US20170342199A1

US20170342199A1 - Oligomer, composition and composite material employing the same

Info

Publication number: US20170342199A1
Application number: US15/394,457
Authority: US
Inventors: Wei-Ta YANG; Yen-Yi CHU; Ming-Tsung Hong; Li-Chun Liang; Yun-Ching Lee; Meng-Song Yin
Original assignee: Industrial Technology Research Institute ITRI
Current assignee: Industrial Technology Research Institute ITRI
Priority date: 2016-05-24
Filing date: 2016-12-29
Publication date: 2017-11-30
Also published as: TWI676641B; US20170342200A1; US10179833B2; CN107417862A; TW201741362A; TWI606076B; TW201823294A; TW201741361A; CN107417862B

Abstract

An oligomer, composition, and composite material employing the same are provided. The oligomer has a structure represented by Formula (I)

wherein R¹and R²are independently hydrogen, C_1-20alkyl group, C_2-20alkenyl group, C_6-12aryl group, C_6-12alkylaryl group, C_5-12cycloalkyl group, C_6-20cycloalkylalkyl group, alkoxycarbonyl group, or alkylcarbonyloxy group; R¹is not hydrogen when R²is hydrogen; a is 0 or 1; n≧0; m≧1; n:m is from 0:100 to 99:1; the oligomer has a number average molecular weight of less than or equal to 12,000; and the repeat unit

and the repeat unit

are arranged in a random or block fashion.

Description

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of U.S. Provisional Application No. 62/340,686, filed on May 24, 2016, which is incorporated herein by reference.

TECHNICAL FIELD

The disclosure relates to an oligomer, a composition and a composite material employing the same.

BACKGROUND

The trend in electronic products has been toward smaller sizes, lighter weights, higher operating speeds, and higher-frequency transmission. Therefore, the distribution for printed circuit boards is toward high-density. In order to maintain the transmission rate and signal integrity, the ideal materials for use in printed circuit boards must have a low dielectric constant (dielectric constant, Dk) and a low dissipation factor (dissipation factor, Df).
In general, conventional materials for printed circuit boards have a high dielectric constant (dielectric constant, Dk) and a high dissipation factor (dissipation factor, DO. Accordingly, a novel material for use in printed circuit boards is desired in order to improve performance and reduce Dk and Df without sacrificing thermal resistance and mechanical strength.

SUMMARY

According to embodiments of the disclosure, the disclosure provides an oligomer. The oligomer has a structure represented by Formula (I)
wherein R¹and R²are independently hydrogen, C_1-20alkyl group, C_2-20alkenyl group, C_6-12aryl group, C_6-12alkylaryl group, C_5-12cycloalkyl group, C_6-20cycloalkylalkyl group, alkoxycarbonyl group, or alkylcarbonyloxy group, R¹is not hydrogen when R²is hydrogen; a is 0 or 1; n≧0; m≧1; n:m is from about 0:100 to 99:1; the oligomer number average molecular weight less than or equal to 12,000; and the repeat unit
and the repeat unit
are arranged in a random or block fashion.
According to embodiments of the disclosure, the disclosure also provides a composition including about 1-99 parts by weight of the aforementioned oligomer; and about 1-99 parts by weight of resin.
According to embodiments of the disclosure, the disclosure also provides a composite material including a cured product or a semi-cured product prepared from the aforementioned composition; and a substrate, wherein the cured product or the semi-cured product is disposed on the substrate or disposed within the substrate.
A detailed description is given in the following embodiments with reference to the accompanying drawings.

DETAILED DESCRIPTION

Embodiments of the disclosure provide an oligomer, a composition, and a composite material employing the same. The oligomer of the disclosure can be prepared by copolymerizing a first monomer (such as vinyl norbornene) and a second monomer (such as norbornene) via ring-opening polymerization, and α-olefin can be introduced during copolymerization in order to control the molecular weight of the obtained copolymer (i.e. the obtained copolymer can have a number average molecular weight less than or equal to 12,000). As a result, due to the high solubility in organic solvent, the oligomer exhibits high processability. In addition, due to the low polarity and the crosslinkable functional groups of the chemical structure of the oligomer, the oligomer can enhance the mechanical strength of the substrate material when the oligomer is used as a reactant for preparing the substrate material. Embodiments of the disclosure also provide a composition including the aforementioned oligomer and a composite material (such as a prepreg) including a cured product or a semi-cured product prepared from the composition. The cured product of the composition of the disclosure exhibits a relatively low dielectric constant (Dk) (less than 3.0 (at 10 GHz)) and a relatively low dissipation factor (Df) (less than 0.0033 (at 10 GHz)), and can serve as a good material for the high-frequency substrate in order to improve the problem of insertion loss.
According to embodiments of the disclosure, the oligomer has a structure represented by Formula (I)
wherein R¹and R²are independently hydrogen, C_1-20alkyl group, C_2-20alkenyl group, C_6-12aryl group, C_6-12alkylaryl group, C_5-12cycloalkyl group, C_6-20cycloalkylalkyl group, alkoxycarbonyl group, or alkylcarbonyloxy group, R¹is not hydrogen when R²is hydrogen; a is 0 or 1; n≧0 (such as n≧1); m≧1; n:m is from about 0:100 to 99:1; the oligomer number average molecular weight less than or equal to 12,000; and the repeat unit
and the repeat unit
are arranged in a random or block fashion.
According to embodiments of the disclosure, the alkyl group of the disclosure can be linear or branched alkyl group. For example, R¹and R²can be independently a linear or branched alkyl group having 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 carbon atoms. According to embodiments of the disclosure, the alkenyl group of the disclosure can be linear or branched alkenyl group. For example, R¹and R²can be independently a linear or branched alkenyl group having 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 carbon atoms.
According to embodiments of the disclosure, R¹and R²can be independently hydrogen, or
wherein b can be 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, or 19; and R¹is not hydrogen when R²is hydrogen.
According to embodiments of the disclosure, the C_6-12aryl group of the disclosure can be phenyl group, biphenyl group, or naphthyl group.
According to embodiments of the disclosure, R¹and R²are independently hydrogen, or
wherein c can be 0, 1, 2, 3, 4, 5, or 6; and R¹is not hydrogen when R²is hydrogen.
According to embodiments of the disclosure, R¹and R2 can be independently hydrogen, or
wherein d can be 0, 1, 2, 3, 4, 5, or 6; and R¹is not hydrogen when R²is hydrogen.
According to embodiments of the disclosure, R¹and R²can be independently hydrogen, or
wherein e can be 0, 1, 2, 3, 4, 5, or 6; and R¹is not hydrogen when R²is hydrogen.
According to embodiments of the disclosure, R¹and R²can be independently hydrogen, or
wherein f can be 0, 1, 2, 3, 4, 5, or 6, R³can be C_1-6alkyl group, R¹is not hydrogen when R²is hydrogen. For example, R³can be methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, or hexyl group.
According to embodiments of the disclosure, R¹and R²can be independently hydrogen, or
wherein g can be 0, 1, 2, 3, 4, 5, or 6, R⁴can be C_1-6alkyl group; and R¹is not hydrogen when R²is hydrogen. For example, R⁴can be methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, or hexyl group.
According to embodiments of the disclosure, R¹and R²can be independently hydrogen, or
wherein h can be 1, 2, 3, 4, 5, or 6; and R¹is not hydrogen when R²is hydrogen.
According to embodiments of the disclosure, R¹and R²can be independently hydrogen, or
wherein i can be 0, 1, 2, 3, 4, 5, or 6; and R¹is not hydrogen when R²is hydrogen.
According to embodiments of the disclosure, R¹and R²can be independently hydrogen, or
wherein j can be 0, 1, 2, 3, 4, 5, or 6; and R¹is not hydrogen when R²is hydrogen.
According to embodiments of the disclosure, the ratio of the repeat unit
to the repeat unit
(i.e. n:m) can be from about 0:100 to 99:1, such as from about 1:9 to 9:1, from about 2:8 to 8:2, from about 3:7 to 7:3, or from about 3:7 to 6:4. Due to the adjustment of the ratio between the two repeat units of the oligomer, the properties of the cured product prepared by crosslinking the oligomer and the resin can be modified. For example, when increasing the amount of the repeat unit
the crosslinking density of the cured product can be increased.
In embodiments of the disclosure, due to the introduction of the α-olefin when copolymerizing vinyl norbornene with norbornene, the molecular weight of the coploymer can be controlled. According to embodiments of the disclosure, the number average molecular weight of the oligomer can be less than 12,000, such as from about 800 to 12,000, from about 800 to 9,000, from about 800 to 8,000, from about 800 to 7,000, from about 800 to 6,000, or from about 800 to 5,000. As a result, the oligomer can have high solubility in organic solvent, thereby enhancing the processability of the oligomer. In addition, in comparison with the coploymer merely prepared from vinyl norbornene and norbornene, the oligomer of the disclosure exhibits superior storability.
According to embodiments of the disclosure, the method for preparing the aforementioned oligomer can include mixing and reacting a first monomer, a second monomer, and α-olefin to obtain the oligomer.
According to embodiments of the disclosure, the method for preparing the aforementioned oligomer can include mixing and reacting a metal catalyst, a first monomer, a second monomer, and α-olefin to obtain the oligomer.
According to embodiments of the disclosure, the method for preparing the aforementioned oligomer can include mixing and reacting a photoredox initiator, a photoredox mediator, a first monomer, a second monomer, and α-olefin to obtain the oligomer. In particular, the photoredox initiator can be vinyl ether, 1-methoxy-4-phenyl butene, 2-cyclohexyl-1-methoxyethylene, or a combination thereof. The photoredox mediator can be pyrylium salt, acridinium salt, or a combination thereof.
According to embodiments of the disclosure, the method for preparing the aforementioned oligomer can include mixing and reacting a first monomer, a second monomer, and α-olefin under electrochemical condition to obtain the oligomer.
The metal catalyst can be Grubbs catalyst, such as first-generation Grubbs catalyst, second-generation Grubbs catalyst, Hoveyda-Grubbs catalyst, derivatives thereof, or a combination including at least one of the above catalysts. The first monomer can be
wherein a is 0 or 1. For example, the first monomer is vinyl norbornene. The second monomer can be norbornene
The α-olefin can be
wherein R⁵can be C_1-20alkyl group, C_2-20alkenyl group, C_6-12aryl group, C_6-12alkylaryl group, C_5-12cycloalkyl group, C_6-20cycloalkylalkyl group, alkoxycarbonyl group, or alkylcarbonyloxy group. for example, α-olefin can be
wherein b, c, d, e, f, g, h, i, j, R³, and R⁴have the same definition as above. In the aforementioned methods for preparing the oligomer, the sequence in which components are added is not limited. For example, a metal catalyst can be dissolved in a solvent first, obtaining a metal-catalyst-containing solution. Next, a solution including the first monomer and α-olefin is mixed with the metal-catalyst-containing solution. Finally, the second monomer is added into the above mixture. According to embodiments of the disclosure, the molar ratio of the first monomer to the second monomer can be from about 100:0 (i.e. there is no the second monomer added) to 1:99, such as from about 9:1 to 1:9, from about 8:2 to 2:8, from about 3:7 to 7:3, or from about 3:7 to 6:4. In addition, the molar percentage of α-olefin can be from about 1 mol % to 85 mol %, such as about from 5 mol % to 75 mol %, or about from 10 mol % to 75 mol %, based on the total moles of the first monomer and the second monomer.
In one embodiment, the amount of the α-olefin is inversely proportional to the molecular weight of the oligomer, so that the molecular weight of the oligomer can be controlled by means of the amount of α-olefin. When the molar percentage of α-olefin is too low, the oligomer would have relatively high molecular weight and exhibit poor processability and storability. Conversely, when the molar percentage of α-olefin is too high, the oligomer would have a relatively low molecular weight and the process for preparing the substrate is not easy to control.
According to embodiments of the disclosure, the disclosure also provides a composition including the aforementioned oligomer, and one or at least one resin. The composition can include about 1-99 parts by weight of the oligomer, about 10-90 parts by weight of the oligomer, or about 20-80 parts by weight of the oligomer. Furthermore, the composition can include about 1-99 parts by weight of the resin, about 10-90 parts by weight of the resin, or about 20-80 parts by weight of the resin. The resin can be polyolefin resin (such as polybutadiene resin), polyalkenamer resin, cyclic olefin polymer resin, cycloolefin copolymer resin, epoxy resin, cyanate resin, phenol resin, novolac resin, polystyrene resin, styrene-butadiene copolymer resin (such as polystyrene-butadiene-styrene resin), polyamide resin, polyimide resin, maleimide resin, bismaleimide resin, polyphenylene ether resin, or a combination thereof. In addition, According to embodiments of the disclosure, the weight percentage of the oligomer can be from about 1 wt % to 99 wt %, from about 10 wt % to 90 wt %, or from about 20 wt % to 80 wt %, and the weight percentage of the resin can be from about 1 wt % to 99 wt %, from about 10 wt % to 90 wt %, or from about 20 wt % to 80 wt %, based on the total weight of the oligomer and resin.
According to an embodiment of the disclosure, the disclosure also provides a composite material. The composite material can include a cured product or a semi-cured product of the composition, and a substrate. In particular, the cured product or semi-cured product is disposed on the substrate or within the substrate. According to an embodiment of the disclosure, the substrate can be a glass fiber, or a copper foil. For example, the composite material can include a prepreg, and the method for preparing the prepreg includes immersing a glass fiber (serving as the substrate) into the aforementioned composition. Next, the composition is subjected to a semi-curing process, obtaining the prepreg. In addition, the composite material can further include a copper foil, and the composite material can be a copper foil substrate, a printed circuit board, or an integrated circuit.
The inventive concept of the disclosure may be embodied in various forms without being limited to the exemplary embodiments set forth herein.

Example 1

0.045 g of 1,3-Bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene[2-(i-propoxy)-5-(N,N-dimethylaminosulfonyl)phenyl]methyleneruthenium(II) dichloride (as metal catalyst) was added into a reaction bottle under nitrogen atmosphere, and then 10 ml of toluene was added into the reaction bottle, obtaining a metal-catalyst-containing solution. After the metal catalyst was dissolved in toluene completely, 0.604 mol of 1-hexene (as α-olefin), 73.6 g of vinyl norbornene, 128 ml of toluene, and the metal-catalyst-containing solution were added into another reaction bottle. After stirring completely, a norbornene-containing solution (57.7 g of norbornene (NB) dissolved in 50 ml of toluene) was added into the reaction bottle. Herein, α-olefin (1-hexene) had a molar percentage of 50 mol %, based on the total moles of vinyl norbornene and norbornene. After stopping the reaction, 63 ml of ethyl vinyl ether was added into the reaction bottle. After stirring overnight, the catalyst of the result was removed and then was purified by a reprecipitation with methanol. After concentration, Copolymer (I) was obtained, wherein the ratio of the repeat unit
to the repeat unit
of Copolymer (I) was about 1:1.
Next, the number average molecular weight (Mn), the polydispersity index (PDI), the solubility (in toluene), and the temperature corresponding to a thermogravimetric analysis (TGA) weight loss of 5% of Copolymer (I) were determined, and the results are shown in Table 1.

Example 2

0.045 g of 1,3-Bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene[2-(i-propoxy)-5-(N,N-dimethylaminosulfonyl)phenyl]methyleneruthenium(II) dichloride (as metal catalyst) was added into a reaction bottle under nitrogen atmosphere, and then 10 ml of toluene was added into the reaction bottle, obtaining a metal-catalyst-containing solution. After the metal catalyst was dissolved in toluene completely, 0.362 mol of 1-hexene (α-olefin), 73.6 g of vinyl norbornene, 128 ml of toluene, and the metal-catalyst-containing solution were added into another reaction bottle. After stirring completely, a norbornene-containing solution (57.7 g of norbornene dissolved in 50 ml of toluene) was added into the reaction bottle. Herein, α-olefin (1-hexene) had a molar percentage of 30 mol %, based on the total moles of vinyl norbornene and norbornene. After stopping the reaction, 63 ml of ethyl vinyl ether was added into the reaction bottle. After stirring overnight, the catalyst of the result was removed and then was purified by a reprecipitation with methanol. After concentration, Copolymer (II) was obtained, wherein the ratio of the repeat unit
to the repeat unit
of Copolymer (II) was about 1:1
Next, the number average molecular weight (Mn), the polydispersity index (PDI), the solubility (in toluene), and the temperature corresponding to a thermogravimetric analysis (TGA) weight loss of 5% of Copolymer (II) were determined, and the results are shown in Table 1.

Example 3

0.09 g of 1,3-Bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene[2-(i-propoxy)-5-(N,N-dimethylaminosulfonyl)phenyl]methyleneruthenium(II) dichloride (as metal catalyst) was added into a reaction bottle under nitrogen atmosphere, and then 15 ml of toluene was added into the reaction bottle, obtaining a metal-catalyst-containing solution. After the metal catalyst was dissolved in toluene completely, 0.483 mol of 1-hexene (α-olefin), 147 g of vinyl norbornene, 260 ml of toluene, and the metal-catalyst-containing solution were added into another reaction bottle. After stirring completely, a norbornene-containing solution (115 g of norbornene dissolved in 100 ml of toluene) was added into the reaction bottle. Herein, α-olefin (1-hexene) had a molar percentage of 20 mol %, based on the total moles of vinyl norbornene and norbornene. After stopping the reaction, 125 ml of ethyl vinyl ether was added into the reaction bottle. After stirring overnight, the catalyst of the result was removed and then was purified by a reprecipitation with methanol. After concentration, Copolymer (III) was obtained, wherein the ratio of the repeat unit
to the repeat unit
of Copolymer (III) was about 1:1
Next, the number average molecular weight (Mn), the polydispersity index (PDI), the solubility (in toluene), and the temperature corresponding to a thermogravimetric analysis (TGA) weight loss of 5% of Copolymer (III) were determined, and the results are shown in Table 1.

Example 4

0.045 g of 1,3-Bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene[2-(i-propoxy)-5-(N,N-dimethylaminosulfonyl)phenyl]methyleneruthenium(II) dichloride (as metal catalyst) was added into a reaction bottle under nitrogen atmosphere, and then 10 ml of toluene was added into the reaction bottle, obtaining a metal-catalyst-containing solution. After the metal catalyst was dissolved in toluene completely, 0.362 mol of 1-hexene (α-olefin), 52.1 g of vinyl norbornene, 87 ml of toluene, and the metal-catalyst-containing solution were added into another reaction bottle. After stirring completely, a norbornene-containing solution (75 g of norbornene dissolved in 90 ml of toluene) was added into the reaction bottle. Herein, α-olefin (1-hexene) had a molar percentage of 20 mol %, based on the total moles of vinyl norbornene and norbornene. After stopping the reaction, 63 ml of ethyl vinyl ether was added into the reaction bottle. After stirring overnight, the catalyst of the result was removed and then was purified by a reprecipitation with methanol. After concentration, Copolymer (IV) was obtained, wherein the ratio of the repeat unit
to the repeat unit
of Copolymer (IV) was about 0.5:1.
Next, the number average molecular weight (Mn), the polydispersity index (PDI), the solubility (in toluene), and the temperature corresponding to a thermogravimetric analysis (TGA) weight loss of 5% of Copolymer (IV) were determined, and the results are shown in Table 1.

Example 5

0.054 g of 1,3-Bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene[2-(i-propoxy)-5-(N,N-dimethylaminosulfonyl)phenyl]methyleneruthenium(II) dichloride (as metal catalyst) was added into a reaction bottle under nitrogen atmosphere, and then 15 ml of toluene was added into the reaction bottle, obtaining a metal-catalyst-containing solution. After the metal catalyst was dissolved in toluene completely, 0.145 mol of 1-hexene (α-olefin), 88.3 g of vinyl norbornene, 150 ml of toluene, and the metal-catalyst-containing solution were added into another reaction bottle. After stirring completely, a norbornene-containing solution (69.3 g of norbornene dissolved in 60 ml of toluene) was added into the reaction bottle. Herein, α-olefin (1-hexene) had a molar percentage of 10 mol %, based on the total moles of vinyl norbornene and norbornene. After stopping the reaction, 75 ml of ethyl vinyl ether was added into the reaction bottle. After stirring overnight, the catalyst of the result was removed and then was purified by a reprecipitation with methanol. After concentration, Copolymer (V) was obtained, wherein the ratio of the repeat unit
to the repeat unit
of Copolymer (V) was about 1:1
Next, the number average molecular weight (Mn), the polydispersity index (PDI), the solubility (in toluene), and the temperature corresponding to a thermogravimetric analysis (TGA) weight loss of 5% of Copolymer (V) were determined, and the results are shown in Table 1.

Example 6

0.018 g of 1,3-Bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene[2-(i-propoxy)-5-(N,N-dimethylaminosulfonyl)phenyl]methyleneruthenium(II) dichloride (as metal catalyst) was added into a reaction bottle under nitrogen atmosphere, and then 10 ml of toluene was added into the reaction bottle, obtaining a metal-catalyst-containing solution. After the metal catalyst was dissolved in toluene completely, 0.0245 mol of 1-hexene (α-olefin), 29.4 g of vinyl norbornene, 45 ml of toluene, and the metal-catalyst-containing solution were added into another reaction bottle. After stirring completely, a norbornene-containing solution (23.06 g of norbornene dissolved in 20 ml of toluene) was added into the reaction bottle. Herein, α-olefin (1-hexene) had a molar percentage of 5 mol %, based on the total moles of vinyl norbornene and norbornene. After stopping the reaction, 25 ml of ethyl vinyl ether was added into the reaction bottle. After stirring overnight, the catalyst of the result was removed and then was purified by a reprecipitation with methanol. After concentration, Copolymer (VI) was obtained, wherein the ratio of the repeat unit
to the repeat unit
of Copolymer (VI) was about 1:1.
Next, the number average molecular weight (Mn), the polydispersity index (PDI), the solubility (in toluene), and the temperature corresponding to a thermogravimetric analysis (TGA) weight loss of 5% of Copolymer (VI) were determined, and the results are shown in Table 1.

Example 7

0.009 g of 1,3-Bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene[2-(i-propoxy)-5-(N,N-dimethylaminosulfonyl)phenyl]methyleneruthenium(II) dichloride (as metal catalyst) was added into a reaction bottle under nitrogen atmosphere, 6 ml of toluene was added into the reaction bottle, obtaining a metal-catalyst-containing solution. After the metal catalyst was dissolved in toluene completely, 0.0073 mol of 1-hexene (α-olefin), 14.7 g of vinyl norbornene, 23 ml of toluene, and the metal-catalyst-containing solution were added into another reaction bottle. After stirring completely, a norbornene-containing solution (11.5 g of norbornene dissolved in 10 ml of toluene) was added into the reaction bottle. Herein, α-olefin (1-hexene) had a molar percentage of 3 mol %, based on the total moles of vinyl norbornene and norbornene. After stopping the reaction, 13 ml of ethyl vinyl ether was added into the reaction bottle. After stirring overnight, the catalyst of the result was removed and then was purified by a reprecipitation with methanol. After concentration, Copolymer (VII) was obtained, wherein the ratio of the repeat unit
to the repeat unit
of Copolymer (VII) was about 1:1.
Next, the number average molecular weight (Mn), the polydispersity index (PDI), the solubility (in toluene), and the temperature corresponding to a thermogravimetric analysis (TGA) weight loss of 5% of Copolymer (VII) were determined, and the results are shown in Table 1.

Example 8

0.054 g of 1,3-Bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene[2-(i-propoxy)-5-(N,N-dimethylaminosulfonyl)phenyl]methyleneruthenium(II) dichloride (as metal catalyst) was added into a reaction bottle under nitrogen atmosphere, 30 ml of toluene was added into the reaction bottle, obtaining a metal-catalyst-containing solution. After the metal catalyst was dissolved in toluene completely, 0.725 mol of 1-hexene (α-olefin), 177 g of vinyl norbornene, 300 ml of toluene, and the metal-catalyst-containing solution were added into another reaction bottle. Herein, α-olefin (1-hexene) had a molar percentage of 50 mol %, based on the mole of vinyl norbornene. After stopping the reaction, 75 ml of ethyl vinyl ether was added into the reaction bottle. After stirring overnight, the catalyst of the result was removed and then was purified by a reprecipitation with methanol. After concentration, Copolymer (VIII) was obtained, wherein the only repeat unit of Copolymer (VIII) was
Next, the number average molecular weight (Mn), the polydispersity index (PDI), the solubility (in toluene), and the temperature corresponding to a thermogravimetric analysis (TGA) weight loss of 5% of Copolymer (VIII) were determined, and the results are shown in Table 1.

Example 9

0.0018 g of 1,3-Bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene[2-(i-propoxy)-5-(N,N-dimethylaminosulfonyl)phenyl]methyleneruthenium(II) dichloride (as metal catalyst) was added into a reaction bottle under nitrogen atmosphere, 1 ml of toluene was added into the reaction bottle, obtaining a metal-catalyst-containing solution. After the metal catalyst was dissolved in toluene completely, 0.0005 mol of 1-hexene (α-olefin), 3 g of vinyl norbornene, 4.5 ml of toluene, and the metal-catalyst-containing solution were added into another reaction bottle. After stirring completely, a norbornene-containing solution (2.36 g of norbornene dissolved in 2 ml of toluene) was added into the reaction bottle. Herein, α-olefin (1-hexene) had a molar percentage of 1 mol %, based on the total moles of vinyl norbornene and norbornene. After stopping the reaction, 2.5 ml of ethyl vinyl ether was added into the reaction bottle. After stirring overnight, the catalyst of the result was removed and then was purified by a reprecipitation with methanol. After concentration, Copolymer (IX) was obtained, wherein the ratio of the repeat unit
to the repeat unit
of Copolymer (IX) was about 1:1.
Next, the number average molecular weight (Mn), the polydispersity index (PDI), the solubility (in toluene), and the temperature corresponding to a thermogravimetric analysis (TGA) weight loss of 5% of Copolymer (IX) were determined, and the results are shown in Table 1.

Comparative Example 1

0.018 g of 1,3-Bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene[2-(i-propoxy)-5-(N,N-dimethylaminosulfonyl)phenyl]methyleneruthenium(II) dichloride (as metal catalyst) was added into a reaction bottle under nitrogen atmosphere, and then 10 ml of toluene was added into the reaction bottle, obtaining a metal-catalyst-containing solution. After the metal catalyst was dissolved in toluene completely, 0.245 mol of methylacrylate (α-olefin), 29.4 g of vinyl norbornene, 45 ml of toluene, and the metal-catalyst-containing solution were added into another reaction bottle. After stirring completely, a norbornene-containing solution (23.06 g of norbornene dissolved in 20 ml of toluene) was added into the reaction bottle. Herein, methylacrylate had a molar percentage of 50 mol %, based on the total moles of vinyl norbornene and norbornene. After stopping the reaction, 25 ml of ethyl vinyl ether was added into the reaction bottle. After stirring overnight, the catalyst of the result was removed and then was purified by a reprecipitation with methanol. After concentration, Copolymer (X) was obtained, wherein the ratio of the repeat unit
to the repeat unit
of Copolymer (X) was about 1:1.
Next, the number average molecular weight (Mn), the polydispersity index (PDI), the solubility (in toluene), and the temperature corresponding to a thermogravimetric analysis (TGA) weight loss of 5% of Copolymer (X) were determined, and the results are shown in Table 1.

Comparative Example 2

0.018 g of 1,3-Bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene[2-(i-propoxy)-5-(N,N-dimethylaminosulfonyl)phenyl]methyleneruthenium(II) dichloride (as metal catalyst) was added into a reaction bottle under nitrogen atmosphere, and then 10 ml of toluene was added into the reaction bottle, obtaining a metal-catalyst-containing solution. After the metal catalyst was dissolved in toluene completely, 29.4 g of vinyl norbornene, 35 ml of toluene, and the metal-catalyst-containing solution were added into another reaction bottle. After stirring completely, a norbornene-containing solution (23.06 g of norbornene dissolved in 20 ml of toluene) was added into the reaction bottle. After stopping the reaction, 25 ml of ethyl vinyl ether was added into the reaction bottle. After stirring overnight, the catalyst of the result was removed and then was purified by a reprecipitation with methanol. After concentration, Copolymer (XI) was obtained, wherein the ratio of the repeat unit
to the repeat unit
of Copolymer (XI) was about 1:1
Next, the number average molecular weight (Mn), the polydispersity index (PDI), the solubility (in toluene), and the temperature corresponding to a thermogravimetric analysis (TGA) weight loss of 5% of Copolymer (XI) were determined, and the results are shown in Table 1.

TABLE 1

									Compar-	Compar-
									ative	ative
Example	Example	Example	Example	Example	Example	Example	Example	Example	Example	Example
1	2	3	4	5	6	7	8	9	1	2

VNB(g)	73.6	73.6	147	52.1	88.3	29.4	14.7	177	3	29.4	29.4
NB(g)	57.7	57.7	115	75.0	69.3	23.06	11.5	0	2.36	23.06	23.06
α-olefin	1-	1-	1-	1-	1-	1-	1-	1-	1-	methyl-	—
	hexene	hexene	hexene	hexene	hexene	hexene	hexene	hexene	hexene	acrylate
α-olefin	50	30	20	20	10	5	3	50	1	50	0
(mol %)
number	1,033	1,433	1,939	1,683	3,089	4,916	5,291	1,225	11,017	19,402	33,488
average
molecular
weight
(Mn)
Td_5%(° C.)	166	254	338	295	430	208	400	167	205	421	411
solubility	>70	>70	>70	>70	>60	>60	>40	>70	20	<10	<10
(wt %)

As shown in Table 1, with copolymerization of vinyl norbornene and norbornene, the number average molecular weight (Mn), the polydispersity index (PDI) of the obtained copolymer can be controlled by means of the addition of 1-hexene (α-olefin). Therefore, the obtained copolymer has a molecular weight less than or equal to 12,000, thereby increasing the solubility of the copolymer and promoting the subsequent process.

Example 10

0.018 g of 1,3-Bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene[2-(i-propoxy)-5-(N,N-dimethylaminosulfonyl)phenyl]methyleneruthenium(II) dichloride (as metal catalyst) was added into a reaction bottle under nitrogen atmosphere, and then 10 ml of toluene was added into the reaction bottle, obtaining a metal-catalyst-containing solution. After the metal catalyst was dissolved in toluene completely, 0.247 mol of 1-octadecene (α-olefin), 29.4 g of vinyl norbornene, 45 ml of toluene, and the metal-catalyst-containing solution were added into another reaction bottle, obtaining a metal-catalyst-containing solution. After stirring completely, a norbornene-containing solution (23.06 g of norbornene dissolved in 20 ml of toluene) was added into the reaction bottle. Herein, α-olefin (1-octadecene) had a molar percentage of 50 mol %, based on the total moles of vinyl norbornene and norbornene. After stopping the reaction, 25 ml of ethyl vinyl ether was added into the reaction bottle. After stirring overnight, the catalyst of the result was removed and then was purified by a reprecipitation with methanol. After concentration, Copolymer (XII) was obtained.
Next, the number average molecular weight (Mn), the polydispersity index (PDI), the solubility (in toluene), and the temperature corresponding to a thermogravimetric analysis (TGA) weight loss of 5% of Copolymer (XII) were determined, and the results are shown in Table 2.

Example 11

Example 11 was performed in the same manner as Example 10 except that the amount of 1-octadecene was reduced from 0.247 mol to 0.049 mol, obtaining Copolymer (XIII). The number average molecular weight (Mn), the polydispersity index (PDI), the solubility (in toluene), and the temperature corresponding to a thermogravimetric analysis (TGA) weight loss of 5% of Copolymer (XIII) were determined, and the results are shown in Table 2.

Example 12

Example 12 was performed in the same manner as Example 10 except that the 1-octadecene was replaced with styrene, obtaining Copolymer (XIV). The number average molecular weight (Mn), the polydispersity index (PDI), the solubility (in toluene), and the temperature corresponding to a thermogravimetric analysis (TGA) weight loss of 5% of Copolymer (XIV) were determined, and the results are shown in Table 2.

Example 13

0.006 g of 1,3-Bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene[2-(i-propoxy)-5-(N,N-dimethylaminosulfonyl)phenyl]methyleneruthenium(II) dichloride (as metal catalyst) was added into a reaction bottle under nitrogen atmosphere, and then 4 ml of toluene was added into the reaction bottle, obtaining a metal-catalyst-containing solution. After the metal catalyst was dissolved in toluene completely, 0.008 mol of vinylcyclohexene (α-olefin), 9.8 g of vinyl norbornene, 15 ml of toluene, and the metal-catalyst-containing solution were added into another reaction bottle. After stirring completely, a norbornene-containing solution (7.69 g of norbornene dissolved in 7 ml of toluene) was added into the reaction bottle. Herein, α-olefin (vinylcyclohexene) had a molar percentage of 5 mol %, based on the total moles of vinyl norbornene and norbornene. After stopping the reaction, 8 ml of ethyl vinyl ether was added into the reaction bottle. After stirring overnight, the catalyst of the result was removed and then was purified by a reprecipitation with methanol. After concentration, Copolymer (XV) was obtained.
Next, the number average molecular weight (Mn), the polydispersity index (PDI), the solubility (in toluene), and the temperature corresponding to a thermogravimetric analysis (TGA) weight loss of 5% of Copolymer (XV) were determined, and the results are shown in Table 2.

Example 14

0.0018 g of 1,3-Bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene[2-(i-propoxy)-5-(N,N-dimethylaminosulfonyl)phenyl]methyleneruthenium(II) dichloride (as metal catalyst) was added into a reaction bottle under nitrogen atmosphere, and then 0.5 ml of toluene was added into the reaction bottle, obtaining a metal-catalyst-containing solution. After the metal catalyst was dissolved in toluene completely, 0.043 mol of methylacrylate (α-olefin), 3 g of vinyl norbornene, 4.5 ml of toluene, and the metal-catalyst-containing solution were added into another reaction bottle. Herein, methylacrylate had a molar percentage of 85 mol %, based on the total moles of vinyl norbornene and norbornene. After stopping the reaction, 2.5 ml of ethyl vinyl ether was added into the reaction bottle. After stirring overnight, the catalyst of the result was removed and then was purified by a reprecipitation with methanol. After concentration, Copolymer (XVI) was obtained.
Next, the number average molecular weight (Mn), the polydispersity index (PDI), the solubility (in toluene), and the temperature corresponding to a thermogravimetric analysis (TGA) weight loss of 5% of Copolymer (XVI) were determined, and the results are shown in Table 2.

Example 15

Example 15 was performed in the same manner as Example 10 except that the 1-octadecene was replaced with allyl acetate, obtaining Copolymer (XVII). The number average molecular weight (Mn), the polydispersity index (PDI), the solubility (in toluene), and the temperature corresponding to a thermogravimetric analysis (TGA) weight loss of 5% of Copolymer (XVII) were determined, and the results are shown in Table 2.

Example 16

Example 16 was performed in the same manner as Example 10 except that the 1-octadecene was replaced with 1,5-hexadiene, obtaining Copolymer (XVIII). The number average molecular weight (Mn), the polydispersity index (PDI), the solubility (in toluene), and the temperature corresponding to a thermogravimetric analysis (TGA) weight loss of 5% of Copolymer (XVIII) were determined, and the results are shown in Table 2.

TABLE 2

Example	Example	Example	Example	Example	Example	Example
10	11	12	13	14	15	16

VNB(g)	29.4	29.4	29.4	9.8	3	29.4	29.4
NB(g)	23.06	23.06	23.06	7.69	2.36	23.06	23.06
α-olefin	1-	1-	styrene	vinyl-	methyl-	allyl	1,5-
	octadecene	octadecene		cyclohexene	acrylate	acetate	hexadiene
α-olefin	50	10	50	5	85	50	50
(mol %)
number	871	2,736	1,936	1,988	3,699	2,779	1,072
average
molecular
weight
(Mn)
Td_5%(° C.)	152	118	290	126	378	320	214
solubility	>70	>70	>70	>70	>50	>70	>70
(wt %)

As shown in Table 2, with copolymerization of vinyl norbornene and norbornene, the number average molecular weight (Mn), the polydispersity index (PDI) of the obtained copolymer can be controlled by means of the addition of α-olefin. As shown in Tables 1 and 2, when the α-olefin is methylacrylate, the suitable amount (mol %) of α-olefin is larger than about 70 mol %, such as larger than 80 mol %.
Test of Storability
The copolymers prepared from Examples 1-6 and 9-16 and Comparative Examples 1-2 were kept for one day (or two days), and then the solubility (in toluene) and viscosity of the copolymer were measured. The results are shown in Table 3.

TABLE 3

		Example	Example	Example	Example	Example	Example	Example
		1	2	3	5	6	9	10

solubility	kept	>70	>70	>70	>60	>60	20	>70
in toluene	for one
(wt %)	day
	kept	>70	>70	>70	>60	>60	>15	>70
	for 2
	days

viscosity(cP)	100	534	11,260	376,200	2,754	solid	18

		Example	Example	Example	Example	Comparative	Comparative
		11	12	15	16	Example 1	Example 2

solubility	kept	>70	>70	>70	>70	<10	<10
in toluene	for one
(wt %)	day
	kept	>70	>70	>70	>70	<1	insoluble
	for 2
	days

viscosity(cP)	2,869	11,260	52,140	78	solid	solid

As shown in Table 3, the copolymers prepared from Examples (i.e. the oligomer of the disclosure) exhibit superior solubility after two days, since the molecular weight and polydispersity index of the copolymer can be controlled by means of the addition of α-olefin (the obtained copolymers have a molecular weight less than or equal to 12,000). Accordingly, the oligomer of the disclosure exhibits superior storability.
Composition and properties measurement of cured product thereof

Example 17

Copolymer (I) (40 parts by weight) of Example 1, polyphenylene ether (PPE, manufactured and sold by SABIC with a trade No. of SA9000 (with a molecular weight of about 2,300) (60 parts by weight), and a suitable quantity of initiator were added into a reaction bottle, and then dissolved in toluene. After mixing completely, a composition was obtained. Next, the aforementioned composition was coated on a copper foil (manufactured and sold by Furukawa Circuit Foil Co., Ltd.). Next, the copper foil coated with the composition was heated at 100° C. for a period of time. Next, the above copper foil was then heated gradually and then the composition was subjected to a crosslinking reaction under a temperature less than 250° C. (in order to achieve the best crosslinking density), obtaining Film (I). Next, the dielectric constant (Dk) and the dissipation factor (Df) of Film (I) were measured at 10 GHz, and the results are shown in Table 4.

Example 18

Example 18 was performed in the same manner as Example 17 except that Copolymer (I) of Example 1 was replaced with Copolymer (III) of Example 3, obtaining Film (II). Next, the dielectric constant (Dk) and the dissipation factor (Df) of Film (II) were measured at 10 GHz, and the results are shown in Table 4.

Example 19

Example 19 was performed in the same manner as Example 17 except that Copolymer (I) of Example 1 was replaced with Copolymer (IV) of Example 4, obtaining Film (III). Next, the dielectric constant (Dk) and the dissipation factor (Df) of Film (III) were measured at 10 GHz, and the results are shown in Table 4.

Example 20

Example 20 was performed in the same manner as Example 17 except that Copolymer (I) of Example 1 was replaced with Copolymer (V) of Example 5, obtaining Film (IV). Next, the dielectric constant (Dk) and the dissipation factor (Df) of Film (IV) were measured at 10 GHz, and the results are shown in Table 4.

Example 21

Example 21 was performed in the same manner as Example 17 except that Copolymer (I) of Example 1 was replaced with Copolymer (VI) of Example 6, obtaining Film (V). Next, the dielectric constant (Dk) and the dissipation factor (Df) of Film (V) were measured at 10 GHz, and the results are shown in Table 4.

Example 22

Example 22 was performed in the same manner as Example 17 except that Copolymer (I) of Example 1 was replaced with Copolymer (VIII) of Example 8, obtaining Film (VI). Next, the dielectric constant (Dk) and the dissipation factor (Df) of Film (VI) were measured at 10 GHz, and the results are shown in Table 4.

Example 23

Example 23 was performed in the same manner as Example 17 except that Copolymer (I) of Example 1 was replaced with Copolymer (XII) of Example 10, obtaining Film (VII). Next, the dielectric constant (Dk) and the dissipation factor (Df) of Film (VII) were measured at 10 GHz, and the results are shown in Table 4.

Example 24

Example 24 was performed in the same manner as Example 17 except that Copolymer (I) of Example 1 was replaced with Copolymer (XIII) of Example 11, obtaining Film (VIII). Next, the dielectric constant (Dk) and the dissipation factor (DO of Film (VIII) were measured at 10 GHz, and the results are shown in Table 4.

Example 25

Example 25 was performed in the same manner as Example 17 except that Copolymer (I) of Example 1 was replaced with Copolymer (XIV) of Example 12, obtaining Film (XI). Next, the dielectric constant (Dk) and the dissipation factor (Df) of Film (XI) were measured at 10 GHz, and the results are shown in Table 4.

Example 26

Example 26 was performed in the same manner as Example 17 except that Copolymer (I) of Example 1 was replaced with Copolymer (XV) of Example 13, obtaining Film (X). Next, the dielectric constant (Dk) and the dissipation factor (Df) of Film (X) were measured at 10 GHz, and the results are shown in Table 4.

Example 27

Example 27 was performed in the same manner as Example 17 except that Copolymer (I) of Example 1 was replaced with Copolymer (XVI) of Example 14, obtaining Film (XI). Next, the dielectric constant (Dk) and the dissipation factor (Df) of Film (XI) were measured at 10 GHz, and the results are shown in Table 4.

Example 28

Example 28 was performed in the same manner as Example 17 except that Copolymer (I) of Example 1 was replaced with Copolymer (XVII) of Example 15, obtaining Film (XII). Next, the dielectric constant (Dk) and the dissipation factor (Df) of Film (XII) were measured at 10 GHz, and the results are shown in Table 4.

Example 29

Example 29 was performed in the same manner as Example 17 except that Copolymer (I) of Example 1 was replaced with Copolymer (XVIII) of Example 16, obtaining Film (XIII). Next, the dielectric constant (Dk) and the dissipation factor (DO of Film (XIII) were measured at 10 GHz, and the results are shown in Table 4.

Comparative Example 3

1,3,5-tri-2-propenyl-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (TAIL) (40 parts by weight), polyphenylene ether (PPE, manufactured and sold by SABIC with a trade No. of SA9000 (with a molecular weight of about 2,300) (60 parts by weight), and a suitable quantity of initiator were added into a reaction bottle, and then dissolved in toluene. After mixing completely, a composition was obtained. Next, the aforementioned composition was coated on a copper foil (manufactured and sold by Furukawa Circuit Foil Co., Ltd.). Next, the copper foil coated with the composition was heated at 100° C. for a period of time. Next, the above copper foil was then heated gradually and then the composition was subjected to a crosslinking reaction under a temperature less than 250° C. (in order to achieve the best crosslinking density), obtaining Film (XIV). Next, the dielectric constant (Dk) and the dissipation factor (Df) of Film (XIV) were measured at 10 GHz, and the results are shown in Table 4.

TABLE 4

	dielectric	dissipation
	constant	factor
Components of composition	(10 GHz)	(10 GHz)

Example 17	40 wt % Copolymer (I)	60 wt % PPE	2.49	0.0019
Example 18	40 wt % Copolymer (III)	60 wt % PPE	2.39	0.0022
Example 19	40 wt % Copolymer (IV)	60 wt % PPE	2.46	0.0023
Example 20	40 wt % Copolymer (V)	60 wt % PPE	2.46	0.0022
Example 21	40 wt % Copolymer (VI)	60 wt % PPE	2.43	0.0023
Example 22	40 wt % Copolymer (VII)	60 wt % PPE	2.47	0.0028
Example 23	40 wt % Copolymer (XII)	60 wt % PPE	2.34	0.0016
Example 24	40 wt % Copolymer (XIII)	60 wt % PPE	2.44	0.0021
Example 25	40 wt % Copolymer (XIV)	60 wt % PPE	2.45	0.0018
Example 26	40 wt % Copolymer (XV)	60 wt % PPE	2.41	0.0028
Example 27	40 wt % Copolymer (XVI)	60 wt % PPE	2.45	0.0025
Example 28	40 wt % Copolymer (XVII)	60 wt % PPE	2.48	0.0030
Example 29	40 wt % Copolymer (XVIII)	60 wt % PPE	2.51	0.0018
Comparative	40 wt % TAIC	60 wt % PPE	2.66	0.0048
Example 3

Example 30

Copolymer (I) (31 parts by weight) of Example 1, polyphenylene ether (PPE, manufactured and sold by SABIC with a trade No. of SA9000 (with a molecular weight of about 2,300) (46 parts by weight), polystyrene-butadiene-styrene (SBS, manufactured by Cray Valley with a trade No. of Ricon100) (with a molecular weight of about 4,500) (23 parts by weight) and a suitable quantity of initiator were added into a reaction bottle, and then dissolved in toluene. After mixing completely, a composition was obtained. Next, the aforementioned composition was coated on a copper foil (manufactured and sold by Furukawa Circuit Foil Co., Ltd.). Next, the copper foil coated with the composition was heated at 100° C. for a period of time. Next, the above copper foil was then heated gradually and then the composition was subjected to a crosslinking reaction under a temperature less than 250° C. (in order to achieve the best crosslinking density), obtaining Film (XV). Next, the dielectric constant (Dk) and the dissipation factor (Df) of Film (XV) were measured at 10 GHz, and the results are shown in Table 5.

Example 31

Example 31 was performed in the same manner as Example 30 except that Copolymer (I) of Example 1 was replaced with Copolymer (III) of Example 3, obtaining Film (XVI). Next, the dielectric constant (Dk) and the dissipation factor (Df) of Film (XVI) were measured at 10 GHz, and the results are shown in Table 5.

Example 32

Example 32 was performed in the same manner as Example 30 except that Copolymer (I) of Example 1 was replaced with Copolymer (IV) of Example 4, obtaining Film (XVII). Next, the dielectric constant (Dk) and the dissipation factor (Df) of Film (XVII) were measured at 10 GHz, and the results are shown in Table 5.

Example 33

Example 33 was performed in the same manner as Example 30 except that Copolymer (I) of Example 1 was replaced with Copolymer (V) of Example 5, obtaining Film (XVIII). Next, the dielectric constant (Dk) and the dissipation factor (Df) of Film (XVIII) were measured at 10 GHz, and the results are shown in Table 5.

Example 34

Example 34 was performed in the same manner as Example 30 except that Copolymer (I) of Example 1 was replaced with Copolymer (VI) of Example 6, obtaining Film (XIX). Next, the dielectric constant (Dk) and the dissipation factor (Df) of Film (XIX) were measured at 10 GHz, and the results are shown in Table 5.

Example 35

Example 35 was performed in the same manner as Example 30 except that Copolymer (I) of Example 1 was replaced with Copolymer (VIII) of Example 8, obtaining Film (XX). Next, the dielectric constant (Dk) and the dissipation factor (Df) of Film (XX) were measured at 10 GHz, and the results are shown in Table 5.

Example 36

Example 36 was performed in the same manner as Example 30 except that Copolymer (I) of Example 1 was replaced with Copolymer (XII) of Example 10, obtaining Film (XXI). Next, the dielectric constant (Dk) and the dissipation factor (Df) of Film (XXI) were measured at 10 GHz, and the results are shown in Table 5.

Example 37

Example 37 was performed in the same manner as Example 30 except that Copolymer (I) of Example 1 was replaced with Copolymer (XIII) of Example 11, obtaining Film (XXII). Next, the dielectric constant (Dk) and the dissipation factor (Df) of Film (XXII) were measured at 10 GHz, and the results are shown in Table 5.

Example 38

Example 38 was performed in the same manner as Example 30 except that Copolymer (I) of Example 1 was replaced with Copolymer (XIV) of Example 12, obtaining Film (XXIII). Next, the dielectric constant (Dk) and the dissipation factor (Df) of Film (XXIII) were measured at 10 GHz, and the results are shown in Table 5.

Example 39

Example 39 was performed in the same manner as Example 30 except that Copolymer (I) of Example 1 was replaced with Copolymer (XV) of Example 13, obtaining Film (XXIV). Next, the dielectric constant (Dk) and the dissipation factor (Df) of Film (XXIV) were measured at 10 GHz, and the results are shown in Table 5.

Example 40

Example 40 was performed in the same manner as Example 30 except that Copolymer (I) of Example 1 was replaced with Copolymer (XVI) of Example 14, obtaining Film (XXV). Next, the dielectric constant (Dk) and the dissipation factor (Df) of Film (XXV) were measured at 10 GHz, and the results are shown in Table 5.

Example 41

Example 41 was performed in the same manner as Example 30 except that Copolymer (I) of Example 1 was replaced with Copolymer (XVII) of Example 15, obtaining Film (XXVI). Next, the dielectric constant (Dk) and the dissipation factor (Df) of Film (XXVI) were measured at 10 GHz, and the results are shown in Table 5.

Example 42

Example 42 was performed in the same manner as Example 30 except that Copolymer (I) of Example 1 was replaced with Copolymer (XVIII) of Example 16, obtaining Film (XXVII). Next, the dielectric constant (Dk) and the dissipation factor (Df) of Film (XXVII) were measured at 10 GHz, and the results are shown in Table 5.

Comparative Example 4

1,3,5-tri-2-propenyl-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (TAIL) (31 parts by weight), polyphenylene ether (PPE, manufactured and sold by SABIC with a trade No. of SA9000 (with a molecular weight of about 2,300) (46 parts by weight), polystyrene-butadiene-styrene (SBS, manufactured by Cray Valley with a trade No. of Ricon100) (with a molecular weight of about 4,500) (23 parts by weight) and a suitable quantity of initiator were added into a reaction bottle, and then dissolved in toluene. After mixing completely, a composition was obtained. Next, the aforementioned composition was coated on a copper foil (manufactured and sold by Furukawa Circuit Foil Co., Ltd.). Next, the copper foil coated with the composition was heated at 100° C. for a period of time. Next, the above copper foil was then heated gradually and then the composition was subjected to a crosslinking reaction under a temperature less than 250° C. (in order to achieve the best crosslinking density), obtaining Film (XXVIII). Next, the dielectric constant (Dk) and the dissipation factor (Df) of Film (XXVIII) were measured at 10 GHz, and the results are shown in Table 5.

TABLE 5

	dielectric	dissipation
	constant	factor
Components of composition	(10 GHz)	(10 GHz)

Example 30	31 wt % Copolymer (I)	23 wt % SBS	46 wt % PPE	2.32	0.0012
Example 31	31 wt % Copolymer (III)	23 wt % SBS	46 wt % PPE	2.42	0.0016
Example 32	31 wt % Copolymer (IV)	23 wt % SBS	46 wt % PPE	2.41	0.0015
Example 33	31 wt % Copolymer (V)	23 wt % SBS	46 wt % PPE	2.39	0.0018
Example 34	31 wt % Copolymer (VI)	23 wt % SBS	46 wt % PPE	2.30	0.0015
Example 35	31 wt % Copolymer (VIII)	23 wt % SBS	46 wt % PPE	2.42	0.0025
Example 36	31 wt % Copolymer (XII)	23 wt % SBS	46 wt % PPE	2.34	0.0015
Example 37	31 wt % Copolymer (XIII)	23 wt % SBS	46 wt % PPE	2.38	0.0015
Example 38	31 wt % Copolymer (XIV)	23 wt % SBS	46 wt % PPE	2.37	0.0015
Example 39	31 wt % Copolymer (XV)	23 wt % SBS	46 wt % PPE	2.43	0.0022
Example 40	31 wt % Copolymer (XVI)	23 wt % SBS	46 wt % PPE	2.41	0.0021
Example 41	31 wt % Copolymer (XVII)	23 wt % SBS	46 wt % PPE	2.46	0.0023
Example 42	31 wt % Copolymer (XVIII)	23 wt % SBS	46 wt % PPE	2.47	0.0015
Comparative	31 wt % TAIC	23 wt % SBS	46 wt % PPE	2.61	0.0028
Example 4

Example 43

Copolymer (I) (70 parts by weight) of Example 1, polystyrene-butadiene-styrene (SBS, manufactured by Cray Valley with a trade No. of Ricon100) (with a molecular weight of about 4,500) (30 parts by weight) and a suitable quantity of initiator were added into a reaction bottle, and then dissolved in toluene. After mixing completely, a composition was obtained. Next, the aforementioned composition was coated on a copper foil (manufactured and sold by Furukawa Circuit Foil Co., Ltd.). Next, the copper foil coated with the composition was heated at 90° C. for a period of time. Next, the above copper foil was then heated gradually and then the composition was subjected to a crosslinking reaction under a temperature less than 250° C. (in order to achieve the best crosslinking density), obtaining Film (XXIX). Next, the dielectric constant (Dk) and the dissipation factor (Df) of Film (XXIX) were measured at 10 GHz, and the results are shown in Table 6.

Example 44

Example 44 was performed in the same manner as Example 39 except that Copolymer (I) of Example 1 was replaced with Copolymer (VIII) of Example 8, obtaining Film (XXX). Next, the dielectric constant (Dk) and the dissipation factor (Df) of Film (XXX) were measured at 10 GHz, and the results are shown in Table 6.

Example 45

Copolymer (III) (31 parts by weight) of Example 3, polyphenylene ether (PPE, manufactured and sold by SABIC with a trade No. of SA9000 (with a molecular weight of about 2,300) (46 parts by weight), polybutadiene (PB, manufactured by Nippon Soda with a trade No. of B2000) (with a molecular weight of about 2,100) (23 parts by weight) and a suitable quantity of initiator were added into a reaction bottle, and then dissolved in toluene. After mixing completely, a composition was obtained. Next, the aforementioned composition was coated on a copper foil (manufactured and sold by Furukawa Circuit Foil Co., Ltd.). Next, the copper foil coated with the composition was heated at 100° C. for a period of time. Next, the above copper foil was then heated gradually and then the composition was subjected to a crosslinking reaction under a temperature less than 250° C. (in order to achieve the best crosslinking density), obtaining Film (XXXI). Next, the dielectric constant (Dk) and the dissipation factor (Df) of Film (XXXI) were measured at 10 GHz, and the results are shown in Table 6.

Example 46

Copolymer (V) (38 parts by weight) of Example 5, polyphenylene ether (PPE, manufactured and sold by SABIC with a trade No. of SA9000 (with a molecular weight of about 2,300) (57 parts by weight), bismaleimide (manufactured and sold by Daiwa Kasei Kogyo Co. with a trade No. of BMI-5,100) (with a molecular weight of about 2,100) (5 parts by weight) and a suitable quantity of initiator were added into a reaction bottle, and then dissolved in toluene. After mixing completely, a composition was obtained. Next, the aforementioned composition was coated on a copper foil (manufactured and sold by Furukawa Circuit Foil Co., Ltd.). Next, the copper foil coated with the composition was heated at 100° C. for a period of time. Next, the above copper foil was then heated gradually and then the composition was subjected to a crosslinking reaction under a temperature less than 250° C. (in order to achieve the best crosslinking density), obtaining Film (XXXII). Next, the dielectric constant (Dk) and the dissipation factor (DO of Film (XXXII) were measured at 10 GHz, and the results are shown in Table 6.

TABLE 6

	dielectric	dissipation
	constant	factor
Components of composition	(10 GHz)	(10 GHz)

Example 43	70 wt % Copolymer (I)	30 wt % SBS	—	2.35	0.0021
Example 44	70 wt % Copolymer (VIII)	30 wt % SBS	—	2.25	0.0030
Example 45	31 wt % Copolymer (III)	23 wt % PB	46 wt % PPE	2.35	0.0018
Example 46	38 wt % Copolymer (V)	5 wt % BMI	57 wt % PPE	2.48	0.0026

Example 47

Copolymer (III) (17 parts by weight) of Example 3, polyphenylene ether (PPE, manufactured and sold by Mitsubishi Gas Chemical with a trade No. of OPE-2st (with a molecular weight of about 2,200) (70 parts by weight), polystyrene-butadiene-styrene (manufactured and sold by Cray Valley. with a trade No. of Ricon100) (with a molecular weight of about 4,500) (13 parts by weight) and a suitable quantity of initiator were added into a reaction bottle, and then dissolved in toluene. After mixing completely, a composition was obtained. After stirring completely, a composition was obtained. Next, glass fiber (sold by Asahi Fiber Glass with a trade No. of L2116) was immersed in the aforementioned composition, wherein the impregnated amount was about 59%. After removing the glass fiber from the composition, the glass fiber was baked at 140° C. by hot air circulating oven to control the crosslinking degree of about 50%, obtaining a prepreg. Four prepregs were stacked, and a copper foil, a mirror plate, and a Kraft paper were disposed on the top surface and the bottom surface of the stacked structure. The obtained structure was heated to 210° C. gradually by vacuum molding machine for 3 hr, obtaining Copper foil substrate (I) with a thickness of 0.558 mm. Next, the dielectric constant (Dk) and the dissipation factor (Df) of Copper foil substrate (I) were measured at 10 GHz, and the results are shown in Table 7.

TABLE 7

	dielectric	dissipation
	constant	factor
Components of composition	(10 GHz)	(10 GHz)

Example 47	17 wt % Copolymer (III)	70 wt % PPE	13 wt % SBS	2.96	0.0033

As shown in Tables 4-7, since the composition includes an oligomer having a structure represented by Formula (I), the cured product exhibits a relatively low dielectric constant (less than or equal to 3.0 (at 10 GHz) and a relatively low dissipation factor (less than or equal to 0.0033 (at 10 GHz)), thereby serving as a good material for a high-frequency substrate. As shown in the above Examples, the composition of the disclosure can be crosslinked at a temperature less than 250° C., and the obtained oligomer exhibits superior crosslinking density. Furthermore, the oligomer can achieve optimal crosslinking density which is checked by means of the crosslinking exotherm determined by differential scanning calorimetry.
It will be clear that various modifications and variations can be made to the disclosed methods and materials. It is intended that the specification and examples be considered as exemplary only, with the true scope of the disclosure being indicated by the following claims and their equivalents.

Claims

What is claimed is:

1. An oligomer, having a structure represented by Formula (I)

wherein R¹and R²are independently hydrogen, C_1-20alkyl group, C_2-20alkenyl group, C_6-12aryl group, C_6-12alkylaryl group, C_5-12cycloalkyl group, C_6-20cycloalkylalkyl group, alkoxycarbonyl group, or alkylcarbonyloxy group; R¹is not hydrogen when R²is hydrogen; a is 0 or 1; n≧0; m≧1; n:m is from 0:100 to 99:1; the oligomer has a number average molecular weight of less than or equal to 12,000; and

the repeat unit

and the repeat unit

are arranged in a random or block fashion.

2. The oligomer as claimed in claim 1, wherein R¹and R²are independently hydrogen, or

and wherein b is 0, or an integer from 1 to 19; and R¹is not hydrogen when R²is hydrogen.

3. The oligomer as claimed in claim 1, wherein R¹and R²are independently hydrogen, or

wherein c is 0, or an integer from 1 to 6; and R¹is not hydrogen when R²is hydrogen.

4. The oligomer as claimed in claim 1, wherein R¹and R²are independently hydrogen, or

and wherein d is 0, or an integer from 1 to 6; and R¹is not hydrogen when R²is hydrogen.

5. The oligomer as claimed in claim 1, wherein R¹and R²are independently hydrogen, or

wherein e is 0, or an integer from 1 to 6; and R¹is not hydrogen when R²is hydrogen.

6. The oligomer as claimed in claim 1, wherein R¹and R²are independently hydrogen, or

and wherein f is 0, or an integer from 1 to 6; R³is C_1-6alkyl group; and R¹is not hydrogen when R²is hydrogen.

7. The oligomer as claimed in claim 1, wherein R¹and R²are independently hydrogen, or

and wherein g is 0, or an integer from 1 to 6; R⁴is C_1-6alkyl group; and R¹is not hydrogen when R²is hydrogen.

8. The oligomer as claimed in claim 1, wherein R¹and R²are independently hydrogen, or

wherein h is an integer from 1 to 6; and R¹is not hydrogen when R²is hydrogen.

9. The oligomer as claimed in claim 1, wherein R¹and R²are independently hydrogen, or

wherein i is 0, 1, 2, 3, 4, 5, or 6; and R¹is not hydrogen when R²is hydrogen.

10. The oligomer as claimed in claim 1, wherein R¹and R²are independently hydrogen, or

wherein j is 0, 1, 2, 3, 4, 5, or 6; and R¹is not hydrogen when R²is hydrogen.

11. The oligomer as claimed in claim 1, wherein n:m is from 1:9 to 9:1.

12. A composition, comprising:

1-99 parts by weight of the oligomer as claimed in claim 1; and

1-99 parts by weight of resin.

13. The composition as claimed in claim 12, wherein the resin is polyolefin resin, epoxy resin, cyanate resin, phenol resin, novolac resin, polystyrene resin, styrene-butadiene copolymer resin, polyamide resin, polyimide resin, maleimide resin, bismaleimide resin, polyphenylene ether resin, or a combination thereof.

14. The composition as claimed in claim 13, wherein the polyolefin resin is polybutadiene resin, polyalkenamer resin, cyclic olefin polymer resin, or cycloolefin copolymer resin.

15. A composite material, comprising:

a cured product or a semi-cured product prepared by the composition as claimed in claim 12; and

a substrate, wherein the cured product or the semi-cured product is disposed on the substrate or disposed within the substrate.

16. The composite material as claimed in claim 15, wherein the substrate is glass fiber, or copper foil.

17. The composite material as claimed in claim 15, wherein the composite material is a copper foil substrate, a printed circuit board, or an integrated circuit carrier.