Cycloolefin polymer material and preparation method thereof

Abstract

The invention provides a cycloolefin polymer material and a preparation method thereof. The simply supported beam impact strength of the cycloolefin polymer material at-20 DEG C to-10 DEG C is greater than or equal to 20 kJ / m < 2 >. According to the cycloolefin polymer material provided by the invention, the simply supported beam impact strength at-20 DEG C to-10 DEG C is greater than or equal to 20kJ / m < 2 >, that is, the molecular chain of the material still has certain flexibility at a low temperature, so that the material can effectively absorb and disperse energy when being impacted, thereby reducing the generation and expansion of cracks and improving the performance of the material. The toughness of the cycloolefin polymer material at low temperature is improved.

Description

Technical Field

[0001] The present invention belongs to the technical field of materials, and in particular relates to a cycloolefin polymer material and a preparation method thereof. Background Art

[0002] Cyclic olefin polymer (COP) has become a key material in optical materials and high-end pharmaceutical packaging due to its excellent optical and physical properties. COP's high transparency, low birefringence, and excellent water vapor barrier properties make it an excellent choice for applications requiring high-precision optical properties and moisture resistance. Furthermore, its high rigidity and heat resistance make it competitive in many industrial applications.

[0003] However, the polarity of COP materials makes them prone to cracking under low-temperature conditions, especially during low-temperature transportation and storage. This defect limits their application in extreme environments. Therefore, developing a COP material with good low-temperature toughness has become a research focus. Summary of the Invention

[0004] The main purpose of the present invention is to provide a cycloolefin polymer material, which has good toughness at low temperatures.

[0005] The present invention also provides a method for preparing a cycloolefin polymer material. The method can prepare the cycloolefin polymer material, and the process is simple and the cost is low.

[0006] In a first aspect, the present invention provides a cycloolefin polymer material having a simple supported beam impact strength of greater than or equal to 20 kJ / m at -20°C to -10°C. 2 .

[0007] The cycloolefin polymer material as described above has a simple supported beam impact strength of 20 kJ / m at -20°C to -10°C. 2 ~30kJ / m 2 .

[0008] The cycloolefin polymer material as described above has a transmittance greater than or equal to 90%, preferably 92% to 96%.

[0009] The cycloolefin polymer material as described above, wherein the cycloolefin polymer material comprises a toughening agent, and the toughening agent comprises modified highly chlorinated polyethylene;

[0010] The modified highly chlorinated polyethylene is obtained by modifying highly chlorinated polyethylene with a modifier;

[0011] The modifier includes silicone oil and / or white oil.

[0012] The cycloolefin polymer material as described above, wherein the modified highly chlorinated polyethylene is obtained by mixing the highly chlorinated polyethylene with a modifier accounting for 1 to 5 times the mass of the highly chlorinated polyethylene and heat-treating the mixture;

[0013] And / or, the mass proportion of chlorine element in the highly chlorinated polyethylene is 64% to 75%;

[0014] And / or, the weight average molecular weight of the highly chlorinated polyethylene is 40,000 to 100,000;

[0015] and / or, the modifier comprises silicone oil and white oil;

[0016] The mass ratio of the silicone oil to the white oil is 1:(1-4).

[0017] In the cycloolefin polymer material as described above, the toughening agent accounts for 2.5% to 8% by mass of the cycloolefin polymer material.

[0018] The cycloolefin polymer material as described above, comprising a cycloolefin polymer resin, satisfies:

[0019] The glass transition temperature of the cycloolefin polymer resin is greater than 163°C;

[0020] and / or, the melt flow rate of the cycloolefin polymer resin is less than or equal to 10 g / 10 min;

[0021] And / or, the weight average molecular weight of the cycloolefin polymer resin is 20,000 to 50,000.

[0022] The cycloolefin polymer material as described above, further comprising at least one of an antioxidant, a lubricant, a stabilizer, and an ultraviolet absorber;

[0023] Preferably, the antioxidant comprises hindered phenol and phosphite;

[0024] Preferably, the mass ratio of the hindered phenol to the phosphite is 1:(1-4).

[0025] In a second aspect, the present invention provides a method for preparing the cycloolefin polymer material as described above, comprising the following steps:

[0026] The mixed material including the cycloolefin polymer resin and the toughening agent is subjected to a molding process to obtain the cycloolefin polymer material.

[0027] The method for preparing the cycloolefin polymer material as described above, wherein the molding process comprises sequentially melting, extruding, and granulating the mixed material to obtain the cycloolefin polymer material;

[0028] And / or, the mixture further comprises at least one of an antioxidant, a lubricant, a stabilizer, and an ultraviolet absorber.

[0029] The cycloolefin polymer material provided by the present invention has a simply supported beam impact strength of greater than or equal to 20 kJ / m at -20°C to -10°C. 2 , that is, the molecular chain of the material still has a certain flexibility at low temperatures, so that the material can effectively absorb and disperse energy when impacted, thereby reducing the generation and expansion of cracks and improving the toughness of cycloolefin polymer materials at low temperatures. DETAILED DESCRIPTION

[0030] To make the objectives, technical solutions, and advantages of the present invention more clear, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts shall fall within the scope of protection of the present invention.

[0031] COP materials, primarily cycloolefin polymers (COPs), are a class of polymers with broad application prospects. They are formed through the ring-opening heterogeneous polymerization of bicycloheptene (norbornene) under a metallocene catalyst, followed by hydrogenation to form an amorphous homopolymer. COP materials exhibit high transparency, low birefringence, low water absorption, high rigidity, high heat resistance, and excellent water vapor tightness. Therefore, they are widely used in optical materials and high-end pharmaceutical packaging. However, due to their inherent polarity, they are prone to cracking during use, particularly during low-temperature transportation, which significantly limits their application at low temperatures.

[0032] The brittleness of COP materials is primarily related to their molecular structure and polarity. At low temperatures, the material's molecular chain mobility decreases, leading to a decrease in toughness and increased susceptibility to cracking and breakage. This phenomenon not only affects the material's mechanical properties but can also degrade its optical properties, ultimately impacting the overall performance and reliability of the product. Therefore, addressing the brittleness of COP materials at low temperatures has become a research priority.

[0033] The inventors of the present application have discovered through research that by limiting the simply supported beam impact strength of a cycloolefin polymer material at low temperatures, its toughness at low temperatures can be significantly improved.

[0034] Based on this, in the first aspect, the present invention provides a cycloolefin polymer (COP) material, wherein the cycloolefin polymer (COP) has a simple supported beam impact strength greater than or equal to 20 kJ / m at -20°C to -10°C. 2 , for example, it can be 20kJ / m2 , 21kJ / m 2 , 22kJ / m 2 , 23kJ / m 2 , 24kJ / m 2 , 25kJ / m 2 , 26kJ / m 2 , 27kJ / m 2 , 28kJ / m 2 , 29kJ / m 2 、30kJ / m 2 The temperature may be -20°C, -19°C, -18°C, -17°C, -16°C, -15°C, -14°C, -13°C, -12°C, -11°C, -10°C, or a range consisting of any two thereof.

[0035] As you can understand, the simply supported beam impact strength test, also known as the Charpy impact test or Izod impact test, is a widely used standard test method for evaluating the impact resistance of materials. This method involves placing a standard-sized specimen horizontally on two supports to form a simply supported beam structure. A pendulum with a specified mass is then dropped from a certain height to strike one side of the specimen. The height of the pendulum's rebound or the energy absorbed by the fractured specimen is recorded to evaluate the material's impact toughness.

[0036] The simply supported beam impact test, based on the principle of energy conservation, indirectly reflects a material's energy absorption capacity when subjected to an impact load by measuring the change in energy of the pendulum before and after the impact. A higher energy absorption value indicates that the material is more effectively able to disperse and absorb energy during an impact, thereby reducing damage to the material structure.

[0037] The cycloolefin polymer material provided by the present invention has good toughness at low temperatures. The reason for this is that the simply supported beam impact strength of the cycloolefin polymer material at -20°C to -10°C is greater than or equal to 20 kJ / m 2 , which means that the molecular chain of the material still has a certain flexibility at low temperatures. This flexibility enables the material to effectively absorb and disperse energy when impacted, thereby reducing the generation and expansion of cracks, that is, improving the toughness of cycloolefin polymer materials at low temperatures and solving the problem of cracking and breakage at low temperatures.

[0038] Therefore, the cycloolefin polymer material provided by the present invention has a simply supported beam impact strength of greater than or equal to 20 kJ / m at -20°C to -10°C. 2 , which can improve its toughness at low temperatures.

[0039] The present invention is not limited to the shape of the cycloolefin polymer material. For example, the cycloolefin polymer material may be in the form of particles, blocks, or other regular or irregular shapes.

[0040] The Charpy impact strength of the cycloolefin polymer material of the present invention can be tested according to ISO 179.

[0041] The present invention is not limited to the size of the block made of the material when testing the simply supported beam impact strength. For example, the size can be 80 mm×6 mm×4 mm.

[0042] In some embodiments of the present invention, the cycloolefin polymer material has a simple supported beam impact strength of 20 kJ / m at -20°C to -10°C. 2 ~30kJ / m 2 , for example, it can be 20kJ / m 2 , 21kJ / m 2 , 22kJ / m 2 , 23kJ / m 2 , 24kJ / m 2 , 25kJ / m 2 , 26kJ / m 2 , 27kJ / m 2 , 28kJ / m 2 , 29kJ / m 2 、30kJ / m 2 or a range consisting of any two of them.

[0043] The cycloolefin polymer material provided by the present invention has a simple supported beam impact strength of 20 kJ / m at -20°C to -10°C. 2 ~30kJ / m 2 In a preferred range, the toughness of the cycloolefin polymer material at low temperatures can be further improved. The simply supported beam impact strength of the cycloolefin polymer material at -20°C to -10°C is less than or equal to 30 kJ / m 2 , which can keep the material consistent during the production process and keep the material easy to operate during the processing. In addition, it can also keep the material stable and reliable during use.

[0044] In some embodiments of the present invention, the transmittance of the cycloolefin polymer material is greater than or equal to 90%, for example, it can be 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99% or a range consisting of any two thereof, preferably 92% to 96%.

[0045] In the present invention, the transmittance of the cycloolefin polymer material is within the above range, and light can effectively pass through the material without being significantly scattered or absorbed, so that the cycloolefin polymer material has good transparency and can meet the needs of various industries.

[0046] The transmittance of the cycloolefin polymer material of the present invention can be tested according to ASTM D-1003.

[0047] The present invention is not limited to the size of the block made of the material when testing the transmittance. For example, the size can be 60 mm×50 mm×3 mm.

[0048] In some embodiments of the present invention, the cycloolefin polymer material includes a toughening agent, wherein the toughening agent includes modified highly chlorinated polyethylene (CPE); the modified highly chlorinated polyethylene is obtained by modifying highly chlorinated polyethylene (CPE) with a modifier; the modifier includes silicone oil and / or white oil, wherein the silicone oil includes dimethyl silicone oil.

[0049] The cycloolefin polymer material in the present invention includes a toughening agent, which includes modified highly chlorinated polyethylene. The highly chlorinated polyethylene is modified by silicone oil and / or white oil, which can improve the toughness of the cycloolefin polymer material at low temperatures and maximize the transmittance of the cycloolefin polymer material.

[0050] The organic functional groups in the silicone oil used in the modifier of this invention chemically bond with the chlorine atoms in the CPE, forming a stable bonding layer that enhances the compatibility between the CPE and the cycloolefin polymer matrix (e.g., a cycloolefin polymer resin). The cycloalkanes in the white oil bind to the chlorine atoms in the CPE, making them more active. This improves the compatibility between the CPE and the cycloolefin polymer matrix and addresses the issues of poor transmittance and cracking caused by agglomeration during processing.

[0051] The preparation method of the modified highly chlorinated polyethylene of the present invention may comprise the following steps:

[0052] The raw materials including the modifier and the highly chlorinated polyethylene are mixed and heat-treated, and allowed to stand to obtain modified highly chlorinated polyethylene.

[0053] Preferably, the heat treatment temperature can be 70°C~120°C, for example, it can be 70°C, 80°C, 90°C, 100°C, 110°C, 120°C or a range consisting of any two thereof; the heat treatment time can be 5min~10min, for example, it can be 5min, 6min, 7min, 8min, 9min, 10min or a range consisting of any two thereof.

[0054] The standing may be performed in an anaerobic environment, and the standing time may be 4 to 8 hours, for example, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, or a range consisting of any two of these hours.

[0055] In specific implementation, the heat treatment can be performed before mixing or after mixing, without any specific limitation.

[0056] In one embodiment, the preparation method of modified highly chlorinated polyethylene may include the following steps:

[0057] 1) Add the modifier into a beaker and mix evenly. Heat the beaker to 70°C~120°C and mix for 5min~10min to obtain a mixed solution.

[0058] 2) Add highly chlorinated polyethylene to the mixed solution of step 1) and mix evenly, and place it in an oxygen-free environment for 4 hours to 8 hours to obtain modified highly chlorinated polyethylene.

[0059] In some embodiments of the present invention, the modified highly chlorinated polyethylene is obtained by mixing and heat-treating highly chlorinated polyethylene with a modifier in an amount of 1 to 5 times its mass, for example, 1, 2, 3, 4, 5 times, or any combination thereof. This allows for sufficient modification of the highly chlorinated polyethylene, and the modified highly chlorinated polyethylene, as a toughening agent, can further enhance the toughness of the cycloolefin polymer material at low temperatures.

[0060] In some embodiments, the mass proportion of chlorine element in the highly chlorinated polyethylene is 64% to 75%, for example, it can be 64%, 66%, 68%, 70%, 72%, 75% or a range of any two thereof, which can further improve the toughness of the cycloolefin polymer material at low temperatures and improve the weather resistance.

[0061] In some embodiments, the weight average molecular weight of the highly chlorinated polyethylene is 40,000 to 100,000, for example, 40,000, 50,000, 60,000, 70,000, 80,000, 90,000, 100,000, or any two thereof, which can improve the impact strength and weather resistance of the cycloolefin polymer material.

[0062] In a specific embodiment, the modifier includes silicone oil and white oil; the mass ratio of silicone oil to white oil is 1:(1~4), for example, it can be 1:1, 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5, 1:4 or a range consisting of any two thereof.

[0063] In the present invention, when the modifier includes silicone oil and white oil, and the mass ratio of silicone oil to white oil is 1:(1-4), the low-temperature flexibility of silicone oil is combined with the plasticizing effect of white oil, so that the material can still maintain good mechanical properties and impact resistance under low temperature conditions.

[0064] In some embodiments of the present invention, the toughening agent accounts for 2.5% to 8% by mass of the cycloolefin polymer material, for example, it can be 2.5%, 3%, 4%, 5%, 6%, 7%, 8% or any two thereof.

[0065] In the present invention, the toughening agent content in the cycloolefin polymer material within the above-mentioned mass percentage range effectively improves the material's impact resistance and toughness at low temperatures, making the material less susceptible to brittle cracking or breakage when subjected to mechanical stress. Furthermore, the toughening agent content does not significantly affect the material's transparency and optical properties.

[0066] In some embodiments of the present invention, the cycloolefin polymer material comprises a cycloolefin polymer resin; satisfying:

[0067] The glass transition temperature of the cycloolefin polymer resin is greater than 163°C, for example, 163°C, 165°C, 167°C, 170°C, 173°C, 175°C, 180°C, 190°C, 200°C, or a range consisting of any two thereof. This glass transition temperature enables the cycloolefin polymer material to maintain its rigidity and shape at higher temperatures. Under high temperature conditions, the material is less likely to deform, ensuring its dimensional stability and reliability during use.

[0068] In some embodiments, the melt flow rate (MFR) of the cycloolefin polymer resin is less than or equal to 10 g / 10 min, for example, 1 g / 10 min, 2 g / 10 min, 3 g / 10 min, 4 g / 10 min, 5 g / 10 min, 6 g / 10 min, 7 g / 10 min, 8 g / 10 min, 9 g / 10 min, 10 g / 10 min, or any two thereof. This MFR allows the cycloolefin polymer material to have good shape retention at low temperatures, further improving its toughness and impact resistance at low temperatures.

[0069] The melt flow rate of the cycloolefin polymer resin of the present invention can be tested according to TM D1238, with a test temperature of 260° C. and a test load of 2.16 kg.

[0070] In some embodiments, the cycloolefin polymer resin has a weight average molecular weight of 20,000 to 50,000, for example, 20,000, 25,000, 30,000, 35,000, 40,000, 45,000, 50,000, or any two thereof, which can provide good mechanical properties and make the material easy to handle during processing.

[0071] In some embodiments of the present invention, the cycloolefin polymer material further includes at least one of an antioxidant, a lubricant, a stabilizer, and a UV absorber. This can significantly enhance the performance and durability of the material. The presence of an antioxidant helps maintain the material's mechanical properties, such as strength and toughness, and prevents performance degradation due to oxidative degradation. The UV absorber can further protect the material from damage by ultraviolet radiation and prevent photodegradation. This is particularly important for outdoor applications and products that require prolonged exposure to sunlight. The addition of a lubricant can improve the material's processing properties, reduce friction and heat generation during processing, and increase production efficiency.

[0072] Preferably, the antioxidant includes hindered phenols and phosphites.

[0073] Preferably, the mass ratio of the hindered phenol to the phosphite is 1:(1-4), for example, it can be 1:1, 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5, 1:4 or a range consisting of any two thereof.

[0074] Hindered phenols, as effective free radical scavengers, can interrupt the oxidation chain reaction, thereby preventing the degradation of polymers. Phosphites, as auxiliary antioxidants, can decompose peroxides, further improving the antioxidant properties of the material.

[0075] By combining hindered phenols and phosphites and limiting their mass ratio, a synergistic effect can be achieved, providing stronger antioxidant protection and more effectively delaying the aging process of the material.

[0076] The raw materials of the cycloolefin polymer material of the present invention may include the following components in parts by mass: 70 to 100 parts of cycloolefin polymer resin, for example, it can be in the range of 70 parts, 80 parts, 85 parts, 90 parts, 100 parts or any two thereof; 3 to 8 parts of toughening agent, for example, it can be in the range of 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts or any two thereof; 0.3 to 0.5 parts of antioxidant, for example, it can be in the range of 0.3 part, 0.34 part, 0.4 part, 0.45 part, 0.5 part or any two thereof.

[0077] In a second aspect, the present invention provides a method for preparing the cycloolefin polymer material as described above, comprising the following steps:

[0078] The mixed material including the cycloolefin polymer resin and the toughening agent is subjected to a molding process to obtain a cycloolefin polymer material.

[0079] In the present invention, the cycloolefin polymer resin and the toughening agent can be dry-mixed in a high-speed mixer for 3 to 5 minutes to obtain a mixture; and then the mixture is subjected to a molding process to obtain the cycloolefin polymer material.

[0080] In the present invention, other additives, such as antioxidants, can be added to the mixture as needed to optimize the performance of the material.

[0081] The present invention can perform molding processing on the mixed material as required to obtain a product of a desired shape.

[0082] The method for preparing the cycloolefin polymer material of the present invention can prepare the cycloolefin polymer material provided by the first aspect of the present invention, and the material has good toughness at low temperatures.

[0083] In some embodiments of the present invention, the molding process includes sequentially melting, extruding, and granulating the mixed material to obtain a cycloolefin polymer material.

[0084] In the present invention, the melting step ensures that the cycloolefin polymer resin, toughening agent, and other additives are evenly distributed throughout the material, forming a homogeneous melt. The extrusion process effectively removes bubbles and inhomogeneities from the mixture, improving the material's density and mechanical properties. The granulation process converts the material into pellets that are easy to handle and transport, facilitating subsequent processing and applications.

[0085] The molding process of the present invention may specifically include the following steps: placing the mixed material into a twin-screw extruder as the main feed, and then melting, extruding, and granulating to obtain a cycloolefin polymer material. The melt treatment temperature is 240°C to 260°C, for example, 240°C, 245°C, 250°C, 255°C, 260°C, or any two thereof; the extrusion pressure is 10 MPaG to 15 MPaG, for example, 10 MPaG, 11 MPaG, 12 MPaG, 13 MPaG, 14 MPaG, 15 MPaG, or any two thereof. Specifically, the melt treatment can be divided into ten zones: the temperature of zone one is 240°C to 245°C, the temperatures of zones two and three are 250°C to 255°C, the temperatures of zones four, five, and six are 255°C to 260°C, and the temperatures of zones seven, eight, nine, and ten are 240°C to 255°C.

[0086] In some embodiments, the mixture further includes at least one of an antioxidant, a lubricant, a stabilizer, and an ultraviolet absorber, which can further enhance the performance and durability of the cycloolefin polymer material.

[0087] The technical solution of the present invention is further described below with reference to specific embodiments.

[0088] The raw materials and instruments used in the following examples and comparative examples are as follows:

[0089] COP resin: 790R, Japan Zeon Co., Ltd.

[0090] Highly chlorinated polyethylene: 135A, Zibo Huaxing Company.

[0091] Antioxidant: B215, BASF.

[0092] Dimethyl silicone oil: Wanhua Chemical Company.

[0093] Twin-screw extruder: Coperion twin-screw extruder.

[0094] Example 1

[0095] The preparation method of the cycloolefin polymer material of the present embodiment comprises the following steps:

[0096] 1) Mix 500 g of dimethyl silicone oil with 500 g of white oil, heat to 70°C and stir for 5 minutes, then add 1000 g of highly chlorinated polyethylene and mix for 5 minutes. Place the mixture in an oxygen-free environment and let it stand for 4 hours to obtain modified highly chlorinated polyethylene, wherein the mass ratio of dimethyl silicone oil to white oil is 1:1, the mass ratio of the modifier (dimethyl silicone oil and white oil) to highly chlorinated polyethylene is 1:1, the mass proportion of chlorine element in the highly chlorinated polyethylene is 64%, and the weight average molecular weight of the highly chlorinated polyethylene is 40,000.

[0097] 2) 100 parts by weight of COP resin, 3 parts by weight of toughening agent-modified high-chlorinated polyethylene, and 0.4 parts by weight of antioxidant were dry-blended in a high-speed mixer for 5 minutes to obtain a mixture. The mixture was placed in a twin-screw extruder as the main feed, melted, extruded, and pelletized to obtain a cycloolefin polymer material. The COP resin had a glass transition temperature of 169°C, a melt flow rate of 9.5 g / 10 min, and a weight-average molecular weight of 20,000. The antioxidant consisted of a hindered phenol and a phosphite in a 1:1 ratio by weight. The melting temperature was 245°C, and the extrusion pressure was 10 MPaG. The toughening agent accounted for 2.9% by weight of the cycloolefin polymer material.

[0098] Example 2

[0099] The preparation method of the cycloolefin polymer material of Example 2 comprises the following steps:

[0100] 1) 500 g of dimethyl silicone oil was mixed with 2000 g of white oil, heated to 120° C. and stirred for 10 min. 2500 g of highly chlorinated polyethylene was then added and mixed for 10 min. The mixture was allowed to stand in an oxygen-free environment for 8 h to obtain modified highly chlorinated polyethylene, wherein the mass ratio of dimethyl silicone oil to white oil was 1:4, the mass ratio of the modifier (dimethyl silicone oil and white oil) to highly chlorinated polyethylene was 1:1, the mass proportion of chlorine element in the highly chlorinated polyethylene was 75%, and the weight average molecular weight of the highly chlorinated polyethylene was 100,000.

[0101] 2) 100 parts by weight of COP resin, 8 parts by weight of toughening agent-modified high-chlorinated polyethylene, and 0.4 parts by weight of antioxidant were dry-blended in a high-speed mixer for 5 minutes to obtain a mixture. The mixture was placed in a twin-screw extruder as the main feed, melted, extruded, and pelletized to obtain a cycloolefin polymer material. The COP resin had a glass transition temperature of 170°C, a melt flow rate of 8.8 g / 10 min, and a weight-average molecular weight of 50,000. The antioxidant consisted of a hindered phenol and a phosphite in a 1:4 weight ratio. The melting temperature was 260°C, and the extrusion pressure was 12 MPaG. The toughening agent accounted for 7.4% by weight of the cycloolefin polymer material.

[0102] Example 3

[0103] The preparation method of the cycloolefin polymer material of Example 3 comprises the following steps:

[0104] 1) 500 g of dimethyl silicone oil was mixed with 1300 g of white oil, heated to 100°C and stirred for 6 minutes, and then 1800 g of highly chlorinated polyethylene was added and mixed for 7 minutes. The mixture was allowed to stand in an oxygen-free environment for 6 hours to obtain modified highly chlorinated polyethylene, wherein the mass ratio of dimethyl silicone oil to white oil was 1:2.6, the mass ratio of the modifier (dimethyl silicone oil and white oil) to highly chlorinated polyethylene was 1:1, the mass proportion of chlorine element in the highly chlorinated polyethylene was 70%, and the weight average molecular weight of the highly chlorinated polyethylene was 70,000.

[0105] 2) 100 parts by weight of COP resin, 5 parts by weight of toughening agent-modified high-chlorinated polyethylene, and 0.4 parts by weight of antioxidant were dry-blended in a high-speed mixer for 5 minutes to obtain a mixture. The mixture was placed in a twin-screw extruder as the main feed, melted, extruded, and pelletized to obtain a cycloolefin polymer material. The COP resin had a glass transition temperature of 170.5°C, a melt flow rate of 9.6 g / 10 min, and a weight-average molecular weight of 35,000. The antioxidant consisted of a hindered phenol and a phosphite in a 1:3 weight ratio. The melting temperature was 250°C, and the extrusion pressure was 14.5 MPaG. The toughening agent accounted for 4.7% by weight of the cycloolefin polymer material.

[0106] Example 4

[0107] The preparation methods of the cycloolefin polymer material in Example 4 are substantially the same as those in Example 3, except that, in step 1), the dimethyl silicone oil and the white oil are not subjected to heating treatment.

[0108] Example 5

[0109] The preparation methods of the cycloolefin polymer materials of Example 5 and Example 3 are basically the same, except that the glass transition temperature of the COP resin is 160° C., the melt flow rate is 20 g / 10 min, and the weight average molecular weight is 18,000.

[0110] Example 6

[0111] The preparation methods of the cycloolefin polymer materials of Example 6 and Example 3 are basically the same, except that the glass transition temperature of the COP tree is 160° C., the melt flow rate is 15 g / 10 min, and the weight average molecular weight is 60,000.

[0112] Example 7

[0113] The preparation methods of the cycloolefin polymer materials of Example 7 and Example 3 are basically the same, except that the mass ratio of hindered phenol to phosphite is 1:0.6.

[0114] Example 8

[0115] The preparation methods of the cycloolefin polymer materials in Example 8 are substantially the same as those in Example 3, except that the mass ratio of hindered phenol to phosphite is 1:5.

[0116] Example 9

[0117] The preparation method of the cycloolefin polymer material in Example 9 is basically the same as that in Example 3, except that 600 g of highly chlorinated polyethylene is added so that the mass ratio of the modifier (dimethyl silicone oil and white oil) to highly chlorinated polyethylene is 3:1.

[0118] Example 10

[0119] The preparation method of the cycloolefin polymer material in Example 10 is basically the same as that in Example 3, except that 360 g of highly chlorinated polyethylene is added so that the mass ratio of the modifier (dimethyl silicone oil and white oil) to highly chlorinated polyethylene is 5:1.

[0120] Comparative Example 1

[0121] The preparation methods of the cycloolefin polymer materials of Comparative Example 1 and Example 3 are basically the same, except that unmodified highly chlorinated polyethylene is used as the toughening agent.

[0122] Comparative Example 2

[0123] The preparation methods of the cycloolefin polymer materials of Comparative Example 2 and Example 3 are basically the same, except that tetrahydrofuran is used as a modifier to modify the highly chlorinated polyethylene, and the modified highly chlorinated polyethylene is used as a toughening agent.

[0124] Comparative Example 3

[0125] The preparation methods of the cycloolefin polymer materials of Comparative Example 3 and Example 3 are basically the same, except that acrylic acid is used as a toughening agent.

[0126] Test example:

[0127] The granular material granulated according to the above method was dried in a blast oven at 80° C. for 4 hours in advance, and then the dried granular material was injection molded on an injection molding machine to prepare samples.

[0128] 1. Simply supported beam impact strength: tested in accordance with ISO 179, the test temperature is -20°C, and the sample size is 80mm×6mm×4mm;

[0129] 2. Transmittance: Tested in accordance with ASTM D-1003, with a sample size of 60 mm × 50 mm × 3 mm.

[0130] 3. Melt flow rate: tested according to TM D1238, with a test temperature of 260°C and a test load of 2.16 kg.

[0131] 4. Glass transition temperature: Tested in accordance with GB / T19466.2-2009, plastic differential scanning calorimetry (DSC).

[0132] 5. Weight average molecular weight: tested in accordance with ASTM D4001-93 (2006).

[0133] 6. Mass percentage of chlorine in highly chlorinated polyethylene: Tested in accordance with GB / T 7139-2023.

[0134] Table 1

[0135]

[0136] As shown in Table 1, compared with the comparative example, the cycloolefin polymer material provided by the present invention has a simple supported beam impact strength of greater than or equal to 20 kJ / m at -20°C to -10°C. 2 , that is, the molecular chain of the material still has a certain flexibility at low temperatures, so that the material can effectively absorb and disperse energy when impacted, thereby reducing the generation and expansion of cracks and improving the toughness of cycloolefin polymer materials at low temperatures.

[0137] Compared with Examples 5-6, the COP resins of Examples 1-3 have a glass transition temperature greater than 163° C., a melt flow rate less than or equal to 10 g / 10 min, and a weight-average molecular weight between 20,000 and 50,000, which can further improve the transmittance and toughness of the cycloolefin polymer material at low temperatures.

[0138] Compared with Examples 7-8, the mass ratio of hindered phenol to phosphite in the antioxidant of Examples 1-3 is between 1:(1~4), which can further improve the transmittance and toughness of the cycloolefin polymer material at low temperatures.

[0139] Finally, it should be noted that those skilled in the art will readily identify other embodiments of the present invention after considering the specification and practicing the invention disclosed herein. The present invention is intended to cover any variations, uses, or adaptations of the present invention that follow the general principles of the present invention and include common knowledge or customary techniques in the art not disclosed herein. The present invention is not limited to the precise structure described and illustrated above, and various modifications and variations may be made without departing from the scope thereof. The scope of the present invention is limited solely by the appended claims.

Claims

1. A cycloolefin polymer material, characterized in that: The cycloolefin polymer material has a simply supported beam impact strength of greater than or equal to 20 kJ / m at -20°C to -10°C. 2 .

2. The cycloolefin polymer material according to claim 1, characterized in that The cycloolefin polymer material has a simple supported beam impact strength of 20 kJ / m at -20°C to -10°C. 2 ~30kJ / m 2 .

3. The cycloolefin polymer material according to claim 1 or 2, characterized in that The transmittance of the cycloolefin polymer material is greater than or equal to 90%, preferably 92% to 96%.

4. The cycloolefin polymer material according to any one of claims 1 to 3, characterized in that The cycloolefin polymer material includes a toughening agent, and the toughening agent includes modified highly chlorinated polyethylene; The modified highly chlorinated polyethylene is obtained by modifying highly chlorinated polyethylene with a modifier; The modifier includes silicone oil and / or white oil.

5. The cycloolefin polymer material according to claim 4, characterized in that The modified highly chlorinated polyethylene is obtained by mixing the highly chlorinated polyethylene with a modifier accounting for 1 to 5 times of the mass of the highly chlorinated polyethylene and subjecting the mixture to heat treatment; And / or, the mass proportion of chlorine element in the highly chlorinated polyethylene is 64% to 75%; And / or, the weight average molecular weight of the highly chlorinated polyethylene is 40,000 to 100,000; and / or, the modifier comprises silicone oil and white oil; The mass ratio of the silicone oil to the white oil is 1:(1-4).

6. The cycloolefin polymer material according to claim 4 or 5, characterized in that The toughening agent accounts for 2.5% to 8% by mass of the cycloolefin polymer material.

7. The cycloolefin polymer material according to any one of claims 1 to 6, characterized in that The cycloolefin polymer material includes a cycloolefin polymer resin; and satisfies: The glass transition temperature of the cycloolefin polymer resin is greater than 163°C; and / or, the melt flow rate of the cycloolefin polymer resin is less than or equal to 10 g / 10 min; And / or, the weight average molecular weight of the cycloolefin polymer resin is 20,000 to 50,000.

8. The cycloolefin polymer material according to any one of claims 1 to 7, characterized in that The cycloolefin polymer material further comprises at least one of an antioxidant, a lubricant, a stabilizer, and an ultraviolet absorber; Preferably, the antioxidant comprises hindered phenol and phosphite; Preferably, the mass ratio of the hindered phenol to the phosphite is 1:(1-4).

9. A method for preparing the cycloolefin polymer material according to any one of claims 1 to 8, characterized in that: The following steps are involved: The mixed material including the cycloolefin polymer resin and the toughening agent is subjected to a molding process to obtain the cycloolefin polymer material.

10. The method for preparing a cycloolefin polymer material according to claim 9, characterized in that: The molding process includes sequentially melting, extruding, and granulating the mixed material to obtain the cycloolefin polymer material; And / or, the mixture further comprises at least one of an antioxidant, a lubricant, a stabilizer, and an ultraviolet absorber.

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