A method for preparing a soluble multifunctional olefin polymer and a hydrogenation degree-controllable soluble multifunctional olefin polymer

Abstract

This invention provides a soluble multifunctional olefin polymer and a method for preparing it with controllable hydrogenation degree. The soluble multifunctional olefin polymer with controllable hydrogenation degree exhibits excellent dielectric properties even after moisture absorption under high temperature and high humidity conditions, and also possesses a high glass transition temperature and flame retardancy. When used in the fabrication of optical waveguides or high-frequency, high-speed copper-clad laminates, it demonstrates good heat resistance, resistance to thermal decomposition, solvent solubility, processability, and compatibility with specific resins. Furthermore, pure hydrocarbons, due to their combined advantages of low dielectric constant, high heat resistance, low water absorption, and processability, have become the core resin choice for high-frequency, high-speed copper-clad laminates, especially irreplaceable in fields such as 5G / millimeter-wave and high-speed computing.

Description

Technical Field

[0001] This invention belongs to the field of new materials, specifically relating to a soluble multifunctional olefin polymer and a method for preparing it with controllable hydrogenation degree. Background Technology

[0002] With the rapid development of high-density assembly and integration technology in microelectronics, the assembly density of electronic devices has increased dramatically, and the size of electronic components and logic circuits has been reduced by tens of millions of times. At the same time, the heat generated by these devices has also increased dramatically. Under normal ambient temperatures, to ensure the long-term reliable and stable operation of electronic components, thermally conductive and insulating materials with high heat dissipation performance have become an indispensable key element in thermal design. Furthermore, for high-end applications such as high-power LEDs and power systems for new energy vehicles, even more stringent requirements are placed on the materials used to further improve system reliability and lifespan: they must simultaneously possess excellent heat resistance, resistance to thermal decomposition, solvent solubility, processability, and good compatibility with specific resins.

[0003] To meet the above needs, relevant materials are now available on the market. Mitsubishi Gas Chemical Co., Ltd. has mass-produced and commercialized a modified PPE resin (brand name OPE-2st), whose structure is similar to the vinyl benzyl-terminated structure disclosed by Panasonic Electric Works in some patents, and is specifically designed for high-speed substrates. The preparation process of this resin is as follows: first, a thermosetting small molecule PPE resin (brand name OPE) is prepared by hydroxyl (OH)-terminated PPE, and then further modified to generate a styrene derivative, namely vinyl benzyl ether polyphenylene ether, specifically for resin compositions for high-speed substrates.

[0004] Patent CN103664541A discloses an aromatic vinyl benzyl ether compound, a curable composition containing the same, and their applications. The product invented in this patent exists in the form of a resin adhesive and can be used to prepare insulating layers or films for circuit boards, as well as as a raw material for manufacturing flexible printed circuit boards, rigid PCBs, or sealing materials for semiconductor devices. However, the aforementioned existing materials suffer from insufficient performance stability after being used to fabricate optical waveguides or high-frequency, high-speed copper-clad laminates. Performance degradation is particularly severe under high-temperature and high-humidity environments, with dielectric properties showing the most significant deterioration, directly leading to a decline in product quality. Therefore, there is an urgent need in the field to develop a novel multifunctional olefin polymer that can adapt to high-temperature and high-humidity environments to overcome the performance shortcomings of existing materials.

[0005] Multifunctional olefin polymers, due to the presence of multiple active functional groups in their molecular structure, possess excellent crosslinking, mechanical, and processing properties, making them of significant application value in the field of polymer materials. Furthermore, hydrogenation-modified multifunctional olefin polymers exhibit significantly increased molecular chain saturation, effectively improving their heat resistance, weather resistance, chemical stability, and dielectric properties, thereby further broadening their application range and meeting the demands of more high-end application scenarios.

[0006] Currently, existing hydrogenation methods for multifunctional olefin polymers still face numerous bottlenecks, primarily including difficulty in precisely controlling the degree of hydrogenation, poor polymer solubility, demanding reaction conditions, and complex preparation processes. Furthermore, some hydrogenation methods utilize catalysts with low activity, requiring reactions at high temperatures and hydrogen pressures. This not only increases production costs but may also trigger polymer chain degradation, thus affecting the final product's performance. Additionally, some hydrogenated polymers prepared by other methods exhibit poor solubility in common solvents due to excessive crosslinking or inhomogeneous molecular structures, failing to meet the requirements for subsequent processing and molding.

[0007] In addition, existing technologies mostly adopt a process route of single monomer polymerization followed by hydrogenation modification, which makes it difficult to control the functional group distribution and overall performance of polymers through monomer combination, and cannot adapt to the personalized needs of different application scenarios. Summary of the Invention

[0008] In view of this, the purpose of this invention is to provide a soluble multifunctional olefin polymer and a method for preparing it with controllable hydrogenation degree. Specifically, the soluble multifunctional olefin polymer A is prepared by polymerization of a vinyl aromatic olefin compound B and a conjugated olefin compound C. The method for preparing the soluble multifunctional olefin polymer D with controllable hydrogenation degree is specifically to use soluble multifunctional olefin polymer A as a monomer, polymerizing it under a specific catalyst and in a hydrogen environment. The resulting polymer exhibits excellent dielectric properties even after moisture absorption under high temperature and high humidity conditions, and also possesses a high glass transition temperature and flame retardancy. After being used in the fabrication of optical waveguides or high-frequency, high-speed copper-clad laminates, it exhibits good heat resistance, resistance to thermal decomposition, solvent solubility, processability, and compatibility with specific resins.

[0009] To achieve this objective, the present invention adopts the following technical solution:

[0010] In a first aspect, the present invention provides a method for preparing a soluble multifunctional olefin polymer A, comprising the following steps:

[0011] The product is obtained by polymerizing a vinyl aromatic olefin compound B and an optional conjugated olefin compound C as monomers.

[0012] It should be noted that the present invention uses vinyl aromatic olefin compound B as the main component, which provides an aromatic structure to polymer A, improves the heat resistance and dielectric properties of polymer A, and introduces vinyl active sites to provide a basis for subsequent hydrogenation reaction and crosslinking modification; conjugated olefin compound C provides a conjugated double bond structure to polymer A, increases the number of functional groups in polymer A, and regulates the flexibility and solubility of polymer A.

[0013] In some embodiments of the present invention, the vinyl aromatic olefin compound B is selected from polyvinyl aromatic olefin compounds and / or monovinyl aromatic olefin compounds. The polyvinyl aromatic olefin compounds include any one or more of o-divinylbenzene, m-divinylbenzene, p-divinylbenzene, or trivinylbenzene; the monovinyl aromatic olefin compounds include any one or more of styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o-dimethylstyrene, p-dimethylstyrene, o-ethylvinylbenzene, m-ethylvinylbenzene, p-ethylvinylbenzene, vinylnaphthalene, vinyl biphenyl, m-ethylvinylbenzene, or p-ethylvinylbenzene. The conjugated olefin compound C includes any one or more of butadiene, isoprene, or cyclopentadiene.

[0014] In some preferred embodiments of the present invention, during the above polymerization reaction, the molar content of the vinyl aromatic olefin compound B is 2-98%, and the balance is compound C or a mixture thereof. More preferably, the specific selection can be: the molar content of compound B is 2-98%, such as 2%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, or 98%; the molar content of conjugated olefin compound C is 98-2%, such as 98%, 95%, 90%, 80%, 70%, 60%, 50%, 40%, 30%, 20%, 10%, or 2%.

[0015] In some preferred embodiments of the present invention, for vinyl aromatic olefin compound B, it is preferably a composition of polyvinyl aromatic olefin compound and monovinyl aromatic olefin compound. In this composition, the molar content of the polyvinyl aromatic olefin compound is 2-95%, such as 2%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, or 95%; the molar content of the monovinyl aromatic olefin compound is 5-98%, such as 98%, 95%, 90%, 80%, 70%, 60%, 50%, 40%, 30%, 20%, 10%, or 5%.

[0016] In this invention, the polymerization reaction is preferably carried out in the presence of an initiator selected from protic acids and / or Lewis acids. The protic acids include, but are not limited to, any one or more of concentrated sulfuric acid, phosphoric acid, perchloric acid, chlorosulfonic acid, fluorosulfonic acid, trichloroacetic acid, or trifluoroacetic acid. The Lewis acids include, but are not limited to, any one or more of AlCl3, BF3, SnCl4, ZnCl2, TiCl4, or SbCl5. Preferably, they are metal fluorides or complexes, such as boron trifluoride, and more preferably, a diethyl ether solution of boron trifluoride.

[0017] In this invention, the molar ratio of the total number of moles of the initiator to the total number of moles of the polymeric monomer is 8:1 to 60:1, preferably 9:1 to 50:1, and more preferably 10:1 to 40:1.

[0018] As a preferred technical solution, a trace amount of co-initiator can be added to the Lewis acid as a cation source. The amount of co-initiator is 0-1% of the weight of the initiator, such as 0%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, or 1%. The co-initiator is selected from proton donors or carbocation consortia. The proton donor is selected from any one or more of H2O, ROH, RCOOH, or HX. The carbocation consortia are selected from any one or more of RX, RCOX, or (RCO)2O.

[0019] In ROH, RCOOH, RX, RCOX, or (RCO)2O, the R is selected from substituted or unsubstituted C1-C6 alkyl groups or substituted or unsubstituted C6-C30 aromatic groups. Specifically, it can be -CH3, -C2H5, propyl, etc., or more complex aliphatic hydrocarbon groups, or phenyl groups.

[0020] The X in HX, RX, or RCOX is selected from halogens, such as fluorine (F), chlorine (Cl), bromine (Br), iodine (I), astatine (At), and thiocyanate (Ts).

[0021] In this invention, the polymerization reaction is preferably carried out in an inert gas atmosphere and in the presence of a weakly polar solvent.

[0022] The inert gas atmosphere is selected from one or more of nitrogen or inert gases (helium, argon, neon, krypton, xenon), with nitrogen or argon being preferred.

[0023] The weakly polar solvent is selected from one or more of hydrocarbon solvents, alcohol solvents, ether solvents, ketone solvents, or ester solvents. Specifically, hydrocarbon solvents mainly include some or more of alkanes, aromatic hydrocarbons, or halogenated hydrocarbons, and can be selected from one or more of cyclohexane, octane, benzene, toluene, nitrobenzene, chloromethane, dichloromethane, trichloromethane, and carbon tetrachloride; alcohol solvents mainly include long-chain alcohols, such as tert-butanol and / or octanol; ether solvents include diethyl ether; ketone solvents include acetone; and ester solvents include ethyl acetate, CS2, etc. In some embodiments of the present invention, one or more of cyclohexane, toluene, and xylene are preferably used as the reaction solvent.

[0024] In this invention, the amount of the weakly polar solvent is 5 to 25 times the total mass of the polymerized monomers, such as 5 times, 10 times, 15 times, 20 times, or 25 times.

[0025] As a preferred technical solution, after the polymerization reaction is completed, a cationic polymerization terminator is used to terminate the polymerization reaction. The cationic polymerization terminator is selected from any one or more of water, alcohol, acid, ether, amine, quinone, or salt, specifically from any one or more of saturated sodium bicarbonate aqueous solution, methanol, ethanol, water, or triethylamine. The amount of the terminator is 1 to 5 times the mass of the initiator, such as 1, 2, 3, 4, or 5 times.

[0026] In summary, in some embodiments of the present invention, the polymerization conditions for the soluble multifunctional olefin polymer A are as follows: using a protic acid and / or a Lewis acid as an initiator, using a vinyl aromatic olefin compound B and optionally a conjugated olefin compound C as monomers, the polymerization is carried out via cationic polymerization in an inert gas atmosphere and a weakly polar solvent, and the polymerization reaction is finally terminated with a cationic polymerization terminator. The temperature of the cationic polymerization reaction is -20 to 150°C, such as -20°C, -10°C, 0°C, 10°C, 30°C, 50°C, 80°C, 100°C, 120°C, or 150°C; the time is 5 min to 6 h, such as 5 min, 10 min, 20 min, 30 min, 40 min, 50 min, 1 h, 2 h, 3 h, 4 h, 5 h, or 6 h.

[0027] In this invention, the polymerization time is determined based on the molecular weight of the target polymer. Furthermore, the inventors discovered during their research that increasing the polymerization temperature can significantly shorten the polymerization time; however, this makes the polymerization process difficult to control and prone to burst polymerization. Additionally, the addition of an initiator can also affect the polymerization process. Therefore, considering various polymerization conditions, the inventors limited the aforementioned temperature and time.

[0028] It should be noted that in the above cationic polymerization reaction, the position and number of vinyl groups in the vinyl aromatic olefin compound B affect the polymerization behavior. Furthermore, due to the presence of Friedel-Crafts alkylation side reactions, the benzene ring can directly participate in the polymerization reaction, forming spherical or near-spherical polymers. The conjugated olefin compound C is a linear polymer. Therefore, depending on the adjustment of the polymerization process, one or more of the following can be selected to prepare BB-type, BCB-type, or CBC-type soluble multifunctional olefin polymers A: BB-type, CBC-type, and BCB-type. Specifically, BB-type is a multifunctional spherical polymer, CBC-type is a ball-and-stick structure polymer, and BCB-type is a variable ball-and-stick structure polymer.

[0029] Meanwhile, based on the aforementioned properties of vinyl aromatic olefin compound B, the polymerization of a single vinyl aromatic olefin compound B yields a compound with high rigidity; the higher the glass transition temperature, the worse the toughness of the compound. Therefore, the inventors creatively introduced a conjugated olefin compound C containing olefin bonds, wherein the conjugated olefin compound C is a conjugated olefin, and after the polymerization of compound B, some unreacted functional groups remain. Through further polymerization, the unreacted double bonds are opened, and a polymerization reaction is carried out with the conjugated olefin of the conjugated olefin compound C, incorporating linear compound long chains onto a rigid spherical or near-spherical structure. The linear length increases with the increase of incorporated structural units. When a certain length is reached, spherical or near-spherical vinyl aromatic olefin compounds B are then incorporated, forming a ball-and-stick structure polymer A. This polymer A not only possesses the rigidity of vinyl aromatic olefin compound B but also the flexibility of compound C, and its toughness is increased. The glass transition temperature of polymer A is lowered, and the dielectric constant (Dk) of polymer A does not change significantly under normal conditions and after high temperature and high humidity treatment. The dielectric loss tangent Df (×10) is also lower. -3 The change rate after normal conditions and high temperature and high humidity treatment is between 0.5% and 2%.

[0030] Characterization showed that the number-average molecular weight of the soluble polyfunctional olefin polymer A obtained by the above method was 100 to 100,000, and the ratio of its weight-average molecular weight to its number-average molecular weight, i.e., the molecular weight distribution was below 100. Furthermore, the soluble polyfunctional olefin polymer A was soluble in toluene, xylene, tetrahydrofuran, dichloroethane, or chloroform.

[0031] Secondly, the present invention also provides a method for preparing a soluble multifunctional olefin polymer D with controllable hydrogenation degree, comprising the following steps:

[0032] The soluble multifunctional olefin polymer A prepared by the above method is used as a monomer and polymerized in a catalyst and hydrogen environment to obtain the final product.

[0033] In this invention, the catalyst is selected from any one or more of nickel naphthenate, triisobutylaluminum, Raney nickel, metallocene catalyst or n-butyllithium; the amount of the catalyst is 0.05-3% of the mass of the soluble polyfunctional olefin polymer, such as 0.05%, 0.1%, 0.5%, 0.8%, 1%, 1.5%, 2%, 2.5% or 3%, etc.

[0034] In some preferred embodiments of the present invention, a compound catalyst is typically used. For example, nickel naphthenate can be compounded with triisobutylaluminum, and the molar ratio of nickel naphthenate to triisobutylaluminum is 1:2.5 to 7, such as 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5, 1:5, 1:5.5, 1:6, 1:6.5, or 1:7, etc.; metallocene catalysts can be compounded with n-butyllithium, and the molar ratio of n-butyllithium to metallocene catalyst is 4:1 to 20:1, such as 4:1, 6:1, 8:1, 10:1, 12:1, 14:1, 16:1, 18:1, or 20:1. More preferably, the catalyst is a composite system of nickel naphthenate and triisobutylaluminum, with a molar ratio of 1:3 to 5. This composite catalyst exhibits high selectivity and activity, enabling precise hydrogenation of the conjugated double bonds in polymer A without affecting other functional groups such as the benzene ring. It also enhances the stability of the hydrogenation reaction, ensuring controllable hydrogenation degree. In this invention, the composite catalyst can first undergo a complexation reaction and aging treatment. The complexation reaction temperature is 45 to 65°C, preferably 50 to 55°C, and the reaction time is 5 to 20 min, preferably 10 to 15 min. The aging temperature is 50 to 70°C, preferably 55 to 65°C, and the aging time is 20 to 60 min, preferably 30 to 50 min, further enhancing the catalyst's activity and stability and optimizing the hydrogenation effect.

[0035] The pressure of the hydrogenation environment is 0.5~5 MPa, preferably 1~3 MPa; the temperature of the polymerization reaction is 60~80℃, preferably 65~70℃; and the time of the polymerization reaction is 1~4 h, preferably 2~3 h. Under these conditions, the hydrogenation reaction rate is moderate, the degree of hydrogenation is easier to control, and it will not cause cross-linking or degradation of polymer D.

[0036] It should be noted that the preparation method of the soluble multifunctional olefin polymer D with controllable hydrogenation degree also needs to be carried out in the presence of a weakly polar solvent. The selection of the weakly polar solvent is as described in the relevant content in the "First Aspect" above, and will not be repeated here.

[0037] In summary, this invention provides two parts: a method for preparing a soluble multifunctional olefin polymer, and a method for preparing the polymer with controllable hydrogenation degree. Specifically, the soluble multifunctional olefin polymer A is prepared by polymerizing a vinyl aromatic olefin compound B and a conjugated olefin compound C. The method for preparing the soluble multifunctional olefin polymer D with controllable hydrogenation degree is specifically to polymerize the soluble multifunctional olefin polymer A as a monomer under a specific catalyst and in a hydrogen atmosphere. The resulting soluble multifunctional olefin polymer D with controllable hydrogenation degree exhibits excellent dielectric properties even after moisture absorption under high temperature and high humidity conditions, and also possesses a high glass transition temperature and flame retardancy. When used in the fabrication of optical waveguides or high-frequency, high-speed copper-clad laminates, it exhibits good heat resistance, resistance to thermal decomposition, solvent solubility, processability, and compatibility with specific resins. Furthermore, thanks to its comprehensive advantages of low dielectric constant, high heat resistance, low water absorption, and process-friendly properties, this polymer has become the core resin matrix for high-frequency and high-speed copper-clad laminates, and has irreplaceable application value in high-end fields such as 5G / millimeter wave and high-speed computing.

[0038] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0039] This invention provides a method for preparing a soluble polyfunctional olefin polymer, which is obtained by polymerizing a vinyl aromatic olefin compound and optionally a conjugated olefin compound. The soluble polyfunctional olefin polymer has a number average molecular weight of 100-100,000, and the ratio of weight average molecular weight to number average molecular weight (Mw / Mn) is less than 100. Furthermore, the polymer is soluble in toluene, xylene, tetrahydrofuran, dichloroethane, or chloroform.

[0040] Furthermore, by using the aforementioned soluble multifunctional olefin polymer as a monomer for hydrogenation polymerization, and by controlling the hydrogen pressure, reaction temperature, reaction time, and catalyst dosage of the hydrogenation reaction, the degree of hydrogenation of the polymer can be precisely controlled between 30% and 99%. This allows for the preparation of polymer products with different degrees of hydrogenation according to the needs of different application scenarios, adapting to the performance requirements of different fields such as copper clad laminates and electronic packaging.

[0041] Therefore, by selecting appropriate monomer combinations, polymerization conditions, and post-treatment methods, this invention prepares polymers A and D, both of which exhibit good solubility and can dissolve in common weakly polar solvents, facilitating subsequent processing and molding. This solves the technical problem of poor solubility in existing hydrogenated polymers. Furthermore, the polymer's solubility allows for better compatibility with other resin systems in applications such as high-frequency, high-speed copper-clad laminates, improving the dielectric and processing properties of the materials. Attached Figure Description

[0042] Figure 1Polymer A obtained in Example 5 (i.e., Figure 1 SBS in Example 6), and the medium-hydrogenated soluble multifunctional olefin polymer D2 obtained in Example 6 (i.e., SBS in Example 6), Figure 1 SEBS (HD=51%) in Example 7 and the medium-hydrogenated soluble multifunctional olefin polymer D3 obtained in Example 7 (i.e., Figure 1 The 1H NMR spectrum of SEBS (HD=92%). Detailed Implementation

[0043] The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0044] To further illustrate the present invention, the following embodiments provide a detailed description. Unless otherwise specified, the experimental materials used in the following embodiments of the present invention are all commercially available products.

[0045] High humidity treatment conditions: Samples were treated at 85% relative humidity for 2 weeks before measurement. High temperature treatment conditions: Samples were placed at 140℃ in air for 168 hours before measurement.

[0046] Example 1

[0047] A method for preparing a soluble polyfunctional cyclic olefin polymer A, comprising the following specific steps:

[0048] A mixture of 0.217 mol styrene, 0.547 mol divinylbenzene, and a purified 0.497 mol toluene solution was thoroughly mixed and purified by filtration using alkaline alumina. 0.397 mol toluene was added to the reactor, and 0.00977 mol boron trifluoride was added as a polymerization catalyst at 70°C. The purified mixture was then added back to the reactor for polymerization, with the polymerization temperature maintained at 70-90°C and the polymerization time controlled at 1 h. The polymerization was terminated with a saturated sodium bicarbonate aqueous solution. After termination, the solution was washed with acetone and filtered. The filtered clear liquid was then deashed to obtain polymer A.

[0049] The resulting polymer had Mn=9373, Mw=12558, and PDI=9.757, and was obtained through... 13 C-NMR and 1¹H-NMR analysis revealed that the content of divinyl structural units was 34.2 mol%, vinyl structural units were 11.4 mol%, and styrene structural units were 54.4 mol%. Furthermore, the obtained polymer A was soluble in toluene, xylene, tetrahydrofuran, dichloroethane, dichloromethane, and deuterated chloroform, without any gelation, and the resulting solution was colorless and transparent. DMA determination showed a glass transition temperature (Tg) of 203 °C, and TGA analysis showed a weight loss of 2.84 wt% at 350 °C.

[0050] Example 2

[0051] A method for preparing a soluble polyfunctional cyclic olefin polymer A, comprising the following specific steps:

[0052] A mixture of 0.326 mol styrene, 0.106 mol divinylbenzene, and 0.284 mol purified toluene solution was thoroughly mixed and purified by filtration with alkaline alumina. 0.237 mol toluene and 0.544 mol acetone were added to a reactor, and 0.00977 mol boron trifluoride was added as a polymerization catalyst at 70°C. The purified mixture was then added to the reactor for polymerization, with the polymerization temperature controlled at 70–90°C and the polymerization time controlled at 10–30 min. After 1 h of polymerization, the polymerization was terminated using a saturated sodium bicarbonate aqueous solution. After termination, the solution was washed with acetone and methanol, then filtered. The filtered clear liquid was deashed to obtain polymer A.

[0053] The obtained polymer had Mn=3471, Mw=48420, and PDI=13.95. Furthermore, 13C-NMR and 1H-NMR analyses revealed a content of 31.2 mol% of divinyl structural units, 13.4 mol% of vinyl structural units, and 55.4 mol% of styrene structural units. The obtained polymer was soluble in toluene, xylene, tetrahydrofuran, dichloroethane, dichloromethane, and deuterated chloroform, without any gelation, and the resulting solutions were colorless and transparent. DMA determination showed a glass transition temperature (Tg) of 197℃, and TGA analysis showed a weight loss of 2.24 wt% at 350℃.

[0054] Example 3

[0055] A method for preparing a soluble polyfunctional cyclic olefin polymer A, comprising the following specific steps:

[0056] A mixture of 0.326 mol styrene, 0.106 mol divinylbenzene, and a purified 0.284 mol toluene solution was thoroughly mixed and purified by filtration using alkaline alumina (excluding polymerization inhibitors). 0.237 mol toluene and 0.544 mol acetone were added to a reactor, and 0.00977 mol boron trifluoride was added at 30°C as a polymerization catalyst. The purified mixture was then added to the reactor for polymerization, with the polymerization time controlled between 10 and 30 minutes. After 1 hour of polymerization, the polymerization was terminated using a saturated sodium bicarbonate aqueous solution. After termination, the solution was washed with acetone and methanol, then filtered. The filtered clear liquid was deashed to obtain polymer A.

[0057] The resulting polymer had Mn=4965, Mw=8510, and PDI=1.714. Furthermore, it was obtained through... 13 C-NMR and 1 ¹H-NMR analysis revealed that the content of divinyl structural units was 22.7 mol%, vinyl structural units were 9.3 mol%, and styrene structural units were 68 mol%. The obtained polymer was soluble in toluene, xylene, tetrahydrofuran, dichloroethane, dichloromethane, and deuterated chloroform, without any gelation, and the resulting solution was colorless and transparent. DMA determination showed a glass transition temperature (Tg) of 158 °C, and TGA analysis showed a weight loss of 17.3 wt% at 350 °C.

[0058] Example 4

[0059] A method for preparing a soluble polyfunctional cyclic olefin polymer A, comprising the following specific steps:

[0060] A mixture of 0.22 mol styrene, 0.053 mol divinylbenzene, and a purified 0.53 mol toluene solution was thoroughly mixed and purified by alkaline alumina before being fed into reactor A. 0.4 mol toluene and acetone were added to reactor B. 0.01 mol boron trifluoride was added as a polymerization catalyst at 70°C. The purified mixture was then added to reactor B. Simultaneously, 0.36 mol butadiene and reactor A were injected into reactor B. The polymerization temperature was maintained at 70–90°C, and the polymerization time was controlled at 20 min. After 40–60 min of polymerization, the polymerization was terminated using a saturated sodium bicarbonate aqueous solution. After termination, the solution was washed with water and filtered. The filtered clear liquid was then deashed to obtain polymer A.

[0061] The obtained polymers had Mn=4569, Mw=43741, and PDI=6.32. Furthermore, 13C-NMR and 1H-NMR analyses revealed a content of 28.3 mol% for divinyl structural units, 18.5 mol% for vinyl structural units, and 53.2 mol% for styrene structural units. The obtained polymers A and C were soluble in toluene, xylene, tetrahydrofuran, dichloroethane, dichloromethane, and deuterated chloroform, without any observed gelation, and the resulting solutions were colorless and transparent. DMA measurements showed a glass transition temperature (Tg) of 182℃, and TGA measurements showed a weight reduction of 2.1 wt% at 350℃. This is attributed to the structural alteration of polymer A due to the addition of butadiene, which lowered its glass transition temperature.

[0062] The dielectric constant (Dk) of polymer A obtained after introducing compound C did not change significantly under normal conditions and after high temperature and high humidity treatment. The dielectric loss tangent Df (×10) -3 The change rate after normal conditions and high temperature and humidity treatment is between 0.5% and 1.5%, while the dielectric loss tangent Df (×10) of polymer A prepared solely from compound B is much higher. -3 The change rate after normal conditions and high temperature and high humidity treatment is 2-6%. It can be seen that the change rate of dielectric loss tangent of polymer A obtained after introducing compound C is significantly lower than that of polymer A prepared solely by compound B, which ensures the dielectric requirements and thermal stability of polymer A obtained after introducing compound C under high temperature and high humidity conditions.

[0063] Comparative Example 1

[0064] A vinyl aromatic copolymer from Nippon Steel Chemical Materials Co., Ltd. was used as a control. This vinyl aromatic copolymer, when tested, contained 33.1% divinyl aromatic compounds, 14.2% styrene aromatic compounds, and 52.7% styrene by molar percentage. The glass transition temperature of the polymer in Comparative Example 1 was tested to be 186.6℃; the change rate of Dk before and after the heat treatment was not significant, but the change rate of Df after the damp heat treatment was 2.4%.

[0065] Performance testing

[0066] The mechanical properties of the polymers obtained in Examples 1-4 and Comparative Example 1 were tested using the following methods:

[0067] Tensile properties such as tensile stress, tensile strain, and elastic modulus should be referenced to GB / T 1040 series (Determination of tensile properties of plastics).

[0068] The impact strength of simply supported beams without notches is referenced in GB / T 1043.1-2008.

[0069] The test results are shown in Table 1:

[0070] Table 1

[0071]

[0072] Table 1 shows that the different styrene contents in Examples 1-3 resulted in significant differences in the rigidity of the polymer molecular weight after polymerization, leading to substantial differences in elastic modulus. Example 4, with the incorporation of linear molecular chains, exhibited increased chain flexibility and thus the lowest elastic modulus. Physical properties indicate that the introduction of compound C improved the material's physical properties to some extent under high temperature and humidity conditions, and the dielectric loss tangent Df (×10) was also reduced. -3 The change rate after normal conditions and high temperature and humidity treatment is between 0.5% and 1.5%, which can meet the requirements of high-speed copper-clad laminates for low dielectric properties and dielectric characteristics after a humid heat process, thus increasing their service life. As can be seen from the comparison of the examples and comparative examples, changes in molecular structure lead to changes in performance.

[0073] Example 5 - Preparation of soluble multifunctional olefin polymers with low hydrogenation degree (30%-40%)

[0074] Step 1: Preparation of Polymer A: Styrene and butadiene were used as monomers in a molar ratio of 1:0.5; boron trifluoride was used as the initiator, with an amount of 0.1% of the total mass of the monomers; nitrogen was used as the inert gas; a mixed solvent of cyclohexane and toluene (volume ratio 1:1) was used as the weakly polar solvent, with an amount of 5 times the total mass of the monomers; the polymerization temperature was controlled at 0℃, and the polymerization time was 4 h; after the reaction was completed, methanol (terminant, with an amount of 1 times the mass of the initiator) was added to terminate the polymerization, yielding soluble polyfunctional olefin polymer A, whose 1H NMR spectrum is shown below. Figure 1 .

[0075] Step 2: Preparation of Polymer D: Using Polymer A prepared in Step 1 as raw material, a complex system of nickel naphthenate and triisobutylaluminum (molar ratio 1:3) was selected as the catalyst. The complex catalyst was first subjected to a complexation reaction at 45℃ for 20 min, and then aged at 50℃ for 60 min. The amount of catalyst used was 0.05% of the mass of Polymer A. The weakly polar solvent was the same as in Step 1, and the amount used was 8 times the mass of Polymer A. The hydrogen pressure was controlled at 0.5 MPa, the hydrogenation temperature was 60℃, and the hydrogenation time was 1 h. After the reaction was completed, the mixture was cooled to room temperature, anhydrous ethanol was added to precipitate the polymer, and the catalyst residue and impurities were removed by filtration to obtain a low-hydrogenation soluble multifunctional olefin polymer D1.

[0076] Example 6 - Preparation of soluble multifunctional olefin polymers with medium hydrogenation degree (50%-70%)

[0077] Preparation of Polymer D: Using Polymer A prepared in Step 1 of Example 5 as the raw material, a nickel naphthenate and triisobutylaluminum complex catalyst (complex molar ratio 1:4) was selected. The complex catalyst was first subjected to a complexation reaction at 55°C for 30 min, followed by aging at 60°C for 60 min. The catalyst dosage was 1.5% of the mass of Polymer A. The weakly polar solvent was the same as in Step 1, and the dosage was 16 times the mass of Polymer A. The hydrogen pressure was controlled at 2.5 MPa, the hydrogenation temperature at 70°C, and the hydrogenation time at 2.5 h. After the reaction, the mixture was cooled to room temperature, and anhydrous ethanol was added to precipitate the polymer. The catalyst residue and impurities were removed by filtration to obtain a medium-hydrogenation soluble multifunctional olefin polymer D2. Its 1H NMR spectrum is shown below. Figure 1 .

[0078] Example 7 - Preparation of highly hydrogenated (90%-99%) soluble multifunctional olefin polymers

[0079] Preparation of Polymer D: Using Polymer A prepared in step 1 of Example 5 as the raw material, a nickel naphthenate and triisobutylaluminum complex catalyst (complex molar ratio 1:5) was selected. The complex catalyst was first subjected to a complexation reaction at 65°C for 30 min, and then aged at 70°C for 20 min. The amount of catalyst used was 3% of the mass of Polymer A. The weakly polar solvent was the same as in step 1, and the amount used was 25 times the mass of Polymer A. The hydrogen pressure was controlled at 5 MPa, the hydrogenation temperature was 80°C, and the hydrogenation time was 4 h. After the reaction was completed, the mixture was cooled to room temperature, anhydrous ethanol was added to precipitate the polymer, and the catalyst residue and impurities were removed by filtration to obtain a highly hydrogenated soluble multifunctional olefin polymer D3. Its 1H NMR spectrum is shown in [reference needed]. Figure 1 .

[0080] Performance testing

[0081] The polymers obtained in Examples 5-7 above were tested using the following methods:

[0082] The degree of hydrogenation was calculated using ¹H-NMR spectroscopy.

[0083] Number-average molecular weight (Mn) and molecular weight distribution (PDI) are tested according to GB / T 36214 series (gel permeation chromatography GPC).

[0084] The dielectric constant (Dk, 1 MHz) and dielectric loss (Df, 1 MHz) are tested according to the specific national standard: GB / T 31838.8-2024 (1MHz~300 MHz);

[0085] Glass transition temperature test reference standard GB / T 19466.2-2004.

[0086] The test results are shown in Table 2 below:

[0087] Table 2

[0088]

[0089] As shown in Table 2, Examples 5-7 successfully achieved precise control of the degree of hydrogenation between 30% and 99% by adjusting the combination of hydrogen pressure, reaction temperature, reaction time and catalyst dosage. Moreover, the deviation between the measured degree of hydrogenation and the target degree of hydrogenation was within ±5%, demonstrating the core advantage of the present invention: controllable degree of hydrogenation.

[0090] Dielectric constant (Dk) and dielectric loss (Df) are core indicators for polymers used in high-frequency, high-speed electronic materials. Lower Dk and Df indicate better high-frequency signal transmission performance. The test data shows that as the degree of hydrogenation increases, the Dk and Df of the polymer gradually decrease: D1 (35.2% hydrogenation) has a Dk of 3.15 and a Df of 0.0032; D2 (51% hydrogenation) has a Dk of 2.98 and a Df of 0.0021; and D3 (92% hydrogenation) has a Dk of 2.82 and a Df of 0.0015. This is because hydrogenation increases the saturation of the polymer molecular chain, reduces unsaturated bonds in the molecular chain, and lowers the molecular polarizability, thereby reducing the dielectric constant and dielectric loss. Among them, the high hydrogenation degree D3 (92% hydrogenation degree) has the lowest Dk and Df, which can meet the requirements of high-frequency and high-speed copper clad laminates (such as substrates for 5G / 6G base stations) for low dielectric performance, while the low hydrogenation degree D1 can be adapted to electronic packaging, adhesives and other scenarios with moderate dielectric performance requirements, further demonstrating the advantages of this invention in adapting to different application scenarios by adjusting the hydrogenation degree.

[0091] The above description of the disclosed embodiments enables those skilled in the art to make or use the invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Therefore, the invention is not to be limited to the embodiments shown herein, but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A method for preparing a soluble multifunctional olefin polymer, characterized in that, Includes the following steps: The product is obtained by polymerizing vinyl aromatic olefins and optionally conjugated olefins as monomers. The vinyl aromatic olefin compounds are selected from polyvinyl aromatic olefin compounds and / or monovinyl aromatic olefin compounds; The polyvinyl aromatic olefin compounds include any one or more of o-divinylbenzene, m-divinylbenzene, p-divinylbenzene, or trivinylbenzene; The monovinyl aromatic olefin compounds include any one or more of styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o-dimethylstyrene, p-dimethylstyrene, o-ethylvinylbenzene, m-ethylvinylbenzene, p-ethylvinylbenzene, vinylnaphthalene, vinyl biphenyl, m-ethylvinylbenzene, or p-ethylvinylbenzene; The conjugated olefin compounds include any one or more of butadiene, isoprene, or cyclopentadiene.

2. The preparation method according to claim 1, characterized in that, The molar ratio of the vinyl aromatic olefin compound and the conjugated olefin compound is (2~98):(98~2); The vinyl aromatic olefin compounds contain polyvinyl aromatic olefin compounds in a molar content of 2% to 95% and monovinyl aromatic olefin compounds in a molar content of 5% to 98%.

3. The preparation method according to claim 1 or 2, characterized in that, The polymerization reaction is carried out in the presence of an initiator; The initiator includes protic acids and / or Lewis acids; The protic acid includes any one or more of concentrated sulfuric acid, phosphoric acid, perchloric acid, chlorosulfonic acid, fluorosulfonic acid, trichloroacetic acid, or trifluoroacetic acid; the Lewis acid includes any one or more of AlCl3, BF3, SnCl4, ZnCl2, TiCl4, or SbCl5. The molar ratio of the total molar number of the initiator to the total molar number of the polymer monomer is 8:1 to 60:

1.

4. The preparation method according to claim 3, characterized in that, The Lewis acid contains a co-initiator, and the amount of the co-initiator is 0-1% of the weight of the initiator. The co-initiator is selected from proton donors and / or carbocation co-initiators, wherein the proton donor is selected from any one or more of H2O, ROH, RCOOH or HX; and the carbocation co-initiator is selected from any one or more of RX, RCOX or (RCO)2O. Wherein, R in ROH, RCOOH, RX, RCOX or (RCO)2O is selected from substituted or unsubstituted C1~C6 alkyl groups or substituted or unsubstituted C6~C30 aromatic groups; The X in HX, RX, or RCOX is selected from halogens.

5. The preparation method according to any one of claims 1 to 4, characterized in that, The polymerization reaction is carried out in the presence of a weakly polar solvent; The weakly polar solvent is selected from any one or more of hydrocarbon solvents, alcohol solvents, ether solvents, ketone solvents, or ester solvents; The amount of the weakly polar solvent is 5 to 25 times the total mass of the polymerized monomers.

6. The preparation method according to any one of claims 1 to 5, characterized in that, After the polymerization reaction is completed, a cationic polymerization terminator is used to terminate the polymerization reaction. The cationic polymerization terminator is selected from any one or more of saturated sodium bicarbonate aqueous solution, methanol, ethanol, water, or triethylamine; The amount of the terminator is 1 to 5 times the mass of the initiator; The polymerization reaction is carried out at a temperature of -20 to 150°C for a duration of 5 min to 6 h.

7. The preparation method according to any one of claims 1 to 6, characterized in that, The number-average molecular weight of the soluble polyfunctional olefin polymer is 100 to 100,000, and the ratio of its weight-average molecular weight to its number-average molecular weight is below 100.

8. A method for preparing a soluble multifunctional olefin polymer with controllable hydrogenation degree, characterized in that, Includes the following steps: The soluble polyfunctional olefin polymer prepared by any one of claims 1 to 7 is used as a monomer, and a polymerization reaction is carried out in a catalyst and hydrogen environment to obtain the product.

9. The preparation method according to claim 8, characterized in that, The catalyst is selected from any one or more of nickel naphthenate, triisobutylaluminum, Raney nickel, metallocene catalyst or n-butyllithium; The amount of catalyst used is 0.05-3% of the mass of the soluble polyfunctional olefin polymer; The pressure of the hydrogenation environment is 0.5~5 MPa, the temperature of the polymerization reaction is 60~80℃, and the time of the polymerization reaction is 1~4 h.

10. The preparation method according to claim 9, characterized in that, The catalyst is selected from a combination of nickel naphthenate and triisobutylaluminum, wherein the molar ratio of nickel naphthenate to triisobutylaluminum is 1:(2.5~7); or The catalyst is selected from a combination of a metallocene catalyst and n-butyllithium, wherein the molar ratio of the metallocene catalyst to n-butyllithium is 4:1 to 20:1.

Images