CN114479333B - Low-creep high-toughness cycloolefin copolymer composite material and preparation method thereof - Google Patents

Low-creep high-toughness cycloolefin copolymer composite material and preparation method thereof Download PDF

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CN114479333B
CN114479333B CN202210038719.9A CN202210038719A CN114479333B CN 114479333 B CN114479333 B CN 114479333B CN 202210038719 A CN202210038719 A CN 202210038719A CN 114479333 B CN114479333 B CN 114479333B
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cycloolefin copolymer
toughness
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creep
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CN114479333A (en
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潘爱玉
林辉
吴峰
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Xiamen Toppla Material Technology Co ltd
Xiamen Make Security Technology Co Ltd
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Xiamen Make Security Technology Co Ltd
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    • C08L45/00—Compositions of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Compositions of derivatives of such polymers
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Abstract

The invention discloses a low-creep high-toughness cycloolefin copolymer composite material which comprises the following components in parts by weight: 100 parts of cycloolefin copolymer resin or derivative thereof, 5-30 parts of toughening modifier and 0.1-3 parts of anti-aging agent. The invention also provides a preparation method of the cycloolefin copolymer, which comprises the following steps: firstly preparing a toughening modifier by using a melt grafting method, and then preparing the toughening modifier and cycloolefin copolymer resin or derivatives thereof into the low-creep high-toughness cycloolefin copolymer composite material by using a double-screw extruder. The invention can adopt the reclaimed cycloolefin copolymer as the main raw material, improves the toughness of reclaimed materials, solves the problem of resource shortage and solves the problem of environment.

Description

Low-creep high-toughness cycloolefin copolymer composite material and preparation method thereof
Technical Field
The invention relates to the field of engineering plastics, in particular to a low-creep high-toughness cycloolefin polymer and a preparation method thereof.
Background
Engineering plastics are widely applied to various fields of production and life, and not only have higher requirements on the strength of the engineering plastics, but also have higher and higher requirements on the dimensional stability of the engineering plastics along with the continuous expansion of the application field. However, the creep property of the polymer material under stress conditions causes weaker dimensional stability of materials such as ABS and the like of conventional engineering plastics, and although the creep property can be improved by adding glass fibers, mineral fillers and the like, the creep property is always a key problem for restricting the popularization of the conventional engineering plastics aiming at the requirements of products with high gloss and high fluidity. Creep behavior of plastic products during loading often has a great impact on the dimensional stability of the products.
In order to prepare engineering plastics with high dimensional stability, cycloolefin copolymers are selected as matrix for the composite material. Cycloolefin copolymers are used for various applications represented by the fields of optical materials such as optical disk substrates, optical films, optical fibers, and the like, and have characteristics of high transparency, high gloss, high water vapor barrier property, high rigidity, high strength, excellent chemical resistance, and the like. The cycloolefin copolymer mainly refers to a copolymer of norbornene and other olefins, a large number of norbornene chain segments exist on a macromolecular chain, the large steric hindrance effect of the copolymer causes difficult rotation in the molecular chain, and further the copolymer has higher glass transition temperature and good rigidity, and meanwhile, the macromolecular chain segments are not easy to move due to difficult rotation in the molecular chain segments, so that the copolymer has lower creep property. Currently, the more commercial cycloolefin copolymers are ethylene-norbornene copolymers (COC) and styrene-norbornene Copolymers (COP).
On the other hand, in view of environmental protection, the requirement of the application fields such as optics on COC or COP materials is high, and the recycled materials are not suitable for the application in the field after reprocessing, so that the recycled materials are applied to other new fields. The regenerated COC or the regenerated COP material refers to COC or COP material generated after scrapping, but the recycled material is required to be toughened and modified due to poor toughness so as to meet the application of the recycled material as an injection molding part.
Disclosure of Invention
Based on the technical problems, the invention provides a low-creep high-toughness cycloolefin composite material and a preparation method thereof in order to prepare engineering plastics with high dimensional stability. In order to achieve the above purpose, the present invention adopts the following technical scheme: the low-creep high-toughness cycloolefin composite material comprises the following components in parts by weight: 100 parts of cycloolefin copolymer or derivative thereof; 5-30 parts of toughening modifier; 0.1-3 parts of an anti-aging agent; the toughening modifier is a graft copolymer of cycloolefin copolymer and a toughening agent; the toughening agent is polyolefin elastomer or styrene thermoplastic elastomer. A graft copolymer refers to a copolymer having side chains of polymer segments of different chemical structure from the backbone attached to some atoms of the polymer backbone.
Further, the cycloolefin copolymer has a glass transition temperature of not less than 150 ℃.
Preferably, the cycloolefin copolymer is one or a combination of two or more of ethylene-norbornene copolymer (COC), styrene-norbornene Copolymer (COP), COC derivative and COP derivative.
Preferably, the polyolefin elastomer is selected from one or more of polyethylene-olefin random copolymer (POE) and polyethylene-Olefin Block Copolymer (OBC), and the styrene thermoplastic elastomer is selected from one or more of hydrogenated styrene-butadiene-styrene block copolymer (SEBS) and hydrogenated styrene-isoprene-styrene block copolymer (SEPS). SEBS, SEPS, POE these elastomers all have ethylene units which are structurally compatible with COC or COP and can be prepared by melt grafting to form graft copolymers with COC or COP.
In a preferred embodiment of the present invention, the toughening modifier is one or more selected from the group consisting of COC grafted POE (COC-g-POE), COC grafted SEBS (COC-g-SEBS), COC grafted SEPS (COC-g-SEPS), COP grafted POE (COP-g-POE), COP grafted SEBS (COP-g-SEBS), and COP grafted SEPS (COP-g-SEPS).
In a preferred embodiment of the present invention, the antioxidant comprises an antioxidant for plastics and rubber, and is one or a combination of more than two of antioxidants 1010, 168 and 264. Because part of the styrene copolymer elastomer contains a large number of unsaturated groups, mainly unsaturated double bonds in structural units such as butadiene, isoprene and the like, and can generate a large number of ageing phenomena under high temperature and sunlight conditions, the common anti-ageing agent for plastics and rubber is added into the high polymer material, so that the service life of the resin product is prolonged, and the application range of the resin product is expanded.
In a preferred embodiment of the invention, in order to improve the visual recognition of the product in the use process, a color master is further added to dye the high polymer material. Preferably, the color masterbatch content is 0.1 to 2 parts by weight.
The preparation method of the toughening modifier comprises the following steps: (1) Weighing 100 parts by weight of cycloolefin copolymer resin and 50-160 parts by weight of toughening agent; (2) Melting and blending the weighed raw materials by using a double-screw extruder; (3) Adding the blending materials into an internal mixer, adding 1 to 5 weight parts of free radical initiator, setting the temperature to be 180 to 240 ℃, and reacting for 5 to 25 minutes under the melting condition; (4) After the mixed materials are discharged from the internal mixer, preparing granular materials by utilizing a single screw extruder; the free radical initiator comprises one or more than two of peroxide initiator and azo compound initiator.
The invention also provides a preparation method of the low-creep high-toughness cycloolefin composite material, which comprises the following steps: (1) preparing raw materials according to the components and parts by weight; (2) Uniformly mixing the prepared raw materials in a high-speed stirrer; (3) Adding the mixture into a double-screw extruder, melting, mixing and extruding to granulate at 180-240 ℃ to prepare the granular material.
Alternatively, the low creep high toughness cycloolefin copolymer composite material is a secondary material or a factory scrap or a waste recycle material. The preparation method comprises the following steps: (1) Crushing the recovered COC or COP product to obtain a crushed material; (2) Weighing the crushed materials and the toughening modifier in the step (1) according to a proportion; (3) Uniformly mixing the prepared raw materials in a high-speed stirrer; (4) Adding the mixture into a double-screw extruder, melting, mixing and extruding at 180-240 ℃ and granulating. Other auxiliary agents such as color master, stabilizing agents, release agents and the like can be added according to actual needs.
Further, the invention provides application of the low-creep high-toughness cycloolefin copolymer composite material in household appliances, office supplies, computer parts and plastic storage cabinets.
Further, the low-creep high-toughness cycloolefin copolymer composite material is applied to the plastic storage cabinet and comprises the following steps: drying the low-creep high-toughness cycloolefin copolymer composite material, adding the dried low-creep high-toughness cycloolefin copolymer composite material into an injection molding machine, and directly injection molding a large-area plastic storage cabinet component by utilizing a high-pressure injection molding technology at an injection molding temperature of 180-240 ℃; the plastic locker assembly has a creep deformation ratio of less than 2.5%.
Compared with the prior art, the invention has the following beneficial effects:
1. the toughening modifier provided by the invention is prepared by a melt grafting mode, has good compatibility with the cycloolefin copolymer, can effectively toughen the cycloolefin copolymer, and improves the creep resistance of the material. The high molecular material prepared from the toughening modifier, COC and/or COP and derivatives thereof has high toughness and low creep property, so that the dimensional stability of the product is improved, the application range of the product is expanded, and the service life of the product is prolonged.
2. The low-creep high-toughness cycloolefin copolymer composite material provided by the invention has tensile strength of more than 40MPa, bending strength of more than 52MPa and notch impact strength of more than 10KJ/m 2 Shore hardness (D) is greater than 70 and creep deformation rate is less than 4%.
3. The low-creep high-toughness cycloolefin copolymer composite material prepared by the method is processed into the plastic storage cabinet by injection molding, the creep rate of the plastic storage cabinet is less than 2.5%, and no fracture occurs in a ball falling test under the condition of 1.8 m. Long-acting dimensional stability is realized, the service life of the product is prolonged, and the service efficiency is improved. High Impact Polystyrene (HIPS) with a notch impact strength of 10kJ/m is widely used in the market at present 2 Creep deformation rate reaches 4%. Compared with HIPS, the creep resistance and toughness of the cycloolefin copolymer composite material prepared by the invention are better than those of HIPS, so that the cycloolefin copolymer composite material has a large application space.
4. The low-creep high-toughness cycloolefin copolymer composite material provided by the invention is used as engineering plastics, and the high rigidity and low creep performance of the cycloolefin copolymer material are realized by utilizing the large steric hindrance effect of norbornene on the molecular chain of the low-creep high-toughness cycloolefin copolymer composite material, so that the low-creep high-toughness cycloolefin copolymer composite material has high dimensional stability. The material is nontoxic and pollution-free, does not contain heavy metal elements, and accords with the safety standard of national daily necessities.
5. In order to improve the cost performance, the invention can widely adopt COC or COP reclaimed materials or water gap materials or secondary materials as matrix resin. Waste plastics are used for recycling, so that the environmental protection problem is solved.
Drawings
FIG. 1 is a reaction equation for a toughening modifier according to an embodiment of the present invention.
FIG. 2 is a reaction scheme of a low creep, high toughness cycloolefin copolymer composite according to an embodiment of the present invention.
FIG. 3 shows a preparation process of the present invention.
FIG. 4 is a graph showing the effect of toughening modifier content on product properties.
Detailed Description
The invention will be further elucidated by selecting several representative embodiments. The following examples are only for better illustration of the present invention, but the scope of the present invention is not limited thereto.
Since the molecular chain movement of the cycloolefin copolymer is difficult, the conventional toughening agent has poor toughening effect, such as conventional polyolefin elastomers, e.g., POE, SEBS, SBS, SEPS, and the like, and it is difficult to produce good toughening effect. Therefore, in order to improve the compatibility of the toughening agent and the cycloolefin copolymer, the invention selects to utilize the free radical reaction to graft the polyolefin elastomer on the molecular chain of the cycloolefin copolymer, thereby effectively improving the compatibility of the cycloolefin copolymer and the polyolefin elastomer, further generating good toughening effect and effectively improving the toughness of the cycloolefin copolymer high polymer material.
The preparation steps of the toughening modifier are as follows: (1) Weighing 100 parts by weight of cycloolefin copolymer resin COC or COP, 50-160 parts by weight of toughening agent, wherein the toughening agent is one or more than two of POE, SEBS, SEPS, OBC; (2) Melting and mixing the raw materials in a double-screw extruder; (3) Adding the blending material into an internal mixer, adding 1-5 parts by weight of free radical initiator, and reacting for 5-25 min at the melting temperature of 180-240 ℃; (4) After the mixed material is discharged from the internal mixer, uniform granular materials are prepared in a single screw extruder.
The melt grafting is a reaction that a primary free radical generated by an initiator takes a hydrogen atom on a hydrocarbon chain to generate a macromolecular free radical to initiate polymerization of a monomer, the reaction temperature is generally above the melting point or softening point of a reactant, and the reactant flows in a good area and is lower than the thermal cracking temperature at the same time, so that the thermal decomposition phenomenon is prevented. The reaction is generally carried out in an extruder. The disadvantage is the relatively high reaction temperature (above the melting temperature of the olefin) and the tendency to side reactions such as cleavage, crosslinking, autopolymerization of the added monomers, etc. Taking COC and POE as examples, in theory, the reaction equations that would be involved in an internal mixer are shown in FIG. 1, and in addition to the grafting reaction, there are crosslinking reactions between COC and POE. The reaction of COP with POE and the reaction of COC or COP with other polyolefin elastomers are also the same mechanism, and are all free radical grafting reactions. The reaction of the free radicals between the cycloolefin copolymer and the olefin elastomer is very complicated, not only results in grafting reactions, but also involves a large number of crosslinking reactions which seriously affect the flowability of the toughening agent. Therefore, in the reaction process, the composition of the reaction product can be effectively controlled only by controlling a series of factors such as temperature, reaction time, initiator concentration and the like according to the optimization of experimental conditions, so that the mobility of the toughening agent is ensured to be reduced slightly. Through multiple experiments, preferred process conditions are as specifically described in the examples.
Wherein the cycloolefin copolymer used in the step (1) has a glass transition temperature (Tg) of not less than 150 ℃. Taking COC as an example, commercially available COC resin products have glass transition temperatures ranging from 60℃to 180℃and are related to the content of bicycloheptene in the COC. It has been found through experimental observation that when cycloolefin copolymers having a Tg of less than 150℃are used to prepare toughening modifiers, the lower modulus leads to an increase in the creep rate of the final product.
In the preparation process, through different proportions of the cycloolefin copolymer resin and the toughening agent, when the toughening agent is less than 50 parts by weight, the toughening effect is lower, and the requirement cannot be met. When the toughening agent is more than 160 parts by weight, the modulus of the composite material is lowered and the creep deformation rate is increased due to the lower modulus of the toughening agent. Therefore, the amount of the toughening agent is generally about 50 to 160 parts by weight. If the creep deformation rate is kept low, the amount of the toughening agent is not easy to be higher than 80 parts.
In addition, the free radical initiator in the step (3) comprises one or more than two of peroxide initiator and azo compound initiator.
The preparation method of the low-creep high-toughness cycloolefin copolymer composite material comprises the following steps: (1) preparing raw materials according to the components and parts by weight; (2) Uniformly mixing the prepared raw materials in a high-speed stirrer; (3) Adding the mixture into a double-screw extruder, melting, mixing and extruding to granulate at 180-240 ℃ to prepare the granular material. Wherein the components in the step (1) comprise 100 parts of cycloolefin copolymer or derivative thereof, 5-30 parts of toughening modifier, 0.1-3 parts of anti-aging agent and the like, and other auxiliary agents such as color master batch, stabilizer, release agent and the like can be added according to actual requirements. The glass transition temperature of the cycloolefin copolymer is not less than 150 ℃. It was found through experimental observation that when cycloolefin copolymers having Tg lower than 150 ℃ are used to prepare composite materials, the creep of the prepared polymer materials is greater than 4%.
The raw materials and reagents used in the examples of the present invention are commercially available. Cycloolefin copolymer or its derivative is available from Rayleigh Weng Zhushi Co., mitsui chemical Co., ltd., japan, bao Li Co., ltd. Examples 1-2 are the preparation of toughening modifiers and examples 3-7 are the preparation of low creep, high toughness cycloolefin copolymer composites. The preparation flow of the invention is shown in figure 3.
Example 1 (1) preparation of POE-based toughening modifier: 5kg of POE, 4kg of cycloolefin copolymer (COC) are added, and after thorough mixing in a high-speed stirrer, the mixture is fed into a twin-screw extruder and thoroughly melt-mixed at 180-240 ℃. Then, the resin was charged into an internal mixer, 100g of peroxide initiator (BIPP) was added, and reacted at 200 ℃ in a molten state for 25 minutes, after the completion of the reaction, a uniform particulate material was prepared by a single screw extruder. COC can be adjusted to COP, and the POE toughening modifier is prepared according to the component proportion and steps.
(2) And (3) testing the grafting rate of POE: the product is fully extracted by toluene, and the yield of the condensate is less than 1%. The separation of POE and COC materials is realized by cyclohexane, and the grafting rate of POE is tested by a gravimetric method, wherein the grafting rate of COC molecular chains on POE molecular chains is more than 4.7%. The grafting ratio, which generally refers to the weight ratio of branched polymer to grafted polymer attached to the molecular chain of the polymer, is an important indicator for studying the structural morphology of the grafted product.
Example 2 (1) preparation of SEBS toughening modifier: 5kg of SEBS, 4kg of cycloolefin copolymer (COC) are added, the mixture is thoroughly mixed in a high-speed stirrer, and then the mixture is fed into a twin-screw extruder and is thoroughly melt-mixed at 180-240 ℃. Then, the resin was charged into an internal mixer, 120g of peroxide initiator (BIPP) was added, and reacted at 200 ℃ in a molten state for 25 minutes, after the completion of the reaction, a uniform particulate material was prepared by a single screw extruder. COC can be adjusted to COP, and the SEBS toughening modifier is prepared according to the component proportion and steps.
(2) Testing the grafting rate of SEBS: the product is fully extracted by toluene, and the yield of the condensate is less than 0.8 percent. The separation of SEBS and COC materials is realized by cyclohexane, and the grafting rate of the SEBS is tested by a gravimetric method, wherein the grafting rate of the COC molecular chain on the molecular chain of the SEBS is more than 6.4 percent.
Example 3 (1) preparation of low creep high toughness cycloolefin copolymer composite (COC as substrate): 5kg of cycloolefin copolymer (COC), 1kg of the toughening modifier (COC-g-POE) prepared according to the procedure described in example 1, 40g of the antioxidant 168 and 20g of the antioxidant 1010 are added, after thorough mixing in a high-speed stirrer, a twin-screw extruder is added, melt mixing is achieved in the melt state at 180-240 ℃, and a uniform particle material is prepared by means of a water-ring granulating technique.
(2) The basic mechanical properties of this composite are as follows:
tensile strength: 42MPa; elongation at break greater than 20%; flexural strength: 52MPa; notched impact strength: 10.7KJ/m 2 The method comprises the steps of carrying out a first treatment on the surface of the Creep rate: 1.8%.
(3) Preparation of comparative example: the toughening modifier (COC-g-POE) is adjusted to be an unmodified POE toughening agent, and the mechanical properties of the comparative examples in table 1 are obtained by testing the components in the proportion and the steps.
Example 4 (1) preparation of low creep high toughness cycloolefin copolymer composite (COP as substrate): 5kg of cycloolefin Copolymer (COP), 1kg of the toughening modifier (COP-g-POE) prepared according to the procedure described in example 1, 40g of the antioxidant 168 and 20g of the antioxidant 1010 are added, after thorough mixing in a high-speed stirrer, a twin-screw extruder is added, melt mixing is achieved in the melt state at 180-240 ℃, and a uniform particle material is prepared by using a water ring granulation technology.
(2) The basic mechanical properties of this composite are as follows:
tensile strength: 51MPa; elongation at break greater than 21%; flexural strength: 58MPa; notched impact strength: 15.2KJ/m 2 The method comprises the steps of carrying out a first treatment on the surface of the Creep rate: 1.4%.
(3) Preparation of comparative example: the toughening modifier (COP-g-POE) is adjusted to be an unmodified POE toughening agent, the toughening modifier is prepared according to the component proportion and the steps, and the mechanical properties of the comparative examples in table 1 are obtained through testing.
Example 5 (1) preparation of low creep high toughness cycloolefin copolymer composite (COC as substrate): 5kg of cycloolefin copolymer (COC), 1.2kg of the toughening modifier (COC-g-SEBS) prepared according to the procedure described in example 2, 40g of the antioxidant 168 and 20g of the antioxidant 1010 are added, after thorough mixing in a high-speed stirrer, the mixture is fed into a twin-screw extruder, melt mixing is achieved in the melt state at 180℃to 240℃and a homogeneous particulate material is prepared by means of the water-ring granulation technique.
(2) The basic mechanical properties of this composite are as follows:
tensile strength: 42MPa; elongation at break greater than 28%; flexural strength: 53MPa; notched impact strength: 16.3KJ/m 2 The method comprises the steps of carrying out a first treatment on the surface of the Creep rate: 2.1%.
(3) Preparation of comparative example: the toughening modifier (COC-g-SEBS) is adjusted to be an unmodified SEBS toughening agent, the toughening modifier is prepared according to the component proportion and the steps, and the mechanical properties of the comparative examples in the table 1 are obtained through testing.
Example 6 (1) preparation of low creep high toughness cycloolefin copolymer composite (COP as substrate): 5kg of cycloolefin Copolymer (COP), 1.2kg of the toughening modifier (COP-g-SEBS) prepared according to the procedure described in example 2, 40g of the antioxidant 168 and 20g of the antioxidant 1010 are added, after thorough mixing in a high-speed stirrer, a twin-screw extruder is added, melt mixing is achieved in the melt state at 180℃to 240℃and a homogeneous particulate material is prepared by means of the water-ring granulation technique.
(2) The basic mechanical properties of this composite are as follows:
tensile strength: 48MPa; elongation at break greater than 27%; flexural strength: 59MPa; notched impact strength: 18.1KJ/m 2 The method comprises the steps of carrying out a first treatment on the surface of the Creep rate: 1.7%.
(3) Preparation of comparative example: the toughening modifier (COP-g-SEBS) is adjusted to be an unmodified SEBS toughening agent, the toughening modifier is prepared according to the component proportion and the steps, and the mechanical properties of the comparative examples in the table 1 are obtained through testing.
Example 7 (1) preparation of low creep high toughness cycloolefin copolymer composite (COC as substrate): 3kg of cycloolefin copolymer (COC), 2kg of cycloolefin Copolymer (COP), 1kg of the toughening modifier (COP-g-POE) prepared according to the procedure described in example 1, 40g of antioxidant 168 and 20g of antioxidant 1010 are added, after thorough mixing in a high-speed stirrer, a twin-screw extruder is added, melt mixing is achieved in the melt state at 180℃to 240℃and a homogeneous particulate material is prepared by means of the water ring dicing technique.
(2) The basic mechanical properties of this composite are as follows:
tensile strength: 46MPa; elongation at break greater than 25%; flexural strength: 55MPa; notched impact strength: 14.3KJ/m 2 The method comprises the steps of carrying out a first treatment on the surface of the Creep rate: 1.9%.
(3) Preparation of comparative example: the toughening modifier (COP-g-POE) is adjusted to be an unmodified POE toughening agent, the toughening modifier is prepared according to the component proportion and the steps, and the mechanical properties of the comparative examples in table 1 are obtained through testing.
Table 1 mechanical properties data for examples and comparative examples
Figure BDA0003469219150000071
Further, the composite materials prepared in examples 3 to 7 were dried, and then fed into an injection molding machine to be processed into a part of components of a plastic locker. The injection molding temperature is 180-240 ℃, and various components of different plastic storage cabinets are directly prepared by utilizing a high-pressure injection molding process; the creep deformation rate of the plastic locker assembly was tested to be less than 2.5%. Wherein the drying temperature of the composite material is preferably 80-90 ℃, and the drying is carried out for 4-10 hours. Excessive drying times can cause thermal aging and can result in deterioration of the color tone of the composite.
Further, the invention may employ COC or COP secondary or factory scrap or waste recycle. And crushing the recovered COC or COP product to obtain crushed material. Composite materials were then prepared following the procedure described in examples 3 to 7. Other auxiliary agents such as color master, stabilizing agents, release agents and the like can be added according to actual needs.
In addition, the inventors consider the influence of the ratio of cycloolefin copolymer to toughening modifier. As shown in fig. 4, the change of the creep property of the material at different ratios of the cycloolefin copolymer to the toughening modifier is reflected. A series of samples and tests were carried out using the procedure of example 3, with the difference that the cycloolefin copolymer (COC) was used in a fixed amount of 5kg (corresponding to 100 parts by weight), the parts by weight of the toughening modifier was gradually increased from 5 parts to 30 parts, and the creep rate of the samples thus obtained was examined to be lower than 2.8%, which was superior to the commercially available High Impact Polystyrene (HIPS). When other cycloolefin copolymers or toughening modifiers are used, the resulting product properties are also superior to HIPS.
In the above examples, a three-point bending creep test was used, in which a constant vertical force was applied to the material for 3600 seconds, and a constant pressure was about 60% of the maximum bending load of the material, and a humidity of 55% at room temperature.
The above examples and drawings are not intended to limit the form or style of the present invention, and any suitable changes or modifications, such as changes in parameters of process conditions, etc., will be apparent to those skilled in the art without departing from the scope of the present invention.

Claims (9)

1. The low-creep high-toughness cycloolefin copolymer composite material is characterized by comprising the following components in parts by weight:
100 parts of cycloolefin copolymer or derivative thereof;
5-30 parts of toughening modifier;
0.1-3 parts of an anti-aging agent;
the toughening modifier is a graft copolymer of cycloolefin copolymer and a toughening agent; the toughening agent is polyolefin elastomer or styrene thermoplastic elastomer;
the preparation method of the toughening modifier comprises the following steps:
(1) Weighing 100 parts by weight of cycloolefin copolymer resin and 50-160 parts by weight of toughening agent;
(2) Melting and blending the weighed raw materials by using a double-screw extruder;
(3) Adding the blending materials into an internal mixer, adding 1-5 parts by weight of free radical initiator, setting the temperature to 180-240 ℃, and reacting for 5-25 min under the melting condition; the free radical initiator comprises a peroxide initiator or an azo compound initiator;
(4) After the mixed materials are discharged from the internal mixer, the single screw extruder is used for preparing the granular materials.
2. The low creep, high toughness cyclic olefin copolymer composite according to claim 1, wherein the glass transition temperature of the cyclic olefin copolymer is not less than 150 ℃.
3. The low-creep high-toughness cycloolefin copolymer composite according to claim 2, wherein the cycloolefin copolymer is one or a combination of two or more of an ethylene-norbornene copolymer, a styrene-norbornene copolymer, a COC derivative and a COP derivative.
4. The low creep, high toughness cyclic olefin copolymer composite according to claim 1, wherein the toughening agent is selected from one or more of POE, SEBS, SEPS.
5. The low creep high-toughness cycloolefin copolymer composite according to claim 1, wherein the toughening modifier is one or more of COC grafted POE, COC grafted SEBS, COC grafted SEPS, COP grafted POE, COP grafted SEBS, COP grafted SEPS.
6. The low creep, high toughness cyclic olefin copolymer composite according to claim 1, wherein the antioxidant comprises an antioxidant selected from the group consisting of antioxidant 1010, antioxidant 168, antioxidant 264, and combinations thereof.
7. The low-creep high-toughness cycloolefin copolymer composite according to claim 1, further comprising 0.1 to 2 parts by weight of a masterbatch.
8. The method for preparing the low-creep high-toughness cycloolefin copolymer composite material according to claim 1, which is characterized by comprising the following steps:
(1) Preparing raw materials according to the components and parts by weight;
(2) Uniformly mixing the prepared raw materials in a high-speed stirrer;
(3) Adding the mixture into a double-screw extruder, melting, mixing and extruding to granulate at 180-240 ℃ to prepare the granular material.
9. Use of the low creep, high toughness cyclic olefin copolymer composite material according to any one of claims 1 to 7 or the composite material obtained by the preparation method according to claim 8 in plastic lockers, household appliances, office supplies, computer parts.
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