TWI573780B - Dicoline Monomers Containing Adamantane and Their Polyimide Derivatives and Its preparation method - Google Patents

Description

Diamine monomer having adamantane structure and polyimine derivative thereof Preparation method

The present invention relates to a bisamine monomer and a polybendimimine derivative thereof, and a process for the preparation thereof, and more particularly to a bisamine monomer having an adamantane structure and a polyimine derivative thereof and a process for preparing the same.

Polyimide (PI) is one of the commonly used engineering plastics. It has excellent thermal stability, mechanical properties, dimensional stability, high resistance and wear resistance. Semiconductor industry, flexible printed circuit (FPC), liquid crystal display and other related electronics industries.

In response to the development of electronic products, the electrical properties of soft substrates are becoming more and more stringent. The widely used polyamidide materials will also face challenges. How to reduce the dielectric constant is one of the key research and development projects of this material.

Adamantane is a rigid, cyclic aliphatic structure. Its aliphatic properties contribute to the improvement of hydrophobicity and dielectric properties after being introduced into a polymer material, and compared with other long-chain aliphatic structures. The thermal stability is preferred. Therefore, the introduction of the adamantane structure has become one of the strategies for improving the properties of many polymer research in recent years.

For example, in 1997, the Chen team synthesized a polyalkylenimine with an adamantane structure (Macromolecules 1997; 30(16): 4646-4651), and the obtained material was compared with the currently widely used polyimine product Kapton (D). _k = 3.2-3.4) has superior electrical properties (D _k = 2.77-2.91) and exhibits good thermal properties (T _g = 262-343 ° C from DMA) and thermal stability (T _d5 = 445-501) °C), and due to the soft ether bond in the main chain, the polyimine exhibits good organic solubility.

The following year, in pursuit of low dielectric materials with superior thermal properties, the same team improved the structure in the above literature (Macromolecular Chemistry and Physics 1998; 199(6): 963-969), synthesizing the main chain without a soft chain. The quinone imine retains good electrical properties (D _k = 2.76-2.92) and has a significant breakthrough in thermal properties (T _g >300 ° C from DMA), however, there is still room for improvement in its organic solubility.

In 1998, Xiao team also synthesized polyimine with adamantane structure in the main chain (Macromolecules 1998; 31(21): 7213-7217). Due to the soft ether bond in the structure, the material has excellent organic solubility. Its thermal properties are also affected by the soft chain, and the glass transition temperature falls between 248-308 ° C (from DSC), which has an improved space relative to the polyimine without an ether bond.

It can be seen from the above literature that the introduction of the adamantane structure contributes to the improvement of electrical properties, and the introduction of an ether bond in the polymer main chain can significantly improve the organic solubility, thereby increasing the processability, however, the soft chain will also affect The thermal properties of the material, therefore, how to maintain both excellent thermal properties, dielectric properties, and Organic solubility is the goal of the case.

Therefore, there is a need in the industry for a method for preparing a bisamine monomer having an adamantane structure and incorporating it into a polyimide material to prepare a polythene having low dielectric properties, high thermal properties, mechanical strength, and good organic solubility. Imine derivatives.

In view of the above disadvantages of the prior art, the main object of the present invention is to provide an adamantane structure-containing bisamine monomer and a polyimine derivative thereof and a preparation method thereof, and to provide a adamantane and a naphthalene ring. a bisphenol monomer having a structure, which is reacted with 4-nitrochlorobenzene to form a bisnitro compound, which is reduced to obtain an adamantane structure-containing bisamine compound (I); and the adamantane-containing bisamine compound is further further substituted with a dianhydride. The compound is reacted to form a polyimine derivative (II) having an adamantane structure.

The present invention employs a bisphenol monomer having a bisadamantane and a naphthalene ring structure as a precursor to synthesize the bisamine compound (I). Adamantane is chemically stable and provides the preferred electrical properties of polyimine. In addition, the present invention utilizes a naphthalene ring knot Introduction of the structure to further improve the thermal stability of the polyimide material. The naphthalene ring structure is a flat and rigid structure. Recently, some studies have pointed out that it can be introduced into the polymer main chain to increase the rigidity of the main chain and thereby improve the thermal properties of the material. For example, a poly(ethylene 2,6-naphthalene) (PEN) having a naphthalene ring in the main chain is compared with a general poly(ethylene terephthalate) (PET) (Polymer 1998; 39(17): 4129-4134). In the performance, the glass transition temperature is about 43 ° C higher, the storage modulus is about 50% higher, and the tensile strength (Tensile strength) is also increased by about 33%, which fully shows that the naphthalene ring structure is introduced. In the main chain, it can contribute to the improvement of the thermal properties and mechanical strength of the material. Therefore, the thermal properties, mechanical properties, and dielectric properties of the polyimine are improved by introducing the adamantane-containing and naphthalene ring structures into the polyamidiene backbone.

In order to achieve the above object, according to one aspect of the present invention, there is provided an adamantane structure-containing bisamine compound (I) and a preparation method thereof, the steps comprising: (1) a double adamantane structure having the formula (A) The phenol compound is reacted with 4-nitrochlorobenzene under base catalysis to form a bisnitro compound (B); (2) the bisnitro compound of formula (B) is reduced to obtain a bisamine compound (I).

The base used in the above step (1) is potassium carbonate, the reaction temperature is between 110 and 160 ° C; and the step (2) catalyzes the reduction reaction of the dinitro compound (B) using a palladium carbon catalyst.

The present invention also provides a polyfluorene imide derivative (II) obtained from the above adamantane structure-containing bisamine compound (I), and a process for producing the same. The polyiminoimine derivative of the formula (II) is obtained by condensation polymerization of a compound of the formula (I) with a dianhydride.

Wherein the Ar is selected from the group consisting of the following groups or one of the group consisting of.

When the poly-imine derivative of the above formula (II) is Ar In the case of the adamantane structure, the polyimine derivative is of the formula (II-a).

The polyamidene derivative containing the adamantane structure synthesized by the invention has a glass transition temperature (T _g ) of 358 ° C and a thermal expansion coefficient of 46 ppm / ° C, which is better than the general polyimine material, and shows the introduction of the present invention. The double adamantane and naphthalene ring structure can improve the thermal properties and dimensional stability of the polyimine material. In addition, in the nitrogen or oxygen environment, the adamantane structure of the adamantane structure synthesized by the invention has a 10% weight loss temperature (T _d10 ) of about 500 ° C or more and 800 ° C under nitrogen. The coke residual rate reached 45%, indicating that the introduction of the diamantane aliphatic structure in this case does not cause a decrease in the thermal stability of the material. The polyimine derivative has a dielectric constant of 2.74, which indicates a good low dielectric constant.

The above summary and the following detailed description and drawings are intended to further illustrate the manner, means and effects of the present invention in achieving its intended purpose. Other purposes and advantages of this creation will be explained in the following description and drawings.

S101, S102, S201‧‧‧ steps

The first figure is the diazonene structure containing the adamantane structure of the present invention and the polyimine derivative thereof; the second figure is the preparation method of the diammon monomer containing the adamantane structure of the invention and the polyimine derivative thereof The third graph is a dynamic mechanical analysis diagram of the polyimine derivative of the embodiment of the present invention; and the fourth graph is a thermomechanical analysis diagram of the polyimide derivative of the present invention.

The embodiments of the present invention are described by way of specific examples, and those skilled in the art can readily understand the advantages and effects of the present invention from the disclosure of the present disclosure.

Please refer to the second figure, which is a flow chart of a method for preparing a diamine monomer and a polyimine derivative thereof containing an adamantane structure according to the present invention. First, the adamantane-containing bisphenol monomer and 4-nitrochlorobenzene (4-nitrochlorobenzene) are subjected to a base-catalyzed catalyst to obtain an adamantane-containing bisnitro compound having a reaction temperature of 110 to 160 ° C. Finally; the final reduction of the adamantane-containing nitro compound A bisamine compound having an adamantane structure. In order to further prepare a polyimine derivative obtained by preparing a diammene monomer-containing bisamine monomer, the present invention reacts an adamantane structure-containing bisamine compound with a dianhydride to synthesize a poly-proline, and a poly-proline The solution is formed into a film, and the structure is closed by heating to form a polyimine containing an adamantane structure.

Example:

Synthesis of Compound (A): Compound (A) was obtained by weighing 4 g (0.025 mol) of 1,5-dihydroxynaphthalene according to the literature (High Performance Polymer 2010, 22, 779). 1-bromoadamantane 13.5 g (0.0625 mol), adding 50 ml of nitrobenzene (Nitrobenzene) as a reaction solvent, placed in a three-neck reactor and stirred, and heated to 80 ° C under nitrogen atmosphere before adding Aluminum chloride (AlCl ₃ ) 0.34 g (0.005 mol), reaction for 24 hours, the reaction was completed, poured into methanol to remove the reactants, and then washed with aluminum chloride / water weight ratio of 1:1, placed in a vacuum oven at 100 ° C, A pale green compound (A) powder was obtained. Compound (A) was dissolved in DMSO- d ₆ solvent and analyzed by superconducting nuclear magnetic resonance spectrometry ( ¹ H-NMR). The chemical shifts obtained were as follows: δ = 1.6-2.1 ppm (15H, adamantyl-H), 6.8 and 7.2 ppm (4H, Ar-H), 9.65 (2H, OH).

Synthesis of Compound (B): Weighing 0.4 g (0.935 mmol) of compound (A), 0.2945 g (1.95 mmol) of 4-nitrochlorobenzene, and 0.2842 g of Potassium carbonate (2.057 mmol), and add 12 mL (2:1 by volume) of N-methylpyrrolidone/toluene (NMP/Toluene) co-solvent, place in a three-neck reaction flask, stir and set up Dean Stark unit to remove water, in a nitrogen atmosphere. Next, the temperature was first raised to 120 ° C for two hours, and then the reaction temperature was raised to 140 ° C, and the reaction was carried out for 12 hours. After the reaction is completed, the salt is removed by deionized water to obtain a yellowish compound (B) powder. Compound (B) was dissolved in CDCl ₃ solvent and analyzed by superconducting nuclear magnetic resonance spectrometry ( ¹ H-NMR). The chemical shifts obtained were as follows: δ = 1.6-2.05 ppm (15H, adamantyl-H), 7.05-8.15 ppm (12H, Ar-H).

Synthesis of Compound (I): 1.5 g (2.24 mmol) of compound (B), 0.09 g of Palladium on Carbon (Pd/C), and 60 mL of dimethylformamide (DMF) were weighed and placed. In a high pressure reactor, the reaction was carried out at room temperature under a hydrogen atmosphere, and the pressure was maintained at 140 psi until the pressure no longer decreased. At the end of the reaction, the solvent was washed with deionized water and placed in a vacuum oven at 100 ° C to obtain a white compound (I) powder. Compound (I) was dissolved in CDCl ₃ solvent and analyzed by superconducting nuclear magnetic resonance spectrometry ( ¹ H-NMR). The chemical shifts obtained were as follows: δ = 1.6-2.05 ppm (15H, adamantyl), 3.6 ppm (4H, - NH2), 7.05-8.15 ppm (12H, Ar-H).

Synthesis of Polyimine Derivative (II-a): Weighing 0.3 g (0.5 mmol) of compound (I) and 4,4'-oxydiphthalic anhydride (4,4'-oxydiphthalic anhydride, ODPA) 0.1524 g (0.5 mmol), and 2.562 g of dehydrated dimethylacetamide (DMAc) were added and reacted under a nitrogen atmosphere for 12 hours to obtain a polyamic acid (PAA) solution. Then, the PAA solution is coated on the quartz glass, and the temperature of the circulating oven is controlled at 60 ° C for 12 hours, and the temperature is raised at 100 ° C, 200 ° C, and 300 ° C for 1 hour, and then the PAA is closed to form Polyimide, and the adamantane-containing structure can be obtained. A film of a polyimide derivative, the sample number is a polyimine derivative (II-a).

Please refer to the third figure, which is a dynamic mechanical analysis diagram of a polybendimimine derivative according to an embodiment of the present invention. The hardened cured product was made into a test piece having a length of 20 mm, a width of 10 mm, and a thickness of 2 mm by a dynamic mechanical analyzer (DMA) at a heating rate of 5 ° C/min and a frequency of 1 Hz to measure the storage modulus ( Storage Modulus E') and Tan δ curves. As shown in the figure, the corresponding temperature of the tan δ wave front is the glass transition temperature (Tg), and the storage modulus (E') curve shows that the polyethylenimine derivative (II-a) main chain The naphthalene ring structure makes the molecular chain relatively rigid and achieves a relatively high storage modulus, and in addition, the thermal properties are improved, as described in Reference 1 (Macromolecules 1997; 30(16): 4646-4651) and Reference 2 ( Macromolecules 1998; 31(21): 7213-7217), as shown in Table 1, under the polymerization conditions in which ODPA is also used as an acid anhydride, two kinds of polyimines having the same ether bond and adamantane structure as in the present case were prepared. , Tg = 309 ° C and 293 ° C, respectively, and the poly-imine derivative (II-a) prepared in this case has a Tg of 358 ° C, indicating the strategy of introducing a double adamantane and a naphthalene ring structure in this case. Effectively make a breakthrough in the thermal properties of the material.

Please refer to the fourth figure, which is a thermomechanical analysis diagram of a polybendimimine derivative according to an embodiment of the present invention. The coefficient of thermal expansion (CTE) was measured by a thermal mechanical analyzer (TMA) at a heating rate of 5 ° C/min. As shown in the figure, the coefficient of thermal expansion measured in the range of 50 ° C to 150 ° C was 46 ppm / ° C, indicating that the rigid main chain simultaneously imparts good dimensional stability to the polyimine derivative (II-a).

Further, thermal stability analysis was carried out by a thermal gravimetric analysis (TGA) at a heating rate of 20 ° C/min. As shown in Table 1, the 10% weight loss temperature (T _d10 ) of the polybendimimine derivative (II-a) under nitrogen or oxygen can reach above about 500 ° C, and the coke residual rate at 800 ° C under nitrogen. Up to 45%, similar to the material properties obtained in Reference 2, shows that although the introduction of the diamantane aliphatic structure in this case does not cause a decrease in the thermal stability of the material. The refractive index of the polyimine derivative (II-a) measured at a wavelength of 633 nm was converted to a dielectric constant of 2.74, indicating that the compound (II-a) has a low dielectric constant.

The adamantane structure-containing bisamine monomer of the present invention and the polyimine derivative thereof and the preparation method thereof, the structure comprising the bis-adamantane and the naphthalene ring are introduced into the polyimine, so that the polyimine material has good both Electrical properties and heat resistance; in addition, the polyimine has an ether bond, which preserves the organic solubility of the polyimide and increases the applicability of the polyimide. The polyimine derivatives of this study have low dielectric, high thermal properties, mechanical strength and good organic solubility, making them more widely used in the future.

The above-described embodiments are merely illustrative of the features and functions of the present invention and are not intended to limit the scope of the technical content of the present invention. Any person skilled in the art can modify and change the above embodiments without departing from the spirit and scope of the creation. Therefore, the scope of protection of this creation should be as listed in the scope of the patent application described later.

Claims (7)

a bisamine compound having an adamantane structure of the formula (I), A method for preparing a compound of the formula (I) according to the first aspect of the patent application, the steps comprising: (1) a bisphenol compound having an adamantane structure of the formula (A) and 4-nitrochlorobenzene (4-nitrochlorobenzene) Reacting under base catalysis to form a bisnitro compound (B); (2) reducing a bisnitro compound such as formula (B) to obtain a bisamine compound (I), A method for producing a compound of the formula (I) according to the second aspect of the invention, wherein the base of the step (1) is potassium carbonate. A method for producing a compound of the formula (I) according to the second aspect of the invention, wherein the reaction temperature of the step (1) is between 110 and 160 °C. a polyimine of the adamantane structure of the formula (II), Among them, the Ar system is selected from the following groups: Or one of the groups; n is an integer from 40 to 80. A method for preparing a polyimine according to the formula (II) of claim 5, which comprises condensing a compound of the formula (I) according to the first aspect of the patent application with a dianhydride of the formula (C) Obtaining the polyimine of formula (II), Among them, the Ar system is selected from the following groups: Or one of the grouped groups. Polyimine of the formula (II) as described in claim 6 of the patent application, wherein Ar is The polyamidiene having an adamantane structure is of the formula (II-a); and the n is an integer of 40 to 80;