CN108250720B

CN108250720B - Oligomer, composition containing same and composite material

Info

Publication number: CN108250720B
Application number: CN201711391873.XA
Authority: CN
Inventors: 杨伟达; 朱晏颐; 洪铭聪; 梁丽君; 李云卿; 鄞盟松; 秦羲仪
Original assignee: Industrial Technology Research Institute ITRI
Current assignee: Industrial Technology Research Institute ITRI
Priority date: 2016-12-29
Filing date: 2017-12-21
Publication date: 2021-03-23
Anticipated expiration: 2037-12-21
Also published as: CN108250720A; CN107417891A

Abstract

The application provides an oligomer, a composition containing the oligomer and a composite material. The oligomer has a structure shown in formula (I)

Wherein R is¹And R²Independently of one another is hydrogen, C_1‑20Alkyl (alkyl group), C_2‑20Alkenyl group, C_6‑12Aryl group, C_6‑12Alkylaryl (alkylaryl group), C_5‑12Cycloalkyl (cycloalkyl group), C_6‑20Cycloalkylalkyl (cycloalkylalkyl group), alkoxycarbonyl (alkoxycarbonyl group), or alkylcarbonyloxy (alkylcarbonyloxy group), and R is¹And R²Not hydrogen at the same time; a is 0 or 1; n is not less than 0; m is not less than 1; n is m is 0:100 to 99: 1; the oligomer has a number average molecular weight of less than or equal to 12,000; and, a repeating unit

And a repeating unit

Description

Oligomer, composition containing same and composite material

[ technical field ] A method for producing a semiconductor device

The present disclosure relates to oligomers, compositions and composites comprising the same.

[ background of the invention ]

Electronic products in new times tend to be light, thin, short and small, and are suitable for high-frequency transmission, so that the wiring of circuit boards tends to be high-density. In order to maintain the transmission rate and the integrity of the transmitted signal, the substrate material of the circuit board must have both a low dielectric constant (Dk) and a low dissipation factor (Df).

Since the dielectric constant (Dk) and dissipation factor (Df) of the conventional circuit board materials are generally high, how to improve the dielectric constant and dissipation factor of the circuit board substrate material without affecting the heat-resistant characteristics and mechanical strength is an important issue in the current printed circuit board manufacturing process.

[ summary of the invention ]

In accordance with embodiments of the present disclosure, an oligomer is provided. The oligomer has a structure shown in formula (I)

Wherein R is¹And R²Independently of one another is hydrogen, C_1-20Alkyl (alkyl group), C_2-20Alkenyl group, C_6-12Aryl group, C_6-12Alkylaryl (alkylaryl group), C_5-12Cycloalkyl (cycloalkyl group), C_6-20Cycloalkylalkyl (cycloalkylalkyl group), alkoxycarbonyl (alkoxycarbonyl group), or alkylcarbonyloxy (alkylcarbonyloxy group), and R is¹And R²Not hydrogen at the same time; a is 0 or 1; n is not less than 0; m is not less than 1; n: m is about 0:100 to about 99: 1; the oligomer has a number average molecular weight of about 12,000 or less; and, a repeating unit

And a repeating unit

Are repeated in a random manner or in a block manner.

In accordance with embodiments of the present disclosure, there is also provided a composition comprising: about 10 to about 90 parts by weight of the oligomer; and about 10-90 parts by weight of a resin, wherein the sum of the weight of the oligomer and the resin is 100 parts by weight.

According to an embodiment of the present disclosure, the present disclosure also provides a composite material comprising: a cured product or a semi-cured product formed from the composition; and a substrate, wherein the cured or semi-cured is on or in the substrate.

[ detailed description ] embodiments

Embodiments of the present disclosure provide an oligomer, a composition comprising the same, and a composite material. The oligomers described in this disclosure can be prepared by ring-opening polymerization (ring-opening polymerization) of a first monomer (e.g., vinyl norbornene) with a second monomer (e.g., norbornene) and by introducing an alpha-olefin to control the molecular weight of the resulting copolymer (to control the number average molecular weight of the copolymer to about 12,000 or less). Thus, the obtained oligomer has good solubility in organic solvents, and the processability is improved. In addition, the oligomer disclosed by the disclosure has lower polarity, and the chemical structure of the oligomer has crosslinkable functional groups, so that the oligomer is favorable for being subsequently applied to a substrate material and the mechanical strength of the substrate material is increased. Embodiments of the present disclosure also provide a composition comprising the oligomer and a composite material (e.g., prepreg) comprising a cured product or a prepreg thereof. The cured product of the composition disclosed by the disclosure has low dielectric constants (Dk) (which can be less than 3.0 (at 10 GHz)) and dissipation factors (Df) (which can be less than 0.0045 (at 10 GHz)), and can be used as a high-frequency substrate material to solve the problem of insertion loss (insertion loss).

According to an embodiment of the present disclosure, the oligomer has a structure represented by formula (I)

Wherein R is¹And R²Independently of one another is hydrogen, C_1-20Alkyl (alkyl group), C_2-20Alkenyl group, C_6-12Aryl group, C_6-12Alkylaryl (alkylaryl group), C_5-12Cycloalkyl (cycloalkyl group), C_6-20Cycloalkylalkyl (cycloalkylalkyl group), alkoxycarbonyl (alkoxycarbonyl group), or alkylcarbonyloxy (alkylcarbonyloxy group), and R is¹And R²Not hydrogen at the same time; a is 0 or 1; n ≧ 0 (e.g., n ≧ 1); m is not less than 1; n: m is about 0:100 to about 99: 1; the oligomer has a number average molecular weight of about 12,000 or less; and, a repeating unit

And a repeating unit

Are repeated in a random manner or in a block manner.

According to embodiments of the present disclosure, the alkyl groups described in the present disclosure may be linear or branched (linear or branched) alkyl groups. For example, R¹And R²Alkyl groups having 1, 2,3, 4,5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 carbons, which may independently be straight or branched; according to embodiments of the present disclosure, the alkenyl groups described in the present disclosure may be linear or branched. For example, R¹And R²Can independently be a straight or branched chain alkenyl group having 2,3, 4,5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 carbons.

According to an embodiment of the present disclosure, R¹And R²May independently be 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 R¹And R²Not hydrogen at the same time.

According to the embodiment of the disclosure, C is_6-12The aryl group may be phenyl, biphenyl, or naphthyl.

According to an embodiment of the present disclosure, R¹And R²Independently is hydrogen, or

Wherein c can be 0, 1, 2,3, 4,5, or 6, and R¹And R²Not hydrogen at the same time.

Wherein d can be 0, 1, 2,3, 4,5, or 6, and R¹And R²Not hydrogen at the same time.

Wherein e can be 0, 1, 2,3, 4,5, or 6, and R¹And R²Not hydrogen at the same time.

Wherein f can be 0, 1, 2,3, 4,5, or 6, R³Can be C_1-6Alkyl (alkyl group), and R¹And R²Not hydrogen at the same time. For example, R³And may be methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, or hexyl.

Wherein g can be 0, 1, 2,3, 4,5, or 6, R⁴Can be C_1-6Alkyl (alkyl group), and R¹And R²Not hydrogen at the same time. For example, R⁴And may be methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, or hexyl.

Wherein h can be 1, 2,3, 4,5, or 6, and R¹And R²Not hydrogen at the same time.

Wherein i can be 0, 1, 2,3, 4,5, or 6, and R¹And R²Not hydrogen at the same time.

Wherein j can be 0, 1, 2,3, 4,5, or 6, and R¹And R²Not hydrogen at the same time.

According to an embodiment of the present disclosure, the repeating unit

And a repeating unit

The ratio of (i.e., n: m) may be about 0:100 to 99:1, for example about 1:9 to 9:1, or about 2:8 to 8:2, or about 3:7 to 7:3, or about 3:7 to 6: 4. By proportioning the two repeating units in the oligomer, the oligomer and the tree can be controlledProperties of the cured product obtained after the ester crosslinking. For example, if repeating units are added

The ratio (B) can increase the crosslinkable density of the resulting cured product.

Embodiments of the present disclosure can control the molecular weight of the resulting copolymer by introducing an alpha-olefin into the copolymerization of vinyl norbornene and norbornene. According to embodiments of the present disclosure, the oligomer number average molecular weight may be less than about 12,000, such as between about 800 and 12,000, between about 800 and 9,000, between about 800 and 8,000, between about 800 and 7,000, between about 800 and 6,000, or between about 800 and 5,000. Thus, the obtained oligomer has good solubility in organic solvents, and the processability is improved. In addition, the oligomers of the embodiments of the present disclosure have good storage properties compared to conventional copolymers prepared solely from vinyl norbornene and norbornene.

According to an embodiment of the present disclosure, the above oligomer may be prepared by mixing and reacting the first monomer, the second monomer, and the α -olefin to obtain the oligomer.

According to an embodiment of the present disclosure, the oligomer may be prepared by mixing and reacting a metal catalyst, a first monomer, a second monomer, and an α -olefin to obtain the oligomer.

According to an embodiment of the present disclosure, the oligomer may be prepared by mixing and reacting a photo-redox initiator (initiator), a photo-redox mediator (phoroedox mediator), a first monomer, a second monomer, and an α -olefin to obtain the oligomer. The photo-redox initiator (initiator) may be, for example, a vinyl ether, 1-methoxy-4-phenylbutene (1-methoxy-4-phenyl butane), 2-cyclohexyl-1-methoxyethylene (2-cyclohexyl-1-methoxyethylene), or a combination thereof. The photoredox mediator may be a pyrylium salt, an acridinium salt, or a combination thereof.

According to an embodiment of the present disclosure, the oligomer may be prepared by reacting a first monomer, a second monomer, and an α -olefin under electrochemical conditions to obtain the oligomer.

The metal catalyst may be, for example, a Grubbs (Grubbs) catalyst, such as a first generation Grubbs catalyst, a second generation Grubbs catalyst, a haveda (Hoveyda) -Grubbs catalyst, derivatives thereof, or the like, or a combination comprising at least one of the foregoing Grubbs 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 alpha-olefin may be

Wherein R is⁵Can be C_1-20Alkyl (alkyl group), C_2-20Alkenyl group, C_6-12Aryl group, C_6-12Alkylaryl (alkylaryl group), C_5-12Cycloalkyl (cycloalkyl group), C_6-20A cycloalkylalkyl group (cycloalkylalkyl group), an alkoxycarbonyl group (alkoxycarbonyl group), or an alkylcarbonyloxy group (alkylcarbonyloxy group). For example, the alpha-olefin can be

Wherein b, c, d, e, f, g, h, i, j, R³And R⁴The definitions of (a) are the same as above. In each reaction for producing an oligomer described above, the order of addition of each component is not particularly limited. For example, the metal catalyst may be first dissolved in a solventTo obtain a solution containing the metal catalyst. Next, a solution comprising the first monomer and an alpha-olefin is mixed with the solution containing the metal catalyst. Finally, the second monomer is added. According to embodiments of the present disclosure, the molar ratio of the first monomer and the second monomer may be about 100:0 (i.e., without the addition of the second monomer) to about 1:99, for example, about 9:1 to about 1:9, or about 8:2 to about 2:8, or about 3:7 to about 7:3, or about 3:7 to about 6: 4. In addition, the mole percentage of the α -olefin may be about 1 mol% to about 85 mol%, for example about 5 mol% to about 75 mol%, or about 10 mol% to about 75 mol%, based on the total moles of the first monomer and the second monomer.

In one embodiment, the amount of alpha-olefin added tends to be inversely proportional to the molecular weight of the resulting oligomer, and the molecular weight of the oligomer can be controlled by the amount of alpha-olefin introduced. If the mole percentage of the alpha-olefin is too low, it may result in too high a molecular weight of the oligomer and poor processability and storability; conversely, if the mole percentage of the α -olefin is too high, the molecular weight of the oligomer may be too low and the substrate process may not be easily controlled.

According to an embodiment of the present disclosure, the present disclosure also provides a resin composition comprising the oligomer and one or more resins. The oligomer may be present in an amount of about 10 to about 90, about 15 to about 85, or about 20 to about 80 parts by weight; and, the resin may be present in an amount of about 10 to about 90, about 15 to about 85, or about 20 to about 80 parts by weight. According to an embodiment of the present disclosure, the sum of the weight of the oligomerization and the resin is 100 parts by weight. The resin may be a polyolefin resin (polyolefin resin) (e.g., polybutadiene resin (polybutadiene resin), polycycloolefin resin (polycycloolefin resin), cyclic olefin polymer resin (cycloolefine polymer resin), or cyclic olefin copolymer resin (cycloolefine copolymer resin)), an epoxy resin (epoxy resin), a cyanate resin (cyanate resin), a polystyrene resin (polystyrene resin), a styrene-butadiene copolymer resin (styrene-butadiene copolymer resin) (e.g., polystyrene-butadiene-styrene resin), a polyimide resin (polyimide resin), a maleimide resin (maleinimide resin), a polyphenylene ether resin (phenylenevinylether resin), or a combination thereof. Further, according to embodiments of the present disclosure, the weight percentage of the oligomer is between about 1 wt% and 99 wt%, between about 10 wt% and 90 wt%, or between about 20 wt% and 80 wt%, and the weight of the resin may be between about 1 wt% and 99 wt%, between about 10 wt% and 90 wt%, or between about 20 wt% and 80 wt%, based on the total weight of the oligomer and the resin.

The present disclosure also provides a composite material according to an embodiment of the present disclosure. The composite material can comprise a cured product or a semi-cured product formed by the resin composition; and a substrate, wherein the cured or semi-cured is on or in the substrate. According to embodiments of the present disclosure, the substrate may be fiberglass, or copper foil. For example, the composite material may comprise a prepreg prepared by impregnating glass fibers (as a base material) with the resin composition. Then, the resin composition is semi-cured to obtain the prepreg. In addition, the composite material can further comprise copper foil, and the composite material can be a copper foil substrate, a printed circuit board or an integrated circuit carrier.

In order to make the aforementioned and other objects, features, and advantages of the present disclosure more comprehensible, several embodiments and comparative examples are described in detail below:

example 1

0.045 g of 1,3-bis (2,4,6-trimethylphenyl) -4,5-dihydroimidazol-2-yl [2- (isopropoxy-5- (N, N-dimethylaminosulfonyl) phenyl ] was added]Methyl ruthenium dichloride (1,3-Bis (2,4, 6-trimethyonyl) -4, 5-dihydrazod-2-ylidine [2- (i-methoxy) -5- (N, N-dimethylaminosulfonyl) phenyl]methylene (ii) dichloride (as a metal catalyst) was added to a first reaction flask under nitrogen, and 10 ml of toluene (tolumen) was added to the first reaction flask to obtain a metal catalyst solution. After the metal catalyst was completely dissolved in toluene, 0.604mol of 1-hexene (. alpha. -olefin), 73.6 g of vinylnorbornene (vinyl no) were added to the second reaction flaskrbornene, VNB), and 128 ml of toluene. Next, the metal catalyst solution in the first reaction vessel was added to the second reaction vessel. After stirring well, a norbornene solution (57.7 g of Norbornene (NB) in 50 ml of toluene) was added to the second reaction flask. Here, the mole percent ratio of the α -olefin (1-hexene) was 50 mol%, based on the total number of moles of vinyl norbornene and norbornene. After the reaction was complete, 63 ml of ethyl vinyl ether (ethyl vinyl ether) was added to the second reaction flask. After stirring overnight, the resulting solution was freed of the catalyst and reprecipitated in methanol. After reconcentration, a copolymer (I) is obtained in which the recurring units of the copolymer (I)

And a repeating unit

In a ratio of about 1: 1.

Next, the number average molecular weight (Mn), polydispersity index (molecular weight distribution value, PDI), and solubility in toluene of the copolymer (I) were measured, and the temperature at which the copolymer (I) lost 5% by weight was measured by thermogravimetric analysis (TGA), 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-yl [2- (isopropoxy-5- (N, N-dimethylaminosulfonyl) phenyl ] was added]Methyl ruthenium dichloride (as a metal catalyst) was added to the first reaction vessel under nitrogen, and 10 ml of toluene (toluene) was added to the first reaction vessel to obtain a metal catalyst solution. After the metal catalyst was completely dissolved in toluene, 0.362mol of 1-hexene (. alpha. -olefin), 73.6 g of Vinylnorbornene (VNB), and 128 ml of toluene were added to the second reaction flask. Next, the metal catalyst solution in the first reaction vessel was added to the second reaction vessel. After stirring well, a norbornene solution (57.7 g of Norbornene (NB) in 50 ml of toluene) was added to the second reaction flask. Here, the molar percentage of the α -olefin (1-hexene) was 30 mol% based on ethyleneThe total number of moles of norbornene and norbornene is based on. After the reaction was complete, 63 ml of ethyl vinyl ether (ethyl vinyl ether) was added to the second reaction flask. After stirring overnight, the resulting solution was freed of the catalyst and reprecipitated in methanol. After reconcentration, a copolymer (II) is obtained in which the recurring units of the copolymer (II)

And a repeating unit

In a ratio of about 1: 1.

Subsequently, the number average molecular weight (Mn), polydispersity index (PDI), and solubility in toluene of the copolymer (II) were measured, and the temperature at which the copolymer (II) lost 5% of weight was measured by thermogravimetric analysis (TGA), with the results shown in table 1.

Example 3

0.09 g of 1,3-bis (2,4,6-trimethylphenyl) -4,5-dihydroimidazol-2-yl [2- (isopropoxy-5- (N, N-dimethylaminosulfonyl) phenyl ] are added]Methyl ruthenium dichloride (as a metal catalyst) was added to the first reaction vessel under nitrogen, and 15 ml of toluene (toluene) was added to the first reaction vessel to obtain a metal catalyst solution. After the metal catalyst was completely dissolved in toluene, 0.483mol of 1-hexene (. alpha. -olefin), 147 g of Vinylnorbornene (VNB), and 260 ml of toluene were charged into the second reaction flask. Next, the metal catalyst solution in the first reaction vessel was added to the second reaction vessel. After stirring well, a norbornene solution (115 g of Norbornene (NB) dissolved in 100 ml of toluene) was added to the second reaction flask. Here, the mole percent ratio of the α -olefin (1-hexene) was 20 mol%, based on the total number of moles of vinyl norbornene and norbornene. After the reaction was complete, 125 ml of ethyl vinyl ether (ethyl vinyl ether) was added to the second reaction flask. After stirring overnight, the resulting solution was freed of the catalyst and reprecipitated in methanol. After reconcentration, a copolymer (III) is obtained in which the recurring units of the copolymer (III)

And a repeating unit

In a ratio of about 1: 1.

Subsequently, the number average molecular weight (Mn), polydispersity index (PDI), and solubility in toluene of the copolymer (III) were measured, and the temperature at which the copolymer (III) lost 5% in weight was measured by thermogravimetric analysis (TGA), with the results shown in table 1.

Example 4

0.045 g of 1,3-bis (2,4,6-trimethylphenyl) -4,5-dihydroimidazol-2-yl [2- (isopropoxy-5- (N, N-dimethylaminosulfonyl) phenyl ] was added]Methyl ruthenium dichloride (as a metal catalyst) was added to the first reaction vessel under nitrogen, and 10 ml of toluene (toluene) was added to the first reaction vessel to obtain a metal catalyst solution. After the metal catalyst was completely dissolved in toluene, 0.241mol of 1-hexene (. alpha. -olefin), 52.1 g of Vinylnorbornene (VNB), and 87 ml of toluene were added to the second reaction flask. Next, the metal catalyst solution in the first reaction vessel was added to the second reaction vessel. After stirring well, a norbornene solution (75 g of Norbornene (NB) dissolved in 90 ml of toluene) was added to the second reaction flask. Here, the mole percent ratio of the α -olefin (1-hexene) was 20 mol%, based on the total number of moles of vinyl norbornene and norbornene. After the reaction was complete, 63 ml of ethyl vinyl ether (ethyl vinyl ether) was added to the second reaction flask. After stirring overnight, the resulting solution was freed of the catalyst and reprecipitated in methanol. After reconcentration, a copolymer (IV) is obtained in which the recurring units of the copolymer (IV) are

And a repeating unit

In a ratio of about 1: 0.5.

Subsequently, the number average molecular weight (Mn), polydispersity index (PDI), and solubility in toluene of the copolymer (IV) were measured, and the temperature at which the weight loss of the copolymer (IV) was 5% was measured by thermogravimetric analysis (TGA), 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-yl [2- (isopropoxy-5- (N, N-dimethylaminosulfonyl) phenyl ] are reacted]Methyl ruthenium dichloride (as a metal catalyst) was added to the first reaction vessel under nitrogen, and 15 ml of toluene (toluene) was added to the first reaction vessel to obtain a metal catalyst solution. After the metal catalyst was completely dissolved in toluene, 0.145mol of 1-hexene (. alpha. -olefin), 88.3 g of Vinylnorbornene (VNB), and 150 ml of toluene were added to the second reaction flask. Next, the metal catalyst solution in the first reaction vessel was added to the second reaction vessel. After stirring well, a norbornene solution (69.3 g of Norbornene (NB) in 60 ml of toluene) was added to the second reaction flask. Here, the mole percent ratio of the α -olefin (1-hexene) was 10 mol%, based on the total number of moles of vinyl norbornene and norbornene. After the reaction was complete, 75 ml of ethyl vinyl ether (ethyl vinyl ether) was added to the second reaction flask. After stirring overnight, the resulting solution was freed of the catalyst and reprecipitated in methanol. After reconcentration, a copolymer (V) is obtained in which the recurring units of the copolymer (V)

And a repeating unit

In a ratio of about 1: 1.

Subsequently, the number average molecular weight (Mn), polydispersity index (PDI), and solubility in toluene of the copolymer (V) were measured, and the temperature at which the weight loss of the copolymer (V) was 5% was measured by thermogravimetric analysis (TGA), 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-yl [2- (isopropoxy-5- (N, N-dimethylaminosulfonyl) phenyl ] was added]Ruthenium methyl dichloride (asMetal catalyst) was added to the first reaction flask under nitrogen, and 10 ml of toluene (tolumen) was added to the first reaction flask to obtain a metal catalyst solution. After the metal catalyst was completely dissolved in toluene, 0.0245mol of 1-hexene (. alpha. -olefin), 29.4 g of Vinylnorbornene (VNB), and 45 ml of toluene were added to the second reaction flask. Next, the metal catalyst solution in the first reaction vessel was added to the second reaction vessel. After stirring well, a norbornene solution (23.06 g of Norbornene (NB) in 20 ml of toluene) was added to the second reaction flask. Here, the mole percent ratio of the α -olefin (1-hexene) was 5 mol%, based on the total number of moles of vinyl norbornene and norbornene. After the reaction was complete, 25 ml of ethyl vinyl ether (ethyl vinyl ether) was added to the second reaction flask. After stirring overnight, the resulting solution was freed of the catalyst and reprecipitated in methanol. After reconcentration, a copolymer (VI) is obtained in which the recurring units of copolymer (VI) are

And a repeating unit

In a ratio of about 1: 1.

Subsequently, the number average molecular weight (Mn), polydispersity index (PDI), and solubility in toluene of the copolymer (VI) were measured, and the temperature at which the weight loss of the copolymer (VI) was 5% was measured by thermogravimetric analysis (TGA), with the results shown in table 1.

Example 7

0.009 g of 1,3-bis (2,4,6-trimethylphenyl) -4,5-dihydroimidazol-2-yl [2- (isopropoxy-5- (N, N-dimethylaminosulfonyl) phenyl ] are added]Methyl ruthenium dichloride (as a metal catalyst) was added to the first reaction vessel under nitrogen, and 6 ml of toluene (toluene) was added to the first reaction vessel to obtain a metal catalyst solution. After the metal catalyst was completely dissolved in toluene, 0.0073mol of 1-hexene (. alpha. -olefin), 14.7 g of Vinylnorbornene (VNB), and 23 ml of toluene were added to the second reaction flask. Then, the gold in the first reaction bottle is put intoThe catalyst solution was added to the second reaction flask. After stirring well, a norbornene solution (11.5 g of Norbornene (NB) dissolved in 10 ml of toluene) was added to the second reaction flask. Here, the mole percent ratio of the α -olefin (1-hexene) was 3 mol%, based on the total number of moles of vinyl norbornene and norbornene. After the reaction was complete, 13 ml of ethyl vinyl ether (ethyl vinyl ether) was added to the second reaction flask. After stirring overnight, the resulting solution was freed of the catalyst and reprecipitated in methanol. After reconcentration, a copolymer (VII) is obtained in which the recurring units of the copolymer (VII) are

And a repeating unit

In a ratio of about 1: 1.

Next, the number average molecular weight (Mn), polydispersity index (PDI), and solubility in toluene of the copolymer (VII) were measured, and the temperature at which the copolymer (VII) lost 5% by weight was measured by thermogravimetric analysis (TGA), with the results shown in table 1.

Example 8

0.054 g of 1,3-bis (2,4,6-trimethylphenyl) -4,5-dihydroimidazol-2-yl [2- (isopropoxy-5- (N, N-dimethylaminosulfonyl) phenyl ] are reacted]Methyl ruthenium dichloride (as a metal catalyst) was added to the first reaction vessel under nitrogen, and 30 ml of toluene (toluene) was added to the first reaction vessel to obtain a metal catalyst solution. After the metal catalyst was completely dissolved in toluene, 0.725mol of 1-hexene (. alpha. -olefin), 177 g of Vinyl Norbornene (VNB), and 300 ml of toluene were added to the second reaction flask. Next, the metal catalyst solution in the first reaction vessel was added to the second reaction vessel. The molar percentage of the α -olefin (1-hexene) was 50 mol% based on the number of moles of vinyl norbornene. After the reaction was complete, 75 ml of ethyl vinyl ether (ethyl vinyl ether) was added to the second reaction flask. After stirring overnight, the resulting solution was freed of the catalyst and reprecipitated in methanol. After reconcentration, a copolymer is obtainedA copolymer (VIII) in which the recurring units of the copolymer (VIII) are all

Subsequently, the number average molecular weight (Mn), polydispersity index (PDI), and solubility in toluene of the copolymer (VIII) were measured, and the temperature at which the copolymer (VIII) lost 5% by weight was measured by thermogravimetric analysis (TGA), with the results shown in table 1.

Example 9

0.0018 g of 1,3-bis (2,4,6-trimethylphenyl) -4,5-dihydroimidazol-2-yl [2- (isopropoxy-5- (N, N-dimethylaminosulfonyl) phenyl ] is added]Methyl ruthenium dichloride (as a metal catalyst) was added to the first reaction vessel under nitrogen, and 1 ml of toluene (toluene) was added to the first reaction vessel to obtain a metal catalyst solution. After the metal catalyst was completely dissolved in toluene, 0.0005mol of 1-hexene (. alpha. -olefin), 3 g of Vinylnorbornene (VNB) and 4.5 ml of toluene were added to the second flask to add the metal catalyst solution in the first flask to the second flask. After stirring well, a norbornene solution (2.36 g of Norbornene (NB) in 2 ml of toluene) was added to the second reaction flask. Here, the mole percent ratio of the α -olefin (1-hexene) was 1 mol%, based on the total number of moles of vinyl norbornene and norbornene. After the reaction was complete, 2.5 ml of ethyl vinyl ether (ethyl vinyl ether) was added to the second reaction flask. After stirring overnight, the resulting solution was freed of the catalyst and reprecipitated in methanol. After reconcentration, a copolymer (IX) is obtained in which the recurring units of the copolymer (IX)

And a repeating unit

In a ratio of about 1: 1.

Next, the number average molecular weight (Mn), polydispersity index (PDI), and solubility in toluene of the copolymer (IX) were measured, and the temperature at which the weight loss of the copolymer (IX) was 5% was measured by thermogravimetric analysis (TGA), 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-yl [2- (isopropoxy-5- (N, N-dimethylaminosulfonyl) phenyl ] was added]Methyl ruthenium dichloride (as a metal catalyst) was added to the first reaction vessel under nitrogen, and 10 ml of toluene (toluene) was added to the first reaction vessel to obtain a metal catalyst solution. After the metal catalyst was completely dissolved in toluene, 0.245mol of methyl acrylate (α -olefin), 29.4 g of Vinyl Norbornene (VNB), and 45 ml of toluene were added to the second reaction flask. Next, the metal catalyst solution in the first reaction vessel was added to the second reaction vessel. After stirring well, a norbornene solution (23.06 g of Norbornene (NB) in 20 ml of toluene) was added to the second reaction flask. Here, the molar percentage of methyl acrylate is 50 mol%, based on the total molar number of vinyl norbornene and norbornene. After the reaction was complete, 25 ml of ethyl vinyl ether (ethyl vinyl ether) was added to the second reaction flask. After stirring overnight, the resulting solution was freed of the catalyst and reprecipitated in methanol. After reconcentration, a copolymer (X) is obtained in which the recurring units of the copolymer (X)

And a repeating unit

In a ratio of about 1: 1.

Next, the number average molecular weight (Mn), polydispersity index (PDI), and solubility in toluene of the copolymer (X) were measured, and the temperature at which the weight loss of the copolymer (X) was 5% was measured by thermogravimetric analysis (TGA), 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-yl [2- (isopropoxy-5- (N, N-dimethylaminosulfonyl) phenyl ] was added]Methyl ruthenium dichloride (as a metal catalyst) was added to the first reaction flask under nitrogenAnd 10 ml of toluene (tolumen) was added to the first reaction flask to obtain a metal catalyst solution. After the metal catalyst was completely dissolved in toluene, 29.4 g of Vinylnorbornene (VNB) and 35 ml of toluene were placed in a second reaction flask. Next, the metal catalyst solution in the first reaction vessel was added to the second reaction vessel. After stirring well, a norbornene solution (23.06 g of Norbornene (NB) in 20 ml of toluene) was added to the second reaction flask. After the reaction was complete, 25 ml of ethyl vinyl ether (ethyl vinyl ether) was added to the second reaction flask. After stirring overnight, the resulting solution was freed of the catalyst and reprecipitated in methanol. After reconcentration, a copolymer (XI) is obtained in which the recurring units of copolymer (XI)

And a repeating unit

In a ratio of about 1: 1.

Subsequently, the number average molecular weight (Mn), polydispersity index (PDI), and solubility in toluene of the copolymer (XI) were measured, and the temperature at which the polymer (XI) lost 5% of weight was measured by thermogravimetric analysis (TGA), and the results are shown in Table 1.

TABLE 1

In response to the requirement of the subsequent thin film process of the present disclosure, the solubility of the oligomer disclosed in the present disclosure in toluene needs to be greater than or equal to 20, and as can be seen from table 1, when the molecular weight of the copolymer (i.e. the oligomer described in the present disclosure) obtained by the copolymerization of vinyl norbornene, norbornene and 1-hexene (α -olefin) is less than or equal to 12,000, the solubility is suitable for the subsequent thin film process.

Example 10

0.018 g of 1,3-bis (2,4,6-trimethylphenyl) -4,5-dihydroimidazol-2-yl [2- (isopropoxy-5- (N, N-dimethylaminosulfonyl) phenyl ] methylruthenium dichloride (as a metal catalyst) was added under nitrogen to a first reaction flask, and 10 ml of toluene (toluene) was added to the first reaction flask to obtain a metal catalyst solution, after the metal catalyst was completely dissolved in toluene, 0.247mol of 1-octadecene (1-octadecene) (α -olefin), 29.4 g of Vinylnorbornene (VNB), and 45 ml of toluene were added to a second reaction flask, and then, the metal catalyst solution in the first reaction flask was added to the second reaction flask, after stirring well, a norbornene solution (23.06 g of Norbornene (NB) was dissolved in 20 ml of toluene) was added to the second reaction flask, the mole percent of the α -olefin (1-octadecene) was 50 mol%, based on the total moles of vinyl norbornene and norbornene. After the reaction was complete, 25 ml of ethyl vinyl ether (ethyl vinyl ether) was added to the second reaction flask. After stirring overnight, the resulting solution was freed of the catalyst and reprecipitated in methanol. After further concentration, copolymer (XII) was obtained.

Next, the number average molecular weight (Mn), polydispersity index (PDI), and solubility in toluene of the copolymer (XII) were measured, and the temperature at which the weight loss of the copolymer (XII) was 5% was measured by thermogravimetric analysis (TGA), and the results are shown in table 2.

Example 11

The procedure is as described in example 10, except that 1-octadecene (1-octadecene) is reduced from 0.247mol to 0.049mol to give copolymer (XIII). The number average molecular weight (Mn), polydispersity index (PDI), and solubility in toluene of the copolymer (XIII) were measured, and the temperature at which the copolymer (XIII) lost 5% of weight was measured by thermogravimetric analysis (TGA), and the results are shown in Table 2.

Example 12

The procedure was carried out in the same manner as described in example 10 except that 1-octadecene (1-octadecene) was replaced with styrene (styrene) to obtain copolymer (XIV). The number average molecular weight (Mn), polydispersity index (PDI), and solubility in toluene of the copolymer (XIV) were measured, and the temperature at which the weight loss of the copolymer (XIV) was 5% was measured by thermogravimetric analysis (TGA), with the results shown in table 2.

Example 13

0.006 g of 1,3-bis (2,4,6-trimethylphenyl) -4,5-dihydroimidazol-2-yl [2- (isopropoxy-5- (N, N-dimethylaminosulfonyl) phenyl ] methylruthenium dichloride (as a metal catalyst) was added under nitrogen to a first reaction flask, and 4 ml of toluene (toluene) was added to the first reaction flask to obtain a metal catalyst solution, after the metal catalyst was completely dissolved in toluene, 0.008mol of 1-vinylcyclohexene (α -olefin), 9.8 g of Vinylnorbornene (VNB), and 15 ml of toluene were added to a second reaction flask, and then, the metal catalyst solution in the first reaction flask was added to the second reaction flask, and after stirring well, a norbornene solution (7.69 g of Norbornene (NB) was dissolved in 7 ml of toluene) was added to the second reaction flask, the mole percent of the α -olefin (1-vinylcyclohexene) was 5 mole percent based on the total moles of vinylnorbornene and norbornene. After the reaction was complete, 8 ml of ethyl vinyl ether (ethyl vinyl ether) was added to the second reaction flask. After stirring overnight, the resulting solution was freed of the catalyst and reprecipitated in methanol. After further concentration, copolymer (XV) was obtained.

Subsequently, the number average molecular weight (Mn), polydispersity index (PDI), and solubility in toluene of the copolymer (XV) were measured, and the temperature at which the weight loss of the copolymer (XV) was 5% was measured by thermogravimetric analysis (TGA), 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-yl [2- (isopropoxy-5- (N, N-dimethylaminosulfonyl) phenyl ] methylruthenium dichloride (as a metal catalyst) was added to a first reaction flask under nitrogen and 0.5 ml of toluene (tolene) was added to the first reaction flask to obtain a metal catalyst solution, after the metal catalyst was completely dissolved in toluene, 0.043mol of methyl acrylate (α -olefin), 3 g of Vinylnorbornene (VNB), and 4.5 ml of toluene were added to a second reaction flask, and then, the metal catalyst solution in the first reaction flask was added to the second reaction flask, and after stirring, a norbornene solution (2.36 g of Norbornene (NB) was dissolved in 5 ml of toluene) was added to the second reaction flask, the mole percent ratio of methyl acrylate was 85 mole percent based on the total moles of vinyl norbornene and norbornene. After the reaction was complete, 2.5 ml of ethyl vinyl ether (ethyl vinyl ether) was added to the second reaction flask. After stirring overnight, the resulting solution was freed of the catalyst and reprecipitated in methanol. After further concentration, copolymer (XVI) is obtained.

Subsequently, the number average molecular weight (Mn), polydispersity index (PDI), and solubility in toluene of the copolymer (XVI) were measured, and the temperature at which the weight loss of the copolymer (XVI) was 5% was measured by thermogravimetric analysis (TGA), and the results are shown in Table 2.

Example 15

The procedure was carried out as described in example 10, except that 1-octadecene (1-octadecene) was replaced with allyl acetate (allyl acetate), to give copolymer (XVII). The number average molecular weight (Mn), polydispersity index (PDI), and solubility in toluene of the copolymer (XVII) were measured, and the temperature at which the weight loss of the copolymer (XVII) was 5% was measured by thermogravimetric analysis (TGA), with the results shown in Table 2.

Example 16

The procedure was carried out as described in example 10, except that 1-octadecene (1-octadiene) was replaced with 1,5-hexadiene (1,5-hexadiene) to give a copolymer (XVIII). The number average molecular weight (Mn), polydispersity index (PDI), and solubility in toluene of the copolymer (XVIII) were measured, and the temperature at which the copolymer (XVIII) lost 5% by weight was measured by thermogravimetric analysis (TGA), with the results shown in Table 2.

TABLE 2

As can be seen from Table 2, when the copolymerization of vinylnorbornene and norbornene is performed, the solubility of 1-hexene (α -olefin) to 1-octadecene, styrene, 1-vinylcyclohexene, methyl acrylate, 1,5-hexadiene and allyl acetate in toluene is also satisfactory for the subsequent coating or impregnation process, and the obtained copolymer (i.e., oligomer of the present disclosure) having a molecular weight of 12,000 or less is obtained.

Storage test

The copolymers obtained in examples 1-6 and 9-16 and comparative examples 1-2 were allowed to stand for 1 day and 2 days, respectively, and then the solubility and viscosity of the copolymers in toluene were measured, and the results are shown in Table 3.

TABLE 3

As can be seen from Table 3, the copolymers obtained by copolymerizing vinyl norbornene, norbornene and α -olefin (i.e., the oligomers described in this disclosure) in the examples of the present disclosure having a number average molecular weight of 12,000 or less still have good solubility after two days of standing. From this, it can be seen that the oligomers described in the present disclosure have good storability.

Measurement of Properties of resin composition and cured product thereof

Example 17

The copolymer (I) (40 parts by weight) obtained in example 1, polyphenylene ether (PPE) (manufactured and sold by SABIC, product number SA9000, molecular weight 2,300) (60 parts by weight), and initiator (1 part by weight) were dissolved in toluene (60 parts by weight). After uniform mixing, a resin composition was obtained. Then, the resin composition was coated on a metal copper foil (manufactured and sold from gulhe copper foil). Then, the mixture was heated to 100 ℃ under nitrogen. After a certain period of time, gradually raising the temperature to below 250 ℃ to carry out crosslinking reaction (so as to achieve the optimal crosslinking density), thereby obtaining the film (I). Then, the dielectric constant (Dk) and dissipation factor (Df) of the film (I) were measured at a frequency of 10GHz, and the results are shown in table 4.

Example 18

The procedure was carried out as described in example 17, except that the copolymer (I) obtained in example 1 was replaced with the copolymer (III) obtained in example 3 to obtain a film (II). Then, the dielectric constant (Dk) and dissipation factor (Df) of the film (II) were measured at a frequency of 10GHz, and the results are shown in table 4.

Example 19

The procedure was carried out as described in example 17, except that the copolymer (I) obtained in example 1 was replaced with the copolymer (IV) obtained in example 4 to obtain a film (III). Then, the dielectric constant (Dk) and dissipation factor (Df) of the film (III) were measured at a frequency of 10GHz, and the results are shown in table 4.

Example 20

A film (IV) was obtained by following the procedure of example 17 except that the copolymer (I) obtained in example 1 was replaced with the copolymer (V) obtained in example 5. Then, the dielectric constant (Dk) and dissipation factor (Df) of the film (IV) were measured at a frequency of 10GHz, and the results are shown in table 4.

Example 21

A film (V) was obtained in the same manner as in example 17 except that the copolymer (I) obtained in example 1 was replaced with the copolymer (VI) obtained in example 6. Then, the dielectric constant (Dk) and dissipation factor (Df) of the film (V) were measured at a frequency of 10GHz, and the results are shown in table 4.

Example 22

The procedure was carried out in the same manner as described in example 17, except that the copolymer (I) obtained in example 1 was replaced with the copolymer (VIII) obtained in example 8 to obtain a film (VI). Then, dielectric constants (Dk) and dissipation factors (Df) of the film (VI) were measured at a frequency of 10GHz, and the results are shown in table 4.

Example 23

A film (VII) was obtained in the same manner as in example 17 except that the copolymer (I) obtained in example 1 was replaced with the copolymer (IX) obtained in example 9. Then, the dielectric constant (Dk) and dissipation factor (Df) of the film (VII) were measured at a frequency of 10GHz, and the results are shown in table 4.

Example 24

A film (VIII) was obtained in the same manner as in example 17 except that the copolymer (I) obtained in example 1 was replaced with the copolymer (XII) obtained in example 10. Then, the dielectric constant (Dk) and dissipation factor (Df) of the film (VIII) were measured at a frequency of 10GHz, and the results are shown in table 4.

Example 25

A film (IX) was obtained by following the procedure described in example 17, except that the copolymer (I) obtained in example 1 was replaced with the copolymer (XIII) obtained in example 11. Then, the dielectric constant (Dk) and dissipation factor (Df) of the film (IX) were measured at a frequency of 10GHz, and the results are shown in table 4.

Example 26

A film (X) was obtained in the same manner as in example 17 except that the copolymer (I) obtained in example 1 was replaced with the copolymer (XIV) obtained in example 12. Then, the dielectric constant (Dk) and dissipation factor (Df) of the film (X) were measured at a frequency of 10GHz, and the results are shown in table 4.

Example 27

A film (XI) was obtained by following the procedure described in example 17, except that the copolymer (I) obtained in example 1 was replaced with the copolymer (XV) obtained in example 13. Then, the dielectric constant (Dk) and dissipation factor (Df) of the film (XI) were measured at a frequency of 10GHz, and the results are shown in table 4.

Example 28

A film (XII) was obtained in the same manner as in example 17, except that the copolymer (I) obtained in example 1 was replaced with the copolymer (XVI) obtained in example 14. Then, the dielectric constant (Dk) and dissipation factor (Df) of the film (XII) were measured at a frequency of 10GHz, and the results are shown in table 4.

Example 29

A film (XIII) was obtained in the same manner as in example 17, except that the copolymer (I) obtained in example 1 was replaced with the copolymer (XVII) obtained in example 15. Next, the dielectric constant (Dk) and dissipation factor (Df) of the film (XIII) were measured at a frequency of 10GHz, and the results are shown in Table 4.

Example 30

The procedure was carried out in the manner described in example 17, except that the copolymer (I) obtained in example 1 was replaced with the copolymer (XVIII) obtained in example 16 to obtain a film (XIV). Then, dielectric constants (Dk) and dissipation factors (Df) of the thin film (XIV) were measured at a frequency of 10GHz, and the results are shown in table 4.

Comparative example 3

Triallyl isocyanurate (1,3, 5-tri-2-propynyl-1, 3,5-triazine-2,4,6(1H,3H,5H) -trione, TAIC) (40 parts by weight), polyphenylene ether (PPE) (product number SA9000, molecular weight 2,300) (60 parts by weight, manufactured and sold by SABIC), and an initiator (1 part by weight) were dissolved in toluene (50 parts by weight). After uniform mixing, a resin composition was obtained. Then, the resin composition was coated on a metal copper foil (manufactured and sold from gulhe copper foil). Then, the mixture was heated to 100 ℃ under nitrogen. After maintaining for a period of time, gradually raising the temperature to nearly 250 ℃ to carry out a crosslinking reaction, thereby obtaining a film (XV). Then, dielectric constants (Dk) and dissipation factors (Df) of the thin film (XV) were measured at a frequency of 10GHz, and the results are shown in table 4.

TABLE 4

Example 31

The copolymer (I) (31 parts by weight) obtained in example 1, polyphenylene ether (PPE) (manufactured and sold by SABIC, product number SA9000, molecular weight 2,300) (46 parts by weight), polystyrene-butadiene (SBS) (manufactured by Cray Valley, product number Ricon100, molecular weight 4,500) (23 parts by weight), and an initiator (1 part by weight) were dissolved in toluene (60 parts by weight). After uniform mixing, a resin composition was obtained. Then, the resin composition was coated on a metal copper foil (manufactured and sold from gulhe copper foil). Then, the mixture was heated to 100 ℃ under nitrogen. After a certain period of time, the temperature is gradually increased to approximately 250 ℃ to carry out the crosslinking reaction, and the film (XVI) is obtained. Next, the dielectric constant (Dk) and dissipation factor (Df) of the film (XVI) were measured at a frequency of 10GHz, and the results are shown in Table 5.

Example 32

A film (XVII) was obtained in the same manner as in example 31, except that the copolymer (I) obtained in example 1 was replaced with the copolymer (III) obtained in example 3. Next, the dielectric constant (Dk) and dissipation factor (Df) of the film (XVII) were measured at a frequency of 10GHz, and the results are shown in Table 5.

Example 33

A film (XVIII) was obtained in the same manner as in example 31, except that the copolymer (I) obtained in example 1 was replaced with the copolymer (IV) obtained in example 4. Next, the dielectric constant (Dk) and dissipation factor (Df) of the film (XVIII) were measured at a frequency of 10GHz, and the results are shown in Table 5.

Example 34

The procedure was carried out as described in example 31, except that the copolymer (I) obtained in example 1 was replaced with the copolymer (V) obtained in example 5 to obtain a film (XIX). Then, dielectric constants (Dk) and dissipation factors (Df) of the thin film (XIX) were measured at a frequency of 10GHz, and the results are shown in table 5.

Example 35

The procedure was carried out in the same manner as described in example 31 except that the copolymer (I) obtained in example 1 was replaced with the copolymer (VI) obtained in example 6 to obtain a film (XX). Then, the dielectric constant (Dk) and dissipation factor (Df) of the film (XX) were measured at a frequency of 10GHz, and the results are shown in table 5.

Example 36

A film (XXI) was obtained by following the procedure described in example 31, except that the copolymer (I) obtained in example 1 was replaced with the copolymer (VIII) obtained in example 8. Then, dielectric constants (Dk) and dissipation factors (Df) of the film (XXI) were measured at a frequency of 10GHz, and the results are shown in table 5.

Example 37

A film (XXII) was obtained by following the procedure described in example 31, except that the copolymer (I) obtained in example 1 was replaced with the copolymer (IX) obtained in example 9. Next, the dielectric constant (Dk) and dissipation factor (Df) of the film (XXII) were measured at a frequency of 10GHz, and the results are shown in Table 5.

Example 38

A film (XXIII) was obtained by the same procedures as in example 31, except that the copolymer (I) obtained in example 1 was replaced with the copolymer (XII) obtained in example 10. Next, the dielectric constant (Dk) and dissipation factor (Df) of the film (XXIII) were measured at a frequency of 10GHz, and the results are shown in Table 5.

Example 39

A film (XXIV) was obtained by following the procedure described in example 31, except that the copolymer (I) obtained in example 1 was replaced with the copolymer (XIII) obtained in example 11. Next, the dielectric constant (Dk) and dissipation factor (Df) of the film (XXIV) were measured at a frequency of 10GHz, and the results are shown in Table 5.

Example 40

A film (XXV) was obtained by following the procedure described in example 31, except that the copolymer (I) obtained in example 1 was replaced with the copolymer (XIV) obtained in example 12. Then, dielectric constants (Dk) and dissipation factors (Df) of the film (XXV) were measured at a frequency of 10GHz, and the results are shown in table 5.

EXAMPLE 41

A film (XXVI) was obtained by following the procedure described in example 31, except that the copolymer (I) obtained in example 1 was replaced with the copolymer (XV) obtained in example 13. Next, dielectric constants (Dk) and dissipation factors (Df) of the film (XXVI) were measured at a frequency of 10GHz, and the results are shown in Table 5.

Example 42

A film (XXVII) was obtained in the same manner as in example 31 except that the copolymer (I) obtained in example 1 was replaced with the copolymer (XVI) obtained in example 14. Next, the dielectric constant (Dk) and dissipation factor (Df) of the film (XXVII) were measured at a frequency of 10GHz, and the results are shown in Table 5.

Example 43

The procedure was carried out in the manner as described in example 31, except that the copolymer (I) obtained in example 1 was replaced with the copolymer (XVII) obtained in example 15 to obtain a film (XXVIII). Next, the dielectric constant (Dk) and dissipation factor (Df) of the film (XXVIII) were measured at a frequency of 10GHz, and the results are shown in Table 5.

Example 44

A film (XXIX) was obtained by following the procedure described in example 31, except that the copolymer (I) obtained in example 1 was replaced with the copolymer (XVIII) obtained in example 16. Then, dielectric constants (Dk) and dissipation factors (Df) of the film (XXIX) were measured at a frequency of 10GHz, and the results are shown in table 5.

Comparative example 4

Triallyl isocyanurate (1,3,5-tri-2-propenyl-1,3,5-triazine-2,4,6(1H,3H,5H) -trione, TAIC) (31 parts by weight), polyphenylene ether (PPE) (manufactured and sold by SABIC, product number SA9000, molecular weight 2,300) (46 parts by weight), polystyrene-butadiene-styrene (SBS) (manufactured by Cray Valley, product number Ricon100, molecular weight 4,500) (23 parts by weight), and an initiator (1 part by weight) were dissolved in toluene (50 parts by weight). After uniform mixing, a resin composition was obtained. Then, the resin composition was coated on a metal copper foil (manufactured and sold from gulhe copper foil). Then, the mixture was heated to 100 ℃ under nitrogen. After a certain period of time, the temperature is gradually increased to approximately 250 ℃ to carry out the crosslinking reaction, and a film (XXX) is obtained. Next, the dielectric constant (Dk) and dissipation factor (Df) of the film (XXX) were measured at a frequency of 10GHz, and the results are shown in Table 5.

TABLE 5

Example 45

The copolymer (III) (10 parts by weight) obtained in example 3, polyphenylene ether (PPE) (manufactured and sold by SABIC, product number SA9000, molecular weight 2,300) (90 parts by weight), and initiator (1 part by weight) were dissolved in toluene (60 parts by weight). After uniform mixing, a resin composition was obtained. Then, the resin composition was coated on a metal copper foil (manufactured and sold from gulhe copper foil). Then, the mixture was heated to 100 ℃ under nitrogen. After a certain period of time, the temperature is gradually increased to approximately 250 ℃ to carry out the crosslinking reaction, and a film (XXXI) is obtained. Next, the dielectric constant (Dk) and dissipation factor (Df) of the film (XXXI) were measured at a frequency of 10GHz, and the results are shown in Table 6.

Example 46

A film (XXXII) was obtained by the same procedures as in example 45, except that the copolymer (III) used in example 45 was increased from 10 parts by weight to 20 parts by weight and the polyphenylene ether was decreased from 90 parts by weight to 80 parts by weight. Next, the dielectric constant (Dk) and dissipation factor (Df) of the film (XXXII) were measured at a frequency of 10GHz, and the results are shown in Table 6.

Example 47

A film (XXXIII) was obtained by the same procedures as in example 45, except that the copolymer (III) used in example 45 was increased from 10 parts by weight to 80 parts by weight and the polyphenylene ether was decreased from 90 parts by weight to 20 parts by weight. Next, the dielectric constant (Dk) and dissipation factor (Df) of the film (XXXIII) were measured at a frequency of 10GHz, and the results are shown in Table 6.

Example 48

The copolymer (I) (70 parts by weight) obtained in example 1, polystyrene-butadiene-styrene (SBS) (manufactured by Cray Valley, trade name Ricon100, molecular weight 4,500) (30 parts by weight), and an initiator (1 part by weight) were dissolved in toluene. After uniform mixing, a resin composition was obtained. Then, the resin composition was coated on a metal copper foil (manufactured and sold from gulhe copper foil). Subsequently, the mixture was heated to 90 ℃ under nitrogen. After a certain period of time, the temperature is gradually increased to approximately 250 ℃ to carry out the crosslinking reaction, and a film (XXXIV) is obtained. Next, the dielectric constant (Dk) and dissipation factor (Df) of the film (XXXIV) were measured at a frequency of 10GHz, and the results are shown in Table 6.

Example 49

A film (XXXV) was obtained by the same method as in example 48, except that the copolymer (I) obtained in example 1 was replaced with the copolymer (VIII) obtained in example 8. Next, the dielectric constant (Dk) and dissipation factor (Df) of the film (XXXV) were measured at a frequency of 10GHz, and the results are shown in Table 6.

Example 50

The procedure was carried out in the same manner as in example 45 except that polyphenylene ether (PPE) used in example 45 was replaced with polystyrene-butadiene-styrene (SBS) (product number Ricon100, molecular weight 4,500, manufactured by Cray Valley) to obtain a film (XXXVI). Next, the dielectric constant (Dk) and dissipation factor (Df) of the film (XXXVI) were measured at a frequency of 10GHz, and the results are shown in Table 6.

Example 51

A film (XXXVII) was obtained by the same procedures as in example 50, except that the amount of the copolymer (III) used in example 50 was increased from 10 parts by weight to 20 parts by weight, and the amount of the polystyrene butadiene was decreased from 90 parts by weight to 80 parts by weight. Next, the dielectric constant (Dk) and dissipation factor (Df) of the film (XXXVII) were measured at a frequency of 10GHz, and the results are shown in Table 6.

Example 52

A film (XXXVIII) was obtained by the same procedures as in example 50, except that the amount of the copolymer (III) used in example 50 was increased from 10 parts by weight to 50 parts by weight, and the amount of polystyrene butadiene was decreased from 90 parts by weight to 50 parts by weight. Next, the dielectric constant (Dk) and dissipation factor (Df) of the film (XXXVIII) were measured at a frequency of 10GHz, and the results are shown in Table 6.

Example 53

A film (XXXIX) was obtained by following the procedure described in example 50, except that the copolymer (III) used in example 50 was increased from 10 parts by weight to 80 parts by weight and the polystyrene butadiene was decreased from 90 parts by weight to 20 parts by weight. Next, the dielectric constant (Dk) and dissipation factor (Df) of the film (XXXIX) were measured at a frequency of 10GHz, and the results are shown in Table 6.

Example 54

The procedure was carried out as described in example 45, except that the polyphenylene ether (PPE) used in example 45 was replaced with Polybutadiene (PB) (manufactured and sold by Nippon Soda, article No. B2000, molecular weight 2,100) to obtain a film (XL). Then, dielectric constants (Dk) and dissipation factors (Df) of the film (XL) were measured at a frequency of 10GHz, and the results are shown in table 6.

Example 55

The procedure as described in example 54 was followed, except that the copolymer (III) used in example 54 was increased from 10 parts by weight to 20 parts by weight, and the polybutadiene was decreased from 90 parts by weight to 80 parts by weight, to obtain a film (XLI). Then, dielectric constants (Dk) and dissipation factors (Df) of the thin film (XLI) were measured at a frequency of 10GHz, and the results are shown in table 6.

Example 56

The procedure was carried out in the same manner as described in example 45 except that polyphenylene ether (PPE) used in example 45 was replaced with polystyrene resin (polystyrene, PS) (molecular weight 192,000 manufactured and sold by Sigma-Aldrich) to obtain a film (XLII). Then, the dielectric constant (Dk) and dissipation factor (Df) of the thin film (XLII) were measured at a frequency of 10GHz, and the results are shown in table 6.

Example 57

The copolymer (III) obtained in example 3 (70 parts by weight), an epoxy resin (epoxy resin) (product number ERL-4221 manufactured and sold by suggera, 30 parts by weight) and an initiator (1 part by weight) were dissolved in toluene (50 parts by weight). After uniform mixing, a resin composition was obtained. Then, the resin composition was coated on a metal copper foil (manufactured and sold from gulhe copper foil). Subsequently, the mixture was heated to 90 ℃ under nitrogen. After a period of time, gradually raising the temperature to nearly 250 ℃ for crosslinking reaction to obtain the thin film (XLIII). Then, the dielectric constant (Dk) and dissipation factor (Df) of the thin film (XLIII) were measured at a frequency of 10GHz, and the results are shown in table 6.

Example 58

The copolymer (III) (31 parts by weight) obtained in example 3, polyphenylene ether (PPE) (manufactured and sold by SABIC, article No. SA9000, molecular weight 2,300) (46 parts by weight), polybutadiene (polybutadiene, PB) (manufactured and sold by Nippon Soda, article No. B2000, molecular weight 2,100) (23 parts by weight), and an initiator (1 part by weight) were dissolved in toluene (60 parts by weight). After uniform mixing, a resin composition was obtained. Then, the resin composition was coated on a metal copper foil (manufactured and sold from gulhe copper foil). Then, the mixture was heated to 100 ℃ under nitrogen. After a certain period of time, the temperature is gradually increased to nearly 250 ℃ for crosslinking reaction to obtain a film (XLIV). Then, the dielectric constant (Dk) and dissipation factor (Df) of the thin film (XLIV) were measured at a frequency of 10GHz, and the results are shown in table 6.

Example 59

The copolymer (V) obtained in example 5 (38 parts by weight), polyphenylene ether (PPE) (manufactured and sold by SABIC, product number SA9000, molecular weight 2,300) (57 parts by weight), bismaleimide (bismalemide) resin (manufactured and sold by large-volume chemical synthesis, product number BMI-5,100) (5 parts by weight), and initiator (1 part by weight) were dissolved in toluene (60 parts by weight). After uniform mixing, a resin composition was obtained. Then, the resin composition was coated on a metal copper foil (manufactured and sold from gulhe copper foil). Then, the mixture was heated to 100 ℃ under nitrogen. After a certain period of time, the temperature is gradually increased to nearly 250 ℃ for crosslinking reaction to obtain a thin film (XLV). Then, dielectric constants (Dk) and dissipation factors (Df) of the thin film (XLV) were measured at a frequency of 10GHz, and the results are shown in table 6.

Example 60

The copolymer (III) (38 parts by weight) obtained in example 3, polyphenylene ether (PPE) (manufactured and sold by SABIC, product number SA9000, molecular weight 2,300) (57 parts by weight), polystyrene resin (polystyrene, PS) (manufactured and sold by Sigma-Aldrich, molecular weight 192,000) (5 parts by weight), and initiator (1 part by weight) were dissolved in toluene (60 parts by weight). After uniform mixing, a resin composition was obtained. Then, the resin composition was coated on a metal copper foil (manufactured and sold from gulhe copper foil). Then, the mixture was heated to 100 ℃ under nitrogen. After a certain period of time, the temperature is gradually increased to nearly 250 ℃ for crosslinking reaction to obtain a film (XLVI). Then, dielectric constants (Dk) and dissipation factors (Df) of the thin film (XLVI) were measured at a frequency of 10GHz, and the results are shown in table 6.

Example 61

The procedure was followed as described in example 60, except that the polystyrene resin (polystyrene, PS) used in example 60 was replaced with cyanate ester resin (CE) (sold by yongyou under trade name BADCy) to obtain a film (XLVII). Then, dielectric constants (Dk) and dissipation factors (Df) of the thin film (XLVII) were measured at a frequency of 10GHz, and the results are shown in table 6.

Example 62

The procedure was carried out as described in example 60, except that the polystyrene resin (polystyrene, PS) used in example 60 was replaced with a polyimide resin (polyimide, PI), to obtain a film (XLVIII). Then, the dielectric constant (Dk) and dissipation factor (Df) of the thin film (XLVIII) were measured at a frequency of 10GHz, and the results are shown in table 6.

Comparative example 5

A film (XLIX) was obtained in the same manner as in example 45 except that the copolymer (III) used in example 45 was decreased from 10 parts by weight to 1 part by weight and the polyphenylene ether was increased from 90 parts by weight to 99 parts by weight. Then, dielectric constants (Dk) and dissipation factors (Df) of the thin film (XLIX) were measured at a frequency of 10GHz, and the results are shown in table 6.

Comparative example 6

A film (L) was obtained in the same manner as in example 45 except that the copolymer (III) used in example 45 was increased from 10 parts by weight to 90 parts by weight and the polyphenylene ether was decreased from 90 parts by weight to 10 parts by weight. Then, the dielectric constant (Dk) and dissipation factor (Df) of the film (L) were measured at a frequency of 10GHz, and the results are shown in table 6.

Comparative example 7

A film (LI) was obtained in the same manner as in example 57 except that the amount of the copolymer (III) used in example 57 was decreased from 70 parts by weight to 50 parts by weight and the amount of the epoxy resin was increased from 30 parts by weight to 50 parts by weight. Then, dielectric constants (Dk) and dissipation factors (Df) of the thin film (LI) were measured at a frequency of 10GHz, and the results are shown in table 6.

Comparative example 8

Phenol curing agent (product number SD1708 manufactured and sold by Momentive) instead of (45 parts by weight), epoxy resin (product number ERL-4221 manufactured and sold by large size) (55 parts by weight), and initiator (1 part by weight) were dissolved in toluene (50 parts by weight). After uniform mixing, a resin composition was obtained. Then, the resin composition was coated on a metal copper foil (manufactured and sold from gulhe copper foil). Then, the mixture was heated to 100 ℃ under nitrogen. After maintaining for a period of time, gradually heating to near 250 ℃ for crosslinking reaction to obtain a film (LII). Then, the dielectric constant (Dk) and dissipation factor (Df) of the film (LII) were measured at a frequency of 10GHz, and the results are shown in table 6.

Comparative example 9

The copolymer (III) (1 part by weight) obtained in example 3, a polyimide resin (polyimide, PI) (99 parts by weight), and an initiator (1 part by weight) were dissolved in toluene. After uniform mixing, a resin composition was obtained. Then, the resin composition was coated on a metal copper foil (manufactured and sold from gulhe copper foil). Then, the mixture was heated to 100 ℃ under nitrogen. After maintaining for a period of time, gradually raising the temperature to nearly 250 ℃ for crosslinking reaction to obtain the film (LIII). Then, the dielectric constant (Dk) and dissipation factor (Df) of the film (LIII) were measured at a frequency of 10GHz, and the results are shown in table 6.

TABLE 6

Example 63

The copolymer (III) (17 parts by weight) obtained in example 3, polyphenylene ether (PPE) (product number OPE-2st, molecular weight 2,200) (70 parts by weight) manufactured and sold by Mitsubishi Gas Chemical, polystyrene-butadiene (SBS) (product number Ricon100, molecular weight 4,500) (13 parts by weight) and an initiator (1 part by weight) were dissolved in toluene. After uniform mixing, a resin composition was obtained. Next, a Glass Fiber cloth (L2116 available from Asahi Fiber Glass) was impregnated into the above composition to an impregnation amount of about 59%. Taking out, baking in a hot air circulation oven at 140 ℃ for several minutes, and controlling the crosslinking reaction ratio to be about 50% to obtain the film. Stacking four films, placing copper foils, a lens steel plate and kraft paper on the upper and lower sides of the films, and placing the films into a vacuum press molding machine to gradually raise the temperature to 210 ℃ for hot pressing for 3 hours to obtain the copper foil substrate (I) with the thickness of 0.558 mm. Next, the dielectric constant (Dk) and dissipation factor (Df) of the copper foil substrate (I) were measured at a frequency of 10GHz, and the results are shown in table 7.

TABLE 7

As can be seen from tables 4 to 7, since the resin composition of the present disclosure includes the oligomer having the structure of formula (I), the cured product thereof has a low dielectric constant (Dk) (less than or equal to 3.0 (at 10 GHz)) and dissipation factor (Df) (less than or equal to 0.0045 (at 10 GHz)), and is suitable for high frequency substrate materials. As can be seen from the above examples, the resin composition of the present disclosure can achieve good crosslinking density by crosslinking reaction at a temperature lower than 250 ℃, and even the best crosslinking density can be known from the exothermic amount of crosslinking measured by a differential scanning thermal analyzer (differential scanning calorimetry).

Although the present disclosure has been described with reference to several embodiments, it should be understood that various changes and modifications can be made by one skilled in the art without departing from the spirit and scope of the disclosure, and therefore the scope of the disclosure should be determined by that of the appended claims.

Claims

1. An oligomer having a structure represented by formula (I):

wherein R is¹And R²Independently of one another is hydrogen, C_1-20Alkyl radical, C_2-20Alkenyl radical, C_6-12An aromatic group,C_6-12Alkylaryl group, C_5-12Cycloalkyl radical, C_6-20Cycloalkylalkylalkoxycarbonyl, or alkylcarbonyloxy, and R¹And R²Not hydrogen at the same time; a is 0 or 1; n is not less than 0; m is not less than 1; n is m is 0:100 to 99: 1; the oligomer has a number average molecular weight of 800 to 6,000; and, a repeating unit

And a repeating unit

Is repeated in a random manner or in a block manner,

wherein the oligomer is prepared by reacting at

And optionally norbornene, wherein the mole percent of the alpha-olefin is from 3 mole% to 85 mole%, based on the total weight of the catalyst

And optionally norbornene, wherein a is 0 or 1, and

wherein the alpha-olefin is selected from

Wherein b is an integer selected from 0 to 19, c, d, e, f, i, and j are each independently an integer selected from 0 to 6, h is an integer selected from 1 to 6, and R is³And R⁴Each independently is C_1-6An alkyl group.

2. The oligomer of claim 1, wherein R is¹And R²Independently is hydrogen, or

Wherein b is 0, or an integer from 1 to 19, and R¹And R²Not hydrogen at the same time.

3. The oligomer of claim 1, wherein R is¹And R²Independently is hydrogen, or

Wherein c is 0, or an integer from 1 to 6, and R¹And R²Not hydrogen at the same time.

4. The oligomer of claim 1, wherein R is¹And R²Independently is hydrogen, or

Wherein d is 0, or an integer from 1 to 6, and R¹And R²Not hydrogen at the same time.

5. The oligomer of claim 1, wherein R is¹And R²Independently is hydrogen, or

Wherein e is 0, or an integer from 1 to 6, and R¹And R²Not hydrogen at the same time.

6. The oligomer of claim 1, wherein R is¹And R²Independently is hydrogen, or

Wherein f is 0, or an integer of 1 to 6, R³Is C_1-6Alkyl, and R¹And R²Not hydrogen at the same time.

7. Such as rightThe oligomer of claim 1, wherein R¹And R²Independently is hydrogen, or

Wherein h is an integer from 1 to 6, and R¹And R²Not hydrogen at the same time.

8. The oligomer of claim 1, wherein R is¹And R²Independently is hydrogen, or

Wherein i is 0, 1, 2,3, 4,5, or 6, and R¹And R²Not hydrogen at the same time.

9. The oligomer of claim 1, wherein R is¹And R²Independently is hydrogen, or

Wherein j is 0, 1, 2,3, 4,5, or 6, and R¹And R²Not hydrogen at the same time.

10. The oligomer of claim 1, wherein n: m is 1:9 to 9: 1.

11. A resin composition comprising:

10 to 90 parts by weight of an oligomer according to claim 1; and

10-90 parts by weight of resin.

12. The composition of claim 11, wherein the resin is a polyolefin resin (polyolefin resin), an epoxy resin, a cyanate ester resin, a polystyrene resin, a styrene butadiene copolymer resin, a polyimide resin, a maleimide resin, a polyphenylene ether resin, or a combination thereof.

13. The composition of claim 12, wherein the polyolefin resin is a polybutadiene resin, a polycycloolefin resin, a cyclic olefin polymer resin, or a cyclic olefin copolymer resin.

14. A composite material comprising:

a cured product or a semi-cured product formed from the resin composition according to claim 11; and

a substrate, wherein the cured or semi-cured is on or in the substrate.

15. The composite material of claim 14, wherein the substrate is fiberglass, or copper foil.

16. The composite material of claim 14, wherein the composite material is a copper foil substrate, a printed circuit board, or an integrated circuit carrier.