TW201026642A - Manufacture of low-dielectric materials derivatives - Google Patents

Abstract

A series of novel adamantane-based compounds having the following formula (I) are disclosed: Wherein A is NO2, NH2, R1-R7 is independently selected from hydrogen, C1-C6 alkanes, C1-C6 oxyalkanes, C3-C7 cyclic alkanes, -CF3, -OCF3, or halogen.

Description

201026642 VI. Description of the Invention: [Technical Field] The present invention relates to a method for producing a low dielectric constant material and a derivative thereof, and in particular to a method for producing a series of adamantane derivative compounds, the derivatives thereof Further, it is further synthesized into a polymer material such as polyimine or polyamine. [Prior Art]

Adamantane is a highly symmetrical carbon-hydrogen bonded tricyclic compound known for its structure resembling diamonds and diamond alkane. It is pointed out in the literature that although adamantane is a polycyclic aliphatic hydrocarbon, its structure has a high thermal stability, and because aliphatic hydrocarbons are not easily polarized, they have a lower dielectric constant. Introduce other polymer materials such as acrylates (Tsuda, T.; Mathias, L. J. Mzcromo/ecM/es 1993, 26, 4734·), polystyrene (Shengo Kobayashi, Takahiro Matsuzawa, Shin-ichi Matsuoka, Hiroyuki Tajima, and Takashi) Ishizone. Macromolecules, 2006, 39, 5979) 'poly(ether ether ketone)s (Lon J. Mathias, Charles M. Lewis, Kurt N. ® Wiegel. Macromolecules, 1997, 30, 5970) 'polybenzoxazines ( Yi-Che Su , Wan-Chun Chen, Feng-Chih Chang. Journal of Applied Polymer Science, 2004, 94, 932.), etc., to enhance its thermal and mechanical properties, and to reduce the electrical properties of polymers. SUMMARY OF THE INVENTION Accordingly, one aspect of the present invention provides a series of adamantane-derived compounds having a structure as shown in formula (I): 4 201026642

Wherein A can be ΝΑ, NH2; R1_R7 can be selected from hydrogen, respectively, carbon number is 1 to 6

The alkyl group, the oxyalkyl group having 1 to 6 carbon atoms, the cycloalkyl group CF3, -OCF3 or a halogen atom having 3 to 7 carbon atoms.

Another aspect of the present invention provides a method of synthesizing a low dielectric constant material from a monomer represented by ruthenium (1). According to an embodiment of the invention,

Af: 〇

Wherein R1-R7 may be independently selected from the group consisting of hydrogen, an alkyl group having 1 to 6 carbon atoms, an oxyalkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 7 carbon atoms, -CF3, -〇Cf3 or Halogen atom. According to another embodiment of the present invention, when A of the compound represented by the formula (1) is NH2, a low dielectric polyamine can be synthesized. The reaction diagram is as follows: 5 201026642

Ar1: (a) (b) (c)

Wherein R1 to R7 are each independently selected from the group consisting of hydrogen, an alkyl group having 1 to 6 carbon atoms, an oxyalkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 7 carbon atoms, -CF3, -OCF3 or a halogen. atom. [Embodiment] Hereinafter, embodiments of different embodiments of the present invention will be further described. ❿ Synthesis Example 1: Synthesis of monoterpene) Figure 1A is a schematic diagram showing the synthesis of monomer (1) based on adamantane. According to an embodiment of the present invention, the synthesis procedure of monomer (1) is as follows: 24.42 Gram (0.11 mol) of Ι-bromoadamantane and 200 ml of phenol were added to the 500 ml reactor. Then the reaction temperature was raised to 110 ° C, and stirring was stopped after 12 hours of reaction. After the reactor is slightly cooled, it is added dropwise to 1000 ml of warm water and stirred to precipitate a white solid, which is the monomer (1)»precipitate and filter it' and wash it with a large amount of warm water, and put it into a vacuum oven at l〇 Dry at 〇 °C. HR-MS (M) + Calc.228_1514; Found 228.1513. 6 201026642 Figure 1B shows the lHNMR spectrum of monomer (1). It was confirmed by 1hnmr and high-resolution mass spectrometry that the synthesized monomer (1) was structurally correct.

Ul·Example 2: Schematic diagram of the synthesis of the monomer (2) of the body (2), and the synthesis of the monomer (2) according to an embodiment of the present invention is as follows: Take 15 g (65.7 mmol) Monomer (1), l-ful〇r〇-2,4-dinitrobenzene 12·27 g (65.9 mmol), KzCO3 10.88 g and THF 100 ml in a 250 mL liter reactor, followed by raising the reaction temperature At the reflux temperature, the search was stopped after 12 hours of maintaining the reaction. After cooling the reactor to room temperature, it was dropped into 1 ml of methanol aqueous solution and poured out to precipitate a pale yellow solid, which was a single vessel (2). After filtration, it was placed in a vacuum oven and dried at 100 °C. HR-MS (M)+ Calc.394.1529; Found 394.4537. 2B is a 1H NMR spectrum of the monomer (2), and FIG. 2C is a single crystal diffraction pattern of the monomer (2). The synthesized monomer can be confirmed by 1H NMR, a high-resolution mass spectrometer, and single crystal diffraction ( 2) The structure is correct. According to another embodiment of the present invention, the reactant for synthesizing the monomer (2) may be l-chloror-2,4-nitrobenzene, hbromo-zy in addition to the 1-flur-r〇-2,4-nitrobenzene. -nitrobenzene or li〇do-2,4-nitrobenzene. The catalyst may be a compound of the steroid-Vn steroid group, such as CsF, KF, CsCl or KC1; or an inorganic base such as K2C03, Na2C03, KOH or NaOH. Column 3: Synthesis of Monomer Π) Figure 3 is a schematic diagram showing the synthesis of monomer (3). According to one embodiment of the present invention, the synthesis step of monomer (3) is as follows: Take monomer (2) 4 g ( 10.15 mmol), 0.08 g of Pd/C and ethanol 40 ml were added to the high pressure reactor for stirring. The pressure was maintained at 140 psi for 12 hours. After the 201026642 was dissolved by THF, the Pd/C ' was filtered and the filtrate was dropped into deionized water. A white powder was precipitated. The powder was filtered, dried at 1 ° C, and recrystallized using ethanol. Fig. 3B is a graph showing the result of measuring the monomer (3) by DSC, which showed a melting point of 177.匸 Figure 3C is a 1H NMR spectrum of monomer (3), HR-MS (M) + Calc. 334.2045; Found 334.2038, and Figure 3D is a single crystal diffraction pattern of monomer (3). From the 1H NMR, the high-resolution mass spectrometer, and the single crystal diffraction, it was confirmed that the synthesized monomer (3) was structurally correct, and the monomer purity was determined by DSC. Synthesis Example 4: (4 VPI (V>'s Fig. 4 is a schematic diagram of a different embodiment of an embodiment in which a monomeric (3) is synthesized with a different dianhydride (a_e)). Synthesis Example 4 utilizes a monomer (3) Synthesis of low-dielectric polyimine with low-dielectric polyimine (4)-I>I(a) with dianhydride BPDA(a). The synthesis procedure is as follows: First weigh 0.5 g (1.496 mmol) Diamine monomer (3), 0.4399 g (1.496 mmol) BPDA (a), catalyst isoqunoline 〇.〇3 g and 5 ml of m-cresol are stirred in a 100 ml three-necked flask to raise the reaction temperature 2〇〇c»C, after maintaining the reaction for 12 hours, poured into methanol to precipitate and filtered. The product was washed with hot methanol for 24 hours. After filtration, it was dried under vacuum at 100 ° C. The dried product was dissolved in DMAc. The solution has a solid content of about 20 wt/min, and the poly-imine solution is coated on a glass substrate by a coater and the film thickness is controlled to about 30 μm. Heat treatment at 8 ° C in a hot air circulating oven. After 12 hours, after removing most of the solvent, it was heated to 200. After treatment and maintaining for 2 hours, it was cooled to room temperature, and it was immersed in water to make film and glass. Separation of the plate. Synthesis Example 5: (4VPI(b) 厶# Synthesis Example 5 Synthesis of Low Dielectric Polyimine (4)-PI(b) Using Monomer (3) and Diacid anhydride BpDA(b) 'Embodiment As shown in Figure 4, the synthesis steps are as follows: 8 201026642 First weigh 0.5 g (1.496 mmol) of diamine monomer (3), 0.482 g (1.496 mmol) BTDA (b), catalyst isoqunoline 0.03 g and 5 ml of m_cres〇1 was stirred in a 3-100 ml three-necked flask, the reaction temperature was raised to 200 ° C, the reaction was maintained for 12 hours, poured into methanol and precipitated, and the product was washed with hot methanol for 24 hours. Drying at 100 ° C in vacuum. Dissolve the dried product in DMAc to make the solution solid content about 20 wt%. Apply the polyimine solution to the glass substrate by a coater and control the film thickness to be about 30 μιη » Heated at 80 °C for 12 hours in a hot air circulating oven, after removing most of the solvent, then heating to 200 ° C for 2 hours, then dropping to room temperature, soaking it in water to make the film and glass Substrate Separation Synthesis Example 6: (Synthesis Synthesis of 4VPI(c) Example 6 Synthesis of Low Dimer Polymerization Using Monomer (3) and Diacid Anhydride BPDA (c) The imine (4)-PI (c), the embodiment is shown in Figure 4, the synthesis steps are as follows: First, weigh 0.5 g (1.496 mmol) of the diamine monomer (3), 0.464 g (1.496 mmol) ODPA (c), catalyst isoqunoline 0.03g and 5mL of m-cresol were stirred in a 1 liter three-necked flask, raising the reaction temperature to 2 〇〇〇 c, maintaining the reaction for 12 hours, and then pouring into methanol to precipitate. Filter and the product was washed with hot methanol for 24 hours. After filtration, it was vacuum dried at ❿ 1〇〇〇C. The dried product was dissolved in DMAc to have a solid content of about 20% by weight. The polyimide solution was coated on a glass substrate by a coater, and the film thickness was controlled to be about 30 μm. After heat treatment in a hot air circulating oven for 12 hours, most of the solvent was removed, and then heated to 2 〇〇 并c and maintained for 2 hours, then cooled to room temperature, and immersed in water to separate the film from the glass substrate. Synthesis Example 7: Synthesis of (4)-ΡΙ(<1) Example 7 Synthesis of low dielectric polyimine (4)-PI(d) using monomer (3) and dianhydride BPDA (d), The embodiment is as shown in Fig. 4 'The synthesis steps are as follows: 9 201026642 First weigh 0.5 g (1.496 mmol) of diamine monomer (3), 0. 778 g (1.496 mmol) BPADA (d), catalyst Is〇qUnoline 〇·〇3 g and 5 ml of m-cresol are stirred in a 100 ml three-necked flask, the reaction temperature is raised to 2 ° C, the reaction is maintained for 12 hours, poured into methanol and precipitated, and the product is filtered. Wash with hot methanol for 24 hours. After filtration, it was vacuum dried at 10 ° C. The dried product was dissolved in DMAc to have a solution solid content of about 20% by weight, and the polyimide solution was coated on a glass substrate by a coater and the film thickness was controlled to be about 30 μm. Heat treatment at 80 ° C for 12 hours in a hot air circulating oven. After removing most of the solvent, the temperature was raised to 2 Torr. (: and after 2 hours, φ was lowered to room temperature, and it was immersed in water to separate the film from the glass substrate. Synthesis Example 8: (4VPI(e) 厶忐 Synthesis Example 8 Using monomer (3) and dianhydride PMDA (e) Synthesis of low dielectric polyimine (4)-PI(e) 'The embodiment is shown in Fig. 4, and the synthesis steps thereof are as follows: First, 0.5 g (1.496 mmol) of the diamine monomer is weighed ( 3), 0.3261 g (1.496 mniol) PMDA (e), catalyst isoqunoline 0.03 g and 5 ml of m-cresol

Stirring in a 100 ml three-necked flask, raising the reaction temperature to 2 〇〇 0 C, and insoluble matter is precipitated during the reaction, indicating that (4)-PI(e) cannot be dissolved in m-cresol, so that the coating process cannot be continued. . Comparative Example 1: i5VPI (a_d) synthesized by a two-step method. Figure 5 is a prepolymerization of polyamidoimine at a low temperature using a monomer having no adamantane structure, m-phenyldiamine (5) and a different diacid needle (ad). The synthesis of polyaniline (5)-PI(ad) by the two-step synthesis of polyimidazolium polyamic acid by thermal closed-loop dehydration to form polyamidiamine. The synthesis steps of different dianhydrides (ad) are similar. Only the synthesis of polystyrene (5)-PI(a) is used as a representative example. The steps are as follows: First, the reactor is purged with nitrogen for 1 hour and then 0.5 g (4.6266 mmol) of diamine 201026642 monomer (5) and DMAc are added. 7.1712g was stirred and dissolved in the reactor to prepare a solution with a solid content of 20 wt%, and stirred for 3 minutes in an ice bath, then 136 〇 3 g (4.6266 mmol) of BPDA (a) was continuously stirred in an ice bath. It was viscous, and the solution was diluted to a solid content of 15 wt% and coated on a glass substrate by a coater to control a film thickness of about 30 μm. 80 in a hot air circulation oven. (: After heating for 12 hours, the temperature was raised to l〇〇 ° C, 200 ° C, and 300 ° C for one hour each time to dehydrate the closed ring to obtain polyimine (5)-PI(ad)', and finally immersed it in water to make a film. Separation from the glass substrate. ❹ Synthesis Example 9: (6VPAfa-e, gas phase 6 is a synthesis of polymethane based on adamantane using diamine monomer (3) and different polyamine PA (a_e) 6) Schematic diagram of different embodiments of the embodiment of _PA(a_e). Since the synthesis steps of polyamine (6)-PA (ae) are similar, only the synthesis of polyamine (6)·ΡΑ (a) is used as a representative example. The synthesis procedure is as follows: First, nitrogen gas is introduced for 30 minutes, and 0.5013 g (1.5 mmol) of diamine monomer, 0.249 g (1.5 mmol) of TPAC (a), 0.35 g of CaCl2, and 1.1021 g of TPP, 1 are weighed. · 3 ml of pyridine and 5 ml of NMP are added to the reactor of 1 〇〇 ml. Stir at 200 ° C for 4 hours. After cooling to room temperature, slowly pour the polymer solution obtained after the reaction. Precipitated in 15 ml of sterol, and the obtained product was filtered, washed with methanol and hot water, and the product was collected and dried in iONC under vacuum. The polyetheramine polymer is dissolved in DMAc or ΝΜρ to make the solution solid content of about 20 wt%, and the polyamine solution is coated on a glass substrate by a coater, and the film thickness is controlled to be about 30 μm. The hot air circulating oven was heat treated for 12 hours, and most of the solvent was removed, and then the temperature was raised to 2 Torr. After 2 hours, the temperature was lowered to room temperature, and it was immersed in water to separate the film from the glass substrate. - According to the above, In the embodiment of the present invention, a series of low-dielectric polyimine and a diamine monomer 11 201026642 m-phenyldiamine (5) without an adanaantane side chain substituent are synthesized by a one-step method (5). The results of the comparison of the nature of PI(ad) are summarized in Tables 1 and 2. Table 1 shows the ultimate viscosity and solubility of two series of p〇iyiniides, and Table 2 shows the thermal and mechanical properties of the two series of poiyimides. Determination of dielectric constant. Table 1. Determination of ultimate viscosity and solubility of polyimide (4-5)-PI(ad)_

Polyimides m-Cresol NMP DMSO DMAc DMF 4a 4b _ 4c 4d 5a 5b 5c - + + 0.41 + + 0.37 + + 0.42 + + + - + + + + + + + + + + + + + + H - + + ++ + ++ ++ ++ ++ +- 5d a + ^— a: 5 mg sample dissolved in 0.5 ml solvent Solubility b: at 30 ° C, dissolved in 〇.5g / dLDMAc ++: in the room Soluble under temperature +: soluble at 60 ° C soluble +-: heated at 60 ° C, slightly soluble, still insoluble, the results shown in Table 1 show that the 4 series has introduced soft ether segments and The side chain substituent of the adamantane structure hinders the stacking of the molecular chains, making them all amorphous; as shown in Figure 7, Figure 7 is a scan of the XRJD of polyimide (4)-PI(ad); It has better organic solubility than the 5 series. In the ultimate viscosity measurement, the 4 series ranged from 0.37 to 0.42 dL/g, while the 5 series could not be measured because it could not be dissolved in DMAc. Fig. 8 is a DMA diagram of the p〇lyimides 4 series, and the results are summarized in Table 2. The results show that the glass transition temperature of the synthesized polymer series 4 and 5 is affected by 12 201026642 dianhydride structure between 236-355 °C. However, even in the polyimides 4 series in which a side chain substituent is introduced into the structure, the polymer synthesized by the same dianhydride has a glass transition temperature higher than that of the polyimides 5 series under the influence of the rigid adamantane; The results are consistent. Figure 9 is a TMA plot of the polyimides 4 series. The expansion coefficient is slightly higher than the polyimides 5 series. The reason is that the space between the 4 series molecular structures is larger than that of the 5 series, and the reaction coefficient is increased. Figure 10 shows the TGA囷 of the polyimides 4 series. In this experiment, TGA was used to determine the thermal stability of the polymer. The data was compiled in Table 2. The Td5% thermal cracking temperature of the 4 series was 485-499 °C, and the 5 series was 474_537 °C. The lower ether group will break at the lower temperature, but the thermal stability of the adamantane structure will make the char yield higher than that of the 5 series. The results in Table 2 show that the polyimide 4 series has the ability to be polarized with a damantane side chain substituent, which in turn has a lower dielectric constant than the polyimide 5 series. Table 2, Polyimide (4-5)-PI (ad) thermal, mechanical properties and dielectric constant determination

Polyimides E, at 50〇C (GPa) Tg(°C) (DMA)3 Tg(°C) (TMA) CTE (ppm/°C) Td5% rc> Char yieldb e (1kHz) 4a 3.53 355 334 34 485 62 2.74 4b 3.11 330 305 52 499 59 2.77 4c 2.45 317 292 58 474 46 2.85 4d 1.92 267 247 59 485 42 2.87 5a 7.11 335 - - 521 50 3.32 5b 4.9 308 295 32 537 58 3.38 5c 4.3 294 278 37 512 51 3.41 5d 4.03 236 220 50 474 37 3.44 a: Peak temperature of tan δ at heating rate of 5 ° C /min, b: Residual weight at 800 ° C in nitrogen. Although the invention has been disclosed in the above embodiments, it is not used In order to limit the invention, it is intended that those skilled in the art will be able to make various changes and modifications, which are defined by the scope of the invention, without departing from the spirit and scope of the invention. Therefore, the scope of the present invention is set forth in the accompanying drawings, which are set forth in the accompanying drawings.

A schematic diagram of the synthesis of a monomer (1) based on adamantane. Figure 1B is an NMR spectrum of the early body (1). Figure 2A is a schematic diagram showing the synthesis of monomer (2). Figure 2B shows the 1H NMR spectrum of a single vessel (2). Figure 2C is a single crystal diffraction diagram of a single ship (2). The third diagram is a schematic diagram of the synthesis of a single vessel (3). The third diagram is the result of measuring the monomer (3) by Dsc. Figure 3C is a 1H NMR spectrum of monomer (3). The features, advantages, and embodiments of the invention can be more clearly illustrated. Figure 4 is a schematic representation of various embodiments of the synthesis of low dielectric polyamines and polystyrene using a single Zhao (3) and a different dianhydride (a_e). Figure 5 shows the use of m-phenyldiamineO, which has no adamantane structure monomer, and different dianhydrides (ad) to prepolymerize at a low temperature to form a polyamidamine precursor polyamic acid polyamic acid. A schematic diagram of the synthesis of polyimine (5)-PI(ad) by a two-step process of amines. Figure 6 shows the synthesis of adamantane based on diamine monomer (3) and different polyamines PA(ae). A schematic representation of a different embodiment of an embodiment of indoleamine (6)-PA (ae). Figure 7 is a scan of the XRD of polyimide (4)-PI(a-d). 201026642 Figure 8 shows the DMA diagram of the polyimides 4 series. Figure 9 is a TMA plot of the polyimides 4 series. Figure 10 is a TGA diagram of the polyimides 4 series. [Main component symbol description]

Claims (1)

201026642 VII. Patent application scope: 1. A low dielectric constant material having a structure as shown in formula (I) (I) Ο Α Α Ν〇 Ν〇 2, NH2; R1 - R7 are respectively selected from hydrogen, an alkyl group having 1 to 6 carbon atoms, an oxyalkyl group having 1 to 6 carbon atoms, and a carbon number of 3 to 7 Cycloalkyl, -CF3, OCF3 or a halogen atom. 2. A method of synthesizing a low dielectric constant material, comprising: providing a compound having a structure as shown in formula (I), wherein A is NH2, and R1-R7 are each selected from hydrogen and having a carbon number of 1 to 6 An alkyl group, an oxyalkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 7 carbon atoms, -CF3, -OCF3 or a halogen atom; and a reaction of the compound with a double acid needle monomer to synthesize adamantane As a matrix of polyimine, the dianhydride monomer has a structure as shown in formula (II): 〇Ύ乂 p 〇 0 (II) wherein Ar' comprises at least the structure of the following formulas (a)-(d): BPADA (d) PMDA (e) 16 201026642 3. The method of synthesizing a low dielectric constant material according to claim 2, wherein the reaction is The process for forming a polymerized imine in adamantane is as follows: 4. The method of synthesizing a low dielectric constant material according to claim 2, wherein Ar' comprises at least the following formula (a), (b), (c), (d), (e) or (f) Structure: Ar1: XT 5. A method for synthesizing a low dielectric constant material, comprising: providing a compound having a structure as shown in formula (I), wherein Α is ΝΗ2, and R1-R7 are each selected from hydrogen and having a carbon number of 1 An alkyl group of 6 to 6, an oxyalkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 7 carbon atoms, -CF3, -OCF3 or a halogen atom; and a reaction of the compound with a diacid monomer to synthesize Adamantane is a matrix polyamine having a structure represented by formula (III): HOOC-Ar'-COOH (III) wherein Ar' contains at least the following formulas (a)-(e) Structure of the structure: 17 201026642 6. The method of synthesizing a low dielectric constant material according to claim 5, wherein the process for synthesizing the polyammonium based on adamantane is as follows: 18