Resin composition, and preparation method therefor and use thereof
Patent Information
- Authority / Receiving Office
- WO · WO
- Patent Type
- Applications
- Current Assignee / Owner
- Filing Date
- 2025-09-12
- Publication Date
- 2026-08-13
Smart Images
Figure CN2025121164_13082026_PF_FP_ABST
Abstract
Description
Resin Compositions, Preparation Methods, and Applications
[0001] This application claims priority to Chinese Patent Application No. 202510142109.7, filed on February 8, 2025, entitled "Resin Composition and Preparation Method Thereof and Application", the entire contents of which are incorporated herein by reference. Technical Field
[0002] This application belongs to the field of polymer materials technology, and particularly relates to a resin composition, its preparation method and application. Background Technology
[0003] With the rapid development of communication technology, the demand for high-frequency radio frequency (RF) devices is increasing. This requires materials to not only have ultra-low loss to reduce insertion loss, but also high-temperature resistance to cope with the heat generated by high-power operation. Cyclic olefin copolymers (COCs) have become ideal low-loss dielectric materials due to their extremely low dielectric loss and excellent heat resistance. However, the high insertion rate of the cyclic olefin structure leads to excessive rigidity, insufficient toughness, and extremely low notched impact resistance, limiting their widespread use in engineering applications.
[0004] Therefore, developing a resin composition that can maintain the low loss and heat resistance of cyclic olefin copolymers while improving their toughness and impact resistance is particularly important for meeting the multiple performance requirements of radio frequency device materials. Summary of the Invention
[0005] The purpose of this application is to provide a resin composition, its preparation method, and its application, aiming to solve the problems of low reliability and insufficient toughness of existing cycloolefin resins.
[0006] To achieve the above-mentioned objectives, the technical solution adopted in this application is as follows:
[0007] A first aspect of this application provides a resin composition comprising a cyclic olefin copolymer and a toughening agent, wherein the toughening agent comprises a polyolefin thermoplastic elastomer and a styrene thermoplastic elastomer.
[0008] The resin composition provided in this application utilizes a cyclic olefin copolymer, which exhibits extremely low dielectric loss and excellent heat resistance, making it an ideal low-loss dielectric material. By introducing polyolefin thermoplastic elastomers and styrene thermoplastic elastomers as toughening agents into the cyclic olefin copolymer, the polyolefin thermoplastic elastomer improves the toughness and impact strength of the resin material, ensuring high heat resistance while toughening and modifying the material. The styrene thermoplastic elastomer further enhances the flexibility and processability of the resin material, and also strengthens the compatibility between the resin and the toughening agent, thereby achieving a superior toughening effect. This resin composition, by combining the properties of cyclic olefin copolymers, polyolefin thermoplastic elastomers, and styrene thermoplastic elastomers, improves the heat resistance and impact strength of the material while maintaining low dielectric loss and high heat distortion temperature, achieving low dielectric loss, high impact strength, and high heat resistance, thus comprehensively optimizing the material's properties. This solves the problems of low reliability and insufficient toughness in cyclic olefin resins.
[0009] In some possible implementations, the polyolefin thermoplastic elastomer has at least one of the following characteristics:
[0010] (1) The crystallinity of the polyolefin thermoplastic elastomer is 5% to 25%;
[0011] (2) The melting temperature of the polyolefin thermoplastic elastomer is not lower than 110°C;
[0012] (3) The melt index of the polyolefin thermoplastic elastomer is not higher than 1 g / 10 min;
[0013] (4) The number average molecular weight of the polyolefin thermoplastic elastomer is not less than 100,000.
[0014] In this context, polyolefin thermoplastic elastomers can better improve the toughness and impact strength of resin compositions, ensuring that the material maintains high heat resistance while being toughened and modified.
[0015] In some possible implementations, the styrene thermoplastic elastomer has at least one of the following characteristics:
[0016] (1) The number-average molecular weight of the styrene thermoplastic elastomer is 200,000 to 500,000;
[0017] (2) The styrene content in the styrene thermoplastic elastomer is 15% to 35%;
[0018] (3) The melt index of the styrene thermoplastic elastomer is less than 1 g / 10 min.
[0019] In this context, styrene thermoplastic elastomers can better improve the flexibility and processing performance of resin compositions. Styrene can also enhance the compatibility between the resin and the toughening agent, thereby achieving a superior toughening effect.
[0020] In some possible implementations, the toughening agent in the resin composition comprises 12% to 30% by mass. In this case, the content of toughening agent in the resin composition can sufficiently ensure that the heat resistance and impact strength of the material are improved while maintaining low dielectric loss and high heat distortion temperature, thus achieving low dielectric loss, high impact strength and high heat resistance.
[0021] In some possible implementations, the mass ratio of the styrene thermoplastic elastomer to the polyolefin thermoplastic elastomer is 1:(0.5 to 10). In this case, it is possible to better ensure improved heat resistance and impact strength of the resin composition while maintaining low dielectric loss and high heat distortion temperature, so that the resin composition simultaneously possesses properties such as low dielectric loss, high impact strength, and high heat resistance.
[0022] In some possible implementations, the glass transition temperature of the cyclic olefin copolymer is 150°C to 220°C. In this case, the glass transition temperature of the cyclic olefin copolymer is higher than 150°C, which helps to improve the thermal stability of the cyclic olefin copolymer and achieve high-temperature reliability of the resin composition.
[0023] In some possible implementations, the glass transition temperature of the cyclic olefin copolymer is 150°C to 170°C.
[0024] In some possible implementations, the resin composition includes at least two cyclic olefin copolymers with different glass transition temperatures. In this case, by blending multiple cyclic olefin copolymers with different glass transition temperatures, the overall performance of the resin composition, such as high-temperature reliability, low dielectric loss, and processability, can be better ensured.
[0025] In some possible implementations, the notched impact of the resin composition is greater than 12 kJ / m. 2 In this case, it indicates that the resin composition has high impact strength; the notched impact strength is continuous, indicating that the material has good toughness.
[0026] In some possible implementations, the dielectric loss of the resin composition is less than 4 × 10⁻⁶ in the frequency range of 1 GHz to 10 GHz. -4 In this case, it is shown that the resin composition has low energy consumption characteristics at high frequencies.
[0027] In some possible implementations, the heat distortion temperature of the resin composition is greater than 145°C. In this case, it is demonstrated that the material maintains stable physical properties at high temperatures and exhibits good heat resistance.
[0028] Secondly, this application provides a method for preparing a resin composition, comprising the following steps:
[0029] A resin composition is obtained by melt extrusion granulation after mixing a cyclic olefin copolymer and a toughening agent; wherein the toughening agent includes a polyolefin thermoplastic elastomer and a styrene thermoplastic elastomer.
[0030] The method for preparing the resin composition of this application involves mixing a cyclic olefin copolymer and a toughening agent, followed by melt extrusion granulation. Exemplarily, the raw materials are heated to a certain temperature using a twin-screw extruder to melt and thoroughly mix them. The mixture is then drawn through the extruder head, cooled, and cut into granules using a cutter to obtain the resin composition. The preparation process is simple and suitable for large-scale industrial production and application. In the prepared resin composition, the cyclic olefin copolymer exhibits extremely low dielectric loss and excellent heat resistance, making it an ideal low-loss dielectric material. By introducing polyolefin thermoplastic elastomers and styrene thermoplastic elastomers as toughening agents into the cyclic olefin copolymer, the polyolefin thermoplastic elastomer can improve the toughness and impact strength of the resin material, ensuring that the material maintains high heat resistance while undergoing toughening modification. The styrene thermoplastic elastomer can further enhance the flexibility and processing performance of the resin material, and styrene can also enhance the compatibility between the resin and the toughening agent, thereby achieving a superior toughening effect. Therefore, the resin composition simultaneously possesses low dielectric loss, high impact strength, and high heat resistance.
[0031] In some possible implementations, the melt extrusion granulation employs a twin-screw extruder with an extrusion temperature of 220℃~270℃, a screw speed of 400rpm~600rpm, and a screw length-to-diameter ratio of (35~45):1.
[0032] In this case, it can be fully ensured that the polyolefin thermoplastic elastomer and styrene thermoplastic elastomer toughening agent are melted and uniformly blended with the cyclic olefin copolymer.
[0033] Thirdly, this application provides an application of a resin composition, wherein the above-described resin composition and / or the resin composition prepared by the above-described preparation method are applied to at least one of the fields of insulating materials, electronic component packaging materials, and communication medium materials.
[0034] The resin composition of this application has low dielectric loss, high impact strength and high heat resistance, and therefore can be widely used in the fields of insulating materials, electronic component packaging materials, communication medium materials and other technical fields. It has a wide range of applications and is flexible and convenient to use.
[0035] The above description is only an overview of the technical solution of this application. In order to better understand the technical means of this application and to implement it in accordance with the contents of the specification, and to make the above and other objects, features and advantages of this application more obvious and understandable, the following are specific embodiments of this application. Attached Figure Description
[0036] Figure 1 is a schematic flowchart of the preparation method of the cyclic olefin resin composition provided in the embodiments of this application. Detailed Implementation
[0037] To make the technical problems, technical solutions, and beneficial effects of this application clearer, the following detailed description is provided in conjunction with embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the scope of this application.
[0038] In this application, the term "and / or" describes the relationship between related objects, indicating that three relationships can exist. For example, A and / or B can represent: A existing alone, A and B existing simultaneously, or B existing alone. A and B can be singular or plural. The character " / " generally indicates that the preceding and following related objects have an "or" relationship.
[0039] In this application, "at least one" means one or more, and "more than one" means two or more. "At least one of the following" or similar expressions refer to any combination of these items, including any combination of single or multiple items. For example, "at least one of a, b, or c", or "at least one of a, b, and c", can both mean: a, b, c, ab (i.e., a and b), ac, bc, or abc, where a, b, and c can be single or multiple.
[0040] It should be understood that in the various embodiments of this application, the order of the above processes does not imply the order of execution. Some or all steps may be executed in parallel or sequentially. The execution order of each process should be determined by its function and internal logic, and should not constitute any limitation on the implementation process of the embodiments of this application.
[0041] The terminology used in the embodiments of this application is for the purpose of describing particular embodiments only and is not intended to be limiting of this application. The singular forms “a,” “the,” and “the” used in the embodiments of this application and the appended claims are also intended to include the plural forms unless the context clearly indicates otherwise.
[0042] The term "COC" is an abbreviation for "Cyclic Olefin Copolymer," which refers to a cyclic olefin copolymer. It is an amorphous polymer typically produced by the polymerization of cyclic olefins through specific reactions. The COC molecule contains rigid, nonpolar cyclic branches, which endows it with a series of unique properties such as high transparency, low water absorption, excellent chemical resistance, and high heat resistance.
[0043] The term "OBC" is an abbreviation for "Olefin Block Copolymer," a type of polymer material with unique structure and properties. It features alternating "soft" and "hard" block structures, giving OBC a good balance between elasticity and temperature resistance. OBCs can be copolymerized from two different types of olefin monomers, or homopolymerized from α-olefins to prepare segments with different degrees of stereoregularity.
[0044] The term "POE" is an abbreviation for "Polyolefin Thermoplastic Elastomer," representing a special material composed of octene and polyolefin resin. Polyolefin thermoplastic elastomers have a low density, which gives them an advantage in certain lightweight applications; they possess high flexural strength, allowing them to withstand large deformations without breaking; and they maintain high impact resistance even at low temperatures.
[0045] The term "SBC" is an abbreviation for "Styrene Butadiene Copolymer," a high-molecular-weight polymer copolymerized from styrene and butadiene. The molecular structure of SBC contains benzene rings and olefin segments, which endow the material with good rigidity and flexibility. The presence of benzene rings increases the material's hardness, while the olefin segments ensure its toughness and processability. Depending on the polymerization conditions, SBC can form different structural types, such as random copolymers and block copolymers. In random copolymers, styrene and butadiene monomers are randomly distributed in the molecular chain; while block copolymers have specific segmental structures, such as styrene-butadiene-styrene (SBS) block copolymers.
[0046] The term "SEBS" is an abbreviation for "Styrene Ethylene Butadiene Styrene," representing a styrene-ethylene-butadiene-styrene copolymer, an important thermoplastic elastomer, and a derivative of hydrogenated styrene-butadiene-styrene block copolymer (SBS). SEBS consists of hard segments (polystyrene) and soft segments (hydrogenated polybutadiene), forming a multiphase structure. The hard segments provide strength and rigidity, while the soft segments impart elasticity. Compared to SBS, the unsaturated double bonds in the polybutadiene segments of SEBS have been selectively hydrogenated and saturated, thus containing no active carbon double bonds, resulting in better stability and aging resistance.
[0047] The term "Dk" is an abbreviation for "Dielectric Constant," representing the dielectric constant, which is the ability of a dielectric medium to respond to an electric field. It is the ratio of the dielectric's permittivity to its free space permittivity. It reflects the degree to which the dielectric responds to an electric field. The larger the dielectric constant, the stronger the dielectric's response to an electric field, and the greater the influence of the electric field on the dielectric. The dimension of the dielectric constant is I. 2 T 4 M -1 L -3 (The square of current, the fourth power of time, the first and negative first power of mass, and the negative third power of length) The unit of dielectric constant in the International System of Units (SI) is the farad per meter (F / m). Absolute dielectric constant (ε) and relative dielectric constant (ε0) are commonly used. r The dielectric constant is expressed as (absolute permittivity) to the permittivity of vacuum, while the relative permittivity is the ratio of the dielectric constant of the medium to the permittivity of vacuum. The magnitude of the dielectric constant is related to factors such as the molecular structure, polarity, and density of the medium. For example, the dielectric constant of polar molecules is usually larger than that of nonpolar molecules. Furthermore, factors such as temperature, frequency, humidity, electric field strength, and the structure and shape of the material also affect the dielectric constant. The parallel-plate capacitance method is a commonly used method for measuring the dielectric constant. Its basic principle is based on the capacitance formula C = εA / d (where C is capacitance, ε is dielectric constant, A is the area of the capacitor plates, and d is the distance between the plates), determining the dielectric constant by measuring the capacitance change of the capacitor in different media.
[0048] The term "Df" is an abbreviation for "Dielectric Loss," which refers to the degree of energy loss of a dielectric material in an electric field. It reflects the dielectric's ability to absorb electric fields. The smaller the dielectric loss, the smaller the energy loss of the dielectric in an electric field. The magnitude of dielectric loss is commonly measured by the dielectric loss tangent (tanδ) or the dielectric loss factor. The dielectric loss tangent is the tangent of the ratio of dielectric loss power to reactive power. Dielectrics contain charge carriers that can conduct electricity. Under the influence of an applied electric field, these charge carriers generate a conductive current, consuming some electrical energy and converting it into heat energy, thus producing dielectric loss.
[0049] The term "HDT" is an abbreviation for "Heat Distortion Temperature," representing the heat distortion temperature, and is an important indicator for measuring the heat resistance of polymer materials such as plastics. HDT refers to the temperature at which a polymer material undergoes a specified deformation under a specific load and heating rate. This temperature reflects the material's stability and durability in high-temperature environments. It is of great significance for assessing the application potential of materials in high-temperature environments. By testing and evaluating the HDT of materials, their performance at high temperatures can be predicted, thereby guiding material selection and design. HDT testing typically uses the three-point bending method. In the test, a standard specimen is placed on a three-point bending device, a certain static load is applied, and the specimen is heated at a constant heating rate. When the specimen reaches the specified deflection, the temperature at this point is recorded as the HDT.
[0050] The term "Tg" is an abbreviation for "Glass Transition Temperature," which represents the temperature at which an amorphous polymer (including the amorphous portion of crystalline polymers) transitions from a glassy state to a rubbery state, or vice versa. It is the lowest temperature at which the macromolecular chains of an amorphous polymer can move freely, and also the upper limit of the operating temperature for amorphous plastic products. At this temperature, the physical properties of the polymer, such as modulus, coefficient of thermal expansion, specific heat capacity, and refractive index, undergo significant changes. The glass transition temperature is one of the important indicators for evaluating the heat resistance of polymers. There are various methods for measuring the glass transition temperature, including differential scanning calorimetry (DSC), thermomechanical analysis (TMA), and dynamic thermomechanical analysis (DMA). These methods determine the glass transition temperature by measuring the thermal effects, deformation, or modulus changes of the polymer during heating.
[0051] Currently, from a market perspective, with the rapid development of communication technology, the demand for high-frequency radio frequency (RF) devices is increasing. This requires materials to not only have ultra-low loss to reduce insertion loss but also high-temperature resistance to cope with the heat generated by high-power operation. Cyclic olefin copolymers (COCs) have become ideal low-loss dielectric materials due to their extremely low dielectric loss and excellent heat resistance. However, the high insertion rate of the cyclic olefin structure leads to excessive rigidity, insufficient toughness, and extremely low notched impact resistance, limiting their widespread use in engineering applications.
[0052] To improve the toughness and impact resistance of cyclic olefin copolymers, some embodiments propose physical blending by adding flexible segments or copolymers, such as styrene-butene copolymer (SBC) or ethyl styrene rubber elastomers, to enhance the toughness of the cyclic olefin copolymer. While this method can improve the toughness of the material, it significantly impacts the temperature resistance, reducing the material's temperature resistance level. Other embodiments propose chemical modification methods, using chemical grafting to graft polyolefin elastomers onto the cyclic olefin copolymer to obtain a cyclic olefin copolymer elastomer with better compatibility. This elastomer is then blended with the cyclic olefin copolymer to improve its toughness. While this method can improve the toughness of the material, the chemical grafting reaction process is complex and costly, and it can lead to the degradation of the grafted material, thus affecting the dielectric loss of the overall blend.
[0053] Based on the above considerations, and in order to address the problems of low reliability and insufficient toughness of cyclic olefin resins, this application proposes a resin composition that, through the introduction of specific toughening agents, enhances the heat resistance and impact strength of the material while maintaining low dielectric loss and high heat distortion temperature, thereby achieving comprehensive optimization of material properties.
[0054] For ease of understanding, this application is specifically described through the following embodiments. It should be understood that the following embodiments are only used to further illustrate the solution of this application and are not intended to limit the scope of this application.
[0055] In a first aspect, embodiments of this application provide a resin composition comprising a cyclic olefin copolymer and a toughening agent, wherein the toughening agent comprises a polyolefin thermoplastic elastomer and a styrene thermoplastic elastomer.
[0056] Thus, the resin composition provided in this application embodiment, with its cyclic olefin copolymer exhibiting extremely low dielectric loss and excellent heat resistance, is an ideal low-loss dielectric material. By introducing polyolefin thermoplastic elastomers and styrene thermoplastic elastomers as toughening agents into the cyclic olefin copolymer, the polyolefin thermoplastic elastomer can improve the toughness and impact strength of the resin material, ensuring that the material maintains high heat resistance while undergoing toughening modification; the styrene thermoplastic elastomer can further enhance the flexibility and processability of the resin material, and styrene can also enhance the compatibility between the resin and the toughening agent, thereby achieving a superior toughening effect. The resin composition in this application embodiment, by combining the characteristics of cyclic olefin copolymers, polyolefin thermoplastic elastomers, and styrene thermoplastic elastomers, improves the heat resistance and impact strength of the material while maintaining low dielectric loss and high heat distortion temperature, achieving low dielectric loss, high impact strength, and high heat resistance, thus achieving comprehensive optimization of material properties. This solves the problems of low reliability and insufficient toughness of cyclic olefin resins.
[0057] In the resin composition of this application embodiment, no chemical reaction occurs between the cyclic olefin copolymer, the polyolefin thermoplastic elastomer, and the styrene thermoplastic elastomer toughening agent. The cyclic olefin copolymer and the toughening agent exist in the form of a blend, forming an island-island structure with the toughening agent as the island and the cyclic olefin copolymer as the sea. This island-island structure refers to the structure in which the toughening agent dispersed phase (island) is dispersed in the continuous phase (sea) of the cyclic olefin copolymer. In this island-island structure, the toughness, strength, heat resistance, and other properties of the resin composition can be improved. At the same time, due to the interaction between the dispersed phase and the continuous phase, the chemical corrosion resistance and aging resistance of the resin composition can also be improved. Among them, the continuous phase cyclic olefin copolymer has excellent optical properties such as high transparency, low birefringence, and high Abbe value, giving the blended resin composition significant advantages in optical applications. The resin composition can maintain high transparency and is suitable for optical applications such as lenses, display screen light guide plates, and optical films. At the same time, the cyclic olefin copolymer has high heat resistance, allowing the resin composition to maintain stable performance even at high temperatures. Furthermore, polyolefin thermoplastic elastomers can improve the toughness and impact strength of resin materials, ensuring that the material maintains high heat resistance while undergoing toughening modification; styrene thermoplastic elastomers can further enhance the flexibility and processing performance of resin materials. They can improve the mechanical properties of resin compositions, increase toughness, and to a certain extent improve the impact resistance of blended resin compositions. They also improve processing performance, reduce processing temperature, and increase production efficiency. This allows the resin composition to combine the advantages of all three materials, achieving low dielectric loss, high impact strength, and high heat resistance, while also possessing good elasticity and flexibility, making it suitable for various applications requiring bending or stretching.
[0058] In some possible implementations, the crystallinity of the polyolefin thermoplastic elastomer is 5% to 25%. The crystallinity of the polyolefin thermoplastic elastomer contributes to toughening modification while maintaining high heat resistance. With a crystallinity of 5% to 25%, the polyolefin thermoplastic elastomer ensures that the material maintains high heat resistance while undergoing toughening modification. A certain degree of crystallinity in the polyolefin thermoplastic elastomer can better improve the toughness and impact strength of the resin composition. If the crystallinity of the polyolefin thermoplastic elastomer is too high, the toughening effect on the resin material is not ideal; if the crystallinity of the polyolefin thermoplastic elastomer is too low, the temperature resistance of the resin material is low, which will reduce the heat distortion temperature. Exemplarily, the crystallinity of the polyolefin thermoplastic elastomer can be any typical but non-limiting point value or a range between any point values, such as 5%, 8%, 10%, 13%, 15%, 18%, 20%, 22%, and 25%.
[0059] In some possible implementations, the melt temperature of the polyolefin thermoplastic elastomer is not lower than 110°C. In this case, the higher melt temperature of the polyolefin thermoplastic elastomer means that the material can maintain its physical and chemical properties unchanged at higher temperatures, retaining high heat resistance while undergoing toughening modification, thereby expanding its application range, especially in applications requiring high-temperature environments. Furthermore, under these conditions, the polyolefin thermoplastic elastomer typically exhibits high stiffness and strength while maintaining good elasticity, which can improve the toughness and impact strength of the resin composition.
[0060] In some possible implementations, the melting temperature of the polyolefin thermoplastic elastomer is 110°C to 130°C. Exemplary examples include any typical but non-limiting point value or a range between any point values such as 110°C, 115°C, 120°C, 125°C, and 130°C.
[0061] In some possible implementations, the melt index (MI) of the polyolefin thermoplastic elastomer is not higher than 1 g / 10 min. In this case, the MI is an important indicator of the polyolefin thermoplastic elastomer's flowability, reflecting the melt flow rate at a given temperature and pressure. When the MI of the polyolefin thermoplastic elastomer is not higher than 1 g / 10 min, its low MI indicates a large molecular weight, which can increase the heat distortion temperature of the polyolefin thermoplastic elastomer. A lower MI generally means that the material has higher melt strength in the molten state, which allows the material to better maintain shape and dimensional stability during processing. In extrusion processing, a lower MI helps reduce melt flow fluctuations, thereby improving the uniformity and consistency of extruded products. Furthermore, polyolefin thermoplastic elastomers with lower MIs tend to have higher strength and toughness, possibly due to their more compact and ordered molecular chain structure. Because a compact molecular chain structure helps resist chemical attack, better maintains the material's thermal stability, and thus has better chemical corrosion resistance and helps improve the material's heat resistance. Furthermore, during injection molding, a lower melt index helps reduce shrinkage and warpage of the product, thereby improving the dimensional accuracy and surface quality of the product.
[0062] In some embodiments, the melt index of the polyolefin thermoplastic elastomer is 0.5 g / 10 min to 1 g / 10 min, and exemplary values may be any typical but non-limiting point value or a range between any point values such as 0.5 g / 10 min, 0.6 g / 10 min, 0.7 g / 10 min, 0.8 g / 10 min, 0.9 g / 10 min, and 1.0 g / 10 min.
[0063] In some possible implementations, the number-average molecular weight of the polyolefin thermoplastic elastomer is not less than 100,000. In this case, the polyolefin thermoplastic elastomer has a higher molecular weight, which results in higher tensile strength and elongation at break, meaning the material is better able to resist deformation and fracture under external forces. High molecular weight polyolefin thermoplastic elastomers also help improve the material's impact resistance, making it exhibit better durability and reliability in various applications. Furthermore, high molecular weight polyolefin thermoplastic elastomers have a more compact molecular chain structure, which helps resist chemical attack, thereby extending the material's service life. This also gives it better thermal stability and weather resistance, enabling it to maintain stable performance under high temperature or harsh environmental conditions.
[0064] In some embodiments, the number-average molecular weight of the polyolefin thermoplastic elastomer is 100,000 to 300,000. Exemplary examples include any typical but non-limiting point value or a range between any point values such as 100,000, 120,000, 150,000, 180,000, 200,000, 220,000, 250,000, 280,000, and 300,000.
[0065] In some possible implementations, the polyolefin thermoplastic elastomer has a crystallinity of 5% to 25%; a melting temperature of not less than 110°C; a melt index of not more than 1 g / 10 min; and a number-average molecular weight of not less than 100,000. In this case, the polyolefin thermoplastic elastomer can better improve the toughness and impact strength of the resin composition, ensuring that the material maintains high heat resistance while being toughened and modified.
[0066] In some possible implementations, the number-average molecular weight of the styrene thermoplastic elastomer is between 200,000 and 500,000. In this case, the styrene thermoplastic elastomer has a high molecular weight, which results in higher yield strength and tensile strength, enabling it to withstand greater external forces without easily breaking. High molecular weight styrene thermoplastic elastomers typically possess a more stable chemical structure and higher heat resistance, maintaining stable physical properties at higher temperatures. Furthermore, it resists the attack of various chemicals, such as acids, alkalis, and organic solvents, exhibiting excellent chemical resistance.
[0067] For example, the number average molecular weight of styrene thermoplastic elastomers can be any typical but non-limiting point value or a range between any point values, such as 200,000, 250,000, 300,000, 350,000, 400,000, 450,000, and 500,000.
[0068] In some possible implementations, the styrene content in the styrene thermoplastic elastomer is 15% to 35%. In this case, the introduction of styrene gives the styrene thermoplastic elastomer higher elastic modulus, yield strength, and tensile strength, while maintaining good elasticity. This allows the material to quickly return to its original shape under external force, preventing permanent deformation. Furthermore, the high styrene content gives the styrene thermoplastic elastomer good impact resistance, enabling it to withstand greater impact forces without cracking or damage. Therefore, the high styrene content in styrene thermoplastic elastomer toughening agents can enhance the compatibility between the resin and the toughening agent, further improving the flexibility and processing performance of the resin material, thereby achieving a superior toughening effect.
[0069] For example, in styrene thermoplastic elastomers, the styrene content can be any typical but non-limiting point value or a range between any point values, such as 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%.
[0070] In some possible implementations, the melt index of the styrene thermoplastic elastomer is less than 1 g / 10 min. In this case, a melt index less than 1 g / 10 min indicates that the material has a high molecular weight and strong intermolecular forces, giving it a series of unique performance advantages: due to its higher molecular weight, styrene thermoplastic elastomers with a melt index less than 1 g / 10 min typically have higher tensile strength and breaking strength, capable of withstanding greater external forces without easily breaking. Simultaneously, its wear resistance is significantly improved, maintaining good physical properties over long-term use. Furthermore, styrene thermoplastic elastomers themselves have good elasticity, and materials with a melt index less than 1 g / 10 min typically have higher resilience. This allows such materials to quickly return to their original shape after being subjected to external forces, reducing the likelihood of permanent deformation. Moreover, styrene thermoplastic elastomers with a melt index less than 1 g / 10 min have poor flowability during processing, which helps reduce dimensional changes during processing, generally exhibiting better dimensional stability and meeting the needs of applications requiring high dimensional accuracy.
[0071] In some embodiments, the melt index of the styrene thermoplastic elastomer is less than 1 g / 10 min and not less than 0.5 g / 10 min. Exemplary values may be any typical but non-limiting point value or a range between any point values, such as 0.5 g / 10 min, 0.6 g / 10 min, 0.7 g / 10 min, 0.8 g / 10 min, 0.9 g / 10 min, and 0.95 g / 10 min.
[0072] In some possible embodiments, the number-average molecular weight of the styrene thermoplastic elastomer is 200,000 to 500,000; the styrene content is 15% to 35%; and the melt index of the styrene thermoplastic elastomer is less than 1 g / 10 min. In this case, the styrene thermoplastic elastomer can better improve the flexibility and processing performance of the resin composition, wherein styrene can also enhance the compatibility between the resin and the toughening agent, thereby achieving a better toughening effect.
[0073] In some possible embodiments, the toughening agent in the resin composition comprises 12% to 30% by mass. In this case, the amount of toughening agent in the resin composition is sufficient to ensure that the heat resistance and impact strength of the material are improved while maintaining low dielectric loss and high heat distortion temperature, thus achieving low dielectric loss, high impact strength, and high heat resistance. This avoids problems such as insufficient toughening agent content leading to poor toughening effect on the resin composition and resulting in too low notched impact resistance; conversely, it avoids excessive toughening agent content, which could affect properties such as the heat distortion temperature and tensile strength of the resin composition.
[0074] For example, the mass percentage of toughening agent in the resin composition can be any typical but non-limiting point value or a range between any point values, such as 12%, 15%, 18%, 20%, 22%, 24%, 25%, 28%, 30%.
[0075] In some possible implementations, the mass ratio of styrene thermoplastic elastomer to polyolefin thermoplastic elastomer is 1:(0.5–10). In this case, it is possible to better ensure improved heat resistance and impact strength of the resin composition while maintaining low dielectric loss and high heat distortion temperature, thus giving the resin composition properties such as low dielectric loss, high impact strength, and high heat resistance. If the styrene thermoplastic elastomer content is too high, the dielectric loss of the resin composition will be too high; if the styrene thermoplastic elastomer content is too low, the improvement in the flexibility, processability, and compatibility of the resin composition will not be significant. By precisely controlling the ratio of the toughening agent and the mixing ratio of the cyclic olefin copolymer to the toughening agent, the performance of the resin composition can be better optimized.
[0076] For example, the mass ratio of styrene thermoplastic elastomer to polyolefin thermoplastic elastomer can be any typical but non-limiting point value or a range between any point values, such as 1:0.5, 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10.
[0077] In some possible embodiments, the toughening agent comprises 12% to 30% by mass in the resin composition, and the mass ratio of styrene thermoplastic elastomer to polyolefin thermoplastic elastomer is 1:(0.5 to 10). In this case, by precisely adjusting the ratio of the cyclic olefin copolymer to the styrene thermoplastic elastomer and the polyolefin thermoplastic elastomer, the resin composition not only exhibits stability at high temperatures and is risk-free in drop vibration tests, but also possesses low dielectric loss characteristics, making it ideal for applications in the information and communication field. This ensures that the material provides stable and high-quality communication performance over a wide operating temperature range.
[0078] In some possible embodiments, the glass transition temperature of the cyclic olefin copolymer is 150°C to 220°C. In this case, the glass transition temperature of the cyclic olefin copolymer is higher than 150°C, which helps to improve the thermal stability of the cyclic olefin copolymer and achieve high-temperature reliability of the resin composition.
[0079] For example, the glass transition temperature of the cyclic olefin copolymer can be any typical but non-limiting point value or a range between any point values, such as 150°C, 160°C, 170°C, 180°C, 190°C, 200°C, 210°C, 220°C.
[0080] In some possible embodiments, the glass transition temperature of the cyclic olefin copolymer is 150°C to 170°C. In this case, the glass transition temperature of the cyclic olefin copolymer is beneficial for both improving the high-temperature reliability of the resin composition and ensuring the processability of the resin composition.
[0081] In some possible embodiments, the resin composition includes at least two cyclic olefin copolymers with different glass transition temperatures. In this case, by blending multiple cyclic olefin copolymers with different glass transition temperatures, the overall performance of the resin composition, such as high-temperature reliability, low dielectric loss, and processability, can be better ensured.
[0082] In some possible embodiments, the notched impact of the resin composition is greater than 12 kJ / m. 2 In this case, it indicates that the resin composition has high impact strength; the continuous notched impact strength indicates that the material has good toughness.
[0083] In some embodiments, the notched impact strength of the resin composition is 12 kJ / m. 2 ~20kJ / m 2 An exemplary notch impact could be 12 kJ / m 2 12.6 kJ / m 2 13kJ / m 2 14kJ / m 2 15kJ / m 2 16kJ / m 2 16.5kJ / m 2 18kJ / m 2 20kJ / m 2 22kJ / m 2 25kJ / m 2 28kJ / m 2 30kJ / m 2 Typical but not restrictive arbitrary point values or intervals between arbitrary point values.
[0084] In some possible embodiments, the dielectric loss of the resin composition is less than 4 × 10⁻⁶ in the frequency range of 1 GHz to 10 GHz. -4 In this case, it is shown that the resin composition has low energy consumption characteristics at high frequencies.
[0085] In some embodiments, the dielectric loss of the resin composition is 2 × 10⁻⁶ in the frequency range of 1 GHz to 10 GHz. -4 ~3.8×10 -4 An example dielectric loss could be 2 × 10⁻⁶. -4 2.3×10 -4 2.4×10 -4 2.5×10 -4 2.8×10 -4 3×10 -4 3.1×10 -4 3.2×10 -4 3.5×10 -4 3.8×10 -4 Typical but not restrictive arbitrary point values or intervals between arbitrary point values.
[0086] In some possible implementations, the heat distortion temperature of the resin composition is greater than 145°C. In this case, it is demonstrated that the material maintains stable physical properties at high temperatures and exhibits good heat resistance.
[0087] In some embodiments, the heat distortion temperature of the resin composition is 145°C to 170°C. Exemplary heat distortion temperatures can be any typical but non-limiting point value or a range between any point values, such as 145°C, 145.3°C, 148°C, 150°C, 151.9°C, 153°C, 155°C, 155.5°C, 158.7°C, 160°C, 160.4°C, 161.5°C, 163°C, 165°C, 168°C, and 170°C.
[0088] In some possible embodiments, the notched impact of the resin composition is greater than 12 kJ / m. 2 The dielectric loss is less than 4×10⁻⁶ in the frequency range of 1GHz to 10GHz. -4 The heat distortion temperature is greater than 145°C. In this case, this embodiment introduces polyolefin thermoplastic elastomers and styrene thermoplastic elastomers with specific crystallinity into the cyclic olefin copolymer as toughening agents, which not only improves the impact strength and toughness of the material, but also achieves a balance between low dielectric loss and high heat resistance by optimizing the mixing ratio.
[0089] The resin compositions described in the above embodiments of this application can be prepared by the methods described in the following embodiments.
[0090] Secondly, embodiments of this application provide a method for preparing a resin composition, comprising the following steps:
[0091] S10. After mixing the cyclic olefin copolymer and the toughening agent, the mixture is melt-extruded and granulated to obtain a resin composition; wherein the toughening agent includes polyolefin thermoplastic elastomer and styrene thermoplastic elastomer.
[0092] The method for preparing the resin composition in this application involves mixing a cyclic olefin copolymer and a toughening agent, followed by melt extrusion granulation. Exemplarily, the raw materials are heated to a certain temperature using a twin-screw extruder to melt and thoroughly mix them. The mixture is then drawn through the extruder head, cooled, and cut into granules using a cutter to obtain the resin composition. This preparation process is simple and suitable for large-scale industrial production and application. In the prepared resin composition, the cyclic olefin copolymer exhibits extremely low dielectric loss and excellent heat resistance, making it an ideal low-loss dielectric material. By introducing polyolefin thermoplastic elastomers and styrene thermoplastic elastomers as toughening agents into the cyclic olefin copolymer, the polyolefin thermoplastic elastomer can improve the toughness and impact strength of the resin material, ensuring that the material maintains high heat resistance while undergoing toughening modification. The styrene thermoplastic elastomer can further enhance the flexibility and processing performance of the resin material. Styrene also enhances the compatibility between the resin and the toughening agent, thereby achieving a superior toughening effect. Therefore, the resin composition simultaneously possesses low dielectric loss, high impact strength, and high heat resistance.
[0093] In step S10 above:
[0094] In some possible implementations, melt extrusion granulation is performed using a twin-screw extruder. The cyclic olefin copolymer resin component is mixed and fed into the main feed system of the twin-screw extruder. The polyolefin thermoplastic elastomer and styrene thermoplastic elastomer toughening filler components are mixed evenly and fed into the side feed system of the twin-screw extruder. The feed flow rate is set according to the ratio of resin to filler. After melt mixing, extrusion, cooling, and granulation, the resin composition particles are obtained.
[0095] In some possible implementations, melt extrusion granulation is performed using a twin-screw extruder with an extrusion temperature of 220°C to 270°C, a screw speed of 400 rpm to 600 rpm, and a screw length-to-diameter ratio of (35 to 45):1. In this case, it is possible to sufficiently ensure the melt and uniform blending of the polyolefin thermoplastic elastomer and the styrene thermoplastic elastomer toughening agent with the cyclic olefin copolymer.
[0096] For example, the extrusion temperature of a twin-screw extruder can be any typical but non-limiting point value or a range between any points, such as 220℃, 230℃, 240℃, 250℃, 260℃, 270℃, etc.; the screw speed can be any typical but non-limiting point value or a range between any points, such as 400rpm, 450rpm, 500rpm, 550rpm, 600rpm, etc.; and the screw length-to-diameter ratio can be any typical but non-limiting point value or a range between any points, such as 35:1, 38:1, 40:1, 43:1, 45:1, etc.
[0097] In some embodiments, during the preparation process, the cyclic olefin copolymer and toughening agent are first physically blended, added to a twin-screw extruder, heated to a molten state, drawn into strands, cooled, and granulated. The twin-screw extruder has an extrusion temperature of 220°C–270°C, a screw speed of 400 rpm–600 rpm, and a screw length-to-diameter ratio of 40:1. Then, the resin composition product is obtained through injection molding and other steps.
[0098] In some possible implementations, the polyolefin thermoplastic elastomer has at least one of the following characteristics:
[0099] (1) The crystallinity of polyolefin thermoplastic elastomers is 5% to 25%;
[0100] (2) The melting temperature of polyolefin thermoplastic elastomers shall not be lower than 110℃;
[0101] (3) The melt index of polyolefin thermoplastic elastomers shall not exceed 1 g / 10 min;
[0102] (4) The number average molecular weight of polyolefin thermoplastic elastomers shall not be less than 100,000.
[0103] In this context, polyolefin thermoplastic elastomers can better improve the toughness and impact strength of resin compositions, ensuring that the material maintains high heat resistance while being toughened and modified.
[0104] In some possible implementations, the styrene thermoplastic elastomer has at least one of the following characteristics:
[0105] (1) The number-average molecular weight of styrene thermoplastic elastomers is 200,000 to 500,000;
[0106] (2) In styrene thermoplastic elastomers, the styrene content is 15% to 35%;
[0107] (3) The melt index of styrene thermoplastic elastomer is less than 1 g / 10 min.
[0108] In this context, styrene thermoplastic elastomers can better improve the flexibility and processing performance of resin compositions. Styrene can also enhance the compatibility between the resin and the toughening agent, thereby achieving a superior toughening effect.
[0109] In some possible implementations, the average particle size of the polyolefin thermoplastic elastomer raw material is 3 mm to 6 mm, and the average particle size of the styrene thermoplastic elastomer raw material is 3 mm to 6 mm. In this case, it is advantageous to melt-mix and granulate the toughening agent comprising the polyolefin thermoplastic elastomer and the styrene thermoplastic elastomer with the cyclic olefin copolymer.
[0110] In some possible embodiments, the toughening agent in the resin composition comprises 12% to 30% by mass. In this case, the content of toughening agent in the resin composition is sufficient to ensure that the heat resistance and impact strength of the material are improved while maintaining low dielectric loss and high heat distortion temperature, thus achieving low dielectric loss, high impact strength and high heat resistance.
[0111] In some possible implementations, the mass ratio of styrene thermoplastic elastomer to polyolefin thermoplastic elastomer is 1:(0.5 to 10). In this case, it is possible to better ensure improved heat resistance and impact strength of the resin composition while maintaining low dielectric loss and high heat distortion temperature, so that the resin composition simultaneously possesses properties such as low dielectric loss, high impact strength, and high heat resistance.
[0112] In some possible embodiments, the glass transition temperature of the cyclic olefin copolymer is 150°C to 220°C. In this case, the glass transition temperature of the cyclic olefin copolymer is higher than 150°C, which helps to improve the thermal stability of the cyclic olefin copolymer and achieve high-temperature reliability of the resin composition.
[0113] In some possible implementations, the glass transition temperature of the cyclic olefin copolymer is 150°C to 170°C.
[0114] In some possible embodiments, the resin composition includes at least two cyclic olefin copolymers with different glass transition temperatures. In this case, by blending multiple cyclic olefin copolymers with different glass transition temperatures, the overall performance of the resin composition, such as high-temperature reliability, low dielectric loss, and processability, can be better ensured.
[0115] In some possible embodiments, the notched impact of the resin composition is greater than 12 kJ / m. 2 The dielectric loss of the resin composition is less than 4 × 10⁻⁶ in the frequency range of 1 GHz to 10 GHz. -4The heat distortion temperature of the resin composition is greater than 145°C. In this case, this embodiment introduces polyolefin thermoplastic elastomers and styrene thermoplastic elastomers with specific crystallinity into the cyclic olefin copolymer as toughening agents, which not only improves the impact strength and toughness of the material, but also achieves a balance between low dielectric loss and high heat resistance by optimizing the mixing ratio.
[0116] Thirdly, embodiments of this application provide an application of a resin composition, in which the above-described resin composition and / or the resin composition prepared by the above-described preparation method are applied to at least one of the fields of insulating materials, electronic component packaging materials, and communication medium materials.
[0117] The resin composition of this application embodiment has low dielectric loss, high impact strength and high heat resistance, and therefore can be widely used in the fields of insulating materials, electronic component packaging materials, communication medium materials and other technical fields. It has a wide range of applications and is flexible and convenient to use.
[0118] The resin composition described in this application can be applied in the electronics and electrical fields, such as in the manufacture of insulating materials, cable sheaths, and electronic component encapsulation. In a system architecture, the resin composition can be used as a core material, combined with other functional materials to form a composite material system to achieve specific performance requirements. Application scenarios include: 1) encapsulation materials for electronic components, providing good insulation performance and impact resistance; 2) insulating components for power equipment, improving the heat resistance and service life of the equipment; 3) dielectric materials in the communications field, meeting the requirement for low dielectric loss.
[0119] In some embodiments, it can be used to manufacture the insulation layer of motors and transformers, improving the insulation and heat resistance of the equipment; it can also be used to manufacture the insulation sheath of cables and wires, improving the high temperature resistance and insulation strength of the cables, and ensuring stable power transmission.
[0120] In other embodiments, the resin composition provides better resistance to external impacts during encapsulation, protecting electronic components from damage. Its low dielectric loss and high heat resistance contribute to maintaining the stability and reliability of electronic components, extending their lifespan. The resin composition can be used for encapsulating integrated circuits, improving the reliability and stability of the encapsulation and protecting the circuit from external environmental interference. It can also be used for encapsulating semiconductor devices, improving their heat resistance and shock resistance, ensuring their normal operation.
[0121] In other embodiments, the resin composition can be used in the manufacture of 5G base station radomes to improve their heat resistance and impact resistance, while reducing signal loss and ensuring stable 5G signal transmission. It can also be used in the manufacture of fiber optic connectors to improve connector stability and reliability and reduce signal loss during transmission.
[0122] Example
[0123] The following description uses specific embodiments. These embodiments are exemplary and are only used to explain this application, and should not be construed as limiting the application. Where specific techniques or conditions are not specified in the embodiments, they are performed according to the techniques or conditions described in the literature in this field or according to the product instructions. Reagents or instruments used, unless otherwise specified, are all commercially available conventional products.
[0124] Example 1
[0125] This application provides a resin composition comprising 80 wt% of a cyclic olefin copolymer (glass transition temperature 170°C, labeled COC17), 10 wt% of a polyolefin thermoplastic elastomer, and 10 wt% of a styrene thermoplastic elastomer; wherein the polyolefin thermoplastic elastomer has a crystallinity of 12%, a melting temperature of 120°C, a melt index of 1 g / min, and a number-average molecular weight of 15 W; labeled OBC. The styrene thermoplastic elastomer has a number-average molecular weight of 25 W, a melt index of 0.5 g / 10 min, and a styrene content of 30%; labeled SEBS.
[0126] Its preparation includes the following steps:
[0127] The resin component of the cyclic olefin copolymer is mixed and added to the main feeding system of a twin-screw extruder. The filler components of the polyolefin thermoplastic elastomer and the styrene thermoplastic elastomer are mixed and shaken and then added to the side feeding system of the twin-screw extruder. The feed flow rate is set according to the ratio of resin to filler. After melt mixing, extrusion, and granulation, the extrusion temperature of the twin-screw extruder is 220℃~270℃, the screw speed is 400rpm~600rpm, and the screw length-to-diameter ratio is 40:1, to obtain particles of the resin composition.
[0128] Example 2
[0129] This application provides a resin composition comprising 78 wt% of a cyclic olefin copolymer (glass transition temperature 170°C, labeled COC17), 14 wt% of a polyolefin thermoplastic elastomer, and 8 wt% of a styrene thermoplastic elastomer; wherein the polyolefin thermoplastic elastomer has a crystallinity of 12%, a melting temperature of 120°C, a melt index of 1 g / min, and a number-average molecular weight of 15 W; labeled OBC. The styrene thermoplastic elastomer has a number-average molecular weight of 25 W, a melt index of 0.5 g / 10 min, and a styrene content of 30%; labeled SEBS.
[0130] The preparation method is the same as in Example 1.
[0131] Example 3
[0132] This application provides a resin composition comprising 75 wt% of a cyclic olefin copolymer (glass transition temperature 170°C, labeled COC17), 20 wt% of a polyolefin thermoplastic elastomer, and 5 wt% of a styrene thermoplastic elastomer; wherein the polyolefin thermoplastic elastomer has a crystallinity of 12%, a melting temperature of 120°C, a melt index of 1 g / min, and a number-average molecular weight of 15 W; labeled OBC. The styrene thermoplastic elastomer has a number-average molecular weight of 25 W, a melt index of 0.5 g / 10 min, and a styrene content of 30%; labeled SEBS.
[0133] The preparation method is the same as in Example 1.
[0134] Example 4
[0135] This application provides a resin composition comprising 70 wt% of a cyclic olefin copolymer (glass transition temperature 170°C, labeled COC17), 20 wt% of a polyolefin thermoplastic elastomer, and 10 wt% of a styrene thermoplastic elastomer; wherein the polyolefin thermoplastic elastomer has a crystallinity of 12%, a melting temperature of 120°C, a melt index of 1 g / min, and a number-average molecular weight of 15 W; labeled OBC. The styrene thermoplastic elastomer has a number-average molecular weight of 25 W, a melt index of 0.5 g / 10 min, and a styrene content of 30%; labeled SEBS.
[0136] The preparation method is the same as in Example 1.
[0137] Example 5
[0138] This application provides a resin composition comprising 50 wt% of a cyclic olefin copolymer (glass transition temperature 170°C, labeled COC17), 25 wt% of a cyclic olefin copolymer (glass transition temperature 150°C, labeled COC15), 10 wt% of a polyolefin thermoplastic elastomer, and 10 wt% of a styrene thermoplastic elastomer; wherein the polyolefin thermoplastic elastomer has a crystallinity of 12%, a melting temperature of 120°C, a melt index of 1 g / min, and a number-average molecular weight of 15 W; labeled OBC. The styrene thermoplastic elastomer has a number-average molecular weight of 25 W, a melt index of 0.5 g / 10 min, and a styrene content of 30%; labeled SEBS.
[0139] The preparation method is the same as in Example 1.
[0140] Example 6
[0141] This application provides a resin composition comprising 85 wt% of a cyclic olefin copolymer (glass transition temperature 150°C, labeled COC15), 5 wt% of a polyolefin thermoplastic elastomer, and 10 wt% of a styrene thermoplastic elastomer; wherein the polyolefin thermoplastic elastomer has a crystallinity of 12%, a melting temperature of 120°C, a melt index of 1 g / min, and a number-average molecular weight of 15 W; labeled OBC. The styrene thermoplastic elastomer has a number-average molecular weight of 25 W, a melt index of 0.5 g / 10 min, and a styrene content of 30%; labeled SEBS.
[0142] The preparation method is the same as in Example 1.
[0143] Example 7
[0144] This application provides a resin composition comprising 68 wt% of a cyclic olefin copolymer (glass transition temperature 170°C, labeled COC17), 22 wt% of a polyolefin thermoplastic elastomer, and 10 wt% of a styrene thermoplastic elastomer; wherein the polyolefin thermoplastic elastomer has a crystallinity of 12%, a melting temperature of 120°C, a melt index of 1 g / min, and a number-average molecular weight of 15 W; labeled OBC. The styrene thermoplastic elastomer has a number-average molecular weight of 25 W, a melt index of 0.5 g / 10 min, and a styrene content of 30%; labeled SEBS.
[0145] The preparation method is the same as in Example 1.
[0146] Example 8
[0147] This application provides a resin composition comprising 90 wt% of a cyclic olefin copolymer (glass transition temperature 170°C, labeled COC17), 5 wt% of a polyolefin thermoplastic elastomer, and 5 wt% of a styrene thermoplastic elastomer; wherein the polyolefin thermoplastic elastomer has a crystallinity of 12%, a melting temperature of 120°C, a melt index of 1 g / min, and a number-average molecular weight of 15 W; labeled OBC. The styrene thermoplastic elastomer has a number-average molecular weight of 25 W, a melt index of 0.5 g / 10 min, and a styrene content of 30%; labeled SEBS.
[0148] The preparation method is the same as in Example 1.
[0149] Example 9
[0150] This application provides a resin composition comprising 88 wt% of a cyclic olefin copolymer (glass transition temperature 170°C, labeled COC17), 2 wt% of a polyolefin thermoplastic elastomer, and 10 wt% of a styrene thermoplastic elastomer; wherein the polyolefin thermoplastic elastomer has a crystallinity of 12%, a melting temperature of 120°C, a melt index of 1 g / min, and a number-average molecular weight of 15 W; labeled OBC. The styrene thermoplastic elastomer has a number-average molecular weight of 25 W, a melt index of 0.5 g / 10 min, and a styrene content of 30%; labeled SEBS.
[0151] Example 10
[0152] This application provides a resin composition comprising 83.5 wt% of a cyclic olefin copolymer (glass transition temperature 130°C, labeled COC13), 15 wt% of a polyolefin thermoplastic elastomer, and 1.5 wt% of a styrene thermoplastic elastomer; wherein the polyolefin thermoplastic elastomer has a crystallinity of 12%, a melting temperature of 120°C, a melt index of 1 g / min, and a number-average molecular weight of 15 W; labeled OBC. The styrene thermoplastic elastomer has a number-average molecular weight of 25 W, a melt index of 0.5 g / 10 min, and a styrene content of 30%; labeled SEBS.
[0153] Example 11
[0154] This application provides a resin composition comprising 88 wt% of a cyclic olefin copolymer (glass transition temperature 220°C, labeled COC22), 11 wt% of a polyolefin thermoplastic elastomer, and 1 wt% of a styrene thermoplastic elastomer; wherein the polyolefin thermoplastic elastomer has a crystallinity of 12%, a melting temperature of 120°C, a melt index of 1 g / min, and a number-average molecular weight of 15 W; labeled OBC. The styrene thermoplastic elastomer has a number-average molecular weight of 25 W, a melt index of 0.5 g / 10 min, and a styrene content of 30%; labeled SEBS.
[0155] Example 12
[0156] This application provides a resin composition comprising 86 wt% of a cyclic olefin copolymer (glass transition temperature 170°C, labeled COC17), 4 wt% of a polyolefin thermoplastic elastomer, and 10 wt% of a styrene thermoplastic elastomer; wherein the polyolefin thermoplastic elastomer has a crystallinity of 12%, a melting temperature of 120°C, a melt index of 1 g / min, and a number-average molecular weight of 15 W; labeled OBC. The styrene thermoplastic elastomer has a number-average molecular weight of 25 W, a melt index of 0.5 g / 10 min, and a styrene content of 30%; labeled SEBS.
[0157] Example 13
[0158] This application provides a resin composition comprising 92 wt% of a cyclic olefin copolymer (glass transition temperature 150°C, labeled COC15), 6 wt% of a polyolefin thermoplastic elastomer, and 2 wt% of a styrene thermoplastic elastomer; wherein the polyolefin thermoplastic elastomer has a crystallinity of 12%, a melting temperature of 120°C, a melt index of 1 g / min, and a number-average molecular weight of 15 W; labeled OBC. The styrene thermoplastic elastomer has a number-average molecular weight of 25 W, a melt index of 0.5 g / 10 min, and a styrene content of 30%; labeled SEBS.
[0159] Comparative Example 1
[0160] This comparative example provides a resin composition comprising 75 wt% of a cyclic olefin copolymer (glass transition temperature of 170°C, labeled COC17) and 25 wt% of a polyolefin thermoplastic elastomer; wherein the polyolefin thermoplastic elastomer has a crystallinity of 12%, a melting temperature of 120°C, a melt index of 1 g / min, and a number-average molecular weight of 15 W; labeled OBC.
[0161] The preparation method is the same as in Example 1.
[0162] Comparative Example 2
[0163] This comparative example provides a resin composition comprising 75 wt% of a cyclic olefin copolymer (glass transition temperature of 170°C, labeled COC17) and 25 wt% of a styrene thermoplastic elastomer; wherein the styrene thermoplastic elastomer has a number-average molecular weight of 25W, a melt index of 0.5 g / 10 min, and a styrene content of 30%; labeled SEBS.
[0164] The preparation method is the same as in Example 1.
[0165] Comparative Example 3
[0166] This comparative example provides a resin composition comprising 80 wt% of a cyclic olefin copolymer (glass transition temperature of 130°C, labeled COC13) and 20 wt% of a styrene thermoplastic elastomer; wherein the styrene thermoplastic elastomer has a number-average molecular weight of 25 W, a melt index of 0.5 g / 10 min, and a styrene content of 30%; labeled SEBS.
[0167] The preparation method is the same as in Example 1.
[0168] The raw material components and their proportions in the above embodiments and comparative examples are shown in Table 1 below:
[0169] Table 1
[0170] To verify the progressiveness of the embodiments of this application, the resin compositions provided in the above embodiments and comparative examples were subjected to the following performance tests:
[0171] 1. Izod notch impact test; for specific test details, refer to ISO 180.
[0172] 2. Tensile strength test: For specific test details, refer to ISO 527, tensile rate 50 mm / min;
[0173] 3. Heat distortion temperature (HDT) test: For specific test details, please refer to ISO 75. This test is conducted under a pressure of 0.45 MPa.
[0174] 4. Dielectric constant test: Refer to IEC 61189-2-721 for specific test methods;
[0175] 5. Dielectric loss test: Refer to IEC 61189-2-721 for specific test methods;
[0176] The test results are shown in Table 2 below:
[0177] Table 2
[0178] As shown in Table 2, the resin compositions prepared in the embodiments of this application all exhibit low dielectric loss, high impact strength, and high heat resistance. In particular, the resin compositions provided in Examples 1 to 6, when the glass transition temperature of the cyclic olefin copolymer is 150°C to 220°C, the mass percentage of the toughening agent is 12% to 30%, and the mass ratio of styrene thermoplastic elastomer to polyolefin thermoplastic elastomer in the toughening agent is 1:(0.5 to 10), exhibit a notched impact strength greater than 12 kJ / m. 2 The highest value can reach 28.8 kJ / m 2 This indicates that the material has high impact strength; the continuously increasing notched impact strength indicates that the material has good toughness. Furthermore, the dielectric loss is less than 4 × 10⁻⁶. -4 (1-10GHz), indicating that the material has low energy consumption characteristics at high frequencies. The heat distortion temperature is greater than 145℃, proving that the material can maintain stable physical properties at high temperatures.
[0179] By comparing Examples 1-6 and Example 7, it can be seen that when the mass percentage of toughening agent in the resin composition is higher than 30%, the tensile strength of the resin composition will be reduced to a certain extent.
[0180] By comparing Examples 1-6 and Example 8, it can be seen that when the mass percentage of toughening agent in the resin composition is less than 10%, the notched impact of the resin composition is significantly reduced.
[0181] In the toughening agent of Example 9, the mass ratio of styrene thermoplastic elastomer to polyolefin thermoplastic elastomer is 5:1, and in the toughening agent of Example 12, the mass ratio of styrene thermoplastic elastomer to polyolefin thermoplastic elastomer is 2.5:1. In these cases, the notched impact of the resin composition is reduced to some extent.
[0182] The glass transition temperature of the cyclic olefin copolymer in Example 10 was reduced to 130°C, which to some extent lowered the heat distortion temperature of the resin composition. The glass transition temperature of the cyclic olefin copolymer in Example 13 was reduced to 220°C, which to some extent increased the heat distortion temperature of the resin composition and reduced the notched impact resistance of the resin composition.
[0183] In Comparative Example 1, the toughening agent in the resin composition was only a polyolefin thermoplastic elastomer, which had poor compatibility and could not be granulated. In Comparative Examples 2 and 3, the toughening agent in the resin compositions was only a styrene thermoplastic elastomer, and the impact strength, dielectric loss, or thermal stability were affected to varying degrees.
[0184] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of this application, and not to limit them. Although this application has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features therein. These modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of this application, and they should all be covered within the scope of the claims and specification of this application. In particular, as long as there is no structural conflict, the various technical features mentioned in the embodiments can be combined in any way. The protection scope of this application is not limited to the specific embodiments disclosed herein, but includes all technical solutions falling within the scope of the claims. Therefore, the protection scope of this application should be determined by the protection scope of the claims.
Claims
1. A resin composition, characterized in that, It includes cyclic olefin copolymers and toughening agents, wherein the toughening agents include polyolefin thermoplastic elastomers and styrene thermoplastic elastomers.
2. The resin composition according to claim 1, characterized in that, The polyolefin thermoplastic elastomer has at least one of the following characteristics: (1) The crystallinity of the polyolefin thermoplastic elastomer is 5% to 25%; (2) The melting temperature of the polyolefin thermoplastic elastomer is not lower than 110°C; (3) The melt index of the polyolefin thermoplastic elastomer is not higher than 1 g / 10 min; (4) The number average molecular weight of the polyolefin thermoplastic elastomer is not less than 100,000.
3. The resin composition according to claim 1 or 2, characterized in that, The styrene thermoplastic elastomer has at least one of the following characteristics: (1) The number-average molecular weight of the styrene thermoplastic elastomer is 200,000 to 500,000; (2) The styrene content in the styrene thermoplastic elastomer is 15% to 35%; (3) The melt index of the styrene thermoplastic elastomer is less than 1 g / 10 min.
4. The resin composition according to claim 3, characterized in that, In the resin composition, the toughening agent has a mass percentage content of 12% to 30%.
5. The resin composition according to claim 4, characterized in that, The mass ratio of the styrene thermoplastic elastomer to the polyolefin thermoplastic elastomer is 1:(0.5-10).
6. The resin composition according to any one of claims 1, 2, 4 or 5, characterized in that, The glass transition temperature of the cyclic olefin copolymer is 150℃~220℃.
7. The resin composition according to claim 6, characterized in that, The glass transition temperature of the cyclic olefin copolymer is 150℃~170℃.
8. The resin composition according to claim 6, characterized in that, The resin composition includes at least two cyclic olefin copolymers with different glass transition temperatures.
9. The resin composition according to any one of claims 1, 2, 4, 5, 7 or 8, characterized in that, The notched impact strength of the resin composition is greater than 12 kJ / m. 2 .
10. The resin composition according to any one of claims 1, 2, 4, 5, 7 or 8, characterized in that, The dielectric loss of the resin composition is less than 4 × 10⁻⁶ in the frequency range of 1 GHz to 10 GHz. -4 .
11. The resin composition according to any one of claims 1, 2, 4, 5, 7 or 8, characterized in that, The heat distortion temperature of the resin composition is greater than 145°C.
12. A method for preparing a resin composition, characterized in that, Includes the following steps: A resin composition is obtained by melt extrusion granulation after mixing a cyclic olefin copolymer and a toughening agent; wherein the toughening agent includes a polyolefin thermoplastic elastomer and a styrene thermoplastic elastomer.
13. The method for preparing the resin composition according to claim 12, characterized in that, The melt extrusion granulation is performed using a twin-screw extruder. The extrusion temperature of the twin-screw extruder is 220℃~270℃, the screw speed is 400rpm~600rpm, and the screw length-to-diameter ratio is (35~45):
1.
14. The application of a resin composition, characterized in that, The resin composition according to any one of claims 1 to 11 and / or the resin composition prepared by the preparation method according to any one of claims 12 to 13 are applied to at least one of the fields of insulating materials, electronic component packaging materials, and communication medium materials.