Cycloolefin polymer with good antistatic performance and preparation method thereof

Abstract

The invention belongs to the technical field of cycloolefin polymers, and particularly relates to a cycloolefin polymer with good antistatic performance and a preparation method thereof. According to the cycloolefin polymer provided by the invention, norbornene is taken as a polymerizable core, imidazolium salt is introduced as an ionic functional center, and an oligo-polyether chain segment and an alkyl hydrophobic chain are synergistically integrated in the structure, so that the ionic conductivity is remarkably enhanced, and the surface resistance is effectively reduced; on the premise that high transparency, dimensional stability and machinability are kept, lasting and efficient intrinsic antistatic performance can be achieved.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of cyclic olefin polymers, and particularly relates to a cyclic olefin polymer with good antistatic property and a preparation method thereof. BACKGROUND

[0002] Cyclic olefin polymers (COP) are a class of high-performance thermoplastic materials prepared by ring-opening metathesis polymerization (ROMP) or coordination polymerization, etc. with norbornene and its derivatives as main monomers. Since commercialization in the 1990s, COP has been widely used in many high-tech fields due to its unique molecular structure and a series of excellent comprehensive properties.

[0003] However, the inherent insulating property of COP leads to easy accumulation of static electricity on its surface. Due to the lack of polar groups or free-moving ions / electrons in the COP molecular chain, its volume resistivity is usually as high as 10^15 Ω·cm or more, and the surface resistivity is also at a very high level. This strong insulating property makes it easy to generate and accumulate static electricity during production, processing, transportation and use, especially in dry environments or when rubbing or contact-separation with other materials. The adverse effects caused by static electricity accumulation include: in a clean room environment (such as semiconductor, biomedical, precision optical manufacturing), charged COP components can adsorb particles in the air, seriously affecting the cleanliness and yield of the product; secondly, electrostatic discharge (ESD) may cause instantaneous high-voltage breakdown or potential damage to sensitive electronic components, leading to device failure and posing a major risk to electronic packaging, chip carriers and other applications; thirdly, electrostatic adsorption may also cause film and sheet to stick together and deviate on the automated production line, affecting production efficiency and product quality; finally, in certain environments, high-energy electrostatic discharge may even cause fires or explosions and other safety accidents.

[0004] The conventional methods for solving the problem of static electricity of polymer materials mainly include adding antistatic agents, surface coating, physical doping of conductive fillers (such as carbon black, metal fibers, carbon nanotubes, and graphene), and plasma treatment. However, these methods have obvious limitations when applied to high-performance COPs. Migrating antistatic agents: small-molecule antistatic agents (such as quaternary ammonium salts and ethoxylated amines) can reduce surface resistance in the short term, but they are prone to migrate from the interior to the surface of the material and volatilize or be wiped off, resulting in a lack of durability of the antistatic effect and potential contamination of the product or impact on optical performance. Permanent antistatic agents: high-molecular-weight antistatic agents have good stability, but they often have poor compatibility with COPs, which can lead to increased haze and decreased mechanical properties of the material, and the addition amount is usually high, which affects the intrinsic advantages of the material. Conductive filler filling: the introduction of carbon or metal fillers can significantly reduce the resistivity, but it can severely damage the high transparency and low dielectric performance of COPs, and may also affect the processing flowability and mechanical strength of the material, making it unsuitable for optical and high-frequency electronic fields. Surface treatment: such as vacuum coating, sputtering, or coating of transparent conductive oxides (TCO) or conductive polymers (such as PEDOT:PSS), which can maintain the performance of the substrate, but the process is complex, the cost is high, and the coating is prone to wear, has poor adhesion, and lacks durability, making it difficult to meet long-term use requirements.

[0005] Therefore, it is urgent to develop a solution that can effectively impart COPs with durable and reliable antistatic properties while maximizing the maintenance of their high transparency, low dielectric loss, excellent mechanical properties, and good processability. SUMMARY

[0006] The present application aims to provide a cyclo-olefin polymer with good antistatic properties to meet the growing demand for high-performance antistatic materials in high-end electronics, optics, medical, and other industries.

[0007] The present application provides a cyclo-olefin polymer with good antistatic properties, the structure of which is shown in formula (I):

[0008] wherein a is 30-120, b is 1-4, X - is a counter anion, R1 is C1-C4 alkyl.

[0009] Preferably, R1 is methyl, ethyl, or n-butyl; the counter anion is TsO - or TfO - .

[0010] Preferably, the cyclo-olefin polymer is obtained by polymerization of the monomer shown in formula (II):

[0011] wherein b is 1-4.

[0012] The application further provides a preparation method of the cyclic olefin polymer, and the method comprises the following steps: The monomer shown in formula (II) is dissolved in an organic solvent to obtain a raw material solution; the raw material solution is pre-cooled to -5-5 ℃, and then a catalyst is added; after 5-15 min of reaction, conversion is performed at 24-28 ℃ for 30-45 min; after the conversion is completed, a terminating agent is added to terminate the reaction after 5-10 min of stirring, to obtain a reaction stock solution; diethyl ether is added to the reaction stock solution to perform precipitation; the precipitate is collected by filtration, and is dried to obtain a polymer. The polymer is prepared into a 5-10% wt solution, a quaternary ammonium reagent is added, and then a quaternary ammonium reaction is performed to obtain a quaternary ammonium polymer; the quaternary ammonium reagent is any one of methyl p-toluenesulfonate, ethyl p-toluenesulfonate, propyl p-toluenesulfonate, methyl trifluoromethanesulfonate, ethyl trifluoromethanesulfonate and butyl trifluoromethanesulfonate; the quaternary ammonium polymer is subjected to a hydrogenation reaction to obtain a cyclic olefin polymer with good antistatic performance.

[0013] The quaternary ammonium reagent is further preferably any one of methyl p-toluenesulfonate, methyl trifluoromethanesulfonate and ethyl trifluoromethanesulfonate.

[0014] Preferably, the organic solvent is dichloromethane, trichloromethane, 1,2-dichloroethane, toluene or chlorobenzene.

[0015] Preferably, the catalyst is Grubbs-II or Grubbs-III; and the terminating agent is ethyl vinyl ether or benzaldehyde.

[0016] Preferably, the water content of the monomer A is ≤20 ppm; and the concentration of the monomer A in the raw material solution is 0.3-0.7 mol / L.

[0017] Preferably, the molar ratio of the catalyst to the monomer A is 1:100-400, based on the amount of the catalyst; and the molar ratio of the catalyst to the terminating agent is 1:3-10.

[0018] Preferably, the volume ratio of the reaction stock solution to diethyl ether is 1:3-8.

[0019] Preferably, the molar ratio of the polymer to the quaternary ammonium reagent is 1:3-5; the quaternary ammonium reaction is performed at 0-80 ℃ for 12-48 h; after the quaternary ammonium reaction is completed, 50-75% v / v aqueous ethanol solution is further added to perform precipitation, the precipitate is collected by filtration, and is dried to obtain the quaternary ammonium polymer.

[0020] More preferably, when the quaternary ammonium reagent is methyl triflate, ethyl triflate or butyl triflate, the quaternary ammonium reaction is carried out at 0-30℃ for 12-16h; when the quaternary ammonium reagent is methyl tosylate, ethyl tosylate or propyl tosylate, the quaternary ammonium reaction is carried out at 30-80℃ for 12-48h.

[0021] Preferably, the hydrogenation reaction comprises the following steps: dissolving the quaternary ammonium polymer in anhydrous ethanol, adding palladium / activated carbon after dissolution, then filling hydrogen, heating to 50-90℃ for 12-72h, and then filtering to remove the palladium / activated carbon, and drying to obtain a cycloolefin polymer with good antistatic performance. The amount of palladium / activated carbon is preferably 3-15wt% of the mass of the quaternary ammonium polymer; the pressure of the hydrogen filled is preferably 2-6MPa.

[0022] The beneficial effects of the present application are: The cycloolefin polymer provided by the present application takes norbornene as the polymerizable core, introduces imidazole salt as the ionic functional center, and cooperatively integrates oligomeric ether chain segments and alkyl hydrophobic chains in its structure, significantly enhancing the ionic conductivity and effectively reducing the surface resistance, enabling long-lasting and efficient intrinsic antistatic performance while maintaining high transparency, dimensional stability and processability.

[0023] Meanwhile, the cycloolefin polymer of the present application also has a "polar-nonpolar" microphase separation structure, which can effectively balance ionic conductivity, dimensional stability, optical transparency and mechanical flexibility without sacrificing the core advantages of the material; it can also be blended with other commercial COPs at a lower addition amount to impart long-lasting antistatic performance to the composite material, providing a simplified and efficient intrinsic antistatic solution for high-transparency and high-stability optical products.

[0024] The imidazole ring forms a stable cation (imidazole ) after subsequent quaternary ammonium reaction, which forms an ion pair with the counter anion to provide an ion source for ionic conduction; in addition, imidazole salt generally has a high thermal decomposition temperature and can withstand the processing temperature of COPs, ensuring the durability of the function.

[0025] The oligomeric ether chain segment has high polarity, which helps to weaken the coulombic force between the imidazole cation formed after quaternary ammonium and its counter anion (such as I - or Tf2N - ), promoting the dissociation of the ion pair and increasing the concentration of free ions, thereby effectively improving the ionic conductivity. Imidazole The salt coordination solves the problem of "high ion concentration but low conductivity" commonly found in ion-conducting polymers. Moreover, the oligomeric ether segment is a typical flexible segment, which significantly reduces the glass transition temperature (Tg) of the polymer after being introduced, making the polymer chain have a higher free volume and segment motion ability at room temperature, providing a dynamic convenience for ion migration.

[0026] The short alkyl chain R1 has non-polar characteristics, and together with the bulky hydrophobic anion, it forms a layer of hydrophobic microenvironment around the imidazole The shielding layer effectively limits the excessive absorption of water, preventing the polymer from swelling, softening or increasing haze due to excessive water absorption, thereby ensuring the dimensional stability and optical transparency of the material; the hydrophobic environment also helps to disperse ion pairs and prevent them from forming large ion clusters due to strong electrostatic interaction, maintaining uniform dispersion of ions and helping to maintain high conductivity and material uniformity. The oligomeric ether segment forms a synergistic and balancing relationship, enabling the cycloolefin polymer of the present application to achieve the effect of "moderate moisture absorption, high efficiency of conduction, and stable existence".

[0027] The counter anion is TsO - or TfO - , TsO - has low cost, high water solubility, and is easy to synthesize and then quickly remove byproduct salts and further ion exchange by water washing; TfO - has strong hydrophobicity and weak coordination ability, which can endow the material with intrinsic antistatic properties and is almost insensitive to humidity. Both have no absorption in the visible light region, can maintain film transmittance > 90% and yellowing index b* < 1, and completely avoid the risk of oxidative discoloration of I - / Br - ; the sulfonate structure of both is also compatible with the polymer matrix, which can inhibit migration and precipitation, achieve long-term stable antistatic effect, and meet the application requirements of high-end optical devices and dry environment electronic packaging. DETAILED DESCRIPTION

[0028] In order to further illustrate the present application, the schemes provided by the present application are described in detail below in conjunction with examples, but they should not be understood as limiting the scope of protection of the present application.

[0029] Example 1 Monomer A1 was used for the reaction: Monomer A1 The monomer A1 was vacuum dried at 45℃ to a water content <20ppm, then dissolved in CH2CI2 under nitrogen protection to obtain a raw material solution with a monomer A1 concentration of 0.5mol / L. 40mL of the raw material solution was taken in a reaction bottle, which was pre-cooled to 0℃ in an ice box.

[0030] G3 (Grubbs-III) was prepared as a 0.5 mol / L solution in CH2CI2. The G3 solution was then added dropwise to the reaction flask placed in an ice bath, and the total amount of G3 added was 400 μL. After 10 min of reaction at 0 °C, the ice bath was removed, and the reaction flask was allowed to gradually return to room temperature, and the reaction was continued for 30 min.

[0031] After the reaction was completed, the termination agent ethyl vinyl ether was prepared as a 1:1 solution in CH2CI2, and then added dropwise to the reaction flask. The total amount of termination agent added was 5 times the molar amount of catalyst. After the termination agent was added, the stirring was continued for 5 min to ensure complete quenching. Then, 5 times the volume of cold diethyl ether was added to the reaction flask, and the polymer was collected by filtration after the precipitate was formed. The polymer was dried at 40 °C for 12 h to obtain the polymer.

[0032] The polymer was dissolved in anhydrous DMF to a concentration of about 10% wt, and stirred under nitrogen until completely dissolved. Under ice bath cooling, methyl-p-toluenesulfonate was added dropwise slowly, and the final amount of methyl-p-toluenesulfonate was 3 times the molar amount of the polymer. The reaction system was then warmed to 80 °C, and stirred under nitrogen for 24 h. After the reaction was completed, the reaction solution was cooled to room temperature, and then slowly poured into a 50% v / v ethanol solution to precipitate the polymer. The polymer was collected by filtration, and washed with 50% v / v ethanol solution 3 times to remove the unreacted methyl-p-toluenesulfonate and by-products. The polymer was dried under vacuum to a constant weight to obtain the quaternized polymer.

[0033] The quaternized polymer was dissolved in anhydrous THF / ethanol (1:1 by volume) solution, and heated to 50 °C. After the quaternized polymer was completely dissolved, 10% Pd / C (palladium on activated carbon) was added in an amount of 10% of the mass of the quaternized polymer, and sonicated for 5 min under nitrogen. The mixture was then transferred to a 100 mL stainless steel autoclave, sealed, and purged with N2 3 times and H2 3 times. H2 was charged to 4.0 MPa, and the reaction was carried out at 70 °C for 36 h under stirring at 600 rpm. After the reaction was completed, the reaction solution was cooled to room temperature, and slowly depressurized. The Pd / C was removed by filtration using a 0.45 μm PTFE filter membrane, and the solvent was removed by rotary evaporation. The cycloolefin polymer with good antistatic properties was obtained by drying under vacuum at 50 °C for 24 h.

[0034] Example 2 The monomer A2 was used for the reaction: Monomer A2 The monomer A2 was dried under vacuum at 45 °C to a water content of <20 ppm, and then dissolved in CH2CI2 under nitrogen to obtain a monomer A2 solution with a concentration of 0.5 mol / L. 40 mL of the monomer A2 solution was placed in a reaction flask, and the reaction flask was placed in an ice bath and cooled to -5 °C.

[0035] G3 (Grubbs-III) was prepared as a 0.5 mol / L solution in CH2CI2. The G3 solution was then added dropwise to the reaction flask placed in an ice bath, and the total amount of G3 added was 600 μL. After 10 min of reaction at 0 °C, the ice bath was removed, and the reaction flask was allowed to gradually return to room temperature, and the reaction was continued for 30 min.

[0036] After the reaction was completed, the termination agent ethyl vinyl ether was prepared as a 1:1 solution in CH2CI2, and then added dropwise to the reaction flask. The total amount of termination agent added was 3 times the molar amount of catalyst. After the termination agent was added, the stirring was continued for 5 min to ensure complete quenching. Then, 5 times the volume of cold diethyl ether was added to the reaction flask, and the polymer was precipitated and collected by filtration and dried at 40 °C for 12 h.

[0037] The polymer was dissolved in anhydrous DMF at a concentration of about 10% wt, and stirred under nitrogen until completely dissolved. Under ice bath cooling, ethyl triflate was added dropwise slowly, and the final amount of ethyl triflate was 3 times the molar amount of the polymer. The reaction system was warmed to 80 °C, and then stirred under nitrogen for 24 h. After the reaction was completed, the reaction solution was cooled to room temperature, and then slowly poured into a 50% v / v ethanol solution to precipitate the polymer. The polymer was collected by filtration and washed with 50% v / v ethanol solution 3 times to remove unreacted ethyl triflate and byproducts. The polymer was dried under vacuum to constant weight to obtain the quaternized polymer.

[0038] The quaternized polymer was dissolved in anhydrous THF / ethanol (1:1 v / v) solution, and heated to 50 °C. After stirring until completely dissolved, 10% Pd / C (palladium on activated carbon) was added in an amount of 15% of the mass of the quaternized polymer, and sonicated for 5 min. The mixture was then transferred to a 100 mL stainless steel autoclave, sealed, and purged with N2 3 times and H2 3 times. H2 was charged to 4.0 MPa, and the reaction was carried out at 70 °C with stirring at 600 rpm for 36 h. After the reaction was completed, the reaction solution was cooled to room temperature, and then slowly released to atmospheric pressure. The Pd / C was removed by filtration using a 0.45 μm PTFE filter membrane, and the solvent was removed by rotary evaporation. The product was dried under vacuum at 50 °C for 24 h to obtain a cycloolefin polymer with good antistatic properties.

[0039] Example 3 The monomer A3 was used for the reaction: Monomer A3 The monomer A3 was dried under vacuum at 45 °C to a water content of <20 ppm, and then dissolved in CH2CI2 under nitrogen to obtain a monomer A3 solution with a concentration of 0.5 mol / L. 40 mL of the monomer A3 solution was placed in a reaction flask, and the reaction flask was placed in an ice bath and cooled to -5 °C.

[0040] G3 (Grubbs-III) was prepared as a 0.5 mol / L solution in CH2CI2. The G3 solution was then added dropwise to the reaction flask placed in an ice bath, and the total amount of G3 added was 800 μL. After 10 min of reaction at 0 °C, the ice bath was removed, and the reaction flask was allowed to gradually return to room temperature, and the reaction was continued for 30 min.

[0041] After the reaction was completed, the termination agent benzaldehyde was prepared as a 1:1 solution in CH2CI2, and then added dropwise to the reaction flask. The total amount of termination agent added was 10 times the molar amount of catalyst. After the termination agent was added, the stirring was continued for 5 min to ensure complete quenching. Then, 5 times the volume of cold ether was added to the reaction flask, and the polymer was precipitated and collected by filtration. The polymer was dried at 40 °C for 12 h to obtain the polymer.

[0042] The polymer was dissolved in anhydrous DMF to a concentration of about 10% wt, and stirred under nitrogen until completely dissolved. Under ice bath cooling, propyl p-toluenesulfonate was added dropwise slowly, and the final amount of propyl p-toluenesulfonate was 3 times the molar amount of the polymer. The reaction system was then warmed to 80 °C, and stirred under nitrogen for 24 h. After the reaction was completed, the reaction solution was cooled to room temperature, and then slowly poured into a 50% v / v ethanol solution to precipitate the polymer. The polymer was collected by filtration, and washed with 50% v / v ethanol solution 3 times to remove unreacted propyl p-toluenesulfonate and byproducts. The polymer was dried under vacuum to a constant weight to obtain the quaternized polymer.

[0043] The quaternized polymer was dissolved in anhydrous THF / ethanol (1:1 v / v) solution, and heated to 50 °C. After stirring until completely dissolved, 10% Pd / C (palladium on activated carbon) was added in an amount of 8% of the mass of the quaternized polymer, and sonicated for 5 min. The mixture was then transferred to a 100 mL stainless steel autoclave, sealed, and purged with N2 3 times and H2 3 times. The H2 was charged to 4.0 MPa, and the reaction was carried out at 70 °C with stirring at 600 rpm for 36 h. After the reaction was completed, the reaction was cooled to room temperature, and slowly depressurized. The Pd / C was removed by filtration using a 0.45 μm PTFE filter membrane, and the solvent was removed by rotary evaporation. The product was dried under vacuum at 50 °C for 24 h to obtain a cycloolefin polymer with good antistatic properties.

[0044] Comparative Example 1 The only difference between this example and Example 1 is that monomer B1 was used in the reaction. Monomer B1 The monomer A1 was dried under vacuum at 45 °C to a water content of <20 ppm, and then dissolved in CH2CI2 under nitrogen to obtain a monomer A1 solution with a concentration of 0.5 mol / L. 40 mL of the monomer A1 solution was placed in a reaction flask, and the reaction flask was placed in an ice bath and cooled to 0 °C.

[0045] G3 (Grubbs-III) was prepared as a 0.5 mol / L solution in CH2CI2. The G3 solution was then added dropwise to the reaction flask placed in an ice bath, and the total amount of G3 added was 400 μL. After 10 min at 0 °C, the ice bath was removed and the reaction flask was allowed to gradually return to room temperature, and the reaction was allowed to proceed for 30 min.

[0046] After the reaction was complete, the termination agent ethyl vinyl ether was prepared as a 1:1 solution in CH2CI2, and then added dropwise to the reaction flask. The total amount of termination agent added was 5 times the molar amount of catalyst. After the termination agent was added, the stirring was continued for 5 min to ensure complete quenching. Then, 5 volumes of cold diethyl ether was added to the reaction flask, and the polymer was collected by filtration after the precipitate was formed. The polymer was dried at 40 °C for 12 h.

[0047] The polymer was dissolved in anhydrous DMF at a concentration of about 10% wt, and stirred under nitrogen until completely dissolved. Methyl-p-toluenesulfonate was added slowly dropwise under ice bath cooling, and the final amount of methyl-p-toluenesulfonate was 3 times the molar amount of the polymer. The reaction system was warmed to 80 °C, and then stirred under nitrogen for 24 h. After the reaction was complete, the reaction solution was slowly poured into a 50% v / v ethanol solution to precipitate the polymer. The polymer was collected by filtration, and washed with 50% v / v ethanol solution 3 times to remove unreacted methyl-p-toluenesulfonate and byproducts. The polymer was dried under vacuum to constant weight to obtain the quaternized polymer.

[0048] The quaternized polymer was dissolved in anhydrous THF / ethanol (1:1 by volume) solution, and heated to 50 °C. After the quaternized polymer was completely dissolved, 10% Pd / C (palladium on activated carbon) was added in an amount of 10% of the mass of the quaternized polymer, and sonicated for 5 min. The mixture was then transferred to a 100 mL stainless steel autoclave, sealed, and purged with N2 3 times and H2 3 times. The H2 was charged to 4.0 MPa, and the reaction was carried out at 70 °C with stirring at 600 rpm for 36 h. After the reaction was complete, the reaction solution was cooled to room temperature, and then slowly depressurized. The Pd / C was removed by filtration using a 0.45 μm PTFE filter membrane, and the solvent was removed by rotary evaporation. The sample was dried under vacuum at 50 °C for 24 h to obtain the cycloolefin polymer.

[0049] Comparative Example 2 The difference from Example 1 is that the quaternization reaction was not performed.

[0050] The monomer A1 was used for the reaction: Monomer A1 The monomer Al was vacuum dried at 45 °C to a water content of <20 ppm, then dissolved in CH2CI2under nitrogen to give a stock solution of monomer Al at a concentration of 0.5 mol / L. 40 mL of the stock solution was taken in a reaction flask, which was pre-cooled to 0 °C in an ice box.

[0051] G3 (Grubbs-III) was also prepared as a 0.5 mol / L solution in CH2CI2. Then 400 μL of the G3 solution was added dropwise to the reaction flask in the ice box. After 10 min of reaction at 0 °C, the ice box was removed and the reaction flask was allowed to gradually return to room temperature, and the reaction was continued for 30 min.

[0052] After the reaction was completed, a solution of the termination agent ethyl vinyl ether in CH2CI2was prepared at a volume ratio of 1:1, and then added dropwise to the reaction flask. The total amount of termination agent added was 5 times the molar amount of catalyst. After the termination agent was added, the stirring was continued for 5 min to ensure complete quenching. Then 5 times the volume of cold diethyl ether was added to the reaction flask, and the precipitate was collected by filtration and dried at 40 °C for 12 h to give the polymer.

[0053] The polymer was dissolved in anhydrous THF / ethanol (volume ratio of THF / ethanol 1:1) solution, heated to 50 °C, and stirred until completely dissolved. Then 10% Pd / C (palladium on activated carbon) was added to the solution, which was 10% of the mass of the polymer, and ultrasonically dispersed for 5 min under nitrogen. The mixture was then transferred to a 100 mL stainless steel autoclave, sealed, purged with N2for 3 times, and then purged with H2for 3 times. H2was charged to 4.0 MPa, and the temperature was raised to 70 °C. The reaction was carried out at 600 rpm for 36 h. After the reaction was completed, the temperature was cooled to room temperature, and the pressure was slowly released. The Pd / C was removed by filtration using a 0.45 μm PTFE filter membrane, and the solvent was removed by rotary evaporation. The sample was vacuum dried at 50 °C for 24 h to give the cycloolefin polymer sample.

[0054] Comparative Example 3 The difference from Example 1 is that the quaternary ammonium reagent is methyl iodide.

[0055] The monomer Al was used for the reaction: Monomer Al The monomer Al was vacuum dried at 45 °C to a water content of <20 ppm, then dissolved in CH2CI2under nitrogen to give a stock solution of monomer Al at a concentration of 0.5 mol / L. 40 mL of the stock solution was taken in a reaction flask, which was pre-cooled to 0 °C in an ice box.

[0056] G3 (Grubbs-III) was prepared into a 0.5 mol / L solution with CH2Cl2as solvent. Then G3 solution was added dropwise into the reaction bottle placed in an ice box, and the total amount of G3 solution was 400 μL. After 10 min of reaction at 0 ℃, the ice box was removed, and the reaction bottle was gradually returned to room temperature, and the conversion was performed for 30 min.

[0057] After the conversion was completed, the quenching agent ethyl vinyl ether was prepared into a solution with CH2Cl2at a volume ratio of 1:1, and then was added dropwise into the reaction bottle, and the total amount of the quenching agent was 5 times the molar amount of the catalyst. After the quenching agent was added, stirring was continued for 5 min to ensure complete quenching. Then 5 times the volume of cold ether was added to the liquid in the reaction bottle, and the precipitate was filtered and collected, and was dried at 40 ℃ for 12 h to obtain the polymer.

[0058] The polymer was dissolved in anhydrous DMF at a concentration of about 10% wt, and was stirred under nitrogen protection until complete dissolution. Under ice bath cooling, iodomethane was slowly added dropwise, and the final amount of iodomethane was 3 times the molar amount of the polymer. The reaction system was warmed to 80 ℃, and then was stirred under nitrogen protection for 24 h. After the reaction was completed, the reaction liquid was slowly poured into a 50% v / v ethanol solution to precipitate the polymer. Filtration and washing with a 50% v / v ethanol solution for 3 times were performed to remove unreacted iodomethane and by-products. Vacuum drying was performed to a constant weight to obtain the quaternized polymer.

[0059] The quaternized polymer was dissolved in anhydrous THF / ethanol (THF / ethanol at a volume ratio of 1:1) solution, and was heated to 50 ℃. After complete dissolution, 10% Pd / C (palladium / activated carbon) was added in an amount of 10% of the mass of the quaternized polymer, and was ultrasonically dispersed for 5 min. Then the mixture was transferred into a 100 mL stainless steel high-pressure reaction kettle, was sealed, was purged with N2for 3 times, and was purged with H2for 3 times. H2was filled to 4.0 MPa, and the reaction was performed at 70 ℃ for 36 h under stirring at 600 rpm. After the reaction was completed, the reaction liquid was cooled to room temperature, was slowly depressurized, and then was filtered to remove Pd / C using a 0.45 μm PTFE filter membrane. The solvent was removed by rotary evaporation, and vacuum drying was performed at 50 ℃ for 24 h to obtain a cycloolefin polymer with good antistatic performance.

[0060] Test Example 1 The cycloolefin polymers prepared in Examples 1 to 3 and Comparative Examples 1 to 3 were used as samples, and photophysical electrochemical performance tests were performed.

[0061] The surface resistivity of the samples was determined according to the method described in IEC 61340-5-1, the surface resistance after 50 times of IPA wiping (50% RH) was determined according to the method described in IEC 61340-5-3, and the yellowing index b* and the change in b* after aging were determined according to the method described in ASTM E313. The glass transition temperature Tg (℃) was determined by the method described in ISO 11357-2 (DSC, 10℃ / min), the haze and total light transmittance were determined by the method described in ASTM D1003, and the tensile modulus and elongation at break were determined by the method described in ASTM D882. The results are shown in Tables 1-2.

[0062] Table 1 COP antistatic performance

[0063] Table 2 COP photochemical performance

[0064] As can be seen from the results in Table 1, the cycloolefin polymers prepared in Examples 1-3 of the present application have a smaller change in surface resistivity under a humidity change of 30%RH-80%RH, and always remain at the order of magnitude of 10 8 Ω / sq; in contrast, Comparative Example 3 uses I - The surface resistivity of the cycloolefin polymer prepared with a counter anion differs by 10 5 times, and it can be seen that the cycloolefin polymer provided by the present application has good antistatic performance and is not affected by the environmental humidity. After 50 times of IPA wiping, the surface resistance of the sample only increases by 1.44-1.59 times, which is still much lower than 10 10 Ω / sq, indicating that the cycloolefin polymer provided by the present application has excellent and long-lasting antistatic performance.

[0065] As can be seen from the results in Table 2, the cycloolefin polymer samples of the present application have good antistatic performance while maintaining high transparency, high stability, and a lower glass transition temperature, meeting the application requirements of high-end optical devices and dry environment electronic packaging.

[0066] Although the above examples have made a detailed description of the present application, it is only a part of the embodiments of the present application, but not all the embodiments, and other embodiments can be obtained by the present embodiments without creativity, which all belong to the protection scope of the present application.

Claims

1. A cyclic olefin polymer having excellent antistatic properties, characterized in that, The structure of the cyclic olefin polymer is shown in formula (I): wherein a is 30 to 120, b is 1 to 4, X - is a counter anion, and R1is a C1-C4 alkyl group.

2. The cyclic olefin polymer according to claim 1, characterized in that, R1is methyl, ethyl or n-butyl; the counter anion is TsO - or TfO - .

3. The cyclic olefin polymer according to claim 1, characterized in that, The cyclic olefin polymer is obtained by polymerization of monomers shown in formula (II): Wherein b is 1-4.

4. The process for the preparation of a cyclic olefin polymer according to any one of claims 1 to 3, characterized in that The method comprises the following steps: The monomers shown in formula (II) are dissolved in an organic solvent to obtain a raw material solution; the raw material solution is pre-cooled to -5-5°C and then a catalyst is added, and the reaction is carried out for 5-15 min, and then the conversion is carried out at 24-28°C for 30-45 min; after the conversion is completed, a terminating agent is added and stirred for 5-10 min to terminate the reaction, to obtain a reaction original solution, and diethyl ether is added to the reaction original solution for precipitation; the precipitate is collected by filtration, and dried to obtain a polymer; The polymer is prepared into a 5-10%wt solution, and then a quaternary ammonium reagent is added to carry out a quaternary ammonium reaction to obtain a quaternary ammonium polymer; the quaternary ammonium reagent is any one of methyl p-toluenesulfonate, ethyl p-toluenesulfonate, propyl p-toluenesulfonate, methyl triflate, ethyl triflate and butyl triflate; The quaternary ammonium polymer is subjected to a hydrogenation reaction to obtain a cyclic olefin polymer with good antistatic property.

5. The method of claim 4, wherein, The organic solvent is dichloromethane, chloroform, 1,2-dichloroethane, toluene or chlorobenzene.

6. The method of claim 4, wherein, The catalyst is Grubbs-II or Grubbs-III; and the terminating agent is ethyl vinyl ether or benzaldehyde.

7. The method of claim 4, wherein, The water content of the monomer A is ≤20 ppm; and the concentration of the monomer A in the raw material solution is 0.3-0.7 mol / L.

8. The method of claim 4, wherein, The molar ratio of the catalyst to the monomer A is 1:20-150 based on the amount of the catalyst; and the molar ratio of the catalyst to the terminating agent is 1:3-10.

9. The method of claim 4, wherein, The volume ratio of the reaction original solution to diethyl ether is 1:3-8.

10. The method of claim 4, wherein, The molar ratio of the polymer to the quaternary ammonium reagent is 1:3-5; the quaternary ammonium reaction is carried out at 60-100°C for 12-48 h; and after the quaternary ammonium reaction is completed, 50-75%v / v aqueous ethanol solution is further added for precipitation, the precipitate is collected by filtration, and dried to obtain the quaternary ammonium polymer.

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