Preparation method and application of hydrogenated polycycloolefin material
By combining molecular weight adjustment with supported catalysts, the problems of high viscosity and high purity of hydrogenated polycyclic olefin materials have been solved, resulting in low viscosity and high light transmittance hydrogenated polycyclic olefin materials suitable for high-end optics and electronic packaging.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2026-01-27
- Publication Date
- 2026-03-27
AI Technical Summary
Traditional hydrogenated polycyclic olefin materials have high viscosity, which makes potting and coating difficult, making it hard to form a uniform film, and metal catalyst residue affects the long-term reliability of the material in optical and electronic applications.
By combining molecular weight regulators with catalytic modification systems, polymerization reactions are precisely designed, and deep hydrogenation is carried out using supported catalysts. After purification through multi-stage filtration membranes, low-viscosity, high-purity hydrogenated polycyclic olefin materials are obtained.
It achieves good leveling properties, bubble-free potting, high light transmittance, and low metal residue in low-viscosity materials, making it suitable for high-end optical and electronic packaging applications, and exhibiting good batch-to-batch consistency.
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Figure CN121736232A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of polymer material synthesis technology, specifically relating to a method for preparing and applying hydrogenated polycyclic olefin materials. Background Technology
[0002] Hydrogenated polycyclic olefins (HPOIs) are a class of thermoplastic polymers obtained by deep hydrogenation of cyclic olefin monomers through ring-opening metathesis polymerization. Due to their highly saturated molecular chains and the absence of double bonds, they possess extremely high chemical stability, excellent optical properties (high transmittance, low birefringence), low hygroscopicity, good electrical insulation, and outstanding heat aging resistance. These properties make HPOIs exhibit enormous application potential in high-end optical lenses, semiconductor packaging, fiber optic coatings, and display materials.
[0003] However, traditional hydrogenated polycyclic olefin materials typically have high molecular weights, resulting in high melt or solution viscosities. High-viscosity materials present numerous challenges in application. In optical packaging, high viscosity leads to difficulties in potting or coating, easily generating bubbles and affecting device yield and performance. When used as coatings, they exhibit poor leveling properties, making it difficult to form uniform films. Furthermore, when used as resin matrices in composite materials, they exhibit poor wetting properties for fillers. While existing technologies employ methods to adjust molecular weight and reduce viscosity by controlling polymerization conditions, these often result in problems such as excessively wide molecular weight distribution, high catalyst residue, and poor product color. Moreover, conventional purification methods are inefficient for high molecular weight polymers and struggle to effectively remove residual metal catalysts, which severely impact the long-term reliability of materials in optical and electronic applications.
[0004] Therefore, developing a hydrogenated polycyclic olefin material that can effectively reduce viscosity while ensuring high purity, excellent optical properties and thermal stability, and its preparation method, has become an urgent technical problem to be solved in this field. Summary of the Invention
[0005] This invention provides a method for preparing and applying hydrogenated polycyclic olefin materials with low viscosity, high purity, high light transmittance, and excellent overall performance.
[0006] To achieve this objective, the present invention adopts the following technical solution: In a first aspect, the present invention provides a method for preparing a hydrogenated polycyclic olefin material, comprising the following steps: (1) Under the protection of inert gas, the cyclic olefin monomer, ring-opening metathesis polymerization catalyst, polymerization catalyst modifier, polymerization catalyst ligand, and molecular weight regulator are polymerized in an organic solvent at -10℃ to 100℃ for 0.5 to 10 h. After the reaction is completed, a terminator is added to terminate the reaction and a polycyclic olefin solution is obtained. (2) Add a hydrogenation catalyst to the polycyclic olefin solution and carry out the hydrogenation reaction for 2 to 12 hours under the conditions of hydrogen pressure of 0.5 to 10 MPa and temperature of 50 to 250°C to obtain a hydrogenated polycyclic olefin solution. (3) The hydrogenated polycyclic olefin solution is sequentially filtered through filter membranes with pore sizes of 20~50μm, 5~15μm, 0.5~2μm and 0.2~1μm, the filtrate is collected, and the hydrogenated polycyclic olefin material is obtained after solvent removal. The hydrogenated polycyclic olefin preparation method provided by this invention has the core advantage of overcoming the industry challenge of balancing high viscosity and high purity in traditional materials through the synergy of "precise molecular design and efficient physical purification." This method first introduces a molecular weight regulator and catalytic modification system during the polymerization stage, pre-setting and narrowing the polymer chain length from the source, laying the molecular foundation for low viscosity. Subsequently, a supported catalyst is used for deep hydrogenation, efficiently saturating double bonds while transforming the metal active centers into solid particles that are easily separated later. The entire process forms a precise closed loop, avoiding the common drawbacks of sacrificing molecular weight to reduce viscosity or introducing complex chemical post-treatments for purification. Thus, with a simple and efficient process, advanced materials with excellent processability, optical properties, and extremely high purity are directly obtained, perfectly meeting the stringent requirements of high-end optics and electronic packaging for core materials.
[0007] Optionally, the cyclic olefin monomer is a compound represented by the structure shown in formula (I): Formula (I), Further optionally, the cycloolefin monomer includes one or more of cyclopentene, cyclopentadiene, dimercyclopentadiene, trimercyclopentadiene, cyclopentadiene polymer, norbornene, methyl norbornene, ethyl norbornene, vinyl norbornene, ethylidene norbornene, tetracyclododecene, methyl tetracyclododecene, ethyl tetracyclododecene, vinyl tetracyclododecene, and their derivatives.
[0008] Further optionally, the organic solvent includes one or more of n-hexane, cyclohexane, n-heptane, n-octane, benzene, toluene, xylene, chlorobenzene, o-dichlorobenzene, dichloromethane, trichloromethane, carbon tetrachloride, and their derivatives.
[0009] Optionally, the ring-opening metathesis polymerization catalyst includes one or more of ruthenium-based, tungsten-based, or molybdenum-based catalysts.
[0010] The polymerization catalyst modifier includes one or more of trimethylaluminum, triethylaluminum, diethylaluminum chloride, diethylaluminum chloride, tri-n-butylaluminum, triisobutylaluminum, dibutylaluminum chloride, dibutylaluminum chloride, tri-n-octylaluminum, dioctylaluminum chloride, dioctylaluminum chloride, and their derivatives. Optionally, the polymerization catalyst ligand includes one or more of alcohols, phenols, ethers, acids, acyls, esters, heterocyclic compounds and their derivatives.
[0011] Optionally, the molecular weight regulator includes one or more of ethylene, propylene, butene, hexene, octene, pentene, cyclohexene, cyclopentene, methpropylene and their derivatives.
[0012] Optionally, the hydrogenation catalyst is at least one of a supported catalyst or a homogeneous catalyst; The active metal component of the supported heavy metal catalyst is selected from one or more of ruthenium, palladium, and iridium, and the support is selected from at least one of activated carbon, alumina, silica, or diatomaceous earth. The homogeneous catalyst is an organometallic complex catalyst containing a rhodium or iridium metal center. Secondly, the present invention provides hydrogenated polycyclic olefin materials prepared by the above method.
[0013] Optionally, the hydrogenated polycyclic olefin material has a number-average molecular weight of 500-50000 g / mol, a molecular weight distribution index of 1.0-3.0, a rotational dynamic viscosity of 10-100 mPa·s at 25°C, a light transmittance of ≥85%, a gelation rate of ≤1%, an ash content of ≤1%, and an impact toughness of ≥15 J / m². Thirdly, the present invention provides applications of the above-mentioned hydrogenated polycyclic olefin materials.
[0014] Optionally, the hydrogenated polycyclic olefin material is used to prepare optical devices, electronic packaging materials, high-performance coatings, or optical fiber coating materials. Beneficial effects 1. This invention obtains a low-viscosity hydrogenated polycyclic olefin material through optimized polymerization process and subsequent purification. It has good coating leveling properties, no bubbles in the potting process, and is suitable for the processing requirements of precision electronic components.
[0015] 2. The key step of the present invention, graded filtration, efficiently removes trace amounts of residual metal catalyst and colored impurities generated by side reactions, resulting in a product with a transmittance of ≥85% and an extremely low yellow index, meeting the requirements of high-end optical applications.
[0016] 3. By adjusting the polymerization reaction conditions and hydrogenation parameters, this invention can precisely control the key indicators such as molecular weight and viscosity of the final product, resulting in good batch-to-batch consistency.
[0017] 4. While maintaining the inherent excellent thermal stability and electrical properties of hydrogenated polycyclic olefin materials, this material solves the processing difficulties caused by high viscosity, and can expand its application in many emerging fields with strict requirements for viscosity and purity, such as micro-LED packaging and high-performance composite coatings. Attached Figure Description
[0018] Figure 1 Infrared spectrum of hydrogenated polycyclic olefin material in Example 1. Detailed Implementation
[0019] The technical solution of the present invention will be described in detail below with reference to specific embodiments, so that those skilled in the art can better understand the essence of the present invention and its beneficial effects. The following embodiments are only for illustrating the present invention and should not be regarded as limiting the present invention. Any limited modifications made within the scope of the claims of the present invention are still within the protection scope of the present invention.
[0020] Unless otherwise specified, the raw materials and reagents used in the following examples are all commercially available products in the art, and the experimental methods are all conventional methods in the art.
[0021] Example 1 A method for preparing a hydrogenated polycyclic olefin material includes the following steps: (1) Polymerization reaction Add 1.5 L of dehydrated toluene to a dry 5 L reactor. Then add 0.5 mol tetracyclododecene, 0.5 mol tricyclodecene, and 5 × 10⁻⁶ mol of [agent / reagent] in sequence. - ²mol of hexene, then add 5×10 - After removing impurities with 3 mol of triethylaluminum and stirring evenly, add 8 × 10⁻⁶ mol of triethylaluminum. -4 Activation was performed using 1 mol of sec-butanol. In a glove box under a high-purity nitrogen atmosphere, 5 × 10⁻⁶ mol of sec-butanol was used. -4 1 mol of tungsten hexachloride was placed in a dehydrated Schlenk flask, dissolved in 50 mL of toluene, and then uniformly added to the reaction system. The reaction was carried out at 0 °C for 30 min, then the temperature was increased to 70 °C and the reaction continued for 2 h. After the reaction was completed, 5 × 10⁻⁶ mol of tungsten hexachloride was added. - The reaction was terminated with 2 mol of vinyl diethyl ether to give a polycyclic olefin solution. (2) Catalytic hydrogenation After the above reaction is complete, add 5×10 - ³mol of carbon-supported palladium catalyst was transferred to a high-pressure reactor, hydrogen was introduced to a pressure of 5 MPa, and the temperature was raised to 180℃ for 5 h to obtain a hydrogenated polycyclic olefin solution. (3) Filtration and purification The obtained hydrogenated polycyclic olefin solution was sequentially filtered through titanium rod continuous filter presses with pore sizes of 30 μm, 10 μm, 1 μm and 0.45 μm for staged filtration. The colorless and transparent filtrate was collected and the solvent was removed by vacuum distillation to obtain particulate hydrogenated polycyclic olefin material.
[0022] The triethylaluminum was purchased from Shanghai Saen Chemical Technology Co., Ltd. The sec-butanol was purchased from Shanghai Anaiji Chemical Co., Ltd. The tungsten hexachloride was purchased from Anhui Zesheng Technology Co., Ltd. The carbon-supported palladium hydrogenation catalyst was purchased from Shaanxi Ruike Catalysis Technology Co., Ltd.
[0023] Example 2 The specific implementation method is the same as in Example 1, except that the polymerization catalyst modifier is replaced by an equimolar amount of triisobutylaluminum.
[0024] Example 3 The specific implementation method is the same as in Example 1, except that the amount of triethylaluminum, the polymerization catalyst modifier, is changed to 8 × 10⁻⁶. -3 mol.
[0025] Example 4 The specific implementation method is the same as in Example 1, except that the polymerization catalyst ligand is replaced with an equimolar amount of isopropanol.
[0026] Example 5 The specific implementation method is the same as in Example 1, except that the amount of polymerization catalyst ligand is changed to 5 × 10⁻⁶. -4 mol.
[0027] Example 6 The specific implementation method is the same as in Example 1, except that the hydrogenation catalyst carbon-supported palladium catalyst is replaced with a carbon-supported ruthenium catalyst.
[0028] Example 7 The specific implementation method is the same as in Example 1, except that the amount of carbon-supported palladium catalyst used in the hydrogenation catalyst is changed to 8 × 10⁻⁶. -3 mol.
[0029] Comparative Example 1 A method for preparing a hydrogenated polycyclic olefin material includes the following steps: (1) Polymerization reaction Add 1.5 L of dehydrated toluene to a dry 5 L reactor. Then add 0.5 mol tetracyclododecene, 0.5 mol tricyclodecene, and 5 × 10⁻⁶ mol of [agent / reagent] in sequence. - ²mol of hexene. In a glove box under a high-purity nitrogen atmosphere, take 5 × 10⁻⁶ mol of hexene. -4 1 mol of tungsten hexachloride was placed in a dehydrated Schlenk flask, dissolved in 50 mL of toluene, and then added evenly to the reaction system. After stirring thoroughly, 8 × 10⁻⁶ mol of tungsten hexachloride was added. -4 Activate with 1 mol of sec-butanol, then add 5 × 10 -Purification was performed using ³mol of triethylaluminum. After reacting at 0°C for 30 min, the temperature was increased to 70°C and the reaction continued for 2 h. After the reaction was complete, 5 × 10⁻⁶ mol of triethylaluminum was added. - The reaction was terminated with 2 mol of vinyl diethyl ether to give a polycyclic olefin solution. (2) Catalytic hydrogenation After the above reaction is complete, add 5×10 - ³mol of alumina-supported nickel 8800p hydrogenation catalyst was transferred to a high-pressure reactor, hydrogen was introduced to a pressure of 5 MPa, and the temperature was raised to 180℃ for 5 h to obtain a hydrogenated polycyclic olefin solution. (3) Filtration and purification The obtained hydrogenated polycyclic olefin solution was sequentially filtered through titanium rod continuous filter presses with pore sizes of 30 μm, 10 μm, 1 μm and 0.45 μm for staged filtration. The colorless and transparent filtrate was collected and the solvent was removed by vacuum distillation to obtain particulate hydrogenated polycyclic olefin material.
[0030] Comparative Example 2 The specific implementation method is the same as in Example 1, except that the ring-opening metathesis polymerization catalyst tungsten hexachloride is replaced with the second-generation Grubbs catalyst.
[0031] Comparative Example 3 The specific implementation method is the same as in Example 1, except that the carbon-supported palladium hydrogenation catalyst is replaced with a carbon-supported nickel catalyst.
[0032] Performance testing The following performance tests were performed on the materials obtained in the above embodiments and comparative examples: Molecular weight (Mw): Relative molecular mass and molecular weight distribution index were calculated using gel permeation chromatography (GPC) with a Waters 1515 isocratic HPLC pump, a Waters 2414 refractive index detector, and a Waters Styragel column (7.8 × 300 mm, particle size 5 mm; pore sizes 10³, 10⁴, 10⁵ Å). Measurements were performed at 40 °C with carbon tetrachloride as the solvent. The polymer solution concentration was approximately 0.2 wt%, and the flow rate for all measurements was set to 1.0 mL / min.
[0033] Molecular weight distribution index (PDI): Same as above.
[0034] Glass transition temperature (Tg): Differential scanning calorimetry (DSC) was performed using a Q2000 DSC instrument in a nitrogen atmosphere. The sample was first heated from 30 °C to 300 °C, held at this temperature for 3 minutes, then cooled to 30 °C, and then heated from 30 °C to 300 °C again, with a heating or cooling rate of 10 °C / min.
[0035] Rotational viscosity: Take a 10% concentration of polymer solution and add it to a rotational viscometer. The stable reading at 25 degrees Celsius is the rotational viscosity.
[0036] Gel ratio: A certain amount of polymer is dissolved in the solvent cyclohexane, and the weight ratio of the undissolved portion to the total amount is the gel ratio.
[0037] Ash content: After being ground into powder, it was burned in a muffle furnace at 600 degrees Celsius for 4 hours, and then weighed.
[0038] Light transmittance: The light transmittance of a 3cm square plate with a thickness of 3mm was tested using a BGI Genomics 0155 color difference haze meter.
[0039] Impact toughness: 2mm national standard 1A specimens were injection molded and tested using a Chu Yinghao ZBC8000B pendulum impact testing machine.
[0040] The results are shown in Tables 1 and 2.
[0041] Table 1
[0042] Table 2
[0043] As can be seen from Tables 1 and 2 above, the products of Examples 1-7 prepared by the method of the present invention have lower viscosity, narrower molecular weight distribution, higher transmittance and lower color, and extremely low metal residue. Their overall performance is significantly better than that of the products of Comparative Examples 1-3.
Claims
1. A method for preparing a hydrogenated polycyclic olefin material, characterized in that, Includes the following steps: (1) Under the protection of inert gas, the cyclic olefin monomer, ring-opening metathesis polymerization catalyst, polymerization catalyst modifier, polymerization catalyst ligand, and molecular weight regulator are polymerized in an organic solvent at -10℃ to 100℃ for 0.5 to 10 h. After the reaction is completed, a terminator is added to terminate the reaction and a polycyclic olefin solution is obtained. (2) Add a hydrogenation catalyst to the polycyclic olefin solution and carry out the hydrogenation reaction for 2 to 12 hours under the conditions of hydrogen pressure of 0.5 to 10 MPa and temperature of 50 to 250°C to obtain a hydrogenated polycyclic olefin solution. (3) The hydrogenated polycyclic olefin solution is sequentially filtered through filter membranes with pore sizes of 20~50μm, 5~15μm, 0.5~2μm and 0.2~1μm, the filtrate is collected, and the hydrogenated polycyclic olefin material is obtained after solvent removal.
2. The preparation method according to claim 1, characterized in that, The cyclic olefin monomer is a compound represented by the structure shown in formula (I): Equation (I), Where n is an integer from 0 to 10, and R1 and R2 are each independently selected from any one of (i) to (iv) below, at least one of which is selected from (iii). (i) Hydrogen atom, (ii) Halogen atoms, (iii) Polar groups in alkoxy, hydroxyl, ester, cyano, amino, and thiol groups, (iv) An aliphatic hydrocarbon group, alicyclic hydrocarbon group, or aromatic hydrocarbon group with 1 to 10 carbon atoms that can be replaced by a halogen atom or the above-mentioned polar group (iii).
3. The preparation method according to claim 1, characterized in that, The cyclic olefin monomers include one or more of cyclopentene, cyclopentadiene, dicyclopentadiene, tricyclopentadiene, cyclopentadiene polymer, norbornene, methyl norbornene, ethyl norbornene, vinyl norbornene, ethylidene norbornene, tetracyclododecene, methyl tetracyclododecene, ethyl tetracyclododecene, or vinyl tetracyclododecene and their derivatives.
4. The preparation method according to claim 1, characterized in that, In step (1), the ring-opening metasomatic polymerization catalyst includes one or more of ruthenium-based, tungsten-based, or molybdenum-based catalysts.
5. The preparation method according to claim 1, characterized in that, In step (1), the polymerization catalyst modifier includes one or more of trimethylaluminum, triethylaluminum, diethylaluminum chloride, diethylaluminum chloride, tri-n-butylaluminum, triisobutylaluminum, dibutylaluminum chloride, dibutylaluminum chloride, tri-n-octylaluminum, dioctylaluminum chloride or dioctylaluminum chloride and their derivatives.
6. The preparation method according to claim 1, characterized in that, In step (1), the polymerization catalyst ligand includes one or more of alcohols, phenols, ethers, acids, acyls, esters, heterocyclic compounds and their derivatives.
7. The preparation method according to claim 1, characterized in that, In step (1), the molecular weight regulator includes one or more of ethylene, propylene, butene, hexene, octene, pentene, cyclohexene, cyclopentene or methpropylene and their derivatives.
8. The preparation method according to claim 1, characterized in that, In step (2), the hydrogenation catalyst is at least one of a supported catalyst or a homogeneous catalyst; The active metal component of the supported heavy metal catalyst is selected from one or more of ruthenium, palladium, and iridium, and the support is selected from at least one of activated carbon, alumina, silica, or diatomaceous earth. The homogeneous catalyst is an organometallic complex catalyst containing a rhodium or iridium metal center.
9. A hydrogenated polycyclic olefin material prepared by the preparation method according to any one of claims 1-8, characterized in that, The hydrogenated polycyclic olefin material has a number-average molecular weight of 500-50000 g / mol, a molecular weight distribution index of 1.0-3.0, a rotational dynamic viscosity of 10-100 mPa·s at 25℃, a light transmittance of ≥85%, a gelation rate of ≤1%, an ash content of ≤1%, and an impact toughness of ≥15 J / m².
10. An application of the hydrogenated polycyclic olefin material as described in claim 9, characterized in that, The hydrogenated polycyclic olefin material is used to prepare optical devices, electronic packaging materials, high-performance coatings, or optical fiber coating materials.