Hydrocarbon resin polymer, manufacturing method thereof and substrate structure

Abstract

The invention relates to a hydrocarbon resin polymer, a manufacturing method thereof and a substrate structure. The hydrocarbon resin polymer comprises a repeating unit (A) derived from dicyclopentadiene (D CPD). The hydrocarbon resin polymer has a fluorine substituent group, and the content of the fluorine substituent group is 100-4500 ppm based on the total weight of the hydrocarbon resin polymer.

Description

[Technical field]

[0001] The present disclosure relates to a resin polymer and a manufacturing method thereof and a substrate structure, and in particular to a hydrocarbon resin polymer and a manufacturing method thereof and a substrate structure. [Background technology]

[0002] The fifth generation of mobile communication technology (5G mobile communication technology for short) is the latest generation of mobile communication technology. 5G mobile communication technology has the characteristics of high-speed transmission, wide connection, and low latency. At present, 5G mobile communication technology can be divided into three types according to the frequency band used: high-frequency 5G, medium-frequency 5G, and low-frequency 5G. High-frequency 5G can provide ultra-high connection speed.

[0003] However, high-frequency 5G transmission will affect the quality of signal reception and transmission due to high-frequency path loss, conductor loss, and dielectric loss. Therefore, it is necessary to develop copper foil substrate (CCL) materials with low dielectric loss to reduce the dielectric loss of high-frequency 5G transmission, thereby improving the quality of signal reception and transmission.

[0004] The goal of reducing dielectric loss can be achieved by reducing the dielectric properties (dielectric constant (Dk) and dielectric loss tangent (Df)) of copper foil substrate materials. Hydrocarbon resins or polyolefin materials composed of carbon and hydrogen atoms have low dielectric loss characteristics due to their small number of polar functional groups. However, hydrocarbon resins are easily oxidized by heating during processing. The electrical performance of oxidized hydrocarbon resins will deteriorate (i.e., the dielectric constant and dielectric loss tangent will increase).

[0005] Fluorine substituents are known to provide two important properties to resins: hydrophobicity and electron-withdrawing properties. These two properties have a significant effect on the dielectric properties of the resin. Specifically, fluorine substituents increase the hydrophobicity of the resin by reducing the surface energy. Hydrophobicity helps to improve the water resistance and anti-fouling properties of the material, making it suitable for use in electronic components to prevent the effects of humid environments on dielectric properties. In addition, the electron-withdrawing property of the fluorine substituent reduces the polarization ability of the material, thereby reducing the dielectric constant and dielectric loss, making resins with fluorine substituents perform well in high-frequency applications and help improve the speed and stability of signal transmission. [Summary of the invention]

[0006] In view of the above problems, the present disclosure provides a hydrocarbon resin polymer having a fluorine substituent and a method for manufacturing the same. The hydrocarbon resin polymer of the present disclosure has good electrical performance. A substrate structure having a resin layer made by cross-linking a resin composition including the hydrocarbon resin polymer of the present disclosure can also have good electrical performance.

[0007] In some embodiments, the present disclosure provides a hydrocarbon resin polymer, comprising a repeating unit (A) derived from dicyclopentadiene (DCPD), the hydrocarbon resin polymer having a fluorine substituent, and the content of the fluorine substituent is 100 to 4500 ppm based on the total weight of the hydrocarbon resin polymer.

[0008] In some embodiments, the present disclosure provides a method for producing a hydrocarbon resin polymer, comprising polymerizing a mixture in the presence of a fluorine-containing compound, wherein the fluorine-containing compound is a boron trifluoride complex and the mixture comprises dicyclopentadiene.

[0009] In some embodiments, the present disclosure provides a substrate structure, comprising a resin layer and a conductive layer disposed on the resin layer. The resin layer is formed by a resin composition comprising a hydrocarbon resin polymer through a crosslinking process. The hydrocarbon resin polymer has a fluorine substituent and comprises a repeating unit (A) derived from dicyclopentadiene (DCPD), wherein the content of the fluorine substituent is 100 to 4500 ppm based on the total weight of the hydrocarbon resin polymer.

Brief Description of the Drawings

[0010] In order to make the purpose, features and advantages of the present disclosure more obvious and easy to understand, the specific embodiments of the present disclosure are described in detail below with reference to the accompanying drawings, wherein: Figure 1 is a schematic diagram of a substrate structure according to an embodiment of the present disclosure; Figure 2 The hydrocarbon resin polymer according to one embodiment of the present disclosure 19 F NMR spectrum.

Explanation of symbols

[0011] It will be further understood that when "include" and / or "comprising" are used in this specification, they specifically refer to the presence of the characteristic components, integers, steps, operations, components, ingredients, and / or groups thereof, but do not exclude the presence or addition of one or more other characteristic components, integers, steps, operations, components, ingredients, and / or groups thereof. When the singular form "a" or "an" is used in this specification, it is intended to include the plural form unless the context clearly indicates otherwise.

[0012] It will be understood that although the terms "first", "second", etc. may be used herein to describe various components, elements, regions, layers and / or portions, these components, elements, regions, layers and / or portions should not be limited by these terms. These terms are only used to distinguish one component, element, region, layer or portion from another component, element, region, layer or portion.

[0013] It will be understood that the terms "about", "approximately", and "roughly" herein generally refer to within 20% of a given value or range, preferably within 10%, and more preferably within 5%, or within 3%, or within 2%, or within 1%, or within 0.5%. The quantity given here is an approximate quantity, that is, in the absence of a specific description of "about", "approximately", "roughly", the meaning of "about", "approximately", and "roughly" may still be implied. Further, the numerical values ​​represented in the present disclosure may include the numerical values ​​and deviation values ​​within the deviation range acceptable to those of ordinary knowledge in the art. It will be understood that the expression "a~b" used herein to represent a specific numerical range is defined as "≧a and ≦b".

[0014] Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meanings as those commonly understood by those skilled in the art. It is understood that these terms, such as those defined in commonly used dictionaries, should be interpreted as having meanings consistent with the background or context of the relevant technology and the present application, and should not be interpreted in an idealized or overly formal manner unless specifically defined in the present disclosure. The following will omit descriptions that may unnecessarily confuse the known functions and structures of the present disclosure.

[0015] In this disclosure, “C 1-20 "Alkyl" refers to a linear, branched or cyclic aliphatic hydrocarbon monovalent group having 1 to 20 carbon atoms in the main carbon chain. 1-20 Examples of the alkyl group may include methyl, ethyl, propyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, hexyl, dodecyl, dodecyl, cyclohexyl, cyclooctyl, and cyclododecyl, but the present disclosure is not limited thereto.

[0016] Some embodiments of the present disclosure provide a hydrocarbon resin polymer, which includes a repeating unit (A) derived from dicyclopentadiene (DCPD). The hydrocarbon resin polymer has a fluorine substituent, and the content of the fluorine substituent is 100 to 4500 ppm based on the total weight of the hydrocarbon resin polymer. When the content of the fluorine substituent in the hydrocarbon resin polymer is within the above range, the hydrocarbon resin polymer can have better electrical performance. The "content of fluorine substituent" in the present disclosure is based on the hydrocarbon resin polymer obtained using trifluorotoluene (TFT) as an internal standard. 19 F NMR spectrum is calculated. Specifically, the "content of fluorine substituents" in the present disclosure is calculated by the following formula: Fluorine Substituent Content The integral value of fluoride ion is obtained by using trifluorotoluene (TFT) as the internal standard for hydrocarbon resin polymer. 19 In the F NMR spectrum, the sum of the areas of all peaks in the range of -125 ppm to -230 ppm.

[0017] In some embodiments, the repeating unit (A) may have the following structure, but the present disclosure is not limited thereto: In some embodiments, the repeating unit (A) may have a fluorine substituent (structure not shown).

[0018] The "*" in the above structure indicates the connection position with other groups or units. Compared with the linear repeating unit, the repeating unit (A) derived from dicyclopentadiene (DCPD) has higher rigidity, so it can increase the glass transition temperature of the hydrocarbon resin polymer or improve the thermal properties of the hydrocarbon resin polymer.

[0019] In some embodiments, the number average molecular weight (Mn) of the hydrocarbon resin polymer may be 500 to 15,000 g / mol. When the number average molecular weight of the hydrocarbon resin polymer is too high, the solubility of the hydrocarbon resin polymer may decrease. In some embodiments, the number average molecular weight (Mn) of the hydrocarbon resin polymer may be 700 to 15,000 g / mol, 800 to 14,000 g / mol, or 900 to 13,000 g / mol.

[0020] The average number of fluorine substituents per molecule of the hydrocarbon resin polymer in the present disclosure can be calculated based on the content of fluorine substituents in the hydrocarbon resin polymer of the present disclosure and the number average molecular weight of the hydrocarbon resin polymer of the present disclosure. Specifically, the average number of fluorine substituents per molecule of the hydrocarbon resin polymer in the present disclosure is calculated by the following formula: The average hydrocarbon resin polymer per molecule

[0021] According to the above formula, it can be calculated that each molecule of the hydrocarbon resin polymer of the present disclosure has an average of 0.02 to 2 fluorine substituents. In some embodiments, each molecule of the hydrocarbon resin polymer of the present disclosure has an average of 0.03 to 1.5 fluorine substituents, 0.03 to 1.0 fluorine substituents, 0.03 to 0.8 fluorine substituents, or 0.03 to 0.5 fluorine substituents. When each molecule of the hydrocarbon resin polymer has an average of the above range of fluorine substituents, the hydrocarbon resin polymer may have better electrical performance.

[0022] In some embodiments, the polymer dispersion index (PDI) of the hydrocarbon resin polymer may be less than 22. When the polymer dispersion index of the hydrocarbon resin polymer is less than 22, the hydrocarbon resin polymer has better processability. In some embodiments, the polymer dispersion index of the hydrocarbon resin polymer may be greater than 1.5. In some embodiments, the polymer dispersion index of the hydrocarbon resin polymer may be 1.5-20, 2-18, or 2.2-16.5.

[0023] In some embodiments, the hydrocarbon resin polymer of the present disclosure may further include repeating units (B) derived from a monovinyl aromatic compound and repeating units (C) derived from a divinyl aromatic compound.

[0024] Here, the monovinyl aromatic compound refers to a compound including a carbocyclic aromatic structure, and one hydrogen atom on the ring-forming carbon atom of the carbocyclic aromatic structure is replaced by a vinyl group. In some embodiments, the vinyl group may be unsubstituted. In some embodiments, at least one hydrogen atom on the vinyl group may be replaced by a C 1-20 In some embodiments, the carbocyclic aromatic structure may include 6 to 60 or 6 to 20 ring-forming carbon atoms. In some embodiments, the carbocyclic aromatic structure may be unsubstituted. In some embodiments, at least one hydrogen on the ring-forming carbon atom in the carbocyclic aromatic structure may be replaced by a C 1-20 Examples of the monovinyl aromatic compound may include styrene, methylstyrene, or ethylstyrene, but the present disclosure is not limited thereto.

[0025] The repeating unit (B) derived from a monovinyl aromatic compound includes a carbocyclic aromatic structure derived from a monovinyl aromatic compound. For example, in some embodiments, the repeating unit (B) may have the following structure, but the present disclosure is not limited thereto: The "*" in the above structure indicates the contact position with other groups or units.

[0026] Here, the divinyl aromatic compound refers to a compound including a carbocyclic aromatic structure, and two hydrogen atoms on the ring carbon atoms of the carbocyclic aromatic structure are replaced by vinyl groups. In some embodiments, the vinyl group may be unsubstituted. In some embodiments, at least one hydrogen atom on the vinyl group may be replaced by a C 1-20 In some embodiments, the carbocyclic aromatic structure may include 6 to 60 or 6 to 20 ring-forming carbon atoms. In some embodiments, the carbocyclic aromatic structure may be unsubstituted. In some embodiments, at least one hydrogen on the ring-forming carbon atom of the carbocyclic aromatic structure may be replaced by a C 1-20 Examples of the divinyl aromatic compound may include divinylbenzene or p-isopropenyl-α-methylstyrene (diisopropenylbenzene, IPAM S), but the present disclosure is not limited thereto.

[0027] The repeating unit (C) derived from a divinyl aromatic compound includes a carbocyclic aromatic structure derived from a divinyl aromatic compound. In some embodiments, the repeating unit (C) may include a cross-linkable repeating unit (C1) and a cross-linked repeating unit (C2):

[0028] R1, R2, R3, and R4 in the crosslinkable repeating unit (C1) and the crosslinked repeating unit (C2) can each independently be H or C 1-20 alkyl, and Ar 1 and Ar 2 may be phenylene groups; * represents the connection position between the cross-linkable repeating unit (C 1) and / or the cross-linked repeating unit (C 2) and other groups or units. In some embodiments, the cross-linkable repeating unit (C 1) may include the following structure, but the present disclosure is not limited thereto: In some embodiments, the cross-linked repeating unit (C2) may include a structure as shown below, but the present disclosure is not limited thereto:

[0029] In some embodiments, based on the total of all units in the hydrocarbon resin polymer being 100 mol%, the hydrocarbon resin polymer may include 0.15 to 15 mol% of repeating units (A), 14 to 95 mol% of repeating units (B), and 4 to 85 mol% of repeating units (C). When the content of repeating units (A) in the hydrocarbon resin polymer is within the above range, the hydrocarbon resin polymer may have better thermal properties and lower manufacturing costs. When the content of repeating units (B) and repeating units (C) in the hydrocarbon resin polymer is within the above range, the hydrocarbon resin polymer may have better thermal properties and / or processability. In some embodiments, based on the total of all units in the hydrocarbon resin polymer being 100 mol%, the hydrocarbon resin polymer may include 0.5 to 10 mol% of repeating units (A), 50 to 90 mol% of repeating units (B), and 8 to 40 mol% of repeating units (C). In some embodiments, based on the total of all units in the hydrocarbon resin polymer being 100 mol%, the hydrocarbon resin polymer may include 1 to 8 mol% of the repeating unit (A), 60 to 89 mol% of the repeating unit (B), and 10 to 30 mol% of the repeating unit (C). In some embodiments, based on the total of all units in the hydrocarbon resin polymer being 100 mol%, the hydrocarbon resin polymer may include 1 to 30 mol% of the crosslinkable repeating unit (C1). When the content of the crosslinkable repeating unit (C1) in the hydrocarbon resin polymer is within the above range, the hydrocarbon resin polymer may have good thermal properties, electrical performance, and / or processability. In some embodiments, based on the total of all units in the hydrocarbon resin polymer being 100 mol%, the hydrocarbon resin polymer may include 3 to 28 mol%, 5 to 25 mol%, or 6 to 22 mol% of the crosslinkable repeating unit (C1).

[0030] Repeating unit (A) and repeating unit (C) affect the thermal properties and thermal stability of hydrocarbon resin polymer. In some embodiments, based on the total of all units in the hydrocarbon resin polymer being 100 mol%, the sum of the contents of repeating unit (A) and repeating unit (C) of the hydrocarbon resin polymer is greater than or equal to 13 mol%. The sum of repeating unit (A) and repeating unit (C) being greater than or equal to 13 mol% can provide excellent thermal properties and thermal stability of hydrocarbon resin polymer. In some embodiments, based on the total of all units in the hydrocarbon resin polymer being 100 mol%, the sum of the contents of repeating unit (A) and repeating unit (C) of the hydrocarbon resin polymer may be greater than or equal to 15 mol%, 17 mol%, or 20 mol%. In some embodiments, based on the total of all units in the hydrocarbon resin polymer being 100 mol%, the sum of the contents of repeating unit (A) and repeating unit (C) of the hydrocarbon resin polymer may be less than or equal to 45 mol%, 40 mol%, or 35 mol%.

[0031] In some embodiments, the hydrocarbon resin polymer may include reactive double bonds. In the present disclosure, "reactive double bonds" refer to double bonds in repeating unit (A) or repeating unit (C) that can react with other compounds or polymers. For example, in some embodiments, the reactive double bonds include the double bonds in repeating unit (A) shown below: Alternatively, the double bonds on the non-benzene ring in the repeating unit (C) are shown below: However, the present disclosure is not limited thereto.

[0032] In some embodiments, the hydrogen content on the reactive double bonds of the hydrocarbon resin polymer may be less than 10%. When the hydrogen content on the reactive double bonds in the hydrocarbon resin polymer is too high, for example, higher than 10%, the hydrocarbon resin polymer is easily oxidized during the heating process, resulting in poor electrical performance of the hydrocarbon resin polymer. In some embodiments, the hydrogen content on the reactive double bonds in the hydrocarbon resin polymer may be greater than 0.2%. When the hydrogen content on the reactive double bonds in the hydrocarbon resin polymer is too low, for example, lower than 0.2%, the peel strength of the layer including the hydrocarbon resin polymer may be too low. In some embodiments, the hydrogen content on the reactive double bonds in the hydrocarbon resin polymer may be 0.2% to 10%, 0.3% to 9%, 0.4% to 8%, or 0.5% to 7%. When the hydrogen content on the reactive double bonds in the hydrocarbon resin polymer is within the above range, the hydrocarbon resin polymer is not easily oxidized or tends to complete the cross-linking reaction before oxidation in a high temperature environment (for example, above 150°C), so the electrical performance of the hydrocarbon resin polymer can be improved.

[0033] In summary, the hydrocarbon resin polymer of the present disclosure may have good electrical performance (dielectric properties). In some embodiments, the hydrocarbon resin polymer of the present disclosure may also have good thermal properties or processability.

[0034] Some embodiments of the present disclosure provide a method for producing a hydrocarbon resin polymer. The method for producing a hydrocarbon resin polymer of the present disclosure comprises polymerizing a mixture in the presence of a fluorine-containing compound, wherein the fluorine-containing compound is a boron trifluoride complex and the mixture comprises dicyclopentadiene.

[0035] In some embodiments, the boron trifluoride complex may include boron trifluoride tetrahydrofuran complex (BF3·THF), boron trifluoride methanol complex (BF3·MeOH), boron trifluoride hydrate (BF3·H2O), boron trifluoride diethyl ether complex (BF3-OEt2), boron trifluoride anisole complex (BF3·PhOMe), boron trifluoride acetic acid complex (BF3·AcOH), or any combination thereof.

[0036] In some embodiments, the molar ratio of the fluorine-containing compound to the mixture may be 0.05 to 1:20. When the molar ratio of the fluorine-containing compound to the mixture is within the above range, the method for producing the hydrocarbon resin polymer disclosed herein has a better polymerization reaction speed, and thus a hydrocarbon resin polymer with an appropriate degree of crosslinking and molecular weight can be obtained to avoid gelation. In some embodiments, the molar ratio of the fluorine-containing compound to the mixture may be 0.08 to 0.9:20 or 0.1 to 1:20.

[0037] The mixture may further include monovinyl aromatic compounds and / or divinyl aromatic compounds. That is, in some embodiments, the mixture may include dicyclopentadiene and monovinyl aromatic compounds; dicyclopentadiene and divinyl aromatic compounds; or dicyclopentadiene, monovinyl aromatic compounds and divinyl aromatic compounds.

[0038] In some embodiments, the mixture may include 3 to 80 mol% of dicyclopentadiene, 0 to 90 mol% of monovinyl aromatic compounds, and 0 to 50 mol% of divinyl aromatic compounds, based on the total of all components in the mixture being 100 mol%. In some embodiments, the mixture may include 3.5 to 70 mol% of dicyclopentadiene, 20 to 88 mol% of monovinyl aromatic compounds, and 0.05 to 35 mol% of divinyl aromatic compounds, based on the total of all components in the mixture being 100 mol%. In some embodiments, the mixture may include 4 to 60 mol% of dicyclopentadiene, 25 to 87 mol% of monovinyl aromatic compounds, and 0.06 to 25 mol% of divinyl aromatic compounds, based on the total of all components in the mixture being 100 mol%. The definitions and examples of the monovinyl aromatic compounds and divinyl aromatic compounds are as described above, so they are not repeated here.

[0039] In some embodiments, the mixture can be polymerized at a polymerization temperature of 0 to 80° C. In some embodiments, the polymerization temperature can be 0 to 45° C., 0 to 40° C., 0 to 35° C., or 0 to 30° C. In some embodiments, the mixture can be polymerized for a reaction time of 1 to 8 hours. In some embodiments, the reaction time can be 2 to 7 hours.

[0040] The specific structure of the hydrocarbon resin polymer obtained according to the method for producing the hydrocarbon resin polymer disclosed herein is as described above, so it will not be repeated here. The hydrocarbon resin polymer obtained according to the method for producing the hydrocarbon resin polymer disclosed herein may have good electrical performance (dielectric properties). In some embodiments, the hydrocarbon resin polymer obtained according to the method for producing the hydrocarbon resin polymer disclosed herein may also have good thermal properties or processability.

[0041] In some embodiments, the present disclosure provides a substrate structure. Figure 1 Schematic diagram of a substrate structure according to an embodiment of the present disclosure. Figure 1 As shown, the substrate structure of the present disclosure includes a base layer 100, a conductive layer 103 disposed on the base layer 100, and a resin layer 101 disposed between the conductive layer 103 and the base layer 100, wherein the resin layer 101 is formed by a resin composition including the hydrocarbon resin polymer as described above through a cross-linking process.

[0042] In some embodiments, the base layer 100 may include polyimide (PI), polycarbonate (PC), polyethylene terephthalate (PET), glass, quartz, sapphire, ceramic, plastic, Ajinomoto Build-up Film (ABF), glass fiber paper, tissue paper, or any combination thereof, but the present disclosure is not limited thereto.

[0043] In some embodiments, the conductive layer 103 may include copper (Cu), aluminum (Al), molybdenum (Mo), tungsten (W), gold (Au), chromium (Cr), nickel (Ni), platinum (Pt), titanium (Ti), other suitable metal materials, or any combination thereof, but the present disclosure is not limited thereto. In some embodiments, the conductive layer 103 may have a single-layer structure or a multi-layer stacked structure. For example, the conductive layer 103 may include a single-layer metal copper.

[0044] The base layer 100 may have a first surface 100S1 and a second surface 100S2 opposite to the first surface 100S1 . The conductive layer 103 may be disposed on the first surface 100S1 of the base layer 100 , and the resin layer 101 may be disposed between the first surface 100S1 of the base layer 100 and the conductive layer 103 .

[0045] In some embodiments, the substrate structure may further include another conductive layer 104 on the second surface 100S2 of the base layer 100, and another resin layer 102 may be disposed between the second surface 100S2 of the base layer 100 and the conductive layer 104. Another resin layer 102 may include the same material as the resin layer 101. Another conductive layer 104 may include copper (Cu), aluminum (Al), molybdenum (Mo), tungsten (W), gold (Au), chromium (Cr), nickel (Ni), platinum (Pt), titanium (Ti), other suitable metal materials, or any combination of the foregoing, but the present disclosure is not limited thereto. In some embodiments, another conductive layer 104 may have a single-layer structure or a multi-layer stacked structure. Another conductive layer 104 may include the same or different materials and the same or different structures as the conductive layer 103. For example, another conductive layer 104 may include a single layer of metal copper.

[0046] The substrate structure having a resin layer including the hydrocarbon resin polymer disclosed herein may have good electrical performance (dielectric properties). In some embodiments, the substrate structure including the resin layer may also have good thermal performance, processability, and / or reliability.

[0047] One or more embodiments of the present disclosure will now be described in detail with reference to the following examples. However, these examples are only used to illustrate the embodiments of the present disclosure and are not intended to limit the scope of the embodiments of the present disclosure.

[0048] [Preparation of Hydrocarbon Resin Polymers 1 to 27] Hydrocarbon resin polymer 1

[0049] Reaction Procedure

[0050] 6.61 g (5 mol%) of dicyclopentadiene (DCPD), 85.40 g (82 mol%) of styrene, 16.92 g (13 mol%) of divinylbenzene (DVB, purity 63%, the remaining 37% is ethylstyrene), and 289 g of toluene were added to a 1 L four-neck straight jacket reactor under nitrogen, and stirred with a four-blade flat paddle with a stirring speed set at 400 rpm to form a mixture. 2.84 g of boron trifluoride diethyl ether complex (BF3-OEt2, the molar ratio of boron trifluoride diethyl ether complex: mixture is 0.4:20) was injected at a reaction temperature of 10°C using a syringe pump at a rate of 0.25 mL / min. After 3 hours of reaction time, 9.32 g of isopropanol was added to terminate the polymerization reaction to obtain a polymer mother liquor.

[0051] Purification procedures

[0052] First, the polymer mother liquor was diluted with 100 g of toluene. The polymer mother liquor was stirred using a mechanical stirrer at a speed of 500 rpm. The polymer mother liquor was slowly dripped into 5 times the weight of isopropanol through a dropping funnel to obtain a white resin crude product. The solid-liquid phase was filtered by vacuum to obtain a white solid. The obtained white solid was washed with methanol to remove impurities and isopropanol, and finally heated at 60° C. under nitrogen to remove the solvent, to obtain a white powder hydrocarbon resin polymer as hydrocarbon resin polymer 1. The yield was about 45%. Hydrocarbon resin polymer 2

[0053] Reaction Procedure

[0054] 15.23 g (11 mol%) of dicyclopentadiene, 80.39 g (74 mol%) of styrene, 19.5 g (15 mol%) of divinylbenzene (purity 63%, the remaining 37% is ethylstyrene), and 149.82 g of toluene were added to a 1 L four-neck straight jacket reactor under nitrogen, and stirred with a four-blade flat paddle with a stirring speed set at 400 rpm to form a mixture. 2.94 g of boron trifluoride diethyl ether complex (the molar ratio of boron trifluoride diethyl ether complex: mixture is 0.4:20) was injected at a reaction temperature of 10°C using a syringe pump at a rate of 0.25 mL / min. After a reaction time of 3 hours, 10.10 g of isopropanol was added to terminate the polymerization reaction to obtain a polymer mother liquor.

[0055] Purification procedures

[0056] First, the polymer mother liquor was diluted with 94 g of toluene. The polymer mother liquor was stirred using a mechanical stirrer at a speed of 500 rpm. The polymer mother liquor was slowly dripped into 5 times the weight of isopropanol through a dropping funnel to obtain a white resin crude product. The solid-liquid phase was filtered by vacuum to obtain a white solid. The obtained white solid was washed with methanol to remove impurities and isopropanol, and finally heated at 60° C. under nitrogen to remove the solvent, to obtain a white powder hydrocarbon resin polymer as hydrocarbon resin polymer 2. The yield was about 48%. Hydrocarbon resin polymer 3

[0057] Reaction Procedure

[0058] 17.27 g (17 mol%) of dicyclopentadiene, 55.99 g (70 mol%) of styrene, 13 g (13 mol%) of divinylbenzene (purity 63%, the remaining 37% is ethylstyrene), and 110.99 g of toluene were added to a 1 L four-neck straight jacket reactor under nitrogen, and stirred with a four-blade flat paddle with a stirring speed set at 400 rpm to form a mixture. 1.09 g of boron trifluoride diethyl ether complex (the molar ratio of boron trifluoride diethyl ether complex: mixture is 0.2:20) was injected at a reaction temperature of 20°C using a syringe pump at a rate of 0.25 mL / min. After a reaction time of 5.5 hours, 4.32 g of isopropanol was added to terminate the polymerization reaction to obtain a polymer mother solution.

[0059] Purification procedures

[0060] First, the polymer mother liquor was diluted with 52 g of toluene. The polymer mother liquor was stirred using a mechanical stirrer at a speed of 500 rpm. The polymer mother liquor was slowly dripped into 5 times the weight of isopropanol through a dropping funnel to obtain a white resin crude product. The solid-liquid phase was filtered by suction to obtain a white solid. The obtained white solid was washed with methanol to remove impurities and isopropanol, and finally heated at 60° C. under nitrogen to remove the solvent, to obtain a white powder hydrocarbon resin polymer as hydrocarbon resin polymer 3. The yield was about 51%. Hydrocarbon resin polymer 4

[0061] Reaction Procedure

[0062] 21.6 g (17 mol%) of dicyclopentadiene (purity 95%), 70 g (70 mol%) of styrene (purity 99.8%), 16.25 g (13 mol%) of divinylbenzene (purity 63%, the remaining 37% is ethylstyrene) and 160 mL of toluene were added to a 1 L four-neck straight jacket reactor under nitrogen, and stirred with a single-layer four-blade flat paddle set at a stirring speed of 400 rpm to form a mixture. 2.73 g of boron trifluoride diethyl ether complex (the molar ratio of boron trifluoride diethyl ether complex: mixture is 0.4:20) was injected at a low temperature (10°C) using a syringe pump at a rate of 0.25 mL / min. After a reaction time of 2 hours, 8.1 g of isopropanol was added to terminate the polymerization reaction to obtain a colorless polymer mother liquor.

[0063] Purification procedures

[0064] First, the polymer mother liquor is filtered to remove impurities and insolubles. The polymer mother liquor is stirred using a mechanical stirrer at a speed of 500 rpm. The polymer mother liquor is slowly dripped into 5 times the weight of isopropanol through a dropping funnel to obtain a white resin crude product. The solid-liquid phase is filtered by vacuum to obtain a white solid, which is then repeatedly redissolved in toluene to form another mother liquor and isopropanol (the weight ratio of mother liquor / isopropanol is 1:5) is used for precipitation steps, and a purer white resin solid is obtained after filtration. The obtained white resin solid is washed with methanol to remove impurities and isopropanol, and finally heated and stirred under vacuum to remove the solvent to obtain a white powder hydrocarbon resin polymer as hydrocarbon resin polymer 4. Hydrocarbon resin polymer 5

[0065] Reaction Procedure

[0066] 34.53 g (17 mol%) of dicyclopentadiene (purity 95%), 111.99 g (70 mol%) of styrene (purity 99.8%), 26 g (13 mol%) of divinylbenzene (purity 63%, the remaining 37% is ethylstyrene), and 166.48 g of toluene were added to a 1L four-neck straight jacket reactor under nitrogen, and stirred with a four-blade flat paddle with a stirring speed set at 400 rpm to form a mixture. 2.18 g of boron trifluoride diethyl ether complex (the molar ratio of boron trifluoride diethyl ether complex: mixture is 0.2:20) was injected at a reaction temperature of 20°C using a syringe pump at a rate of 0.25 mL / min. After a reaction time of 4.5 hours, 3.89 g of isopropanol was added to terminate the polymerization reaction to obtain a polymer mother solution.

[0067] Purification procedures

[0068] First, the polymer mother liquid was diluted with 75 g of toluene. The polymer mother liquid was stirred with a mechanical stirrer at a speed of 500 rpm. The polymer mother liquid was slowly dripped into 5 times the weight of isopropanol through a dropping funnel to obtain a white resin crude product. The solid-liquid phase was filtered by vacuum to obtain a white solid. The obtained white solid was washed with methanol to remove impurities and isopropanol, and finally heated at 60° C. under nitrogen to remove the solvent, to obtain a white powder hydrocarbon resin polymer as hydrocarbon resin polymer 5. Hydrocarbon resin polymer 6 and 7

[0069] The same reaction and purification procedures as those for the hydrocarbon resin polymer 5 were followed to obtain hydrocarbon resin polymers 6 and 7, respectively, except that the reaction time was 5.5 hours and 6.5 hours, respectively, instead of 4.5 hours. Hydrocarbon resin polymer 8

[0070] Reaction Procedure

[0071] 25.89 g (17 mol%) of dicyclopentadiene, 83.99 g (70 mol%) of styrene, 19.5 g (13 mol%) of divinylbenzene (purity 63%, the remaining 37% is ethylstyrene), and 66.60 g of toluene were added to a 1 L four-neck straight jacket reactor under nitrogen, and stirred with a four-blade flat paddle with a stirring speed set at 400 rpm to form a mixture. 0.82 g of boron trifluoride diethyl ether complex (the molar ratio of boron trifluoride diethyl ether complex: mixture is 0.1:20) was injected at a reaction temperature of 20°C using a syringe pump at a rate of 0.25 mL / min. After 2 hours of reaction time, 3.77 g of isopropanol was added to terminate the polymerization reaction to obtain a polymer mother solution.

[0072] Purification procedures

[0073] First, the polymer mother liquid was diluted with 52 g of toluene. The polymer mother liquid was stirred using a mechanical stirrer at a rotation speed of 500 rpm. The polymer mother liquid was slowly dripped into 5 times the weight of isopropanol through a dropping funnel to obtain a white resin crude product. The solid-liquid phase was filtered by vacuum to obtain a white solid. The obtained white solid was washed with methanol to remove impurities and isopropanol, and finally heated at 60° C. under nitrogen to remove the solvent, to obtain a white powder hydrocarbon resin polymer as hydrocarbon resin polymer 8. Hydrocarbon resin polymer 9 to 12

[0074] Hydrocarbon resin polymers 9 to 12 were obtained by the same reaction and purification procedures as those of hydrocarbon resin polymer 8, except that the reaction time was 2.5 hours, 3 hours, 4 hours, and 4.5 hours, respectively, instead of 2 hours. Hydrocarbon resin polymer 13

[0075] Reaction Procedure

[0076] 20.30 g (20 mol%) of dicyclopentadiene, 53.59 g (67 mol%) of styrene, and 110.976 g of toluene were added to a 400 mL five-necked straight jacket reactor under nitrogen and stirred with a four-blade flat paddle set at a stirring speed of 400 rpm to form a mixture. 4.36 g of boron trifluoride diethyl ether complex (the molar ratio of boron trifluoride diethyl ether complex: mixture was 0.8:20) was injected at a reaction temperature of 20°C using a syringe pump at a rate of 0.25 mL / min. After 0.5 hours, 13 g (13 mol%) of divinylbenzene (purity 63%, the remaining 37% was ethylstyrene) was added. After 1.5 hours of reaction time, 11.8 g of isopropanol was added to terminate the polymerization reaction to obtain a polymer mother liquor.

[0077] Purification procedures

[0078] First, the polymer mother liquor was diluted with 53 g of toluene. The polymer mother liquor was stirred using a mechanical stirrer at a speed of 500 rpm. The polymer mother liquor was slowly dripped into 5 times the weight of isopropanol through a dropping funnel to obtain a pale yellow crude resin product. The solid-liquid phase was filtered by suction to obtain a pale yellow solid. The obtained pale yellow solid was washed with methanol to remove impurities and isopropanol, and finally heated at 60° C. under nitrogen to remove the solvent, to obtain a pale yellow powder hydrocarbon resin polymer as hydrocarbon resin polymer 13. The yield was about 72%. Hydrocarbon resin polymer 14

[0079] Reaction Procedure

[0080] 33.05 g (50 mol%) of dicyclopentadiene, 9.50 g (18.25 mol%) of styrene, 20.67 g (31.75 mol%) of divinylbenzene (purity 63%, the remaining 37% is ethylstyrene), 15.10 g of butyl acetate, and 29.26 g of toluene were added to a 400 mL five-necked straight jacket reactor under nitrogen and stirred with a four-blade flat paddle with a stirring speed set at 400 rpm to form a mixture. 1.42 g of boron trifluoride diethyl ether complex (the molar ratio of boron trifluoride diethyl ether complex: mixture is 0.4:20) was injected at a reaction temperature of 70°C using a syringe pump at a rate of 0.25 mL / min. After a reaction time of 3 hours, 50 g of a 5 wt% sodium bicarbonate aqueous solution was added to terminate the polymerization reaction to obtain a polymer mother liquor.

[0081] Purification procedures

[0082] First, the polymer mother liquor is diluted with 45 g of toluene. The polymer mother liquor is stirred using a mechanical stirrer at a speed of 500 rpm. The polymer mother liquor is slowly dripped into 5 times the weight of isopropanol through a dropping funnel to obtain a light yellow crude resin product. The solid-liquid phase is filtered by suction to obtain a light yellow solid. Then 20 g of the crude product is dissolved in 40 g of toluene and stirred with a 50 mm long olive-shaped stirring bar at a speed of 200 rpm to obtain a polymer solution. The polymer solution is slowly dripped into 5 times the weight of isopropanol through a dropping funnel to obtain a light yellow crude resin product. The solid-liquid phase is filtered by suction to obtain a light yellow solid. The obtained light yellow solid is washed with methanol to remove impurities and isopropanol, and finally heated at 60° C. under nitrogen to remove the solvent to obtain a light yellow powder hydrocarbon resin polymer as hydrocarbon resin polymer 14. Hydrocarbon resin polymer 15

[0083] Reaction Procedure

[0084] 50.67 g (20 mol%) of dicyclopentadiene (purity 95%), 133.98 g (67 mol%) of styrene (purity 99.8%), 32.5 g (13 mol%) of divinylbenzene (purity 63%, the remaining 37% is ethylstyrene), and 320 mL of toluene were added to a 1 L four-neck straight jacket reactor under nitrogen, and stirred using a single-layer four-blade flat paddle with a stirring speed set to 400 rpm to form a mixture. 5.45 g of boron trifluoride diethyl ether complex (the molar ratio of boron trifluoride diethyl ether complex: mixture is 0.4:20) was injected at a reaction temperature of 10°C using a syringe pump at a rate of 0.25 mL / min. After adding the boron trifluoride diethyl ether complex, the reaction temperature was adjusted to 15°C and maintained for 2 hours, and 16.2 g of isopropanol was added to terminate the polymerization reaction to obtain a colorless polymer mother liquor.

[0085] Purification procedures

[0086] First, the polymer mother liquor is filtered to remove impurities and insolubles. The polymer mother liquor is stirred with a mechanical stirrer at a speed of 500 rpm. The polymer mother liquor is slowly dripped into 5 times the weight of isopropanol through a dropping funnel to obtain a white resin crude product. The solid-liquid phase is filtered by vacuum to obtain a white solid. Then it is repeatedly dissolved in toluene to form another mother liquor and isopropanol (the weight ratio of mother liquor / isopropanol is 1:5) is used for precipitation steps, and a purer white resin solid is obtained after filtration. The obtained white resin solid is washed with methanol to remove impurities and isopropanol, and finally heated and stirred under vacuum to remove the solvent to obtain a white powder hydrocarbon resin polymer. It is repeatedly dissolved in tetrahydrofuran to form another mother liquor and isopropanol (the weight ratio of mother liquor / isopropanol is 1:5) is used for precipitation steps, and a purer white resin solid is obtained after filtration. The obtained white resin solid is washed with methanol to remove impurities and isopropanol, and finally heated and stirred under vacuum to remove the solvent to obtain a white powder hydrocarbon resin polymer as hydrocarbon resin polymer 15. Hydrocarbon resin polymer 16

[0087] Reaction Procedure

[0088] 21.6 g (17 mol%) of dicyclopentadiene (purity 95%), 65.99 g (66 mol%) of styrene (purity 99.8%), 21.25 g (17 mol%) of divinylbenzene (purity 63%, the remaining 37% is ethylstyrene), and 160 mL of toluene were added to a 1 L four-neck straight jacket reactor under nitrogen, and stirred with a single-layer four-blade flat paddle set at a stirring speed of 400 rpm to form a mixture. 2.73 g of boron trifluoride diethyl ether complex (the molar ratio of boron trifluoride diethyl ether complex: mixture is 0.4:20) was injected at a reaction temperature of 0°C using a syringe pump at a rate of 0.25 mL / min. After the addition of boron trifluoride diethyl ether complex and the polymerization reaction was allowed to proceed for 2 hours, 8.1 g of isopropanol was added to terminate the polymerization reaction to obtain a colorless polymer mother liquor.

[0089] Purification procedures

[0090] First, the polymer mother liquor is filtered to remove impurities and insolubles. The polymer mother liquor is stirred with a mechanical stirrer at a speed of 500 rpm. The polymer mother liquor is slowly dripped into 5 times the weight of isopropanol through a dropping funnel to obtain a white resin crude product. The solid-liquid phase is filtered by vacuum to obtain a white solid. Then it is repeatedly dissolved in toluene to form another mother liquor and isopropanol (the weight ratio of mother liquor / isopropanol is 1:5) is used for precipitation steps, and a purer white resin solid is obtained after filtration. The obtained white resin solid is washed with methanol to remove impurities and isopropanol, and finally heated and stirred under vacuum to remove the solvent to obtain a white powder hydrocarbon resin polymer. It is repeatedly dissolved in tetrahydrofuran to form another mother liquor and isopropanol (the weight ratio of mother liquor / isopropanol is 1:5) is used for precipitation steps, and a purer white resin solid is obtained after filtration. The obtained white resin solid is washed with methanol to remove impurities and isopropanol, and finally heated and stirred under vacuum to remove the solvent to obtain a white powder hydrocarbon resin polymer as hydrocarbon resin polymer 16. Hydrocarbon resin polymer 17

[0091] Reaction Procedure

[0092] 43.15 g (17 mol%) of dicyclopentadiene (purity 95%), 129.98 g (65 mol%) of styrene (purity 99.8%), 44.99 g (18 mol%) of divinylbenzene (purity 63%, the remaining 37% is ethylstyrene), and 320 mL of toluene were added to a 1 L four-neck straight jacket reactor under nitrogen, and stirred with a single-layer four-blade flat paddle set at a stirring speed of 400 rpm to form a mixture. 5.45 g of boron trifluoride diethyl ether complex (the molar ratio of boron trifluoride diethyl ether complex: mixture is 0.4:20) was injected at a reaction temperature of 0°C using a syringe pump at a rate of 0.25 mL / min. After the addition of boron trifluoride diethyl ether complex and the polymerization reaction was allowed to proceed for 2 hours, 16.2 g of isopropanol was added to terminate the polymerization reaction to obtain a colorless polymer mother liquor.

[0093] Purification procedures

[0094] First, the polymer mother liquor is filtered to remove impurities and insolubles. The polymer mother liquor is stirred with a mechanical stirrer at a speed of 500 rpm. The polymer mother liquor is slowly dripped into 5 times the weight of isopropanol through a dropping funnel to obtain a white resin crude product. The solid-liquid phase is filtered by vacuum to obtain a white solid. Then it is repeatedly dissolved in toluene to form another mother liquor and isopropanol (the weight ratio of mother liquor / isopropanol is 1:5) is used for precipitation steps, and a purer white resin solid is obtained after filtration. The obtained white resin solid is washed with methanol to remove impurities and isopropanol, and finally heated and stirred under vacuum to remove the solvent to obtain a white powder hydrocarbon resin polymer. It is repeatedly dissolved in tetrahydrofuran to form another mother liquor and isopropanol (the weight ratio of mother liquor / isopropanol is 1:5) is used for precipitation steps, and a purer white resin solid is obtained after filtration. The obtained white resin solid is washed with methanol to remove impurities and isopropanol, and finally heated and stirred under vacuum to remove the solvent to obtain a white powder hydrocarbon resin polymer as hydrocarbon resin polymer 17. Hydrocarbon resin polymer 18

[0095] Reaction Procedure

[0096] 21.58 g (17 mol%) of dicyclopentadiene (purity 95%), 56.99 g (57 mol%) of styrene (purity 99.8%), 32.50 g (26 mol%) of divinylbenzene (purity 63%, the remaining 37% is ethylstyrene) and 160 mL of toluene were added to a 1 L four-neck straight jacket reactor under nitrogen, and stirred with a single-layer four-blade flat paddle set at a stirring speed of 400 rpm to form a mixture. 1.36 g of boron trifluoride diethyl ether complex (the molar ratio of boron trifluoride diethyl ether complex: mixture is 0.2:20) was injected at a rate of 0.25 mL / min using a syringe pump at low temperature (0°C). After the addition of boron trifluoride diethyl ether complex and the polymerization reaction was allowed to proceed for 2 hours, 4.1 g of isopropanol was added to terminate the polymerization reaction to obtain a colorless polymer mother liquor.

[0097] Purification procedures

[0098] First, the polymer mother liquor is filtered to remove impurities and insolubles. The polymer mother liquor is stirred with a mechanical stirrer at a speed of 500 rpm. The polymer mother liquor is slowly dripped into 5 times the weight of isopropanol through a dropping funnel to obtain a white resin crude product. The solid-liquid phase is filtered by vacuum to obtain a white solid, and then it is repeatedly redissolved in toluene to form another mother liquor and isopropanol (the weight ratio of mother liquor / isopropanol is 1:5) is used for precipitation steps, and a purer white resin solid is obtained after filtration. The obtained white resin solid is washed with methanol to remove impurities and isopropanol, and finally heated and stirred under vacuum to remove the solvent to obtain a white powder hydrocarbon resin polymer. It is repeatedly redissolved in tetrahydrofuran to form another mother liquor and isopropanol (the weight ratio of mother liquor / isopropanol is 1:5) is used for precipitation steps, and a purer white resin solid is obtained after filtration. The obtained white resin solid is washed with methanol to remove impurities and isopropanol, and finally heated and stirred under vacuum to remove the solvent to obtain a white powder hydrocarbon resin polymer as hydrocarbon resin polymer 18. Hydrocarbon resin polymer 19

[0099] Reaction Procedure

[0100] 20 g (100 mol%) of dicyclopentadiene and 10.93 g of toluene were added to a 100 mL three-necked reactor under nitrogen, and stirred with a stirring bar set at a stirring speed of 400 rpm to form a mixture. 0.43 g of boron trifluoride diethyl ether complex (the molar ratio of boron trifluoride diethyl ether complex: mixture was 0.4:20) was injected at a time at a reaction temperature of 25° C. After a reaction time of 4.5 hours, 1.39 g of isopropanol was added to terminate the polymerization reaction to obtain a polymer mother solution.

[0101] Purification procedures

[0102] The stirring speed was set to 400 rpm, and the polymer mother solution was slowly dripped into 5 times the weight of isopropanol through a dropping funnel to obtain a yellow resin crude product. The solid-liquid phase was filtered by suction to obtain a yellow solid. The obtained light yellow solid was washed with methanol to remove impurities and isopropanol, and finally heated at 60° C. under vacuum to remove the solvent, to obtain a yellow powder hydrocarbon resin polymer as hydrocarbon resin polymer 19. The yield was about 6%. Hydrocarbon resin polymer 20

[0103] Reaction Procedure

[0104] 20 g (55.6 mol%) of styrene, 20 g (44.4 mol%) of divinylbenzene (purity 63%, the remaining 37% is ethylstyrene), and 520.2 g of toluene were added to a 1000 mL five-necked straight jacket reactor under nitrogen, and stirred with a four-blade flat paddle with a stirring speed set at 400 rpm to form a mixture. 2.185 g of boron trifluoride diethyl ether complex (the molar ratio of boron trifluoride diethyl ether complex: mixture is 0.88:20) was injected at a reaction temperature of 20°C using a syringe pump at a rate of 0.25 mL / min. After a reaction time of 3 hours, 11.8 g of isopropanol was added to terminate the polymerization reaction to obtain a polymer mother liquor.

[0105] Purification procedures

[0106] First, the polymer mother liquor was diluted with 260 g of toluene. The polymer mother liquor was stirred using a mechanical stirrer at a speed of 500 rpm. The polymer mother liquor was slowly dripped into 5 times the weight of isopropanol through a dropping funnel to obtain a pale yellow crude resin product. The solid-liquid phase was filtered by suction to obtain a pale yellow solid. The obtained pale yellow solid was washed with methanol to remove impurities and isopropanol, and finally heated at 60° C. under nitrogen to remove the solvent, to obtain a pale yellow powder hydrocarbon resin polymer as hydrocarbon resin polymer 20. The yield was about 40%. Hydrocarbon resin polymer 21

[0107] Reaction Procedure

[0108] 15 g (100 mol%) of divinylbenzene (purity 63%, the remaining 37% is ethylstyrene) and 30 g of toluene are added to a 250 mL round bottom flask under nitrogen at 25°C to obtain a mixture. 1.0 g of boron trifluoride diethyl ether complex (the molar ratio of boron trifluoride diethyl ether complex: mixture is 0.12:20) is added at a reaction temperature of 10°C, at which point the mixture will immediately change from colorless to yellow. The mixture is stirred at 10°C for 20 minutes, and then 1 mL of isopropanol is added to terminate the polymerization reaction to obtain a polymer mother solution.

[0109] Purification procedures

[0110] The light yellow polymer solution was precipitated from isopropanol (500 mL) to obtain a white powder. The obtained white powder was then dried at 60° C. for 3 hours to obtain 9.8 g of hydrocarbon resin polymer 21. The yield was about 65%. Hydrocarbon resin polymer 22

[0111] Reaction Procedure

[0112] 15 g (100 mol%) of styrene and 30 g of toluene were added to a 250 mL round bottom flask under nitrogen at 25° C. to obtain a mixture. 1.0 g of boron trifluoride diethyl ether complex (the molar ratio of boron trifluoride diethyl ether complex: mixture was 0.2:20) was added at a reaction temperature of 10° C., at which point the mixture immediately changed from colorless to yellow. The mixture was stirred at 10° C. for 30 minutes, and then 1 mL of isopropanol was added to terminate the polymerization reaction to obtain a polymer mother solution.

[0113] Purification procedures

[0114] The light yellow polymer solution was precipitated from isopropanol (500 mL) to obtain a white powder. The obtained white powder was then dried at 60° C. for 3 hours to obtain 8.3 g of hydrocarbon resin polymer 22. The yield was about 55%. Hydrocarbon resin polymer 23

[0115] Reaction Procedure

[0116] 40 g (100 mol%) of dicyclopentadiene and 10 g of toluene were added to a 250 mL round bottom flask under nitrogen at 25° C. to obtain a mixture. 0.42 g of boron trifluoride diethyl ether complex (the molar ratio of boron trifluoride diethyl ether complex: mixture was 0.2:20) was added, and the mixture immediately changed from colorless to brown. The mixture was stirred at 25° C. for 24 hours, and then 1 mL of isopropanol was added to terminate the polymerization reaction to obtain a polymer mother solution.

[0117] Purification procedures

[0118] The brown polymer solution was precipitated from isopropanol (250 mL) to obtain a brown-orange powder. The brown-orange powder was then dried at 60°C for 3 hours to obtain 20.0 g of hydrocarbon resin polymer 23. The yield was about 50%. Hydrocarbon resin polymer 24

[0119] Reaction Procedure

[0120] 19.2 g (60 mol%) of styrene, 3.6 g (40 mol%) of divinylbenzene (purity 63%, the remaining 37% is ethylstyrene), and 30 g of toluene are added to a 250 mL round-bottom flask under nitrogen to obtain a mixture. 0.7 g of boron trifluoride diethyl ether complex (the molar ratio of boron trifluoride diethyl ether complex: mixture is 0.46:20) is added at a reaction temperature of 10° C., and the mixture will immediately change from colorless to light yellow. The mixture is stirred at 10° C. for 30 minutes, and then 1 mL of isopropanol is added to terminate the polymerization reaction to obtain a polymer mother liquor.

[0121] Purification procedures

[0122] The light yellow polymer solution was precipitated from isopropanol (500 mL) to obtain a white powder. The obtained white powder was then dried at 60° C. for 3 hours to obtain 14.8 g of hydrocarbon resin polymer 24. The yield was about 65%. Hydrocarbon resin polymer 25

[0123] Reaction Procedure

[0124] 8.4g (20mol%) of dicyclopentadiene, 19.9g (60mol%) of styrene, 10.1g (20mol%) of p-isopropenyl-α-methylstyrene (IPAM S) and 100g of toluene were added to a 250mL round-bottomed flask under nitrogen to obtain a mixture. 0.36g of boron trifluoride diethyl ether complex (boron trifluoride diethyl ether complex: the molar ratio of the mixture is 0.16:20) was added, and the mixture was immediately changed from colorless to yellow. The mixture was stirred at 20°C for 3 hours, and 1mL of isopropanol was then added to terminate the polymerization reaction to obtain a polymer mother liquor.

[0125] Purification procedures

[0126] The yellow polymer solution was precipitated from isopropanol (600 mL) to obtain a white powder. The obtained white powder was then dried at 60° C. for 3 hours to obtain 18.7 g of hydrocarbon resin polymer 25. The yield was about 48.58%. Hydrocarbon resin polymer 26

[0127] Reaction Procedure

[0128] 25.38 g (20 mol%) of dicyclopentadiene, 68.07 g (60 mol%) of methylstyrene, 25 g (20 mol%) of divinylbenzene (purity 63%, the remaining 37% is ethylstyrene), and 320 mL of toluene were added to a 1 L four-neck straight jacket reactor under nitrogen, and stirred using a single-layer four-blade flat paddle with a stirring speed set at 400 rpm to form a mixture. 2.73 g of boron trifluoride diethyl ether complex (the molar ratio of boron trifluoride diethyl ether complex: mixture is 0.4:20) was injected at a reaction temperature of 0°C using a syringe pump at a rate of 0.25 mL / min. After the addition of the boron trifluoride diethyl ether complex, the reaction temperature was raised to 23°C, and after a reaction time of 3 hours, 8.1 g of isopropanol was added to terminate the polymerization reaction to obtain a colorless polymer mother liquor.

[0129] Purification procedures

[0130] First, the polymer mother liquor is filtered to remove impurities and insolubles. The polymer mother liquor is stirred using a mechanical stirrer at a speed of 500 rpm. The polymer mother liquor is slowly dripped into 5 times the weight of isopropanol through a dropping funnel to obtain a white resin crude product. The solid-liquid phase is filtered by vacuum to obtain a white solid. Then it is repeatedly dissolved in toluene to form another mother liquor and isopropanol (the weight ratio of mother liquor / isopropanol is 1:5) is used for precipitation steps, and a purer white resin solid is obtained after filtration. The obtained white resin solid is washed with methanol to remove impurities and isopropanol, and finally heated and stirred under vacuum to remove the solvent to obtain a white powder hydrocarbon resin polymer as hydrocarbon resin polymer 26. Hydrocarbon resin polymer 27

[0131] Reaction Procedure

[0132] 9 g (44 mol%) of norbornene (NB), 9.93 g (43 mol%) of styrene, 3.73 g (13 mol%) of divinylbenzene (purity 63%, the remaining 37% is ethylstyrene), and 30 mL of toluene were added to a 1 L three-neck straight jacket reactor under nitrogen, and stirred with a stirring bar set at a stirring speed of 400 rpm to form a mixture. 0.61 g of boron trifluoride diethyl ether complex (the molar ratio of boron trifluoride diethyl ether complex: mixture is 0.4:20) was injected using a syringe pump at a reaction temperature of 0°C. After the addition of boron trifluoride diethyl ether complex, the reaction temperature was maintained at 0°C, and after a reaction time of 2 hours, the reaction temperature was raised to 23°C, and tetrahydrofuran was added at a reaction time of 2 hours to terminate the polymerization reaction to obtain a colorless polymer mother liquor.

[0133] Purification procedures

[0134] First, the polymer mother liquor is filtered to remove impurities and insolubles. The polymer mother liquor is stirred using a mechanical stirrer at a speed of 500 rpm. The polymer mother liquor is slowly dripped into 5 times the weight of isopropanol through a dropping funnel to obtain a white resin crude product. The solid-liquid phase is filtered by vacuum to obtain a white solid. Then it is repeatedly redissolved in tetrahydrofuran to form another mother liquor and isopropanol (the weight ratio of mother liquor / isopropanol is 1:5) is used for precipitation steps, and a purer white resin solid is obtained after filtration. The obtained white resin solid is washed with methanol to remove impurities and isopropanol, and finally heated and stirred under vacuum to remove the solvent to obtain a white powder hydrocarbon resin polymer as hydrocarbon resin polymer 27.

[0135] The above-mentioned materials for preparing hydrocarbon resin polymers 1 to 27 and their proportions (based on the sum of DCPD, monovinyl aromatic compounds, and divinyl aromatic compounds or NB, monovinyl aromatic compounds, and divinyl aromatic compounds as 100 mol%) are listed in the following Table 1, and their reaction time, reaction temperature, and the content of fluorine-containing compound (boron trifluoride diethyl ether complex) are listed in the following Table 2. Table 1 Table 2 Hydrocarbon resin polymer No. Reaction temperature (℃) Reaction time Fluorinated compound content 1 10 3 hours 2 2 10 3 hours 2 3 20 5.5 hours 1 4 10 2 hours 2 5 20 4.5 hours 1 6 20 5.5 hours 1 7 20 6.5 hours 1 8 20 2 hours 0.5 9 20 2.5 hours 0.5 10 20 3 hours 0.5 11 20 4 hours 0.5 12 20 4.5 hours 0.5 13 20 1.5 hours 4 14 70 3 hours 2 15 10-15 2 hours 2 16 0 2 hours 2 17 0 2 hours 2 18 0 2 hours 2 19 25 4.5 hours 2 20 20 3 hours 4.4 21 10 20 minutes 1 22 10 30 minutes 1 23 25 24 hours 1 24 10 30 minutes 1 25 20 3 hours 0.8 26 0-23 3 hours 1 27 0-23 4 hours 2

[0136] The fluorine-containing compound content listed in the above Table 2 is based on the total of the raw materials listed in Table 1 being 100 moles, and the molar ratio of the total of the raw materials listed in Table 1: the fluorine-containing compound. For example, the fluorine-containing compound content of hydrocarbon resin polymer 1 in Table 2 is 2, which means that the molar ratio of the total of D CPD, monovinyl aromatic compound, and divinyl aromatic compound of hydrocarbon resin polymer 1 listed in Table 1: the fluorine-containing compound is 100:2. [Structural analysis of hydrocarbon resin polymers 1 to 27]

[0137] Using a nuclear magnetic resonance device (Nuclear Magnetic Resonance, NMR, JEOL, JNM-ECZ400 S), 13 C-NMR and 1 H-NMR was used to analyze the structural composition of hydrocarbon resin polymers 1 to 27, and it was found that hydrocarbon resin polymers 1 to 27 included repeating units (A) derived from dicyclopentadiene, repeating units (B) derived from monovinyl aromatic compounds, and repeating units (C) derived from divinyl aromatic compounds. Table 3 discloses the content of repeating unit (A), the content of repeating unit (B), the content of repeating unit (C), and the total content of repeating unit (A) and repeating unit (C) in hydrocarbon resin polymers 1 to 13 and 15 to 24, based on the total content of repeating unit (A), the content of repeating unit (B), and the content of repeating unit (C) being 100 mol%. Table 3 [Measurement of physical / chemical properties of hydrocarbon resin polymers 1 to 27] [Measurement of hydrogen content on reactive double bonds]

[0138] The hydrocarbon resin polymers 1 to 27 were dissolved in deuterated chloroform (CHCl3), respectively. The hydrogen contents on the reactive double bonds of the hydrocarbon resin polymers 1 to 27 were measured by NMR (JEOL, JNM-ECZ400S / L1). Specifically, the hydrogen contents on the reactive double bonds were calculated by dividing the sum of the integrated values ​​of hydrogen on the reactive double bonds by the sum of the integrated values ​​of all hydrogen. [Number average molecular weight (Mn) and polymer dispersity index ( index,PD I) measurement]

[0139] The number average molecular weight (Mn) and polymer dispersibility index (PDI) of hydrocarbon resin polymers 1 to 27 were measured by gel permeation chromatography (GPC) (Waters APC, column: Waters Acquity XT 900) using polystyrene as a standard.

[0140] Specifically, 5 mL of tetrahydrofuran (THF) was added to 0.01 g of hydrocarbon resin polymers 1 to 27 to prepare samples of hydrocarbon resin polymers 1 to 27. The samples of hydrocarbon resin polymers 1 to 27 were filtered with a 0.22 μm filter and then analyzed by instrument to obtain the number average molecular weight (Mn) and polymer dispersibility index (PDI) of hydrocarbon resin polymers 1 to 27.

[0141] [Measurement of cross-linkable repeating unit content (C1)]

[0142] The structures of hydrocarbon resin polymers 1 to 27 were analyzed by NMR (JEOL, JNM-E CZ400 S / L 1) and GPC (waters), CDCl3 was used as a solvent, and the resonance line of CDCl3 was used as an internal standard to obtain the content of crosslinkable repeating units (C1) in hydrocarbon resin polymers 1 to 27.

[0143] The number average molecular weight (Mn), polymer dispersibility index (PDI), hydrogen content on reactive double bonds, and crosslinkable repeating unit content (C1) of hydrocarbon resin polymers 1 to 27 are listed in Table 4 below. Table 4

[0144] [Electrical performance test of hydrocarbon resin polymer]

[0145] 20 g of hydrocarbon resin polymers 1, 2, 4, 13, 15, 16, 17, and 20 were dissolved in 20 g of toluene to form a mixture. The mixture was stirred until the hydrocarbon resin polymer was completely dissolved to form hydrocarbon resin polymer solutions 1, 2, 4, 13, 15, 16, 17, and 20. Glass fiber cloth (As ahi 2116, Dk / D f = 3.3 / 0.0030 at 28 GHz) was immersed in the hydrocarbon resin polymer solutions 1, 2, 4, 13, 15, 16, 17, and 20 for about 16 hours, then taken out and baked at 170° C. for 10 minutes to form samples 1, 2, 4, 13, 15, 16, 17, and 20. The weight of the sample was measured using network analyzer software (network analyzer Keysight, P 5007A, S CR). The dielectric constant / loss factor (Dk / Df) and RC% at 28 GHz are listed in the following Table 5. RC% here represents the resin content. RC% = (weight after baking - weight of glass fiber cloth) / weight after baking * 100%. Table 5 [Measurement of fluorine substituent content]

[0146] Preparation of internal standard solution: Dissolve 2.9 mg of trifluorotoluene (TFT, internal standard) in 4507.9 mg of CDCl3 to prepare internal standard solution (TFT content is 0.0643%)

[0147] Sample preparation: 5 g of hydrocarbon resin polymers 1 to 27 were added to the above internal standard solution to about 1.1 g, and ultrasonically vibrated for 10 minutes. After the hydrocarbon resin polymers 1 to 27 were dissolved, the samples were transferred to an NMR tube (NMR tube, JE OL / JNM-ECZ400 S / L 1) and analyzed at 25°C to obtain the hydrocarbon resin polymers 1 to 27. 19 F NMR spectrum.

[0148] According to the obtained 19 The content of fluorine substituents in hydrocarbon resin polymers 1 to 27 was calculated using the following formula: Fluorine Substituent Content The integral value of fluoride ion is obtained 19 In the F NMR spectrum, the sum of the areas of all peaks in the range of -125 ppm to -230 ppm.

[0149] For example, Figure 2 It is a hydrocarbon resin polymer 1519 F NMR spectrum. The content of fluorine substituents in hydrocarbon resin polymer 15 is based on Figure 2 Shown 19 The above calculation was used to obtain the integral value of fluoride ion by calculating the sum of the areas of all peaks in the range of -125 ppm to -230 ppm in the FNMR spectrum.

[0150] The average number of fluorine substituents in the hydrocarbon resin polymers 1 to 19 is calculated based on the content of fluorine substituents in the hydrocarbon resin polymers 1 to 19 and the number average molecular weight of the hydrocarbon resin polymers 1 to 19. Specifically, the average number of fluorine substituents in each molecule of the hydrocarbon resin polymer in the present disclosure is calculated by the following formula: The average hydrocarbon resin polymer per molecule

[0151] The fluorine substituent contents of the hydrocarbon resin polymers 1 to 19 calculated above and the average number of fluorine substituents per molecule of the hydrocarbon resin polymer are shown in Table 6 below. Table 6

[0152] According to Table 6, hydrocarbon resin polymers 20, 21, 22, and 24 do not have fluorine substituents. Furthermore, hydrocarbon resin polymer 27 obtained by polymerizing norbornene instead of dicyclopentadiene also does not have fluorine substituents. It is clear that dicyclopentadiene and fluorine-containing compounds are necessary raw materials for preparing hydrocarbon resin polymers having fluorine substituents.

[0153] It can be seen from Table 5 and Table 6 that the hydrocarbon resin polymer having fluorine substituents has a lower loss factor (Df). It is obvious that the hydrocarbon resin polymer having fluorine substituents will have better electrical performance.

[0154] Further, according to Table 4, it can be seen that hydrocarbon resin polymers 1 to 19, 23, 25, and 26 all have a polymer dispersion index (PDI) of less than 22, a number average molecular weight (Mn) of 2,500 to 15,000 g / mol, and a hydrogen content on the reactive double bonds greater than 0.2%. The hydrogen content on the reactive double bonds of hydrocarbon resin polymers 1 to 19, 25, and 26 is all less than 10%. Obviously, in addition to having better electrical performance, in some embodiments, the hydrocarbon resin polymers disclosed herein may also have good thermal properties or processability. The resin composition containing the hydrocarbon resin polymers disclosed herein can form a resin layer with good peel strength. The substrate structure including the above-mentioned resin layer can have good electrical performance (dielectric properties). In some embodiments, the substrate structure including the above-mentioned resin layer can also have good thermal properties, processability, and / or reliability.

[0155] The features of the above embodiments are helpful for those with ordinary knowledge in the art to understand the present invention. Those with ordinary knowledge in the art should understand that the present invention can be used as a basis to design and change other processes and structures to achieve the same purpose and / or the same advantages of the above embodiments. Those with ordinary knowledge in the art should also understand that these equivalent substitutions do not depart from the spirit and scope of the present invention, and can be changed, replaced, or modified without departing from the spirit and scope of the present invention.

Claims

1. A hydrocarbon resin polymer comprising: a repeating unit (A) derived from dicyclopentadiene (DCPD), The hydrocarbon resin polymer has a fluorine substituent, and based on the total weight of the hydrocarbon resin polymer, the content of the fluorine substituent is 100-4500 ppm.

2. The hydrocarbon resin polymer as claimed in claim 1, wherein each molecule of the hydrocarbon resin polymer has an average of 0.02 to 2 fluorine substituents. 3 . The hydrocarbon resin polymer as claimed in claim 1 , wherein the number average molecular weight (Mn) of the hydrocarbon resin polymer is 500 to 15,000 g / mol.

4. The hydrocarbon resin polymer as claimed in any one of claims 1 to 3, wherein the molecular weight distribution index (PDI) of the hydrocarbon resin polymer is less than 22.

5. The hydrocarbon resin polymer as claimed in any one of claims 1 to 4, wherein the hydrogen content on the reactive double bonds of the hydrocarbon resin polymer is less than 10%.

6. The hydrocarbon resin polymer according to any one of claims 1 to 5, further comprising: a repeating unit (B) derived from a monovinyl aromatic compound; as well as a repeating unit (C) derived from the divinyl aromatic compound.

7. The hydrocarbon resin polymer as claimed in claim 6, wherein the content of the repeating unit (A) is 0.15-15 mol%, the content of the repeating unit (B) is 14-95 mol%, and the content of the repeating unit (C) is 4-85 mol%, based on the total of all units in the hydrocarbon resin polymer being 100 mol%.

8. The hydrocarbon resin polymer as claimed in claim 6 or 7, wherein the total content of the repeating unit (A) and the repeating unit (C) is greater than or equal to 13 mol%, based on the total content of all units in the hydrocarbon resin polymer being 100 mol%.

9. The hydrocarbon resin polymer according to any one of claims 6 to 8, wherein the repeating unit (C) comprises a cross-linkable repeating unit (C1) and a cross-linked repeating unit (C2): wherein R1, R2, R3, and R4 are each independently H or C 1-20 Alkyl, and Ar1 and Ar2 are phenylene; * represents the connection position between the cross-linkable repeating unit (C1) and / or the cross-linked repeating unit (C2) and other groups or units; and Based on 100 mol % of the total of all units in the hydrocarbon resin polymer, the content of the cross-linkable repeating unit (C1) is 1 to 30 mol %.

10. The hydrocarbon resin polymer according to any one of claims 1 to 9, wherein the hydrocarbon resin polymer 19 In the F NMR spectrum, there is a peak in the range of -125 ppm to -230 ppm.

11. A method for producing a hydrocarbon resin polymer, comprising: polymerizing a mixture in the presence of a fluorine-containing compound, The fluorine-containing compound is a boron trifluoride complex and the mixture includes dicyclopentadiene.

12. The method for producing a hydrocarbon resin polymer as claimed in claim 11, wherein the boron trifluoride complex comprises a boron trifluoride tetrahydrofuran complex. (BF3·THF), boron trifluoride methanol complex (BF3·M eOH), boron trifluoride hydrate (BF3·H2 O), boron trifluoride diethyl ether complex (BF3-O Et2), boron trifluoride anisole complex (BF3·PhOM e), boron trifluoride acetic acid complex (BF3·Ac OH), or any combination thereof. 13 . The method for producing a hydrocarbon resin polymer as claimed in claim 11 , wherein the molar ratio of the fluorine-containing compound to the mixture is 0.01 to 1:

20.

14. The method for producing a hydrocarbon resin polymer according to any one of claims 11 to 13, wherein the mixture further comprises a monovinyl aromatic compound and / or a divinyl aromatic compound.

15. The method for producing a hydrocarbon resin polymer as claimed in claim 14, wherein the content of dicyclopentadiene in the mixture is 3 to 80 mol%, the content of the monovinyl aromatic compound is 0 to 90 mol%, and the content of the divinyl aromatic compound is 0 to 50 mol%, based on the total of all components in the mixture being 100 mol%.

16. A substrate structure comprising: a resin layer, and a conductive layer disposed on the resin layer; The resin layer is formed by a resin composition through a cross-linking process, wherein the resin composition includes a hydrocarbon resin polymer having a fluorine substituent and comprising: a repeating unit (A) derived from dicyclopentadiene (DCPD), Wherein, based on the total weight of the hydrocarbon resin polymer, the content of the fluorine substituent is 100-4500 ppm. 17 . The substrate structure as claimed in claim 16 , wherein each molecule of the hydrocarbon resin polymer has an average of 0.02 to 2 fluorine substituents.

18. The substrate structure of claim 16 or 17, wherein the hydrocarbon resin polymer further comprises: a repeating unit (B) derived from a monovinyl aromatic compound; as well as a repeating unit (C) derived from the divinyl aromatic compound.

19. The substrate structure according to claim 18, wherein the content of the repeating unit (A) in the hydrocarbon resin polymer is 0.15-15 mol%, the content of the repeating unit (B) is 14-95 mol%, and the content of the repeating unit (C) is 4-85 mol%, based on the total of all units in the hydrocarbon resin polymer being 100 mol%. mol%.

20. The substrate structure as claimed in claim 18 or 19, wherein the total content of the repeating unit (A) and the repeating unit (C) in the hydrocarbon resin polymer is greater than or equal to 13 mol%, based on the total content of all units in the hydrocarbon resin polymer being 100 mol%.

21. The substrate structure of claims 18-20, wherein the repeating unit (C) comprises a cross-linkable repeating unit (C1) and a cross-linked repeating unit (C2): wherein R1, R2, R3, and R4 are each independently H or C 1-20 Alkyl, and Ar1 and Ar2 are phenylene; * represents the connection position between the cross-linkable repeating unit (C1) and / or the cross-linked repeating unit (C2) and other groups or units; and Based on 100 mol % of the total of all units in the hydrocarbon resin polymer, the content of the cross-linkable repeating unit (C1) is 1 to 30 mol %.

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