Oligomers and compositions

Abstract

The present invention discloses an oligomer and a composition, wherein the oligomer comprises: a repeating unit (a) and a repeating unit (b1), (b2) or a combination thereof. The ratio of the number of repetitions of the repeating unit (a) to the number of repetitions of the repeating units (b1), (b2) or a combination thereof is 1:1 to 20:1. Q is independently a substituted or unsubstituted aliphatic, cycloaliphatic, aromatic, or siloxane. X can be Y can be, or a combination thereof, and Z can be, or a combination thereof.

Description

Technical Field

[0001] The present invention relates to an oligomer, and more particularly to the types and ratios of repeating units of the oligomer. Background Art

[0002] Today, the communication electronics industry is developing rapidly and is moving towards high speed, high frequency and high density. Therefore, polymers or oligomers with high heat resistance, low dielectric properties, low moisture absorption and high toughness are the main direction of development of electronic packaging and high-frequency substrate materials. Polyimide is a material commonly used in electronic packaging and high-frequency substrates. However, the currently known thermosetting compositions containing polyimide or imide oligomers often have poor heat resistance. Therefore, there is an urgent need to design and develop imide oligomers with both excellent dielectric properties and heat resistance. Summary of the invention

[0003] An oligomer provided by one embodiment of the present invention comprises: a repeating unit (a) and repeating unit (b1) (b2) or a combination thereof, wherein the ratio of the number of repetitions of the repeating unit (a) to the number of repetitions of the repeating unit (b1), (b2), or a combination thereof is 1:1 to 20:1; Q is independently a substituted or unsubstituted aliphatic, cycloaliphatic, aromatic, or siloxane; X is

[0004]

[0005]

[0006] Where 12≥a≥4; 12≥b≥4; R 1 Each is independently hydrogen, C 4-12 Alkyl, C 4-12 Alkenyl, or C 4-12 Alkynyl, and at least 2 R 1 is not hydrogen; Y is or a combination thereof, wherein c is 0 or 1; d is 0 or 1; R 2 ' are each independently hydrogen or C 1-10 alkyl, and at least one R 2 ' is not hydrogen; and R 2 are independently hydrogen or C 1-10 An alkyl group; and Z is or a combination thereof, wherein 12≥e≥1; 12≥f≥1; 12≥g≥1; and R 3 are independently hydrogen or C 1-10of alkyl.

[0007] An embodiment of the present invention provides a composition comprising: an oligomer; and a free radical initiator, wherein the end of the oligomer is modified into a group containing a double bond, and comprises: a repeating unit (a) and repeating unit (b1) (b2) or a combination thereof, wherein the ratio of the number of repetitions of the repeating unit (a) to the number of repetitions of the repeating unit (b1), (b2), or a combination thereof is 1:1 to 20:1; Q is independently a substituted or unsubstituted aliphatic, cycloaliphatic, aromatic, or siloxane; X is

[0008]

[0009]

[0010] Where 12≥a≥4; 12≥b≥4; R 1 Each is independently hydrogen, C 4-12 Alkyl, C 4-12 Alkenyl, or C 4-12 Alkynyl, and at least 2 R 1 Not hydrogen; Y is or a combination thereof, wherein c is 0 or 1; d is 0 or 1; R 2 ' are each independently hydrogen or C 1-10 alkyl, and at least one R 2 ' is not hydrogen; and R 2 are independently hydrogen or C 1-10 An alkyl group; and Z is or a combination thereof, wherein 12≥e≥1; 12≥f≥1; 12≥g≥1; and R 3 are independently hydrogen or C 1-10 of alkyl. DETAILED DESCRIPTION

[0011] An oligomer provided by one embodiment of the present invention comprises: a repeating unit (a) and repeating unit (b1) (b2) Or a combination thereof. In some embodiments, the ratio of the number of repetitions of the repeating unit (a) to the number of repetitions of the repeating unit (b1), (b2), or the combination thereof is 1:1 to 20:1. If the amount of the repeating unit (a) is too low, the oligomer may have poor electrical properties (for example, the high-frequency dielectric loss of the composition is too large). If the amount of the repeating unit (b1), (b2), or the combination thereof is too low, the oligomer may have insufficient thermal stability (for example, the glass transition temperature of the composition is too low). In some embodiments, the ratio of the number of repetitions of the repeating unit (a) to the number of repetitions of the repeating unit (b1) is 1:1 to 5:1.

[0012] In some embodiments, repeating units (b1) and (b2) are used simultaneously, and the ratio of the number of repeating units (b1) to (b2) is 1:1 to 5:1. If the ratio of repeating unit (b1) is too high, the electrical properties of the oligomer are poor (for example, the high-frequency dielectric loss of the composition is too large). If the ratio of repeating unit (b2) is too high, the solvent solubility of the oligomer is poor.

[0013] In some embodiments, the number of repetitions of repeating units (a), (b1), and (b2) is 1-20 respectively.

[0014] In some embodiments, Q is independently a substituted or unsubstituted aliphatic, cycloaliphatic, aromatic, or siloxane. For example, Can Where R 4 C 1-5 alkylene, -SO2-, -O-, -C(=O)-, or a single bond. It should be understood that From For example, Can It can come from

[0015] In some embodiments, X is

[0016]

[0017] Where 12≥a≥4; 12≥b≥4; R 1 Each is independently hydrogen, C 4-12 Alkyl, C 4-12 Alkenyl, or C 4-12 Alkynyl, and at least 2 R 1is not hydrogen. In some embodiments, X is derived from a commercially available dimer diamine. For example, X may be It can be derived from diamines such as

[0018] In some embodiments, Y is or a combination thereof, wherein c is 0 or 1; d is 0 or 1; R 2 ' are each independently hydrogen or C 1-10 alkyl, and at least one R 2 ' is not hydrogen; and R 2 are independently hydrogen or C 1-10 For example, Y is derived from a diamine. For example, Y can be They can each come from

[0019] In one embodiment, Z is or a combination thereof, wherein 12≥e≥1; 12≥f≥1; 12≥g≥1; and R 3 are independently hydrogen or C 1-10 For example, Z is from a triamine. For example, Z can be It can come from

[0020] In some embodiments, repeating unit (a) is And the repeating unit (b1) is

[0021] In some embodiments, repeating unit (a) is And the repeating unit (b1) is

[0022] In some embodiments, repeating unit (a) is And the repeating unit (b1) is

[0023] In some embodiments, repeating unit (a) is And the repeating unit (b1) is

[0024] In some embodiments, repeating unit (a) is And the repeating unit (b2) is

[0025] In some embodiments, repeating unit (a) is The repeating unit (b1) is And the repeating unit (b2) is

[0026] In some embodiments, the oligomer has an amine terminal or is modified to a double bond-containing group. For example, bismaleic anhydride can be firstly taken The oligomer is formed by reacting with a diamine (H2N-X-NH2) and another diamine (H2N-Y-NH2) and / or a triamine (Z-(NH2)3). The terminal of the oligomer has an amine group (-NH2). In some embodiments, the amine group of the oligomer can react with a resin having an epoxy group, an isocyanate group, or other suitable functional groups. In another embodiment, the terminal amine group of the oligomer can react with maleic anhydride to form That is, it is modified into a group containing a double bond.

[0027] In some embodiments, the composition may include the above-mentioned oligomers with modified ends to groups containing double bonds and free radical initiators. After applying energy to the composition, the oligomers in the composition can undergo free radical polymerization. In another embodiment, the composition may include other resins containing double bonds, and the oligomers with modified ends to contain double bonds can be copolymerized with other resins containing double bonds. For example, other resins containing double bonds may be polyphenylene ether resins with methacryloyloxy groups at the ends, polyphenylene ether resins with vinyl benzyl ether at the ends, other suitable resins, or combinations thereof. In some embodiments, the copolymers of the oligomers with modified ends to groups containing double bonds and the modified polyphenylene ether resins have excellent electrical and thermal properties, such as low high-frequency dielectric loss and high glass transition temperature. The above copolymers can be used for high-frequency soft or hard board materials, high-temperature additives, packaging materials, adhesives, or similar applications. It is worth noting that the above oligomers can also be used alone or in combination with other resins, and are not limited to the above-mentioned modified polyphenylene ether resins.

[0028] In order to make the above contents and other purposes, features, and advantages of the present invention more clearly understood, preferred embodiments are specifically cited below and described in detail as follows:

[0029] [Example]

[0030] The composition was prepared and tested for its properties in the following embodiments: Dielectric constant (D k ) is measured according to the IPC-TM-650 2.5.5 test specification. The dielectric constant represents the electronic insulation properties of the manufactured component. The lower the value, the better the electronic insulation properties. The dielectric loss (D f) is measured according to the IPC-TM-650 2.5.5 test specification. Dielectric loss refers to the ability of a material to absorb microwaves of a certain frequency at a certain temperature. Usually in the specifications of communication products, the lower the dielectric loss value, the better. The glass transition temperature is measured using differential scanning calorimetry (DSC) according to the DSC method specified in IPC-TM-6502.4.25.

[0031] Synthesis example 1

[0032] After loading 250 ml of toluene into the reactor, add triethylamine (35 g, 0.35 mol) and then slowly drip methylsulfonic acid (35 g, 0.35 mol) to form an amine salt, and continue stirring for 10 minutes. Then add aliphatic dimeramine (35.2 g, 0.068 mol) and 4,4'-diaminodicyclohexylmethane (3.57 g, 0.017 mol). Next, slowly add pyromellitic dianhydride (10.9 g, 0.05 mol) into the reactor. After connecting the Dean-stark distillation device and the condensation device to the reactor, heat the reactants to make them boil and reflux until the reaction is completed. After the reaction product is cooled to room temperature, maleic anhydride (Maleic anhydride; 12.8g, 0.13mol) and 5g of methanesulfonic acid are added, and the reactants are reheated to boiling reflux until the reaction is completed. After the reaction product is cooled to room temperature, 100g of toluene is added and allowed to stand for stratification. The reaction product is decanted and the salts are rinsed with toluene (2x100 g), and the extracts are combined and allowed to stand overnight to allow the salt and toluene layers to be completely separated. The toluene layer is filtered with silica gel, and the solvent is removed under vacuum to obtain 45g of a dark waxy product. As identified by gel permeation chromatography (GPC), the number average molecular weight of oligomer 1 is approximately 2597, and the PDI value is 1.90. The hydrogen nuclear magnetic resonance (H NMR) of oligomer 1 1 H-NMR) spectrum (400 MHz, solvent is deuterium-chloroform (CDCl3) as follows: δ8.233 (br, 2H), δ6.654 (s, 2H), δ6.602-6.598 (s, 2H), δ3.721-3.684 (br, 6H), δ3.496-3.460 (m, 3H), δ1.668-0.835 (br, 86H). The repeating unit (a) of oligomer 1 is The repeating unit (b1) is The ratio of the number of repetitions of the repeating unit (a) to the number of repetitions of the repeating unit (b1) is 4:1. In addition, the end of oligomer 1 is That is, it is modified into a group containing a double bond.

[0033] Synthesis example 2

[0034] After loading 250 ml of toluene into the reactor, add triethylamine (35 g, 0.35 mol) and then slowly drip methylsulfonic acid (35 g, 0.35 mol) to form an amine salt, and continue stirring for 10 minutes. Then add aliphatic dimeramine (22.3 g, 0.043 mol) and 4,4'-diaminodicyclohexylmethane (9.03 g, 0.043 mol). Next, slowly add pyromellitic dianhydride (10.9 g, 0.05 mol) into the reactor. After connecting the Dean-stark distillation device and the condensation device to the reactor, heat the reactants to make them boil and reflux until the reaction is completed. After the reaction product is cooled to room temperature, maleic anhydride (Maleic anhydride; 12.8g, 0.13mol) and 5g of methanesulfonic acid are added, and the reactants are reheated to boiling reflux until the reaction is completed. After the reaction product is cooled to room temperature, 100g of toluene is added and allowed to stand for stratification. The reaction product is decanted and the salts are rinsed with toluene (2x100 g), and the extracts are combined and allowed to stand overnight to allow the salt and toluene layers to be completely separated. The toluene layer is filtered with silica gel, and the solvent is removed under vacuum to obtain 34g of a dark waxy product. As identified by gel permeation chromatography (GPC), the number average molecular weight of oligomer 2 is approximately 1800, and the PDI value is 1.95. The hydrogen nuclear magnetic resonance (H NMR) of oligomer 2 1 H-NMR) spectrum (400 MHz, solvent is deuterium-chloroform (CDCl3) as follows: δ8.235 (br, 2H), δ6.654 (s, 2H), δ6.608-6.592 (s, 2H), δ3.730-3.680 (br, 6H), δ3.500-3.456 (m, 3H), δ1.674-0.828 (br, 86H). The repeating unit (a) of oligomer 2 is The repeating unit (b1) is The ratio of the number of repetitions of the repeating unit (a) to the number of repetitions of the repeating unit (b1) is 1:1. In addition, the end of oligomer 2 is That is, it is modified into a group containing a double bond.

[0035] Synthesis example 3

[0036] After loading 250 ml of toluene into the reactor, add triethylamine (35 g, 0.35 mol) and then slowly drip methylsulfonic acid (35 g, 0.35 mol) to form an amine salt, and continue stirring for 10 minutes. Then add aliphatic dimeramine (37.3 g, 0.072 mol) and 4,4-diaminodicyclohexylmethane (2.52 g, 0.012 mol). Next, slowly add pyromellitic dianhydride (10.9 g, 0.05 mol) into the reactor. After connecting the Dean-stark distillation device and the condensation device to the reactor, heat the reactants to make them boil and reflux until the reaction is completed. After the reaction product is cooled to room temperature, maleic anhydride (Maleic anhydride; 12.8g, 0.13mol) and 5g methanesulfonic acid are added, and the reactants are reheated to boiling reflux until the reaction is completed. After the reaction product is cooled to room temperature, 100g toluene is added and allowed to stand for stratification. The reaction product is decanted and the salts are rinsed with toluene (2x100 g), and the extracts are combined and allowed to stand overnight to completely separate the salt and toluene layers. The toluene layer is filtered with silica gel, and the solvent is removed under vacuum to obtain 42g of a dark waxy product. As identified by gel permeation chromatography (GPC), the number average molecular weight of oligomer 3 is approximately 3000, and the PDI value is 1.96. The hydrogen nuclear magnetic resonance (H NMR) of oligomer 3 1 H-NMR) spectrum (400 MHz, solvent is deuterium-chloroform (CDCl3) as follows: δ8.233 (br, 2H), δ6.656 (s, 2H), δ6.602-6.598 (s, 2H), δ3.724-3.680 (br, 6H), δ3.496-3.460 (m, 3H), δ1.668-0.835 (br, 86H). The repeating unit (a) of oligomer 3 is The repeating unit (b1) is The ratio of the number of repetitions of the repeating unit (a) to the number of repetitions of the repeating unit (b1) is 6:1. In addition, the end of oligomer 3 is That is, it is modified into a group containing a double bond.

[0037] Synthesis example 4

[0038] After loading 250 ml of toluene into the reactor, add triethylamine (35 g, 0.35 mol) and then slowly drip methylsulfonic acid (35 g, 0.35 mol) to form an amine salt and continue stirring for 10 minutes. Then add aliphatic dimeramine (35.2 g, 0.068 mol) and bis(aminomethyl)norborane (2.62 g, 0.017 mol). Next, slowly add pyromellitic dianhydride (10.9 g, 0.05 mol) into the reactor. After connecting the Dean-stark distillation apparatus and the condensation apparatus to the reactor, heat the reactants to make them boil and reflux until the reaction is completed. After the reaction product is cooled to room temperature, maleic anhydride (Maleic anhydride; 12.8g, 0.13mol) and 5g of methanesulfonic acid are added, and the reactants are reheated to boiling reflux until the reaction is completed. After the reactants are cooled to room temperature, 100g of toluene is added and allowed to stand for stratification. The reactants are decanted and the salts are rinsed with toluene (2x100 g), and the extracts are combined and allowed to stand overnight to allow the salt and toluene layers to be completely separated. The toluene layer is filtered with silica gel, and the solvent is removed under vacuum to obtain 45g of a dark waxy product. As identified by gel permeation chromatography (GPC), the number average molecular weight of oligomer 4 is approximately 2301, and the PDI value is 1.75. The hydrogen nuclear magnetic resonance (H NMR) of oligomer 4 1 H-NMR) spectrum (400 MHz, solvent: deuterium-chloroform (CDCl3)) is as follows: δ8.251-8.210 (br, 2H), δ6.68-6.63 (br, 4H), δ3.72-3.646 (br, 8H), δ3.534-3.459 (m, 4H), δ1.667-0.799 (br, 78H). The repeating unit (a) of oligomer 4 is The repeating unit (b1) is The ratio of the number of repetitions of the repeating unit (a) to the number of repetitions of the repeating unit (b1) is 4:1. In addition, the end of oligomer 4 is That is, it is modified into a group containing a double bond.

[0039] Synthesis example 5

[0040] After loading 250 ml of toluene into the reactor, add triethylamine (35 g, 0.35 mol) and then slowly drip methylsulfonic acid (35 g, 0.35 mol) to form an amine salt and continue stirring for 10 minutes. Then add aliphatic dimeramine (22.3 g, 0.043 mol) and bis(aminomethyl)norborane (6.63 g, 0.043 mol). Next, slowly add pyromellitic dianhydride (10.9 g, 0.05 mol) into the reactor. After connecting the Dean-stark distillation apparatus and the condensation apparatus to the reactor, heat the reactants to make them boil and reflux until the reaction is completed. After the reaction product is cooled to room temperature, maleic anhydride (Maleic anhydride; 12.8g, 0.13mol) and 5g of methanesulfonic acid are added, and the reactants are reheated to boiling reflux until the reaction is completed. After the reactants are cooled to room temperature, 100g of toluene is added and the layers are allowed to stand. The reactants are decanted and the salts are rinsed with toluene (2x100 g), and the extracts are combined and allowed to stand overnight to allow the salt and toluene layers to be completely separated. The toluene layer is filtered with silica gel, and the solvent is removed under vacuum to obtain 33g of a dark waxy product. As identified by gel permeation chromatography (GPC), the number average molecular weight of oligomer 5 is approximately 1850, and the PDI value is 1.71. The hydrogen nuclear magnetic resonance (H NMR) of oligomer 5 1 H-NMR) spectrum (400 MHz, solvent: deuterium-chloroform (CDCl3)) is as follows: δ8.250-8.212 (br, 2H), δ6.70-6.62 (br, 4H), δ3.72-3.646 (br, 8H), δ3.536-3.458 (m, 4H), δ1.667-0.799 (br, 78H). The repeating unit (a) of oligomer 5 is The repeating unit (b1) is The ratio of the number of repetitions of the repeating unit (a) to the number of repetitions of the repeating unit (b1) is 1:1. In addition, the end of oligomer 5 is That is, it is modified into a group containing a double bond.

[0041] Synthesis example 6

[0042] After loading 250 ml of toluene into the reactor, add triethylamine (35 g, 0.35 mol) and then slowly drip methylsulfonic acid (35 g, 0.35 mol) to form an amine salt and continue stirring for 10 minutes. Then add aliphatic dimeramine (36.3 g, 0.070 mol) and bis(aminomethyl)norborane (2.18 g, 0.014 mol). Next, slowly add pyromellitic dianhydride (10.9 g, 0.05 mol) into the reactor. After connecting the Dean-stark distillation apparatus and the condensation apparatus to the reactor, heat the reactants to make them boil and reflux until the reaction is completed. After the reaction product is cooled to room temperature, maleic anhydride (Maleic anhydride; 12.8g, 0.13mol) and 5g of methanesulfonic acid are added, and the reactants are reheated to boiling reflux until the reaction is completed. After the reactants are cooled to room temperature, 100g of toluene is added and allowed to stand for stratification. The reactants are decanted and the salts are rinsed with toluene (2x100 g), and the extracts are combined and allowed to stand overnight to allow the salt and toluene layers to be completely separated. The toluene layer is filtered with silica gel, and the solvent is removed under vacuum to obtain 40g of a dark waxy product. As identified by gel permeation chromatography (GPC), the number average molecular weight of oligomer 6 is approximately 2600, and the PDI value is 1.80. The hydrogen nuclear magnetic resonance (H NMR) of oligomer 6 1 H-NMR) spectrum (400 MHz, solvent: deuterium-chloroform (CDCl3)) is as follows: δ8.254-8.210 (br, 2H), δ6.66-6.61 (br, 4H), δ3.72-3.646 (br, 8H), δ3.536-3.460 (m, 4H), δ1.667-0.800 (br, 78H). The repeating unit (a) of oligomer 6 is The repeating unit (b1) is The ratio of the number of repetitions of the repeating unit (a) to the number of repetitions of the repeating unit (b1) is 5:1. In addition, the end of oligomer 6 is That is, it is modified into a group containing a double bond.

[0043] Synthesis Example 7

[0044] After loading 250 ml of toluene into the reactor, add triethylamine (35 g, 0.35 mol) and then slowly drip methylsulfonic acid (35 g, 0.35 mol) to form an amine salt and continue stirring for 10 minutes. Then add aliphatic dimeramine (35.2 g, 0.068 mol) and isophoronediamine (2.895 g, 0.017 mol). Then, slowly add pyromellitic dianhydride (10.9 g, 0.05 mol) into the reactor. After connecting the Dean-stark distillation apparatus and the condensation apparatus to the reactor, heat the reactants to boil and reflux until the reaction is completed. After the reactants are cooled to room temperature, add maleic anhydride (12.8 g, 0.13 mol) and 5 g methylsulfonic acid, and reheat the reactants to boil and reflux until the reaction is completed. After the reactants were cooled to room temperature, 100 g of toluene was added and the mixture was allowed to stand for separation. The reactants were decanted and the salts were rinsed with toluene (2 x 100 g). The extracts were combined and allowed to stand overnight to allow the salt and toluene layers to be completely separated. The toluene layer was filtered with silica gel and the solvent was removed under vacuum to obtain 45 g of a dark waxy product. The number average molecular weight of oligomer 7 was about 2631 and the PDI value was 1.67 as determined by gel permeation chromatography (GPC). 1 H-NMR) spectrum (400 MHz, solvent: deuterium-chloroform (CDCl3)) is as follows: δ8.244-8.201 (br, 2H), δ6.654-6.633 (s, 2H), δ6.600 (s, 2H), δ3.720-3.683 (br, 7H), δ3.495-3.458 (m, 3H), δ1.683-0.955 (br, 81H). The repeating unit (a) of oligomer 7 is The repeating unit (b1) is The ratio of the number of repetitions of the repeating unit (a) to the number of repetitions of the repeating unit (b1) is 4:1. In addition, the end of oligomer 7 is That is, it is modified into a group containing a double bond.

[0045] Synthesis example 8

[0046] After loading 250 ml of toluene into the reactor, add triethylamine (35 g, 0.35 mol) and then slowly drip methylsulfonic acid (35 g, 0.35 mol) to form an amine salt and continue stirring for 10 minutes. Then add aliphatic dimeramine (22.3 g, 0.043 mol) and isophoronediamine (7.32 g, 0.043 mol). Next, slowly add pyromellitic dianhydride (10.9 g, 0.05 mol) into the reactor. After connecting the Dean-stark distillation apparatus and the condensation apparatus to the reactor, heat the reactants to boil and reflux until the reaction is completed. After the reactants are cooled to room temperature, add maleic anhydride (12.8 g, 0.13 mol) and 5 g methylsulfonic acid, and reheat the reactants to boil and reflux until the reaction is completed. After the reactants were cooled to room temperature, 100 g of toluene was added and the mixture was allowed to stand for separation. The reactants were decanted and the salts were rinsed with toluene (2 x 100 g). The extracts were combined and allowed to stand overnight to allow the salt and toluene layers to separate completely. The toluene layer was filtered with silica gel and the solvent was removed under vacuum to obtain 32 g of a dark waxy product. The number average molecular weight of oligomer 8 was about 2200 and the PDI value was 1.67 as determined by gel permeation chromatography (GPC). The hydrogen nuclear magnetic resonance (H NMR) of oligomer 8 1 H-NMR) spectrum (400 MHz, solvent: deuterium-chloroform (CDCl3)) is as follows: δ8.246-8.200 (br, 2H), δ6.654-6.630 (s, 2H), δ6.600 (s, 2H), δ3.726-3.688 (br, 7H), δ3.495-3.458 (m, 3H), δ1.680-0.950 (br, 81H). The repeating unit (a) of oligomer 8 is The repeating unit (b1) is The ratio of the number of repetitions of the repeating unit (a) to the number of repetitions of the repeating unit (b1) is 1:1. In addition, the end of oligomer 8 is That is, it is modified into a group containing a double bond.

[0047] Synthesis example 9

[0048] After loading 250 ml of toluene into the reactor, add triethylamine (35 g, 0.35 mol) and then slowly drip methanesulfonic acid (35 g, 0.35 mol) to form an amine salt and continue stirring for 10 minutes. Then add aliphatic dimeramine (44.04 g, 0.085 mol). Next, slowly add pyromellitic dianhydride (10.9 g, 0.05 mol) into the reactor. After connecting the Dean-stark distillation apparatus and the condensation apparatus to the reactor, heat the reactants to boil and reflux until the reaction is completed. After the reactants are cooled to room temperature, add maleic anhydride (12.8 g, 0.13 mol) and 5 g of methanesulfonic acid, and reheat the reactants to boiling and reflux until the reaction is completed. After the reactants are cooled to room temperature, add 100 g of toluene and let stand for stratification. The reactants were decanted and the salts were rinsed with toluene (2 x 100 g). The extracts were combined and allowed to stand overnight to allow the salt and toluene layers to separate completely. The toluene layer was filtered with silica gel and the solvent was removed under vacuum to obtain 45 g of a dark waxy product. The number average molecular weight of oligomer 9 was about 2800 and the PDI value was 1.85 as determined by Gel Permeation Chromatography (GPC). 1 H-NMR) spectrum (400 MHz, solvent: deuterium-chloroform (CDCl3)) is as follows: δ8.235 (br, 2H), δ6.655 (s, 2H), δ3.723-3.686 (br, 4H), δ3.499-3.462 (m, 4H), δ1.67-0.800 (br, 66H). The repeating unit of oligomer 9 is In addition, the end of oligo 9 is That is, it is modified into a group containing a double bond.

[0049] Synthesis example 10

[0050] After loading 250 ml of toluene into the reactor, add triethylamine (35 g, 0.35 mol) and then slowly drip methylsulfonic acid (35 g, 0.35 mol) to form an amine salt and continue stirring for 10 minutes. Then add aliphatic dimeramine (36.3 g, 0.070 mol) and isophoronediamine (2.41 g, 0.014 mol). Next, slowly add pyromellitic dianhydride (10.9 g, 0.05 mol) into the reactor. After connecting the Dean-stark distillation apparatus and the condensation apparatus to the reactor, heat the reactants to boil and reflux until the reaction is completed. After the reactants are cooled to room temperature, add maleic anhydride (12.8 g, 0.13 mol) and 5 g methylsulfonic acid, and reheat the reactants to boil and reflux until the reaction is completed. After the reactants were cooled to room temperature, 100 g of toluene was added and the mixture was allowed to stand for separation. The reactants were decanted and the salts were rinsed with toluene (2 x 100 g). The extracts were combined and allowed to stand overnight to allow the salts and toluene layers to separate completely. The toluene layer was filtered with silica gel and the solvent was removed under vacuum to obtain 40 g of a dark waxy product. The number average molecular weight of oligomer 10 was about 2800 and the PDI value was 1.73 as determined by gel permeation chromatography (GPC). 1 H-NMR) spectrum (400 MHz, solvent: deuterium-chloroform (CDCl3)) is as follows: δ8.242-8.200 (br, 2H), δ6.658-6.631 (s, 2H), δ6.602 (s, 2H), δ3.728-3.681 (br, 7H), δ3.490-3.458 (m, 3H), δ1.680-0.952 (br, 81H). The repeating unit (a) of oligomer 10 is The repeating unit (b1) is The ratio of the number of repetitions of the repeating unit (a) to the number of repetitions of the repeating unit (b1) is 5:1. In addition, the end of the oligomer 10 is That is, it is modified into a group containing a double bond.

[0051] Synthesis Example 11

[0052] After loading 250 ml of toluene into the reactor, add triethylamine (35 g, 0.35 mol) and then slowly drip methylsulfonic acid (35 g, 0.35 mol) to form an amine salt and continue stirring for 10 minutes. Then add aliphatic dimeramine (14.7 g, 0.028 mol) and isophoronediamine (9.65 g, 0.057 mol). Then, slowly add pyromellitic dianhydride (10.9 g, 0.05 mol) into the reactor. After connecting the Dean-stark distillation apparatus and the condensation apparatus to the reactor, heat the reactants to boil and reflux until the reaction is completed. After the reactants are cooled to room temperature, add maleic anhydride (12.8 g, 0.13 mol) and 5 g methylsulfonic acid, and reheat the reactants to boil and reflux until the reaction is completed. After the reactants were cooled to room temperature, 100 g of toluene was added and the mixture was allowed to stand for separation. The reactants were decanted and the salts were rinsed with toluene (2 x 100 g). The extracts were combined and allowed to stand overnight to allow the salt and toluene layers to separate completely. The toluene layer was filtered with silica gel and the solvent was removed under vacuum to obtain 29 g of a dark waxy product. The number average molecular weight of oligomer 11 was about 2000 and the PDI value was 1.74 as determined by Gel Permeation Chromatography (GPC). 1 H-NMR) spectrum (400 MHz, solvent: deuterium-chloroform (CDCl3)) is as follows: δ8.238-8.200 (br, 2H), δ6.648-6.638 (s, 2H), δ6.608 (s, 2H), δ3.714-3.678 (br, 7H), δ3.490-3.452 (m, 3H), δ1.683-0.955 (br, 81H). The repeating unit (a) of oligomer 11 is The repeating unit (b1) is The ratio of the number of repetitions of the repeating unit (a) to the number of repetitions of the repeating unit (b1) is 1:2. In addition, the end of the oligomer 11 is That is, it is modified into a group containing a double bond.

[0053] Synthesis example 12

[0054] After loading 250 ml of toluene into the reactor, add triethylamine (35 g, 0.35 mol) and then slowly drip methylsulfonic acid (35 g, 0.35 mol) to form an amine salt and continue stirring for 10 minutes. Then add aliphatic dimeramine (22.3 g, 0.043 mol) and isophoronediamine (7.32 g, 0.043 mol). Next, slowly add cyclohexanetetracarboxylic dianhydride (1,2,4,5-Cyclohexanetetrcarboxylic Dianhydride; 11.2 g, 0.05 mol) into the reactor. After connecting the Dean-stark distillation apparatus and the condensation apparatus to the reactor, heat the reactants to make them boil and reflux until the reaction is completed. After the reactants were cooled to room temperature, maleic anhydride (12.8 g, 0.13 mol) and 5 g of methanesulfonic acid were added, and the reactants were reheated to boiling reflux until the reaction was completed. After the reactants were cooled to room temperature, 100 g of toluene was added and allowed to stand for stratification. The reactants were decanted and the salts were rinsed with toluene (2 x 100 g), and the extracts were combined and allowed to stand overnight to allow the salt and toluene layers to be completely separated. The toluene layer was filtered with silica gel, and the solvent was removed under vacuum to obtain 33 g of a dark waxy product. As determined by gel permeation chromatography (GPC), the number average molecular weight of oligomer 12 was approximately 2150, and the PDI value was 1.80. The hydrogen nuclear magnetic resonance (H NMR) of oligomer 12 1 H-NMR) spectrum (400 MHz, solvent: deuterium-chloroform (CDCl3)) is as follows: δ6.650-6.634 (br, 2H), δ6.604 (s, 2H), δ3.700-3.660 (br, 7H), δ3.496-3.460 (m, 3H), δ2.560 (br, 4H), δ2.064-1.800 (br, 4H), δ1.688-0.960 (br, 81H). The repeating unit (a) of oligomer 12 is The repeating unit (b1) is The ratio of the number of repetitions of the repeating unit (a) to the number of repetitions of the repeating unit (b1) is 1:1. In addition, the end of the oligomer 12 is That is, it is modified into a group containing a double bond.

[0055] Synthesis example 13

[0056] After loading 250 ml of toluene into the reactor, add triethylamine (35 g, 0.35 mol) and then slowly drip methylsulfonic acid (35 g, 0.35 mol) to form an amine salt and continue stirring for 10 minutes. Then add aliphatic dimeramine (37.3 g, 0.072 mol) and isophoronediamine (2.05 g, 0.012 mol). Next, slowly add pyromellitic dianhydride (10.9 g, 0.05 mol) into the reactor. After connecting the Dean-stark distillation apparatus and the condensation apparatus to the reactor, heat the reactants to boil and reflux until the reaction is completed. After the reactants are cooled to room temperature, add maleic anhydride (12.8 g, 0.13 mol) and 5 g methylsulfonic acid, and reheat the reactants to boil and reflux until the reaction is completed. After the reactants were cooled to room temperature, 100 g of toluene was added and the mixture was allowed to stand for separation. The reactants were decanted and the salts were rinsed with toluene (2 x 100 g). The extracts were combined and allowed to stand overnight to allow the salts and toluene layers to separate completely. The toluene layer was filtered with silica gel and the solvent was removed under vacuum to obtain 40 g of a dark waxy product. The number average molecular weight of oligomer 13 was about 2800 and the PDI value was 1.73 as determined by gel permeation chromatography (GPC). The hydrogen nuclear magnetic resonance (H NMR) of oligomer 13 was 1 H-NMR) spectrum (400 MHz, solvent: deuterium-chloroform (CDCl3)) is as follows: δ8.246-8.200 (br, 2H), δ6.658-6.631 (s, 2H), δ6.606 (s, 2H), δ3.726-3.684 (br, 7H), δ3.490-3.458 (m, 3H), δ1.680-0.954 (br, 81H). The repeating unit (a) of oligomer 13 is The repeating unit (b1) is The ratio of the number of repetitions of the repeating unit (a) to the number of repetitions of the repeating unit (b1) is 6:1. In addition, the end of the oligomer 13 is That is, it is modified into a group containing a double bond.

[0057] Synthesis Example 14

[0058] After loading 250 ml of toluene into the reactor, add triethylamine (35 g, 0.35 mol) and then slowly drip methylsulfonic acid (35 g, 0.35 mol) to form an amine salt and continue stirring for 10 minutes. Then add aliphatic dimeramine (14.7 g, 0.028 mol) and isophorone diamine (9.65 g, 0.057 mol). Next, slowly add cyclohexanetetracarboxylic dianhydride (1,2,4,5-Cyclohexanetetrcarboxylic Dianhydride; 11.2 g, 0.05 mol) into the reactor. After connecting the Dean-stark distillation apparatus and the condensation apparatus to the reactor, heat the reactants to make them boil and reflux until the reaction is completed. After the reactants were cooled to room temperature, maleic anhydride (12.8 g, 0.13 mol) and 5 g of methanesulfonic acid were added, and the reactants were reheated to boiling reflux until the reaction was completed. After the reactants were cooled to room temperature, 100 g of toluene was added and allowed to stand for stratification. The reactants were decanted and the salts were rinsed with toluene (2 x 100 g), and the extracts were combined and allowed to stand overnight to allow the salt and toluene layers to be completely separated. The toluene layer was filtered with silica gel, and the solvent was removed under vacuum to obtain 29 g of a dark waxy product. As determined by gel permeation chromatography (GPC), the number average molecular weight of oligomer 14 was approximately 1800, and the PDI value was 1.78. The hydrogen nuclear magnetic resonance (H NMR) of oligomer 14 1 H-NMR) spectrum (400 MHz, solvent: deuterium-chloroform (CDCl3)) is as follows: δ6.642-6.630 (s, 2H), δ6.600 (s, 2H), δ3.700-3.660 (br, 7H), δ3.498-3.458 (m, 3H), δ2.562 (br, 4H), δ2.062-1.800 (br, 4H), δ1.690-0.960 (br, 81H). The repeating unit (a) of oligomer 14 is The repeating unit (b1) is The ratio of the number of repetitions of the repeating unit (a) to the number of repetitions of the repeating unit (b1) is 1:2. In addition, the end of the oligomer 14 is That is, it is modified into a group containing a double bond.

[0059] Synthesis Example 15

[0060] After loading 250 ml of toluene into the reactor, add triethylamine (35 g, 0.35 mol) and then slowly drip methylsulfonic acid (35 g, 0.35 mol) to form an amine salt, and continue stirring for 10 minutes. Then add aliphatic dimeramine (35.2 g, 0.068 mol) and melamine (0.95 g, 0.0075 mol). Then, slowly add pyromellitic dianhydride (13.08 g, 0.060 mol) into the reactor. After connecting the Dean-stark distillation apparatus and the condensation apparatus to the reactor, heat the reactants to boil and reflux until the reaction is completed. After the reaction product is cooled to room temperature, add maleic anhydride (9.8 g, 0.1 mol) and 5 g methylsulfonic acid, and reheat the reactants to boil and reflux until the reaction is completed. After the reaction product was cooled to room temperature, 100 g of toluene was added and the mixture was allowed to stand for separation. The reaction product was decanted and the salts were rinsed with toluene (2 x 100 g). The extracts were combined and allowed to stand overnight to allow the salt and toluene layers to be completely separated. The toluene layer was filtered with silica gel and the solvent was removed under vacuum to obtain 40 g of a dark waxy product. The number average molecular weight of oligomer 15 was about 3000 and the PDI value was 1.80 as determined by gel permeation chromatography (GPC). The hydrogen nuclear magnetic resonance (H NMR) of oligomer 15 was 1 H-NMR) spectrum (400 MHz, solvent is deuterium-chloroform (CDCl3) as follows: δ8.234 (br, 2H), δ6.655 (s, 2H), δ3.722-3.685 (br, 4H), δ3.497-3.461 (m, 4H), δ1.669-0.800 (br, 66H). The repeating unit (a) of oligomer 15 is The repeating unit (b2) is

[0061] The ratio of the number of repetitions of the repeating unit (a) to the number of repetitions of the repeating unit (b2) is 9:1. In addition, the end of the oligomer 15 is That is, it is modified into a group containing a double bond.

[0062] Synthesis example 16

[0063] After loading 250 ml of toluene into the reactor, add triethylamine (35 g, 0.35 mol) and then slowly drip methylsulfonic acid (35 g, 0.35 mol) to form an amine salt, and continue stirring for 10 minutes. Then add aliphatic dimeramine (23.4 g, 0.045 mol) and melamine (1.9 g, 0.015 mol). Next, slowly add pyromellitic dianhydride (9.81 g, 0.045 mol) into the reactor. After connecting the Dean-stark distillation apparatus and the condensation apparatus to the reactor, heat the reactants to boil and reflux until the reaction is completed. After the reaction product is cooled to room temperature, add maleic anhydride (9.8 g, 0.1 mol) and 5 g methylsulfonic acid, and reheat the reactants to boil and reflux until the reaction is completed. After the reaction product was cooled to room temperature, 100 g of toluene was added and the mixture was allowed to stand for separation. The reaction product was decanted and the salts were rinsed with toluene (2 x 100 g). The extracts were combined and allowed to stand overnight to allow the salt and toluene layers to be completely separated. The toluene layer was filtered with silica gel and the solvent was removed under vacuum to obtain 30 g of a dark waxy product. The number average molecular weight of oligomer 16 was about 2000 and the PDI value was 1.90 as determined by gel permeation chromatography (GPC). The hydrogen nuclear magnetic resonance (H NMR) of oligomer 16 was 1 H-NMR) spectrum (400 MHz, solvent is deuterium-chloroform (CDCl3) as follows: δ8.234 (br, 2H), δ6.655 (s, 2H), δ3.722-3.685 (br, 4H), δ3.497-3.461 (m, 4H), δ1.669-0.800 (br, 66H). The repeating unit (a) of oligomer 16 is The repeating unit (b2) is The ratio of the number of repetitions of the repeating unit (a) to the number of repetitions of the repeating unit (b2) is 3:1. In addition, the end of the oligomer 16 is That is, it is modified into a group containing a double bond.

[0064] Synthesis Example 17

[0065] After loading 250 ml of toluene into the reactor, add triethylamine (35 g, 0.35 mol) and then slowly drip methylsulfonic acid (35 g, 0.35 mol) to form an amine salt and continue stirring for 10 minutes. Then add aliphatic dimeramine (35.2 g, 0.068 mol) and 1,2-diaminocyclohexane (1.90 g, 0.017 mol). Next, slowly add pyromellitic dianhydride (10.9 g, 0.05 mol) into the reactor. After connecting the Dean-stark distillation device and the condensation device to the reactor, heat the reactants to make them boil and reflux until the reaction is completed. After the reactants were cooled to room temperature, maleic anhydride (12.8 g, 0.13 mol) and 5 g of methanesulfonic acid were added, and the reactants were reheated to boiling reflux until the reaction was completed. After the reactants were cooled to room temperature, 100 g of toluene was added and allowed to stand for stratification. The reactants were decanted and the salts were rinsed with toluene (2 x 100 g), and the extracts were combined and allowed to stand overnight to allow the salt and toluene layers to be completely separated. The toluene layer was filtered with silica gel, and the solvent was removed under vacuum to obtain 41 g of a dark waxy product. As determined by gel permeation chromatography (GPC), the number average molecular weight of oligomer 17 was approximately 1800, and the PDI value was 1.81. The hydrogen nuclear magnetic resonance (H NMR) of oligomer 17 1 H-NMR) spectrum (400 MHz, solvent: deuterium-chloroform (CDCl3)) is as follows: δ8.244-8.201 (br, 2H), δ6.660-6.630 (s, 2H), δ6.606 (s, 2H), δ3.724-3.680 (br, 7H), δ3.496-3.450 (m, 3H), δ1.683-0.955 (br, 74H). The repeating unit (a) of oligomer 17 is The repeating unit (b1) is The ratio of the number of repetitions of the repeating unit (a) to the number of repetitions of the repeating unit (b1) is 4:1. In addition, the end of oligomer 17 is That is, it is modified into a group containing a double bond.

[0066] Synthesis example 18

[0067] After loading 250 ml of toluene into the reactor, add triethylamine (35 g, 0.35 mol) and then slowly drip methylsulfonic acid (35 g, 0.35 mol) to form an amine salt and continue stirring for 10 minutes. Then add aliphatic dimeramine (26.0 g, 0.050 mol) and 1,2-diaminocyclohexane (5.70 g, 0.050 mol). Next, slowly add pyromellitic dianhydride (13.0 g, 0.06 mol) into the reactor. After connecting the Dean-stark distillation device and the condensation device to the reactor, heat the reactants to make them boil and reflux until the reaction is completed. After the reactants were cooled to room temperature, maleic anhydride (12.8 g, 0.13 mol) and 5 g of methanesulfonic acid were added, and the reactants were reheated to boiling reflux until the reaction was completed. After the reactants were cooled to room temperature, 100 g of toluene was added and allowed to stand for stratification. The reactants were decanted and the salts were rinsed with toluene (2 x 100 g), and the extracts were combined and allowed to stand overnight to allow the salt and toluene layers to be completely separated. The toluene layer was filtered with silica gel, and the solvent was removed under vacuum to obtain 35 g of a dark waxy product. As determined by gel permeation chromatography (GPC), the number average molecular weight of oligomer 18 was approximately 1700, and the PDI value was 1.75. The hydrogen nuclear magnetic resonance (H NMR) of oligomer 18 1 H-NMR) spectrum (400 MHz, solvent: deuterium-chloroform (CDCl3)) is as follows: δ8.244-8.201 (br, 2H), δ6.654-6.632 (s, 2H), δ6.604 (s, 2H), δ3.724-3.680 (br, 7H), δ3.496-3.452 (m, 3H), δ1.683-0.950 (br, 74H). The repeating unit (a) of oligomer 18 is The repeating unit (b1) is The ratio of the number of repetitions of the repeating unit (a) to the number of repetitions of the repeating unit (b1) is 1:1. In addition, the end of the oligomer 18 is That is, it is modified into a group containing a double bond.

[0068] Synthesis example 19

[0069] After loading 250 ml of toluene into the reactor, add triethylamine (35 g, 0.35 mol) and then slowly drip methylsulfonic acid (35 g, 0.35 mol) to form an amine salt, and continue stirring for 10 minutes. Then add aliphatic dimeramine (35.2 g, 0.068 mol), isophoronediamine (2.90 g, 0.017 mol) and melamine (0.95 g, 0.0075 mol). Next, slowly add pyromellitic dianhydride (15.00 g, 0.069 mol) into the reactor. After connecting the Dean-stark distillation device and the condensation device to the reactor, heat the reactants to make them boil and reflux until the reaction is completed. After the reaction product is cooled to room temperature, maleic anhydride (9.8 g, 0.1 mol) and 5 g of methanesulfonic acid are added, and the reactants are reheated to boiling reflux until the reaction is completed. After the reaction product is cooled to room temperature, 100 g of toluene is added and allowed to stand for stratification. The reaction product is decanted and the salts are rinsed with toluene (2 x 100 g), and the extracts are combined and allowed to stand overnight to completely separate the salt and toluene layers. The toluene layer is filtered with silica gel, and the solvent is removed under vacuum to obtain 43 g of a dark waxy product. As determined by gel permeation chromatography (GPC), the number average molecular weight of oligomer 19 is approximately 2800, and the PDI value is 1.85. The hydrogen nuclear magnetic resonance (H NMR) of oligomer 19 1 H-NMR) spectrum (400 MHz, solvent is deuterium-chloroform (CDCl3) as follows: δ8.244-8.201 (br, 2H), δ6.654-6.634 (s, 2H), δ6.600 (s, 2H), δ3.720-3.684 (br, 7H), δ3.496-3.458 (m, 3H), δ1.683-0.955 (br, 81H). The repeating unit (a) of oligomer 19 is The repeating unit (b1) is The repeating unit (b2) is The ratio of the repeating numbers of the repeating units (a), (b1), and (b2) is 9:2:1. In addition, the end of oligomer 19 is That is, it is modified into a group containing a double bond.

[0070] Synthesis example 20

[0071] After loading 250 ml of toluene into the reactor, add triethylamine (35 g, 0.35 mol) and then slowly drip methylsulfonic acid (35 g, 0.35 mol) to form an amine salt, and continue stirring for 10 minutes. Then add aliphatic dimeramine (35.2 g, 0.068 mol), isophoronediamine (2.60 g, 0.015 mol) and melamine (1.30 g, 0.015 mol). Next, slowly add pyromellitic dianhydride (13.08 g, 0.060 mol) into the reactor. After connecting the Dean-stark distillation device and the condensation device to the reactor, heat the reactants to make them boil and reflux until the reaction is completed. After the reaction product is cooled to room temperature, maleic anhydride (9.8 g, 0.1 mol) and 5 g of methanesulfonic acid are added, and the reactants are reheated to boiling reflux until the reaction is completed. After the reaction product is cooled to room temperature, 100 g of toluene is added and the mixture is allowed to stand for stratification. The reaction product is decanted and the salts are rinsed with toluene (2 x 100 g), and the extracts are combined and allowed to stand overnight to completely separate the salt and toluene layers. The toluene layer is filtered with silica gel, and the solvent is removed under vacuum to obtain 41 g of a dark waxy product. As determined by gel permeation chromatography (GPC), the number average molecular weight of oligomer 20 is approximately 2000, and the PDI value is 1.83. The hydrogen nuclear magnetic resonance (H NMR) of oligomer 20 1 H-NMR) spectrum (400 MHz, solvent is deuterium-chloroform (CDCl3) as follows: δ8.244-8.200 (br, 2H), δ6.654-6.633 (s, 2H), δ6.600 (s, 2H), δ3.720-3.686 (br, 7H), δ3.496-3.458 (m, 3H), δ1.684-0.956 (br, 81H). The repeating unit (a) of oligomer 20 is The repeating unit (b1) is The repeating unit (b2) is The ratio of the repeating numbers of the repeating units (a), (b1), and (b2) is 4.5:1:1. In addition, the end of the oligomer 20 is That is, it is modified into a group containing a double bond.

[0072] Example 1

[0073] First, 6 grams of the above oligomer 1, 14 grams of polyphenylene ether oligomer (trade name SA9000, manufacturer SABIC, terminal modified with methacryloyloxy), and 30 grams of toluene were added to a reaction bottle, and heated and stirred until dissolved. After all dissolved, the mixture was cooled to room temperature, and then 0.2 grams of dicumyl peroxide (Dicumyl peroxide) as a free radical initiator and 8 grams of triallyl isocyanurate (TAIC) were added and stirred until completely dissolved to obtain composition 1. Composition 1 was subjected to removal of volatiles and degassing, and film-formed at 150°C and cured at 200°C for 3 hours to obtain a thermally cured product. The dielectric constant (Dk@10GHz) of the cured product was 3.26, the dielectric loss (Df@10GHz) was 0.0033, and the glass transition temperature was 208°C.

[0074] Example 2

[0075] First, add 6 grams of the above oligomer 2, 14 grams of polyphenylene ether oligomer (trade name SA9000, manufacturer SABIC, terminal modified with methacryloyloxy), and 30 grams of toluene into a reaction bottle, and heat and stir until dissolved. After all dissolved, cool to room temperature, then add 0.2 grams of dicumyl peroxide as a free radical initiator and 8 grams of triallyl isocyanurate (TAIC) and stir until completely dissolved to obtain composition 2. Composition 2 is subjected to removal of volatiles and degassing, and film-forming at 150°C and curing at 200°C for 3 hours to obtain a thermally cured product. The dielectric constant (Dk@10GHz) of this cured product is 3.27, the dielectric loss (Df@10GHz) is 0.0034, and the glass transition temperature is 210°C.

[0076] Example 3

[0077] First, 6 grams of the above oligomer 3, 14 grams of polyphenylene ether oligomer (trade name SA9000, manufacturer SABIC, terminal modified with methacryloyloxy), and 30 grams of toluene were added to a reaction bottle, and heated and stirred until dissolved. After all dissolved, the mixture was cooled to room temperature, and then 0.2 grams of dicumyl peroxide (Dicumyl peroxide) as a free radical initiator and 8 grams of triallyl isocyanurate (TAIC) were added and stirred until completely dissolved to obtain composition 3. Composition 3 was subjected to removal of volatiles and degassing, and film-formed at 150°C and cured at 200°C for 3 hours to obtain a thermally cured product. The dielectric constant (Dk@10GHz) of this cured product was 3.25, the dielectric loss (Df@10GHz) was 0.0033, and the glass transition temperature was 198°C.

[0078] Example 4

[0079] First, 6 grams of the above oligomer 4, 14 grams of polyphenylene ether oligomer (trade name SA9000, manufacturer SABIC, terminal modified with methacryloyloxy), and 30 grams of toluene were added to a reaction bottle, and heated and stirred until dissolved. After all dissolved, the mixture was cooled to room temperature, and then 0.2 grams of dicumyl peroxide (Dicumyl peroxide) as a free radical initiator and 8 grams of triallyl isocyanurate (TAIC) were added and stirred until completely dissolved to obtain composition 4. Composition 4 was subjected to removal of volatiles and degassing, and film-formed at 150°C and cured at 200°C for 3 hours to obtain a thermally cured product. The dielectric constant (Dk@10GHz) of this cured product was 3.25, the dielectric loss (Df@10GHz) was 0.0034, and the glass transition temperature was 207°C.

[0080] Example 5

[0081] First, 6 grams of the above oligomer 5, 14 grams of polyphenylene ether oligomer (trade name SA9000, manufacturer SABIC, terminal modified with methacryloyloxy), and 30 grams of toluene were added to a reaction bottle, and heated and stirred until dissolved. After all dissolved, the mixture was cooled to room temperature, and then 0.2 grams of dicumyl peroxide (Dicumyl peroxide) as a free radical initiator and 8 grams of triallyl isocyanurate (TAIC) were added and stirred until completely dissolved to obtain composition 5. Composition 5 was subjected to removal of volatiles and degassing, and film-formed at 150°C and cured at 200°C for 3 hours to obtain a thermally cured product. The dielectric constant (Dk@10GHz) of this cured product was 3.26, the dielectric loss (Df@10GHz) was 0.0034, and the glass transition temperature was 209°C.

[0082] Example 6

[0083] First, add 6 grams of the above oligomer 6, 14 grams of polyphenylene ether oligomer (trade name SA9000, manufacturer SABIC, terminal modified with methacryloyloxy), and 30 grams of toluene into a reaction bottle, and heat and stir until dissolved. After all dissolved, cool to room temperature, then add 0.2 grams of dicumyl peroxide as a free radical initiator and 8 grams of triallyl isocyanurate (TAIC) and stir until completely dissolved to obtain composition 6. Composition 6 is subjected to removal of volatiles and degassing, and film formation at 150°C and curing at 200°C for 3 hours to obtain a thermally cured product. The dielectric constant (Dk@10GHz) of this cured product is 3.24, the dielectric loss (Df@10GHz) is 0.0033, and the glass transition temperature is 207°C.

[0084] Example 7

[0085] First, add 6 grams of the above oligomer 7, 14 grams of polyphenylene ether oligomer (trade name SA9000, manufacturer SABIC, terminal modified with methacryloyloxy), and 30 grams of toluene into a reaction bottle, and heat and stir until dissolved. After all dissolved, cool to room temperature, then add 0.2 grams of dicumyl peroxide as a free radical initiator and 8 grams of triallyl isocyanurate (TAIC) and stir until completely dissolved to obtain composition 7. Composition 7 is subjected to removal of volatiles and degassing, and film-forming at 150°C and curing at 200°C for 3 hours to obtain a thermally cured product. The dielectric constant (Dk@10GHz) of this cured product is 3.25, the dielectric loss (Df@10GHz) is 0.0034, and the glass transition temperature is 207°C.

[0086] Example 8

[0087] First, add 6 grams of the above oligomer 8, 14 grams of polyphenylene ether oligomer (trade name SA9000, manufacturer SABIC, terminal modified with methacryloyloxy), and 30 grams of toluene into a reaction bottle, and heat and stir until dissolved. After all dissolved, cool to room temperature, then add 0.2 grams of dicumyl peroxide as a free radical initiator and 8 grams of triallyl isocyanurate (TAIC) and stir until completely dissolved to obtain composition 8. Composition 8 is subjected to removal of volatiles and degassing, and film-forming at 150°C and curing at 200°C for 3 hours to obtain a thermally cured product. The dielectric constant (Dk@10GHz) of this cured product is 3.26, the dielectric loss (Df@10GHz) is 0.0035, and the glass transition temperature is 210°C.

[0088] Example 9

[0089] First, 6 grams of the above oligomer 10, 14 grams of polyphenylene ether oligomer (trade name SA9000, manufacturer SABIC, terminal modified with methacryloyloxy), and 30 grams of toluene were added to a reaction bottle, and heated and stirred until dissolved. After all dissolved, the mixture was cooled to room temperature, and then 0.2 grams of dicumyl peroxide (Dicumyl peroxide) as a free radical initiator and 8 grams of triallyl isocyanurate (TAIC) were added and stirred until completely dissolved to obtain composition 10. Composition 10 was subjected to removal of volatiles and degassing, and film-formed at 150°C and cured at 200°C for 3 hours to obtain a thermally cured product. The dielectric constant (Dk@10GHz) of the cured product was 3.25, the dielectric loss (Df@10GHz) was 0.0033, and the glass transition temperature was 206°C.

[0090] Example 10

[0091] First, 6 grams of the above oligomer 12, 14 grams of polyphenylene ether oligomer (trade name SA9000, manufacturer SABIC, terminal modified with methacryloyloxy), and 30 grams of toluene were added to a reaction bottle, and heated and stirred until dissolved. After all dissolved, the mixture was cooled to room temperature, and then 0.2 grams of dicumyl peroxide (Dicumyl peroxide) as a free radical initiator and 8 grams of triallyl isocyanurate (TAIC) were added and stirred until completely dissolved to obtain composition 12. Composition 12 was subjected to removal of volatiles and degassing, and film-formed at 150°C and cured at 200°C for 3 hours to obtain a thermally cured product. The dielectric constant (Dk@10GHz) of the cured product was 3.25, the dielectric loss (Df@10GHz) was 0.0033, and the glass transition temperature was 207°C.

[0092] Embodiment 11

[0093] First, 6 grams of the above oligomer 13, 14 grams of polyphenylene ether oligomer (trade name SA9000, manufacturer SABIC, terminal modified with methacryloyloxy), and 30 grams of toluene were added to a reaction bottle, and heated and stirred until dissolved. After all dissolved, the mixture was cooled to room temperature, and then 0.2 grams of dicumyl peroxide (Dicumyl peroxide) as a free radical initiator and 8 grams of triallyl isocyanurate (TAIC) were added and stirred until completely dissolved to obtain composition 13. Composition 13 was subjected to removal of volatiles and degassing, and film-formed at 150°C and cured at 200°C for 3 hours to obtain a thermally cured product. The dielectric constant (Dk@10GHz) of the cured product was 3.25, the dielectric loss (Df@10GHz) was 0.0033, and the glass transition temperature was 197°C.

[0094] Example 12

[0095] First, 6 grams of the above oligomer 15, 14 grams of polyphenylene ether oligomer (trade name SA9000, manufacturer SABIC, terminal modified with methacryloyloxy), and 30 grams of toluene were added to a reaction bottle, and heated and stirred until dissolved. After all dissolved, the mixture was cooled to room temperature, and then 0.2 grams of dicumyl peroxide (Dicumyl peroxide) as a free radical initiator and 8 grams of triallyl isocyanurate (TAIC) were added and stirred until completely dissolved to obtain composition 15. Composition 15 was subjected to removal of volatiles and degassing, and film-forming at 150°C and curing at 200°C for 3 hours to obtain a thermally cured product. The dielectric constant (Dk@10GHz) of the cured product was 3.26, the dielectric loss (Df@10GHz) was 0.0034, and the glass transition temperature was 211°C.

[0096] Embodiment 13

[0097] First, 6 grams of the above oligomer 16, 14 grams of polyphenylene ether oligomer (trade name SA9000, manufacturer SABIC, terminal modified with methacryloyloxy), and 30 grams of toluene were added to a reaction bottle, and heated and stirred until dissolved. After all dissolved, the mixture was cooled to room temperature, and then 0.2 grams of dicumyl peroxide (Dicumyl peroxide) as a free radical initiator and 8 grams of triallyl isocyanurate (TAIC) were added and stirred until completely dissolved to obtain composition 16. Composition 16 was subjected to removal of volatiles and degassing, and film-forming at 150°C and curing at 200°C for 3 hours to obtain a thermally cured product, the dielectric constant (Dk@10GHz) of which was 3.28, the dielectric loss (Df@10GHz) was 0.0035, and the glass transition temperature was 213°C.

[0098] Embodiment 14

[0099] First, 6 grams of the above oligomer 19, 14 grams of polyphenylene ether oligomer (trade name SA9000, manufacturer SABIC, terminal modified with methacryloyloxy), and 30 grams of toluene were added to a reaction bottle, and heated and stirred until dissolved. After all dissolved, the mixture was cooled to room temperature, and then 0.2 grams of dicumyl peroxide (Dicumyl peroxide) as a free radical initiator and 8 grams of triallyl isocyanurate (TAIC) were added and stirred until completely dissolved to obtain composition 19. Composition 19 was subjected to removal of volatiles and degassing, and film-forming at 150°C and curing at 200°C for 3 hours to obtain a thermally cured product. The dielectric constant (Dk@10GHz) of the cured product was 3.24, the dielectric loss (Df@10GHz) was 0.0034, and the glass transition temperature was 212°C.

[0100] Embodiment 15

[0101] First, 6 grams of the above oligomer 20, 14 grams of polyphenylene ether oligomer (trade name SA9000, manufacturer SABIC, terminal modified with methacryloyloxy), and 30 grams of toluene were added to a reaction bottle, and heated and stirred until dissolved. After all dissolved, the mixture was cooled to room temperature, and then 0.2 grams of dicumyl peroxide (Dicumyl peroxide) as a free radical initiator and 8 grams of triallyl isocyanurate (TAIC) were added and stirred until completely dissolved to obtain composition 20. Composition 20 was subjected to removal of volatiles and degassing, and film-formed at 150°C and cured at 200°C for 3 hours to obtain a thermally cured product, the dielectric constant (Dk@10GHz) of which was 3.25, the dielectric loss (Df@10GHz) was 0.0035, and the glass transition temperature was 214°C.

[0102] Comparative Example 1

[0103] First, add 6 grams of the above oligomer 9, 14 grams of polyphenylene ether oligomer (trade name SA9000, manufacturer SABIC, terminal modified with methacryloyloxy), and 30 grams of toluene into a reaction bottle, and heat and stir until dissolved. After all dissolved, cool to room temperature, then add 0.2 grams of dicumyl peroxide as a free radical initiator and 8 grams of triallyl isocyanurate (TAIC) and stir until completely dissolved to obtain composition 9. Composition 9 is subjected to removal of volatiles and degassing, and film-forming at 150°C and curing at 200°C for 3 hours to obtain a thermally cured product. The dielectric constant (Dk@10GHz) of this cured product is 3.26, the dielectric loss (Df@10GHz) is 0.0034, and the glass transition temperature is 196°C.

[0104] Comparative Example 2

[0105] First, 6 grams of the above oligomer 11, 14 grams of polyphenylene ether oligomer (trade name SA9000, manufacturer SABIC, terminal modified with methacryloyloxy), and 30 grams of toluene were added to a reaction bottle, and heated and stirred until dissolved. After all dissolved, the mixture was cooled to room temperature, and then 0.2 grams of dicumyl peroxide (Dicumyl peroxide) as a free radical initiator and 8 grams of triallyl isocyanurate (TAIC) were added and stirred until completely dissolved to obtain composition 11. Composition 11 was subjected to removal of volatiles and degassing, and film-formed at 150°C and cured at 200°C for 3 hours to obtain a thermally cured product. The dielectric constant (Dk@10GHz) of this cured product was 3.27, the dielectric loss (Df@10GHz) was 0.0043, and the glass transition temperature was 212°C.

[0106] Comparative Example 3

[0107] First, 6 grams of the above oligomer 14, 14 grams of polyphenylene ether oligomer (trade name SA9000, manufacturer SABIC, terminal modified with methacryloyloxy), and 30 grams of toluene were added to a reaction bottle, and heated and stirred until dissolved. After all dissolved, the mixture was cooled to room temperature, and then 0.2 grams of dicumyl peroxide (Dicumyl peroxide) as a free radical initiator and 8 grams of triallyl isocyanurate (TAIC) were added and stirred until completely dissolved to obtain composition 14. Composition 14 was subjected to removal of volatiles and degassing, and film-formed at 150°C and cured at 200°C for 3 hours to obtain a thermally cured product. The dielectric constant (Dk@10GHz) of this cured product was 3.26, the dielectric loss (Df@10GHz) was 0.0042, and the glass transition temperature was 210°C.

[0108] Comparative Example 4

[0109] First, 6 grams of the above oligomer 17, 14 grams of polyphenylene ether oligomer (trade name SA9000, manufacturer SABIC, terminal modified with methacryloyloxy), and 30 grams of toluene were added to a reaction bottle, and heated and stirred until dissolved. After all dissolved, the mixture was cooled to room temperature, and then 0.2 grams of dicumyl peroxide (Dicumyl peroxide) as a free radical initiator and 8 grams of triallyl isocyanurate (TAIC) were added and stirred until completely dissolved to obtain composition 17. Composition 17 was subjected to removal of volatiles and degassing, and film-formed at 150°C and cured at 200°C for 3 hours to obtain a thermally cured product. The dielectric constant (Dk@10GHz) of this cured product was 3.27, the dielectric loss (Df@10GHz) was 0.0043, and the glass transition temperature was 197°C.

[0110] Comparative Example 5

[0111] First, add 6 grams of the above oligomer 18, 14 grams of polyphenylene ether oligomer (trade name SA9000, manufacturer SABIC, terminal modified with methacryloyloxy), and 30 grams of toluene into a reaction bottle, and heat and stir until dissolved. After all dissolved, cool to room temperature, then add 0.2 grams of dicumyl peroxide as a free radical initiator and 8 grams of triallyl isocyanurate (TAIC) and stir until completely dissolved to obtain composition 18. Composition 18 is subjected to removal of volatiles and degassing, and film formation at 150°C and curing at 200°C for 3 hours to obtain a thermally cured product. The dielectric constant (Dk@10GHz) of this cured product is 3.30, the dielectric loss (Df@10GHz) is 0.0045, and the glass transition temperature is 200°C.

[0112] From the above, it can be seen that the embodiments of the present invention can simultaneously achieve the characteristics of low high-frequency dielectric loss (≤0.0035) and high glass transition temperature (≥200°C). If there is no repeating unit (b1), (b2), or the above combination, or the amount of repeating unit (b1), (b2), or the above combination is low, the glass transition temperature is insufficient. If the amount of repeating unit (a) is low, the high-frequency dielectric loss is too large. From Comparative Examples 4 and 5, it can be seen that if the structure of the repeating unit (b1) of the introduced alicyclic diamine is different from the repeating unit (b1) of the present invention, the characteristics of low high-frequency dielectric loss (≤0.0035) and high glass transition temperature (≥200°C) cannot be achieved.

[0113] Although the present invention has been disclosed as above with several preferred embodiments, they are not intended to limit the present invention. Anyone with common knowledge in the technical field can make any changes and modifications without departing from the spirit and scope of the present invention. Therefore, the scope of protection of the present invention shall be based on the scope defined by the attached claims.

Claims

1. An oligomer, characterized in that include: Repeating unit (a) as well as Repeating unit (b1) (b2) or a combination of the above; wherein the ratio of the number of repetitions of the repeating unit (a) to the number of repetitions of the repeating units (b1), (b2), or the combination thereof is 1:1 to 9:1; Q is each independently a substituted or unsubstituted aliphatic, cycloaliphatic, aromatic, or siloxane; X is Where 12≥a≥4; 12≥b≥4; R 1 Each is independently hydrogen, C 4-12 Alkyl, C 4-12 Alkenyl, or C 4-12 Alkynyl, and at least 2 R 1 Not hydrogen; Y is or a combination thereof, wherein c is 0 or 1; d is 0 or 1; R 2 ' are each independently hydrogen or C 1-10 alkyl, and at least one R 2 ' is not hydrogen; and R 2 are independently hydrogen or C 1-10 an alkyl group; and Z is The combination above, wherein 12≥e≥1; 12≥f≥1; 12≥g≥1; and R 3 are independently hydrogen or C 1-10 of alkyl.

2. The oligomer according to claim 1, characterized in that The oligomer comprises repeating units (a), (b1), and (b2), and the ratio of the repeating units (b1) to (b2) is 1:1 to 5:

1.

3. The oligomer according to claim 1, characterized in that The oligomer comprises repeating units (a) and (b1), and the ratio of the repeating units (a) to (b1) is 1:1 to 5:

1.

4. The oligomer according to claim 1, characterized in that for Where R 4 C 1-5 alkylene group, -SO2-, -O-, -C(=O)-, or a single bond.

5. The oligomer according to claim 1, characterized in that The repeating unit (a) is And the repeating unit (b1) is 6. The oligomer according to claim 1, characterized in that The repeating unit (a) is And the repeating unit (b1) is 7. The oligomer according to claim 1, characterized in that The repeating unit (a) is And the repeating unit (b1) is 8. The oligomer according to claim 1, characterized in that The repeating unit (a) is And the repeating unit (b1) is 9. The oligomer according to claim 1, characterized in that The repeating unit (a) is And the repeating unit (b2) is 。 10. The oligomer according to claim 1, characterized in that The repeating unit (a) is The repeating unit (b1) is And the repeating unit (b2) is 11. The oligomer according to claim 1, characterized in that Its terminal end is an amine group or modified into a group containing a double bond.

12. A composition, characterized in that include: an oligomer; as well as a free radical initiator; The end of the oligomer is modified to a group containing a double bond, and includes: Repeating unit (a) as well as Repeating Unit or a combination of the above; wherein the ratio of the number of repetitions of the repeating unit (a) to the number of repetitions of the repeating units (b1), (b2), or the combination thereof is 1:1 to 9:1; Q is each independently a substituted or unsubstituted aliphatic, cycloaliphatic, aromatic, or siloxane; Where 12≥a≥4; 12≥b≥4; R 1 Each is independently hydrogen, C 4-12 Alkyl, C 4-12 Alkenyl, or C 4-12 Alkynyl, and at least 2 R 1 Not hydrogen; Y is or a combination thereof, wherein c is 0 or 1; d is 0 or 1; R 2 ' are each independently hydrogen or C 1-10 alkyl, and at least one R 2 ' is not hydrogen; and R 2 are independently hydrogen or C 1-10 an alkyl group; and Z is or a combination thereof, wherein 12≥e≥1; 12≥f≥1; 12≥g≥1; and R 3 are independently hydrogen or C 1-10 of alkyl.

13. The composition according to claim 12, characterized in that The present invention also includes a polyphenylene ether resin having a terminal methacryloyloxy group, a polyphenylene ether resin having a terminal vinyl benzyl ether, or a combination thereof.

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