TWI602853B - Polyadimide containing adamantane imine preparation - Google Patents

Description

Method for preparing polyammine containing adamantane

The invention relates to a method for preparing a polyammine containing adamantane, in particular to a synthesis of a series of novel adamantane-containing diamine monomers, which are then polycondensed with a dianhydride to form a polyimine, which contains adamantane II. The structural main chain of the amine monomer is linked by an ortho-phenol group, and the side chain has an alkyl group and an adamantyl molecular unit, in particular, the polydiimide which contributes to the synthesis of the polydiimide monomer has a low dielectric constant, High glass transition temperature ( _Tg ) and good processability.

At present, an electronic device is mainly used as an insulating layer by a chemical vapor deposition method (CVD), but its dielectric constant is high, and it is difficult to meet the characteristics of high-speed semiconductors and high-performance semiconductors in the future. The low dielectric material acts as a protective layer, insulating layer or substrate for the device, which reduces the interference of signals and enhances the speed of signal transmission.

Polyimide is a kind of high performance polymer with excellent thermal and mechanical properties, and is widely used in aviation, petrochemical, and now microelectronics. However, in essence, in addition to the high dielectric properties, there is another fatal disadvantage. When it exists in the quinone imine form, it is difficult to be processed, which makes the application in many fields considerably limited. Its high melting point and limited solubility are caused. In addition, it also has considerable potential to replace the current use of glass substrates. The substrate materials used in general flexible displays include ultra-thin glass, stainless steel soft board and plastic substrate materials. However, although the plastic substrate material has good light transmittance, flexibility and surface flatness, it has problems such as heat resistance, dimensional stability and poor gas barrier properties, and needs to be reinforced to fully meet the requirements of the flexible display. In order to achieve the purpose of thinning, lightweight, and flexible plastic film substrates. Therefore, recent research directions have gradually evolved toward low dielectric constant, high glass transition temperature (T _g ), and organic solvent soluble polyimine.

Many studies have used chemical structure design to improve the processability of polyimine and minimize the adverse effects on its thermal stability. A method for generally improving solvent solubility of a polyimide resin, comprising: introducing a soft segment (-O-, -SO ₂ -, -CH ₂ -, C=O in a diamine structure, such as the Republic of China Patent Publication No. Nos. 593227, No. I318219, No. 475939, No. 179679, and No. I278471) improve the processability of polyimine, but also sacrifice dielectric properties. Since the main chain skeleton introduces an asymmetric bond such as a bent bond such as an ether bond or a meta bond, a molecular design for improving molecular mobility is formed. However, if the thermoplasticity is to be increased, the glass transition temperature is greatly lowered, and it is difficult to balance the thermoplasticity with the high glass transition temperature in molecular design. For example, a commercially available polyimine having both organic solvent solubility and thermoplasticity is known as ULTEM 1000 (General Electric), but the glass transition temperature is only 215 ° C, and the solder heat resistance is insufficient, and it is not suitable for softness. Printed circuit board (FPC) use. Therefore, the general practitioners cannot meet the needs of the user in actual use.

The main object of the present invention is to overcome the above problems encountered in the prior art and to provide a series of special diamine monomers and a method for producing the same, which are used to synthesize polyimine with dianhydride to improve processability and maintain physical properties. In particular, the polyimine polymer has characteristics such as low dielectric constant, high _Tg, and good processability to improve problems in the prior art.

For the purpose of the above, the diamine single system of the present invention consists of a simple synthesis method, the chemical structure of which comprises a main chain linked by an ortho-phenol group, and a side chain having an alkyl group and an adamantyl unit. (1) means:

Wherein R is represented by C _n H _2n+1 and an alkyl group of n=1-6. The novel diamine monomer (formula (1)) is synthesized by the following steps, comprising: step (A) forming alkyl-containing catechol and halogenated adamantane to form adamantane in an organic solvent. a diphenol compound; (B) in an alkaline environment, the adamantane-containing diphenol compound and the 4-halogenated nitrobenzene are subjected to a nucleophilic substitution reaction in a polar aprotic solution to produce a diammonium-containing dinitrate a phenolic compound; and a step (C) of reducing the adamantyl dinitrophenol compound to an amino group to form an adamantane-containing diaminophenol monomer, which is a novel adamantane-containing product of the present invention. Diamine monomer. The diamine monomer can be applied to a curing agent of an epoxy resin, a polyamine, and a polyimine.

In the above embodiment of the present invention, the alkyl-substituted catechol in the step (A) is selected from the alkyl group on the 2 or 3 carbon of catechol, and the alkyl carbon number is determined by C _n H _{2n +1} (n=1~6) means.

In the above embodiment of the present invention, the organic solvent in the step (A) is selected from the group consisting of benzene, toluene, or xylene.

In the above embodiment of the present invention, the haloadamantane in the step (A) is selected from any one of fluorinated adamantane, adamantane chloride, adamantane bromide, and adamantane iodide or any combination thereof.

In the above embodiment of the present invention, the alkaline environment in the step (B) is selected from the group consisting of inorganic salts of carbonates or hydroxides.

In the above embodiment of the present invention, the polar aprotic solution in the step (B) is selected from the group consisting of N-Methyl-2-Pyrrolidone (NMP) and Dimethylformamide (DMF). , Dimethyl Sulfoxide (DMSO), N, N-dimethylacetamide (DMAe), tetrahydrothiophene-1 (1-dioxide), tetramethyl urea or γ - Butyrolactone (γ-butyrolactone).

In the above embodiment of the present invention, the 4-halogenated nitrobenzene in the step (B) is selected from the group consisting of p-fluoronitrobenzene, p-chloronitrobenzene, p-bromonitrobenzene, and p-iodonitrobenzene. One or any combination thereof.

In the present invention, a series of polyimines are subjected to ring-opening addition of the diamine monomer and dianhydride to form polyamic acid (PAA), followed by dehydration cyclization by chemical or thermal means. Formed. A series of low dielectric constant, high _Tg, and processability polyimine structures according to the present invention can be represented by the following repeating unit formula (2):

Among them, Ar ₁ is selected from the following categories, including: Composed of.

In the polyimine prepared according to the present invention, another diamine may be introduced together with the adamantane-containing diamine monomer (1) to react with a dianhydride to produce a polyimine copolymer, and the reaction equation (3) is expressed as follows :

Wherein m ₁ + m ₂ = 100, and m ₁ ranges from 5 to 100, Ar ₁ is the same as above, and Ar ₂ is selected from the following categories, including:

Any or any combination thereof forms a copolymer.

The above polyamidiene copolymer (formula (3)) comprises the following repeating unit fragments, And the ratio of the overlapping unit segment to m ₁ /m ₂ is between 0.05 and 20 (assuming m ₁ +m ₂ =100, m ₁ /m ₂ =5/95 to 100/5).

In addition, the present invention can also selectively add a suitable amount of unsaturated mono-anhydride compound in a condensation polymerization reaction to prepare a cross-linked polyimine, as shown in the following reaction formula (4):

Among them, the X system is the following structure:

The polyimine and its copolymer mentioned in the present invention may also be synthesized by adding different dianhydrides in a reactor, and are subjected to ring-opening addition polymerization to PAA by selecting an appropriate solvent. Subsequently, the catalyst and the dehydrating agent are chemically added (the catalyst may be any combination of any one or more of a heterocyclic tertiary amine, an aliphatic tertiary amine, and an aromatic tertiary amine; and the dehydrating agent may be a fatty aliphatic anhydride The ruthenium imidization is carried out by dehydration ring closure in a heated manner by a dehydration ring closure in a heated manner, and the polyimine and its copolymer are formed by the two-step procedure. Alternatively, the one-step synthesis of polyimine and its copolymers is carried out directly in high boiling solvents such as N-methylpyrrolidone/o-xylene or m-cresol. The reactants are heated to undergo condensation polymerization and dehydration with a ring to form a product. The above reaction is shown in equation (5) as follows: two-step method:

One-step method:

Among them, Ar ₁ has been defined above. Different Ar ₁ tetracarboxylic dianhydrides can be reacted with the diamine monomer (formula (1)) to form a copolymer. In addition, different tetracarboxylic acid dianhydrides of Ar ₁ may also react with the diamine monomer (formula (1)) and different diamines to form a copolymer, and the invention is not limited thereto.

In order to make the foregoing content more succinct, an experimental example will be provided, and an attempt will be made to enable the reviewing committee to better understand the technical contents of the present invention.

S11~s14‧‧‧Steps

Fig. 1 is a schematic view showing the preparation process of the present invention.

In order to enable the reviewing committee to better understand the technical contents of the present invention, the preferred embodiments are described below.

Please refer to FIG. 1 for a schematic diagram of the preparation process of the present invention. As shown in the figure, the present invention is a method for preparing a polyammine containing adamantane having a low dielectric constant, a high glass transition temperature ( _Tg ) and an excellent solubility in an organic solvent, which comprises at least the following steps. Step s11: synthesizing an alkyl-substituted catechol and an adamantane in an organic solvent, and controlling the temperature range to 60-140 ° C for 12-72 hours to synthesize adamantane-containing diphenol compound Step s12: in an alkaline environment, the adamantane-containing diphenol compound and 4-halogenated nitrobenzene in a polar aprotic solution, heated under reflux and stirred for nucleophilic substitution reaction for 12 to 24 hours, synthesizing containing gold Alkane dinitrophenol compound; step s13: reducing the adamantane-containing dinitrophenol compound to an amino group by a reduction method to form an adamantane-containing diaminophenol monomer; and step s14: using the gold-containing The alkane diaminophenol monomer is completely dissolved in a high boiling point solvent (one-step method) or a polar aprotic solution (two-step method), with a dianhydride monomer (with or without a catalyst and/or a dehydrating agent) at 0-30 After stirring at °C for 2.5~3.5 hours, it is placed in an oil bath and heated from 80~120°C to 160~240°C in 2.5~3.5 hours, maintaining 160~240°C and then dehydrating ring closure reaction for another 8~12 hours. A polyammine containing adamantane is synthesized. If so, a novel method for preparing a polyammine containing adamantane is formed by the above disclosed procedure.

In order to show that the polyimine synthesized by the present invention has a low dielectric constant, a high _Tg, and an organic solvent solubility, it is presented using the following evaluation items and methods.

1. Organic solvent solubility test

The dissolution of the polymer was observed at a concentration of 1 g/dL at room temperature and 100 ° C to understand the solvent resistance of the polymer or the type of processing solvent. The organic solvents used include: N-Methyl-2-Pyrrolidone (NMP), N, N-dimethylacetamide (DMAc), o-chlorophenol (o-CP) ), m-cresol, chloroform (CHCl ₃ ), and tetrahydrofuran (THF).

2. Viscosity test

The polymer amount scale 0.05g was dissolved in 10ml test solution, and the solution flow time was completely dissolved into the viscosity tube at 30 ° C constant temperature water tank test solution, and compared with the blank test, the inherent viscosity value of the polymer was calculated. The formula is as follows: η _inh =ln(t/t ₀ )/C

Wherein, t is the time required for the solution containing the polymer to flow through the capillary, t ₀ is the time required for the pure test solution to flow through the capillary, and the concentration of the C-based polymer solution is 0.5 g/dL.

3. Heat resistance test

The heat resistance was evaluated by a glass transition temperature (T _g ) and a thermal degradation temperature (T _d ). The glass transition temperature was measured by a dynamic mechanical analyzer (TA instrument-DMA Q800) and a differential scanning calorimeter (Perkin-Elmer DSC 7), and the DMA was measured at a heating rate of 5 ° C/min and a frequency of 1 Hz. The maximum peak of the loss modulus is taken as the glass transition temperature, and the DSC is taken as the glass transition temperature at a temperature increase rate of 20 ° C/min and a change in the Cp value at the second scan.

In addition, the thermal decomposition temperature was determined by using a TG/DTA measuring instrument (TA instrument-TGA Q500) under air and nitrogen conditions at a temperature of 10 ° C/min, and the weight was measured. The temperature at 10% is reduced as the thermal decomposition temperature.

4. Dielectric constant

A uniform metal-gold electrode was formed on both sides of the film by vacuum sputtering, and the dielectric constant was measured by TA Instruments-DEA 2970. The measurement environment was controlled at 25 ° C, 1 kHz, and the relative humidity was 0%.

5. Hygroscopicity test

The dried polymer weight (W ₁ ) was measured, placed in a 25 ° C water bath for 100 hours, and the surface moisture was wiped off, and the polymer weight (W ₂ ) was measured, using the percentage difference in weight difference before and after moisture absorption. As shown below: (W ₂ -W ₁ )/W ₁ *100%

[Example 1] Synthesis of 3-(1-adamantyl)-5-methylcatechol

Add 15 g (120 mmol) of 4-methylcatechol, 25 g (116 mmol) of 1-bromoadamantane and 25 ml to a 150 ml reaction flask. The benzene was stirred under reflux with heating for 72 hours. After the reaction, purification and separation were carried out to obtain an off-white solid powder. After drying, the crude product was obtained in a weight of 24.1 g (melting point: 194 to 198 ° C, yield: 80.5%), and the solid was further purified to obtain a beige transparent needle weighing 18.8. The yield was 78% and the melting point was 200-202 °C.

[Embodiment 2] Synthesis of 3-(1-adamantyl)-5-tert butylcatechol

The adamantane-containing diphenol compound was synthesized as in the procedure of Example 1, except that 4-methylcatechol was changed to 4-(t-butyl) catechol (4-tert butylcatechol) to give a crude product weighing 27.5 g (melting point 205~) 208 ° C, yield 85.7%). Further purification gave a clear needle weighing 20.1 g, a yield of 73.1% and a melting point of 214 to 216 °C.

[Example 3] Synthesis of 3-(1-adamantyl)-5-methyl-1,2-bis(4-nitrophenyoxy)benzene

To the reactor was added 2.63 g (10.2 mmol) of 3-(1-adamantyl)-5-methylcatechol dissolved in 50 ml of dimethylformamide (DMF) solvent. Subsequently, 3.09 g (22.4 mmol) of potassium carbonate and 3.55 g (22.5 mmol) of 4-nitronitrobenzene were added to the above DMF solution, and after mixing, the mixture was stirred under reflux with heating for 12 hours. After completion of the reaction, the crude product was weighed 4.7 g (melting point: 236 to 239 ° C, yield: 94%) after solvent precipitation and washing with water. Thereafter, the powder was further purified to give a yellow powder weighing 2.9 g, a yield of 61% and a melting point of 242 to 244 °C.

[Example 4] Synthesis of 3-(1-adamantyl)-5-methyl-1,2-bis(4-nitrophenyoxy)benzene

The adamantane-containing dinitrophenol compound was synthesized as in the procedure of Example 3. However, the DMF solvent was changed to Dimethyl Sulfoxide (DMSO) solvent, washed with water and dried to obtain a crude product weighing 3.9 g (melting point 236). ~239 ° C, yield 78%). Thereafter, the powder was further purified to obtain a yellow powder weighing 1.95 g, a yield of 50% and a melting point of 242 to 244 °C.

[Example 5] Synthesis of 3-(1-adamantyl)-5-tert butyl-1,2-bis(4-nitrophenyoxy)benzene

The adamantane-containing dinitrophenol compound was synthesized as in the procedure of Example 3, whereas 3-(1-adamantyl)-5-methylcatechol was changed to 3-(1-adamantyl)-5-tert. Butylcatechol. After washing with water and drying, the crude product of pale yellow powder was 23 g (melting point: 208-211 ° C, yield 86.5%). Thereafter, the yellowish powder was further purified to a weight of 19.9 g, a yield of 75% and a melting point of 209 to 211 °C.

[Embodiment 6] Synthesis of 3-(1-adamantyl)-5-methyl-1,2-bis(4-aminophenyoxy)benzene

Add 6.02 g (12.0 mmol) of 3-(1-adamantyl)-5-methyl-1,2-bis(4-nitrophenyoxy)benzene, 0.6 g of 10% palladium on carbon (Pd/C), 80 ml of ethanol and 50 Million THF was placed in a three-necked reactor and heated to 90 ° C, followed by the dropwise addition of 60 ml of hydrazine (NH ₂ NH ₂ .H ₂ O). After the reaction, the catalyst Pd/C was removed by filtration, and the white powder was analyzed by cooling and concentrating the solution. After filtration, it was washed several times with water to obtain a crude product weighing 3.63 g (melting point: 233-235 ° C, yield). 68%). The powder was further purified to give a clear needle-like powder weighing 3.14 g, a yield of 86.7% and a melting point of 234 to 236 °C.

[Embodiment 7] Synthesis of 3-(1-adamantyl)-5-tert butyl-1,2-bis(4-aminophenyoxy)benzene

The adamantane-containing diaminophenol monomer was synthesized as in the procedure of Example 6, whereas 3-(1-adamantyl)-5-methyl-1,2-bis(4-nitrophenyoxy)benzene was changed to 3-(1-adamantyl). -5-tert butyl-1,2-bis(4-nitrophenyoxy)benzene was used as the reactant. After washing with water and drying, the crude product weighed 7.11 g (melting point: 200-202 ° C, yield 80%). The powder was further purified to give a clear crystal weight of 5.46 g, a yield of 86.7% and a melting point of 201 to 203 °C.

[Embodiment 8] Synthesis of 3-(1-adamantyl)-5-tert butyl-1,2-bis(4-aminophenyoxy)benzene

After 3 g of the catalyst-Engelhard Ni-3288 was reduced with hydrogen, 5.0 g (10 mmol) of 3-(1-adamantyl)-5-tert butyl-1,2-bis(4-nitrophenyoxy)benzene was dissolved in In a solvent, pour into a pressure cooker. Thereafter, the nitro group is reduced to an amino group for 3 to 5 hours by mechanically stirring with a hydrogen pressure of 100 to 200 psig and a temperature setting of 60 to 200 °C. After the reaction, the catalyst and solvent were removed to give a white product weighing 4.1 g, which had a melting point of 201 to 203 ° C and a yield of 92.1%.

[Embodiment 9] Synthetic polyimine

0.909 g (2.066 mmol) of 3-(1-adamantyl)-5-methyl-1,2-bis(4-aminophenyoxy)benzene was completely dissolved in 6 ml of m-cresol in a 25 ml reactor (including 2% different) Quinoline (isoquinoline) solvent. Subsequently, 0.6074 g (2.066 mmol) of 3,3',4,4'-biphenyltetracarboyic dianhydride (BPDA) was added to the diamine solution. After stirring the reaction at 30 ° C for 3 hours, it was placed in an oil bath and heated to 200 ° C in 3 hours, and kept at 200 ° C for another 10 hours. After the reaction is cooled, the precipitate is precipitated by pouring methanol, and the polyimine is obtained after collection, washing, and drying. The polyimine polymer has an intrinsic viscosity of 1.02 dl/g and is soluble in organic solvents such as NMP, o-chlorophenol, m-cresol and CHCl ₃ . The glass transition temperatures measured by DSC and DMA were 314 ° C and 308 ° C, respectively.

[Embodiment 10] Synthetic polyimine

The polyimine was synthesized as in Example 9, except that m-cresol and isoquinoline were changed to 6 ml of NMP and 1.5 ml of o-xylene, respectively. After the reaction was dried, the obtained polyimine had an intrinsic viscosity of 0.86 dl/g.

[Example 11] Synthetic polyimine

The polyimine was synthesized as in Example 9, but BPDA was changed to Pyromellitic dianhydride (PMDA). After the reaction is dried, the obtained polyimine has an intrinsic viscosity of 0.87 dl/g and is soluble in an organic solvent such as o-chlorophenol and m-cresol. The glass transition temperatures measured by DSC and DMA were 363 ° C and 367 ° C, respectively.

[Embodiment 12] Synthetic polyimine

The polyimine was synthesized as in the procedure of Example 9, but BPDA was changed to 3,3',4,4'-benzophenone tetracarboxylic dianhydride (BTDA). ). After the reaction is dried, the obtained polyimine has an intrinsic viscosity of 0.65 dl/g and is soluble in an organic solvent such as NMP, DMAc, o-chlorophenol, m-cresol and CHCl ₃ . The glass transition temperatures measured by DSC and DMA were 300 ° C and 306 ° C, respectively.

[Example 13] Synthetic polyimine

The polyimine was synthesized as in Example 9, but BPDA was changed to 4,4'-oxydiphthalic dianhydride (ODPA). After the reaction is dried, the obtained polyimine has an intrinsic viscosity of 0.72 dl/g and is soluble in an organic solvent such as NMP, DMAc, o-chlorophenol, m-cresol, CHCl ₃ and THF. The glass transition temperatures measured by DSC and DMA were 292 ° C and 288 ° C, respectively.

[Embodiment 14] Synthetic polyimine

The polyimine was synthesized as in the procedure of Example 9, whereas BPDA was changed to 4,4'-hexafluoroisoprorylidene-diphthalic anhydride (6FDA). After the reaction is dried, the obtained polyimine has an intrinsic viscosity of 0.72 dl/g and is soluble in an organic solvent such as NMP, DMAc, o-chlorophenol, m-cresol, CHCl ₃ and THF. The glass transition temperatures measured by DSC and DMA were 300 ° C and 296 ° C, respectively.

[Example 15] Synthetic polyimine

The polyimine was synthesized as in the procedure of Example 9, whereas BPDA was changed to 1,4,5,8-Naphthalene-tetracarboxylic dianhydride (NTDA). After the reaction is dried, the obtained polyimine has an intrinsic viscosity of 0.87 dl/g and is soluble in an organic solvent such as NMP, o-chlorophenol, m-cresol and CHCl ₃ . The glass transition temperatures measured by DSC and DMA were 417 ° C and 411 ° C, respectively.

[Example 16] Synthetic polyimine

The polyimine was synthesized as in Example 9, but 3-(1-adamantyl)-5-methyl-1,2-bis(4-aminophenyoxy)benzene was changed to 3-(1-adamantyl)-5-tert butyl -1,2-bis(4-aminophenyoxy)benzene. After the reaction is dried, the obtained polyimine has an intrinsic viscosity of 0.69 dl/g and is soluble in an organic solvent such as NMP, DMAc, o-chlorophenol, m-cresol, CHCl ₃ and THF. The glass transition temperatures measured by DSC and DMA were 310 ° C and 299 ° C, respectively.

[Example 17] Synthetic polyimine

The polyimine was synthesized as in the procedure of Example 9, whereas 3-(1-adamantyl)-5-methyl-1,2-bis(4-aminophenyoxy)benzene and m-cresol/isoquinoline were changed to 3-(1- Adamantyl)-5-tert butyl-1,2-bis(4-aminophenyoxy)benzene and NMP/o-xylene. After the reaction, the polyimine obtained by drying had an intrinsic viscosity of 0.53 dl/g.

[Embodiment 18] Synthetic polyimine

The polyimine was synthesized as in the procedure of Example 9, whereas 3-(1-adamantyl)-5-methyl-1,2-bis(4-aminophenyoxy)benzene and BPDA were changed to 3-(1-adamantyl)-5, respectively. -tert butyl-1,2-bis(4-aminophenyoxy)benzene and BTDA. After the reaction is dried, the obtained polyimine has an intrinsic viscosity of 0.84 dl/g and is soluble in an organic solvent such as NMP, DMAc, o-chlorophenol, m-cresol and CHCl ₃ . The glass transition temperatures measured by DSC and DMA were 298 ° C and 295 ° C, respectively.

[Embodiment 19] Synthetic polyimine

The polyimine was synthesized as in the procedure of Example 9, whereas 3-(1-adamantyl)-5-methyl-1,2-bis(4-aminophenyoxy)benzene and BPDA were changed to 3-(1-adamantyl)-5, respectively. -tert butyl-1,2-bis(4-aminophenyoxy)benzene and ODPA. After the reaction is dried, the obtained polyimine has an intrinsic viscosity of 0.50 dl/g and is soluble in an organic solvent such as NMP, DMAc, o-chlorophenol, m-cresol, CHCl ₃ and THF. The glass transition temperatures measured by DSC and DMA were 288 ° C and 285 ° C, respectively.

[Example 20] Synthetic polyimine

The polyimine was synthesized as in the procedure of Example 9, whereas 3-(1-adamantyl)-5-methyl-1,2-bis(4-aminophenyoxy)benzene and BPDA were changed to 3-(1-adamantyl)-5, respectively. -tert butyl-1,2-bis(4-aminophenyoxy)benzene and 6FDA. After the reaction is dried, the obtained polyimine has an intrinsic viscosity of 0.62 dl/g and is soluble in an organic solvent such as NMP, DMAc, o-chlorophenol, m-cresol, CHCl ₃ and THF. The glass transition temperatures measured by DSC and DMA were 297 ° C and 293 ° C, respectively.

[Example 21] Synthetic polyimine

The polyimine was synthesized as in the procedure of Example 9, whereas 3-(1-adamantyl)-5-methyl-1,2-bis(4-aminophenyoxy)benzene and BPDA were changed to 3-(1-adamantyl)-5, respectively. -tert butyl-1,2-bis(4-aminophenyoxy)benzene and NTDA. After the reaction is dried, the obtained polyimine has an intrinsic viscosity of 0.56 dl/g and is soluble in an organic solvent such as NMP, DMAc, o-chlorophenol, m-cresol, CHCl ₃ and THF. The glass transition temperatures measured by DSC and DMA were 400 ° C and 399 ° C, respectively.

[Comparative Example 1] Synthesis of 1,2-bis(4-aminophenoxy)benzene

The dinitrophenol monomer was synthesized as in the procedure of Example 3, whereas 3-(1-adamantyl)-5-methylcatechol was changed to catechol. After washing with water and drying, a crude product was obtained, and the powder was further purified to obtain 1,2-bis(4-nitrophenoxy)benzene powder, which had a yield of 47.7% and a melting point of 134 to 136 °C. Subsequently, a diaminophenol monomer was synthesized as in the procedure of Example 6 to carry out a reaction. After washing with water and drying, a crude product was obtained, which was purified in one step to obtain a transparent crystal of 1,2-bis(4-aminophenoxy)benzene with a yield of 87.3% and a melting point of 136 to 138 °C.

[Comparative Example 2] Synthesis of 4-tert butyl-1,2-bis(4-aminophenoxy)benzene

The dinitrophenol monomer was synthesized as in the procedure of Comparative Example 1, whereas catechol was changed to 4-tert butylcatechol. 4-tert butyl-1,2-bis(4-nitrophenoxy)benzene powder can be obtained in a yield of 54.0% and a melting point of 147-149 ° C, and a transparent crystal 4-tert butyl-1,2-bis (4) -aminophenoxy)benzene having a yield of 86.0% and a melting point of 129 to 131 °C.

[Comparative Example 3] Synthetic polyimine

The polyimine was synthesized as in Example 9, but the diamine and dianhydride monomers were changed to Comparative Example 1 and BPDA, respectively. After the reaction is dried, the obtained polyimine has an intrinsic viscosity of a swelling state (concentrated sulfuric acid (H ₂ SO ₄ ), 0.5 g/dL measured at 30 ° C), and is soluble in an organic solvent such as NMP and m-cresol. The glass transition temperature measured by DSC was 246 °C.

[Comparative Example 4] Synthetic polyimine

The polyimine was synthesized as in the procedure of Example 9, except that the diamine and the dianhydride monomer were changed to Comparative Example 1 and PMDA, respectively. After the reaction was dried, the obtained polyimine had an intrinsic viscosity of 1.28 dl/g (concentrated H ₂ SO ₄ , 0.5 g/dL measured at 30 ° C) and was insoluble in any of the organic solvents tested. No significant glass transition temperature was found by DSC testing.

[Comparative Example 5] Synthetic polyimine

The polyimine was synthesized as in the procedure of Example 9, however, the diamine and the dianhydride monomer were changed to Comparative Example 1 and BTDA, respectively. After the reaction is dried, the obtained polyimine has an intrinsic viscosity of 0.67 dl/g (concentrated H ₂ SO ₄ , 0.5 g/dL measured at 30 ° C), and is partially soluble in NMP and m-cresol at 100 ° C. Organic solvents. The glass transition temperature as measured by DSC was 235 °C.

[Comparative Example 6] Synthetic polyimine

The polyimine was synthesized as in the procedure of Example 9, except that the diamine and the dianhydride monomer were changed to Comparative Example 1 and ODPA, respectively. After the reaction was dried, the obtained polyimine had an intrinsic viscosity of 1.00 dl/g (concentrated H ₂ SO ₄ , 0.5 g/dL measured at 30 ° C), and was insoluble in any of the organic solvents tested. The glass transition temperature measured by DSC was 222 °C.

[Comparative Example 7] Synthetic polyimine

The polyimine was synthesized as in Example 9, but the diamine and dianhydride monomers were changed to Comparative Examples 1 and 6 FDA, respectively. After the reaction is dried, the obtained polyimine has an intrinsic viscosity of 1.33 dl/g (concentrated H ₂ SO ₄ , 0.5 g/dL measured at 30 ° C), and is soluble in organic substances such as NMP, DMAc, m-cresol and THF. Solvent. The glass transition temperature measured by DSC was 250 °C.

[Comparative Example 8] Synthetic polyimine

The polyimine was synthesized as in Example 9, but the diamine and dianhydride monomers were changed to Comparative Example 2 and BPDA, respectively. After the reaction is dried, the obtained polyimine has an intrinsic viscosity of 0.65 dl/g (concentrated H ₂ SO ₄ , 0.5 g/dL measured at 30 ° C), and is soluble in organic substances such as NMP, DMAc, m-cresol and THF. Solvent. The glass transition temperature measured by DSC was 251 °C.

[Comparative Example 9] Synthetic polyimine

The polyimine was synthesized as in Example 9, but the diamine and dianhydride monomers were changed to Comparative Example 2 and PMDA, respectively. After the reaction was dried, the obtained polyimine had an intrinsic viscosity of 0.87 dl/g (concentrated H ₂ SO ₄ , 0.5 g/dL measured at 30 ° C) and was insoluble in any of the organic solvents tested. The glass transition temperature measured by DSC was 260 °C.

[Comparative Example 10] Synthetic polyimine

The polyimine was synthesized as in the procedure of Example 9, except that the diamine and the dianhydride monomer were changed to Comparative Example 2 and BTDA, respectively. After the reaction is dried, the obtained polyimine has an intrinsic viscosity of 0.78 dl/g (concentrated H ₂ SO ₄ , 0.5 g/dL measured at 30 ° C), and is partially soluble in NMP, DMAc, THF, etc. at 100 ° C. Organic solvents. The glass transition temperature as measured by DSC was 239 °C.

[Comparative Example 11] Synthetic polyimine

The polyimine was synthesized as in the procedure of Example 9, except that the diamine and the dianhydride monomer were changed to Comparative Example 2 and ODPA, respectively. After the reaction is dried, the obtained polyimine has an intrinsic viscosity of 0.83 dl/g (concentrated H ₂ SO ₄ , 0.5 g/dL measured at 30 ° C), and is soluble in organic substances such as NMP, DMAc, m-cresol and THF. Solvent. The glass transition temperature measured by DSC was 229 °C.

[Comparative Example 12] Synthetic polyimine

The polyimine was synthesized as in Example 9, but the diamine and dianhydride monomers were changed to Comparative Examples 2 and 6 FDA, respectively. After the reaction is dried, the obtained polyimine has an intrinsic viscosity of 0.46 dl/g (concentrated H ₂ SO ₄ , 0.5 g/dL measured at 30 ° C), and is soluble in organic substances such as NMP, DMAc, m-cresol and THF. Solvent. The glass transition temperature measured by DSC was 242 °C.

Table 1 to Table 4 below respectively show the intrinsic viscosity, moisture absorption rate and organic solvent solubility test of the novel adamantane diamine monomer of the present invention synthesized with a series of dianhydrides respectively; And 3, the intrinsic viscosity and organic solvent solubility test of the polyazinium synthesized by the series of dianhydrides; the heat resistance and electrical property test of a series of adamantane-containing polyimides synthesized by the present invention; and Comparative Example 2, respectively 3, a high glass transition temperature (T _g ) of the polyimine synthesized by the series of dianhydrides.

Tables ++, +, +-, and - indicate solubility, wherein ++ means soluble in room temperature, + means dissolved in 100 ° C, + - means partially soluble in 100 ° C, and - means insoluble.

In Table 2, b represents swelling.

It can be clearly seen from Tables 1 to 4 that the novel adamantane-containing diamine monomer (1) and aromatic dianhydride can successfully synthesize a series of polyimine, and have good solubility in organic solvent and low dielectric. Constant and high T _g properties. Table 1 shows that the intrinsic viscosity of the polyimine synthesized by the novel adamantane-containing diamine and dianhydride is between 0.50 and 1.02 dl/g, indicating that the series of polymers have a relatively high molecular weight. At the same time, the polymer is almost all soluble in organic solvents such as NMP, DMAc, o-chlorophenol, m-cresol, CHCl ₃ and THF, which contributes to subsequent processability. From Tables 1 and 2, it can be found that the introduction of a large free-volume and rigid alkyl and adamantane structure in the side chain can destroy the regularity of the polymer, reduce the molecular chain bulk density, and increase the intermolecular distance. The molecular solvent infiltrates, thereby improving the solubility of the polymer. Taking the above Comparative Examples 5, 10 and Example 18 as an example, this phenomenon can be clearly found. If NMP is used as a solvent, the polymer can be solvent cast into a film having a hardness (tensile strength > 72 MPa) and flexibility. At the same time, they have low hygroscopicity and low dielectric constant of at least 0.35% and 2.75 (1 kHz), respectively. According to Tables 3 and 4, a series of polyimines synthesized by a novel adamantane-containing diamine and a dianhydride have superior heat resistance properties, and the T _g temperature ranges from 288 to 417 ° C and 10% thermogravimetry. The loss temperature is at least greater than 470 ° C. Compared with Comparative Examples 3 to 12, the introduction of the adamantane structure in the polyimine significantly increased the T _{g by} at least 50 ° C or more, indicating that the adamantane structure contributes to the improvement of the heat resistance of the polymer. Therefore, the present invention provides a novel polyamidene containing adamantane diamine and a dianhydride having high _Tg , low dielectric constant and good solubility of an organic solvent, and has the potential to be applied to industrial structural materials and integration. Circuit insulators and soft electronic substrates.

In summary, the present invention is a method for preparing a polyammine containing adamantane, which can effectively improve various disadvantages of the prior art, and provides a novel glass with a polyammine derived from adamantane diamine and a dianhydride. The transfer temperature (T _g ), low dielectric constant, and good solubility of organic solvents will have potential for application to industrial structural materials, integrated circuit insulators, and flexible electronic substrates, thereby enabling the production of the present invention to be more Progress, more practical, and more in line with the needs of users, it has indeed met the requirements of the invention patent application, and filed a patent application according to law. However, the above is only the preferred embodiment of the present invention, and the scope of the present invention is not limited thereto; therefore, the simple equivalent changes and modifications made in accordance with the scope of the present invention and the contents of the invention are modified. All should remain within the scope of the invention patent.

S11~s14‧‧‧Steps

Claims (8)

The invention relates to a method for preparing a polyammine containing adamantane, which comprises: (A) reacting an alkyl substituted catechol with a halogenated adamantane in an organic solvent at a temperature ranging from 60 to 140 ° C; 12 to 72 hours, synthesizing an adamantane-containing diphenol compound, wherein the alkyl-substituted catechol is selected from the alkyl group on the 2 or 3 carbon of catechol, and the alkyl carbon number is C _n H _2n+1 (n=1~6) means; (B) in an alkaline environment, the adamantane-containing diphenol compound and 4-halogenated nitrobenzene in a polar aprotic solution, heated under reflux and stirred for nucleophilic a substituting reaction for 12 to 24 hours to synthesize a dipentylphenol compound containing adamantane; (C) reducing the adamantane-containing dinitrophenol compound to an amino group by reduction to form an adamantane-containing diaminophenol The monomer, the adamantane-containing diaminophenol mono system, has the structure represented by the following formula (1): Wherein R represents C _n H _2n+1 and an alkyl group of n=1-6; and (D) completely dissolved in a high boiling solvent (one-step method) or a polar aprotic using the adamantane-containing diaminophenol monomer In the solution (two-step method), the reaction is stirred with the dianhydride monomer at 0 to 30 ° C for 2.5 to 3.5 hours, and then placed in an oil bath and heated from 80 to 120 ° C to 160 to 240 ° C in 2.5 to 3.5 hours. The dehydration ring-closing reaction was carried out at 160 to 240 ° C for another 8 to 12 hours, and finally a polyammine containing adamantane was synthesized. a method for preparing a polyammine containing adamantane according to claim 1 of the patent application scope, Wherein, the organic solvent in the step (A) is selected from the group consisting of benzene, toluene, or xylene. The method for preparing a polyammine-containing adamantane according to the first aspect of the invention, wherein the halogenated adamantane in the step (A) is selected from the group consisting of fluorinated adamantane, adamantane chloride, and bromide Any of alkane, iodide adamantane or any combination thereof. The method for preparing a polyammine containing an adamantane according to the first aspect of the invention, wherein the alkaline environment in the step (B) is selected from an inorganic base derived from a carbonate or a hydroxide. Provided. The method for preparing a polyammine containing adamantane according to claim 1, wherein the polar aprotic solution in the step (B) is selected from the group consisting of N-methylpyrrolidone (N-Methyl-2- Pyrrolidone, NMP), Dimethylformamide (DMF), Dimethyl Sulfoxide (DMSO), N, N-dimethylacetamide (DMAc), tetrahydrothiophene- 1,1-dioxide), tetramethyl urea (tetramethyl urea) or γ - butyrolactone (γ -butyrolactone). The method for preparing a polyammine-containing adamantane according to the first aspect of the invention, wherein the 4-halogenated nitrobenzene in the step (B) is selected from the group consisting of p-fluoronitrobenzene and p-chloronitro Any of benzene, p-bromonitrobenzene, p-iodonitrobenzene or any combination thereof. The method for preparing a polyammine-containing adamantane according to the first aspect of the patent application, wherein the step (D) is based on the adamantane-containing diaminophenol monomer of the formula (1). The polyimine is synthesized by reacting with a dianhydride, and the polymer structure of the polyimine is represented by a repeating unit of the following formula (2): Among them, Ar ₁ is selected from the following categories, including: Composed of. The method for preparing a polyammine containing an adamantane according to the first aspect of the invention, wherein the adamantane-containing diaminophenol single system in the step (D) is completely dissolved in the high boiling solvent in a one-step process. Or completely dissolved in a polar aprotic solution in a two-step process.