Oligomer, method for preparing oligomer, and method for preparing cured product of oligomer

Abstract

An oligomer having a structure as shown in Formula (I): , wherein, X is a structure of , Y are each independently a structure of hydrogen, halogen, , , or , R 0and R 1are each independently a structure of hydrogen, C 1-C 6alkyl, phenyl or , and n and m are each independently an integer from 0 to 300. The oligomer of the present invention is suitable for forming a cured product which can be used as a low dielectric resin material. The present invention also relates to a method for preparing an oligomer and a method for preparing a cured product of the oligomer.

Description

[Technical Field]

[0001] This invention relates to an oligomer, and more particularly to an oligomer having the structure shown in formula (I): Formula (I). This invention also relates to a method for preparing an oligomer and a method for preparing a cured oligomer. [Previous Technology]

[0002] In recent years, due to the intensification of global warming, environmental awareness has risen in countries around the world, and they have begun to pay attention to the carbon footprint and carbon emissions generated in the production process. Many countries have successively formulated relevant policies and regulations such as carbon rights, hoping to present carbon emissions in a quantitative way and levy carbon taxes to limit emissions and reduce the greenhouse effect.

[0003] Bio-based materials have a lower carbon footprint than petrochemical-based materials, which can help reduce carbon dioxide emissions and environmental impact. Moreover, since they are mostly produced by plants, they are considered renewable resources. Therefore, the demand to replace traditional petroleum-based materials with low-carbon and bio-based materials has become the primary development direction for related industries.

[0004] On the other hand, with the evolution of technology and the continuous development of semiconductor technology, the size of electronic components is shrinking, and the spacing between metal wires is also decreasing, leading to signal interference between metal wirings. Furthermore, the interaction between wires and dielectric layers can easily cause signal transmission delays. Therefore, the electrical properties of the resin layer play a crucial role in the circuit board. The smaller the dielectric constant Dk and dielectric loss Df of the dielectric layer, the better it is for reducing signal loss during signal transmission and increasing transmission speed. Therefore, the relevant industries currently urgently need low-dielectric resin materials that meet the above requirements. [Summary of the Invention]

[0005] Traditional resin materials still have room for improvement. Therefore, one object of the present invention is to provide a novel oligomer suitable for forming cured products that can serve as low-dielectric resin materials.

[0006] Poly(2,6-dimethylphenylene ether) (PPO) is one of the five major engineering plastics. It is a non-crystalline thermoplastic polymer with characteristics such as high molecular weight, rigid structure, high glass transition temperature, impact resistance and low coefficient of expansion. Furthermore, due to the absence of hydrolyzable bonds and polar functional groups, it has excellent electrical properties. However, its high molecular weight also leads to high viscosity and poor solubility, which limits the application range of poly(2,6-dimethylphenylene ether).

[0007] In recent years, studies have been conducted to modify poly(2,6-dimethylphenyl ether) into (2,6-dimethylphenyl ether) oligomers, but their heat resistance is poor, so the ends need to be modified to form a structure with crosslinkable end groups. In view of this, developing a bio-based (2,6-dimethylphenyl ether) oligomer with excellent performance, wide application and simple preparation method has become the goal of relevant industries.

[0008] One objective of this invention is to provide a functionalized (2,6-dimethylphenyl ether) oligomer containing bio-based materials and their derivatives, and a method for preparing the same, which has the advantages of simplifying steps and reducing production costs.

[0009] Another object of the present invention is to provide a method for preparing a cured oligomer, wherein the oligomer is subjected to a curing reaction to prepare a cured product, and the cured product has a low dielectric constant, low dielectric loss and good thermal stability.

[0010] To achieve the above and other objectives, the present invention provides an oligomer having a structure as shown in formula (I): wherein X is a structure, Y is each independently hydrogen, halogen, or one of the structures, R0 and R1 are each independently hydrogen, C1 to C6 alkyl, phenyl, or n and m are each independently an integer from 0 to 300.

[0011] In one embodiment of the present invention, the oligomer may have one of the structures shown in formula (I-1), formula (I-2), formula (I-3) or formula (I-4):

[0012] To achieve the above and other objectives, the present invention also provides a method for preparing an oligomer, comprising the following steps: (a) heating a bio-based diene compound and a phenolic compound in a Lewis acid catalyst to 80-150°C and stirring to allow them to react, then washing with water and neutralizing and purifying to obtain a phenolic reactant; (b) mixing the phenolic reactant obtained in step (a) with 2,6-dimethylphenol in a methanol-water cosolvent containing a copper catalyst and an amine catalyst, and carrying out an oxidative polymerization reaction in an oxygen environment and at a temperature of 0-70°C to obtain a bisphenol polyphenylene ether oligomer; and (c) reacting the bisphenol polyphenylene ether oligomer obtained in step (b) with methacrylic anhydride or vinylbenzyl halide at a temperature of 45-100°C and under the catalysis of an alkaline catalyst to obtain the oligomer.

[0013] In one embodiment of the present invention, the molar ratio of the bio-based diene compound to the phenolic compound in step (a) may be 1:2 to 1:10, and the molar ratio of the phenolic reactant to the 2,6-dimethylphenol in step (b) may be 1:2 to 1:10.

[0014] In one embodiment of the present invention, in step (a), the bio-based diene compound may be selected from the group consisting of phenol, 2,6-xylenol and 2,3,6-trimethylphenol; and the Lewis acid catalyst may be selected from the group consisting of BF3 and aluminum halide.

[0015] In one embodiment of the present invention, in step (b), the copper catalyst may be selected from the group consisting of CuCl, CuCl2, CuBr and CuBr2; and the amine catalyst may be selected from the group consisting of (trialkyl)amine and dialkylamino pyridine, wherein each alkyl group is independently a C1 to C6 alkyl group.

[0016] In one embodiment of the present invention, the oxygen source of the oxygen environment in step (b) may be pure oxygen or air.

[0017] To achieve the above and other objectives, the present invention also provides a method for preparing a cured oligomer, comprising the following steps: (a) taking the oligomer prepared by the above preparation method; and (b) copolymerizing the oligomer with a peroxide to obtain a cured oligomer.

[0018] In one embodiment of the present invention, the peroxide in step (b) may be selected from the group consisting of benzoyl peroxide and tert-butyl peroxide.

[0019] In one embodiment of the present invention, in step (b), the content of the peroxide may be from 0.1% by weight to 1.0% by weight, based on the total weight of the oligomer and the peroxide.

[0020] The oligomer of the present invention, through its unique molecular structure, can form a cured product with excellent dielectric properties, making the cured product a low-dielectric resin material for use in the semiconductor industry. The method for preparing the oligomer of the present invention, by using a bio-based diene compound, can form the oligomer as described above, and can effectively reduce the carbon footprint. The method for preparing the cured product of the oligomer of the present invention, by preparing the oligomer by the above method, can form a cured product with excellent dielectric properties, making the cured product a low-dielectric resin material for use in the semiconductor industry.

Implementation Method

[0021] To fully understand the purpose, features, and effects of the present invention, the present invention will be described in detail below with reference to the specific embodiments, as follows: Embodiments 1-4

[0022] Example 1, Preparation of bisphenol monomer (LN-core): 30.8 g (0.12 * 2.1 mole) of 2,6-dimethylphenol and 2.67 g (0.12 * 0.17 mole) of aluminum chloride (AlCl3) were placed in a 250 ml single-necked flask and stirred at 80 °C for about 30 minutes, at which point a reddish-black transparent liquid was formed. Then, 16.3 g (0.12 mole) of (±)-limonene was weighed and slowly added dropwise to the solution, and the reaction was continued for three hours. After the reaction was completed, 25 g of 10 wt% sodium hydroxide aqueous solution (NaOH(aq)) was added dropwise and stirred for about 1 hour to neutralize the catalyst and terminate the reaction. After the reaction was completed, the solution was dissolved in toluene and extracted several times with water. Toluene and excess 2,6-dimethylphenol were removed by vacuum distillation to obtain a brown solid. The reaction equations for Example 1 are shown in Table 1 below.

[0023]

[0024] Example 2, Preparation of bisphenol oligomer (LN-OPE): 2.7 g (0.092*0.3 mole) of copper(I) chloride and 18 g (0.092*1.65 mole) of 4-dimethylaminopyridine (DMAP) were dissolved in 300 ml of methanol and placed in a 1000 ml three-necked flask. Oxygen was introduced below the liquid surface and the mixture was stirred for about 30 minutes. Simultaneously, 35.1 g (0.092 mole) of bisphenol monomer (LN-core) obtained in Example 1 and 90 g (0.092*8 mole) of 2,6-dimethylphenol were dissolved in 450 ml of methanol and poured into the aforementioned copper catalyst solution. Oxygen was introduced and the reaction was continued for eight hours. After the reaction was completed, the mixture was directly filtered. The filter cake was washed twice with 2 L of methanol containing 10 ml of HCl, and then washed several times with methanol to obtain a brown powder. The reaction equations for Example 2 are shown in Table 2 below.

[0025]

[0026] Example 3, Preparation of oligomer (LN-OPE-PM): 5.00 g (3.125 mmol) of bisphenol oligomer (LN-OPE) prepared in Example 2, 1.93 g (3.125*4 mmol) of methacrylic anhydride, and 0.1 g (2 wt%) of sodium acetate (AcONa) were dissolved in 50 ml of dimethylacetamide (DMAc) and placed in a 100 ml three-necked flask. The mixture was heated to 80 °C and nitrogen gas was introduced for 24 hours. After the reaction was completed, the solution was poured into a methanol / water co-solvent (v:v / 4:1) to precipitate the product. After washing several times, the filter cake was placed in a 78 °C oven and dried to obtain a light gray powder, which is the (2,6-dimethylphenyl ether) oligomer with terminal methyl acrylic groups of Example 3. The reaction equations for Example 3 are shown in Table 3 below.

[0027]

[0028] Example 4, Preparation of Oligopolymer (LN-OPE-VB): 5.00 g of the bisphenol oligopolymer (LN-OPE) prepared in Example 2, 1.43 g (3.125*3 mmol) of 4-(chloromethyl)styrene, and 1.29 g (3.125*3 mmol) of potassium carbonate (K2CO3) were dissolved in 50 ml of dimethylacetamide (DMAc) and placed in a 100 ml three-necked flask. The mixture was heated to 80 °C and nitrogen gas was introduced for 24 hours. After the reaction was completed, the solution was poured into a methanol / water co-solvent (v:v / 4:1) to precipitate the product. After washing several times, the filter cake was placed in a 78 °C oven and dried to obtain a light gray powder, which is the styrene-terminated (2,6-dimethylphenyl ether) oligopolymer of Example 4. The reaction equation for Example 4 is shown in Table 4 below.

[0029]

[0030] Examples 5-6

[0031] Example 5, Cured product of oligomer (LN-OPE-PM)

[0032] The oligomer (LN-OPE-PM) prepared in Example 3 was mixed with dicumyl peroxide (DCP) as a free radical initiator, and then a solution with a solid content of 20% was prepared with xylene, wherein the content of DCP was 1.0 weight percentage of the oligomer. Next, after mixing evenly, the mixture was poured into a mold and cured under nitrogen atmosphere. The heating conditions were 80°C (8 hours), 120°C (2 hours), 140°C (2 hours), 180°C (2 hours), 200°C (2 hours), and 220°C (2 hours). After demolding, the cured oligomer (LN-OPE-PM) of Example 3 was obtained.

[0033] Example 6, Cured product of oligomer (LN-OPE-VB)

[0034] Using the same preparation process as in Example 5, but replacing the oligomer (LN-OPE-PM) prepared in Example 3 with the oligomer (LN-OPE-VB) prepared in Example 4, a cured product of the oligomer (LN-OPE-VB) of Example 4 can be obtained.

[0035] Comparative Examples 1-2

[0036] Comparative Example 1, Preparation of cured SA9000: SA9000, a product of Saudi Basic Industries Corporation (SABIC), was prepared into a solution with a solid content of 20 wt% using xylene, and 1.0 wt% of dicumyl peroxide (DCP) of SA9000 was added. The solution was poured into a mold and cured under nitrogen atmosphere. The heating conditions were 80°C (8 hours), 120°C (2 hours), 140°C (2 hours), 180°C (2 hours), 200°C (2 hours), and 220°C (2 hours). After demolding, the cured product C-SA-9000 of Comparative Example 1 was obtained.

[0037] Comparative Example 2, Preparation of cured OPE-2st: OPE-2st, a product of Mitsubishi Gas Chemical Co., Ltd., was prepared into a solution with a solid content of 20 wt% using xylene, and 1.0 wt% of dicumyl peroxide (DCP) of OPE-2st was added. The solution was poured into a mold and cured under nitrogen atmosphere. The heating conditions were 80°C (8 hours), 120°C (2 hours), 140°C (2 hours), 180°C (2 hours), 200°C (2 hours), and 220°C (2 hours). After demolding, the cured product C-OPE-2st of Comparative Example 2 was obtained.

[0038] Test Example 1: Evaluation of the thermal properties of various cured products

[0039] (1) The storage modulus and the relationship between the Tan delta curve and temperature and the glass transition temperature (Tg) of the cured material were measured using a Dynamic Mechanical Analyzer (DMA), wherein the heating rate was 5℃ / min and the temperature range was 40℃ to 300℃.

[0040] (2) The glass transition temperature and coefficient of thermal expansion (CTE) of the cured material were measured using thermomechanical analysis (TMA), wherein the heating rate was 5℃ / min and the temperature range was 50℃ to 150℃.

[0041] (3) Thermogravimetric analysis (TGA) was used to measure the 5% thermogravimetric loss temperature (Td5%) and the char yield at 800°C. The thermogravimetric analysis was performed under a nitrogen atmosphere at a heating rate of 20°C / min, using a thermogravimetric analyzer to measure the weight change of the sample. The 5% thermogravimetric loss temperature refers to the temperature at which the sample loses 5% of its weight, and a higher 5% thermogravimetric loss temperature indicates better thermal stability of the sample. The char yield at 800°C refers to the percentage of the sample's residual weight when heated to 800°C, and a higher percentage of the residual weight at 800°C indicates better thermal stability of the sample.

[0042] The results of the thermal property evaluation of the cured products of Examples 5 and 6, and Comparative Examples 1 and 2 are shown in Table 5 below:

[0043] Test Example 2: Evaluation of the electrical properties of various cured products at 10 GHz

[0044] The cured products of Examples 5 and 6, as well as Comparative Examples 1 and 2, were evaluated for their electrical properties by measuring the dielectric constant and dielectric loss of the cured films at 10 GHz using a dielectric constant meter. The results of the electrical property evaluation of the cured products of Examples 5 and 6, as well as Comparative Examples 1 and 2, are shown in Table 6 below.

[0045]

[0046] As shown in Tables 5 and 6, the present invention introduces a bio-based structure into (2,6-dimethylphenyl ether) oligomers, which can reduce the use of petroleum-based raw materials to meet the needs of future low-carbon development. Furthermore, the end-capsulated functionalization results in a cured product with good glass transition temperature, thermal stability, and excellent electrical properties, meeting the current requirements for high-frequency communication substrate material resins. In addition to being used as a high-frequency communication substrate material resin, the oligomers of the present invention can also be used in high-temperature additives, coating materials, and adhesives.

[0047] The present invention has been disclosed above with reference to preferred embodiments. However, those skilled in the art should understand that these embodiments are only used to describe the present invention and should not be construed as limiting the scope of the present invention. It should be noted that all variations and substitutions equivalent to these embodiments should be included within the scope of the present invention. Therefore, the scope of protection of the present invention shall be determined by the claims.

Claims

1. An oligomer having the structure shown in formula (I): in, X represents the structure, Y is independently hydrogen, halogen, or one of these structures, R0 and R1 are independently hydrogen, C1~C6 alkyl, phenyl, or n and m are independently integers from 1 to 300.

2. The oligomer as described in claim 1, having a structure as shown in formula (I-1) or formula (I-4):

3. A method for preparing an oligomer as described in claim 1, comprising the following steps: (a) heating a bio-based diene compound and a phenolic compound in a Lewis acid catalyst to 80-150°C and stirring to allow them to react, followed by washing with water and neutralization purification to obtain a phenolic reactant; (b) mixing the phenolic reactant obtained in step (a) with 2,6-dimethylphenol in a methanol-water cosolvent containing a copper catalyst and an amine catalyst, and performing an oxidative polymerization reaction in an oxygen environment and at a temperature of 0-70°C to obtain a bisphenol polyphenylene ether oligomer; and (c) reacting the bisphenol polyphenylene ether oligomer obtained in step (b) with methacrylic anhydride or vinylbenzyl halide at a temperature of 45-100°C and under the catalysis of an alkaline catalyst to obtain the oligomer.

4. The preparation method as described in claim 3, wherein in step (a) the molar ratio of the bio-based diene compound to the phenolic compound is 1:2 to 1:10, and in step (b) the molar ratio of the phenolic reactant to the 2,6-dimethylphenol is 1:2 to 1:

10.

5. The preparation method as described in claim 3, wherein in step (a), the bio-based diene compound is selected from the group consisting of phenol, 2,6-xylenol and 2,3,6-trimethylphenol; and the Lewis acid catalyst is selected from the group consisting of BF3 and aluminum halide.

6. The preparation method as described in claim 3, wherein in step (b) the copper catalyst is selected from the group consisting of CuCl, CuCl2, CuBr and CuBr2; and the amine catalyst is selected from the group consisting of (trialkyl)amine and dialkylamino pyridine, wherein each alkyl group is independently a C1 to C6 alkyl group.

7. The preparation method as described in claim 3, wherein the oxygen source of the oxygen environment in step (b) is pure oxygen or air.

8. A method for preparing a cured oligomer, comprising the following steps: (a) taking an oligomer prepared by any one of claims 3 to 7; and (b) copolymerizing the oligomer with a peroxide to obtain a cured oligomer.

9. The preparation method as described in claim 8, wherein the peroxide in step (b) is selected from the group consisting of benzoyl peroxide and tert-butyl peroxide.

10. The preparation method as claimed in claim 8, wherein in step (b), the content of the peroxide is from 0.1% by weight to 1.0% by weight, based on the total weight of the oligomer and the peroxide.