CN114853615B - Diamine monomer, polyimide film, and preparation methods and applications thereof - Google Patents
Diamine monomer, polyimide film, and preparation methods and applications thereof Download PDFInfo
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Abstract
The invention discloses a methyl-containing terphenyl diamine monomer, the structural formula of which is shown as a general formula M
Wherein R1-R12 are each independently selected from methyl and hydrogen atoms, and at least one of R1-R12 is methyl. The diamine monomer has unique structural characteristics, and polyimide prepared by the diamine monomer has excellent light transmittance and heat resistance. Meanwhile, the invention also discloses a preparation method of the diamine monomer, which is simple in preparation procedure and high in yield, and polyimide with excellent light transmittance and heat resistance, which is prepared by adopting the diamine monomer.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a diamine monomer containing methyl, a polyimide film, a preparation method thereof and application of the diamine monomer in preparation of the polyimide film.
Background
Polyimide is widely used as a substrate material for flexible devices due to its excellent heat resistance and good optical properties. Diamine monomer is one of main raw materials for preparing polyimide, and the structure and the performance of the diamine monomer have direct influence on the structure and the performance of the prepared polyimide. Currently, common wholly aromatic polyimides exhibit a darker color in the visible region due to intermolecular and intramolecular generated Charge Transfer Complexes (CTCs), affecting their optical properties, limiting their further applications. The heat resistance and optical properties of polyimide are closely related to their molecular structure, which are contradictory. Therefore, the balance and unification of the high temperature resistance and the transparency are required to be realized through reasonable molecular design.
Diamine monomer used for preparing polyamide at present mainly realizes improvement of transparency and thermal performance of polyimide by introducing strong electron withdrawing groups such as-CF 3, alicyclic structure, large side group, constructing asymmetric non-coplanar structure and the like, but is difficult to realize improvement of transparency and thermal performance at the same time. In addition, the existing diamine monomer has complex preparation procedures and low total yield, and the steps of hydrogenation reduction and the like are needed, so that the method is not beneficial to industrial application. Meanwhile, transparent polyimide prepared from the polyimide has the problems of poor thermal performance and difficulty in exceeding 400 ℃.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a diamine monomer with simple preparation process and higher yield and a preparation method thereof; meanwhile, the invention also provides polyimide with excellent light transmittance and heat resistance, which is prepared by adopting the diamine monomer.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows: a diamine monomer, wherein the structural formula of the diamine monomer is shown as a general formula M:
wherein R1-R12 are each independently selected from methyl and hydrogen atoms, and at least one of R1-R12 is methyl.
The diamine monomer has the structural characteristics represented by the general formula M, wherein R1-R12 can be selected from methyl and hydrogen atoms independently, at least one of R1-R12 is methyl, namely the diamine monomer is a methyl-containing terphenyl diamine monomer, and the specific structure can enable polyimide prepared from the diamine monomer to have excellent light transmittance and heat resistance.
As a preferred embodiment of the diamine monomer according to the present invention, the diamine monomer has a structural formula selected from the group consisting of M-1 to M-15:
the structural formula of the diamine monomer is preferably, but not limited to, at least one of the above structural formulae M-1 to M-15. The inventor of the present application found in experimental study that when the structure of the diamine monomer is selected as one of the above structural formulas M-1 to M-15, the transmittance and heat resistance of the polyimide prepared from the diamine monomer of the structure are better improved.
In addition, the invention also provides a diamine monomer preparation method with simple procedure and higher yield, which comprises the following steps:
reacting a compound with a structural formula I with a compound with a structural formula II through Suzuki-Miyaura reaction to obtain the diamine monomer;
or the compound of the structural formula III and the compound of the structural formula IV are subjected to Suzuki-Miyaura reaction to obtain the diamine monomer;
in the structural formulas I-IV:
each of R1-R4 is independently selected from methyl, hydrogen atom;
x is selected from Cl, br and I;
the Y is-B (OH) 2 Or (b)
The Suzuki-Miyaura reaction is carried out in the presence of a metallic palladium catalyst, a solvent and an alkaline solution.
The diamine monomer can be prepared by adopting the compounds with structural formulas I and II shown above or adopting the compounds with structural formulas III and IV shown above through Suzuki-Miyaura reaction in the presence of a metallic palladium catalyst, a solvent and an alkaline solution, and the preparation method has simple procedure, does not need hydrogenation reduction step and has higher yield.
As a preferred embodiment of the method for producing a diamine monomer according to the present invention, the metallic palladium catalyst in the Suzuki-Miyaura reaction is Pd (PPh) 3 ) 4 、PdCl 2 、PdCl 2 (dppf)、Pd(OAc) 2 、Pd(PPh 3 ) 2 Cl 2 、PdCl 2 At least one of (dtbpf). In the method for preparing the diamine monomer, the metal palladium catalyst in the Suzuki-Miyaura reaction is preferably, but not limited to Pd (PPh) 3 ) 4 、PdCl 2 、PdCl 2 (dppf)、Pd(OAc) 2 、Pd(PPh 3 ) 2 Cl 2 、PdCl 2 At least one of (dtbpf).
As a preferred embodiment of the method for preparing the diamine monomer, the solvent in the Suzuki-Miyaura reaction is at least one of tetrahydrofuran, dioxane, N-dimethylformamide, toluene and methanol. In the preparation method of the diamine monomer, the solvent in the Suzuki-Miyaura reaction is preferably at least one of tetrahydrofuran, dioxane, N-dimethylformamide, toluene and methanol, but not limited to the solvent.
As a preferred embodiment of the method for producing a diamine monomer according to the present invention, the basic solvent in the Suzuki-Miyaura reaction is KOH, naOH, cs 2 CO 3 、K 2 CO 3 、Na 2 CO 3 、NaHCO 3 、K 3 PO 4 At least one of CsF aqueous solution. In the method for producing the diamine monomer of the present invention, the basic solvent in the Suzuki-Miyaura reaction is preferably, but not limited to, KOH, naOH, cs 2 CO 3 、K 2 CO 3 、Na 2 CO 3 、NaHCO 3 、K 3 PO 4 At least one of CsF aqueous solution.
As a preferred embodiment of the method for producing a diamine monomer of the present invention, the concentration of the basic solvent in the Suzuki-Miyaura reaction is 2 to 10mol/L. As a more preferable embodiment of the method for producing a diamine monomer of the present invention, the concentration of the basic solvent in the Suzuki-Miyaura reaction is 4 to 8mol/L.
As a preferred embodiment of the method for producing a diamine monomer of the present invention, the temperature of the Suzuki-Miyaura reaction is 60 to 110 ℃, and the Suzuki-Miyaura reaction is carried out under an inert atmosphere. As a more preferred embodiment of the process for producing a diamine monomer according to the present invention, the inert atmosphere is argon or nitrogen.
In addition, the invention also provides application of the diamine monomer in preparing polyimide.
Finally, the present invention also provides a polyimide film having excellent light transmittance and heat resistance, which is prepared using the diamine monomer as described above.
As a preferred embodiment of the polyimide film, the polyimide film is prepared by the following method:
(1) Mixing at least one of the diamine monomers with dianhydride monomer, and carrying out homopolymerization or copolymerization reaction in a polar aprotic solvent or a phenolic solvent to obtain a polyamic acid solution or a polyimide solution;
(2) And (3) curing the polyamic acid solution or polyimide solution obtained in the step (1) to obtain the polyimide film.
In a preferred embodiment of the polyimide film according to the present invention, the polar aprotic solvent or the phenolic solvent is at least one of N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, acetone, phenol, and tolyldiphenol.
The diamine monomer has special structural characteristics, and the high temperature resistance and the transparency of polyimide prepared from the diamine monomer are both improved; meanwhile, the preparation method of the diamine monomer is simple in procedure, high in yield and favorable for industrial popularization and application.
The polyimide is prepared from the diamine monomer with the specific structure, the high temperature resistance and the transparency of the polyimide are effectively improved, and the polyimide has excellent light transmittance and heat resistance.
Drawings
FIG. 1 is a structural general formula of the diamine monomer of the present invention.
FIG. 2 is a chemical reaction scheme of one embodiment of the diamine monomer of the present invention.
FIG. 3 is a chemical reaction scheme of another embodiment of the diamine monomer of the present invention.
FIG. 4 is a chemical reaction scheme of another embodiment of the diamine monomer of the present invention.
FIG. 5 is a chemical reaction scheme of another embodiment of the diamine monomer of the present invention.
FIG. 6 is a chemical reaction scheme of another embodiment of the diamine monomer of the present invention.
FIG. 7 is an ultraviolet-visible spectrum of a polyimide film prepared using the diamine monomer of the present invention.
FIG. 8 is an optical photograph of a polyimide film prepared using the diamine monomer of the present invention.
Detailed Description
For a better description of the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to the accompanying drawings and specific embodiments.
The starting materials used in the examples below are either commercially available directly or prepared by conventional methods known in the art.
The structural formula of the diamine monomer is shown in the structural formula of figure 1, and the diamine monomer is a methyl-containing terphenyl diamine monomer.
In the following examples, the 1HNMR and 13CNMR spectra were obtained on a bruck AVANCEIIIHD spectrometer, germany, with deuterated chloroform as solvent. The High Resolution Mass Spectrum (HRMS) was detected by an ACQUITYTMUPLC & Q-TOFMSPremier mass spectrometer in the united states.
Example 1
An example of the diamine monomer of the present invention, the chemical name of the diamine monomer is: 2,2' -dimethyl- [1,1':4', 1' -terphenyl ] -4, 4' -diamine (DMTD) having the structural formula:
in this embodiment, the preparation method of the diamine monomer includes the following steps:
(1) In a 250ml Schlenk flask, 4-bromo-3-methylaniline (3.71 g,19.95mmol,2.1 eq) and 1, 4-phenyldiboronic acid (1.57 g,9.50mmol,1.0 eq) were added in sequence, followed by 60ml of ultra-dry tetrahydrofuran and 2mol/L K 2 CO 3 Solution (28.5 ml,57mmol,6 eq);
(2) Defoaming the system in the step (1) for 20 minutes in an argon atmosphere, and then rapidly adding Pd (PPh) in the argon atmosphere 3 ) 4 (399 mg, 0.284 mmol,0.03 eq) to give a reaction mixture;
(3) The reaction mixture was refluxed for 24 hours at 85 ℃ with vigorous stirring and the reaction completion was followed by thin layer chromatography;
(4) After the reaction was cooled, most of tetrahydrofuran was removed, the mixture was extracted with ethyl acetate, washed with deionized water and saturated sodium chloride solution, and dried over anhydrous magnesium sulfate; the crude product was further purified by flash prep. liquid chromatograph to give a white product (2.0 g, 73%) which was the diamine monomer described in this example.
The chemical reaction formula of the diamine monomer in this example is shown in figure 2.
The hydrogen and carbon spectra of the diamine monomer described in this example are as follows:
1 HNMR (400 MHz, chloroform-d) delta 7.30 (s, 4H), 7.10 (d, j=8.0 hz, 2H), 6.63 (d, j=2.4 hz, 2H), 6.60 (dd, j=7.9, 2.5hz, 2H), 3.65 (s, 4H), 2.27 (s, 6H).
13 CNMR (100 MHz, chloroform-d) delta (ppm): 145.44,139.76,136.42,132.40,130.91,128.99,116.90,112.69,20.69.HRMS (ESI, m/z): C 20 H 20 N 2 ,[M+H] + Theoretical value 289.1700; experimental value 289.1701.
Example 2
An example of the diamine monomer of the present invention, the chemical name of the diamine monomer is: 2,2', 5' -tetramethyl- [1,1':4',1 '-terphenyl ] -4, 4' -diamine (TMTD) having the structural formula:
in this example, the diamine monomer was synthesized from 4-bromo-2, 5-dimethylaniline (2.90 g,14.50mmol,2.2 eq) and 1, 4-phenyldiboronic acid (1.09 g,6.58mmol,1.0 eq), the remaining reagent selections, sequence of steps, process parameters, etc. were the same as in example 1.
In the preparation method of the diamine monomer described in this example, the crude product was further purified by flash chromatography (EA: pe=1:3) to give a white product (1.4 g, 67%), which was the diamine monomer described in this example.
The chemical reaction formula of the diamine monomer in this example is shown in fig. 3.
The hydrogen and carbon spectra of the diamine monomer described in this example are as follows:
1 HNMR (400 MHz, chloroform-d) delta 7.30 (s, 4H), 7.01 (s, 2H), 6.62 (s, 2H), 3.58 (s, 4H), 2.26 (s, 6H), 2.19 (s, 6H).
13 CNMR (100 MHz, chloroform-d) delta (ppm): 143.57,139.78,133.89,132.40,132.09,128.96,119.79,116.79,20.19,16.83.HRMS (ESI, m/z): C 22 H 24 N 2 ,[M+H] + Theoretical value 317.2013; experimental value 317.2009.
Example 3
An example of the diamine monomer of the present invention, the chemical name of the diamine monomer is: 2,2', 3' -tetramethyl- [1,1':4',1 '-terphenyl ] -4, 4' -diamine (23 TMTD) having the structural formula:
in this example, the diamine monomer was synthesized from 4-bromo-2, 3-dimethylaniline (1.01 g,5.04mmol,2.1 eq) and 1, 4-phenyldiboronic acid (0.40 g,2.40mmol,1.0 eq), and the remaining reagent selections, sequence of steps, process parameters, etc. were the same as in example 1.
In the preparation method of the diamine monomer described in this example, the crude product was further purified by flash chromatography (EA: pe=1:3) to give off-white product (700 mg, 92%), which is the diamine monomer described in this example.
The chemical reaction formula of the diamine monomer in this example is shown in fig. 4.
The hydrogen and carbon spectra of the diamine monomer described in this example are as follows:
1 HNMR (400 MHz, chloroform-d) delta 7.27 (s, 4H), 7.01 (d, j=8.0 hz, 2H), 6.65 (d, j=8.0 hz, 2H), 3.63 (s, 4H), 2.25 (s, 6H), 2.17 (s, 6H).
13 CNMR (100 MHz, chloroform-d) delta (ppm): 143.58,140.75,134.55,133.39,129.24,128.05,121.23,112.81,17.88,13.37.HRMS (ESI, m/z): C 22 H 24 N 2 ,[M+H] + Theoretical value 317.2013; experimental value 317.2014.
Example 4
An example of the diamine monomer of the present invention, the chemical name of the diamine monomer is: 2,2',2", 5',5" -hexamethyl- [1,1':4',1 "-terphenyl ] -4,4" -diamine (HMTD), having the structural formula:
in this example, the diamine monomer was synthesized from 4-bromo-2, 5-dimethylaniline (4.14 g,20.68mmol,2.2 eq) and 2- (2, 5-dimethyl-4- (4, 5-trimethyl-1, 3, 2-dioxaborolan-2-yl) phenyl) -4, 5-tetramethyl-1, 3, 2-dioxaborane (3.36 g,9.40mmol,1.0 eq), and the remaining reagent selections, sequence of steps, process parameters, etc. were the same as in example 1.
The 2- (2, 5-dimethyl-4- (4, 5-trimethyl-1, 3, 2-dioxaborolan-2-yl) phenyl) -4, 5-tetramethyl-1, 3, 2-dioxaborane in the synthetic raw material is prepared by the following method:
(1) 4,4', 5' -octamethyl-2, 2' -bis (1, 3, 2-dioxaborane) (20.34 g,78.9mmol,2.1 eq), 1, 4-dibromo-2, 5-dimethylbenzene (9.92 g,37.6mmol,1.0 eq) and potassium acetate (14.81 g,150.9mmol,4.0 eq) were sequentially added to a 300ml single-neck flask, followed by 150ml ultra-dry dioxane;
(2) Defoaming the system in the step (1) for 20 minutes in an argon atmosphere, and then rapidly adding Pd (dppf) Cl in the argon atmosphere 2 (1.19 g,1.50mmol,0.04 eq) to give a reaction mixture;
(3) The reaction mixture was reacted at 95 ℃ for 48 hours and followed by thin layer chromatography;
(4) After the reaction was completed, most of the solvent was removed, and the black residue was washed with deionized water and extracted several times with dichloromethane; the crude product was purified by flash preparative liquid chromatograph (DCM: pe=1:4) and then recrystallized from n-hexane to give colorless crystals of 2- (2, 5-dimethyl-4- (4, 5-trimethyl-1, 3, 2-dioxaborolan-2-yl) phenyl) -4, 5-tetramethyl-1, 3, 2-dioxaborane (12.22 g, 91%).
The hydrogen spectrum of the 2- (2, 5-dimethyl-4- (4, 5-trimethyl-1, 3, 2-dioxaborolan-2-yl) phenyl) -4, 5-tetramethyl-1, 3, 2-dioxaborane is as follows:
1 HNMR (400 MHz, chloroform-d) delta 7.54 (s, 2H), 2.48 (s, 6H), 1.34 (s, 24H).
In the preparation method of the diamine monomer described in this example, the crude product was further purified by a flash liquid chromatograph (EA: pe=1:5 to 1:3) to obtain a white product (2.7 g, 85%), which is the diamine monomer described in this example.
The chemical reaction formula of the diamine monomer in this example is shown in FIG. 5.
The hydrogen and carbon spectra of the diamine monomer described in this example are as follows:
1 HNMR (400 MHz, chloroform-d) delta 6.95 (d, j=5.7 hz, 2H), 6.86 (s, 2H), 6.61 (s, 2H), 3.56 (s, 4H), 2.17 (s, 6H), 2.09-2.00 (m, 12H).
13 CNMR (100 MHz, chloroform-d) delta (ppm): 143.24,143.22,140.05,139.99,134.43,134.38,133.10,132.99,132.42,132.35,131.57,131.49,131.19,131.16,119.44,116.23,116.21,19.56,19.42,19.44,16.86,16.90。HRMS(ESI,m/z):C 24 H 28 N 2 ,[M+H] + Theoretical value 345.2326; experimental value 345.2325.
Example 5
An example of the diamine monomer of the present invention, the chemical name of the diamine monomer is: 2,2',2", 3",5' -hexamethyl- [1,1':4',1 "-terphenyl ] -4,4" -diamine (23 HMTD), structural formula:
in this example, the diamine monomer was synthesized from 4-bromo-2, 3-dimethylaniline (4.14 g,20.68mmol,2.2 eq) and 2- (2, 5-dimethyl-4- (4, 5-trimethyl-1, 3, 2-dioxaborolan-2-yl) phenyl) -4, 5-tetramethyl-1, 3, 2-dioxaborane (3.36 g,9.40mmol,1.0 eq), the remaining reagent selections, sequence of steps, process parameters, etc. were the same as in example 1.
The 2- (2, 5-dimethyl-4- (4, 5-trimethyl-1, 3, 2-dioxaborolan-2-yl) phenyl) -4, 5-tetramethyl-1, 3, 2-dioxaborane in the synthetic raw material is prepared by the following method:
(5) 4,4', 5' -octamethyl-2, 2' -bis (1, 3, 2-dioxaborane) (20.34 g,78.9mmol,2.1 eq), 1, 4-dibromo-2, 5-dimethylbenzene (9.92 g,37.6mmol,1.0 eq) and potassium acetate (14.81 g,150.9mmol,4.0 eq) were sequentially added to a 300ml single-neck flask, followed by 150ml ultra-dry dioxane;
(6) Defoaming the system in the step (1) for 20 minutes in an argon atmosphere, and then rapidly adding Pd (dppf) Cl in the argon atmosphere 2 (1.19 g,1.50mmol,0.04 eq) to give a reaction mixture;
(7) The reaction mixture was reacted at 95 ℃ for 48 hours and followed by thin layer chromatography;
(8) After the reaction was completed, most of the solvent was removed, and the black residue was washed with deionized water and extracted several times with dichloromethane; the crude product was purified by flash preparative liquid chromatograph (DCM: pe=1:4) and then recrystallized from n-hexane to give colorless crystals of 2- (2, 5-dimethyl-4- (4, 5-trimethyl-1, 3, 2-dioxaborolan-2-yl) phenyl) -4, 5-tetramethyl-1, 3, 2-dioxaborane (12.22 g, 91%).
The hydrogen spectrum of the 2- (2, 5-dimethyl-4- (4, 5-trimethyl-1, 3, 2-dioxaborolan-2-yl) phenyl) -4, 5-tetramethyl-1, 3, 2-dioxaborane is as follows:
1 HNMR (400 MHz, chloroform-d) delta 7.54 (s, 2H), 2.48 (s, 6H), 1.34 (s, 24H).
In the preparation method of the diamine monomer described in this example, the crude product was further purified by a flash liquid chromatograph (EA: pe=1:5 to 1:3) to obtain a white product (2.6 g, 83%), which is the diamine monomer described in this example.
The chemical reaction formula of the diamine monomer in this example is shown in FIG. 6.
The hydrogen and carbon spectra of the diamine monomer described in this example are as follows:
1 HNMR (400 MHz, chloroform-d) delta 6.95 (d, j=6.9 hz, 2H), 6.87 (dd, j=8.0, 3.0hz, 2H), 6.63 (d, j=8.0 hz, 2H), 3.59 (s, 4H), 2.16 (s, 6H), 2.04 (d, j=2.1 hz, 6H), 2.01 (d, j=1.4 hz, 6H).
13 CNMR (100 MHz, chloroform-d) delta (ppm): 143.23,143.21,141.00,140.95,135.02,134.94,133.25,133.13,133.06,132.97,131.25,131.21,127.51,127.42,120.93,112.70,112.67,19.51,17.32,17.24,13.30.HRMS (ESI, m/z): C 24 H 28 N 2 ,[M+H] + Theoretical value 345.2326; experimental value 345.2333.
Example 6
An embodiment of polyimide prepared by adopting the diamine monomer disclosed by the invention is polyimide PI-1, and the polyimide prepared by the embodiment has the following structural formula:
wherein n is 1 to 15.
The polyimide of this embodiment may be prepared by a one-step method or a two-step method, and the chemical imine method in the two-step method is taken as an example, and the preparation method includes the following steps:
(1) DMTD (432.59 mg,1.5mmol,1 eq) was dissolved in dry DMAc in a 50ml flask equipped with a mechanical stirrer and an argon inlet, and then hexafluoroanhydride 6FDA (666.36 mg,1.5mmol,1 eq) was added to give a mixture;
(2) Maintaining the initial solid content at 12-15%, and stirring the mixture obtained in the step (1) for 24 hours at room temperature under the protection of argon to form viscous polyamic acid solution;
(3) Slowly adding a mixed solution of acetic anhydride/pyridine (v/v: 7/3) into the polyamic acid glue solution in the step (2) according to the molar ratio of acetic anhydride/carboxyl=5, continuously stirring for 24 hours, pouring the obtained viscous glue solution into 300ml of methanol to obtain white fibrous precipitate, washing for 3 times, and then drying in vacuum at 80 ℃ for 36 hours to obtain the polyimide of the embodiment.
Meanwhile, the polyimide film is prepared by adopting the polyimide, and the preparation method of the polyimide film comprises the following steps:
(1) Redissolving the polyimide obtained in the above manner in dry DMAc to form a glue solution with a solid content of 15%;
(2) Uniformly spreading the glue solution obtained in the step (1) on a clean glass plate by using a scraper, sequentially solidifying in a vacuum drying oven at the temperature rising program of 100 ℃ for 50 minutes, 150 ℃ for 50 minutes, 200 ℃ for 100 minutes and 250 ℃ for 120 minutes, and peeling in water to obtain a transparent polyimide film when naturally cooling to room temperature.
Example 7
In one embodiment of the polyimide of the present invention, the polyimide in this embodiment is polyimide PI-2, the polyimide is prepared by using the diamine monomer in embodiment 2, and the selection and preparation methods of the other raw materials except for the diamine monomer in this embodiment are the same as those in embodiment 6.
This example also used the polyimide to prepare a polyimide film, which was identical to example 6 except that the polyimide film of this example was different in structure from example 6.
Example 8
In one embodiment of the polyimide of the present invention, the polyimide of this embodiment is polyimide PI-3, the polyimide is prepared by using the diamine monomer of embodiment 4, and the polyimide of this embodiment is prepared by the same method as in embodiment 6 except for the diamine monomer, and the selection and preparation methods of the other raw materials are the same.
This example also used the polyimide to prepare a polyimide film, which was identical to example 6 except that the polyimide film of this example was different in structure from example 6.
Example 9
In one embodiment of the polyimide of the present invention, the polyimide of this embodiment is polyimide PI-4, the polyimide is prepared by using the diamine monomer of embodiment 3, and the polyimide of this embodiment is prepared by the same method as in embodiment 6 except for the diamine monomer, and the selection and preparation methods of the other raw materials are the same.
This example also used the polyimide to prepare a polyimide film, which was identical to example 6 except that the polyimide film of this example was different in structure from example 6.
Example 10
In one embodiment of the polyimide of the present invention, the polyimide of this embodiment is polyimide PI-5, and the polyimide is prepared by using the diamine monomer of embodiment 5, and the polyimide of this embodiment is prepared by the same method as in embodiment 6 except for the diamine monomer, and the selection and preparation methods of the other raw materials are the same.
This example also used the polyimide to prepare a polyimide film, which was identical to example 6 except that the polyimide film of this example was different in structure from example 6.
Example 11
Performance test of polyimide film prepared by using diamine monomer of the invention
The polyimide films PI-1, PI-2, PI-3, PI-4 and PI-5 prepared in examples 6 to 10 are used as test objects, and the ultraviolet visible spectrum, the optical photo, the glass transition temperature, the dimensional stability and the like of the polyimide films PI-1, PI-2, PI-3, PI-4 and PI-5 are detected respectively to obtain the optical transmittance, the heat resistance, the mechanical property and the like of the obtained polyimide films PI-1, PI-2, PI-3, PI-4 and PI-5.
The high-resolution mass spectrum detection method of the polyimide film comprises the following steps: detection was by using ACQUITYTMUPLC & Q-TOFMSPremier.
The ultraviolet visible spectrum detection method of the polyimide film comprises the following steps: the test range was 200-800nm as assessed by a UV-1800 spectrophotometer of Shimadzu.
The glass transition temperature detection method of the polyimide film comprises the following steps: analysis was performed in tension mode by a Q800DMA instrument from TA corporation in the united states.
The method for detecting the dimensional stability of the polyimide film comprises the following steps: the test was performed by a TA company Q400TMA analyzer in the united states.
The detection method of the yellowness index of the polyimide film comprises the following steps: analysis was performed in transmission mode by a Lamda950 spectrometer from Perkin inc.
The results of the measurements are shown in FIGS. 7 and 8, and in tables 1 and 2, respectively.
TABLE 1 optical property data for polyimide films PI-1, PI-2, PI-3, PI-4, PI-5
TABLE 2 thermal and mechanical Property data for polyimide films PI-1, PI-2, PI-3, PI-4, PI-5
As is clear from the results shown in FIGS. 7, 8 and tables 1 and 2, the polyimide film prepared from the diamine monomer of the present invention has excellent optical transmittance (average transmittance in visible light region is not less than 84%) and excellent heat resistance (glass transition temperature is 391 to 413 ℃). In addition, the obtained polyimide film has good mechanical properties, the tensile strength is between 96 and 158Mpa, and the tensile modulus can reach 3.4GPa at the highest.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted equally without departing from the spirit and scope of the technical solution of the present invention.
Claims (11)
1. A diamine monomer, characterized in that the diamine monomer has a structural formula selected from the group consisting of M-2~M-15:
2. a process for the preparation of the diamine monomer as described in claim 1, wherein the process comprises the steps of:
reacting a compound with a structural formula I with a compound with a structural formula II through Suzuki-Miyaura reaction to obtain the diamine monomer;
or reacting a compound of a structural formula III with a compound of a structural formula IV through a Suzuki-Miyaura reaction to obtain the diamine monomer;
in the structural formulas I-IV:
each of R1-R4 is independently selected from methyl, hydrogen atom;
x is selected from Cl, br and I;
the Y is-B (OH) 2 Or (b)
；
The Suzuki-Miyaura reaction is carried out in the presence of a metallic palladium catalyst, a solvent and an alkaline solution.
3. The method for producing diamine monomer as described in claim 2, wherein the metallic palladium catalyst in the Suzuki-Miyaura reaction is Pd (PPh 3 ) 4 、PdCl 2 、PdCl 2 (dppf)、Pd(OAc) 2 、Pd(PPh 3 ) 2 Cl 2 、PdCl 2 At least one of (dtbpf).
4. The preparation method according to claim 2, wherein the solvent in the Suzuki-Miyaura reaction is at least one of tetrahydrofuran, dioxane, N-dimethylformamide, toluene and methanol.
5. The preparation method according to claim 2, wherein the alkaline solution in the Suzuki-Miyaura reaction is KOH, naOH, cs 2 CO 3 、K 2 CO 3 、Na 2 CO 3 、NaHCO 3 、K 3 PO 4 At least one of CsF aqueous solution.
6. The method according to claim 5, wherein the concentration of the alkaline solution is 2 to 10mol/L.
7. The production method according to any one of claims 2 to 6, wherein the temperature of the Suzuki-Miyaura reaction is 60 to 110 ℃, and the Suzuki-Miyaura reaction is carried out in an inert atmosphere.
8. The method of claim 7, wherein the inert atmosphere is argon or nitrogen.
9. Use of the diamine monomer of claim 1 for preparing polyimide.
10. A polyimide film prepared from the diamine monomer of claim 1.
11. The polyimide film of claim 10, wherein the polyimide film is prepared by the following method:
(1) Mixing at least one of the diamine monomers according to claim 1 with dianhydride monomer, and carrying out homopolymerization or copolymerization reaction in a polar aprotic solvent or a phenolic solvent to obtain a polyamic acid solution or a polyimide solution;
(2) And (3) curing the polyamic acid solution or polyimide solution obtained in the step (1) to obtain the polyimide film.
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