High-transparency scratch-resistant polycarbonate material

Abstract

The invention belongs to the field of modified polycarbonate materials, and discloses a high-transparency scratch-resistant polycarbonate material which comprises the following components in parts by weight: 90-100 parts of polycarbonate resin, 1-4 parts of a fluorinated cycloolefin scratch-resistant agent, 0.2-1 part of an antioxidant, 0.2-1 part of a heat stabilizer and 0.2-1 part of a light stabilizer, the fluorinated cycloolefin scratch-resistant agent is formed by addition copolymerization of a cycloolefin monomer, an alpha-olefin monomer and a fluorinated olefin monomer. According to the invention, the fluorinated olefin monomer, the cycloolefin monomer and the alpha-olefin monomer are copolymerized to prepare the fluorinated cycloolefin copolymer with a special structure, the fluorinated cycloolefin is used as a scratch-resistant agent of the polycarbonate material, and the high transparency, high glossiness, high rigidity, high strength and low surface friction coefficient of the fluorinated cycloolefin are utilized; the composite material has the advantages of high transparency, high surface hardness and scratch resistance, is not easy to generate scratches under the action of external force, and can effectively prevent abrasion and maintain good appearance.

Description

Technical Field

[0001] The present invention belongs to the field of modified polycarbonate materials, and particularly relates to a highly transparent and scratch-resistant polycarbonate material. Background Art

[0002] Components such as keyboards, displays, casings, and other easily worn parts of devices and instruments such as mobile phones, computers, and digital cameras are prone to wear during long-term use. Although polycarbonate is an excellent choice for preparing the above-mentioned accessories, due to its low surface hardness and poor scratch resistance, it is easy to produce scratches when subjected to external forces. It is necessary to perform a surface hardening coating treatment on the resin or reduce the surface friction coefficient by adding fluororesin to prevent wear and maintain a good appearance. Currently, the commonly used method to improve the scratch resistance of polycarbonate is to coat a high-hardness photocurable coating after polycarbonate molding. However, this method has a complex process flow, low production efficiency, and the impact performance of the material will be affected to a certain extent, restricting the application of polycarbonate.

[0003] In response to the weakness of polycarbonate's poor wear resistance, many companies have also developed scratch-resistant polycarbonates. The products can be applied to places with certain requirements for the surface hardness of materials such as automotive parts like electronic device housings, touch displays, knobs, and instrument panels, as well as optical glasses products. For example, Lexan DMX resin developed by GE Plastics uses a unique PC copolymerization technology to greatly improve the surface hardness and is very suitable for manufacturing components such as transparent soft keys, infrared lenses, bases, and displays. In tests conducted by an independent laboratory using the pencil hardness (1 kg) standard, the hardness of these materials reached the H grade, much higher than the 2B grade of ordinary PC. Compared with standard PC, GE Lexan DMX resin can enhance the surface hardness without the need for surface hardening treatment. Teijin of Japan has launched two scratch-resistant PCs based on the filling of fluororesin (polytetrafluoroethylene), which are respectively reinforced with glass fiber and carbon fiber, and can be used for electrical appliances, electronic components, mechanical parts, lighting fixtures, and containers with high fatigue resistance requirements, as well as mechanical parts, lighting systems, instrument panels, etc. with high requirements for high and low temperature resistance performance. However, it has a greater impact on transparency. How to develop a polycarbonate material with high transparency and high scratch resistance is still a difficult problem that needs to be solved in the industry.

[0004] Cycloolefin copolymer (COC) is an amorphous transparent polymer material with a cyclic structure. It is an amorphous transparent resin obtained by copolymerizing ethylene and norbornene (bicycloheptene) using a metallocene catalyst. The main characteristics of COC materials are high transparency, high gloss, high heat resistance, good water vapor tightness, and belong to high heat resistance transparent resins. Its glass transition temperature reaches 140 - 170 °C, and it has high rigidity and strength, excellent extrusion moldability and thermoformability, affinity with polyolefins, excellent biocompatibility and chemical inertness, hydrolysis resistance, resistance to polar organic solvents, acid resistance, and alkali resistance. COC materials are mainly used in optical applications such as lenses and light guide plates for liquid crystal displays, optical films, etc., in the packaging material field for the modification of polyethylene and polypropylene, in the medical and testing instrument fields, and in the electronic device fields.

[0005] In the prior art, mixing cycloolefin copolymer with polycarbonate can be used to prepare light diffusing materials, but the research on using cycloolefin copolymer, especially fluorinated cycloolefin copolymer, to compound with polycarbonate to prepare high transparent and scratch-resistant materials still needs to be explored. Summary of the Invention

[0006] The purpose of the present invention is to provide a high transparent and scratch-resistant polycarbonate material. The polycarbonate material contains a fluorinated cycloolefin scratch-resistant agent, which is formed by addition copolymerization of a cycloolefin monomer, an α-olefin monomer, and a fluorinated olefin monomer. The fluorinated cycloolefin scratch-resistant agent has high transparency, high gloss, high rigidity, high strength, and a low surface friction coefficient. Using fluorinated cycloolefin as the scratch-resistant agent of the polycarbonate material makes the composite material have high transparency, high surface hardness, scratch resistance, and is not easy to produce scratches when subjected to external forces, and can effectively prevent wear and maintain a good appearance.

[0007] The purpose of the present invention is achieved through the following technical solutions:

[0008] The present invention provides a high transparent and scratch-resistant polycarbonate material. By weight, the polycarbonate material includes the following raw materials:

[0009] 90 - 100 parts of polycarbonate resin, 1 - 4 parts of fluorinated cycloolefin scratch-resistant agent, 0.2 - 1 part of antioxidant, 0.2 - 1 part of heat stabilizer, 0.2 - 1 part of light stabilizer; the fluorinated cycloolefin scratch-resistant agent is formed by addition copolymerization of a cycloolefin monomer, an α-olefin monomer, and a fluorinated olefin monomer.

[0010] In some embodiments, the cycloolefin monomer is selected from at least one of the following structures:

[0011]

[0012] Among them, R is selected from hydrogen, C 1 -C6 at least one of a hydrocarbyl group, a vinyl group, an acetyl group, a phenyl group, or a non-fluorinated halogen; the α-olefin monomer is selected from at least one of ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methylhexene, 4-methylhexene, 5-methylhexene, 1-octene, or 1-decene; the fluorinated olefin monomer is selected from at least one of fluorinated ethylene, trifluoroethylene ether, perfluorobutylethylene, or perfluorohexylethylene.

[0013] In some embodiments, based on the sum of the molar percentages of the cycloolefin monomer, α-olefin monomer, and fluorinated olefin monomer being 100 mol%, the molar percentage of the cycloolefin monomer is 5 mol% - 20 mol%, the molar percentage of the α-olefin monomer is 30 mol% - 65 mol%, and the molar percentage of the fluorinated olefin monomer is 30 mol% - 50 mol%.

[0014] In some embodiments, the addition copolymerization reaction of the cycloolefin monomer, α-olefin monomer, and fluorinated olefin monomer is carried out in a reaction medium under the action of a catalyst;

[0015] Preferably, the addition amount of the catalyst is 0.01 wt% - 0.05 wt% of the total mass of the cycloolefin monomer, α-olefin monomer, and fluorinated olefin monomer;

[0016] Preferably, the catalyst is composed of a metallocene catalyst and a cocatalyst mixed;

[0017] Preferably, the mass ratio of the metallocene catalyst to the cocatalyst is 1:(10 - 1000);

[0018] Preferably, the cocatalyst is selected from at least one of an organoboron salt compound or an organoaluminum compound.

[0019] Furthermore, the structural general formula of the metallocene catalyst is as follows:

[0020]

[0021] Wherein: R 1 -R 4 each independently selected from hydrogen, C 1 -C 6 one or more of a hydrocarbyl group and an aromatic group; R 5 is C 3 -C 8 a hydrocarbyl group; X is selected from dimethylsilyl, diphenylsilyl, or diphenylmethyl; M is Ti, Zr, or Hf.

[0022] Furthermore, the organoboron salt compound is an ionic compound formed by an organoboron anion and a cation;

[0023] More preferably, the organic boron anion is selected from at least one of tetraphenylborate, tetrakis(monofluorophenyl)borate, tetrakis(difluorophenyl)borate, tetrakis(trifluorophenyl)borate, tetrakis(tetrafluorophenyl)borate, tetrakis(pentafluorophenyl)borate, tetrakis(tetrafluoromethylphenyl)borate, tetrakis(tolyl)borate, tetrakis(xylenyl)borate, (triphenyl, pentafluorophenyl)borate, [tris(pentafluorophenyl), phenyl]borate, or undecahydro-7,8-dicarbaundecaborate;

[0024] More preferably, the cation is selected from at least one of a carbonium cation, an oxonium cation, an ammonium cation, a phosphonium cation, a cycloheptatrienyl cation, or a ferrocenium cation containing a transition metal.

[0025] Furthermore, the organoaluminum compound is selected from at least one of trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, triisopropylaluminum, triisobutylaluminum, tripentylaluminum, trihexylaluminum, tricyclohexylaluminum, trioctylaluminum, triphenylaluminum, tri-p-tolylaluminum, tribenzylaluminum, ethyldibenzylaluminum, or ethyldi(p-tolyl)aluminum;

[0026] Furthermore, the reaction medium is selected from at least one of aliphatic saturated alkanes, aromatic hydrocarbons, aryl halides, and cycloalkanes;

[0027] More preferably, the reaction medium is selected from at least one of n-hexane, toluene, or n-pentane.

[0028] More preferably, the addition amount of the reaction medium is 2 to 10 times the sum of the masses of the cycloolefin monomer, the α-olefin monomer, and the fluorinated olefin monomer.

[0029] In some embodiments, the antioxidant is selected from at least one of tea polyphenols, butylated hydroxyanisole, dibutylhydroxytoluene, tert-butylhydroquinone, pentaerythritol tetra[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], triethylene glycol ether-bis(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate, tris(2,4-di-tert-butylphenyl)phosphite, n-octadecyl β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, or 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione; and / or

[0030] The heat stabilizer is selected from at least one of tribasic lead sulfate, dibasic lead phosphite, dibasic lead stearate, dibasic lead phthalate, tribasic lead maleate, lead silicate, lead stearate, lead salicylate, dibasic lead phthalate, basic lead carbonate, cadmium stearate, barium stearate, calcium stearate, lead stearate, zinc stearate, dibutyltin dilaurate, dioctyltin dilaurate; and / or

[0031] The light stabilizer is selected from at least one of carbon black, light stabilizer 622, light stabilizer 770, light stabilizer 856, light stabilizer 944, light stabilizer HS-112, light stabilizer HS-508.

[0032] Compared with the prior art, the beneficial technical effects of the present invention are as follows:

[0033] The present invention copolymerizes fluorinated olefin monomers with cycloolefin monomers and α-olefin monomers to prepare a fluorinated cycloolefin copolymer with a special structure. On the one hand, the addition of the fluorinated olefin structure enables the fluorinated olefin to insert into the α-olefin chain segment during the growth of the polymer chain, preventing the generation of long olefin sequences in the polymer chain and avoiding the formation of crystalline olefin crystal regions, thereby improving the optical properties of the product. On the other hand, the fluorinated olefin has stronger rigidity compared to ordinary olefins due to its structural characteristics, which mainly stems from the size and electronic properties of fluorine atoms, and the cycloolefin itself has high rigidity due to its strong ring structure, so that the fluorinated cycloolefin has high rigidity and high hardness, and the fluorinated structure can bring a low surface friction coefficient.

[0034] In the present invention, fluorinated cycloolefin is used as a scratch-resistant agent for polycarbonate materials, making full use of the high transparency and high gloss of the cycloolefin copolymer itself. The composite material obtained by blending it with polycarbonate materials as a modifier also has excellent optical properties and exhibits high light transmittance. In addition, the high rigidity, high strength and low surface friction coefficient of the fluorinated cycloolefin prepared by the present invention endow the composite material with high surface hardness, scratch resistance, and it is not easy to generate scratches when subjected to external forces, which can effectively prevent wear and maintain a good appearance. The polycarbonate composite material prepared by the solution of the present invention has a light transmittance of more than 90%, a pencil hardness of 2H level, and only slight scratches appear in the five-finger scratch test, and the brightness change value ΔL does not exceed 0.3, showing a significant performance improvement effect compared with the unmodified sample and the control sample. In summary, by using fluorinated cycloolefin as a scratch-resistant agent, a high-transparency and scratch-resistant polycarbonate material can be obtained. Detailed Embodiments

[0035] The present invention will be further described in detail in combination with specific embodiments. The following embodiments can enable those skilled in the art to understand the present invention more comprehensively, but do not limit the present invention in any way.

[0036] The present invention provides a highly transparent and scratch-resistant polycarbonate material. By weight, the polycarbonate material comprises the following raw materials:

[0037] 90 - 100 parts of polycarbonate resin, 1 - 4 parts of fluorinated cycloolefin scratch-resistant agent, 0.2 - 1 part of antioxidant, 0.2 - 1 part of heat stabilizer, and 0.2 - 1 part of light stabilizer; the fluorinated cycloolefin scratch-resistant agent is formed by addition copolymerization of cycloolefin monomers, α-olefin monomers, and fluorinated olefin monomers;

[0038] Specifically, based on the sum of the molar percentages of the cycloolefin monomers, α-olefin monomers, and fluorinated olefin monomers being 100 mol%, 5 mol% - 20 mol% of the cycloolefin monomers, 30 mol% - 65 mol% of the α-olefin monomers, and 30 mol% - 50 mol% of the fluorinated olefin monomers are subjected to addition copolymerization in a reaction medium under the action of a catalyst;

[0039] Specifically, the antioxidant is selected from at least one of tea polyphenols, butylated hydroxyanisole, dibutylhydroxytoluene, tert-butylhydroquinone, pentaerythritol tetra[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], triethylene glycol ether-bis(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate, tris(2,4-di-tert-butylphenyl) phosphite, n-octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, or 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione; and / or the heat stabilizer is selected from at least one of tribasic lead sulfate, dibasic lead phosphite, dibasic lead stearate, dibasic lead phthalate, tribasic lead maleate, lead silicate, lead stearate, lead salicylate, dibasic lead phthalate, basic lead carbonate, cadmium stearate, barium stearate, calcium stearate, lead stearate, zinc stearate, dibutyltin dilaurate, dioctyltin dilaurate; and / or the light stabilizer is selected from at least one of carbon black, light stabilizer 622, light stabilizer 770, light stabilizer 856, light stabilizer 944, light stabilizer HS-112, light stabilizer HS-508.

[0040] It should be noted that the reason for selecting the above-mentioned ratio of olefin monomers is that the fluorinated cycloolefin copolymer prepared from the cycloolefin monomer and α-olefin monomer within this ratio range has good basic rigidity, so that the fluorinated cycloolefin has high rigidity and high hardness. If the content of the cycloolefin monomer in the system is too high, the brittleness of the prepared material will increase, which will affect the mechanical properties of the matrix material. If the content of the α-olefin monomer in the system is too high, the light transmittance of the composite polycarbonate material will decrease. However, the fluorinated olefin monomer within this range can not only play a good role in enhancing scratch resistance without affecting the optical properties of the matrix, but even improve them to some extent.

[0041] The cycloolefin monomer is selected from at least one of the following structures:

[0042]

[0043] Among them, R is selected from at least one of hydrogen, C 1 -C 6 hydrocarbyl, vinyl, acetyl, phenyl, or non-fluorine halogen; the α-olefin monomer is selected from at least one of ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methylhexene, 4-methylhexene, 5-methylhexene, 1-octene, or 1-decene; the fluorinated olefin monomer is selected from at least one of fluorinated ethylene, trifluoroethylene ether, perfluorobutylethylene, or perfluorohexylethylene; the addition amount of the catalyst is 0.01 wt% - 0.05 wt% of the total mass of the cycloolefin monomer, α-olefin monomer, and fluorinated olefin monomer; the catalyst is composed of a metallocene catalyst and a cocatalyst; the mass ratio of the metallocene catalyst to the cocatalyst is 1:(10 - 1000); the cocatalyst is selected from at least one of an organic borate compound or an organic aluminum compound.

[0044] Specifically, the structural general formula of the metallocene catalyst is as follows:

[0045]

[0046] Among them: R 1 -R 4 each independently is selected from one or more of hydrogen, C 1 -C 6 hydrocarbyl, aromatic group; R 5 is C 3 -C 8Hydrocarbyl; X is selected from dimethylsilyl, diphenylsilyl, or benzhydryl; M is Ti, Zr or Hf; the organic borate compound is an ionic compound formed by an organic boron anion and a cation; the organoaluminum compound is selected from at least one of trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, triisopropylaluminum, triisobutylaluminum, tripentylaluminum, trihexylaluminum, tricyclohexylaluminum, trioctylaluminum, triphenylaluminum, tri-p-tolylaluminum, tribenzylaluminum, ethyldibenzylaluminum, or ethyldi(p-tolyl)aluminum; the reaction medium is selected from at least one of aliphatic saturated alkanes, aromatic hydrocarbons, aryl halides, and cycloalkanes;

[0047] Specifically, the organic boron anion is selected from at least one of tetraphenylborate, tetrakis(monofluorophenyl)borate, tetrakis(difluorophenyl)borate, tetrakis(trifluorophenyl)borate, tetrakis(tetrafluorophenyl)borate, tetrakis(pentafluorophenyl)borate, tetrakis(tetrafluoromethylphenyl)borate, tetrakis(tolyl)borate, tetrakis(xylenyl)borate, (triphenyl, pentafluorophenyl)borate, [tris(pentafluorophenyl), phenyl]borate, or undecahydro-7,8-dicarbadecaborate; the cation is selected from at least one of a carbonium cation, an oxonium cation, an ammonium cation, a phosphonium cation, a cycloheptatrienylium cation, or a ferrocenium cation containing a transition metal; the reaction medium is selected from at least one of n-hexane, toluene, or n-pentane; the addition amount of the reaction medium is 2-10 times the sum of the masses of the cycloolefin monomer, the α-olefin monomer, and the fluorinated olefin monomer.

[0048] It should be noted that the metallocene catalyst and cocatalyst composite catalytic system selected in the present invention has high catalytic activity and appropriate reaction activity at the addition ratio of the present invention, has a relatively high reaction efficiency during the polymerization process and is not prone to explosive polymerization, and can simultaneously well control the molecular structure and molecular weight distribution of the copolymer.

[0049] Specifically, in one embodiment, the preparation method of the fluorinated cycloolefin scratch-resistant agent is as follows:

[0050] 1) Add the cycloolefin monomer and the fluorinated olefin monomer to the reaction kettle, and then add the reaction medium;

[0051] 2) After closing the reaction kettle, start stirring under a nitrogen atmosphere, heat up to 60-120 °C, introduce gaseous α-olefin monomer (the α-olefin monomer is selected from gaseous ethylene, propylene or 1-butene) and maintain the pressure at 0.5-5 MPa, and balance for 30-60 min;

[0052] 3) Then, a metallocene catalyst and a cocatalyst are added to the reaction kettle. After maintaining the temperature at 60 - 120 °C and the pressure at 0.5 - 5 MPa for a polymerization reaction for 30 - 240 min, ethanol is added to terminate the reaction, and then the temperature is lowered, the stirring is stopped, and the pressure is released; the product is precipitated in ethanol, filtered and collected, and vacuum dried to a constant weight.

[0053] Specifically, in one embodiment, the preparation method of the fluorinated cycloolefin scratch-resistant agent is as follows:

[0054] 1) Add a cycloolefin monomer, an α-olefin monomer (the α-olefin monomer is selected from liquid 1-pentene, 1-hexene, 3-methylhexene, 4-methylhexene, 5-methylhexene, 1-octene, 1-decene), and a fluorinated olefin monomer into the reaction kettle, and then add a reaction medium;

[0055] 2) After sealing the reaction kettle, start stirring under a nitrogen atmosphere, heat up to 60 - 120 °C, and maintain the pressure at 0.5 - 5 MPa for equilibration for 30 - 60 min;

[0056] 3) Then, a metallocene catalyst and a cocatalyst are added to the reaction kettle. After maintaining the temperature at 60 - 120 °C and the pressure at 0.5 - 5 MPa for a polymerization reaction for 30 - 240 min, ethanol is added to terminate the reaction, and then the temperature is lowered, the stirring is stopped, and the pressure is released; the product is precipitated in ethanol, filtered and collected, and vacuum dried to a constant weight.

[0057] The present invention also provides a preparation method of a highly transparent scratch-resistant polycarbonate material, and the method includes the following steps:

[0058] 1) Thoroughly dry the polycarbonate resin, add a fluorinated cycloolefin scratch-resistant agent, an antioxidant, a heat stabilizer, and a light stabilizer, and mix evenly;

[0059] 2) Add the mixture obtained in step 1) into an extruder for uniform mixing, cooling, and then granulate using a granulator, and dry to obtain polycarbonate modified pellets;

[0060] 3) Inject and mold the polycarbonate modified pellets obtained in step 2) through an injection molding machine to obtain a highly transparent scratch-resistant polycarbonate material.

[0061] Specifically, the mixing is carried out using a high-speed mixer, the rotation speed of the high-speed mixer is 500 - 800 rpm, the mixing temperature is 20 - 50 °C, and the mixing time is 3 - 10 min; the extruder is a twin-screw extruder, the temperature of each zone is 220 - 260 °C, and the screw rotation speed is 300 - 500 rpm; the temperature of each zone of the injection molding machine is 250 - 300 °C.

[0062] The present invention also conducts performance tests on the composite materials prepared in each example and comparative example:

[0063] Samples of 50*90*2 mm were made according to a unified injection molding process, and their light transmittance, haze, and scratch resistance were tested. Among them, the light transmittance and haze were tested according to the standard ASTM D1003. Scratch resistance: The five-finger scratch test method was used for testing. The test conditions were as follows: a 7-mm indenter was used, the load was 10 N, the scratching speed was 100 mm / s, and the scratching distance was 100 mm. The scratching results were observed, and a color difference meter was used to measure the brightness change value (ΔL) at the scratch. The lighter the scratch, the smaller the ΔL value, indicating better scratch resistance of the resin. The pencil hardness of the test sample was tested according to the standard GB / T6739-2006. First, wipe the sample with a cloth, grind the tip of the Chinese pencil lead flat with NO.400 abrasive paper, point the pencil at the coating surface, hold it by hand to keep it at about 45°, and scratch forward each hardness pencil at a speed of 1 mm / s, press it with a force of 750 g and scratch five times each. If less than two of the five scratches have obvious scratches, the hardness of the sample is represented by the hardness of this pencil. The higher the hardness, the better the scratch resistance (pencil hardness: 4B < 3B < 2B < B < HB < F < H < 2H < 3H < 4H).

[0064] Example 1:

[0065] Preparation of fluorinated cycloolefin scratch-resistant agent A1:

[0066] 1) Weigh 18.83 g (0.2 mol) of norbornene and 23.02 g (0.5 mol) of vinyl fluoride and add them to the reaction kettle, and then add 2 L of toluene.

[0067] 2) After closing the reaction kettle, start stirring under a nitrogen atmosphere, heat up to 80 °C, introduce 12.62 g (0.3 mol) of propylene and maintain the pressure at 2 MPa, and equilibrate for 30 min.

[0068] 3) Then add 1 mg of metallocene catalyst (in the structural general formula, R 1 -R 4 is methyl, R 5 is cyclohexyl, X is dimethylsilyl, M is Ti) and 10 mg of cocatalyst tris(pentafluorophenyl)boron, maintain the temperature at 70 °C and the pressure at 2 MPa, and carry out a polymerization reaction for 240 min. Then add ethanol to terminate the reaction, cool down, stop stirring, and relieve the pressure. The product is precipitated in ethanol, filtered and collected, and vacuum dried to constant weight, denoted as fluorinated cycloolefin scratch-resistant agent A1.

[0069] Preparation of polycarbonate material:

[0070] 1) Weigh 100 parts by weight of polycarbonate resin (SABIC PC2200R) and 1 part by weight of fluorinated cycloolefin scratch-resistant agent A1. After drying them thoroughly, add 0.2 part by weight of antioxidant 168, 0.1 part by weight of antioxidant 1010, 1 part by weight of dioctyltin dilaurate, and 0.5 part by weight of light stabilizer 770, and mix them evenly using a high-speed mixer.

[0071] 2) Add the mixture obtained in step 1) to a twin-screw extruder and mix it evenly. The temperature range of each zone of the extruder is 220 - 260 °C, the screw speed is 500 rpm. After granulation using a granulator and drying, polycarbonate modified pellets are obtained.

[0072] 3) Inject the polycarbonate modified pellets obtained in step 2) using an injection molding machine. The temperature range of each zone of the injection molding machine is 250 - 300 °C to obtain a test sample, and test the light transmittance, haze, and scratch resistance of the sample.

[0073] Example 2:

[0074] Replace 1 part by weight of fluorinated cycloolefin scratch-resistant agent A1 in Example 1 with 3 parts by weight of fluorinated cycloolefin scratch-resistant agent A1, and keep the other components and steps unchanged to obtain a test sample, and test the light transmittance, haze, and scratch resistance of the sample.

[0075] Example 3:

[0076] Replace 1 part by weight of fluorinated cycloolefin scratch-resistant agent A1 in Example 1 with 4 parts by weight of fluorinated cycloolefin scratch-resistant agent A1, and keep the other components and steps unchanged to obtain a test sample, and test the light transmittance, haze, and scratch resistance of the sample.

[0077] Example 4:

[0078] Preparation of fluorinated cycloolefin scratch-resistant agent A2:

[0079] 1) Weigh 18.83 g (0.2 mol) of norbornene and 18.42 g (0.4 mol) of fluoroethylene and add them to a reaction kettle, and then add 2 L of toluene.

[0080] 2) After closing the reaction kettle, start stirring under a nitrogen atmosphere, heat up to 80 °C, introduce 16.83 g (0.4 mol) of propylene and maintain the pressure at 2 MPa, and balance for 30 min.

[0081] 3) Then add 1 mg of metallocene catalyst (in the structural general formula, R 1 -R 4 is methyl, R 5(where R is cyclohexyl, X is dimethylsilyl, and M is Ti) and 10 mg of the cocatalyst tris(pentafluorophenyl)borane. After maintaining the temperature at 70 °C and the pressure at 2 MPa for 240 min of the polymerization reaction, ethanol was added to terminate the reaction, and then the temperature was lowered, the stirring was stopped, and the pressure was released; the product was precipitated in ethanol, filtered and collected, and dried in vacuo to a constant weight, denoted as fluorinated cycloolefin scratch-resistant agent A2.

[0082] Preparation of polycarbonate material:

[0083] Replace 3 parts by weight of the fluorinated cycloolefin scratch-resistant agent A1 in Example 2 with 3 parts by weight of the fluorinated cycloolefin scratch-resistant agent A2, and keep the other components and steps unchanged to obtain a test sample, and test the light transmittance, haze, and scratch resistance of the sample.

[0084] Example 5:

[0085] Preparation of fluorinated cycloolefin scratch-resistant agent A3:

[0086] 1) Weigh 28.25 g (0.3 mol) of norbornene and 13.81 g (0.3 mol) of fluoroethylene and add them to the reaction kettle, and then add 2 L of toluene;

[0087] 2) After sealing the reaction kettle, start stirring under a nitrogen atmosphere, heat up to 80 °C, introduce 16.83 g (0.4 mol) of propylene and maintain the pressure at 2 MPa, and equilibrate for 30 min;

[0088] 3) Then add 1 mg of metallocene catalyst (in the structural general formula, R 1 -R 4 is methyl, R 5 is cyclohexyl, X is dimethylsilyl, and M is Ti) and 10 mg of the cocatalyst tris(pentafluorophenyl)borane. After maintaining the temperature at 70 °C and the pressure at 2 MPa for 240 min of the polymerization reaction, ethanol was added to terminate the reaction, and then the temperature was lowered, the stirring was stopped, and the pressure was released; the product was precipitated in ethanol, filtered and collected, and dried in vacuo to a constant weight, denoted as fluorinated cycloolefin scratch-resistant agent A3.

[0089] Preparation of polycarbonate material:

[0090] Replace 3 parts by weight of the fluorinated cycloolefin scratch-resistant agent A1 in Example 2 with 3 parts by weight of the fluorinated cycloolefin scratch-resistant agent A3, and keep the other components and steps unchanged to obtain a test sample, and test the light transmittance, haze, and scratch resistance of the sample.

[0091] Example 6:

[0092] Preparation of fluorinated cycloolefin scratch-resistant agent B:

[0093] 1) Weigh 26.44 g (0.2 mol) of dicyclopentadiene, 39.28 g (0.4 mol) of 3-methylhexene, and 138.44 g (0.4 mol) of perfluorohexylethylene and add them to the reaction kettle, then add 1.5 L of n-hexane;

[0094] 2) After sealing the reaction kettle, start stirring under a nitrogen atmosphere, heat up to 120 °C, and maintain the pressure at 0.5 MPa for 60 min;

[0095] 3) Then add 10 mg of metallocene catalyst (in the structural general formula, R 1 -R 4 is methyl, R 5 is tert-butyl, X is dimethylsilyl, M is Hf) and 80 mg of co-catalyst triethylaluminum to the reaction kettle. After maintaining the temperature at 100 °C and the pressure at 0.5 MPa for 180 min of polymerization reaction, add ethanol to terminate the reaction, cool down, stop stirring, and relieve the pressure; precipitate the product in ethanol, filter and collect it, and dry it in vacuum until constant weight, denoted as fluorinated cycloolefin scratch-resistant agent B.

[0096] Preparation of polycarbonate material:

[0097] 1) Weigh 100 parts by weight of polycarbonate resin (SABIC PC2200R) and 3 parts by weight of fluorinated cycloolefin scratch-resistant agent B. After drying them sufficiently, add 0.5 part by weight of antioxidant BHT, 0.2 part by weight of lead stearate, and 0.2 part by weight of light stabilizer 622, and mix them evenly using a high-speed mixer;

[0098] 2) Add the mixture obtained in step 1) to a twin-screw extruder and mix it evenly. The temperature range of each zone of the extruder is 220 - 260 °C, the screw speed is 500 rpm, and granulate it using a granulator and then dry it to obtain polycarbonate modified pellets;

[0099] 3) Inject the polycarbonate modified pellets obtained in step 2) through an injection molding machine. The temperature range of each zone of the injection molding machine is 250 - 300 °C to obtain a test sample, and test the light transmittance, haze, and scratch resistance of the sample.

[0100] Example 7:

[0101] Preparation of fluorinated cycloolefin scratch-resistant agent C:

[0102] 1) Weigh 6.01 g (0.05 mol) of vinyl norbornene, 72.94 g (0.65 mol) of 1-octene, and 37.82 g (0.3 mol) of trifluoroethylene ether and add them to the reaction kettle, then add 650 mL of n-hexane;

[0103] 2) After sealing the reactor, start stirring under a nitrogen atmosphere, heat up to 80 °C, and maintain the pressure at 5 MPa for 30 min of equilibration;

[0104] 3) Then add 3 mg of metallocene catalyst (in the structural general formula, R 1 -R 4 is methyl, R 5 is tert-butyl, X is dimethylsilyl, M is Ti) and 0.03 g of cocatalyst trimethylaluminum to the reactor. After maintaining the temperature at 80 °C and the pressure at 5 MPa for 30 min of polymerization reaction, add ethanol to terminate the reaction, cool down, stop stirring, and relieve the pressure; precipitate the product in ethanol, filter and collect it, and dry it under vacuum to constant weight, denoted as fluorinated cycloolefin scratch-resistant agent C.

[0105] Preparation of polycarbonate material:

[0106] 1) Weigh 100 parts by weight of polycarbonate resin (SABIC PC2200R) and 4 parts by weight of fluorinated cycloolefin scratch-resistant agent C. After thorough drying, add 0.8 part by weight of antioxidant 168, 0.2 part by weight of antioxidant 1010, 0.8 part by weight of dibutyltin dilaurate, and 1 part by weight of light stabilizer HS-112, and mix them evenly using a high-speed mixer;

[0107] 2) Add the mixture obtained in step 1) to a twin-screw extruder and mix it evenly. The temperature range of each zone of the extruder is 220 - 260 °C, the screw speed is 500 rpm, and granulate it using a granulator and then dry it to obtain polycarbonate modified pellets;

[0108] 3) Inject the polycarbonate modified pellets obtained in step 2) into a mold using an injection molding machine. The temperature range of each zone of the injection molding machine is 250 - 300 °C to obtain a test sample, and test the light transmittance, haze, and scratch resistance of the sample.

[0109] Example 8:

[0110] Preparation of fluorinated cycloolefin scratch-resistant agent D:

[0111] 1) Weigh 9.42 g (0.1 mol) of norbornene and 98.43 g (0.4 mol) of perfluorobutylethylene and add them to the reactor, and then add 800 mL of toluene;

[0112] 2) After sealing the reactor, start stirring under a nitrogen atmosphere, heat up to 100 °C, introduce 28.06 g (0.5 mol) of 1-butene and maintain the pressure at 3 MPa for 60 min of equilibration;

[0113] 3) Then add 3 mg of metallocene catalyst (in the structural general formula, R 1 -R 4 is methyl, R5 (wherein R is cyclohexyl, X is benzhydryl, and M is Zr) and 0.04 g of the cocatalyst triphenylmethyltetrakis(pentafluorophenyl)borate were used. After the polymerization reaction was carried out at 100 °C and a pressure of 3 MPa for 120 min, ethanol was added to terminate the reaction, and then the temperature was lowered, stirring was stopped, and the pressure was released; the product was precipitated in ethanol, filtered and collected, and dried in vacuo to a constant weight, denoted as the fluorinated cycloolefin scratch-resistant agent D.

[0114] Preparation of polycarbonate material:

[0115] 1) After weighing 90 parts by weight of polycarbonate resin (SABIC PC2200R) and 2 parts by weight of the fluorinated cycloolefin scratch-resistant agent D and drying them sufficiently, 0.5 part by weight of antioxidant 1076, 0.5 part by weight of dibutyltin dilaurate, and 0.3 part by weight of light stabilizer 622 were added, and they were mixed evenly by a high-speed mixer;

[0116] 2) The mixture obtained in step 1) was added to a twin-screw extruder and kneaded evenly. The temperature range of each zone of the extruder was 220 - 260 °C, the screw speed was 500 rpm, and it was granulated by a granulator and then dried to obtain polycarbonate modified pellets;

[0117] 3) The polycarbonate modified pellets obtained in step 2) were injection-molded by an injection machine. The temperature range of each zone of the injection machine was 250 - 300 °C to obtain a test sample, and the light transmittance, haze, and scratch resistance of the sample were tested.

[0118] Comparative Example 1:

[0119] Preparation of polycarbonate material:

[0120] 1) After weighing 100 parts by weight of polycarbonate resin (SABIC PC2200R) and drying it sufficiently, the fluorinated cycloolefin scratch-resistant agent was not added, and only 0.2 part by weight of antioxidant 168, 0.1 part by weight of antioxidant 1010, 1 part by weight of dioctyltin dilaurate, and 0.5 part by weight of light stabilizer 770 were added, and they were mixed evenly by a high-speed mixer;

[0121] 2) The mixture obtained in step 1) was added to a twin-screw extruder and kneaded evenly. The temperature range of each zone of the extruder was 220 - 260 °C, the screw speed was 500 rpm, and it was granulated by a granulator and then dried to obtain polycarbonate pellets;

[0122] 3) The polycarbonate modified pellets obtained in step 2) were injection-molded by an injection machine. The temperature range of each zone of the injection machine was 250 - 300 °C to obtain a test sample, and the light transmittance, haze, and scratch resistance of the sample were tested.

[0123] Comparative Example 2:

[0124] Replace 3 parts by weight of the fluorinated cycloolefin scratch-resistant agent A1 in Example 2 with 6 parts by weight of the fluorinated cycloolefin scratch-resistant agent A1 as the scratch-resistant agent, and keep the other components and steps unchanged to obtain a test sample, and test the light transmittance, haze and scratch resistance of the sample.

[0125] Comparative Example 3:

[0126] Preparation of cycloolefin copolymer E:

[0127] 1) Weigh 37.66 g (0.4 mol) of norbornene and 25.25 g (0.6 mol) of propylene and add them to a reaction kettle, and then add 500 mL of n-hexane;

[0128] 2) After sealing the reaction kettle, start stirring under a nitrogen atmosphere, heat up to 80 °C, and keep the pressure at 5 MPa, and equilibrate for 30 min;

[0129] 3) Then add 5 mg of a metallocene catalyst (in the structural general formula, R 1 -R 4 is methyl, R 5 is tert-butyl, X is dimethylsilyl, M is Ti) and 0.02 g of cocatalyst trimethylaluminum, maintain the temperature at 80 °C and the pressure at 5 MPa, and carry out a polymerization reaction for 60 min, then add ethanol to terminate the reaction, cool down, stop stirring, and relieve the pressure; precipitate the product in ethanol, filter and collect it, and vacuum dry it to constant weight, denoted as cycloolefin copolymer E.

[0130] Preparation of polycarbonate material:

[0131] Replace 3 parts by weight of the fluorinated cycloolefin scratch-resistant agent A1 in Example 2 with the same weight of cycloolefin copolymer E as the scratch-resistant agent, and keep the other components and steps unchanged to obtain a test sample, and test the light transmittance, haze and scratch resistance of the sample.

[0132] Comparative Example 4:

[0133] Replace 3 parts by weight of the fluorinated cycloolefin scratch-resistant agent A1 in Example 2 with the same weight of commercially available polytetrafluoroethylene (grade L-5F, Daikin, Japan) as the scratch-resistant agent, and keep the other steps in the preparation method of the polycarbonate material unchanged to obtain a test sample, and test the light transmittance, haze and scratch resistance of the sample.

[0134] Comparative Example 5:

[0135] Replace 3 parts by weight of the fluorinated cycloolefin scratch-resistant agent A1 in Example 2 with the same weight of commercially available organosiloxane (grade LYSI-306, Chengdu Silike Technology) as the scratch-resistant agent, and keep the other steps in the preparation method of the polycarbonate material unchanged to obtain a test sample, and test the light transmittance, haze and scratch resistance of the sample.

[0136] Table 1 Comparison Table of Test Performance of Samples in Each Example and Comparative Example

[0137] Light transmittance Haze ΔL Scratch degree Pencil hardness Example 1 92％ 1.6％ 0.3 Slight 2H Example 2 94％ 2.5％ 0.2 Slight 2H Example 3 90％ 3.6％ 0.2 Slight 2H Example 4 92％ 3.1％ 0.2 Slight 2H Example 5 91％ 3.3％ 0.2 Slight 2H Example 6 93％ 1.8％ 0.2 Slight 2H Example 7 91％ 4.5％ 0.2 Slight 2H Example 8 93％ 2.1％ 0.3 Slight 2H Comparative example 1 89％ 1.0％ 1.8 Obvious B Comparative example 2 83％ 9.7％ 0.3 Slight 2H Comparative example 3 90％ 12.3％ 0.6 Relatively obvious H Comparative example 4 84％ 22.3％ 0.5 Relatively obvious H Comparative example 5 72％ 37.8％ 1.2 Relatively obvious HB

[0138] As can be seen from the content of Table 1, the light transmittance of the polycarbonate composites prepared in Examples 1-8 of the present invention all reached more than 90%, the pencil hardness all reached the 2H level, only slight scratches appeared in the five-finger scratch test, and the brightness change value ΔL did not exceed 0.3, indicating that the high-transparency and scratch-resistant polycarbonate material in the present invention has excellent light transmittance and good scratch resistance. Compared with Examples 1-5, in Comparative Example 1, the fluorinated cycloolefin scratch-resistant agent was not added to the raw materials for preparing the composite material. Obvious scratches appeared in the five-finger scratch test, the ΔL value was relatively high, and the pencil hardness only reached the B level, indicating that the polycarbonate material without adding the fluorinated cycloolefin scratch-resistant agent itself does not have good scratch resistance. After adding 1-4 parts by weight of the fluorinated cycloolefin scratch-resistant agent of the present invention, not only the scratch resistance of the material was significantly improved, the pencil hardness was increased from the B level to the 2H level, but also the light transmittance of the material increased, and a high-transparency and scratch-resistant polycarbonate material can be obtained. Among them, the data of Examples 2, 4, and 5 show that when the content of the fluorinated olefin monomer in the fluorinated cycloolefin scratch-resistant agent decreases, its light transmittance decreases slightly and the haze increases slightly, indicating the role of the fluorinated olefin structure in the fluorinated cycloolefin scratch-resistant agent in improving the optical properties of the material. In Comparative Example 2, when the addition amount of the fluorinated cycloolefin scratch-resistant agent is greater than 4 parts by weight, it will have a relatively large impact on the light transmittance of the material. Therefore, the addition amount of the fluorinated cycloolefin scratch-resistant agent in the present invention is limited to 1-4 parts by weight. In Comparative Example 3, the ordinary cycloolefin copolymer (fluorine-free) was added. Compared with the test results of Example 2, its light transmittance decreased, the haze increased, and the scratch resistance also decreased, indicating that only adding the ordinary cycloolefin copolymer as the scratch-resistant agent cannot achieve the significant improvement effect in the present invention. In Comparative Examples 4 and 5, polytetrafluoroethylene and organosiloxane used in the prior art were added as scratch-resistant agents respectively, and the light transmittance of the composite material decreased significantly, and the scratch resistance of the material was also inferior to the effect of the present invention. In summary, the present invention provides a polycarbonate material solution with high transparency and excellent scratch resistance.

[0139] Although the embodiments of the present invention have been shown and described above, it can be understood that the above embodiments are exemplary and should not be construed as limiting the present invention. Those of ordinary skill in the art can make changes, modifications, substitutions, and variations to the above embodiments within the scope of the present invention without departing from the principle and purpose of the present invention.

Claims

1. A highly transparent and scratch-resistant polycarbonate material, characterized in that: The polycarbonate material comprises the following raw materials in parts by weight: 90-100 parts of polycarbonate resin, 1-4 parts of fluorinated cycloolefin scratch resistant agent, 0.2-1 parts of antioxidant, 0.2-1 parts of heat stabilizer and 0.2-1 parts of light stabilizer; the fluorinated cycloolefin scratch resistant agent is prepared by addition copolymerization of cycloolefin monomer, alpha-olefin monomer and fluorinated olefin monomer.

2. The highly transparent and scratch-resistant polycarbonate material according to claim 1, characterized in that: The cycloolefin monomer is selected from at least one of the following structures: Wherein, R is selected from at least one of hydrogen, C1-C6 hydrocarbon group, vinyl group, acetyl group, phenyl group, or non-fluorine halogen; The α-olefin monomer is selected from at least one of ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methylhexene, 4-methylhexene, 5-methylhexene, 1-octene, or 1-decene; The fluorinated olefin monomer is selected from at least one of fluorinated ethylene, trifluoroethylene ether, perfluorobutylethylene, and perfluorohexylethylene.

3. The highly transparent and scratch-resistant polycarbonate material according to claim 1, characterized in that: Taking the sum of the molar percentages of the cycloolefin monomer, the α-olefin monomer and the fluorinated olefin monomer as 100 mol%, the molar percentage of the cycloolefin monomer is 5 mol%-20 mol%, the molar percentage of the α-olefin monomer is 30 mol%-65 mol%, and the molar percentage of the fluorinated olefin monomer is 30 mol%-50 mol%.

4. The highly transparent and scratch-resistant polycarbonate material according to claim 1, characterized in that: The cycloolefin monomer, α-olefin monomer and fluorinated olefin monomer are subjected to addition copolymerization reaction in a reaction medium under the action of a catalyst.

5. The highly transparent and scratch-resistant polycarbonate material according to claim 4, characterized in that: The amount of the catalyst added is 0.01wt%-0.05wt% of the total mass of the cycloolefin monomer, the α-olefin monomer, and the fluorinated olefin monomer; The catalyst is composed of a mixture of a metallocene catalyst and a co-catalyst; The mass ratio of the metallocene catalyst to the co-catalyst is 1:(10-1000); The co-catalyst is selected from at least one of an organic boron salt compound or an organic aluminum compound.

6. The highly transparent scratch-resistant polycarbonate material according to claim 5, characterized in that: The general structural formula of the metallocene catalyst is as follows: Wherein: R1-R4 are independently selected from one or more of hydrogen, C1-C6 hydrocarbon group, aromatic group; R5 is C3-C8 hydrocarbon group; X is selected from dimethylsilyl, diphenylsilyl, or diphenylmethyl; M is Ti, Zr or Hf.

7. The highly transparent and scratch-resistant polycarbonate material according to claim 5, characterized in that: The organic boron salt compound is an ionic compound formed by an organic boron anion and a cation; Preferably, the organic boron anion is selected from at least one of tetraphenylborate, tetrakis(monofluorophenyl)borate, tetrakis(difluorophenyl)borate, tetrakis(trifluorophenyl)borate, tetrakis(tetrafluorophenyl)borate, tetrakis(pentafluorophenyl)borate, tetrakis(tetrafluoromethylphenyl)borate, tetrakis(tolyl)borate, tetrakis(xylyl)borate, (triphenyl, pentafluorophenyl)borate, [tris(pentafluorophenyl), phenyl]borate, or undecyl-7,8-dicarbonundecanoate; Preferably, the cation is selected from at least one of a carbonium cation, an oxonium cation, an ammonium cation, a phosphonium cation, a cycloheptatrienyl cation, or a ferrocenium cation containing a transition metal.

8. The highly transparent and scratch-resistant polycarbonate material according to claim 5, characterized in that: The organoaluminum compound is selected from at least one of trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, triisopropylaluminum, triisobutylaluminum, tripentylaluminum, trihexylaluminum, tricyclohexylaluminum, trioctylaluminum, triphenylaluminum, tri-p-tolylaluminum, tribenzylaluminum, ethyldibenzylaluminum, or ethyldi(p-tolyl)aluminum.

9. The highly transparent and scratch-resistant polycarbonate material according to claim 4, characterized in that: The reaction medium is selected from at least one of aliphatic saturated alkanes, aromatic hydrocarbons, aromatic halides and cycloalkanes; Preferably, the reaction medium is selected from at least one of n-hexane, toluene, or n-pentane.

10. The highly transparent and scratch-resistant polycarbonate material according to claim 1, characterized in that: The antioxidant is selected from at least one of tea polyphenols, butylated hydroxyanisole, butylated hydroxytoluene, tert-butylhydroquinone, pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, triethylene glycol ether-di(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate, tris[2,4-di-tert-butylphenyl]phosphite, β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, or 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione; and / or The heat stabilizer is selected from at least one of tribasic lead sulfate, dibasic lead phosphite, dibasic lead stearate, dibasic lead phthalate, tribasic lead maleate, lead silicate, lead stearate, lead salicylate, dibasic lead phthalate, basic lead carbonate, cadmium stearate, barium stearate, calcium stearate, lead stearate, zinc stearate, di-n-butyltin dilaurate, and di-n-octyltin dilaurate; and / or The light stabilizer is selected from at least one of carbon black, light stabilizer 622, light stabilizer 770, light stabilizer 856, light stabilizer 944, light stabilizer HS-112, and light stabilizer HS-508.

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