A hydrophobic high-toughness cyclic olefin copolymer and a method for preparing the same

Abstract

The application relates to a hydrophobic high-toughness cycloolefin copolymer and a preparation method thereof, and belongs to the technical field of polymer materials; the method comprises the following steps: grafting a silane coupling agent containing a double bond to norbornene to obtain an intermediate; reacting the intermediate and alkyl mercaptan to obtain modified norbornene; carrying out ring-opening metathesis polymerization and hydrogenation on the modified norbornene to obtain a cycloolefin copolymer; and grafting a silane coupling agent with a vinyl group to the surface of norbornene through surface grafting; due to the -CH3 and the vinyl group on the silane coupling agent, the hydrophobic property of the norbornene is improved, and the O-Si-O structure helps to improve the flexibility of the norbornene; then, alkyl mercaptan is grafted to the norbornene to further improve the hydrophobic property; finally, the modified norbornene and a large steric hindrance norbornene derivative are subjected to ring-opening metathesis polymerization and hydrogenation to obtain a cycloolefin copolymer, and the large steric hindrance norbornene helps to improve the glass transition temperature of the cycloolefin copolymer.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of high polymer materials, in particular to a hydrophobic high-toughness cyclic olefin copolymer and a preparation method thereof. BACKGROUND

[0002] Cyclic olefin copolymer (COC) is a kind of high value-added thermoplastic engineering plastics obtained by polymerization of cyclic olefin monomers, which can be prepared by ring-opening metathesis polymerization and addition polymerization. Due to its high transparency, low moisture absorption, low birefringence, low density, excellent chemical corrosion resistance and excellent thermal stability, it can be widely used in the fields of drug packaging, electronic devices, optical prisms, optical information storage and the like. However, cyclic olefin copolymer also has some performance defects. The toughness of commercial COC is not high, which is due to the presence of too many rigid norbornene structural units, which is brittle and greatly limits the application of cyclic olefin materials in high temperature environment. In addition, with the rapid development of information technology and electronic equipment, COC materials are also required to have good hydrophobic properties. Materials with hydrophobic surface have the characteristics of waterproof, antifouling and reducing friction coefficient, which can reduce heat generation and dust accumulation. Therefore, improving the toughness and hydrophobicity of the material at the same time helps to broaden the application range of cyclic olefin materials.

[0003] At present, the main method to improve the toughness of cyclic olefin copolymer (COC) is to add toughening modifier to COC material to improve its toughness by blending modification. There are few studies on improving the toughness by synthesis modification. Blending modification is to add toughening modifier to cyclic olefin copolymer to improve its toughness, which has simple preparation process and is suitable for large-scale production. However, the compatibility of the obtained copolymer is poor, and the processing aid is easy to disperse unevenly in the copolymer, thereby reducing its mechanical strength. The methods for improving the hydrophobicity of polymers mainly include introducing flexible structure, fluorine-containing structure, silicon-containing structure and surface plating hydrophobic modification, so as to improve the hydrophobicity of polymers.

[0004] At present, there are few studies on the synthesis of cyclic olefin copolymer with high toughness and surface hydrophobicity. With the rapid development of electronic technology, higher requirements are also put forward for the material itself. Therefore, it is crucial to prepare a cyclic olefin copolymer with high toughness and hydrophobicity. SUMMARY

[0005] The present application provides a cyclic olefin copolymer with high toughness and hydrophobicity and a preparation method thereof, so as to improve the toughness and hydrophobicity of the cyclic olefin copolymer.

[0006] In a first aspect, the present application provides a preparation method of a cyclic olefin copolymer with high toughness and hydrophobicity, which comprises:

[0007] grafting a silane coupling agent containing double bonds to norbornene to obtain an intermediate;

[0008] reacting the intermediate with an alkyl mercaptan to incorporate the alkyl mercaptan into the intermediate to obtain a modified norbornene;

[0009] ring-opening metathesis polymerization and hydrogenation of the modified norbornene to obtain a cyclic olefin copolymer.

[0010] As an optional implementation, the norbornene includes at least one of 5-norbornene-2-ol, 5-norbornene-2-methanol and 5-norbornene-2,2-dimethanol.

[0011] As an optional implementation, the double-bond-containing silane coupling agent includes at least one of methyl vinyl dimethoxysilane and vinyl trimethoxysilane.

[0012] As an optional implementation, the grafting of the double-bond-containing silane coupling agent to the norbornene to obtain the intermediate includes:

[0013] dispersing the norbornene in a solvent, and then mixing the norbornene with the double-bond-containing silane coupling agent to obtain a mixture;

[0014] mixing and reacting the mixture with a base catalyst to obtain the intermediate.

[0015] As an optional implementation, the pH value of the mixing and reacting is 8-9.

[0016] As an optional implementation, the reacting of the intermediate with an alkyl mercaptan to incorporate the alkyl mercaptan into the intermediate to obtain a modified norbornene includes:

[0017] refluxing the intermediate, the alkyl mercaptan and an initiator to incorporate the alkyl mercaptan into the intermediate to obtain a modified norbornene.

[0018] As an optional implementation, the ring-opening metathesis polymerization and hydrogenation of the modified norbornene to obtain a cyclic olefin copolymer includes:

[0019] mixing a norbornene derivative and the modified norbornene in a solvent, and then adding a chain transfer agent and a catalyst to perform a ring-opening metathesis polymerization reaction to obtain an unhydrogenated polymer;

[0020] hydrogenating the polymer to obtain a cyclic olefin copolymer.

[0021] As an optional implementation, the catalyst includes a Grubbs third-generation catalyst solution, and a mass ratio of the Grubbs third-generation catalyst in the Grubbs third-generation catalyst solution is 1: (900-1100); and / or

[0022] The mass ratio of Grubbs third generation catalyst to the norbornene derivative in the Grubbs third generation catalyst solution is 1: (200-500).

[0023] In a second aspect, the application provides a hydrophobic high-toughness cyclic olefin copolymer, which is prepared by the method of any one of claims 1 to 8.

[0024] As an optional embodiment, the chemical formula of the cyclic olefin copolymer is:

[0025]

[0026] wherein x, y and n are independently selected from any positive integer.

[0027] Compared with the prior art, the above technical solution provided by the embodiments of the application has the following advantages:

[0028] The method provided by the embodiments of the application grafts the silane coupling agent with a vinyl group to the surface of the norbornene through surface grafting. Due to the -CH3 and vinyl group on the silane coupling agent, the hydrophobic property of the norbornene is improved, and the structure of Si-O-Si helps to improve the flexibility of the norbornene. Then, the alkyl mercaptan is grafted to the norbornene to further improve the hydrophobic property. Finally, the cyclic olefin copolymer is obtained by ring-opening metathesis polymerization and hydrogenation of the modified norbornene and the norbornene derivative with large steric hindrance. The norbornene derivative with large steric hindrance helps to improve the glass transition temperature of the cyclic olefin copolymer. BRIEF DESCRIPTION OF DRAWINGS

[0029] The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the application and serve to explain the principles of the application together with the specification.

[0030] In order to more clearly illustrate the technical solutions in the embodiments of the application or the prior art, the accompanying drawings needed to be used in the embodiments or prior art description will be briefly introduced. Obviously, for those of ordinary skill in the art, other drawings can also be obtained based on these drawings without creative labor.

[0031] Figure 1 The flowchart of the method provided by the embodiments of the application. DETAILED DESCRIPTION

[0032] In order to make the purposes, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application will be described clearly and completely below with reference to the drawings in the embodiments of the present application. Obviously, the described embodiments are some but not all of the embodiments of the present application. Based on the embodiments in the present application, all other embodiments obtained by those of ordinary skill in the art without creative work fall within the protection scope of the present application.

[0033] Unless otherwise specifically indicated, all of the various raw materials, reagents, instruments and equipment and the like used in the present application can be purchased from the market or can be prepared by the existing method.

[0034] As shown in Figure 1 The embodiments of the present application provide a preparation method of a hydrophobic high-toughness cyclic olefin copolymer, which comprises:

[0035] S1. grafting a double-bond-containing silane coupling agent to norbornene to obtain an intermediate;

[0036] In some embodiments, the norbornene comprises at least one of 5-norbornene-2-ol, 5-norbornene-2-methanol and 5-norbornene-2,2-dimethanol. The double-bond-containing silane coupling agent comprises at least one of methyl vinyl dimethoxysilane and vinyl trimethoxysilane.

[0037] In some embodiments, grafting a double-bond-containing silane coupling agent to norbornene to obtain an intermediate comprises:

[0038] S1.1. dispersing the norbornene in a solvent, and then mixing the double-bond-containing silane coupling agent to obtain a mixture;

[0039] S1.2. mixing and reacting the mixture and a base catalyst to obtain the intermediate.

[0040] In some embodiments, the pH value of the mixing and reacting is 8-9.

[0041] Specifically, in the present embodiment, norbornene and dichloromethane are added into a three-necked flask, and after ultrasonic dispersion, an aqueous solution of the prepared silane coupling agent is added, and then a base catalyst is added dropwise to adjust the pH of the solution to 8-9. Finally, the mixed solution is reacted at a certain stirring speed to obtain the intermediate.

[0042] S2. reacting the intermediate and an alkyl mercaptan to introduce the alkyl mercaptan into the intermediate to obtain a modified norbornene;

[0043] In some embodiments, reacting the intermediate and an alkyl mercaptan to introduce the alkyl mercaptan into the intermediate to obtain a modified norbornene comprises:

[0044] refluxing the intermediate, the alkyl mercaptan, and an initiator to introduce the alkyl mercaptan to the intermediate to obtain the modified norbornene.

[0045] Specifically, in this embodiment, a modifier and an initiator are added to the intermediate, and the mixture is stirred and refluxed at a certain temperature. After the reaction is completed, the mixture is cooled to room temperature, poured into distilled water, extracted with diethyl ether, and dried to obtain the modified norbornene.

[0046] S3. Ring-opening metathesis polymerization and hydrogenation are performed on the modified norbornene to obtain a cyclic olefin copolymer.

[0047] In some embodiments, performing ring-opening metathesis polymerization and hydrogenation on the modified norbornene to obtain a cyclic olefin copolymer comprises:

[0048] S3.1. The norbornene derivative and the modified norbornene are mixed in a solvent, and a chain transfer agent and a catalyst are then added to perform ring-opening metathesis polymerization to obtain an unhydrogenated polymer.

[0049] Specifically, in this embodiment, the polymerization reaction is performed in a glove box. A three-necked flask is charged with the norbornene derivative, the modified norbornene, and dichloromethane. After the mixture is stirred and mixed uniformly, 1-hexene and a dichloromethane solution of the prepared Grubbs third-generation catalyst are sequentially added, and the reaction is performed at room temperature. After the reaction is completed, the mixture is slowly poured into a large amount of methanol stirred rapidly, and the unhydrogenated polymer is obtained by filtration, washing, and drying. In the dichloromethane solution of the Grubbs third-generation catalyst, the mass ratio of the Grubbs catalyst to dichloromethane is 1:1000, and the mass ratio of the Grubbs third-generation catalyst to the monomer (i.e., the norbornene derivative) is 1:500-1:200.

[0050] S3.2. The polymer is hydrogenated to obtain a cyclic olefin copolymer.

[0051] In some embodiments, the catalyst comprises a Grubbs third-generation catalyst solution, the mass ratio of the Grubbs third-generation catalyst in the Grubbs third-generation catalyst solution is 1:(900-1100), and the mass ratio of the Grubbs third-generation catalyst in the Grubbs third-generation catalyst solution to the norbornene derivative is 1:(200-500).

[0052] Specifically, in this embodiment, the unhydrogenated polymer, p-toluenesulfonyl hydrazide, 2,6-di-tert-butyl-4-methylphenol are added into a three-necked flask, vacuumized and purged with nitrogen, so that the system is kept in a nitrogen atmosphere, then tri-n-propylamine and anhydrous toluene are added, and after stirring, the temperature is increased to a certain temperature for refluxing reaction. After the mixed solution is cooled to room temperature, it is slowly added dropwise into rapidly stirred ethanol, and the product is dissolved in hot toluene and then precipitated in ethanol for repeated cleaning three times, and then dried to obtain the target product (i.e. the cyclic olefin copolymer).

[0053] The following is specifically described with 5-norbornene-2-ol:

[0054] S1. The silane coupling agent containing double bond is grafted to norbornene to obtain an intermediate, and the reaction process is as shown below:

[0055] wherein n is selected from any positive integer.

[0056] S2. The intermediate and alkyl mercaptan are reacted to introduce the alkyl mercaptan into the intermediate to obtain a modified norbornene, and the reaction process is as shown below:

[0057]

[0058] wherein n is selected from any positive integer.

[0059] S3. The modified norbornene is subjected to ring-opening metathesis polymerization and hydrogenation to obtain a cyclic olefin copolymer, and the reaction process is as shown below:

[0060]

[0061] wherein x, y and n are independently selected from any positive integer.

[0062] Based on the overall inventive concept, the embodiments of the present application further provide a hydrophobic high-toughness cyclic olefin copolymer, which is prepared by the method for preparing a hydrophobic high-toughness cyclic olefin copolymer provided above.

[0063] The cyclic olefin copolymer is prepared based on the above method, and the specific steps of the method can refer to the above embodiments. Since the cyclic olefin copolymer adopts part or all of the technical solutions of the above embodiments, it at least has all the beneficial effects brought by the technical solutions of the above embodiments, which will not be repeated here.

[0064] In some embodiments, the chemical formula of the cyclic olefin copolymer is:

[0065]

[0066] wherein x, y and n are independently selected from any positive integer.

[0067] The present application is further described in conjunction with the following specific examples. It should be understood that these examples are only intended to illustrate the present application and are not intended to limit the scope of the present application. The experimental methods in the following examples, if not otherwise specified, are generally determined according to the national standards. If there is no corresponding national standard, the international standard, the conventional condition, or the condition suggested by the manufacturer is used.

[0068] Example 1

[0069] A method for preparing a hydrophobic high-toughness cycloolefin copolymer, the method comprising:

[0070] (1) A method for preparing modified norbornene

[0071] In a three-necked flask, 5 g of 5-norbornene-2-ol, 80 g of dichloromethane were added, and after ultrasonic dispersion for 30 min, 11 g of a prepared aqueous solution of vinyltrimethoxysilane (mass ratio of vinyltrimethoxysilane to water: 1:10) was added, then tetramethylammonium hydroxide pentahydrate was added dropwise to adjust the pH of the solution to 8-9. Finally, the mixed solution was reacted for 2 h at a stirring speed of 450 rpm. After the reaction was completed, 0.5 g of 1-nonyl mercaptan and 0.1 g of azobisisobutyronitrile (AIBN) were added, and the reaction was stirred at reflux at 60°C for 10 h. After the reaction was completed, the reaction system was cooled to room temperature, and the mixture was poured into distilled water, extracted with diethyl ether, and dried to obtain the modified norbornene.

[0072] (2) A method for preparing a cycloolefin copolymer

[0073] The polymerization reaction was carried out in a glove box. In a three-necked flask, 12 g of norbornene derivative, 8 g of modified norbornene and 200 g of dichloromethane were added, and after stirring until uniform, 0.2 g of 1-hexene and 5 g of a prepared dichloromethane solution of Grubbs third-generation catalyst were added in sequence. The reaction was carried out at room temperature for 2 h. After the reaction was completed, the mixture was slowly poured into a large amount of methanol under rapid stirring, and the unhydrogenated polymer was obtained by filtration, washing and drying. Then, 5 g of the unhydrogenated polymer, 16 g of p-toluenesulfonyl hydrazide and 6 mg of 2,6-di-tert-butyl-4-methylphenol were added to a three-necked flask, vacuum was applied and nitrogen was introduced to maintain a nitrogen atmosphere in the system. Then, 20 g of tri-n-propylamine and 120 g of anhydrous toluene were added, and after stirring until uniform, the temperature was raised to 120°C. After reflux reaction for 16 h, the mixed solution was cooled to room temperature, and then slowly added dropwise to rapidly stirred ethanol. The product was dissolved in hot toluene and then repeatedly washed with ethanol for 3 times. After drying, the target product was obtained. Finally, the sample for testing was prepared by flow casting.

[0074] Example 2

[0075] A method for preparing a hydrophobic high-toughness cycloolefin copolymer, the method comprising:

[0076] (1) A method for preparing modified norbornene

[0077] In a three-necked flask, 5 g of 5-norbornene-2-methanol and 100 g of dichloromethane were added, and after ultrasonic dispersion for 30 min, a prepared 22 g aqueous solution of methylvinyl dimethoxysilane (mass ratio of methylvinyl dimethoxysilane to water: 1:10) was added, and then tetramethylammonium hydroxide pentahydrate was added dropwise to adjust the pH of the solution to 8-9. Finally, the mixed solution was reacted for 4 h at a stirring speed of 300 rpm. After the reaction was completed, 0.5 g of 1-nonyl mercaptan and 0.3 g of azobisisobutyronitrile (AIBN) were added, and the reaction was stirred at reflux at 80°C for 10 h. After the reaction was completed, the reaction system was cooled to room temperature, and the mixture was poured into distilled water, extracted with diethyl ether, and dried to obtain modified norbornene.

[0078] (2) A method for preparing a cycloolefin copolymer

[0079] The polymerization reaction was carried out in a glove box. In a three-necked flask, 10 g of norbornene derivative, 10 g of modified norbornene and 150 g of dichloromethane were added, and after being uniformly mixed and stirred, 0.2 g of 1-hexene and a prepared 10 g dichloromethane solution of Grubbs third-generation catalyst were added in sequence. The reaction was carried out at room temperature for 2 h. After the reaction was completed, the mixture was slowly poured into a large amount of methanol stirred at a high speed, and then the unhydrogenated polymer was obtained by filtration, washing and drying. Then, 5 g of the unhydrogenated polymer, 16 g of p-toluenesulfonyl hydrazide and 6 mg of 2,6-di-tert-butyl-4-methylphenol were added to a three-necked flask, and the system was maintained in a nitrogen atmosphere by vacuumizing and purging with nitrogen. Then, 20 g of tri-n-propylamine and 120 g of anhydrous toluene were added, and after being uniformly stirred, the temperature was raised to 120°C, and the reaction was carried out at reflux for 16 h. After the reaction was completed, the mixed solution was cooled to room temperature, and then it was slowly added dropwise to ethanol stirred at a high speed. The product was dissolved in hot toluene and then precipitated in ethanol for repeated washing three times, and then the target product was obtained by drying.

[0080] Example 3

[0081] A method for preparing a hydrophobic high-toughness cycloolefin copolymer, the method comprising:

[0082] (1) A method for preparing modified norbornene

[0083] In a three-neck flask, 10 g of 5-norbornene-2,2-dimethanol and 100 g of dichloromethane were added, and after ultrasonic dispersion for 30 min, a prepared 22 g aqueous solution of vinyltrimethoxysilane (mass ratio of vinyltrimethoxysilane to water was 1:10) was added, and then tetramethylammonium hydroxide pentahydrate was added dropwise to adjust the pH of the solution to 8-9. Finally, the mixed solution was reacted at a stirring speed of 300 rpm for 6 h. After the reaction was completed, 1 g of N-octadecyl mercaptan and 0.5 g of azobisisobutyronitrile (AIBN) were added, and the reaction was stirred at 60°C under reflux conditions for 10 h. After the reaction was completed, the reaction system was cooled to room temperature, and the mixture was poured into distilled water, extracted with diethyl ether, and dried to obtain the modified norbornene.

[0084] (2) Preparation method of cyclic olefin copolymer

[0085] The polymerization reaction was carried out in a glove box. In a three-neck flask, 8 g of norbornene derivative, 12 g of modified norbornene and 100 g of dichloromethane were added, and after uniform stirring, 0.2 g of 1-hexene and a prepared 10 g dichloromethane solution of Grubbs third-generation catalyst were added in sequence. The reaction was carried out at room temperature for 2 h. After the reaction was completed, the mixture was slowly poured into a large amount of methanol under rapid stirring, and the unhydrogenated polymer was obtained by filtration, washing and drying. Then, 5 g of unhydrogenated polymer, 16 g of p-toluenesulfonyl hydrazide and 6 mg of 2,6-di-tert-butyl-4-methylphenol were added to a three-neck flask. The system was maintained in a nitrogen atmosphere by vacuumizing and purging with nitrogen. Then, 20 g of tri-n-propylamine and 120 g of anhydrous toluene were added, and the temperature was increased to 120°C after uniform stirring. The reaction was carried out under reflux for 16 h. After the mixed solution was cooled to room temperature, it was slowly added dropwise to rapidly stirred ethanol. The product was dissolved in hot toluene and then precipitated in ethanol for repeated cleaning three times. The target product was obtained by drying.

[0086] Example 4

[0087] A preparation method of a hydrophobic high-toughness cyclic olefin copolymer, the method comprising:

[0088] (1) Preparation method of modified norbornene

[0089] In a three-necked flask, 10 g of 5-norbornene-2,2-dimethanol and 120 g of dichloromethane were added and ultrasonically dispersed for 30 min, then a prepared 32 g aqueous solution of methylvinyl dimethoxysilane (mass ratio of methylvinyl dimethoxysilane to water was 1:10) was added, and then tetramethylammonium hydroxide pentahydrate was added dropwise to adjust the pH of the solution to 8-9. Finally, the mixed solution was reacted at 450 rpm for 6 h. After the reaction was completed, 1 g of n-dodecyl mercaptan and 0.3 g of azobisisobutyronitrile (AIBN) were added, and the reaction was stirred at 80°C under reflux for 10 h. After the reaction was completed, the reaction system was cooled to room temperature, and the mixture was poured into distilled water, extracted with diethyl ether, and dried to obtain the modified norbornene.

[0090] (2) Preparation method of cyclic olefin copolymer

[0091] The polymerization reaction was carried out in a glove box. In a three-necked flask, 6 g of norbornene derivative, 14 g of modified norbornene and 150 g of dichloromethane were added, and after being uniformly mixed and stirred, 0.2 g of 1-hexene and a prepared 5 g dichloromethane solution of Grubbs third-generation catalyst were added in sequence, and the reaction was carried out at room temperature for 2 h. After the reaction was completed, the mixture was slowly poured into a large amount of methanol under rapid stirring, and the unhydrogenated polymer was obtained by filtration, washing and drying. Then 5 g of unhydrogenated polymer, 16 g of p-toluenesulfonyl hydrazide and 6 mg of 2,6-di-tert-butyl-4-methylphenol were added to a three-necked flask, vacuum was applied and nitrogen was introduced to maintain a nitrogen atmosphere in the system. Then 20 g of tri-n-propylamine and 120 g of anhydrous toluene were added, and the temperature was increased to 120°C after uniform stirring. After refluxing for 16 h, the mixed solution was cooled to room temperature, and then slowly added dropwise to rapidly stirred ethanol. The product was dissolved in hot toluene and then precipitated in ethanol for repeated washing 3 times, and then dried to obtain the target product.

[0092] Example 5

[0093] A preparation method of a hydrophobic high-toughness cyclic olefin copolymer, the method comprising:

[0094] (1) Preparation method of modified norbornene

[0095] In a three-necked flask, 8 g of 5-norbornene-2-methanol and 120 g of dichloromethane were added, and after ultrasonic dispersion for 30 min, a prepared 33 g of a vinyltrimethoxysilane aqueous solution (vinyltrimethoxysilane and water in a mass ratio of 1:10) was added, and then tetramethylammonium hydroxide pentahydrate was added dropwise to adjust the pH of the solution to 8-9. Finally, the mixed solution was reacted at a stirring speed of 300 rpm for 6 h. After the reaction was completed, 0.5 g of n-dodecyl mercaptan and 0.5 g of azobisisobutyronitrile (AIBN) were added, and the reaction was stirred at reflux at 80°C for 10 h. After the reaction was completed, the reaction system was cooled to room temperature, and the mixture was poured into distilled water, extracted with diethyl ether, and dried to obtain the modified norbornene.

[0096] (2) Preparation method of the cyclic olefin copolymer

[0097] The polymerization reaction was carried out in a glove box. In a three-necked flask, 6 g of norbornene derivative, 14 g of modified norbornene and 100 g of dichloromethane were added, and after uniform stirring, 0.2 g of 1-hexene and 5 g of a prepared Grubbs third-generation catalyst dichloromethane solution were added in sequence, and the reaction was carried out at room temperature for 2 h. After the reaction was completed, the mixture was slowly poured into a large amount of methanol under rapid stirring, and the unhydrogenated polymer was obtained by filtration, washing and drying. Then 5 g of the unhydrogenated polymer, 16 g of p-toluenesulfonyl hydrazide and 6 mg of 2,6-di-tert-butyl-4-methylphenol were added to a three-necked flask, vacuum was applied, nitrogen was introduced, and a nitrogen atmosphere was maintained in the system. Then 20 g of tri-n-propylamine and 120 g of anhydrous toluene were added, and after uniform stirring, the temperature was increased to 120°C, and the reaction was carried out at reflux for 16 h. After the reaction was completed, the mixed solution was cooled to room temperature, and then it was slowly added dropwise to rapidly stirred ethanol. The product was dissolved in hot toluene and then precipitated in ethanol for repeated washing three times, and the target product was obtained by drying.

[0098] Comparative Example 1

[0099] The COC was commercially available.

[0100] The cyclic olefin copolymers provided in Examples 1 to 5 and Comparative Example 1 were subjected to performance tests, and the results are shown in the following table.

[0101]

[0102] As shown in the above table, the cyclic olefin copolymers prepared by the method provided in the present application have better hydrophobic properties and better toughness.

[0103] Various embodiments of the application can exist in a variety of forms; it should be understood that the description of the embodiments as being in a specific form is merely for convenience and brevity and should not be construed to limit the scope of the application; therefore, the description of a specific form should be considered to have specifically disclosed all possible sub-combinations of the described form and individual numerical values within the described range. For example, it should be considered that a description of a range from 1 to 6 has specifically disclosed sub-ranges such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as individual numbers within the described range, such as 1, 2, 3, 4, 5, and 6, regardless of the range. Additionally, whenever a numerical range is indicated herein, it is meant to include any cited number (fractional or integral) within the indicated range.

[0104] In the present application, the orientation words such as "upper" and "lower" are specifically the directions of the drawing surface in the drawings unless otherwise stated. In addition, in the description of the present application, the terms "comprise", "include" and the like mean "including but not limited to". In the present text, relational terms such as "first" and "second" and the like are used only to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply that there is any such actual relationship or order between these entities or operations. In the present text, "and / or" describes the association relationship of the associated objects, which means that there can be three relationships, for example, A and / or B can represent the cases of A alone, A and B together, and B alone. Where A and B can be singular or plural. In the present text, "one or more" means one or more, and "multiple" means two or more. "At least one", "at least one of the following" or the like means any combination of these items, including any combination of single or multiple items. For example, "at least one of a, b, or c", or "at least one of a, b, and c", can represent a, b, c, a-b (i.e. a and b), a-c, b-c, or a-b-c, where a, b, and c can be single or multiple.

[0105] The above description is merely a specific implementation of the present application, enabling those skilled in the art to understand or implement the present application. Various modifications to these embodiments will be apparent to those skilled in the art, and the general principles defined herein can be implemented in other embodiments without departing from the spirit or scope of the present application. Therefore, the present application should not be limited to the embodiments shown herein, but should be consistent with the widest scope of the principles and novel features applied herein.

Claims

1. A process for the production of a hydrophobic, high toughness, cyclic olefin copolymer, characterized in that, The method comprises: grafting a silane coupling agent containing double bond to norbornene to obtain an intermediate; reacting the intermediate with an alkyl mercaptan to introduce the alkyl mercaptan into the intermediate to obtain a modified norbornene; ring-opening metathesis polymerization and hydrogenation of the modified norbornene to obtain a cyclic olefin copolymer; the norbornene comprises at least one of 5-norbornene-2-ol, 5-norbornene-2-methanol and 5-norbornene-2,2-dimethanol; the silane coupling agent containing double bond comprises at least one of methyl vinyl dimethoxysilane and vinyl trimethoxysilane.

2. The method for preparing the hydrophobic and highly tough cyclic olefin copolymer according to claim 1, characterized in that, The grafting of the silane coupling agent containing double bond to norbornene to obtain an intermediate comprises: dispersing the norbornene in a solvent, and then mixing the norbornene with the silane coupling agent containing double bond to obtain a mixture; mixing the mixture with a base catalyst to obtain an intermediate.

3. The method for preparing the hydrophobic, high-toughness cyclic olefin copolymer according to claim 2, characterized in that, The pH value of the mixing reaction is 8-9.

4. The method for preparing the hydrophobic and highly tough cyclic olefin copolymer according to claim 1, characterized in that, The reaction of the intermediate with an alkyl mercaptan to introduce the alkyl mercaptan into the intermediate to obtain a modified norbornene comprises: refluxing the intermediate, the alkyl mercaptan and an initiator to introduce the alkyl mercaptan into the intermediate to obtain a modified norbornene.

5. The method for preparing the hydrophobic and highly tough cyclic olefin copolymer according to claim 1, characterized in that, The ring-opening metathesis polymerization and hydrogenation of the modified norbornene to obtain a cyclic olefin copolymer comprises: mixing the norbornene derivative and the modified norbornene in a solvent, and then adding a chain transfer agent and a catalyst to perform a ring-opening metathesis polymerization reaction to obtain an unhydrogenated polymer; hydrogenating the polymer to obtain a cyclic olefin copolymer.

6. The method for preparing the hydrophobic and highly tough cyclic olefin copolymer according to claim 5, characterized in that, The catalyst comprises a Grubbs third-generation catalyst solution, and the mass ratio of the Grubbs third-generation catalyst in the Grubbs third-generation catalyst solution to the norbornene derivative is 1: (200-500). The cyclic olefin copolymer is prepared by the method for preparing a hydrophobic high-toughness cyclic olefin copolymer according to any one of claims 1-6.

7. A hydrophobic, high toughness, cyclic olefin copolymer characterized by, The chemical formula of the cyclic olefin copolymer is:

8. The hydrophobic, high-tenacity cyclic olefin copolymer of claim 7, wherein, wherein x, y and n are independently selected from any positive integer. The method comprises: grafting a silane coupling agent containing double bond to norbornene to obtain an intermediate; reacting the intermediate with an alkyl mercaptan to introduce the alkyl mercaptan into the intermediate to obtain a modified norbornene; ring-opening metathesis polymerization and hydrogenation of the modified norbornene to obtain a cyclic olefin copolymer; the norbornene comprises at least one of 5-norbornene-2-ol, 5-norbornene-2-methanol and 5-norbornene-2,2-dimethanol; the silane coupling agent containing double bond comprises at least one of methyl vinyl dimethoxysilane and vinyl trimethoxysilane. The grafting of the silane coupling agent containing double bond to norbornene to obtain an intermediate comprises: dispersing the norbornene in a solvent, and then mixing the norbornene with the silane coupling agent containing double bond to obtain a mixture; mixing the mixture with a base catalyst to obtain an intermediate. The pH value of the mixing reaction is 8-9. The reaction of the intermediate with an alkyl mercaptan to introduce the alkyl mercaptan into the intermediate to obtain a modified norbornene comprises: refluxing the intermediate, the alkyl mercaptan and an initiator to introduce the alkyl mercaptan into the intermediate to obtain a modified norbornene. The ring-opening metathesis polymerization and hydrogenation of the modified norbornene to obtain a cyclic olefin copolymer comprises: mixing the norbornene derivative and the modified norbornene in a solvent, and then adding a chain transfer agent and a catalyst to perform a ring-opening metathesis polymerization reaction to obtain an unhydrogenated polymer; hydrogenating the polymer to obtain a cyclic olefin copolymer. The catalyst comprises a Grubbs third-generation catalyst solution, and the mass ratio of the Grubbs third-generation catalyst in the Grubbs third-generation catalyst solution to the norbornene derivative is 1: (200-500). The cyclic olefin copolymer is prepared by the method for preparing a hydrophobic high-toughness cyclic olefin copolymer according to any one of claims 1-6. The chemical formula of the cyclic olefin copolymer is: wherein x, y and n are independently selected from any positive integer.

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