Cycloolefin copolymer composite material as well as preparation method and application thereof

Abstract

The invention relates to a cycloolefin copolymer composite material as well as a preparation method and application thereof. The cycloolefin copolymer composite material is prepared from the following raw materials: a cycloolefin copolymer, a thermoplastic elastomer, a nucleating agent and a flow promoter, the total mass of the cycloolefin copolymer and the thermoplastic elastomer is 100%, and the content of the thermoplastic elastomer is 0.5-4%. The cycloolefin copolymer composite material disclosed by the invention has better impact resistance and drop resistance, eliminates microcracks after high-temperature moist heat sterilization, is high in material transparency and excellent in light transmittance, and can be well applied to medicine packaging and medical equipment.

Description

Technical Field

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

[0002] With the development of the pharmaceutical, cosmetic and food packaging industries, especially the development of biopharmaceuticals in the sub-sector, higher requirements are placed on direct product packaging throughout the product shelf life. Compared with traditional glass packaging, cycloolefin copolymer (COC) materials have the following advantages in pharmaceutical, cosmetic and food packaging materials: First, they are stronger, not easy to break during production, transportation and application, lighter in specific gravity, and save transportation costs; second, they have excellent processing performance, are easy to make and shape at one time, and have more prominent advantages when packaging with larger volumes, have low low-temperature shrinkage, are easy to match with pistons, and have better sealing; third, drugs are more compatible with packaging materials, no metal ion precipitation, better resistance to protein aggregation and adsorption, and no risk of delamination when pH>8. Therefore, cycloolefin copolymer materials are used as packaging materials by more and more research and development institutions and manufacturers.

[0003] Cyclic olefin copolymer is a polymer material obtained by copolymerization of dicycloheptene (norbornene) monomer and ethylene monomer under the action of metallocene catalyst. In cycloolefin copolymer, as the molar proportion of dicycloheptene increases, the glass transition temperature of the material gradually increases, and the heat resistance of the material gradually improves. Since the molecular structure contains a large molar proportion of dicycloheptene rigid units, the material has strong rigidity and poor impact resistance, especially at low temperatures. At the same time, when high-temperature moist heat sterilization is carried out at 121°C (Chinese Pharmacopoeia 1421 General Technical Requirements-Sterilization Method), due to the stress in the processing process, tiny silver streaks are easily generated, and the surface of the product becomes foggy, affecting the transparency, thus limiting the promotion of cycloolefin copolymer materials in the industry.

[0004] Therefore, it is of great significance to design and develop a reinforced cycloolefin copolymer composite material with high transparency, good impact resistance and drop performance. Summary of the invention

[0005] In order to solve the above technical problems, the present invention provides a cyclic olefin copolymer composite material and a preparation method and application thereof. The cyclic olefin copolymer composite material has good impact resistance, improves the drop performance of the product, has no micro cracks and fogging after high temperature and wet heat sterilization, and has high material transparency and excellent light transmittance.

[0006] To achieve this object, the present invention adopts the following technical solutions:

[0007] In a first aspect, the present invention provides a cyclic olefin copolymer composite material, wherein the raw materials of the cyclic olefin copolymer composite material include a cyclic olefin copolymer, a thermoplastic elastomer, a nucleating agent and a flow aid;

[0008] Taking the total mass of the cycloolefin copolymer and the thermoplastic elastomer as 100%, the content of the thermoplastic elastomer is 0.5-4%, for example, it can be 0.5%, 0.8%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5% or 4%, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the said range.

[0009] The present invention adds a specific content of thermoplastic elastomer to the cycloolefin copolymer and compounds it with a nucleating agent and a flow aid, so that the obtained cycloolefin copolymer composite material can effectively improve its impact resistance while maintaining good light transmittance, and at the same time, it can be sterilized in a wet heat sterilization environment at 121°C without small silver streaks and fogging, thereby meeting the safety requirements for medical packaging and medical devices in the Chinese Pharmacopoeia, and can be well applied to pharmaceutical packaging and medical devices.

[0010] In the present invention, when the content of the thermoplastic elastomer is 0.5-4% of the total mass of the cycloolefin copolymer and the thermoplastic elastomer, the obtained cycloolefin copolymer composite material can have better comprehensive performance. When its content is lower than 0.5%, due to the low content of the thermoplastic elastomer, the improvement effect on the toughness of the cycloolefin copolymer is not good, and tiny silver streaks appear on the surface after wet heat sterilization; when the content of the thermoplastic elastomer is too high, the light transmittance of the obtained cycloolefin copolymer composite material is significantly reduced, and fogging occurs on the surface after wet heat sterilization.

[0011] Preferably, the weight average molecular weight of the cycloolefin copolymer is 50,000-250,000, for example, 50,000, 80,000, 100,000, 120,000, 150,000, 180,000, 200,000, 220,000 or 250,000, as well as specific values ​​between the above values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific values ​​included in the range.

[0012] Preferably, the melt index of the cycloolefin copolymer at 260°C and 2.16kg is 6-45g / 10min, for example, it can be 6g / 10min, 10g / 10min, 15g / 10min, 20g / 10min, 25g / 10min, 30g / 10min, 35g / 10min, 40g / 10min or 45g / 10min, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0013] Preferably, the glass transition temperature of the cycloolefin copolymer is 140-160°C, for example, it may be 140°C, 142°C, 144°C, 146°C, 148°C, 150°C, 152°C, 154°C, 156°C, 158°C or 160°C, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0014] In the present invention, cycloolefin copolymer is compounded with thermoplastic elastomer, nucleating agent and flow aid, and the glass transition temperature of cycloolefin copolymer is selected to be above 143°C so as to withstand wet heat sterilization at 121°C. The composite material is obtained by melt granulation, and after injection-blowing into bottles, there is no tiny silver streaks and fogging after wet heat sterilization at 121°C, and the transparency is good, thereby achieving the purpose of good appearance and high safety.

[0015] Preferably, the cycloolefin copolymer comprises any one or a combination of at least two of the structural compounds represented by Formula I, Formula II or Formula III:

[0016]

[0017] Wherein, R1 and R2 are each independently selected from hydrogen, C1-C10 branched or straight chain alkyl, wherein C1-C10 can be, for example, C1, C2, C3, C4, C5, C6, C7, C8, C9 or C10; further preferably, R1 and R2 are each independently selected from hydrogen, methyl, ethyl, propyl or isobutyl.

[0018] x / (x+y) is 0.20-0.90, for example, it can be 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8 or 0.9, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the said range.

[0019] The cycloolefin copolymer used in the present invention can be obtained by commercial purchase or synthesis according to the prior art, which can be synthesized by referring to the method disclosed in "A Tailor-Made Metallocene for the Copolymerization of Ethene with Bulky Cycloalkenes, Angew. Chem. Int. Engl. 1995, 34, No. 20" for example.

[0020] Preferably, the thermoplastic elastomer includes any one or a combination of at least two of polyolefin elastomer (POE), ethylene vinyl acetate copolymer (EVA), styrene-butadiene-styrene block copolymer (SBS) or hydrogenated styrene-butadiene-styrene block copolymer (SEBS).

[0021] The specific thermoplastic elastomer selected by the present invention has flexible butadiene and ethylene segments in its molecular structure, and the cycloolefin copolymer (COC) has ethylene segments in its molecular structure, so that the thermoplastic elastomer has good compatibility with the COC molecule. At the same time, the addition of the thermoplastic elastomer enables the prepared composite product to absorb part of the energy when subjected to external force impact, thereby achieving toughening of the cycloolefin copolymer, thereby greatly improving the impact resistance of the obtained cycloolefin copolymer composite material; and in the process of high-temperature moist heat sterilization, the flexible segment can also improve the stress of the composite material, thereby reducing the generation of tiny silver streaks.

[0022] Preferably, the weight average molecular weight of the thermoplastic elastomer is 42000-96000, for example, it can be 42000, 45000, 50000, 60000, 70000, 80000, 90000 or 96000, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0023] Preferably, the nucleating agent is a sorbitol nucleating agent.

[0024] Preferably, the sorbitol nucleating agent includes any one of dibenzylidene sorbitol (DBS), p-methyldibenzylidene sorbitol (MDBS), Milliken Millad 3988 or Millad NX8000, or a combination of at least two thereof.

[0025] In the present invention, the addition of nucleating agent and thermoplastic elastomer can improve the segment crystallization state of the cyclic olefin copolymer composite material after high-temperature wet heat sterilization in terms of microstructure, thereby improving the transparency, surface gloss and impact resistance of the composite material, and thus making the obtained cyclic olefin copolymer composite material have good light transmittance and impact resistance, and no tiny silver streaks and fogging after wet heat sterilization at 121°C.

[0026] Preferably, based on the total mass of the cycloolefin copolymer and the thermoplastic elastomer as 100%, the content of the nucleating agent is 0.07-1.3%, for example, it can be 0.07%, 0.1%, 0.3%, 0.5%, 0.7%, 0.9%, 1.1% or 1.3%, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0027] Preferably, the flow aid comprises amide wax and / or polyethylene wax.

[0028] Preferably, the amide wax comprises ethylene bisstearamide wax.

[0029] Preferably, based on the total mass of the cycloolefin copolymer and the thermoplastic elastomer as 100%, the content of the flow aid is 0.09-1.2%, for example, it can be 0.09%, 0.2%, 0.4%, 0.6%, 0.8%, 1% or 1.2%, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0030] The flow aid used in the present invention can not only improve the fluidity of the system, thereby improving its processing performance, improving the surface finish and transparency of the product; but also has good lubrication and dispersing effects, thereby reducing stress concentration and improving the impact resistance of the processed product.

[0031] Preferably, the raw materials of the cyclic olefin copolymer composite material further include an antioxidant.

[0032] Preferably, based on the total mass of the cycloolefin copolymer and the thermoplastic elastomer as 100%, the content of the antioxidant is 0.06-0.8%, for example, it can be 0.06%, 0.1%, 0.15%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7% or 0.8%, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0033] Preferably, the antioxidant comprises a primary antioxidant.

[0034] Preferably, the primary antioxidant comprises a hindered phenol antioxidant.

[0035] Preferably, the hindered phenol antioxidant includes any one of antioxidant 1010, antioxidant 1098, antioxidant 1790 or antioxidant 1076, or a combination of at least two thereof.

[0036] Preferably, the antioxidant comprises a secondary antioxidant.

[0037] Preferably, the secondary antioxidant comprises a phosphite antioxidant.

[0038] Preferably, the phosphite antioxidant includes any one of antioxidant 168, antioxidant 618 or antioxidant 9928, or a combination of at least two of them.

[0039] In the present invention, by using an antioxidant, the degree of thermal oxidation degradation of the obtained cycloolefin copolymer composite material can be effectively reduced, thereby increasing its service life.

[0040] Preferably, the raw materials for preparing the cyclic olefin copolymer composite material include the following components in parts by weight:

[0041]

[0042] In the present invention, the content of cycloolefin copolymer is 96-99.5 parts by weight, for example, it can be 96 parts by weight, 96.5 parts by weight, 97 parts by weight, 97.5 parts by weight, 98 parts by weight, 98.5 parts by weight, 99 parts by weight or 99.5 parts by weight, as well as specific points between the above points. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific points included in the range.

[0043] The content of thermoplastic elastomer is 0.5-4 parts by weight, for example, it can be 0.5 parts by weight, 0.8 parts by weight, 1 part by weight, 1.5 parts by weight, 2 parts by weight, 2.5 parts by weight, 3 parts by weight, 3.5 parts by weight or 4 parts by weight, as well as specific points between the above points. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific points included in the range.

[0044] The content of nucleating agent is 0.07-1.3 parts by weight, for example, it can be 0.07 parts by weight, 0.1 parts by weight, 0.2 parts by weight, 0.4 parts by weight, 0.6 parts by weight, 0.8 parts by weight, 1 part by weight, 1.2 parts by weight or 1.3 parts by weight, as well as specific points between the above points. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific points included in the range.

[0045] The content of the flow aid is 0.09-1.2 parts by weight, for example, it can be 0.09 parts by weight, 0.2 parts by weight, 0.4 parts by weight, 0.6 parts by weight, 0.8 parts by weight, 1 part by weight or 1.2 parts by weight, as well as specific values ​​between the above points. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific points included in the range.

[0046] The content of antioxidant is 0.06-0.8 weight part, for example, it can be 0.06 weight part, 0.08 weight part, 0.1 weight part, 0.2 weight part, 0.3 weight part, 0.4 weight part, 0.5 weight part, 0.6 weight part, 0.7 weight part or 0.8 weight part, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the said range.

[0047] Preferably, based on the total mass of the raw materials for preparing the cyclic olefin copolymer composite material as 100%, the total mass of the nucleating agent and the flow aid is 0.2-1.2%, for example, it can be 0.2%, 0.4%, 0.6%, 0.8%, 1.0% or 1.2%, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0048] In the present invention, the nucleating agent and the flow aid are compounded so that the two can play a synergistic role, improve the internal crystal state of the cycloolefin copolymer, improve the fluidity of the cycloolefin copolymer during processing to reduce processing stress, and improve the surface finish of the processed product. Therefore, the prepared cycloolefin copolymer composite material can be sterilized at high temperature and humidity without tiny silver streaks and fogging on the basis of good transparency and impact resistance. By limiting the content of the two, the comprehensive performance of the obtained composite material can be further improved. When the content of the two is too high, the plastic bottle made of the obtained cycloolefin copolymer composite material will fog after high temperature and humidity sterilization, thereby reducing its transparency.

[0049] In a second aspect, the present invention provides a method for preparing the cyclic olefin copolymer composite material as described in the first aspect, the preparation method comprising the following steps:

[0050] The cycloolefin copolymer, thermoplastic elastomer, nucleating agent and flow aid are mixed, melt co-extruded and injection molded to obtain the cycloolefin copolymer composite material.

[0051] Preferably, the melt coextrusion is performed by a twin-screw extruder.

[0052] Preferably, the screw speed of the twin-screw extruder is 35-60 r / min.

[0053] Preferably, the temperature of the twin-screw extruder is 245-265°C, for example, it can be 245°C, 247°C, 250°C, 252°C, 255°C, 258°C, 260°C, 262°C or 265°C, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0054] Preferably, the injection molding temperature is 250-265°C, for example, it can be 250°C, 252°C, 255°C, 258°C, 260°C, 261°C, 262°C, 263°C, 264°C or 265°C, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0055] In a third aspect, the present invention provides an application of the cyclic olefin copolymer composite material as described in the first aspect in pharmaceutical packaging and medical devices.

[0056] In the present invention, the prepared cyclic olefin copolymer composite material can be injection-blown into a plastic packaging bottle with a volume of 1-200 mL by an injection-blowing process, which can meet the requirements of the Chinese Pharmacopoeia for medical packaging.

[0057] Compared with the prior art, the present invention has at least the following beneficial effects:

[0058] The present invention adds a specific content of thermoplastic elastomer to the cycloolefin copolymer and compound it with a nucleating agent and a flow aid, so that the obtained cycloolefin copolymer composite material can effectively improve its impact resistance (not less than 2.8 kJ / m2) while maintaining a good light transmittance (greater than 75%, Chinese Pharmacopoeia 2020 General Rules 0401). 2 , compared with cycloolefin copolymer 1.8kJ / m 2 At the same time, it can be sterilized in a 121°C wet heat environment without silver streaks or fogging, meeting the safety requirements for medical packaging and medical devices in the Chinese Pharmacopoeia, and can be well applied to pharmaceutical packaging and medical devices. DETAILED DESCRIPTION

[0059] For the convenience of understanding the present invention, the present invention lists the following embodiments. It should be understood by those skilled in the art that the embodiments are only to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0060] The information of some raw materials used in the following examples and comparative examples is as follows:

[0061] Cycloolefin copolymers 1 and 2 were synthesized by referring to the method disclosed in "A Tailor-Made Metallocene for the Copolymerization of Ethene with Bulky Cycloalkenes, Angew. Chem. Int. Engl. 1995, 34, No. 20".

[0062] Among them, cycloolefin copolymer 1, glass transition temperature Tg143 ° C, 260 ° C, 2.16 kg melt index MFR 12.3g / 10min; structural formula is formula I, x / (x+y) is 0.48-0.50, R1 and R2 are hydrogen, and the weight average molecular weight is 117000; cycloolefin copolymer 2, glass transition temperature Tg152 ° C, 260 ° C, 2.16 kg melt index MFR 8.6g / 10min; structural formula is formula II, x / (x+y) is 0.59-0.61, R1 and R2 are hydrogen, and the weight average molecular weight is 126000;

[0063]

[0064] Thermoplastic elastomer SEBS, purchased from Kraton Polymers (Kraton) G1645;

[0065] Thermoplastic elastomer POE, purchased from Dow Chemical Co., Ltd. (Dow Chemical) Engage 8003;

[0066] Thermoplastic elastomer EVA, purchased from Celanese 2803;

[0067] Nucleating agent, purchased from Milliken Millad NX8000;

[0068] Flow aid, purchased from Clariant Chemicals Licowax C wax powder;

[0069] Antioxidant 1010 and Antioxidant 1076 were purchased from Basf Chemical Company.

[0070] Example 1

[0071] This embodiment provides a cycloolefin copolymer composite material, and the raw materials for preparing the composite material include the following components in parts by weight:

[0072]

[0073] The preparation method of the cyclic olefin copolymer composite material comprises:

[0074] Cyclic olefin copolymer 1, thermoplastic elastomer SEBS, nucleating agent, flow aid and antioxidant 1010 are added to a high-speed mixer and stirred evenly to obtain a mixed material, and the mixed material is added to a twin-screw extruder, granulated by melt co-extrusion, and then injection molded to obtain the cyclic olefin copolymer composite material. The screw speed of the twin-screw extruder is 41r / min, the twin-screw granulation temperature is 250°C, and the injection molding temperature is 250°C.

[0075] Example 2

[0076] This embodiment provides a cycloolefin copolymer composite material, and the raw materials for preparing the composite material include the following components in parts by weight:

[0077]

[0078] The preparation method of the cyclic olefin copolymer composite material comprises:

[0079] Cyclic olefin copolymer 1, thermoplastic elastomer SEBS, nucleating agent, flow aid and antioxidant 1010 are added to a high-speed mixer and stirred evenly to obtain a mixture, and the mixture is added to a twin-screw extruder, melt co-extrusion granulated, and then injection molded to obtain the cyclic olefin copolymer bottle. The screw speed of the twin-screw extruder is 35r / min, the twin-screw granulation temperature is 245°C, and the injection molding processing temperature is 255°C.

[0080] Example 3

[0081] This embodiment provides a cycloolefin copolymer composite material, and the raw materials for preparing the composite material include the following components in parts by weight:

[0082]

[0083] The preparation method of the cyclic olefin copolymer composite material comprises:

[0084] Cyclic olefin copolymer 1, thermoplastic elastomer POE, nucleating agent, flow aid and antioxidant 1010 are added to a high-speed mixer and stirred evenly to obtain a mixed material, and the mixed material is added to a twin-screw extruder, granulated by melt co-extrusion, and then injection molded to obtain the cyclic olefin copolymer composite material. The screw speed of the twin-screw extruder is 60r / min, the twin-screw granulation temperature is 265°C, and the injection molding processing temperature is 265°C.

[0085] Example 4

[0086] This embodiment provides a cycloolefin copolymer composite material, and the raw materials for preparing the composite material include the following components in parts by weight:

[0087]

[0088] The preparation method of the cycloolefin copolymer composite material is the same as that of Example 1.

[0089] Example 5

[0090] This embodiment provides a cycloolefin copolymer composite material, and the raw materials for preparing the composite material include the following components in parts by weight:

[0091]

[0092] The preparation method of the cycloolefin copolymer composite material is the same as that of Example 1.

[0093] Example 6

[0094] This embodiment provides a cycloolefin copolymer composite material, and the raw materials for preparing the composite material include the following components in parts by weight:

[0095]

[0096] The preparation method of the cycloolefin copolymer composite material is the same as that of Example 1.

[0097] The preparation methods of Examples 7-10 and Comparative Examples 1-5 are the same as that of Example 1, and the weight proportions of the corresponding raw material components are shown in Table 1.

[0098] Table 1

[0099] Cyclic olefin copolymer 1 Thermoplastic Elastomer SEBS Nucleating Agent Flow aid Antioxidants Example 1 97 3 0.4 0.2 0.15 Example 7 97 3 1.3 1.2 0.8 Example 8 97 3 0.07 0.09 0.06 Example 9 99.5 0.5 0.4 0.2 0.15 Example 10 96 4 0.4 0.2 0.15 Comparative Example 1 100 - 0.4 0.2 0.15 Comparative Example 2 99.6 0.4 0.4 0.2 0.15 Comparative Example 3 95.9 4.1 0.4 0.2 0.15 Comparative Example 4 97 3 0.6 0 0.15 Comparative Example 5 97 3 0 0.6 0.15

[0100] The above-mentioned Examples 1-10 and Comparative Examples 1-5 were subjected to performance tests, and the performance evaluation method and reference standards were as follows:

[0101] (1) Izod notched impact strength: simply supported beam impact strength test is performed according to ISO179 standard;

[0102] (2) Light transmittance: tested according to GB / T2410-2008;

[0103] (3) Sterilization micro silver streaks and fogging conditions:

[0104] The cyclic olefin copolymer composite material was injection-blown into a plastic bottle with a volume of 4 mL using an injection-blowing process, the injection-blowing mold temperature was 120° C., and the injection-blowing pressure was 11 bar. According to the requirements of the Chinese Pharmacopoeia 1421 regulations, the injection-blown plastic bottle was sterilized with wet heat at 121° C. for 30 minutes, and the surface micro silver streaks and fogging were checked.

[0105] The test results are shown in Table 2.

[0106] Table 2

[0107]

[0108] The test results show that:

[0109] (1) It can be seen from Examples 1 to 6 that the present invention can effectively improve the impact resistance (not less than 2.8 kJ / m2) of the obtained cycloolefin copolymer composite material while maintaining a good light transmittance (greater than 75%) by adding a specific content of thermoplastic elastomer to the cycloolefin copolymer and compounding it with a nucleating agent and a flow aid.2 ), which improves the drop performance of the product. At the same time, it can be sterilized in a 121°C wet heat environment without small silver streaks and fogging, meeting the safety requirements of the Chinese Pharmacopoeia for medical packaging and medical devices, and can be well applied to pharmaceutical packaging and medical devices.

[0110] (2) It can be seen from Examples 7 and 8 that when the content of the nucleating agent, the flow aid and the antioxidant is within a specific range, the impact resistance and light transmittance of the cycloolefin copolymer can be effectively improved, and no tiny silver streaks appear on the surface after high-temperature moist heat sterilization. However, when the total mass of the nucleating agent and the flow aid is too high, fogging appears on the surface after high-temperature moist heat sterilization. This shows that the present invention can improve the light transmittance and impact resistance of the obtained cycloolefin copolymer composite material to a certain extent by further limiting the content of the nucleating agent and the flow aid in the preparation process of the cycloolefin copolymer composite material, and at the same time, it can prevent the surface from having tiny cracks and fogging after high-temperature moist heat sterilization, thereby improving the transparency of the product.

[0111] (3) By comparing Example 1 with Comparative Example 1, it can be seen that the addition of the specific thermoplastic elastomer in the present invention can significantly improve the impact resistance of the obtained cycloolefin copolymer composite material. When the thermoplastic elastomer is not added, the obtained cycloolefin copolymer composite material has a high light transmittance, but its Izod notched impact strength is only 1.8 kJ / m 2 , that is, the technical effect of improving the toughness of cycloolefin copolymer cannot be achieved. At the same time, tiny silver streaks and fogging appear on its surface after wet heat sterilization.

[0112] (4) By comparing Example 1, Example 9, Example 10 with Comparative Example 2 and Comparative Example 3, it can be seen that the present invention can effectively improve the comprehensive properties such as impact resistance and light transmittance of the obtained cycloolefin copolymer composite material by limiting the content of the thermoplastic elastomer. When the addition amount of the thermoplastic elastomer is too low, the impact resistance is poor, that is, the improvement effect on the toughness of the cycloolefin copolymer is not good, and tiny silver streaks appear on the surface after high-temperature moist heat sterilization; when the addition amount of the thermoplastic elastomer is too high, the light transmittance of the obtained cycloolefin copolymer composite material is significantly reduced, and fogging occurs on the surface after high-temperature moist heat sterilization.

[0113] (5) By comparing Example 1 with Comparative Examples 4 and 5, it can be seen that the addition of the nucleating agent and the flow aid allows the two to play a synergistic role, so that the obtained cycloolefin copolymer composite material not only ensures good light transmittance and impact resistance, but also does not fog under a wet heat sterilization environment of 121°C, thereby improving the surface smoothness and transparency of the product, so that it can be well applied to the fields of pharmaceutical packaging and medical devices.

[0114] In summary, the present invention obtains a cycloolefin copolymer composite material that can be well applied to pharmaceutical packaging and medical devices by adding a specific content of thermoplastic elastomer to the cycloolefin copolymer and compounding it with a nucleating agent and a flow aid. The material has good impact resistance, improves the drop performance of the product, eliminates microcracks after high-temperature wet heat sterilization, and has high transparency and excellent light transmittance.

[0115] The applicant declares that the above is only a specific implementation mode of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily thought of by those skilled in the art within the technical scope disclosed by the present invention shall fall within the protection scope and disclosure scope of the present invention.

Claims

1. A cyclic olefin copolymer composite material, characterized in that: The raw materials for preparing the cyclic olefin copolymer composite material include cyclic olefin copolymer, thermoplastic elastomer, nucleating agent and flow aid; Based on the total mass of the cycloolefin copolymer and the thermoplastic elastomer being 100%, the content of the thermoplastic elastomer is 0.5-4%.

2. The cyclic olefin copolymer composite material according to claim 1, characterized in that: The weight average molecular weight of the cycloolefin copolymer is 50,000-250,000; Preferably, the cycloolefin copolymer has a melt index of 6-45 g / 10 min at 260° C. and 2.16 kg; Preferably, the glass transition temperature of the cycloolefin copolymer is 140-160°C; Preferably, the cycloolefin copolymer comprises any one or a combination of at least two of the structural compounds represented by Formula I, Formula II or Formula III: Wherein, R1 and R2 are each independently selected from hydrogen, C1-C10 branched or straight chain alkyl; x / (x+y) is 0.20-0.

90.

3. The cyclic olefin copolymer composite material according to claim 1 or 2, characterized in that: The thermoplastic elastomer includes any one or a combination of at least two of a polyolefin elastomer, an ethylene vinyl acetate copolymer, a styrene-butadiene-styrene block copolymer or a hydrogenated styrene-butadiene-styrene block copolymer; Preferably, the weight average molecular weight of the thermoplastic elastomer is 42,000-96,000.

4. The cyclic olefin copolymer composite material according to any one of claims 1 to 3, characterized in that: The nucleating agent is a sorbitol nucleating agent; Preferably, the sorbitol nucleating agent includes any one of dibenzylidene sorbitol, p-methyldibenzylidene sorbitol, Milliken Millad 3988 or Millad NX8000, or a combination of at least two thereof; Preferably, based on 100% of the total mass of the cycloolefin copolymer and the thermoplastic elastomer, the content of the nucleating agent is 0.07-1.3%.

5. The cyclic olefin copolymer composite material according to any one of claims 1 to 4, characterized in that: The flow aid comprises amide wax and / or polyethylene wax; Preferably, the amide wax comprises ethylene bisstearamide wax; Preferably, based on 100% of the total mass of the cycloolefin copolymer and the thermoplastic elastomer, the content of the flow aid is 0.09-1.2%.

6. The cyclic olefin copolymer composite material according to any one of claims 1 to 5, characterized in that: The raw materials for preparing the cyclic olefin copolymer composite material also include an antioxidant; Preferably, based on 100% of the total mass of the cycloolefin copolymer and the thermoplastic elastomer, the content of the antioxidant is 0.06-0.8%.

7. The cyclic olefin copolymer composite material according to any one of claims 1 to 6, characterized in that: The raw materials for preparing the cyclic olefin copolymer composite material include the following components in parts by weight: Preferably, based on the total mass of the raw materials for preparing the cycloolefin copolymer composite material being 100%, the total mass of the nucleating agent and the flow aid is 0.2-1.2%.

8. A method for preparing the cyclic olefin copolymer composite material according to any one of claims 1 to 7, characterized in that: The preparation method comprises the following steps: The cycloolefin copolymer, thermoplastic elastomer, nucleating agent and flow aid are mixed, melt co-extruded and injection molded to obtain the cycloolefin copolymer composite material.

9. The method for preparing the cyclic olefin copolymer composite material according to claim 8, characterized in that: The melt coextrusion is carried out by a twin-screw extruder; Preferably, the screw speed of the twin-screw extruder is 35-60r / min; Preferably, the temperature of the twin-screw extruder is 245-265°C; Preferably, the injection molding temperature is 250-265°C.

10. Use of the cyclic olefin copolymer composite material according to any one of claims 1 to 7 in pharmaceutical packaging and medical devices.

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