Diamine monomer, polyimide and preparation method and application thereof

Abstract

The invention provides a diamine monomer prepared based on magnolol. The invention also provides a preparation method and application of the diamine monomer. Furthermore, the invention also provides polyimide prepared from the diamine monomer, and a preparation method and application of the polyimide. Compared with a diamine monomer derived from fossil fuel, the diamine monomer provided by the invention has lower carbon footprint, and is favorable for constructing a more sustainable chemical industry. Furthermore, polyimide obtained by polymerizing the diamine monomer, an aromatic diamine monomer and an aromatic dianhydride monomer has good solubility in a conventional solvent, can meet the process requirements of solution processing, contains an allyl group, has photo-crosslinking performance, and can be used for preparing a polyimide film. The polyimide can be applied to the fields of optical data storage equipment, photoresist, photosensitive optical materials and the like, and the application range of polyimide is expanded.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer compounds, and in particular to a diamine monomer, a polyimide, and a preparation method and application thereof. Background Art

[0002] Polyimide (abbreviated as PI) refers to a class of polymers containing an imide ring (-CO-NR-CO-) in the main chain. As a special engineering material, it has been widely used in aviation, aerospace, microelectronics, nano, liquid crystal, separation membrane, laser and other fields.

[0003] Polyimide can be obtained by polymerizing dianhydride monomers and diamine monomers. Commonly used diamine monomers include 4,4'-diaminodiphenyl ether and p-phenylenediamine. These diamine monomers are mostly made from fossil fuels and are not environmentally friendly. In addition, polyimide made from these traditional diamine monomers cannot be used in the fields of optical data storage devices, photoresists, and photosensitive optical materials, which limits its application range. Summary of the invention

[0004] Based on this, the object of the present invention is to provide a diamine monomer, a polyimide and a preparation method and application thereof.

[0005] In a first aspect, the present invention provides a diamine monomer, wherein the diamine monomer has the general structural formula:

[0006]

[0007] Wherein, R1 is selected from any one of an ester group or an ether bond; Ar1 ​​is selected from any one of the following structures:

[0008]

[0009] wherein R1, R2, R3, and R4 are the same or different from each other, and are independently selected from hydrogen, fluorine, methyl, ethyl, trifluoromethyl, tert-butyl, oxymethyl, or oxybutyl;

[0010] Ar2 is selected from any one of the following structures:

[0011]

[0012] In the formula, R5, R6, R7, and R8 are the same as each other or different, and are independently selected from hydrogen, fluorine, methyl, ethyl, trifluoromethyl, tert-butyl, oxymethyl, or oxybutyl.

[0013] In a second aspect, the present invention provides a method for preparing the aforementioned diamine monomer, comprising the following steps:

[0014] (1) reacting magnolol with bromobenzoyl chloride containing R1, R2, R3 and R4 in an aprotic solvent and alkaline environment at low temperature to obtain a brominated compound containing an allyl group;

[0015] (2) The brominated compound is reacted with aminophenylboronic acid or phenylboronic acid ester containing R5, R6, R7 and R8 through Suzuki reaction to obtain the diamine monomer.

[0016] In a third aspect, the present invention provides a method for preparing the aforementioned diamine monomer, comprising the following steps:

[0017] (1) reacting magnolol with bromonitrobenzene containing R1, R2, R3 and R4 in a non-protonic high-polar solvent and an alkaline environment to obtain a dinitro compound containing an allyl group;

[0018] (2) The dinitro compound is reacted with aminophenylboronic acid or phenylboronic acid ester containing R5, R6, R7 and R8 through Suzuki-Miyaura coupling reaction to obtain the diamine monomer.

[0019] In a fourth aspect, the present invention provides use of the aforementioned diamine monomer in the preparation of polyimide, polyamideimide or polyamide.

[0020] In a fifth aspect, the present invention provides a polyimide, wherein the general structural formula of the polyimide is:

[0021]

[0022] In the formula, n and m represent the degree of polymerization, n is an integer of 1 to 150, m is an integer of 1 to 150, Ar is the aromatic unit fragment in the diamine monomer described in claim 1, X is a tetravalent aromatic hydrocarbon group, and Ar1 is the residue of the diamine.

[0023] In one embodiment, X is preferably any one of the following:

[0024]

[0025] In one embodiment, Ar1 is preferably any one of the following:

[0026]

[0027] In a sixth aspect, the present invention provides a method for preparing the aforementioned polyimide, comprising mixing the aforementioned diamine monomer, aromatic diamine monomer, aromatic dianhydride monomer and a third organic solvent, and performing copolymerization to obtain polyamic acid; the aromatic diamine monomer is p-phenylenediamine, m-phenylenediamine or flexible aromatic diamine;

[0028] The polyamic acid, a dehydrating agent and a third catalyst are mixed to carry out a chemical imidization reaction to obtain polyimide.

[0029] In one embodiment, the flexible aromatic diamine is selected from 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 1,3-bis(4'-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 2,2'-bis(trifluoromethyl)-4,4'-diaminophenyl ether, 2,2'-bis(trifluoromethyl)diaminobiphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diamino-3,3'-dimethylbiphenyl, 4,4'-diaminodiphenyl sulfone, 4,4'-bis(3-aminophenoxy)benzophenone, 3,3'-diaminodiphenyl sulfone, 2 2'-Diaminodiphenyl sulfide, 4,4-diaminodiphenyl sulfide, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 4,4-diamino-3,3-difluorobiphenyl, 9,9-bis(4-aminophenyl)fluorene, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 3,3'-diaminodiphenylmethane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 1,2-bis(4-aminophenoxy)ethane, 4,4'-bis(3-aminophenoxy)diphenyl sulfone.

[0030] In a seventh aspect, the present invention provides a use of the aforementioned polyimide in the preparation of a photosensitive polyimide photoresist.

[0031] Compared with the prior art, the present invention utilizes the inherent biphenyl-bisphenol structure of magnolol and synthesizes a diamine monomer using magnolol as a raw material. Compared with the diamine monomer derived from fossil fuels, the diamine monomer of the present invention has a lower carbon footprint, which helps to build a more sustainable chemical industry. Furthermore, the polyimide prepared by the diamine monomer, aromatic diamine monomer, and aromatic dianhydride monomer of the present invention has good solubility in conventional solvents and can meet the process requirements of solution processing. The polyimide of the present invention contains an allyl group and has the performance of photocrosslinking, and can be applied in the fields of optical data storage devices, photoresists, and photosensitive optical materials, thereby expanding the application range of polyimide. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] Figure 1 This is the hydrogen NMR spectrum of the diamine monomer prepared in Example 1 of the present invention;

[0033] Figure 2 This is the infrared spectrum of the polyimide prepared in Example 1 of the present invention. DETAILED DESCRIPTION

[0034] In order to further understand the present invention, preferred embodiments of the present invention are described below in conjunction with examples. However, it should be understood that these descriptions are only for further illustrating the features and advantages of the present invention, rather than limiting the claims of the present invention.

[0035] Magnolol is a natural and safe product extracted from the bark of Magnolia officinalis and is widely recognized as an excellent functional bio-based compound. The present invention utilizes the inherent biphenyl-bisphenol structure of magnolia officinalis and synthesizes a diamine monomer using magnolia officinalis as a raw material. Compared with the diamine monomer derived from fossil fuels, the diamine monomer of the present invention has a lower carbon footprint and helps to build a more sustainable chemical industry. Furthermore, the polyimide prepared by the present invention using the diamine monomer, aromatic diamine monomer, and aromatic dianhydride monomer has good solubility in conventional solvents and can meet the process requirements of solution processing. The polyimide of the present invention contains an allyl group and has the property of photo-crosslinking, and can be used in the fields of optical data storage devices, photoresists, and photosensitive optical materials, thereby expanding the application range of polyimide.

[0036] Specifically, the embodiment of the present invention discloses a diamine monomer, the general molecular structure of which is:

[0037]

[0038] Wherein, R1 is selected from any one of an ester group or an ether bond; Ar1 ​​is selected from any one of the following structures:

[0039]

[0040] wherein R1, R2, R3, and R4 are the same or different from each other, and are independently selected from hydrogen, fluorine, methyl, ethyl, trifluoromethyl, tert-butyl, oxymethyl, or oxybutyl;

[0041] Ar2 is selected from any one of the following structures:

[0042]

[0043] In the formula, R5, R6, R7, and R8 are the same as each other or different, and are independently selected from hydrogen, fluorine, methyl, ethyl, trifluoromethyl, tert-butyl, oxymethyl, or oxybutyl.

[0044] The present invention also provides a method for preparing a diamine monomer, comprising the following steps:

[0045] (1) reacting magnolol with bromobenzoyl chloride containing R1, R2, R3 and R4 in an aprotic solvent and alkaline environment at low temperature to obtain a brominated compound containing an allyl group;

[0046] (2) The brominated compound is reacted with aminophenylboronic acid or phenylboronic acid ester containing R5, R6, R7 and R8 through Suzuki reaction to obtain the diamine monomer.

[0047] Preferably, in step (1), the aprotic solvent is N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, sulfolane, 1,4-dioxane, acetone, acetonitrile, toluene, chloroform, dichloromethane or tetrahydrofuran. More preferably, in step (1), the aprotic solvent is dichloromethane or tetrahydrofuran.

[0048] Preferably, in step (1), the alkaline environment is triethylamine or pyridine environment.

[0049] Preferably, in step (1), the low temperature reaction temperature is -15-10°C, more preferably -5-5°C.

[0050] In one embodiment, the present invention also provides a method for preparing a diamine monomer, comprising the following steps:

[0051] (1) reacting magnolol with bromonitrobenzene containing R1, R2, R3 and R4 in a non-protonic high-polar solvent and an alkaline environment to obtain a dinitro compound containing an allyl group;

[0052] (2) The dinitro compound is reacted with aminophenylboronic acid or phenylboronic acid ester containing R5, R6, R7 and R8 through Suzuki-Miyaura coupling reaction to obtain the diamine monomer.

[0053] Preferably, in step (1), the aprotic high polar solvent is N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, or sulfolane.

[0054] Preferably, in step (1), the alkaline environment is a potassium carbonate or sodium carbonate environment.

[0055] Furthermore, the present invention also provides a polyimide, the general molecular structure of which is:

[0056]

[0057] In the formula, n and m represent the degree of polymerization, n is an integer of 1 to 150, m is an integer of 1 to 150, Ar is the aromatic unit fragment in the diamine monomer according to claim 1, X is a tetravalent aromatic hydrocarbon group, and Ar1 is the residue of the diamine. Among them, the structure of X is preferably any one of the following:

[0058]

[0059] Ar1 is preferably any of the following:

[0060]

[0061] The present invention also provides a method for preparing polyimide, comprising the following steps:

[0062] The diamine monomer, aromatic diamine monomer, aromatic dianhydride monomer and a third organic solvent according to claim 1 are mixed and copolymerized to obtain polyamic acid; the aromatic diamine monomer is p-phenylenediamine, m-phenylenediamine or flexible aromatic diamine;

[0063] The polyamic acid, a dehydrating agent and a third catalyst are mixed to carry out a chemical imidization reaction to obtain polyimide.

[0064] Among them, the flexible aromatic diamine refers to an aromatic diamine containing a flexible group. Preferably, the flexible aromatic diamine is selected from 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 1,3-bis(4'-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 2,2'-bis(trifluoromethyl)-4,4'-diaminophenyl ether, 2,2'-bis(trifluoromethyl)diaminobiphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diamino-3,3'-dimethylbiphenyl, 4,4'-diaminodiphenyl sulfone, 4,4'-bis(3-aminophenoxy)benzophenone, 3,3'-diaminodiphenyl sulfone, 2 2'-Diaminodiphenyl sulfide, 4,4-diaminodiphenyl sulfide, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 4,4-diamino-3,3-difluorobiphenyl, 9,9-bis(4-aminophenyl)fluorene, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 3,3'-diaminodiphenylmethane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 1,2-bis(4-aminophenoxy)ethane, 4,4'-bis(3-aminophenoxy)diphenyl sulfone.

[0065] Preferably, the aromatic dianhydride monomer is selected from 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 4,4'-oxydiphthalic anhydride, 2,3,3',4'-diphenyl ether tetracarboxylic dianhydride, 3,3,4,4-diphenyl sulfone tetracarboxylic dianhydride, 4,4'-(hexafluoroisopropylene) diphthalic anhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene diphthalic anhydride, 4,4'-terephthalic anhydride, bisphenol A diether dianhydride, and ethylene glycol ditrimellitate anhydride.

[0066] Preferably, the third organic solvent is selected from one or more mixed solvents of N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, sulfolane, 1,4-dioxane, acetone, acetonitrile, toluene, chloroform, hexamethylphosphoric triamide and tetrahydrofuran.

[0067] Preferably, the dehydrating agent is acetic anhydride, trifluoroacetic anhydride, or a mixture of the two.

[0068] Preferably, the third catalyst is one or a mixture of two or more of pyridine, triethylamine, quinoline, isoquinoline and imidazole.

[0069] Preferably, the specific steps of the chemical imidization are: adding a dehydrating agent and a catalyst to a polyamic acid viscous liquid, wherein acetic anhydride is used as the dehydrating agent and pyridine is used as the catalyst, stirring at room temperature for 24 to 40 hours, then pouring into a large amount of ethanol to obtain a fibrous polyimide, washing with ethanol three times, and drying for standby use.

[0070] In order to further understand the present invention, the preparation method of the diamine monomer and the preparation method of the polyimide provided by the present invention are described in detail below in conjunction with the embodiments. The protection scope of the present invention is not limited by the following embodiments.

[0071] Example 1

[0072] 4-bromobenzoyl chloride (24.14g, 105mmol) was dissolved in 120mL tetrahydrofuran, and then a tetrahydrofuran solution (60mL) of magnolol (13.32g, 50mmol) and triethylamine (20.9mL, 150mmol) was added dropwise thereto. After stirring at room temperature for 12h, the solution was extracted with dilute hydrochloric acid and deionized water to neutralization to obtain an allyl-containing bromo compound. The allyl-containing bromo compound was characterized by nuclear magnetic resonance, and the result was: 1 H NMR(400MHz,Chloroform-d)δ:7.78(dt,J=8.8,2.3Hz,2H),7.54(dt,J=8.9,2.3Hz,2H),7.18(d,J=1.9 Hz,3H),5.82(ddt,J=17.6,9.5,6.7Hz,1H),4.99(dq,J=13.1,1.8Hz,2H),3.33(dt,J=6.6,1.7Hz,2H). 13 C NMR (151MHz, Chloroform-d) δ: 164.44, 146.52, 137.92, 136.93, 131.91, 131.65, 131.33, 130.27, 129.33, 128.76, 128.47, 122.54, 116.31, 39.61.

[0073] Under argon conditions, the above-mentioned allyl-containing brominated compound (9.48 g, 15 mmol) and tetrakistriphenylphosphine palladium were dissolved in 250 mL of tetrahydrofuran. After stirring for 10 minutes, 3M potassium phosphate aqueous solution (60 mL) and (4-aminophenyl) hydrochloride borate (7.80 g, 45 mmol) were added and further stirred at 75 ° C for 24 h. After cooling to room temperature, it was concentrated and purified to obtain a diamine monomer, named DDBA. DDBA was characterized by nuclear magnetic resonance, and the results were: 1 H NMR(400MHz, DMSO-d6)δ:7.89(d,J=8.3Hz,2H),7.69(d,J=8.4Hz,2H),7.48(d,J=8.4Hz,2H),7.32– 7.13(m,3H),6.66(d,J=8.5Hz,2H),5.89–5.73(m,1H),5.45(s,2H),5.09–4.85(m,2H),3.34(s,4H). 13 C NMR (151MHz, DMSO-d6) δ: 164.32, 149.63, 146.21, 145.79, 137.29, 137.19, 130.76, 130.23, 129.83, 129.07, 127.71, 125.42, 125.25, 125.02, 123.00, 116.05, 114.14, 38.65. HR-MS (ESI, m / z). Figure 1 shown.

[0074]

[0075] The diamine monomer DDBA (7.61mmol) and 2,2'-bis(trifluoromethyl)-4,4'-diaminophenyl ether (6FODA, 7.61mmol) were dissolved in anhydrous N-methylpyrrolidone (NMP) solution (57mL), and then 4,4-hexafluoroisopropylphthalic anhydride (6FDA, 14.27mmol) was added to react under nitrogen protection and room temperature to obtain a polyamic acid solution. Subsequently, acetic anhydride (4.02mL) and pyridine (1.73mL) were added for chemical imidization. After the solution was stirred for 24 hours, it was precipitated in a large amount of ethanol, washed three times with ethanol, and dried to obtain a polyimide powder having a structure shown in Formula 1. The obtained polyimide is recorded as PI-1, and the number average molecular weight is 28000g / mol. The infrared spectrum is shown in Figure 2 shown.

[0076]

[0077] Example 2

[0078] 2-trifluoromethyl-4-bromobenzoyl chloride (30.18g, 105mmol) was dissolved in 150mL tetrahydrofuran, and then a tetrahydrofuran solution (60mL) of magnolol (13.32g, 50mmol) and triethylamine (20.9mL, 150mmol) was added dropwise thereto. After stirring at room temperature for 12h, the solution was extracted with dilute hydrochloric acid and deionized water to neutralization to obtain an allyl-containing bromo compound. The allyl-containing bromo compound was characterized by nuclear magnetic resonance, and the result was: 1 H NMR(400MHz,Chloroform-d)δ:8.02(d,J=8.3Hz,1H),7.93(d,J=2.0Hz,1H),7.64(dd,J=8.3,2.0Hz,1H),7.31-7.24(m, 2H), 7.21 (ddt, J=8.8, 2.0, 1.0Hz, 1H), 5.94 (tt, J=9.8, 7.5Hz, 1H), 5.10 (d, J=9.6Hz, 2H), 3.33 (dt, J=7.5, 1.0Hz, 2H). 13 C NMR(151MHz,Chloroform-d)δ:166.76,148.53,137.67,134.25,133.08,132.71,132. 25,130.96,130.59,130.29,129.03,126.28,125.44,123.14,119.01,115.61,39.44.

[0079] Under argon conditions, the above-mentioned allyl-containing brominated compound (11.53 g, 15 mmol) and tetrakistriphenylphosphine palladium were dissolved in 250 mL of tetrahydrofuran. After stirring for 10 minutes, 3M potassium phosphate aqueous solution (60 mL) and (4-aminophenyl) hydrochloride borate (7.80 g, 45 mmol) were added and further stirred at 75 ° C for 24 h. After cooling to room temperature, it was concentrated and purified to obtain a diamine monomer named F-DDBA. F-DDBA was characterized by nuclear magnetic resonance, and the results were: 1H NMR(400MHz,Chloroform-d)δ:8.07(d,J=7.5Hz,1H),7.93(d,J=2.0Hz,1H),7.6 4-7.57(m,2H),7.57(dd,J=7.6,2.1Hz,1H),7.31-7.24(m,2H),7.21(ddt,J=8.8, 2.0,1.0Hz,1H),6.72-6.66(m,2H),5.94(tt,J=9.8,7.5Hz,1H),5.10(d,J=9.6H z, 2H), 4.21 (d, J = 5.7Hz, 1H), 4.13 (d, J = 5.7Hz, 1H), 3.33 (dt, J = 7.5, 1.0Hz, 2H). 13 C NMR(151MHz,Chloroform-d)δ:167.71,148.86,148.53,143.97,137.67,134.83,134.25,131.80,131. 36,130.59,130.29,129.03,127.73,126.72,125.88,125.82,123.13,119.01,115.61,115.35,39.44.

[0080]

[0081] The preparation method of the polyimide in this example is basically the same as that in Example 1, except that DDBA is replaced by F-DDBA. In this example, a polyimide powder having a structure shown in Formula 2 is obtained, which is denoted as PI-2 and has a number average molecular weight of 32000 g / mol.

[0082]

[0083] Example 3

[0084] 2-trifluoromethyl-4-bromobenzoyl chloride (30.18g, 105mmol) was dissolved in 150mL tetrahydrofuran, and then a tetrahydrofuran solution (60mL) of magnolol (13.32g, 50mmol) and triethylamine (20.9mL, 150mmol) was added dropwise thereto. After stirring at room temperature for 12h, the solution was extracted with dilute hydrochloric acid and deionized water to neutralization to obtain an allyl-containing bromo compound. The allyl-containing bromo compound was characterized by nuclear magnetic resonance, and the result was: 1H NMR(400MHz,Chloroform-d)δ:8.02(d,J=8.3Hz,1H),7.93(d,J=2.0Hz,1H),7.64(dd,J=8.3,2.0Hz,1H),7.31-7.24(m, 2H), 7.21 (ddt, J=8.8, 2.0, 1.0Hz, 1H), 5.94 (tt, J=9.8, 7.5Hz, 1H), 5.10 (d, J=9.6Hz, 2H), 3.33 (dt, J=7.5, 1.0Hz, 2H). 13 C NMR(151MHz,Chloroform-d)δ:166.76,148.53,137.67,134.25,133.08,132.71,132. 25,130.96,130.59,130.29,129.03,126.28,125.44,123.14,119.01,115.61,39.44.

[0085] Under argon conditions, the above-mentioned allyl-containing brominated compound (11.53 g, 15 mmol) and tetrakistriphenylphosphine palladium were dissolved in 250 mL of tetrahydrofuran. After stirring for 10 minutes, 3M potassium phosphate aqueous solution (60 mL) and (3-amino-5-methylphenyl) boronic acid (6.80 g, 45 mmol) were added and further stirred at 75 ° C for 24 h. After cooling to room temperature, it was concentrated and purified to obtain a diamine monomer named F-DDBA-CH3. F-DDBA-CH3 was characterized by nuclear magnetic resonance, and the results were: 1 H NMR(400MHz,Chloroform-d)δ:7.99(d,J=7.5Hz,1H),7.92(d,J=2.1Hz,1H),7.46(dd,J=7.5,2.1Hz,1H),7.31-7.24(m,3H),7.21(ddt,J=8.8,2.0 ,1.0Hz,1H),6.96(t,J=2.1Hz,1H),6.58-6.53(m,1H),6.01-5.87(m,1H) ,5.10(dd,J=13.3,3.6Hz,2H),4.38(s,2H),3.33(dt,J=7.5,1.0Hz,2H). 13C NMR(151MHz,Chloroform-d)δ:167.71,148.53,147.44,144.09,141.21,140.45,137.67,134.25,131.83,131.33, 130.59,130.29,129.03,125.82,124.78,124.43,123.13,120.90,119.01,115.69,115.61,110.85,39.44,21.13.

[0086]

[0087] The preparation method of the polyimide in this embodiment is basically the same as that in embodiment 1, except that DDBA is replaced by F-DDBA-CH3. In this embodiment, a polyimide powder having a structure shown in formula 3 is obtained, which is denoted as PI-3 and has a number average molecular weight of 30,000 g / mol.

[0088]

[0089] Example 4

[0090] Magnolol (6.00 g, 22.5 mmol), p-bromonitrobenzene (13.64 g, 67.5 mmol) and potassium carbonate (12.44 g, 90.0 mmol) were dissolved in 100 mL of anhydrous N, N-dimethylacetamide and reacted under nitrogen protection. After the reaction, the solid was collected by filtration and recrystallized to obtain a dinitro compound. The dinitro compound was characterized by nuclear magnetic resonance, and the result was: 1 H NMR(400MHz,Chloroform-d)δ:8.28-8.22(m,2H),7.29(dt,J=2.0,1.1Hz,1H),7.25-7.19(m,1H),7.19-7.13( m,2H),7.01(d,J=8.6Hz,1H),5.94(tt,J=9.8,7.5Hz,1H),5.10(d,J=9.7Hz,2H),3.33(dt,J=7.5,1.0Hz,2H). 13 C NMR (151MHz, Chloroform-d) δ: 162.43, 154.71, 142.77, 137.67, 134.27, 130.13, 129.67, 128.70, 125.57, 118.42, 117.02, 115.61, 39.44.

[0091] Under nitrogen atmosphere, the above dinitro compound (2.00 g, 3.9 mmol), (4-aminophenyl) hydrochloride borate (2.03 g, 11.7 mmol), palladium acetate (catalytic amount), BrettPhos ligand (catalytic amount) and potassium phosphate (6.62 g, 31.2 mmol) were dissolved in 50 mL of 1,4-dioxane and further stirred at 130 ° C for 24 h. After cooling to room temperature, it was concentrated and purified to obtain a diamine monomer named DBA. DBA was characterized by nuclear magnetic resonance, and the results were: 1 H NMR(400MHz,Chloroform-d)δ:7.63-7.57(m,2H),7.51-7.45(m,2H),7.29(dt,J =2.0,1.0Hz,1H),7.25-7.17(m,1H),7.20(s,1H),7.18(d,J=1.6Hz,1H),7.00(d ,J=8.5Hz,1H),6.72-6.66(m,2H),5.94(tt,J=9.8,7.5Hz,1H),5.10(d,J=9.6Hz ,2H),4.21(d,J=5.7Hz,1H),4.13(d,J=5.7Hz,1H),3.33(dt,J=7.5,1.0Hz,2H). 13 C NMR(151MHz,Chloroform-d)δ:158.26,154.53,148.86,137.67,134.27,132.93,130. 13,130.05,129.67,129.28,128.87,128.70,119.76,117.02,116.49,115.61,39.44.

[0092]

[0093] The preparation method of the polyimide in this embodiment is substantially the same as that in Embodiment 1, except that DDBA is replaced by DBA.

[0094] In this example, a polyimide powder having a structure shown in Formula 4 is obtained, which is denoted as PI-4 and has a number average molecular weight of 27500 g / mol.

[0095]

[0096] Example 5

[0097] Magnolol (6.00 g, 22.5 mmol), p-bromonitrobenzene (13.64 g, 67.5 mmol) and potassium carbonate (12.44 g, 90.0 mmol) were dissolved in 100 mL of anhydrous N, N-dimethylacetamide and reacted under nitrogen protection. After the reaction, the solid was collected by filtration and recrystallized to obtain a dinitro compound. The dinitro compound was characterized by nuclear magnetic resonance, and the result was: 1 H NMR(400MHz,Chloroform-d)δ:8.28-8.22(m,2H),7.29(dt,J=2.0,1.1Hz,1H),7.25-7.19(m,1H),7.19-7.13( m,2H),7.01(d,J=8.6Hz,1H),5.94(tt,J=9.8,7.5Hz,1H),5.10(d,J=9.7Hz,2H),3.33(dt,J=7.5,1.0Hz,2H). 13 C NMR (151MHz, Chloroform-d) δ: 162.43, 154.71, 142.77, 137.67, 134.27, 130.13, 129.67, 128.70, 125.57, 118.42, 117.02, 115.61, 39.44.

[0098] Under nitrogen atmosphere, the above dinitro compound (2.00 g, 3.9 mmol), (3-amino-5-methylphenyl) boronic acid (1.77 g, 11.7 mmol), palladium acetate (catalytic amount), BrettPhos ligand (catalytic amount) and potassium phosphate (6.62 g, 31.2 mmol) were dissolved in 50 mL of 1,4-dioxane and further stirred at 130 ° C for 24 h. After cooling to room temperature, it was concentrated and purified to obtain a diamine monomer named DBA-CH3. DBA-CH3 was characterized by nuclear magnetic resonance, and the results were: 1 H NMR(400MHz,Chloroform-d)δ:7.63-7.57(m,2H),7.51-7.45(m,2H),7.29(dt,J =2.0,1.0Hz,1H),7.25-7.17(m,1H),7.20(s,1H),7.18(d,J=1.6Hz,1H),7.00(d ,J=8.5Hz,1H),6.72-6.66(m,2H),5.94(tt,J=9.8,7.5Hz,1H),5.10(d,J=9.6Hz ,2H),4.21(d,J=5.7Hz,1H),4.13(d,J=5.7Hz,1H),3.33(dt,J=7.5,1.0Hz,2H). 13C NMR(151MHz,Chloroform-d)δ:158.26,154.53,148.86,137.67,134.27,132.93,130. 13,130.05,129.67,129.28,128.87,128.70,119.76,117.02,116.49,115.61,39.44.

[0099]

[0100] The preparation method of the polyimide in this embodiment is basically the same as that in embodiment 1, except that DDBA is replaced by DBA-CH3. In this embodiment, a polyimide powder having a structure shown in Formula 5 is obtained, which is denoted as PI-5 and has a number average molecular weight of 33000 g / mol.

[0101]

[0102] Comparative Example 1

[0103] 4,4'-diaminodiphenyl ether (ODA, 5mmol) was dissolved in anhydrous N-methylpyrrolidone (NMP) solution (15mL), and then 4,4-hexafluoroisopropylphthalic anhydride (6FDA, 4.69mmol) was added, and the polyamic acid solution was obtained under nitrogen protection and room temperature. Subsequently, acetic anhydride (1.32mL) and pyridine (0.57mL) were added for chemical imidization reaction. After the solution was stirred for 24 hours, it was precipitated in a large amount of ethanol, washed three times with ethanol, and dried to obtain a polyimide powder having a structure shown in Formula 6, which was recorded as PI-6. The number average molecular weight is 29800g / mol.

[0104]

[0105] Comparative Example 2

[0106] The preparation method of this comparative example is basically the same as that of comparative example 1, except that ODA is replaced with 4,4'-diamino-2,2'-dimethylbiphenyl (M-tolidine) to prepare a polyimide having a structure of formula 7, which is denoted as PI-7. The number average molecular weight is 31000 g / mol.

[0107]

[0108] The solubility performance test of the polyimide prepared in Examples 1-5 and Comparative Examples 1-2 was performed, and the results are shown in Table 1.

[0109] Table 1 Solubility data of polyimide

[0110] Polyimide Solvents NMP DMF DMAc THF DCM EA PGEMA Example 1 ++ ++ ++ ++ ++ ++ ++ Example 2 ++ ++ ++ ++ ++ ++ ++ Example 3 ++ ++ ++ ++ ++ ++ ++ Example 4 ++ ++ ++ ++ ++ ++ ++ Example 5 ++ ++ ++ ++ ++ ++ ++ Comparative Example 1 ++ ++ ++ +- +- - - Comparative Example 2 ++ ++ ++ +- +- - -

[0111] Among them, ++ means soluble at room temperature, +- means partially soluble at room temperature, and - means insoluble at room temperature; NMP is N-methylpyrrolidone, DMF is N,N-dimethylformamide, DMAc is N,N-dimethylacetamide, THF is tetrahydrofuran, DCM is dichloromethane, EA is ethyl acetate, and PGEMA is propylene glycol methyl ether acetate.

[0112] As shown in Table 1, compared with Comparative Examples 1 and 2, the polyimide prepared by the present invention can be dissolved in most high-boiling point polar solvents (NMP, DMF, DMAc) at room temperature, can also be dissolved in low-boiling point solvents (DCM, THF), and can also be dissolved in non-toxic solvents (EA and PGEMA). Therefore, the polyimide resin prepared by the present invention has good solubility in conventional solvents and can meet the process requirements of solution processing.

[0113] In addition, compared with Comparative Examples 1 and 2, the polyimide prepared in the present invention contains an allyl group. Since the allyl group is a photo-crosslinking group, the polyimide prepared in the present invention has a photo-crosslinking property, and can be applied in the fields of optical data storage devices, photoresists, and photosensitive optical materials, thereby expanding the application range of polyimide.

[0114] The above-mentioned embodiments only express several implementation methods of the present invention, and the description is relatively specific and detailed, but it cannot be understood as limiting the scope of the invention patent. It should be pointed out that for ordinary technicians in this field, several modifications and improvements can be made without departing from the concept of the present invention, which all belong to the protection scope of the present invention.

Claims

1. A diamine monomer, characterized in that The general structural formula of the diamine monomer is: Wherein, R1 is selected from any one of an ester group or an ether bond; Ar1 ​​is selected from any one of the following structures: wherein R1, R2, R3, and R4 are the same or different from each other, and are independently selected from hydrogen, fluorine, methyl, ethyl, trifluoromethyl, tert-butyl, oxymethyl, or oxybutyl; Ar2 is selected from any one of the following structures: In the formula, R5, R6, R7, and R8 are the same as each other or different, and are independently selected from hydrogen, fluorine, methyl, ethyl, trifluoromethyl, tert-butyl, oxymethyl, or oxybutyl.

2. A method for preparing a diamine monomer as claimed in claim 1, comprising the following steps: (1) reacting magnolol with bromobenzoyl chloride containing R1, R2, R3 and R4 in an aprotic solvent and alkaline environment at low temperature to obtain a brominated compound containing an allyl group; (2) The brominated compound is reacted with aminophenylboronic acid or phenylboronic acid ester containing R5, R6, R7 and R8 through Suzuki reaction to obtain the diamine monomer.

3. A method for preparing the diamine monomer as claimed in claim 1, comprising the following steps: (1) reacting magnolol with bromonitrobenzene containing R1, R2, R3 and R4 in a non-protonic high-polar solvent and an alkaline environment to obtain a dinitro compound containing an allyl group; (2) The dinitro compound is reacted with aminophenylboronic acid or phenylboronic acid ester containing R5, R6, R7 and R8 through Suzuki-Miyaura coupling reaction to obtain the diamine monomer.

4. Use of the diamine monomer according to claim 1 in the preparation of polyimide, polyamideimide or polyamide.

5. A polyimide, characterized in that: The general structural formula of the polyimide is: In the formula, n and m represent the degree of polymerization, n is an integer of 1 to 150, m is an integer of 1 to 150, Ar is the aromatic unit fragment in the diamine monomer described in claim 1, X is a tetravalent aromatic hydrocarbon group, and Ar1 is the residue of the diamine.

6. The polyimide according to claim 5, characterized in that The X is preferably selected from any one of the following:

7. The polyimide according to any one of claims 5 or 6, characterized in that The Ar1 is preferably any one of the following:

8. A method for preparing the polyimide according to any one of claims 5 to 7, comprising the following steps: The diamine monomer, aromatic diamine monomer, aromatic dianhydride monomer and a third organic solvent according to claim 1 are mixed and copolymerized to obtain polyamic acid; the aromatic diamine monomer is p-phenylenediamine, m-phenylenediamine or flexible aromatic diamine; The polyamic acid, a dehydrating agent and a third catalyst are mixed to carry out a chemical imidization reaction to obtain polyimide.

9. The method for preparing a polyimide according to claim 8, characterized in that: The flexible aromatic diamine is selected from 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 1,3-bis(4'-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 2,2'-bis(trifluoromethyl)-4,4'-diaminophenyl ether, 2,2'-bis(trifluoromethyl)diaminobiphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diamino-3,3'-dimethylbiphenyl, 4,4'-diaminodiphenyl sulfone, 4,4'-bis(3-aminophenoxy)benzophenone, 3,3'-diaminodiphenyl sulfone, 2 2'-Diaminodiphenyl sulfide, 4,4-diaminodiphenyl sulfide, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 4,4-diamino-3,3-difluorobiphenyl, 9,9-bis(4-aminophenyl)fluorene, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 3,3'-diaminodiphenylmethane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 1,2-bis(4-aminophenoxy)ethane, 4,4'-bis(3-aminophenoxy)diphenyl sulfone.

10. Use of the polyimide according to any one of claims 5 to 7 in the preparation of photosensitive polyimide photoresist.

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