CN102532543A - Copolymerization hot-sealing polyimide and preparation method and application thereof - Google Patents

Abstract

(式i)The invention discloses a copolymerized polyimide as well as its preparation method and application. The general structural formula of the polymer is shown in formula i. The polymer is based on the aromatic dianhydride compound 2,3,3',4'-biphenyl tetra-acid dianhydride (abpda) and 2,3,3',4'-diphenyl ether tetra-acid dianhydride (aodpa) And aromatic diamine compounds as raw materials, prepared by chemical imidization method. By adjusting the ratio of abpda and aodpa, the regulation of heat resistance stability and heat sealing strength of the polyimide material shown in formula i can be realized. The material can be used as a coating or film in high-tech fields such as aerospace, optoelectronics, microelectronics and automobiles.

(formula i)

Description

Copolymerized heat-sealable polyimide and its preparation method and application

technical field

The invention belongs to the field of functional polyimide films, and relates to a copolymerized heat-sealable polyimide and its preparation method and application.

Background technique

Polyimide film has excellent comprehensive properties, including high heat resistance stability, high mechanical properties, high environmental stability, high dielectric properties, etc. It has a wide range of applications in high-tech industries such as aviation, aerospace, machinery, and microelectronics. Value. At present, due to the low free energy of the surface and the lack of polar substituent groups, the commercialized polyimide film has poor adhesion to the surface of substrates with high free energy (such as metals, ceramics, polymers). Poor (Lee K W, et al. Surface Modification of PMDA-ODA Polyimide: Surface Structure-adhesion Relationship, Macromolecules, 1990, 23: 2097-2100); even between polyimide films and polyimide films The problem of poor adhesion. Therefore, in order to improve its adhesion, it is usually necessary to activate the surface of the polyimide film. At present, the surface treatment technology of polyimide film mainly includes dry method (plasma) and wet method (alkali solution). However, these surface treatment processes will have a certain destructive effect on the surface of the film, thereby affecting its comprehensive performance. After the surface-activated polyimide film is coated with an adhesive layer such as fluorine-containing resin, acrylate or epoxy resin, it can be bonded to the surface of other substrates. At present, representative commercial polyimide film products coated with adhesive layer include Dupont's Kapton FN series products, Saint-Gobain's FluoroWrap FH series products, etc. However, since the heat resistance of the coated adhesive is worse than that of the polyimide film, and there are problems such as poor interfacial compatibility and thermal expansion coefficient mismatch between the polyimide film and the adhesive layer, it is obvious that The heat resistance of the polyimide film is reduced.

KJ系列产品以及日本宇部公司的

VT系列产品等。1994年，美国专利(US 5298331)公开了一类耐热性聚酰亚胺粘结树脂，可用于粘结聚酰亚胺薄膜与铜箔以形成柔性聚酰亚胺覆铜板材。该耐热聚酰亚胺粘结树脂由3，3′，4，4′-二苯醚四酸二酐(ODPA)与1，3-双(4-氨基苯氧基)苯通过缩聚+亚胺化反应形成；2003年，Yamaguchi等(J.Photopolym.Sci.Technol.，2003，16：233-236)报道了一种具有热封接性的聚酰亚胺复合薄膜。该复合薄膜是在聚酰亚胺基质薄膜(芯层)的两面分别挤出涂覆一层热塑性聚酰亚胺粘结层(表层)形成的三层夹层结构，芯层用基质薄膜由3，3′，4，4′-联苯四酸二酐(s-BPDA)与对苯二胺(PDA)通过缩聚+亚胺化反应形成，具有热膨胀系数低(12ppm/℃)、热收缩率小、尺寸稳定性好等特点。表层用热塑性聚酰亚胺粘结层树脂由s-BPDA、2，3，3′，4′-联苯四酸二酐(a-BPDA和1，3-双(4-氨基苯氧基)苯通过共聚+亚胺化反应得到；复合薄膜制作过程中采用了多层共挤出工艺方法，所形成的复合薄膜的芯层与表层间无明显的界面，彼此间无法剥离。In order to improve the heat resistance of the adhesive, some people have successfully developed a heat-resistant polyimide resin adhesive in recent years, which is coated on the surface of the polyimide film to form a bonding layer, which can significantly improve the performance of the polyimide resin. Thermal stability of imide film tie coats. At present, commercialized products include Dupont's

KJ series products and Japanese Ube company's

VT series products, etc. In 1994, US Patent (US 5298331) disclosed a heat-resistant polyimide bonding resin, which can be used to bond polyimide film and copper foil to form a flexible polyimide copper clad laminate. The heat-resistant polyimide bonding resin is composed of 3,3',4,4'-diphenyl ether tetra-acid dianhydride (ODPA) and 1,3-bis(4-aminophenoxy)benzene through polycondensation + sub- Formed by amination reaction; in 2003, Yamaguchi et al. (J. Photopolym. Sci. Technol., 2003, 16: 233-236) reported a polyimide composite film with heat sealing properties. The composite film is a three-layer sandwich structure formed by extruding and coating a layer of thermoplastic polyimide bonding layer (surface layer) on both sides of the polyimide matrix film (core layer). The matrix film for the core layer consists of 3, 3',4,4'-biphenyltetraacid dianhydride (s-BPDA) and p-phenylenediamine (PDA) are formed by polycondensation + imidization reaction, with low thermal expansion coefficient (12ppm/℃) and small thermal shrinkage , Good dimensional stability and so on. The thermoplastic polyimide adhesive layer resin for the surface layer is composed of s-BPDA, 2,3,3',4'-biphenyltetraacid dianhydride (a-BPDA and 1,3-bis(4-aminophenoxy) Benzene is obtained through copolymerization + imidization reaction; the multi-layer co-extrusion process is used in the production process of the composite film, and there is no obvious interface between the core layer and the surface layer of the formed composite film, and they cannot be peeled off from each other.

In 2008, Japan Space Development Agency (JAXA) Institute of Space Science (ISAS) successfully developed an intrinsic self-heating sealing polyimide film, which is composed of 2,3,3',4'-diphenyl Ether tetra-acid dianhydride (a-ODPA) and 4,4-diaminodiphenyl ether (4,4-ODA) are formed by polycondensation + imidization reaction, without the need to coat the surface with a polyimide adhesive layer, It has excellent self-heating sealing property. When the film is heated to a certain temperature, its modulus will drop rapidly to a certain level in a narrow temperature range, forming a resin with certain viscoelasticity, and polyimide film and polyimide film can be realized under pressure. Self-heating seal between. However, since the chemical structure of the reported intrinsic self-sealing polyimide film contains a large number of flexible ether bond segments, although it endows the film with excellent self-sealing property, it also significantly reduces the Glass transition temperature (T _g ) and heat resistance. Therefore, how to endow polyimide films with excellent self-heat sealing properties, while maintaining high T _g and heat resistance stability, as well as excellent dimensional stability, has become a problem of concern.

Contents of the invention

The object of the present invention is to provide a copolymerized heat-sealable polyimide and its preparation method and application.

The compound shown in the general formula of formula I structure provided by the present invention (that is, copolymerized polyimide),

(Formula I)

Formula II

In the general structural formula of formula I and formula II, Ar is selected from any one of the following groups:

In the general structural formula of formula I, m/n represents 2,3,3',4'-biphenyl tetraacid dianhydride (aBPDA) and 2,3,3',4'-diphenyl ether tetraacid dianhydride (aODPA) molar ratio, and m:n=0:100～100:0, preferably 40:60～80:20, and both m and n are not 0;

In the general structural formula of formula II, n is an integer of 0-100, n is not 0, preferably n is 30.

The compound described in the above formula I can be prepared according to the following methods provided by the present invention.

The compound described in the above formula II can be prepared according to the following methods provided by the present invention.

The method for preparing the above-mentioned compound provided by the present invention comprises the steps of: mixing aromatic diamine, aromatic dianhydride, 2,3,3', 4'-biphenyltetraacid dianhydride (aBPDA) and 2,3,3 ', 4'-diphenyl ether tetra-acid dianhydride (aODPA) is mixed evenly for polymerization reaction. After the reaction is completed to obtain a homogeneous solution, acetic anhydride and pyridine are added to it for chemical imidization reaction. After the reaction is completed, the described Compound shown in formula I;

Alternatively, the aromatic diamine is mixed with 2,3,3',4'-diphenyl ether tetra-acid dianhydride to carry out polymerization reaction, and after the reaction is completed to obtain a homogeneous solution, acetic anhydride and pyridine mixed Carry out the chemical imidization reaction uniformly, and the compound shown in the formula II is obtained after the reaction is completed.

In the above method, the aromatic diamines are all selected from 4,4'-diaminodiphenyl ether (4,4'-ODA), 3,4'-diaminodiphenyl ether (3,4'-ODA) , 1,4-bis(4-aminophenoxy)benzene (1,4,4-APB), 1,3-bis(4-aminophenoxy)benzene (1,3,4-APB), 1 , 3-bis(3-aminophenoxy)benzene (1,3,3-APB), 1,4-bis[(4-amino-2-trifluoromethyl)phenoxy]benzene (6FAPB), 2,2-bis[(4-aminophenoxy)phenyl]propane (BAPP), 2,2-bis[(4-aminophenoxy)phenyl]hexafluoropropane (BDAF), 2,2' - at least one of bistrifluoromethyl-4,4'-biphenylenediamine (TFDB).

In the method for preparing the compound shown in the formula I, the feeding of the 2,3,3',4'-biphenyltetraacid dianhydride and 2,3,3',4'-diphenyl ether tetraacid dianhydride The molar ratio is 0:100 to 100:0, preferably 40:60 to 80:20, and the molar amount of 2,3,3',4'-biphenyltetraacid dianhydride is not 0;

The total molar dosage of the 2,3,3', 4'-biphenyltetraacid dianhydride and the 2,3,3', 4'-diphenyl ether tetraacid dianhydride and the aromatic diamine The molar ratio of feeding is 1.00: (0.95～1.00), preferably 1.00: (0.99～1.00);

The total molar dosage of the 2,3,3', 4'-biphenyltetraacid dianhydride and the 2,3,3', 4'-diphenyl ether tetraacid dianhydride and the feeding amount of the acetic anhydride The molar ratio is 1.00:(2.00～10.00), preferably 1.00:3.00;

The 2,3,3', 4'-biphenyltetraacid dianhydride and the 2,3,3', 4'-diphenyl ether tetraacid dianhydride total feed mole dosage and the pyridine feed mole The ratio is 1.00:(2.00～8.00), preferably 1.00:3.00;

In the method for preparing the compound represented by the formula II, the molar ratio of the 2,3,3',4'-diphenyl ether tetraacid dianhydride to the aromatic diamine is 1.00:(0.95～1.00) , preferably 1.00:(0.99～1.00);

The molar ratio of the 2,3,3',4'-diphenyl ether tetra-acid dianhydride to the acetic anhydride is 1.00:(2.00-10.00), preferably 1.00:3.00;

The molar ratio of the 2,3,3',4'-diphenyl ether tetra-acid dianhydride to the pyridine is 1.00:(2.00-8.00), preferably 1.00:3.00.

In the polymerization step, the time is 10-30 hours, preferably 20-25 hours, more preferably 24 hours; the temperature is 0-35°C, preferably 15-25°C;

In the chemical imidization reaction step, the time is 10-30 hours, preferably 20-25 hours, more preferably 24 hours; the temperature is 0-35°C, preferably 15-25°C.

The polymerization reaction is carried out in an organic solvent; the organic solvent is selected from N-methylpyrrolidone (NMP), m-cresol, N, N-dimethylformamide (DMF), N, N-di At least one of methylacetamide (DMAc), dimethylsulfoxide (DMSO), and γ-butyrolactone, preferably at least one of N-methylpyrrolidone and m-cresol. The solvent is used in an amount such that the mass percentage of solids in the reaction system is 10%-30%, preferably 15%-20%.

In actual operation, the product system of the compound described in formula I or formula II obtained in step 2) can also be operated as follows to obtain the corresponding resin product: the product system obtained in step 2) is drawn in ethanol, After washing and drying, a filamentous polyimide resin can be obtained; the resin product can also be formed into a film according to a conventional film-forming method to obtain a corresponding film.

The resin or film prepared from the above-mentioned polyimide provided by the present invention, and the application of the resin or film in the preparation of heat-sealable coatings or heat-sealable films of devices; The heat-sealable coating or heat-sealable film of the above-mentioned resin or film device also belongs to the protection scope of the present invention. Wherein, the device is a thermal protection device of a spacecraft, a substrate of a solar battery array, an antenna reflector, an antenna collector or a solar sail.

The polyimide polymer provided by the present invention is based on aromatic dianhydride compound 2,3,3',4'-biphenyltetraacid dianhydride (aBPDA) and 2,3,3',4'-diphenyl Ether tetraacid dianhydride (aODPA) and aromatic diamine compounds are used as raw materials and prepared by chemical imidization. By adjusting the ratio of aBPDA and aODPA, the heat resistance stability and heat sealing strength of the polyimide material shown in formula I can be adjusted. The material not only has good heat sealing properties, but also has excellent heat resistance stability and dimensional stability, and can be used as a coating or film in high-tech fields such as aerospace, optoelectronics, microelectronics and automobiles.

Description of drawings

Fig. 1 is the infrared spectrum of the polyimide film that embodiment 1 prepares.

Fig. 2 is the DSC spectrogram of the obtained polyimide film of embodiment 1.

Fig. 3 is the TGA spectrogram of the polyimide obtained in embodiment 1.

Fig. 4 is the DMA spectrogram of the obtained polyimide film of embodiment 1.

Figure 5 is the infrared spectrum of the polyimide film prepared in Example 2.

Fig. 6 is the DSC spectrogram of the obtained polyimide film of embodiment 2.

Fig. 7 is the TGA spectrogram of the polyimide obtained in embodiment 2.

Fig. 8 is the DMA spectrogram of the obtained polyimide film of embodiment 2.

Figure 9 is the infrared spectrum of the polyimide film prepared in Example 3.

Figure 10 is the DSC spectrogram of the polyimide film obtained in Example 3.

Figure 11 is the TGA spectrogram of the polyimide obtained in Example 3.

Figure 12 is the DMA spectrogram of the polyimide film obtained in Example 3.

Figure 13 is the infrared spectrum of the polyimide film prepared in Example 4.

Figure 14 is the DSC spectrogram of the polyimide film obtained in Example 4.

Figure 15 is the TGA spectrogram of the polyimide obtained in Example 4.

Fig. 16 is the DMA spectrogram of the polyimide film obtained in Example 4.

Figure 17 is the infrared spectrum of the polyimide film prepared in Example 5.

Figure 18 is the DSC spectrogram of the polyimide film obtained in Example 5.

Figure 19 is the TGA spectrogram of the polyimide obtained in Example 5.

Figure 20 is the DMA spectrogram of the polyimide film obtained in Example 5.

Figure 21 is the infrared spectrum of the polyimide film prepared in Example 6.

Figure 22 is the DSC spectrogram of the polyimide film obtained in Example 6.

Figure 23 is the TGA spectrogram of the polyimide obtained in Example 6.

Figure 24 is the DMA spectrogram of the polyimide film obtained in Example 6.

Figure 25 is the infrared spectrum of the polyimide film prepared in Example 7.

Figure 26 is the DSC spectrogram of the polyimide film obtained in Example 7.

Figure 27 is the TGA spectrogram of the polyimide obtained in Example 7.

Figure 28 is the DMA spectrogram of the polyimide film obtained in Example 7.

Figure 29 is the infrared spectrum of the polyimide film prepared in Example 8.

Figure 30 is the DSC spectrogram of the polyimide film obtained in Example 8.

Fig. 31 is the TGA spectrogram of the polyimide obtained in Example 8.

Figure 32 is the DMA spectrogram of the polyimide film obtained in Example 8.

Figure 33 is the infrared spectrum of the polyimide film prepared in Example 9.

Figure 34 is the DSC spectrogram of the polyimide film obtained in Example 9.

Figure 35 is the TGA spectrogram of the polyimide obtained in Example 9.

Figure 36 is the DMA spectrogram of the polyimide film obtained in Example 9.

Figure 37 is the infrared spectrum of the polyimide film prepared in Example 10.

Figure 38 is the DSC spectrogram of the polyimide film obtained in Example 10.

Fig. 39 is the TGA spectrogram of the polyimide obtained in Example 10.

Figure 40 is the DMA spectrogram of the polyimide film obtained in Example 10.

Figure 41 is the relationship between the thermal properties of polyimide film and the weight percentage of aBPDA in dianhydride.

Figure 42 is the relationship between the heat-sealing strength of polyimide film and the weight percentage of aBPDA in dianhydride.

Detailed ways

The present invention will be further described below in conjunction with specific examples, but the present invention is not limited to the following examples. The methods are conventional methods unless otherwise specified. The materials can be obtained from public commercial sources unless otherwise specified. The molecular weights of the polymers obtained in the following examples are all determined according to the GPC method, and the obtained molecular weights are all number average molecular weights.

Glass transition temperature evaluation method:

Calorimetry Differential Scanning (DSC). The prepared polyimide film was tested on a calorimetric differential scanner (TA Company, USA, Q100 series) at a heating rate of 10° C./min.

Dynamic Thermomechanical Analysis (DMA). The prepared polyimide film was tested on a dynamic thermomechanical analyzer (TA Company, USA, Q800 series) with a heating rate of 5° C./min and a frequency of 1 Hz.

Thermal decomposition temperature evaluation method:

The prepared polyimide film was tested on a thermogravimetric analyzer (TA Company, USA, Q50 series) at a heating rate of 10° C./min.

Evaluation method of heat sealability:

Seal the front and back sides of the prepared polyimide film on a heat-sealing press (IDM Company of the United States, L0003-5 experimental hot press) for 1 minute at 320°C and 0.35 MPa to obtain the sealed polyimide film. imide film. According to the industry standard QB/T2358-98, the peeling test is carried out, and the peeling strength obtained is the heat sealing strength.

Embodiment 1 is that the polyimide shown in formula II is prepared by aBPDA and aODPA and BAPP that ratio is 0: 100 (molar ratio)

In a 250mL three-necked flask equipped with a nitrogen inlet, add 12.3153g (0.03mol) BAPP and 60mL N-methylpyrrolidone (NMP). After stirring at room temperature to make it dissolve completely, add 9.3066g (0.03mol) aODPA, and add 63mL NMP to adjust the solid content to 15% (weight percent). After stirring at room temperature for 24 h, 8.58 mL (0.09 mol) of acetic anhydride and 7.35 mL (0.09 mol) of pyridine were added, and stirring was continued for 24 h. The resulting yellow viscous solution was poured into 1000 mL of ethanol to obtain a yellow filamentous solid. The solid was collected, washed three times with ethanol, and then dried in a vacuum oven at 180°C.

Weigh 3 g of solid, add 17 g of N,N-dimethylacetamide (DMAc), and after the solid is completely dissolved, filter to obtain a polyimide solution with a solid content of 15% (percentage by weight). Coat the polymer solution on a glass plate and heat according to the program of 80°C/2h; 150°C/1h; 200°C/1h; 250°C/1h. After cooling to room temperature, the glass plate was soaked in water, and the polyimide film was obtained by peeling off.

Infrared spectrum (cm ^-1 ): 2966, 1779, 1717, 1496, 1373, 1168, 742;

The thermal properties and heat-sealing strength are shown in Table 1;

Infrared spectrum is as shown in accompanying drawing 1;

DSC spectrogram is as shown in accompanying drawing 2;

TGA spectrogram is as shown in accompanying drawing 3;

DMA spectrogram is as shown in accompanying drawing 4;

The structural formula of polyimide is as follows:

It can be known from the above that the compound has a correct structure and is a compound represented by formula II, and n is 30.

Embodiment 2 prepares polyimide by the ratio of aBPDA and aODPA and BAPP of 10:90 (molar ratio)

In a 250mL three-necked flask equipped with a nitrogen inlet, add 12.3153g (0.03mol) BAPP and 60mL N-methylpyrrolidone (NMP). After stirring at room temperature to dissolve it completely, add 8.3757g (0.027mol) aODPA and 0.8827g (0.003mol) aBPDA, and add 62mL NMP to adjust the solid content to 15% (weight percent). After stirring at room temperature for 24 h, 8.58 mL (0.09 mol) of acetic anhydride and 7.35 mL (0.09 mol) of pyridine were added, and stirring was continued for 24 h. The resulting yellow viscous solution was poured into 1000 mL of ethanol to obtain a yellow filamentous solid. The solid was collected, washed three times with ethanol, and then dried in a vacuum oven at 180°C.

Weigh 3 g of solid, add 17 g of N,N-dimethylacetamide (DMAc), and after the solid is completely dissolved, filter to obtain a polyimide solution with a solid content of 15% (percentage by weight). Coat the polymer solution on a glass plate and heat according to the program of 80°C/2h; 150°C/1h; 200°C/1h; 250°C/1h. After cooling to room temperature, the glass plate was soaked in water, and the polyimide film was obtained by peeling off.

Infrared spectrum (cm ^-1 ): 2966, 1779, 1717, 1496, 1373, 1168, 742.

The thermal properties and heat-sealing strength are shown in Table 1.

Infrared spectrum is as shown in accompanying drawing 5;

DSC spectrogram is as shown in accompanying drawing 6;

TGA spectrogram is as shown in accompanying drawing 7;

DMA spectrogram is as shown in accompanying drawing 8;

The structural formula of polyimide is as follows:

It can be seen from the above that the compound has a correct structure and is a compound shown in formula I, and its number average molecular weight is 20500.

Embodiment 3 prepares polyimide by the ratio of aBPDA and aODPA and BAPP of 20:80 (molar ratio)

In a 250mL three-necked flask equipped with a nitrogen inlet, add 12.3153g (0.03mol) BAPP and 60mL N-methylpyrrolidone (NMP). After stirring at room temperature to make it completely dissolved, add 7.4450g (0.024mol) of aODPA and 1.7653g (0.006mol) of aBPDA, and add 62mL of NMP to adjust the solid content to 15% (percentage by weight), after continuing to stir at room temperature for 24h, Add 8.58mL (0.09mol) of acetic anhydride and 7.35mL (0.09mol) of pyridine, and continue stirring for 24h. The resulting yellow viscous solution was poured into 1000 mL of ethanol to obtain a yellow filamentous solid. The solid was collected, washed three times with ethanol, and then dried in a vacuum oven at 180°C.

Weigh 3 g of solid, add 17 g of N,N-dimethylacetamide (DMAc), and after the solid is completely dissolved, filter to obtain a polyimide solution with a solid content of 15% (percentage by weight). Coat the polymer solution on a glass plate and heat according to the program of 80°C/2h; 150°C/1h; 200°C/1h; 250°C/1h. After cooling to room temperature, the glass plate was soaked in water, and the polyimide film was obtained by peeling off.

Infrared spectrum (cm ^-1 ): 2966, 1778, 1717, 1495, 1372, 1168, 743.

The thermal properties and heat-sealing strength are shown in Table 1.

Infrared spectrum is as shown in accompanying drawing 9;

DSC spectrogram is as shown in accompanying drawing 10;

TGA spectrogram is as shown in accompanying drawing 11;

DMA spectrogram is as shown in accompanying drawing 12;

The structural formula of polyimide is as follows:

It can be known from the above that the compound has a correct structure and is a compound shown in formula I, and its number average molecular weight is 21600.

Embodiment 4 prepares polyimide by the ratio of aBPDA and aODPA and BAPP of 30:70 (molar ratio)

In a 250mL three-necked flask equipped with a nitrogen inlet, add 12.3153g (0.03mol) BAPP and 60mL N-methylpyrrolidone (NMP). After stirring at room temperature to make it completely dissolved, add 6.5144g (0.021mol) of aODPA and 2.6480g (0.009mol) of aBPDA, and add 61mL of NMP to adjust the solid content to 15% (percentage by weight), after continuing to stir at room temperature for 24h, Add 8.58mL (0.09mol) of acetic anhydride and 7.35mL (0.09mol) of pyridine, and continue stirring for 24h. The resulting yellow viscous solution was poured into 1000 mL of ethanol to obtain a yellow filamentous solid. The solid was collected, washed three times with ethanol, and then dried in a vacuum oven at 180°C.

Weigh 3 g of solid, add 17 g of N,N-dimethylacetamide (DMAc), and after the solid is completely dissolved, filter to obtain a polyimide solution with a solid content of 15% (percentage by weight). Coat the polymer solution on a glass plate and heat according to the program of 80°C/2h; 150°C/1h; 200°C/1h; 250°C/1h. After cooling to room temperature, the glass plate was soaked in water, and the polyimide film was obtained by peeling off.

Infrared spectrum (cm ^-1 ): 2965, 1778, 1717, 1495, 1372, 1168, 743.

The thermal properties and heat-sealing strength are shown in Table 1.

Infrared spectrum is as shown in accompanying drawing 13;

DSC spectrogram is as shown in accompanying drawing 14;

TGA spectrogram is as shown in accompanying drawing 15;

The DMA spectrogram is shown in Figure 16;

The structural formula of polyimide is as follows:

It can be known from the above that the compound has a correct structure and is a compound shown in formula I.

Embodiment 5 prepares polyimide by the ratio of aBPDA and aODPA and BAPP of 40:60 (molar ratio)

In a 250mL three-necked flask equipped with a nitrogen inlet, add 12.3153g (0.03mol) BAPP and 60mL N-methylpyrrolidone (NMP). After stirring at room temperature to make it dissolve completely, add 5.5838g (0.018mol) aODPA and 3.5306g (0.012mol) aBPDA, and add 61mL NMP to adjust the solid content to 15% (weight percent), continue stirring at room temperature for 24h, add 8.58mL (0.09mol) of acetic anhydride and 7.35mL (0.09mol) of pyridine, and continued stirring for 24h. The resulting yellow viscous solution was poured into 1000 mL of ethanol to obtain a yellow filamentous solid. The solid was collected, washed three times with ethanol, and then dried in a vacuum oven at 180°C.

Weigh 3 g of solid, add 17 g of N,N-dimethylacetamide (DMAc), and after the solid is completely dissolved, filter to obtain a polyimide solution with a solid content of 15% (percentage by weight). Coat the polymer solution on a glass plate and heat according to the program of 80°C/2h; 150°C/1h; 200°C/1h; 250°C/1h. After cooling to room temperature, the glass plate was soaked in water, and the polyimide film was obtained by peeling off.

Infrared spectrum (cm ^-1 ): 2966, 1778, 1717, 1495, 1372, 1168, 737.

The thermal properties and heat-sealing strength are shown in Table 1.

Infrared spectrum is as shown in accompanying drawing 17;

DSC spectrogram is as shown in accompanying drawing 18;

The TGA spectrum is as shown in accompanying drawing 19;

The DMA spectrogram is shown in Figure 20;

The structural formula of polyimide is as follows:

It can be known from the above that the compound has a correct structure and is a compound shown in formula I.

Embodiment 6 prepares polyimide by the ratio of aBPDA and aODPA and BAPP of 50:50 (molar ratio)

In a 250mL three-necked flask equipped with a nitrogen inlet, add 12.3153g (0.03mol) BAPP and 60mL N-methylpyrrolidone (NMP). After stirring at room temperature to dissolve it completely, add 4.6532g (0.015mol) aODPA and 4.4133g (0.015mol) aBPDA, and add 61mL NMP to adjust the solid content to 15% (weight percent), continue stirring at room temperature for 24h, add 8.58mL (0.09mol) of acetic anhydride and 7.35mL (0.09mol) of pyridine, and continued stirring for 24h. The resulting yellow viscous solution was poured into 1000 mL of ethanol to obtain a yellow filamentous solid. The solid was collected, washed three times with ethanol, and then dried in a vacuum oven at 180°C.

Weigh 3 g of solid, add 17 g of N,N-dimethylacetamide (DMAc), and after the solid is completely dissolved, filter to obtain a polyimide solution with a solid content of 15% (percentage by weight). Coat the polymer solution on a glass plate and heat according to the program of 80°C/2h; 150°C/1h; 200°C/1h; 250°C/1h. After cooling to room temperature, the glass plate was soaked in water, and the polyimide film was obtained by peeling off.

Infrared spectrum (cm ^-1 ): 2966, 1778, 1717, 1495, 1372, 1168, 743.

The thermal properties and heat-sealing strength are shown in Table 1.

The infrared spectrum is as shown in accompanying drawing 21;

DSC spectrogram is as shown in accompanying drawing 22;

The TGA spectrum is as shown in accompanying drawing 23;

The DMA spectrogram is shown in Figure 24;

The structural formula of polyimide is as follows:

It can be known from the above that the compound has a correct structure and is a compound shown in formula I.

Embodiment 7 prepares polyimide by the ratio of aBPDA and aODPA and BAPP of 60:40 (molar ratio)

In a 250mL three-necked flask equipped with a nitrogen inlet, add 12.3153g (0.03mol) BAPP and 60mL N-methylpyrrolidone (NMP). After stirring at room temperature to make it completely dissolved, add 3.7225g (0.012mol) aODPA and 5.2960g (0.018mol) aBPDA, and add 61mL NMP to adjust the solid content to 15% (weight percent), continue stirring at room temperature for 24h, add 8.58mL (0.09mol) of acetic anhydride and 7.35mL (0.09mol) of pyridine, and continued stirring for 24h. The resulting yellow viscous solution was poured into 1000 mL of ethanol to obtain a yellow filamentous solid. The solid was collected, washed three times with ethanol, and then dried in a vacuum oven at 180°C.

Weigh 3 g of solid, add 17 g of N,N-dimethylacetamide (DMAc), and after the solid is completely dissolved, filter to obtain a polyimide solution with a solid content of 15% (percentage by weight). Coat the polymer solution on a glass plate and heat according to the program of 80°C/2h; 150°C/1h; 200°C/1h; 250°C/1h. After cooling to room temperature, the glass plate was soaked in water, and the polyimide film was obtained by peeling off.

Infrared spectrum (cm ^-1 ): 2966, 1778, 1717, 1495, 1372, 1168, 743.

The thermal properties and heat-sealing strength are shown in Table 1.

The infrared spectrum is as shown in accompanying drawing 25;

DSC spectrogram is as shown in accompanying drawing 26;

The TGA spectrum is as shown in accompanying drawing 27;

The DMA spectrogram is shown in Figure 28;

The structural formula of polyimide is as follows:

It can be known from the above that the compound has a correct structure and is a compound shown in formula I.

Embodiment 8 prepares polyimide by the ratio of aBPDA and aODPA and BAPP of 70:30 (molar ratio)

In a 250mL three-necked flask equipped with a nitrogen inlet, add 12.3153g (0.03mol) BAPP and 60mL N-methylpyrrolidone (NMP). After stirring at room temperature to dissolve it completely, add 2.7919g (0.009mol) aODPA and 6.1786g (0.021mol) aBPDA, and add 60mL NMP to adjust the solid content to 15% (weight percent), continue stirring at room temperature for 24h, add 8.58 mL (0.09mol) of acetic anhydride and 7.35mL (0.09mol) of pyridine, and continued stirring for 24h. The resulting yellow viscous solution was poured into 1000 mL of ethanol to obtain a yellow filamentous solid. The solid was collected, washed three times with ethanol, and then dried in a vacuum oven at 180°C.

Weigh 3 g of solid, add 17 g of N,N-dimethylacetamide (DMAc), and after the solid is completely dissolved, filter to obtain a polyimide solution with a solid content of 15% (percentage by weight). Coat the polymer solution on a glass plate and heat according to the program of 80°C/2h; 150°C/1h; 200°C/1h; 250°C/1h. After cooling to room temperature, the glass plate was soaked in water, and the polyimide film was obtained by peeling off.

Infrared spectrum (cm ^-1 ): 2966, 1778, 1717, 1495, 1372, 1168, 743.

The thermal properties and heat-sealing strength are shown in Table 1.

The infrared spectrum is as shown in accompanying drawing 29;

DSC spectrogram is as shown in accompanying drawing 30;

The TGA spectrum is as shown in accompanying drawing 31;

The DMA spectrogram is shown in Figure 32;

The structural formula of polyimide is as follows:

It can be known from the above that the compound has a correct structure and is a compound shown in formula I.

Embodiment 9 prepares polyimide by the ratio of aBPDA and aODPA and BAPP of 80:20 (molar ratio)

In a 250mL three-necked flask equipped with a nitrogen inlet, add 12.3153g (0.03mol) BAPP and 60mL N-methylpyrrolidone (NMP). After stirring at room temperature to make it dissolve completely, add 1.8163g (0.006mol) aODPA and 7.0613g (0.024mol) aBPDA, and add 60mL NMP to adjust the solid content to 15% (weight percent), continue stirring at room temperature for 24h, add 8.58mL (0.09mol) of acetic anhydride and 7.35mL (0.09mol) of pyridine, and continued stirring for 24h. The resulting yellow viscous solution was poured into 1000 mL of ethanol to obtain a yellow filamentous solid. The solid was collected, washed three times with ethanol, and then dried in a vacuum oven at 180°C.

Weigh 3 g of solid, add 17 g of N,N-dimethylacetamide (DMAc), and after the solid is completely dissolved, filter to obtain a polyimide solution with a solid content of 15% (percentage by weight). Coat the polymer solution on a glass plate and heat according to the program of 80°C/2h; 150°C/1h; 200°C/1h; 250°C/1h. After cooling to room temperature, the glass plate was soaked in water, and the polyimide film was obtained by peeling off.

Infrared spectrum (cm ^-1 ): 2966, 1778, 1717, 1495, 1372, 1168, 743.

The thermal properties and heat-sealing strength are shown in Table 1.

The infrared spectrum is as shown in accompanying drawing 33;

The DSC spectrum is as shown in accompanying drawing 34;

The TGA spectrum is as shown in accompanying drawing 35;

The DMA spectrogram is shown in Figure 36;

The structural formula of polyimide is as follows:

It can be known from the above that the compound has a correct structure and is a compound shown in formula I.

Embodiment 10 prepares polyimide by the ratio of aBPDA and aODPA and BAPP of 90:10 (molar ratio)

In a 250mL three-necked flask equipped with a nitrogen inlet, add 12.3153g (0.03mol) BAPP and 60mL N-methylpyrrolidone (NMP). After stirring at room temperature to dissolve it completely, add 0.9306g (0.003mol) aODPA and 7.9439g (0.027mol) aBPDA, and add 60mL NMP to adjust the solid content to 15% (weight percent), continue stirring at room temperature for 24h, add 8.58mL (0.09mol) of acetic anhydride and 7.35mL (0.09mol) of pyridine, and continued stirring for 24h. The resulting yellow viscous solution was poured into 1000 mL of ethanol to obtain a yellow filamentous solid. The solid was collected, washed three times with ethanol, and then dried in a vacuum oven at 180°C.

Weigh 3 g of solid, add 17 g of N,N-dimethylacetamide (DMAc), and after the solid is completely dissolved, filter to obtain a polyimide solution with a solid content of 15% (percentage by weight). Coat the polymer solution on a glass plate and heat according to the program of 80°C/2h; 150°C/1h; 200°C/1h; 250°C/1h. After cooling to room temperature, the glass plate was soaked in water, and the polyimide film was obtained by peeling off.

Infrared spectrum (cm ^-1 ): 2966, 1778, 1717, 1495, 1372, 1168, 743.

The thermal properties and heat-sealing strength are shown in Table 1.

The infrared spectrum is as shown in accompanying drawing 37;

The DSC spectrogram is as shown in accompanying drawing 38;

The TGA spectrum is as shown in accompanying drawing 39;

The DMA spectrogram is as shown in accompanying drawing 40;

The structural formula of polyimide is as follows:

It can be known from the above that the compound has a correct structure and is a compound shown in formula I.

Table 1, the performance of polyimide film

The data in Table 1 are summarized and the results are shown in Figures 41 and 42. It can be seen from Figure 41 that with the increase of the aBPDA content in the dianhydride, the glass transition temperature and thermal decomposition temperature of the polyimide film both show an upward trend. When the molar percentage of aBPDA reaches more than 70%, its thermal performance remains basically unchanged. It can be seen from Figure 42 that with the increase of the aBPDA content in the dianhydride, the heat-sealing strength of the polyimide film showed a trend of first increasing and then decreasing. When the molar percentage of aBPDA reaches 70%, its heat-sealing strength reaches the maximum. When the molar percentage of aBPDA is between 40% and 80%, the heat-sealing strength of the polyimide film can reach above 0.6N/mm.

Claims (10)

1. polyimide shown in formula I or formula II structure general formula, Formula I Formula II In the general structural formula of formula I and formula II, Ar is selected from any one of the following groups: In the general structural formula of formula I, m:n=0:100～100:0, and both m and n are not 0; In the general structural formula of formula II, n is an integer of 0-100, and n is not 0. 2. The polyimide according to claim 1, characterized in that: in the general structural formula of the formula I, m:n=40:60～80:20; In the general structural formula of formula II, n is 30. 3. A method for preparing the polyimide described in claim 1 or 2, comprising the steps of: aromatic diamine, 2,3,3 ', 4'-biphenyltetraacid dianhydride and 2,3, 3', 4'-diphenyl ether tetra-acid dianhydride is mixed uniformly for polymerization reaction, after the reaction is completed to obtain a homogeneous solution, acetic anhydride and pyridine are added to it and mixed for chemical imidization reaction, and the reaction is completed to obtain the Compound shown in formula I; Alternatively, the aromatic diamine is mixed with 2,3,3',4'-diphenyl ether tetra-acid dianhydride to carry out polymerization reaction, and after the reaction is completed to obtain a homogeneous solution, acetic anhydride and pyridine mixed Carry out the chemical imidization reaction uniformly, and the compound shown in the formula II is obtained after the reaction is completed. 4. The method according to claim 3, characterized in that: in the method, the aromatic diamines are all selected from 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether , 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,4- Bis[(4-amino-2-trifluoromethyl)phenoxy]benzene, 2,2-bis[(4-aminophenoxy)phenyl]propane, 2,2-bis[(4-aminobenzene At least one of oxy)phenyl]hexafluoropropane and 2,2'-bistrifluoromethyl-4,4'-biphenylenediamine. 5. The method according to claim 3 or 4, characterized in that: in the method for preparing the compound shown in the formula I, the 2,3,3',4'-biphenyltetraacid dianhydride and 2, The molar ratio of 3,3',4'-diphenyl ether tetra-acid dianhydride is 0:100～100:0, preferably 40:60～80:20, the 2,3,3',4'-linked The molar amount of pyromellitic dianhydride is not 0; The total molar dosage of the 2,3,3', 4'-biphenyltetraacid dianhydride and the 2,3,3', 4'-diphenyl ether tetraacid dianhydride and the aromatic diamine The molar ratio of feeding is 1.00: (0.95～1.00), preferably 1.00: (0.99～1.00); The total molar dosage of the 2,3,3', 4'-biphenyltetraacid dianhydride and the 2,3,3', 4'-diphenyl ether tetraacid dianhydride and the feeding amount of the acetic anhydride The molar ratio is 1.00:(2.00～10.00), preferably 1.00:3.00; The 2,3,3', 4'-biphenyltetraacid dianhydride and the 2,3,3', 4'-diphenyl ether tetraacid dianhydride total feed mole dosage and the pyridine feed mole The ratio is 1.00:(2.00～8.00), preferably 1.00:3.00; In the method for preparing the compound represented by the formula II, the molar ratio of the 2,3,3',4'-diphenyl ether tetraacid dianhydride to the aromatic diamine is 1.00:(0.95～1.00) , preferably 1.00:(0.99～1.00); The molar ratio of the 2,3,3',4'-diphenyl ether tetra-acid dianhydride to the acetic anhydride is 1.00:(2.00-10.00), preferably 1.00:3.00; The molar ratio of the 2,3,3',4'-diphenyl ether tetra-acid dianhydride to the pyridine is 1.00:(2.00-8.00), preferably 1.00:3.00. 6. The method according to any one of claims 3-5, characterized in that: in the polymerization reaction step, the time is 10-30 hours, preferably 20-25 hours, more preferably 24 hours; the temperature is 0-30 hours. 35°C, preferably 15-25°C; In the chemical imidization reaction step, the time is 10-30 hours, preferably 20-25 hours, more preferably 24 hours; the temperature is 0-35°C, preferably 15-25°C. 7. according to the arbitrary described method of claim 3-6, it is characterized in that: described polyreaction all is carried out in organic solvent; Described organic solvent is selected from N-methylpyrrolidone, m-cresol, N, At least one of N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, γ-butyrolactone, preferably at least one of N-methylpyrrolidone and m-cresol ; The amount of solvent used is to make the mass percentage of solid in the reaction system be 10%-30%, preferably 15%-20%. 8. A resin or film prepared from the polyimide according to claim 1 or 2. 9. the polyimide described in claim 1 or 2 or the application of resin or film described in claim 8 in the heat-sealable coating or heat-sealable film of preparation device; Contain polyimide described in claim 1 or 2 Heat-sealable coatings for devices of imines or resins or films as claimed in claim 8. 10. The application or heat-sealable coating or heat-sealable film according to claim 9, characterized in that: the device is a thermal protection device of a spacecraft, a substrate of a solar cell array, an antenna reflector, an antenna collector or solar sails.

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