyl and biphenyl.

[0041] In some embodiments, in the polybenzimidazole imide, the polybenzimidazole imide comprises one of the structures shown in formula (VI-1) to formula (VI-3):

[0042] .

[0043] The fourth aspect of the present application provides a method for preparing polybenzimidazole imide, comprising the following steps:

[0044] The benzimidazole diamine or the benzimidazole diamine prepared by the preparation method of the benzimidazole diamine, a dibasic acid anhydride and a non-protonic organic solvent are subjected to a polycondensation reaction to prepare polybenzimidazole imide.

[0045] In some of the embodiments, in the method for preparing polybenzimidazole imide, the dibasic acid anhydride includes at least one of pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride and 1,2,3,4-cyclobutanetetracarboxylic anhydride.

[0046] In some of the embodiments, in the method for preparing polybenzimidazole imide, the aprotic organic solvent includes at least one of N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, N-ethylpyrrolidone and dimethyl sulfoxide.

[0047] In some of the embodiments, in the method for preparing polybenzimidazole imide, the polycondensation reaction is carried out under closed conditions with continuous stirring at a speed of 100 r / min to 300 r / min.

[0048] In a fifth aspect, the present application provides a polyimide film, comprising the polybenzimidazole imide or the polybenzimidazole imide prepared by the preparation method of the polybenzimidazole imide.

[0049] The sixth aspect of the present application provides the use of the above-mentioned polyimide film in the preparation of electronic components.

[0050] A seventh aspect of the present application provides an electronic component comprising the above-mentioned polyimide film.

[0051] Compared with the prior art, the benzimidazole diamine of the present application has the following beneficial effects:

[0052] The benzimidazole diamine with a specific structure of the present application contains biphenyl and imidazole rings. It is used to prepare polyimide. On the basis of ensuring that the glass transition temperature and thermal decomposition temperature of the polyimide are high, the linear expansion coefficient of the polyimide is effectively reduced. At the same time, the Young's modulus, tensile strength and elongation at break of the polyimide can be effectively improved, so that the polyimide has good thermal stability. BRIEF DESCRIPTION OF THE DRAWINGS

[0053] In order to more clearly illustrate the specific implementation methods of the present application or the technical solutions in the prior art, the drawings required for use in the specific implementation methods or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are some implementation methods of the present application. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0054] Figure 1The H NMR spectrum of the compound of formula V-1 prepared in Example 1;

[0055] Figure 2 The H NMR spectrum of the compound of formula I-1 prepared in Example 1;

[0056] Figure 3 The infrared spectra of the polybenzimidazole imide prepared in each embodiment;

[0057] Figure 4 The thermal stability test diagram of the polyimide film prepared in each embodiment;

[0058] Figure 5 TMA test graph of the polyimide film prepared in each embodiment;

[0059] Figure 6 The diagram is a tensile test diagram of the polyimide film prepared in each embodiment. DETAILED DESCRIPTION

[0060] References to embodiments of the present invention will now be provided in detail, one or more examples of which are described below. Each example is provided as an explanation rather than a limitation of the present invention. In fact, it will be apparent to those skilled in the art that various modifications and variations may be made to the present invention without departing from the scope or spirit of the present invention. For example, a feature illustrated or described as part of one embodiment may be used in another embodiment to produce a further embodiment.

[0061] Therefore, it is intended that the present invention covers such modifications and variations that fall within the scope of the appended claims and their equivalents. Other objects, features and aspects of the present invention are disclosed in or are obvious from the following detailed description. Those of ordinary skill in the art will appreciate that this discussion is only a description of exemplary embodiments and is not intended to limit the broader aspects of the present invention.

[0062] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art of the present invention. The terms used in the specification of the present invention herein are only for the purpose of describing specific embodiments and are not intended to limit the present invention.

[0063] The term "comprises", "comprising" or any other variant thereof is intended to cover non-exclusive inclusion, so that the process, method, article or equipment including a series of elements includes not only those elements, but also includes other elements not explicitly listed, or also includes elements inherent to such process, method, article or equipment. In the absence of more restrictions, the elements defined by the sentence "comprising one..." do not exclude the presence of other identical elements in the process, method, article or equipment including the elements. The indefinite articles "a kind of" and "an" before the elements or components of the present invention are not restrictive to the quantity requirements (i.e., the number of occurrences) of the elements or components. Therefore, "a" or "a kind of" should be interpreted as including one or at least one, and the elements or components in the singular form also include the plural form, unless the number clearly refers only to the singular form. The meaning of "multiple" is at least two, such as two, three, etc., unless otherwise clearly and specifically defined.

[0064] The weight of the relevant components mentioned in the description of the embodiments of the present invention may not only refer to the specific content of each component, but also indicate the weight ratio between the components. Therefore, as long as the content of the relevant components is proportionally enlarged or reduced according to the description of the embodiments of the present invention, it is within the scope disclosed in the description of the embodiments of the present invention. Specifically, the weight described in the description of the embodiments of the present invention may be a mass unit known in the chemical industry such as μg, mg, g, kg, etc.

[0065] Except as shown in the operating examples or otherwise indicated, all numbers used in the specification and claims to indicate the amount of ingredients, physicochemical properties, etc. are understood to be adjusted by the term "about" in all cases. For example, therefore, unless otherwise indicated, the numerical parameters listed in the above specification and the attached claims are approximate values, and those skilled in the art can use the teachings disclosed herein to seek to obtain the desired properties and appropriately change these approximate values. The use of numerical ranges expressed as endpoints includes all numbers within the range and any range within the range, for example, 1 to 5 includes 1, 1.1, 1.3, 1.5, 2, 2.75, 3, 3.80, 4 and 5, etc.

[0066] In the present invention, the term "substituted or unsubstituted" means that the group described subsequently may be substituted but need not be substituted, for example, "substituted or unsubstituted phenyl" means that the phenyl may be further substituted or unsubstituted. Furthermore, when the substituent of the present invention may be further substituted, it may be substituted by the following groups: alkyl, cycloalkyl, alkoxy, heterocyclic group, aryl, heteroaryl or halogen. Furthermore, it may be substituted by the following groups: C1~C6 alkyl, 3~8 membered cycloalkyl, C1~C6 alkoxy, 3~8 membered heterocyclic group, 6~10 membered aryl, 5~10 membered heteroaryl or halogen.

[0067] "Alkyl" refers to a saturated aliphatic hydrocarbon group, including straight and branched groups. C1~C6 alkyl refers to an alkyl group containing 1 to 6 carbon atoms. Non-limiting examples include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, n-pentyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, 2-methylbutyl, 3-methylbutyl, n-hexyl, 1-ethyl-2-methylpropyl, 1,1,2-trimethylpropyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 2,2-dimethylbutyl, 1,3-dimethylbutyl, 2-ethylbutyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 2,3-dimethylbutyl. C1~C4 alkyl refers to an alkyl group containing 1 to 4 carbon atoms. In one embodiment, the C1-C4 alkyl group is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, or sec-butyl. The alkyl group may be substituted or unsubstituted, and when substituted, the substituent may be substituted at any available attachment point.

[0068] "Cycloalkyl" refers to a saturated or partially unsaturated monocyclic or polycyclic cyclic hydrocarbon substituent. A 4-8 membered cycloalkyl refers to a cycloalkyl group having 4 to 8 carbon atoms. In one embodiment, a 4-8 membered monocyclic cycloalkyl group is a cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, cyclohexadienyl, cycloheptyl, cycloheptatrienyl, cyclooctyl, etc. Polycyclic cycloalkyl groups include cycloalkyl groups of spiro rings, fused rings, and bridged rings. A cycloalkyl group may be optionally substituted with one or more substituents.

[0069] "Heterocyclyl" refers to a saturated or partially unsaturated monocyclic or polycyclic hydrocarbon substituent, wherein one or more ring atoms are selected from nitrogen, oxygen or S(O)m (wherein m is an integer from 0 to 2), preferably nitrogen or oxygen heteroatoms; but does not include the ring part of -OO-, -OS- or -SS-, and the remaining ring atoms are carbon. 4-10 membered heterocyclyl means that the ring contains 4 to 10 ring atoms, of which 1 to 3 are heteroatoms; preferably, the heterocyclyl ring contains 5 to 6 ring atoms, of which 1 to 2 are heteroatoms.

[0070] "Aromatic group" or "aryl" refers to an all-carbon monocyclic or fused polycyclic (i.e., rings that share adjacent pairs of carbon atoms) group with a conjugated π electron system, preferably 6 to 10 members, more preferably phenyl and naphthyl, most preferably phenyl. The aryl ring may be fused to a heteroaryl, heterocyclyl or cycloalkyl ring, and the aryl group may be substituted or unsubstituted.

[0071] 5-10 membered "heteroaromatic group" or "heteroaryl" refers to a heteroaromatic system containing 1 to 4 heteroatoms and 5 to 10 ring atoms, wherein the heteroatoms include oxygen, sulfur and nitrogen. Heteroaryl is preferably 5-membered or 6-membered, such as furanyl, thienyl, pyridyl, pyrrolyl, N-alkylpyrrolyl, pyrimidyl, pyrazinyl, imidazolyl, tetrazolyl, etc. The heteroaryl ring can be fused to an aryl, heterocyclyl or cycloalkyl ring, and the ring connected to the parent structure is the heteroaryl ring. The heteroaryl group can be optionally substituted or unsubstituted.

[0072] "Alkylene" refers to a saturated aliphatic hydrocarbon subunit, which is a divalent free bond structure formed by losing two hydrogen atoms. C1~C6 alkylene refers to an alkylene group containing 1 to 6 carbon atoms. Non-limiting examples include: methylene, ethylene, n-propylene, n-butylene, n-pentylene, and n-hexylene.

[0073] "Ether group" refers to a group containing -O-. The general formula of ether is ROR'. When R and R' are the same, it is called a simple ether; when R and R' are different, it is called a mixed ether. When R' and R' are both aliphatic hydrocarbon groups, it is aliphatic ether; when R or R' is an aromatic hydrocarbon group, it is an aromatic ether.

[0074] "Respectively independently" means that the same group or different groups may be selected.

[0075] An embodiment of the present application provides a benzimidazole diamine, the structural formula of which is shown in formula (I):

[0076]

[0077] Wherein, R1 and R2 are independently selected from hydrogen, substituted or unsubstituted C1~C8 alkyl.

[0078] The benzimidazole diamine with a specific structure of the present application contains biphenyl and imidazole rings. It is used to prepare polyimide. On the basis of ensuring that the glass transition temperature and thermal decomposition temperature of the polyimide are high, the linear expansion coefficient of the polyimide is effectively reduced. At the same time, the Young's modulus, tensile strength and elongation at break of the polyimide can be effectively improved, so that the polyimide has better thermal stability and the dimensional stability of the polyimide is improved.

[0079] It will be appreciated that the positions of R1, R2 and NH2 on the benzene ring in the benzimidazole ring are not limited.

[0080] In some of the examples, in the benzimidazole diamine, R1 and R2 are independently selected from one of hydrogen and C1-C4 alkyl.

[0081] It is understood that the C1~C4 alkyl group includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl and sec-butyl.

[0082] In some of the examples, in the benzimidazole diamine, R1 and R2 are independently selected from one of hydrogen (-H) and methyl (-CH3).

[0083] In some of the examples, in the benzimidazole diamine, R1 and R2 are both hydrogen.

[0084] In some of the examples, the structural formula of benzimidazole diamine is shown in formula (I-1):

[0085] .

[0086] An embodiment of the present application provides a method for preparing benzimidazole diamine, comprising the following steps:

[0087] Step S10: subjecting the compound of formula (II) and the compound of formula (III) to a condensation reaction to prepare a compound of formula (IV).

[0088] In some of the examples, in step S10, the condensation reaction is carried out in the presence of an acid-binding agent, and the acid-binding agent includes at least one of triethylamine, diisopropylethylamine, pyridine, sodium carbonate, sodium bicarbonate and potassium carbonate.

[0089] In some examples, in step S10, the solvent used in the condensation reaction includes at least one of dichloroethane, dichloromethane, benzene, toluene, chloroform, carbon tetrachloride and tetrahydrofuran.

[0090] In some of the examples, in step S10, the condensation reaction temperature is 0°C to 10°C, and the reaction time is 5h to 16h.

[0091] It is understood that the temperature of the condensation reaction includes but is not limited to 0°C, 2°C, 5°C, 8°C, and 10°C, and the time includes but is not limited to 5h, 8h, 10h, 12h, 15h, and 16h. In some examples, any two of these point values ​​can be used as end values ​​within the range, the same below.

[0092] It is understood that the chemical name of the compound of formula (III) is 4'-nitro-[1,1'-biphenyl]-4-carbonyl chloride, which can be obtained from the market or prepared by oneself.

[0093] In some examples, in step S10, the preparation of the compound of formula (III) comprises the following steps:

[0094] Step S11: 4'-nitrobiphenyl-4-carboxylic acid and an acyl chlorination agent are subjected to an acyl chlorination reaction to prepare a compound of formula (III).

[0095] Wherein, the structural formula of 4'-nitrobiphenyl-4-carboxylic acid is shown in formula (VII):

[0096]

[0097] In some of the examples, in step S11, the chlorination reagent includes at least one of phosphorus trichloride and thionyl chloride.

[0098] In some examples, in step S11, the molar ratio of 4'-nitrobiphenyl-4-carboxylic acid to the acyl chloride reagent is 1:(5-10).

[0099] It is understood that the molar ratio of 4'-nitrobiphenyl-4-carboxylic acid to the acyl chloride reagent includes but is not limited to 1:5, 1:6, 1:8, and 1:10.

[0100] In some of the examples, in step S11, the temperature of the acyl chlorination reaction is 50°C to 90°C, and the time is 4 h to 10 h.

[0101] It is understood that the temperature of the acyl chloride reaction includes but is not limited to 50° C., 60° C., 70° C., 80° C., and 90° C., and the time includes but is not limited to 4 h, 5 h, 8 h, and 10 h.

[0102] In some examples, in step S11, the solvent used in the chlorination reaction includes N,N-dimethylformyl.

[0103] In some examples, in step S11, the molar ratio of 4'-nitrobiphenyl-4-carboxylic acid to the organic solvent is 1:(0.1-0.5).

[0104] It is understood that the molar ratio of 4'-nitrobiphenyl-4-carboxylic acid to the organic solvent includes, but is not limited to, 1:0.1, 1:0.2, 1:0.3, 1:0.4, and 1:0.5.

[0105] Step S20: subjecting the compound of formula (IV) to a ring-closing reaction to prepare a compound of formula (V);

[0106] In some of the examples, in step S20, the ring-closure reaction is carried out under the condition of an acidic catalyst, and the acidic catalyst includes at least one of acetic acid, sulfuric acid, hydrochloric acid and p-toluenesulfonic acid.

[0107] In some of the examples, in step S20, the solvent used in the cyclization reaction includes at least one of N-methylpyrrolidone, butyrolactone, sulfolane and dichlorobenzene.

[0108] In some of the examples, in step S20, the ring-closure reaction is carried out at a temperature of 180° C. to 220° C. and for a time of 8 h to 16 h.

[0109] It is understood that the temperature of the ring-closure reaction includes but is not limited to 180°C, 190°C, 200°C, 210°C, 220°C, and the time includes but is not limited to 8h, 10h, 12h, 15h, 16h.

[0110] Step S30: hydrogenating the compound of formula (V) to prepare benzimidazole diamine, the structural formula of which is shown in formula (I):

[0111]

[0112]

[0113] Among them, in formula (I) to formula (V), R1 and R2 are independently selected from hydrogen, substituted or unsubstituted C1~C8 alkyl.

[0114] In some of the examples, in step S30, the hydrogenation reaction is carried out under the condition of a metal catalyst, and the metal catalyst includes at least one of palladium carbon, platinum carbon, activated nickel and rhodium carbon.

[0115] In some of the examples, in step S30, the solvent used in the hydrogenation reaction includes at least one of tetrahydrofuran, ethanol, methanol, isopropanol, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dioxane, ethyl acetate, benzene, toluene and xylene.

[0116] In some of the examples, in step S30, the temperature of the hydrogenation reaction is 40°C to 100°C, the pressure is 0.5MPa to 3MPa, and the time is 4 h to 10 h.

[0117] It is understood that the temperature of the hydrogenation reaction includes but is not limited to 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, and 100°C, the pressure includes but is not limited to 0.5Mpa, 1Mpa, 2Mpa, and 3MPa, and the time includes but is not limited to 4h, 5h, 8h, and 10h.

[0118] One embodiment of the present application provides a polybenzimidazole imide, which includes a structure shown in formula (VI):

[0119]

[0120] Wherein, R1 and R2 are independently selected from hydrogen, substituted or unsubstituted C1~C8 alkyl, and R3 is selected from C4~C 20 wherein n is an integer of 40 to 60.

[0121] Understandably, C4~C 20The cycloalkyl group includes, but is not limited to, cyclobutyl, cyclopentyl, cyclopentenyl, cyclohexyl, cycloheptyl, cyclooctyl, and at least one of spirocyclic, condensed-ring, and bridged-ring polycyclic cycloalkyl groups; C4~C 20 The aryl group includes, but is not limited to, at least one of phenyl, naphthyl, biphenyl and the like.

[0122] n includes but is not limited to 40, 42, 45, 48, 50, 52, 55, 58, 60.

[0123] In some examples, in the polybenzimidazole imide, R3 is selected from one of cyclobutyl, phenyl and biphenyl.

[0124] In some examples, in the polybenzimidazole imide, R3 is selected from at least one of the following structures:

[0125] .

[0126] In some of the examples, the polybenzimidazole imide comprises one of the structures shown in formula (VI-1) to formula (VI-3):

[0127] .

[0128] In some of the examples, the polybenzimidazole imide comprises one of the structures shown in formula (VI-1-1) to formula (VI-3-1):

[0129]

[0130] An embodiment of the present application provides a method for preparing polybenzimidazole imide, comprising the following steps:

[0131] Step S100: subjecting the benzimidazole diamine or the benzimidazole diamine prepared in steps S10 to S30, a dibasic acid anhydride and an aprotic organic solvent to a condensation polymerization reaction to prepare polybenzimidazole imide.

[0132] In some of the examples, in step S100 , the dibasic acid anhydride includes at least one of pyromellitic dianhydride (PMDA), 3,3′,4,4′-biphenyltetracarboxylic dianhydride (BPDA), and 1,2,3,4-cyclobutanetetracarboxylic anhydride (CBDA).

[0133] In some of the examples, in step S100 , the aprotic organic solvent includes at least one of N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, N-ethylpyrrolidone and dimethyl sulfoxide.

[0134] In some of the examples, in step S100, the polycondensation reaction is carried out under closed conditions with continuous stirring at a rotation speed of 100 r / min to 300 r / min.

[0135] In some of the examples, in step S100, the polycondensation reaction is carried out at a temperature of 0°C to 60°C and for a time of 12h to 48h.

[0136] Optionally, the temperature of the polycondensation reaction is 10°C to 25°C.

[0137] It can be understood that the polycondensation reaction in step S100 is a thermal imide method and does not require the use of a catalyst.

[0138] One embodiment of the present application provides a polyimide film, including the polybenzimidazole imide or the polybenzimidazole imide prepared by the preparation method of the polybenzimidazole imide.

[0139] One embodiment of the present application provides the use of the above-mentioned polyimide film in the preparation of electronic components.

[0140] An embodiment of the present application provides an electronic component, comprising the above-mentioned polyimide film.

[0141] The present application is further described in detail below in conjunction with specific implementation methods, but the implementation methods of the present application are not limited thereto.

[0142] Example 1

[0143]

[0144] (1) Add 5g of the compound of formula II-1 (4-nitro-o-phenylenediamine), 3.1g of triethylamine and 50ml of tetrahydrofuran (THF) into a 250ml single-necked flask, place it in an ice-water bath, and slowly dropwise add 8.1g of the compound of formula III (4'-nitro-[1,1'-biphenyl]-4-carbonyl chloride) in 100ml of THF solution while keeping the system temperature below 10°C, and stir for 2 hours. After returning to room temperature and continuing the reaction for 12 hours and monitoring the completion of the reaction by thin layer chromatography (TLC), the reaction solution is vacuum-rotated and poured into methanol to produce a large amount of precipitation. After suction filtration and drying, 5.8g of a yellow solid product (compound of formula IV-1) is obtained.

[0145] (2) Add the compound of formula IV-1 prepared in step (1), 60 ml of cyclopentane and 6.8 g of p-toluenesulfonic acid into a 100 ml single-necked flask, slowly heat to 200 °C and stir for 12 h to complete the ring-closure reaction. Pour the reaction solution into water to obtain a dark brown solid (8.5 g). Finally, recrystallize from dimethyl sulfoxide (DMSO) to obtain a biphenyl-containing benzimidazole dinitro (compound of formula V-1) with a yield of 73%. The H NMR spectrum is as follows: Figure 1shown.

[0146] (3) Add the compound of formula V-1 (5 g) prepared in step (2), Pd / C (0.5 g), and dioxane (50 ml) into an autoclave. First, ventilate the autoclave three times with high-purity nitrogen, then fill the autoclave with hydrogen to a pressure of 1.0 MPa, and keep it at 80°C for 8 hours. TLC is used to detect whether the reaction is complete. The reaction solution after the reaction is first filtered under reduced pressure to recover the palladium carbon catalyst, and then the obtained filtrate is cooled, crystallized, filtered, and dried to obtain the benzimidazole diamine containing biphenyl (compound of formula I-1), with a yield of 89%. The hydrogen nuclear magnetic resonance spectrum is as follows: Figure 2 shown.

[0147] (4) The compound of formula I-1 (5 g) prepared in step (3) and PMDA (3.6 g) were dissolved in NMP (78 g), and the mixture was stirred at a speed of 200 r / min for 24 h under closed conditions to obtain a clear polyamic acid solution containing polybenzimidazole imide (compound of formula VI-1-1) with a solid content of 10%.

[0148] (5) The polyamic acid solution was poured onto a clean glass plate for film casting, and then the glass plate was placed in a vacuum oven at 100°C, 200°C, 300°C, and 400°C for 1 hour to obtain a polyimide film with a thickness of 30-35 μm.

[0149] Example 2

[0150] The method is basically the same as Example 1, except that in step (4), PMDA is replaced with BPDA of equal mass, and the polybenzimidazole imide in the obtained clear polyamic acid solution is as shown in Formula VI-2-1:

[0151]

[0152] Example 3

[0153] The method is basically the same as Example 1, except that in step (4), PMDA is replaced with CBDA of equal mass, and the polybenzimidazole imide in the obtained clear polyamic acid solution is as shown in Formula VI-3-1:

[0154]

[0155] The infrared spectra of the polybenzimidazole imide prepared in each embodiment are as follows: Figure 3 shown.

[0156] The polyimide films prepared in the examples were subjected to a thermal stability test. The test method was as follows: a TA company TGA550 thermogravimetric analyzer was used to heat the film from room temperature to 800°C at a heating rate of 10°C / min in a nitrogen atmosphere. The test results are shown in Table 1. The thermal stability test diagram of the polyimide films prepared in each example is shown in Table 1. Figure 4 shown.

[0157] The polyimide film prepared in the examples was subjected to a thermomechanical tensile test. The test method is as follows: the obtained polyimide film was tested using a TMA Q400 thermomechanical analyzer from TA. First, the polyimide film was made into a 50 mm × 5 mm rectangular sample, and the temperature was raised from room temperature to 400 ° C at a heating rate of 5 ° C / min in a nitrogen atmosphere. The test results are shown in Table 1. The TMA test graphs of the polyimide films prepared in each example are shown in Table 1. Figure 5 shown.

[0158] Table 1

[0159]

[0160] Wherein, Td5% represents the 5% thermal weight loss temperature, Td10% represents the 10% thermal weight loss temperature, Rw represents the thermal residual rate at 800°C, CTE is the linear thermal expansion coefficient obtained by TMA test, and Tg is the glass transition temperature obtained by TMA test.

[0161] From Table 1, Figure 4 and Figure 5 It can be seen that the glass transition temperature of the polyimide film prepared in the embodiment is relatively high; in a nitrogen atmosphere, the 5% thermal weight loss temperature is relatively high, and the thermal residual rate at 800° C. is relatively high. In addition, the CTE value of the polyimide film is relatively low.

[0162] The polyimide film prepared in the examples was subjected to a tensile test. The test method is as follows: the obtained polyimide film was tested using an Instron 5966 electronic universal testing machine. The polyimide film was made into a 50 mm × 5 mm rectangular sample with a distance of 30 mm between the clamps. The sample was stretched at a rate of 3 mm / min. The test results are shown in Table 2. The tensile test results of the polyimide films prepared in each example are shown in Table 2. Figure 6 shown.

[0163] Table 2

[0164]

[0165] It can be seen from Table 2 that the polyimide film prepared in the example has excellent mechanical properties.

[0166] The technical features of the above-described embodiments may be arbitrarily combined. To make the description concise, not all possible combinations of the technical features in the above-described embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0167] The above-described embodiments only express several implementation methods of the present application, which is convenient for understanding the technical solution of the present application in detail, but it cannot be understood as limiting the scope of protection of the invention patent. It should be pointed out that for ordinary technicians in this field, without departing from the concept of the present application, several modifications and improvements can be made, which all belong to the scope of protection of the present application. It should be understood that the technical solutions obtained by those skilled in the art through logical analysis, reasoning or limited experiments on the basis of the technical solutions provided in the present application are all within the scope of protection of the claims attached to the present application. Therefore, the scope of protection of the patent of this application shall be based on the contents of the attached claims, and the description and drawings can be used to explain the contents of the claims.

Claims

1. A benzimidazole diamine, characterized in that The structural formula of the benzimidazole diamine is shown in formula (I): Wherein, R1 and R2 are independently selected from hydrogen, substituted or unsubstituted C1~C8 alkyl.

2. The benzimidazole diamine according to claim 1, characterized in that R1 and R2 are independently selected from one of hydrogen and C1~C4 alkyl.

3. The benzimidazole diamine according to any one of claims 1 to 2, characterized in that The structural formula of the benzimidazole diamine is shown in formula (I-1): 。 4. A method for preparing benzimidazole diamine, characterized in that: The following steps are involved: Condensation reaction is performed between the compound of formula (II) and the compound of formula (III) to prepare the compound of formula (IV); Subjecting the compound of formula (IV) to a ring-closing reaction to prepare a compound of formula (V); The compound of formula (V) is subjected to hydrogenation reaction to prepare benzimidazole diamine, the structural formula of which is shown in formula (I): Among them, in formula (I) to formula (V), R1 and R2 are independently selected from hydrogen, substituted or unsubstituted C1~C8 alkyl.

5. The method for preparing the benzimidazole diamine according to claim 4, characterized in that: The condensation reaction satisfies at least one of the following characteristics: (1) the condensation reaction is carried out in the presence of an acid-binding agent, wherein the acid-binding agent comprises at least one of triethylamine, diisopropylethylamine, pyridine, sodium carbonate, sodium bicarbonate and potassium carbonate; (2) The solvent used in the condensation reaction includes at least one of dichloroethane, dichloromethane, benzene, toluene, chloroform, carbon tetrachloride and tetrahydrofuran; (3) The condensation reaction temperature is 0°C to 10°C, and the reaction time is 5 h to 16 h.

6. The method for preparing the benzimidazole diamine according to claim 4, characterized in that: The ring-closing reaction satisfies at least one of the following characteristics: (1) The ring-closing reaction is carried out in the presence of an acidic catalyst, wherein the acidic catalyst comprises at least one of acetic acid, sulfuric acid, hydrochloric acid and p-toluenesulfonic acid; (2) the solvent used in the ring-closure reaction includes at least one of N-methylpyrrolidone, butyrolactone, sulfolane and dichlorobenzene; (3) The temperature of the ring-closure reaction is 180°C to 220°C, and the time is 8 h to 16 h.

7. The method for preparing benzimidazole diamine according to claim 4, characterized in that: The hydrogenation reaction satisfies at least one of the following characteristics: (1) The hydrogenation reaction is carried out in the presence of a metal catalyst, wherein the metal catalyst comprises at least one of palladium carbon, platinum carbon, activated nickel and rhodium carbon; (2) The solvent used in the hydrogenation reaction includes at least one of tetrahydrofuran, ethanol, methanol, isopropanol, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dioxane, ethyl acetate, benzene, toluene and xylene; (3) The temperature of the hydrogenation reaction is 40°C to 100°C, the pressure is 0.5MPa to 3MPa, and the time is 4 h to 10 h.

8. The method for preparing the benzimidazole diamine according to any one of claims 4 to 7, wherein The preparation of the compound of formula (III) comprises the following steps: The compound of formula (III) is prepared by subjecting 4'-nitrobiphenyl-4-carboxylic acid to an acyl chlorination reaction with an acyl chlorination agent.

9. The method for preparing benzimidazole diamine according to claim 8, characterized in that: The acyl chlorination reaction satisfies at least one of the following characteristics: (1) The acyl chlorination agent comprises at least one of phosphorus trichloride and thionyl chloride; (2) The temperature of the acyl chlorination reaction is 50°C to 90°C and the time is 4 h to 10 h; (3) The solvent used in the acyl chlorination reaction includes N,N-dimethylformyl.

10. A polybenzimidazole imide, characterized in that: The polybenzimidazole imide comprises a structure shown in formula (VI): Wherein, R1 and R2 are independently selected from hydrogen, substituted or unsubstituted C1~C8 alkyl, and R3 is selected from C4~C 20 wherein n is an integer of 40 to 60.

11. The polybenzimidazole imide according to claim 10, characterized in that R3 is selected from one of cyclobutyl, phenyl and biphenyl.

12. The polybenzimidazole imide according to claim 10 or 11, characterized in that The polybenzimidazole imide comprises one of the structures shown in formula (VI-1) to formula (VI-3): 。 13. A method for preparing polybenzimidazole imide, characterized in that: The following steps are involved: The polybenzimidazole imide is prepared by polycondensing the benzimidazole diamine as claimed in any one of claims 1 to 3 or the benzimidazole diamine prepared by the preparation method of the benzimidazole diamine as claimed in any one of claims 4 to 9, a dibasic acid anhydride and a non-protonic organic solvent.

14. The method for preparing polybenzimidazole imide according to claim 13, characterized in that: The dibasic acid anhydride includes at least one of pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride and 1,2,3,4-cyclobutanetetracarboxylic anhydride.

15. The method for preparing polybenzimidazole imide according to claim 13, characterized in that: The aprotic organic solvent includes at least one of N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, N-ethylpyrrolidone and dimethyl sulfoxide.

16. The method for preparing polybenzimidazole imide according to any one of claims 13 to 15, characterized in that: The polycondensation reaction is carried out under closed conditions with continuous stirring at a rotation speed of 100 r / min to 300 r / min.

17. A polyimide film, characterized in that: The invention comprises the polybenzimidazole imide as claimed in any one of claims 10 to 12 or the polybenzimidazole imide prepared by the preparation method as claimed in any one of claims 13 to 16.

18. Use of the polyimide film according to claim 17 in preparing electronic components.

19. An electronic component, characterized in that: Comprising the polyimide film as claimed in claim 17.

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