Dianhydroidurol-based diamino compound, PI film and preparation method

Abstract

The invention provides a dianhydroidurol-based diamino compound and a preparation method thereof, and the preparation method comprises the following steps: obtaining a dianhydroidurol-containing dinitro compound based on dianhydromannitol or dianhydrosorbitol, dissolving the dianhydroidurol-containing dinitro compound in ethyl acetate, and reacting to obtain the dianhydroidurol-based diamino compound. And carrying out a reduction reaction in a hydrogen atmosphere to obtain the diamino compound based on the dianhydroidurol. The invention further provides a PI film prepared from the diamino compound based on the dianhydroidurol and a preparation method of the PI film, and the PI film is obtained by doping the diamino compound based on the dianhydroidurol with 3, 4 '-ODA and then adding dianhydride for polycondensation. By introducing the dianhydroidurol, destroying the conjugated structure of the chain segment, weakening the interaction between molecular chains and increasing the distance and free volume between the molecular chains, the polarizability of molecules is reduced, and finally the purposes of enhancing the light transmission and reducing the dielectric constant are achieved.

Description

Technical Field

[0001] The invention relates to the technical field of polyimide, and in particular to a diamino compound based on dianhydroiditol, a PI film and a preparation method thereof. Background Art

[0002] Polyimide (PI) is one of the organic polymer materials with the best comprehensive performance. PI can withstand high temperatures of over 400°C and has a long-term use temperature range of -200 to 300°C. Some of them have no obvious melting point. As a special engineering material, PI has been widely used in aviation, aerospace, microelectronics, nanotechnology, liquid crystal, separation membranes, lasers and other fields.

[0003] However, traditional PI films have disadvantages such as high relative dielectric constant and poor transparency [the relative dielectric constant of Kapton polyimide film at 23°C, 50% humidity, and 1kHz is 3.4 (25-50μm) and 3.5 (75-125μm), and the transmittance within 200-500nm is almost 0], and performance improvement is urgently needed. Summary of the invention

[0004] The purpose of the present invention is to provide a diamino compound based on dianhydroiditol in view of the defects of the prior art, the structure of which is as follows:

[0005]

[0006] Ar 11 for

[0007]

[0008] One of

[0009] Ar 12 for

[0010]

[0011] One of them.

[0012] Further, the structure of the diamino compound based on dianhydroiditol is as follows:

[0013]

[0014] The preparation method of the diamino compound based on dianhydroiditol comprises the following steps:

[0015] Under protective gas, triphenylphosphine, p-nitrobenzoic acid or m-nitrobenzoic acid, and dianhydromannitol are added into tetrahydrofuran to dissolve, and then diisopropyl azodicarboxylate is added to react, purified and dried to obtain a dinitro compound containing dianhydromannitol;

[0016] Under protective gas, a dinitro compound containing dianhydroiditol is dissolved in ethyl acetate, the protective gas is replaced by hydrogen, a catalyst is added to carry out a reduction reaction, and the reaction is purified and dried to obtain a diamino compound based on dianhydroiditol.

[0017] Further, the preparation method of the diamino compound based on dianhydroiditol comprises the following steps:

[0018] Under a nitrogen atmosphere, triphenylphosphine, p-nitrobenzoic acid or m-nitrobenzoic acid, and dianhydromannitol are added to tetrahydrofuran in an ice bath to dissolve, and then diisopropyl azodicarboxylate is added dropwise, and the reaction is carried out in an ice bath for 0.5-1.5 hours, and then the ice bath is removed, and the reaction is carried out at room temperature for 5 hours to 7 hours, and finally the temperature is raised to 60° C. to 70° C. and refluxed for 40 hours to 45 hours, and then purified and dried to obtain a dinitro compound containing dianhydromannitol; wherein the molar ratio of triphenylphosphine: p-nitrobenzoic acid or m-nitrobenzoic acid: dianhydromannitol: diisopropyl azodicarboxylate is 42-46:38-42:18-22:42-46;

[0019] Under nitrogen gas, a dinitro compound containing dehydrated idiol is dissolved in ethyl acetate, and then the protective gas is replaced by hydrogen and a catalyst is added for reduction reaction, which is purified and dried to obtain a diamino compound based on dehydrated idiol. The catalyst is a Pd / C catalyst, and the amount of Pd / C catalyst is 5-10‰wt% of the dinitro compound containing benzocyclobutene.

[0020] The method for preparing a diamino compound based on dianhydroiditol may further comprise the following steps:

[0021] Under protective gas, diisopropyl azodicarboxylate is added to a tetrahydrofuran solution of triphenylphosphine to dissolve, p-nitrobenzoic acid or m-nitrobenzoic acid is added dropwise, then dianhydrosorbitol is added, and finally diisopropylethylamine is added to react, purified and dried to obtain a mononitro compound containing dianhydroiditol;

[0022] The mononitro compound containing dianhydroiditol is dissolved in chloroform, and triethylamine is added, and then p-nitrobenzoyl chloride is added to react, and the reaction is performed by purification and drying to obtain the dinitro compound containing dianhydroiditol;

[0023] Under protective gas, a dinitro compound containing dianhydroiditol is dissolved in ethyl acetate, the protective gas is replaced by hydrogen, a catalyst is added to carry out a reduction reaction, and the reaction is purified and dried to obtain a diamino compound based on dianhydroiditol.

[0024] Further, the preparation method of the diamino compound based on dianhydroiditol comprises the following steps:

[0025] Under a nitrogen atmosphere, diisopropyl azodicarboxylate is added to a tetrahydrofuran solution of triphenylphosphine under an ice bath to dissolve, p-nitrobenzoic acid or m-nitrobenzoic acid is added dropwise within 2-4 minutes, and dianhydrosorbitol is slowly added after 1-3 minutes, and the ice bath is removed to allow the reaction mixture to warm to room temperature, and finally diisopropylethylamine is added and stirred at room temperature for 5-8 hours, and then heated to 60-70°C and refluxed for reaction for 40-45 hours, purified and dried to obtain a mononitro compound containing dianhydroiditol; wherein the molar ratio of diisopropyl azodicarboxylate: triphenylphosphine: p-nitrobenzoic acid or m-nitrobenzoic acid: dianhydrosorbitol: diisopropylethylamine is 5-7: 5-7: 4-5: 4-6: 5-7;

[0026] The mononitro compound containing dianhydroiditol is dissolved in chloroform, and triethylamine is added, and the mixture is stirred in an ice bath, and then p-nitrobenzoyl chloride is added, and the mixture is stirred in an ice bath for about 1 hour, and then the mixture is reacted at 65° C. for 45 hours, and then purified and dried to obtain the dinitro compound containing dianhydroiditol;

[0027] Under nitrogen gas, a dinitro compound containing dehydrated idiol is dissolved in ethyl acetate, and then the protective gas is replaced by hydrogen and a catalyst is added for reduction reaction, which is purified and dried to obtain a diamino compound based on dehydrated idiol. The catalyst is a Pd / C catalyst, and the amount of Pd / C catalyst is 5-10‰wt% of the dinitro compound containing benzocyclobutene.

[0028] A PI film prepared from a diamino compound based on dianhydroiditol has the following structure:

[0029]

[0030] x+y=n, the molar percentage of x and y is x:y=5:95 or 10:90 or 15:85 or 20:80 or 25:75 or 30:70;

[0031] Ar 2 for

[0032]

[0033] One of them.

[0034] The method for preparing a PI film based on a diamino compound of dianhydroiditol comprises the following steps:

[0035] Under protective gas, 3,4'-ODA and an amino compound based on dianhydroiditol are first added to N,N-dimethylacetamide to dissolve, and then dianhydride is added to react to obtain a polyamic acid intermediate solution;

[0036] The polyamic acid intermediate solution is cast on a glass substrate, and after removing the solvent, it is gradually heated in a tubular furnace under the protection of protective gas to form a PI film.

[0037] Further, the preparation method of the PI film prepared by the diamino compound based on dianhydroiditol comprises the following steps:

[0038] The dianhydrides include BPDA dianhydride, 6FDA dianhydride, ODPA dianhydride and BTDA dianhydride;

[0039] The molar ratio of the dianhydroiditol-based amino compound: 3,4'-ODA: BPDA dianhydride is 0.125:2.375:2.5 or 0.375:2.125:2.5 or 0.625:1.875:2.5;

[0040] The molar ratio of the dianhydroiditol-based amino compound: 3,4'-ODA: 6FDA dianhydride is 0.1:1.9:2 or 0.2:1.8:2 or 0.3:1.7:2;

[0041] The molar ratio of the dianhydroiditol-based amino compound: 3,4'-ODA: ODPA dianhydride is 0.1:0.9:1 or 0.2:0.8:1 or 0.3:0.7:1;

[0042] The molar ratio of the dianhydroiditol-based amino compound: 3,4'-ODA: BTDA dianhydride is 0.1:0.9:1 or 0.2:0.8:1 or 0.3:0.7:1.

[0043] Further, the preparation method of the PI film prepared by the diamino compound based on dianhydroiditol comprises the following steps:

[0044] Under a nitrogen atmosphere, 3,4'-ODA and an amino compound based on dianhydroiditol are first added to N,N-dimethylacetamide for dissolution, and then the dianhydride is added after reacting in an ice bath at 0-5°C for 10-40 minutes, and the ice bath is continued for 10-40 minutes, then the ice bath is removed, and the reaction is carried out at room temperature for 22-26 hours to obtain a polyamic acid intermediate solution;

[0045] The polyamic acid intermediate solution was cast on a glass substrate, and after removing the solvent, it was placed in a tubular furnace under nitrogen protection and heated at 150°C, 200°C, 250°C, and 300°C for 1 hour each to form a PI film.

[0046] The beneficial effects of the present invention are:

[0047] 1. Dehydrated mannitol and dehydrated sorbitol have non-planar alicyclic structures. On the one hand, their introduction can maintain relatively stable thermal properties and good mechanical properties; on the other hand, their introduction can destroy the conjugated structure of the chain segments, weaken the interaction between the molecular chains, and increase the distance and free volume between the molecular chains, thereby reducing the polarizability of the molecules, and ultimately achieving the purpose of enhancing light transmittance and reducing the dielectric constant.

[0048] 2. The dianhydrosorbitol and dianhydromannitol raw materials used in the present invention come from cellulose (glucose) and sucrose (fructose part) extracted from natural products, which can be prepared by hydrolysis, hydrogenation and dehydration reaction. In addition, the prepared amino compound based on the dianhydroidi alcohol structure can partially replace some pure organic amino compounds currently used, which has the advantages of green environmental protection, low cost and environmental friendliness.

[0049] 3. The present invention adopts the method of Mitsunobu reaction to synthesize amino compounds based on bio-based dianhydrohexose alcohol structure. Mitsunobu reaction has good stereoselectivity, that is, when chiral alcohol participates in the reaction, a product with hydroxyl configuration flipping is usually obtained. Mitsunobu reaction can not only construct chemical bonds, but also has a wide range of applications, mild reaction conditions, simple operation and high yield, and has a wide range of applications in the field of organic synthesis, especially in the synthesis of natural products and functional organic molecules. It plays an important role. Flipping dianhydro sorbitol and dianhydro mannitol into dianhydro iditool structure can also reduce costs to a certain extent, because the natural source of iditool is extremely rare and chemical synthesis is difficult, resulting in dianhydro iditool expensive. In addition, dianhydro sorbitol is cheaper than dianhydro mannitol, and obtaining dianhydro iditool structure by dianhydro sorbitol can further reduce costs. BRIEF DESCRIPTION OF THE DRAWINGS

[0050] Figure 1 The diamino compound ((3aR,3S,6aR,6S)-2,3,3a,5,6,6a-hexahydrofurano[2,3-d]furan-3,6-diylbis(4-aminobenzoate)) of Example 2 1 H NMR spectrum.

[0051] Figure 2 The diamino compound ((3aR,3S,6aR,6S)-2,3,3a,5,6,6a-hexahydrofurano[2,3-d]furan-3,6-diylbis(4-aminobenzoate)) of Example 2 13 C NMR spectrum.

[0052] Figure 3It is the infrared spectrum of the PI film (p-6FDA-90) of Example 6.

[0053] Figure 4 It is the TGA data chart of the PI film (p-6FDA-90) of Example 6.

[0054] Figure 5 It is the DSC data graph of the PI film (p-6FDA-90) of Example 6.

[0055] Figure 6 It is the UV-Vis absorption spectrum of the PI film (p-6FDA-90) of Example 6.

[0056] Figure 7 This is a diagram of the dielectric properties of the PI film (p-6FDA-90) of Example 6. DETAILED DESCRIPTION

[0057] The drugs used in the following examples are all commercially available products unless otherwise specified, and the methods used are all conventional methods in the art unless otherwise specified.

[0058] The method for preparing the diamino compound based on dianhydroiditol adopts the Mitsunobu reaction method.

[0059] (1) Synthesizing a diamino compound based on dianhydroiditol by dianhydromannitol, comprising the following steps:

[0060] Under protective gas, triphenylphosphine, p-nitrobenzoic acid or m-nitrobenzoic acid, and dianhydromannitol are added to tetrahydrofuran to dissolve, and then diisopropyl azodicarboxylate is added to react, purified and dried to obtain a dinitro compound containing dianhydromannitol. The reaction equation is as follows:

[0061]

[0062] Under protective gas, a dinitro compound containing dianhydroiditol is dissolved in ethyl acetate, a Pd / C catalyst is added, and then the protective gas is replaced by hydrogen to react, purify and dry to obtain a diamino compound based on dianhydroiditol. The reaction equation is as follows:

[0063]

[0064] (2) Synthesizing a diamino compound based on dianhydroiditol via dianhydrosorbitol, comprising the following steps:

[0065] Under protective gas, diisopropyl azodicarboxylate is added to a tetrahydrofuran solution of triphenylphosphine to dissolve, p-nitrobenzoic acid or m-nitrobenzoic acid is added dropwise, then dianhydrosorbitol is added, and finally diisopropylethylamine is added for reaction, purified and dried to obtain a mononitro compound containing dianhydroiditol. The reaction equation is as follows:

[0066]

[0067] The mononitro compound containing dianhydroiditol is dissolved in chloroform, and triethylamine is added, and then p-nitrobenzoyl chloride is added to react to obtain the dinitro compound containing dianhydroiditol. The reaction equation is as follows:

[0068]

[0069] Under protective gas, a dinitro compound containing dianhydroiditol is dissolved in ethyl acetate, a Pd / C catalyst is added, and then the protective gas is replaced by hydrogen to react, purified and dried to obtain a diamino compound based on dianhydroiditol. The reaction equation is as follows:

[0070]

[0071] Among them, THF is tetrahydrofuran, TPP is triphenylphosphine, DIAD is diisopropyl azodicarboxylate, Ethylacetate is ethyl acetate, i-Pr2Net is diisopropylethylamine, and reflux is reflux reaction.

[0072] The preparation method of the PI film prepared by the diamino compound based on dianhydroiditol is synthesized by a two-step method (thermal imidization method), comprising the following steps:

[0073] Under protective gas, 3,4'-ODA (3,4'-diaminodiphenyl ether) and an amino compound based on dianhydroiditol are first added to N,N-dimethylacetamide for dissolution, and then dianhydride is added for reaction to obtain a polyamic acid intermediate solution;

[0074] The polyamic acid intermediate solution is cast on a glass substrate, and after removing the solvent, it is gradually heated in a tubular furnace under the protection of protective gas to form a PI film.

[0075] The synthetic route of PI is shown as follows:

[0076]

[0077] Since dianhydromannitol and dianhydrosorbitol have non-planar alicyclic structures, on the one hand, their introduction can maintain relatively stable thermal properties and better mechanical properties; on the other hand, their introduction can destroy the conjugated structure of the chain segments, weaken the interaction between the molecular chains, and at the same time increase the distance and free volume between the molecular chains, thereby reducing the polarizability of the molecules, ultimately achieving the purpose of enhancing light transmittance and reducing the dielectric constant.

[0078] The raw materials of dianhydrosorbitol and dianhydromannitol used in the present invention come from sucrose (fructose part) and cellulose (glucose) extracted from natural products, which can be prepared by hydrolysis, hydrogenation and dehydration reaction. In addition, the prepared amino compound based on the dianhydroidi alcohol structure can partially replace some pure organic amino compounds currently used, and has the advantages of green environmental protection, low cost, environmental friendliness, etc.

[0079] The present invention adopts the method of Mitsunobu reaction to synthesize an amino compound based on a bio-based dianhydrohexose alcohol structure. The Mitsunobu reaction has good stereoselectivity, that is, when a chiral alcohol participates in the reaction, a product with a hydroxyl configuration flipped is usually obtained. The Mitsunobu reaction can not only construct a chemical bond, but also has a wide range of applications, mild reaction conditions, simple operation, and high yield. It is widely used in the field of organic synthesis, especially in the synthesis of natural products and functional organic molecules. It plays an important role. By flipping dianhydrosorbitol and dianhydromannitol into a dianhydroiditool structure, costs can also be reduced to a certain extent, because iditool is extremely difficult to extract, resulting in an expensive price for dianhydroiditool. Dianhydrosorbitol is even cheaper than dianhydromannitol, and obtaining a dianhydroiditool structure by dianhydrosorbitol can further reduce costs.

[0080] The present invention is further illustrated by the following examples and comparative examples.

[0081] Example 1

[0082] A diamino compound based on dianhydroiditol, having the following structure:

[0083]

[0084] Ar 11 for

[0085]

[0086] One of

[0087] Ar 12 for

[0088]

[0089] One of them.

[0090] Example 2

[0091] The diamino compound based on dianhydroiditol in Example 1 can be prepared by dianhydromannitol, and the specific preparation method is as follows:

[0092] Synthesis of a para-dinitro compound containing dianhydroiditol, i.e. (3aR,3S,6aR,6S)-2,3,3a,5,6,6a-hexahydrofurano[2,3-d]furan-3,6-diylbis(4-nitrobenzoate): Under a nitrogen atmosphere, triphenylphosphine (11.54 g, 44 mmol), p-nitrobenzoic acid (6.77 g, 40 mmol), and dianhydromannitol (2.60 g, 20 mmol) were added to a single-necked flask, and 150 mL of anhydrous tetrahydrofuran was added, and the mixture was placed in an ice bath and stirred for 25 min; diisopropyl azodicarboxylate (9.32 g, 44 mmol) was added dropwise, and the mixture was placed in an ice bath to react for 1 h, and then the ice bath was removed and the mixture was reacted at room temperature for 6 h; finally, the mixture was heated to 65°C in an oil pan and refluxed for 42 h. The product was washed with saturated sodium chloride solution (50 mL × 3 times); dried with an appropriate amount of anhydrous sodium sulfate, purified by column chromatography using petroleum ether: ethyl acetate = 2:1, and then washed with ethanol to obtain 7.83 g of light yellow product (yield 88%). The structure is as follows:

[0093]

[0094] The NMR data are as follows:

[0095] 1 H NMR (400 MHz, CDCl 3 ): δ8.30(dd,J=8.7,1.8Hz,4H),8.25-8.18(m,4H),5.54(q,J=2.2Hz,2H),4.91(d,J=1.6Hz,2H),4.15(t,J=1.9Hz,4H).

[0096] 13 C NMR (101 MHz, CDCl 3 ): δ163.8,151.0,134.8,131.0,123.8,85.6,79.1,72.6.

[0097] MS:445,[M+H] + .

[0098] Synthesis of a para-diamino compound based on didetolide, i.e. (3aR, 3S, 6aR, 6S)-2,3,3a, 5,6,6a-hexahydrofurano[2,3-d]furan-3,6-diylbis(4-aminobenzoate): Under a nitrogen atmosphere, a para-dinitro compound containing didetolide was dissolved in ethyl acetate, 5% Pd / C catalyst was added, and nitrogen was replaced with hydrogen, and the reaction was stirred at room temperature and pressure for 4 days. Finally, a para-diamino compound based on didetolide was obtained. After purification by column chromatography with petroleum ether: ethyl acetate = 1:1, the product was dried and weighed to obtain 10.55g of product (yield 84%). The structure is as follows:

[0099]

[0100] The NMR data are as follows, see Figure 1 and Figure 2 :

[0101] 1 H NMR (400 MHz, DMSO-d 6 ): δ7.64(dd,J=8.6,1.8Hz,4H),6.55(dd,J=8.7,1.8Hz,4H),6.04(s,4H),5.25-5.18(m,2H),4.73(s,2H),4.02-3.89(m,4H).

[0102] 13 C NMR (101 MHz, DMSO-d 6 ): δ165.0,153.9,131.4,115.1,112.6,85.1,77.0,71.9.

[0103] MS:385,[M+H] + .

[0104] Based on the above operation steps, the p-nitrobenzoic acid in the above preparation process is replaced with m-nitrobenzoic acid to obtain a meta-dinitro compound (yield 92%), namely (3aR, 3S, 6aR, 6S)-2,3,3a,5,6,6a-hexahydrofurano[2,3-d]furan-3,6-diylbis(3-nitrobenzoate), the structure of which is as follows:

[0105]

[0106] The NMR data are as follows:

[0107] 1 H NMR (400 MHz, CDCl 3): δ8.87(d,J=2.6Hz,2H),8.48(d,J=8.3Hz,2H),8.41(d,J=7.8Hz,2H),7.75-7 .68(m,2H),5.58(d,J=2.9Hz,2H),4.97(d,J=1.9Hz,2H),4.18(d,J=2.2Hz,4H).

[0108] 13 C NMR (101 MHz, CDCl 3 ): δ163.6,148.4,135.6,131.2,130.0,128.1,124.8,85.6,79.1,72.7.

[0109] MS:445,[M+H] + .

[0110] Further, a meta-diamino compound (yield 82%) was obtained, the structure of which is as follows:

[0111]

[0112] The NMR data are as follows:

[0113] 1 H NMR (400 MHz, DMSO-d 6 ): δ7.21-7.05(m,6H),6.84-6.76(m,2H),5.40(s,4H),5.31(d,J=3.2Hz,2H),4.76(s,2H),4.06-3.95(m,4H).

[0114] 13 C NMR (101 MHz, DMSO-d 6 ): δ165.5,149.0,129.7,129.1,118.7,116.6,114.2,84.9,77.6,71.8.

[0115] MS:385,[M+H] + .

[0116] Example 3

[0117] The diamino compound based on dianhydroiditol in Example 1 can be prepared by dianhydrosorbitol, and the specific preparation method is as follows:

[0118] Synthesis of the para-mononitro compound containing dianhydroiditol, i.e. (3aR,3S,6aR,6S)-6-hydroxy-2,3,3a,5,6,6a-hexahydrofuro[2,3-d]furan-3-yl (4-nitrobenzoate): Diisopropyl azodicarboxylate (1.213 g, 6 mmol) was added to a solution of triphenylphosphine (1.573 g, 6 mmol) in tetrahydrofuran (30 mL) under nitrogen atmosphere at 0-5°C (ice bath) for 2 min. The resulting light yellow suspension was stirred at this temperature for 15 min. A solution of p-nitrobenzoic acid (0.670 g, 4 mmol) in tetrahydrofuran (15 mL) was added dropwise over 3 min. After 2 min, the cooling bath was removed to allow the reaction mixture to warm to room temperature over 15 min. Slowly add a solution of dehydrated sorbitol (0.701 g, 4.8 mmol) in tetrahydrofuran (15 mL), and then add diisopropylethylamine (0.775 g, 1.05 mL, 6 mmol). After stirring the resulting light yellow solution at room temperature for 6 h, react at 65 ° C for 42 h. Wash with saturated sodium chloride solution 3 times; add an appropriate amount of anhydrous sodium sulfate to dry, and purify by column chromatography with petroleum ether: ethyl acetate = 1:1, and then wash with ethanol to finally obtain a para-mononitro compound containing a dehydrated sorbitol structure (yield 65%). The structure is as follows:

[0119]

[0120] The NMR data are as follows:

[0121] 1 H NMR (400 MHz, CDCl 3 ): δ8.30(dd,J=8.8,2.1Hz,2H),8.23-8.18(m,2H),5.46(d,J=3.0Hz,1H),4.86- 4.83(m,1H),4.69-4.65(m,1H),4.42(s,1H),4.06(s,2H),3.93(d,J=2.5Hz,2H).

[0122] 13 C NMR (101 MHz, CDCl 3 ): δ163.8,150.9,134.9,131.0,123.8,88.0,85.1,79.2,76.1,75.0,72.4.

[0123] MS:296[M+H] + .

[0124] Based on the above operation steps, by replacing p-nitrobenzoic acid with m-nitrobenzoic acid, a meta-mononitro compound containing a dianhydroiditol structure can be obtained, and the specific structure is:

[0125]

[0126] The NMR data are as follows:

[0127] 1 H NMR (400 MHz, CDCl 3 ): δ8.84(d,J=2.5Hz,1H),8.45(d,J=8.3Hz,1H),8.37(d,J=7.8Hz,1H),7.68(td,J=8.0,1.8Hz,1H),5.47(s,1H ),4.88-4.85(m,1H),4.70(t,J=2.7Hz,1H),4.43(d,J=4.3Hz,1H),4.07(d,J=2.1Hz,2H),3.94(d,J=2.4Hz,2H).

[0128] 13 C NMR (101 MHz, CDCl 3 ): δ163.7,148.4,135.5,131.4,129.9,128.0,124.8,88.0,85.1,79.2,76.1,75.0,72.4.

[0129] MS:296,[M+H] + .

[0130] The para-mononitro compound containing the didehydroidol structure and the meta-mononitro compound containing the didehydroidol structure are dissolved in chloroform, and triethylamine is added, and the mixture is stirred in an ice bath, and then p-nitrobenzoyl chloride is added, and the mixture is stirred in an ice bath for about 1 hour, and then the mixture is turned to 65°C and reacted for 45 hours. Finally, an asymmetric dinitro compound is obtained, and the structure is as follows:

[0131]

[0132] The NMR data are as follows:

[0133] 1 H NMR (400 MHz, CDCl 3): δ8.83(d,J=2.4Hz,1H),8.45(d,J=8.3Hz,1H),8.37(d,J=7.9Hz,1H),8.30(dd,J=9.0,1.9Hz,2H),8.25-8.19(m,2H),7.72 -7.65(m,1H),5.54(d,J=3.0Hz,2H),4.93(s,2H),4.15(s,4H).

[0134] 13 C NMR (101 MHz, CDCl 3 ): δ163.8,163.6,151.0,148.5,135.6,134.8,131.2,131.1,130.00,128.1,124.8,123.8,85.6,79.10,79.06,72.71,72.67,70.2.

[0135] MS:445,[M+H] + .

[0136] Synthesis of the meta-para-diamino compound based on dianhydroiditol, i.e. (3aR, 3S, 6aR, 6S)-2,3,3a,5,6,6a-hexahydrofurano[2,3-d]furan-3-yl-(3-aminobenzoate),6-yl-(4-aminobenzoate): Referring to the synthesis steps of the diamino compound based on dianhydroiditol in Example 1, a para-mononitro compound containing a dianhydroiditol structure and a meta-mononitro compound containing a dianhydroiditol structure are added simultaneously during the synthesis, and then reduced to obtain an asymmetric diamino compound having the following structure:

[0137]

[0138] The NMR data are as follows:

[0139] 1 H NMR (400MHz, DMSO-d6): δ7.68-7.57(m,2H),7.21-7.07(m,3H),6.80(d,J=7.4Hz,1H),6.56(dd,J=8.7,2.3Hz, 2H),6.04(s,2H),5.39(s,2H),5.27(d,J=24.2Hz,2H),4.79-4.70(m,2H),3.99(dq,J=21.5,10.7,9.3Hz,4H).

[0140] 13C NMR (101MHz, DMSO-d6): δ165.9,165.5,154.3,149.5,131.9,130.2,129.5,119. 1,117.1,115.5,114.6,113.1,85.6,85.3,78.1,77.4,72.4,72.2.MS:385,[M+H] + .

[0141] Similarly, the following structure can be obtained:

[0142]

[0143] Based on the above synthesis steps, if based only on the para-mononitro compound containing the structure of didehydroiditool, a para-diamino compound based on didehydroiditool can be obtained, and if based only on the meta-mononitro compound containing the structure of didehydroiditool, a meta-diamino compound based on didehydroiditool can be obtained, which will not be specifically expanded here, and the structural formula is as follows:

[0144]

[0145] Example 4

[0146] The PI film prepared according to the diamino compound based on dianhydroiditol in Example 1 has the following structure:

[0147]

[0148] x+y=n, the molar percentage of x and y is x:y=5:95 or 10:90 or 15:85 or 20:80 or 25:75 or 30:70;

[0149] Ar 2 for

[0150]

[0151] One of them.

[0152] Example 5

[0153] The PI film prepared from the diamino compound based on dianhydroiditol in Example 4 is prepared by the following method:

[0154] Preparation of polyamic acid intermediate solution: Under nitrogen atmosphere, 3,4'-ODA (0.476g, 2.37mmol) and a para-diamino compound containing a di-dehydroidol structure (48mg, 0.125mmol) were first added to a 50mL single-necked flask, 6mL of N,N-dimethylacetamide was added and stirred in an oil pan by magnetic force until dissolved, then placed in an ice bath and stirred for 25min. BPDA dianhydride (0.736g, 2.5mmol) was added, the ice bath was removed after 20min, and the solution was stirred at room temperature for 24h to obtain a polyamic acid intermediate solution with a solid content of 17%.

[0155] Preparation of film: 2 mL of polyamic acid intermediate solution was cast on a clean glass substrate, the solvent was first removed on a common heating table, and then the imidization process was completed in a tubular furnace under nitrogen protection at 150°C, 200°C, 250°C, and 300°C for 1 h each to obtain a PI film named p-BPDA-95 with the following structure:

[0156]

[0157] The doping ratio of 3,4'-ODA and the para-diamino compound containing the di-dehydroidi alcohol structure was changed to 85:15, that is, 3,4'-ODA (0.426 g, 2.125 mmol) and the para-diamino compound containing the di-dehydroidi alcohol structure (0.144 g, 0.375 mmol) were added to obtain a polyamic acid intermediate solution with a solid content of 17%. The above synthesis steps were repeated to obtain a PI film named p-BPDA-85.

[0158] The doping ratio of 3,4'-ODA and the para-diamino compound containing the di-dehydroidol structure was changed to 75:25, that is, 3,4'-ODA (0.375 g, 1.875 mmol) and the para-diamino compound containing the di-dehydroidol structure (0.240 g, 0.625 mmol) were added to obtain a polyamic acid intermediate solution with a solid content of 15%. The above synthesis steps were repeated to obtain a PI film named p-BPDA-75.

[0159] Similarly, the para-diamino compound containing the dianhydroiditol structure is replaced with the meta-diamino compound containing the dianhydroiditol structure, and the above synthetic steps are repeated to obtain PI containing the meta-diamino group, which are named m-BPDA-95, m-BPDA-85, and m-BPDA-80, respectively, and have the following structures:

[0160]

[0161] Example 6

[0162] The PI film prepared from the diamino compound based on dianhydroiditol in Example 4 is prepared by the following method:

[0163] Under nitrogen atmosphere, 3,4'-ODA (0.380g, 1.9mmol) and a para-diamino compound containing a di-dehydrated idiol structure (38mg, 0.1mmol) were first added to a 50mL single-necked flask, 6.5mL N,N-dimethylacetamide was added and stirred in an oil pan by magnetic force until dissolved, placed in an ice bath, and stirred for 25min. 6FDA dianhydride (0.888g, 2mmol) was added, the ice bath was removed after 20min, and stirred at room temperature for 24h to obtain a polyamic acid intermediate solution with a solid content of 17%. The preparation steps of the film in Example 5 were repeated to obtain a PI film named p-6FDA-95, with the following structure:

[0164]

[0165] The doping ratio of 3,4'-ODA and the para-diamino compound containing the di-dehydroidi alcohol structure was changed to 90:10, that is, 3,4'-ODA (0.360 g, 1.8 mmol) and the para-diamino compound containing the di-dehydroidi alcohol structure (77 mg, 0.2 mmol) were added to obtain a polyamic acid intermediate solution with a solid content of 17%. The above synthesis steps were repeated to obtain a PI film named p-6FDA-90.

[0166] The doping ratio of 3,4'-ODA and the para-diamino compound containing the di-dehydroidi alcohol structure was changed to 85:15, that is, 3,4'-ODA (0.340 g, 1.7 mmol) and the para-diamino compound containing the di-dehydroidi alcohol structure (0.115 g, 0.3 mmol) were added to obtain a polyamic acid intermediate solution with a solid content of 17%. The above synthesis steps were repeated to obtain a PI film named p-6FDA-85.

[0167] Similarly, the para-diamino compound containing the dianhydroiditol structure is replaced with the meta-diamino compound containing the dianhydroiditol structure, and the above synthesis steps are repeated to obtain PI containing the meta-diamino group, which are named m-6FDA-95, m-6FDA-90, and m-6FDA-85, respectively, and have the following structures:

[0168]

[0169] Similarly, based on the meta-diamino compound of dianhydroiditol in Example 3, namely (3aR, 3S, 6aR, 6S)-2,3,3a,5,6,6a-hexahydrofurano[2,3-d]furan-3-yl-(3-aminobenzoate),6-yl-(4-aminobenzoate), the above film preparation steps were repeated to obtain a PI film named pm-6FDA-90, with the following structure:

[0170]

[0171] Example 7

[0172] The PI film prepared from the diamino compound based on dianhydroiditol in Example 4 is prepared by the following method:

[0173] Under nitrogen atmosphere, 3,4'-ODA (0.180g, 0.9mmol) and a para-diamino compound containing a di-dehydrated idiol structure (38mg, 0.1mmol) were first added to a 50mL single-necked flask, 3mL N,N-dimethylacetamide was added and stirred in an oil pan by magnetic force until dissolved, placed in an ice bath, and stirred for 25min. ODPA dianhydride (0.313g, 1mmol) was added, the ice bath was removed after 20min, and stirred at room temperature for 24h to obtain a polyamic acid intermediate solution with a solid content of 15%. The preparation steps of the film in Example 5 were repeated to obtain a PI film named p-ODPA-90, with the following structure:

[0174]

[0175] The doping ratio of 3,4'-ODA and the para-diamino compound containing the di-dehydroidi alcohol structure was changed to 80:20, that is, 3,4'-ODA (0.160 g, 0.8 mmol) and the para-diamino compound containing the di-dehydroidi alcohol structure (77 mg, 0.2 mmol) were added to obtain a polyamic acid intermediate solution with a solid content of 15%. The above synthesis steps were repeated to obtain a PI film named p-ODPA-80.

[0176] The doping ratio of 3,4'-ODA and the para-diamino compound containing the di-dehydroidi alcohol structure was changed to 70:30, that is, 3,4'-ODA (0.140 g, 0.7 mmol) and the amino monomer containing the di-dehydroidi alcohol structure (0.115 g, 0.3 mmol) were added to obtain a polyamic acid intermediate solution with a solid content of 15%. The above synthesis steps were repeated to obtain a PI film named p-ODPA-70.

[0177] Similarly, the para-diamino compound containing the dianhydroiditol structure is replaced with the meta-diamino compound containing the dianhydroiditol structure, and the above synthesis steps are repeated to obtain PI containing the meta-diamino group, which are named m-ODPA-90, m-ODPA-80, and m-ODPA-70, respectively, and have the following structures:

[0178]

[0179] Example 8

[0180] The PI film prepared from the diamino compound based on dianhydroiditol in Example 4 is prepared by the following method:

[0181] Under nitrogen atmosphere, 3,4'-ODA (0.180g, 0.9mmol) and a para-diamino compound containing a di-dehydrated idiol structure (38mg, 0.1mmol) were first added to a 50mL single-necked flask, 3.1mL N,N-dimethylacetamide was added and stirred in an oil pan by magnetic force until dissolved, placed in an ice bath, and stirred for 25min. BTDA dianhydride (0.325g, 1mmol) was added, the ice bath was removed after 20min, and stirred at room temperature for 24h to obtain a polyamic acid intermediate solution with a solid content of 15%. The preparation steps of the film in Example 5 were repeated to obtain a PI film named p-BTDA-90, with the following structure:

[0182]

[0183] The doping ratio of 3,4'-ODA and the para-diamino compound containing the di-dehydroidol structure was changed to 80:20, that is, 3,4'-ODA (0.160 g, 0.8 mmol) and the para-diamino compound containing the di-dehydroidol structure (77 mg, 0.2 mmol) were added to obtain a polyamic acid intermediate solution with a solid content of 15%. The above synthesis steps were repeated to obtain a PI film named p-BTDA-80.

[0184] The doping ratio of 3,4'-ODA and the para-diamino compound containing the di-dehydroidi alcohol structure was changed to 70:30, that is, 3,4'-ODA (0.140 g, 0.7 mmol) and the para-diamino compound containing the di-dehydroidi alcohol structure (0.115 g, 0.3 mmol) were added to obtain a polyamic acid intermediate solution with a solid content of 15%. The above synthesis steps were repeated to obtain a PI film named p-BTDA-70.

[0185] Similarly, the para-diamino compound containing the dianhydroiditol structure is replaced with the meta-diamino compound containing the dianhydroiditol structure, and the above synthesis steps are repeated to obtain PI containing the meta-diamino group, which are named m-BTDA-90, m-BTDA-80, and m-BTDA-70, respectively, and have the following structures:

[0186]

[0187] Performance Description

[0188] Figure 3 This is the infrared spectrum of the PI film (p-6FDA-90) of Example 6. The wavenumbers of 1780-1720 are the characteristic absorption peaks of C=O stretching vibration, the wavenumbers of 1604, 1500, and 1420 are the characteristic absorption peaks of benzene ring CC bond stretching vibration, and the wavenumbers of 1374 and 719 are the stretching and bending vibration absorption of CNC bond. It can be seen that the polyimide is completely imidized, and the stretching vibration absorption peak of CF bond can also be found at about 1247 wavenumbers.

[0189] Figure 4 This is a TGA data chart of the PI film (p-6FDA-90) of Example 6. The 5% thermal decomposition temperature is 464°C, and the carbon residue rate is 52.1%.

[0190] Figure 5 This is a DSC data chart of the PI film (p-6FDA-90) of Example 6. The glass transition temperature is 270°C.

[0191] Figure 6 This is the UV-Vis absorption spectrum of the PI film (p-6FDA-90) of Example 6. The ultraviolet cutoff wavelength is 167 nm, and the light transmittance at 560 nm is 64.1%.

[0192] Figure 7 This is a graph of the dielectric properties of the PI film (p-6FDA-90) of Example 6. The dielectric constant at 25°C and 1 MHz is 2.6, and the dielectric loss is 0.047.

[0193] The relative dielectric constant of Kapton polyimide film at 23°C, 50% humidity, 1kHz is 3.4 (25-50μm) and 3.5 (75-125μm), and the transmittance within 200-500nm is almost 0. Compared with traditional polyimide film, the present invention effectively reduces the dielectric constant and light transmittance.

[0194] The embodiments described above are only used to illustrate the technical solutions of the present application, rather than to limit them. Although the present application has been described in detail with reference to the aforementioned embodiments, a person skilled in the art should understand that the technical solutions described in the aforementioned embodiments may still be modified, or some of the technical features may be replaced by equivalents. Such modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the embodiments of the present application, and should all be included in the protection scope of the present application.

Claims

1. A diamino compound based on dianhydroiditol, characterized in that The structure is as follows: Ar 11 for One of Ar 12 for One of them.

2. The diamino compound based on dianhydroiditol according to claim 1, characterized in that The structure is as follows: 。 3. The method for preparing a diamino compound based on dianhydroiditol according to claim 1, characterized in that: The following steps are involved: Under protective gas, triphenylphosphine, p-nitrobenzoic acid or m-nitrobenzoic acid, and dianhydromannitol are added into tetrahydrofuran to dissolve, and then diisopropyl azodicarboxylate is added to react, purified and dried to obtain a dinitro compound containing dianhydromannitol; Under protective gas, a dinitro compound containing dianhydroiditol is dissolved in ethyl acetate, the protective gas is replaced by hydrogen, a catalyst is added to carry out a reduction reaction, and the reaction is purified and dried to obtain a diamino compound based on dianhydroiditol.

4. The method for preparing a diamino compound based on dianhydroiditol according to claim 3, characterized in that: Under a nitrogen atmosphere, triphenylphosphine, p-nitrobenzoic acid or m-nitrobenzoic acid, and dianhydromannitol are added to tetrahydrofuran in an ice bath to dissolve, and then diisopropyl azodicarboxylate is added dropwise, and the reaction is carried out in an ice bath for 0.5-1.5 hours, and then the ice bath is removed, and the reaction is carried out at room temperature for 5 hours to 7 hours, and finally the temperature is raised to 60° C. to 70° C. and refluxed for 40 hours to 45 hours, and then purified and dried to obtain a dinitro compound containing dianhydromannitol; wherein the molar ratio of triphenylphosphine: p-nitrobenzoic acid or m-nitrobenzoic acid: dianhydromannitol: diisopropyl azodicarboxylate is 42-46:38-42:18-22:42-46; Under nitrogen gas, a dinitro compound containing dehydrated idiol is dissolved in ethyl acetate, and then the protective gas is replaced by hydrogen and a catalyst is added for reduction reaction, which is purified and dried to obtain a diamino compound based on dehydrated idiol. The catalyst is a Pd / C catalyst, and the amount of Pd / C catalyst is 5-10‰wt% of the dinitro compound containing benzocyclobutene.

5. The method for preparing a diamino compound based on dianhydroiditol according to claim 1, characterized in that: The following steps are involved: Under protective gas, diisopropyl azodicarboxylate is added to a tetrahydrofuran solution of triphenylphosphine to dissolve, p-nitrobenzoic acid or m-nitrobenzoic acid is added dropwise, then dianhydrosorbitol is added, and finally diisopropylethylamine is added to react, purified and dried to obtain a mononitro compound containing dianhydroiditol; The mononitro compound containing dianhydroiditol is dissolved in chloroform, and triethylamine is added, and then p-nitrobenzoyl chloride is added to react, and the reaction is performed by purification and drying to obtain the dinitro compound containing dianhydroiditol; Under protective gas, a dinitro compound containing dianhydroiditol is dissolved in ethyl acetate, the protective gas is replaced by hydrogen, a catalyst is added to carry out a reduction reaction, and the reaction is purified and dried to obtain a diamino compound based on dianhydroiditol.

6. The method for preparing a diamino compound based on dianhydroiditol according to claim 5, characterized in that: Under a nitrogen atmosphere, diisopropyl azodicarboxylate is added to a tetrahydrofuran solution of triphenylphosphine under an ice bath to dissolve, p-nitrobenzoic acid or m-nitrobenzoic acid is added dropwise within 2-4 minutes, and dianhydrosorbitol is slowly added after 1-3 minutes, and the ice bath is removed to allow the reaction mixture to warm to room temperature, and finally diisopropylethylamine is added and stirred at room temperature for 5-8 hours, and then heated to 60-70°C and refluxed for reaction for 40-45 hours, purified and dried to obtain a mononitro compound containing dianhydroiditol; wherein the molar ratio of diisopropyl azodicarboxylate: triphenylphosphine: p-nitrobenzoic acid or m-nitrobenzoic acid: dianhydrosorbitol: diisopropylethylamine is 5-7: 5-7: 4-5: 4-6: 5-7; The mononitro compound containing dianhydroiditol is dissolved in chloroform, and triethylamine is added, and the mixture is stirred in an ice bath, and then p-nitrobenzoyl chloride is added, and the mixture is stirred in an ice bath for about 1 hour, and then the mixture is reacted at 65° C. for 45 hours, and then purified and dried to obtain the dinitro compound containing dianhydroiditol; Under nitrogen gas, a dinitro compound containing dehydrated idiol is dissolved in ethyl acetate, and then the protective gas is replaced by hydrogen and a catalyst is added for reduction reaction, which is purified and dried to obtain a diamino compound based on dehydrated idiol. The catalyst is a Pd / C catalyst, and the amount of Pd / C catalyst is 5-10‰wt% of the dinitro compound containing benzocyclobutene.

7. A PI film prepared from a diamino compound based on dianhydroiditol, characterized in that: The structure is as follows: x+y=n, the molar percentage of x and y is x:y=5:95 or 10:90 or 15:85 or 20:80 or 25:75 or 30:70; Ar 2 for One of them.

8. The method for preparing a PI film prepared from a diamino compound based on dianhydroiditol according to claim 7, characterized in that: The following steps are involved: Under protective gas, 3,4'-ODA and an amino compound based on dianhydroiditol are first added to N,N-dimethylacetamide to dissolve, and then dianhydride is added to react to obtain a polyamic acid intermediate solution; The polyamic acid intermediate solution is cast on a glass substrate, and after removing the solvent, it is gradually heated in a tubular furnace under the protection of protective gas to form a PI film.

9. The method for preparing a PI film prepared from a diamino compound based on dianhydroiditol according to claim 7, characterized in that: The dianhydrides include BPDA dianhydride, 6FDA dianhydride, ODPA dianhydride and BTDA dianhydride; The molar ratio of the dianhydroiditol-based amino compound: 3,4'-ODA: BPDA dianhydride is 0.125:2.375:2.5 or 0.375:2.125:2.5 or 0.625:1.875:2.5; The molar ratio of the dianhydroiditol-based amino compound: 3,4'-ODA: 6FDA dianhydride is 0.1:1.9:2 or 0.2:1.8:2 or 0.3:1.7:2; The molar ratio of the dianhydroiditol-based amino compound: 3,4'-ODA: ODPA dianhydride is 0.1:0.9:1 or 0.2:0.8:1 or 0.3:0.7:1; The molar ratio of the dianhydroiditol-based amino compound: 3,4'-ODA: BTDA dianhydride is 0.1:0.9:1 or 0.2:0.8:1 or 0.3:0.7:

1.

10. The method for preparing a PI film based on a diamino compound of dianhydroiditol according to claim 7, characterized in that: Under a nitrogen atmosphere, 3,4'-ODA and an amino compound based on dianhydroiditol are first added to N,N-dimethylacetamide for dissolution, and then the dianhydride is added after reacting in an ice bath at 0-5°C for 10-40 minutes, and the ice bath is continued for 10-40 minutes, then the ice bath is removed, and the reaction is carried out at room temperature for 22-26 hours to obtain a polyamic acid intermediate solution; The polyamic acid intermediate solution was cast on a glass substrate, and after removing the solvent, it was placed in a tubular furnace under nitrogen protection and heated at 150°C, 200°C, 250°C, and 300°C for 1 hour each to form a PI film.

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