TW202305035A - Alicyclic dianhydride monomers and its manufacturing method and application - Google Patents

Abstract

The present invention relates to an alicyclic dianhydride monomer with alkyl substitution on its double bond and a polyimide synthesized using the alicyclic dianhydride monomer, wherein the alicyclic dianhydride monomer is synthesized by Diels-Alder reaction and bromination reaction with the starting materials of maleic anhydride and alkyl-substituted diene. The synthesized polyimide polymer has a higher thermal stability, yellowing resistance at high temperature, better optical transparency and excellent solubility and is suitable for use in flexible display or other optical and electronic manufacturing processes.

Description

Alicyclic dianhydride monomer and its production method and application

The present invention relates to a kind of alicyclic dianhydride monomer and polyimide synthesized therefrom, its production method and application, especially to an alkyl-substituted alicyclic dianhydride monomer and polyimide synthesized therefrom, its Manufacturing methods and applications.

Polyimide is a polymer material with excellent thermal properties, excellent mechanical properties, radiation resistance, excellent dielectric properties, and high stability, so it is widely used in industries, such as semiconductor industry, automobile industry, optoelectronic industry, Biomedical materials and communication materials and other industries. With the development of the optoelectronic industry, polyimide has also become an excellent material for liquid crystal displays, flexible screens, and dielectric layers.

Traditional aromatic polyimides are usually colored and cannot be used to prepare colorless and transparent optical films. Alicyclic polyimides have lower charge transfer forces in the structure, and the prepared films are more complex than aromatic polyimides. Amine is a more suitable material because of its better light transmission and colorless properties.

However, because the synthesis process of alicyclic monomers is easy to produce isomers and other by-products, it is difficult to separate, purify and determine the configuration of the compound, resulting in the limitation of the type of alicyclic polyimide monomers. In view of this, the development of monomers that are easy to synthesize and purify and can be used to synthesize polyimides with excellent light-transmitting properties has become an urgent goal in the industry.

式(I) 其中R ₁係C _1-4烷基，R ₂係氫或C _1-4烷基。 The present invention provides a kind of alicyclic dianhydride monomer in the first aspect, it is represented by formula (I),

Formula (I) wherein R ₁ is C _1-4 alkyl, R ₂ is hydrogen or C _1-4 alkyl.

In the second aspect, the present invention provides a method for producing an alicyclic dianhydride monomer, comprising the following steps: using maleic anhydride and a diene substituted by at least one alkyl group to carry out Diels-Alder reaction; adding bromine water for bromination; and adding maleic anhydride to produce the cycloaliphatic dianhydride monomer.

In a third aspect, the present invention provides an alicyclic polyimide, which is formed by polymerizing at least the alicyclic dianhydride monomer and diamine monomer of the present invention.

According to the fourth aspect, the present invention provides an optical film made by at least using the alicyclic dianhydride monomer of the present invention.

The alicyclic diacid anhydride monomer system with alkyl substitution on the double bond provided by the present invention uses maleic anhydride (Maleic Anhydride, MA) and alkyl substituted diene (Diene) as starting materials, and after di It is synthesized by Diels-Alder reaction and bromination reaction. Compared with BTA, which is a common commercial product, this new type of alicyclic dianhydride monomer has higher thermal stability and high temperature anti-yellowing ability of polyimide polymer, which is suitable for flexible displays or other optical It is more competitive in the electronic manufacturing process, and also has better optical transparency and excellent solubility, and has good performance in the manufacturing process and application of polymer solutions, films, and plates.

Other technical contents, features and effects of the present invention will be clearly presented in the following detailed description of preferred embodiments with reference to the drawings.

式(I) 其中R ₁係C _1-4烷基，R ₂係氫或C _1-4烷基。 The embodiment of the present invention provides an alicyclic dianhydride monomer represented by formula (I),

Formula (I) wherein R ₁ is C _1-4 alkyl, R ₂ is hydrogen or C _1-4 alkyl.

或

。 In a specific embodiment, the cycloaliphatic dianhydride monomer of the present invention is

or

.

An embodiment of the present invention provides a method for producing an alicyclic dianhydride monomer, comprising the following steps: using maleic anhydride and a diene substituted by at least one alkyl group to perform a Diels-Alder reaction; adding bromine water performing a bromination reaction; and adding maleic anhydride to produce the cycloaliphatic dianhydride monomer.

In one embodiment, the molar ratio of the maleic anhydride to the diene is between about 1:1 and about 1:2. Depending on the boiling point of the different dienes and their reactivity with maleic anhydride, the number of moles of diene to be added exceeds the number of moles of maleic anhydride, such as, but not limited to, maleic anhydride with diene The molar ratio is about 1:1, about 1:1.1, about 1:1.2, about 1:1.3, about 1:1.4, about 1:1.5, about 1:1.6, about 1:1.7, about 1:1.8, About 1:1.9 or about 1:2.

In one embodiment, the diene is substituted with one or two alkyl groups, and the alkyl group is C _1-4 alkyl.

。 In a specific embodiment, when the diene is isoprene, the alicyclic dianhydride monomer is

.

。 In a specific embodiment, when the diene is dimethylbutadiene, the alicyclic dianhydride monomer is

.

An embodiment of the present invention provides an alicyclic polyimide, which is formed by polymerizing at least an alicyclic dianhydride monomer and a diamine monomer in claim 1.

In a specific embodiment, the cycloaliphatic polyimide is obtained by polymerizing the cycloaliphatic dianhydride monomer and diamine monomer in an equimolar ratio of Claim 1.

In a specific embodiment, the alicyclic polyimide is polymerized from the alicyclic dianhydride monomer of claim 1 together with other dianhydride monomers and diamine monomers. Other dianhydride monomers may include, but are not limited to: bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, trimellitic anhydride, 4-aminophthalic anhydride anhydride.

In a specific embodiment, the diamine monomer includes aromatic diamine and aliphatic diamine.

(MBCHA)、

(M-MBCHA)、

(t-CHDA)、

(NBDA)、

(IPDA)、

(4,4’-ODA)、

(3,4’-ODA)、

(TFODA)、

(TFMB)、

(1,4,4-APB)、

(1,3,4-APB)、

(BAPS)、

(BAPP)及

(HFBAPP)。 In a specific embodiment, the diamine monomer includes but is not limited to:

(MBCHA),

(M-MBCHA),

(t-CHDA),

(NBDA),

(IPDA),

(4,4'-ODA),

(3,4'-ODA),

(TFODA),

(TFMB),

(1,4,4-APB),

(1,3,4-APB),

(BAPS),

(BAPP) and

(HFBAPP).

、

、

或

。其中n是大於1的整數，依照不同的聚合條件，n可以為約1~500之整數。 In a specific embodiment, the cycloaliphatic polyimide is

,

,

or

. Wherein n is an integer greater than 1, and n can be an integer of about 1-500 according to different polymerization conditions.

An embodiment of the present invention provides an optical film made of at least the cycloaliphatic dianhydride monomer of claim 1.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.

As used herein, the articles "a", "an" and "any" refer to one or more than one (ie, at least one) of the grammatical items of the item. For example, "an element" means one element or more than one element.

As used herein, the term "about", "approximately" or "approximately" means that the stated value or range is within 20%, preferably within 10%, and more preferably within 5%. Numerical quantities provided herein are approximations and are intended to be inferred if the terms "about", "approximately" or "approximately" are not used.

As used herein, the term "C _1-4 alkyl" refers to a straight or branched alkyl chain having one to four carbon atoms, the molecular formula is C _n H _2n+1 , and n is 1-4.

As used herein, the term "alkyl-substituted diene" refers to a diene optionally substituted with 1 to 2 substituents, which may be C _1-4 alkyl.

As used herein, the term "room temperature" or "normal temperature", unless otherwise specified, refers to any temperature range between 18 and 28 ^° C.

The invention is further illustrated by the following examples, which are provided for purposes of illustration and not limitation. Those of skill in the art should, in light of the present disclosure, appreciate that many changes can be made in the specific embodiments which are disclosed and still obtain a like or similar result without departing from the spirit and scope of the invention.

The 1 H nuclear magnetic resonance spectrum ( ¹ H nuclear magnetic resonance spectrum) used in the identification of compounds in this paper, the nuclear magnetic resonance instrument brand: Bruker AVIII HD-600. The brand of X-ray single crystal diffraction instrument used to identify the compound in this case: Bruker D8 Venture IuS 3.0 Dual source. The brand of mass spectrometer used to identify the compound in this case: JEOL JMS-700. The identification unit is the Center for the Use of Precious Instruments of National Normal University, Taipei, Taiwan.

Example 1: Alkyl-substituted alicyclic dianhydrides -MBTA Monomer preparation and properties

Diels – Alder reaction step yields compound 2a (MAIP) : rac (3aR,7aS)-3a,4,7,7a-tetrahydro-5-methylisobenzofuran-1,3-di Ketones (Racemic (3aR,7aS)-3a,4,7,7a-tetrahydro-5-methylisobenzofuran-1,3-dione)

7.5430 g (76.92 mmol) of maleic anhydride (MA) and a small amount of inhibitor 2,6-dibutyl-p-cresol (BHT) were added to a 350 mL pressure bottle containing magnet stirring, and the gas in the reactor was replaced with nitrogen, Then, 15 mL of isoprene (IP) (149.96 mmol, density of isoprene is 0.681 g/cm ³ ) was drawn into the reactor with a long needle, and the temperature was slowly raised to 60°C, and the reaction was vigorously stirred at this temperature 3 Hours, this reaction is exothermic.

、

。 After the exothermic reaction is completed, slowly lower to room temperature, quickly open the lid of the pressure bottle and add about 50mL of hexane (Hexane), then vigorously stir in an ice bath to precipitate a white solid powder, and then pump it under the ice bath temperature (0°C) The white solid was collected by filtration, and the surface of the white solid was washed with a little glacial hexane. The obtained white solid was dried in a vacuum oven at room temperature or below 40°C for 12 hours to obtain 12.6534 g of white solid with a yield of 98.99%. The chemical formula (enantiomer) of compound 2a is as follows:

,

.

Compound 2a was identified using proton NMR spectroscopy as shown in Figure 2a. ¹ H NMR (600MHz, CDCl ₃ , δ, ppm): 5.63 (m, 1H), 3.39 (ddd, J ₁ =10.0 Hz, J ₂ =7.3 Hz, J ₃ = 2.9 Hz, 1H), 3.32 (m, 1H), 2.58 (m, 1H), 2.50 (dd, J ₁ = 15.6, J ₂ = 2.8 Hz, 1H), 2.26 (m, 2H), 1.77 (d, J=0.8 Hz, 3H), s is single peak, d is a doublet, t is a triplet, m is a multiplet, and the total peak areas of a, b, c, d, e, gh, f are respectively 1.000, 1.020, 1.016, 1.086, 1.066, 2.150, 3.170. In addition, as shown in Figure 2b, it is the stereo configuration calculated from the single crystal X-ray structure data of compound 2a obtained by using an X-ray diffractometer.

The bromination step yields compound 3a (MAIPBr) : rac (3aS,5R,6R,7aR)-5,6-dibromo-tetrahydro-6-methylisobenzofuran-1,3-dione (Racemic (3aS,5R,6R,7aR)-5,6-dibromo-hexahydro-6-methylisobenzofuran-1,3-dione)

Take 11.9894 g (72.15 mmol) MAIP and put it into a 250 mL three-neck flask with magnetic stirring and feeding tube, add 150 mL of diethyl ether to dissolve, and then put it in an ice bath to prepare an aqueous solution of sodium sulfite for later use. Use a long needle to draw 7.5 mL (145.62 mmol, Br ₂ Density is 3.1028g/cm ³ ) into the feeding tube and quickly inserted into the aqueous solution of sodium sulfite for cleaning, then slowly drop bromine water at a rate of about 1 s/drop into the reactor that has reached the temperature equilibrium of the ice bath and stir vigorously. The reaction was carried out for 4 hours.

、

、 異構物(b)及其鏡像異構物

、

。 After the reaction is completed, extract with ether/sodium sulfite aqueous solution until the water layer is weakly alkaline, then extract with saturated saline solution until the water layer is neutral, then take the organic solution layer, add anhydrous magnesium sulfate, filter by suction, and concentrate under reduced pressure (not exceeding 50°C) to obtain a light yellow ointment after removing the solvent, ice bath and add a large amount of hexane when the solvent is not completely removed, and shake it with ultrasonic waves overnight to precipitate a white solid (there will be HBr and other Unknown products of bromine are released in the form of smoke, special attention is required). The white solid was collected by suction filtration, and dried in a vacuum oven at room temperature for 12 hours to obtain 14.9066 g of white solid (unpurified yield 63.4%). The chemical formula of compound 3a is as follows: Isomer (a) and its mirror-image isomer

,

, isomer (b) and its mirror image isomer

,

.

As shown in Figure 3, compound 3a was identified using proton magnetic resonance spectroscopy: isomer (a) and isomer (b), wherein a, b, cd, e, f, g, hi, j, k, l, The total peak areas of m, n, o and p are 1.000, 1.103, 4.024, 1.255, 1.148, 1.329, 2.129, 1.264, 1.264, 1.388, 1.598, (0.262, 1.469), 2.723 and 2.925 respectively. ¹ H NMR (600MHz, CDCl ₃ , δ, ppm):

(a) 4.60 (dd, J ₁ = 7.1 Hz, J ₂ = 4.0 Hz,1H), 3.50 (s, 1H), 3.30 (t, J= 8.6 Hz, 1H), 3.00 (m, 1H), 2.87 ( m,1H), 2.63 (ddd, J ₁ = 15.4 Hz, J ₂ = 7.9 Hz, J ₃ = 3.4 Hz, 1H), 2.51 (dd, J ₁ = 16.2 Hz, J ₂ = 8.3 Hz, 1H), 2.04 (s,3H).

(b) 4.58 (m, 1H), 3.50 (m, 1H), 3.23 (t, J= 8.7 Hz, 1H), 3.08 (dtd, J ₁ =13.4 Hz, J ₂ = 8. Hz, J ₃ = 4.5 Hz, 1H), 2.98 (m, 1H), 2.48 (m, 1H), 2.35 (m, 1H), 2.03 (s, 3H).

Then add maleic anhydride to produce compound 4a (MBTA) : bicyclo[2.2.2]oct-7-ene-2-exo, 3-exo, 5-exo, 6-exo, 7-methyltetracarboxy 2,3 :5,6-dianhydride (Bicyclo[2.2.2]oct-7-ene-2-exo, 3-exo, 5-exo, 6-exo, 7-methyltetracarboxylic 2,3:5,6-Dianhydride)

。 Take 5.9849 g of unpurified white solid MAIPBr and add it to a three-neck flask with magnetic stirring, replace the air in the reactor with nitrogen, then add 7.2510 g (73.95 mmol) of maleic anhydride, raise the temperature to 200 ° C and vigorously stir for 24 hours. After the reaction was completed, it was lowered to about 100° C., and acetone was added to reflux for 1 hour and vigorously stirred. Finally, it was cooled to room temperature, and the upper layer of off-white solid was obtained by suction and filtration, and dried in a vacuum oven at 80° C. for 12 hours to obtain 2.2416 g of off-white solid (crude yield : 46.56%). The chemical formula of compound 4a is as follows:

.

Compound 4a was identified using proton NMR spectroscopy as shown in Figure 4a. ¹ H NMR (600MHz, DMSO, δ, ppm): 5.95 (m, 1H), 3.63 (dd, J ₁ = 8.6 Hz, J ₂ = 3.3 Hz, 2H), 3.56 (dd, J ₁ = 8.6 Hz, J ₂ = 3.1 Hz, 2H), 3.39 (dt, J ₁ = 6.1 Hz, J ₂ = 3.1 Hz, 1H), 3.29 (td, J ₁ = 3.3 Hz, J ₂ = 1.7 Hz, 1H), 1.65 (d, J= 1.7 Hz, 3H), where the total peak areas of a, b, c, d, e and f are 1.000, 2.020, 2.025, 1.025, 1.097 and 3.044 respectively. As shown in Fig. 4b, it is the stereoconfiguration calculated from the single crystal X-ray structure data of compound 4a using X-ray diffractometer.

Example 2: Alkyl-substituted alicyclic dianhydrides -DMBTA Monomer preparation and properties

Diels – Alder reaction step yields compound 2b (MADMBD) : (3aS,7aR)-3a,4,7,7a-tetrahydro-5,6-dimethylisobenzofuran-1,3-di Ketone ((3aS,7aR)-3a,4,7,7a-tetrahydro-5,6-dimethylisobenzofuran-1,3-dione)

。 Take 7.1736 g (73.16 mmol) of maleic anhydride (MA) and a little inhibitor 2,6-dibutyl-p-cresol into a 350 mL pressure bottle containing magnetic stirring, and replace the gas in the reactor with nitrogen, and then Draw 10 mL of dimethyl butadiene (DMBD) (87.92 mmol, density of dimethyl butadiene is 0.7222g/cm ³ ) into the reactor with a long needle, slowly raise the temperature to 30°C and then vigorously The reaction was stirred for 0.5 hours, and the reaction in this step was an exothermic reaction. After the exothermic reaction, 12.9589 g of a white solid was precipitated using hexane according to the method of compound 2a, and the yield was 98.30%. The chemical formula of compound 2b is as follows:

.

Compound 2b was identified using proton NMR spectroscopy as shown in Figure 5a. ¹ H NMR (600MHz, CDCl ₃ , δ, ppm): 3.33 (m, 2H), 2.48 (d, J= 15.1 Hz, 2H), 2.28 (m, 2H), 1.72 (d, J= 1.1 Hz, 6H ), the total peak areas of a, b, c, and d are 1.000, 1.096, 1.122, and 3.251, respectively. As shown in Figure 5b, it is the stereo configuration calculated from the single crystal X-ray structure data of compound 2b obtained by using X-ray diffractometer.

The bromination step yields compound 3b (MADMBDBr) : rac (3aR,5S,6S,7aS)-5,6-dibromo-tetrahydro-5,6-dimethylisobenzofuran-1,3 -Diketone (Racemic (3aR,5S,6S,7aS)-5,6-dibromo-hexahydro-5,6-dimethylisobenzofuran-1,3-dione)

Take 11.3958 g (63.24 mmol) of MADMBD and add it to a 250 mL three-neck flask with magnetic stirring and feeding tube, add 400 mL of diethyl ether to dissolve, and then put it in an ice bath to prepare an aqueous solution of sodium sulfite for later use. Use a long needle to draw 6.5 mL (126.20 mmol, Br ₂ Density is 3.1028g/cm3) into the feeding tube and quickly inserted into the aqueous solution of sodium sulfite for cleaning, then slowly drop bromine water at a rate of about 1 s/drop into the reactor that has reached the temperature balance of the ice bath and stir vigorously. React for 4 hours.

、

。 After the reaction was completed, the white solid in the upper layer was collected by air filtration, and the solid surface was washed with glacial ether, and the solid was dried in a vacuum oven at 40° C. for 12 hours to obtain 13.6732 g of white solid (yield 63.59%). The chemical formula (enantiomer) of compound 3b is as follows:

,

.

Compound 3b was identified using proton NMR spectroscopy as shown in Figure 6a. ¹ H NMR (600MHz, CDCl ₃ , δ, ppm): 3.53 (ddd, J ₁ = 11.1 Hz, J ₂ =9.5 Hz, J ₃ = 8.4 Hz, 1H), 3.26 (t, J= 9.1 Hz, 1H) , 2.94 (d, J=16.0 Hz, 1H), 2.70 (m, 1H), 2.63 (dd, J ₁ =15.3 Hz, J ₂ =11.1 Hz, 1H), 2.55 (dd, J ₁ = 15.3 Hz, J ₂ = 8.4 Hz, 1H), 2.03 (s, 3H), 2.02 (s, 3H), where the total peak areas of a, b, c, d, e, f, g and h are respectively 1.000, 0.999, 1.017, 1.040, 1.024, 1.030, 2.953 and 3.038. As shown in Figure 6b, it is the stereo configuration calculated from the single crystal X-ray structure data of compound 3b obtained by using X-ray diffractometer.

Then add maleic anhydride to produce compound 4b (DMBTA) : bicyclo[2.2.2]oct-7-ene-2-exo, 3-exo, 5-exo, 6-exo, 7, 8-dimethyltetracarboxy 2,3:5,6-dianhydride (Bicyclo[2.2.2]oct - 7 -ene - 2-exo, 3-exo, 5-exo, 6-exo, 7, 8- dimethyltetracarboxylic 2,3:5, 6-Dianhydride)

。 Take 13.5449 g (39.84 mmol) of MADMBDBr and add it to a three-necked flask with magnetic stirring, replace the air in the reactor with nitrogen, then add 11.7010 g (119.33 mmol) of maleic anhydride, heat up to 200 °C and stir vigorously for 15 hours. After completion, it was lowered to about 100°C, acetone was added to reflux for 1 hour and vigorously stirred, and finally lowered to room temperature, the upper layer of off-white solid was obtained by suction filtration, and dried in a vacuum oven at 80°C for 12 hours to obtain 7.6534 g of off-white solid (crude yield: 69.55%). The chemical formula of compound 4b is as follows:

.

Compound 4b was identified using proton NMR spectroscopy as shown in Figure 7a. ¹ H NMR (600MHz, DMSO, δ, ppm): 3.57 (m, 4H), 3.23 (m, 2H), 1.59 (s, 6H). Among them, the total peak areas of a, b and c are 1.000, 2.005 and 3.006 respectively. As shown in Figure 7b, it is the stereo configuration calculated from the single crystal X-ray structure data of compound 4b obtained by using X-ray diffractometer. EIMS (m/z): Calcd. for C ₁₄ H ₁₂ O ₆ 276.1; found 276.1 [M]+. _{Anal. Calcd} . for _C14H12O6 : C, 60.87; H, 4.38; O, 34.75; Found: C, 60.14; H, 4.92; O, 34.94.

Embodiment three: with embodiment two DMBTA Cycloaliphatic dianhydride and ODA One-step polymerization of polyimides for aromatic diamines PI-4b-a

，其中n為1~500之整數，例如166。另外，實施例一之MBTA作為脂環族二酸酐與ODA為芳香族二胺亦可以上述方法聚合成聚醯亞胺PI-4a-a，其化學式如下：

，其中n為1~500之整數，例如255。 Please refer to the polymerization equation of polyimide in Figure 8, install a 25 mL three-necked bottle with nitrogen, a condenser, and mechanical stirring, and dry 0.5000 g (2.50 mmol) of 4,4'-diaminodiphenyl ether ( ODA) into the three-necked flask, add 5 mL of m-cresol (m-cresol) distilled with phosphorus pentoxide to remove water, stir slowly at room temperature until the solid is completely dissolved, weigh 0.6898 g (2.50 mmol) DMBTA was added to the reaction solution, and then all the anhydrides were washed into the reaction solution with 6 mL of m-cresol distilled from phosphorus pentoxide to make the total solid content of the reaction system 10% (w/v). To 80°C and keep stirring at this temperature to completely dissolve the solid, then add 0.1 mL of catalyst isoquinoline, raise the reaction temperature to 200°C and stir rapidly. After the reaction was completed, it was slowly lowered to room temperature, and the solution was poured into methanol to precipitate, and the white filamentous solid on the filter cake was collected by filtration, extracted with ethanol by Soxhlet, and dried in a vacuum oven at 200°C to obtain a white solid (PI-4b- a) 1.1589 g, productive rate 97.40%, its chemical formula is as follows:

, where n is an integer ranging from 1 to 500, such as 166. In addition, MBTA in Example 1 as an alicyclic dianhydride and ODA as an aromatic diamine can also be polymerized into polyimide PI-4a-a by the above method, and its chemical formula is as follows:

, where n is an integer from 1 to 500, such as 255.

Embodiment four: with embodiment two DMBTA Cycloaliphatic dianhydride and TFMB One-step polymerization of polyimides for aromatic diamines PI-4b-b

，其中n為1~500之整數，例如113。另外，實施例一之MBTA作為脂環族二酸酐與TFMB為芳香族二胺亦可以上述方法聚合成聚醯亞胺PI-4a-b，其化學式如下：

，其中n為1~500之整數，例如82。 Please refer to the polymerization equation of polyimide in Figure 8, install a 25 mL three-necked bottle with nitrogen, a condenser, and mechanical stirring, and dry 0.5796 g (1.81 mmol) of 2,2'-bis(trifluoromethyl ) benzidine (TFMB) into the three-neck flask, add 5 mL m-cresol distilled with phosphorus pentoxide to remove water, stir slowly at room temperature until the solid is completely dissolved, weigh 0.5000 g (1.81 mmol ) DMBTA is added in the reaction solution, and then with the m-cresol 5mL after distilling of phosphorus pentoxide dewatering, all anhydrides are washed into the reaction solution to make the total solid content of the reaction system about 10% (w/v), until the temperature rises to 100°C and keep stirring at this temperature to completely dissolve the solid, then add 0.1 mL of catalyst isoquinoline, raise the reaction temperature to 200°C and stir rapidly. After the reaction was completed, it was slowly lowered to room temperature, and the solution was poured into methanol to precipitate, and the white powdery solid on the filter cake was collected by filtration, extracted with ethanol and Soxhlet, and dried in a vacuum oven at 200°C to obtain a white solid (PI-4b- b) 0.6879 g, productive rate 63.72%, its chemical formula is as follows:

, where n is an integer from 1 to 500, such as 113. In addition, MBTA in Example 1 as an alicyclic dianhydride and TFMB as an aromatic diamine can also be polymerized into polyimide PI-4a-b by the above method, and its chemical formula is as follows:

, where n is an integer ranging from 1 to 500, such as 82.

Example 5: Preparation of polymer film and other tests with the polyimide prepared in this paper

The aforementioned polyimide polymer was dissolved in dimethylacetamide (DMAc) with a solid content of about 4% (w/v), filtered through a 0.45 μm Teflon filter head, and poured into isopropanol On the surface-treated petri dish, after defoaming, bake in a circulating oven at 60°C, 6 hours → 160°C, 3 hours → 100°C, 0.5 hour → 60°C, 0.5 hour, and gently remove the film from the dish Next, dry in a vacuum oven at 200°C to ensure that the solvent is completely removed, and a transparent polyimide polymer film is obtained, with a film thickness of about 10-30 μm.

Intrinsic Viscosity and Molecular Weight Test of High Molecular Polymers

Table 1 sequentially shows the intrinsic viscosity (η), weight-average molecular weight (Mw), number-average molecular weight (Mn), and molecular weight distribution index (Polydispersity index, PDI) of the four polyimide polymers of Embodiment 3 and Embodiment 4 ). Different polyimide polymers were dissolved in N-methylpyrrolidone (NMP) at a concentration of about 0.5 g/dL, and the intrinsic viscosities of the four polyimide polymers were measured at 35°C with an Oswald viscometer n . The weight-average molecular weight and number-average molecular weight of polyimide polymers were determined by gel permeation chromatography (GPC) calibrated against polystyrene standards using dimethylacetamide (DMAc) as a solvent The measurement was carried out, and the molecular weight distribution index (Mw/Mn) was obtained. Table 1 sample η (dL/g) Mw (kDa) Mn (kDa) PDI Yield 1 PI-MBTA/ODA 0.91 17.1 10.9 1.57 93.96 2 PI-MBTA/TFMB 0.47 6.8 5.0 1.36 71.48 3 PI-DMBTA/ODA 0.54 13.7 9.1 1.50 97.40 4 PI-DMBTA/TFMB 0.43 6.3 4.6 1.37 63.72

Solubility Test of High Molecular Polymers

Table 2 sequentially shows the solubility of the four polyimide polymers in 20 mg of Example 3 and Example 4 after stirring in 1 mL of solvent, such as m-cresol, γ-butyrolactone (GBL), N- Methylpyrrolidone, dimethylacetamide, dimethylsulfoxide (DMSO), tetrahydrofuran, chloroform (CHCl ₃ ), acetone. ++ : soluble at room temperature; + : soluble in heating; +- : partially soluble in heating; - : insoluble in heating. It can be seen that polyimide PI-MBTA/TFMB and PI-DMMBTA/TFMB exhibit excellent solubility, and can be dissolved in all polar aprotic solvents and common solvents such as tetrahydrofuran, chloroform, and acetone at room temperature. Table 2 sample solvent m-cresol GBL NMP DMAc DMSO THF CHCl ₃ Acetone PI- MBTA /ODA ++ ++ ++ ++ ++ +- +- - PI-MBTA /TFMB ++ ++ ++ ++ ++ ++ ++ ++ PI- DMBTA /ODA ++ ++ ++ ++ ++ +- +- - PI-DMMBTA /TFMB ++ ++ ++ ++ ++ ++ ++ ++

Thermal Properties of Polyimide Films

Table 3 shows the coefficient of thermal expansion (CTE), glass transition temperature (Tg) and thermal decomposition temperature ( Td _5% , Td _10% ). The coefficient of thermal expansion and glass transition temperature of the polyimide film were measured using a modulated dynamic thermomechanical analyzer Waters TA (Q-400). Calculate the coefficient of thermal expansion based on the strain when the sample is heated from 50°C to 150°C at 10°C/min when 0.05 Newton is applied to the sample, and its unit is μm m ^-1 °C ^-1 . Use a thermogravimetric loss analyzer TA (Q-500) to measure the thermal decomposition temperature, raise the temperature to 800°C at 10°C/min, and measure the temperature when losing 5% of the sample weight and the temperature when losing 10% of the sample weight to understand The thermal stability of the sample. It can be found that the thermal stability (Td _5% ) of the polyimide polymer of the embodiment of the present invention is higher than the 415°C of the conventional polyimide polymer PI-BTA/ODA (References: Sumio Itamura, Masao Yamada, Shinji Tamura , Toshihiko Matsumoto, and Toshikazu Kurosaki. Soluble Polyimides with Polyalicyclic Structure. 1. Polyimides from Bicyclo[2.2.2]oct-7-ene-2-exo, 3-exo,5-exo,-6-exo-tetracarboxylic 2, 3:5,6-Dianhydrides. Macromolecules 1993, 26, 3490-3493) increased by 7~32°C. table 3 sample CTE Tg (℃) Td _5% (℃) Td _10% (℃) PI-MBTA /ODA 41.3 398 422.6 429.0 PI-MBTA /TFMB 34.7 403 437.3 442.2 PI-DMBTA /ODA 41.8 417 444.8 453.9 PI-DMBTA /TFMB 36.2 372 447.4 453.2

Optical Properties of Polyimide Films

As shown in Figure 9, it shows the light transmittance of the polyimide films of the four polyimide polymers of Example 3 and Example 4 at different wavelengths, and the light transmittance of wavelengths exceeding 400 nm is higher than 80 %, even up to 90%, which means it has extremely high transparency and is a good material for optical products. In particular, the transmittance of the polyimide film PI-MBTA/ODA at wavelengths less than 400nm is greater than that of the other three samples. Table 4 sequentially shows the polyimide film thickness and optical properties of the four polyimide polymers of Example 3 and Example 4. For example, the wavelength of light with a transmittance of 80% (λ _80% ), the cut-off wavelength of light with a transmittance below 1% (λ _{cut -off} ), and the transmittance at a wavelength of 400nm (T ₄₀₀ ). The cut-off wavelength (λ _{cut off} ) is 281~292nm, and the light transmittance (T ₄₀₀ ) at 400nm wavelength is between 83~87%, with extremely high transparency. Table 4 sample thickness λ _80% λ _{cut -off} T ₄₀₀ (%) PI-MBTA /ODA 10 μm 340 nm 281 nm 86 PI-MBTA /TFMB 12 μm 362 nm 291 nm 87 PI-DMBTA /ODA 20μm 377 nm 284 nm 83 PI-DMBTA /TFMB 20μm 360 nm 292 nm 86

Table 5 shows that at room temperature, under 300°C atmospheric environment and 300°C nitrogen environment, the polyimide films of the four polyimide polymers in Example 3 and Example 4 with a film thickness of 10 μm Synthesized with bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride (BTA or BCDA) and diamine ODA with a thickness of 10 μm on the market The light transmittance (T ₄₀₀ ) at a wavelength of 400nm compared with PI-BTA/ODA of cycloaliphatic polyimide film. Table 5 sample deal with thickness T ₄₀₀ (%) PI-BTA/ODA at room temperature 10 μm 85.52 PI-BTA/ODA Under 300℃ atmospheric environment, 30 minutes 10 μm 75.53 PI-BTA/ODA At 300°C under nitrogen atmosphere, 30 minutes 10 μm 75.20 PI-MBTA/ODA at room temperature 10 μm 85.92 PI-MBTA/ODA Under 300℃ atmospheric environment, 30 minutes 10 μm 77.78 PI-MBTA/ODA At 300°C under nitrogen atmosphere, 30 minutes 10 μm 82.40 PI-MBTA/TFMB at room temperature 12 μm 86.40 PI-MBTA/TFMB Under 300℃ atmospheric environment, 30 minutes 12 μm 59.69 PI-MBTA/TFMB At 300°C under nitrogen atmosphere, 30 minutes 12 μm 69.24 PI-DMBTA/ODA at room temperature 20μm 83.12 PI-DMBTA/ODA Under 300℃ atmospheric environment, 30 minutes 20μm 53.77 PI-DMBTA/ODA At 300°C under nitrogen atmosphere, 30 minutes 20μm 81.77 PI-DMBTA/TFMB at room temperature 20μm 86.29 PI-DMBTA/TFMB Under 300℃ atmospheric environment, 30 minutes 20μm 55.85 PI-DMBTA/TFMB At 300°C under nitrogen atmosphere, 30 minutes 20μm 83.57

As shown in Figure 10, based on the above results at room temperature and 300°C nitrogen environment, the polyimides of the four polyimide polymers in Example 3 and Example 4 were compared with commercially available alkyl-free substituted polyimides. Cycloaliphatic polyimide PI-BTA/ODA synthesized from bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride (BTA or BCDA) and diamine ODA compared to. At room temperature, the PI-MBTA/ODA of the present invention has better film light transmittance than the conventional PI-BTA/ODA. The polyimide of the present invention also has better anti-yellowing ability in the high-temperature process. Under the nitrogen environment of 300 ℃, the transparency (T _400% ) of the conventional PI-BTA/ODA is about 10% lower than that at normal temperature. , while the polyimides PI-4a-a and PI-4b-a of the present invention only decreased by 3.52% and 1.35%, respectively. In addition, the polyimide of the present invention also has better thermal stability and solubility, for example, the thermal stability (Td _5% ) is increased by 7~32°C.

The cycloaliphatic polyimide synthesized from the novel cycloaliphatic diacid anhydride monomer of the present invention has a thermal cracking temperature (Td _5% ) of 429.0~453.9°C and a coefficient of thermal expansion (CTE) of 34.7~41.8 ppm/K. The cut-off wavelength (λ _{cut off} ) of the film made of polyimide polymer PI-4a-a, PI-4a-b, PI-4b-a, PI-4b-b is 281~292nm, which has a very high Transparency, 400nm wavelength transmittance (T ₄₀₀ ) between 83~87%, and excellent solubility in polar aprotic solvents and some common solvents, it can be used in flexible displays or other optical and electronic processes. Performance.

The above detailed description is a specific description of a feasible embodiment of the present invention, but this embodiment is not used to limit the patent scope of the present invention, and any equivalent implementation or change that does not depart from the technical spirit of the present invention shall be included in In the patent scope of this case.

To sum up, the technical features disclosed in this case fully meet the requirements of novelty and advancement for statutory invention patents. I would like to file an application in accordance with the law. I urge your bureau to approve this invention patent application to encourage inventions. I am very grateful.

Fig. 1 is a schematic diagram of the synthetic route of the alicyclic dianhydride monomers of Example 1 and Example 2 of the present invention.

Fig. 2a and Fig. 2b are respectively the proton nuclear magnetic resonance spectrum and the X-ray single crystal diffraction molecular three-dimensional structure diagram of compound 2a in Example 1 of the present invention.

Fig. 3 is the proton nuclear magnetic resonance spectrum of compound 3a of Example 1 of the present invention.

Fig. 4a and Fig. 4b are respectively the hydrogen nuclear magnetic resonance spectrum and the X-ray single crystal diffraction molecular three-dimensional structure diagram of the compound 4a of the first embodiment of the present invention.

Figure 5a and Figure 5b are respectively the proton nuclear magnetic resonance spectrum and X-ray single crystal diffraction molecular three-dimensional structure diagram of compound 2b of Example 2 of the present invention.

Figure 6a and Figure 6b are respectively the proton nuclear magnetic resonance spectrum and X-ray single crystal diffraction molecular three-dimensional structure diagram of compound 3b of Example 2 of the present invention.

Fig. 7a, Fig. 7b and Fig. 7c are respectively the proton nuclear magnetic resonance spectrum, X-ray single crystal diffraction molecular three-dimensional structure diagram and mass spectrum diagram of compound 4b of Example 2 of the present invention.

Fig. 8 is a schematic diagram of the synthetic route of the cycloaliphatic polyimides of Example 3 and Example 4 of the present invention.

FIG. 9 is a comparison chart of the optical properties of cycloaliphatic polyimides of Example 3 and Example 4 of the present invention.

FIG. 10 is a comparison chart of the optical properties of cycloaliphatic polyimides of Examples 3 and 4 of the present invention and conventional polyimides.

Claims (11)

A kind of cycloaliphatic dianhydride monomer, it is represented by formula (I),

Formula (I) wherein R ₁ is C _1-4 alkyl, R ₂ is hydrogen or C _1-4 alkyl. The cycloaliphatic diacid anhydride monomer as described in Claim 1, which is

or

. A method for producing an alicyclic dianhydride monomer, comprising the following steps: Diels-Alder reaction using maleic anhydride with a diene substituted with at least one alkyl group; adding bromine water for bromination reaction; and Maleic anhydride is added to yield the cycloaliphatic dianhydride monomer. The production method as described in claim 3, wherein the diene is substituted by one or two alkyl groups, and the alkyl group is a C _1-4 alkyl group. The production method as described in claim 4, wherein when the diene is isoprene, the alicyclic dianhydride monomer is

. The production method as described in claim 4, wherein when the diene is dimethylbutadiene, the alicyclic dianhydride monomer is

. An alicyclic polyimide, which is formed by polymerizing at least the alicyclic dianhydride monomer and diamine monomer of claim 1. The cycloaliphatic polyimide according to claim 7, wherein the diamine monomer comprises aromatic diamine and aliphatic diamine. The alicyclic polyimide as described in claim item 8, wherein the diamine monomer comprises:

,

,

,

,

,

,

,

,

,

,

,

,

and

. The cycloaliphatic polyimide as described in claim item 9, which is

,

,

or

. An optical film made of at least the cycloaliphatic dianhydride monomer of claim 1.

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