Bondable thermoplastic polyurethane flexible optical component as well as preparation method and application thereof

Abstract

The invention provides a bondable thermoplastic polyurethane flexible optical component as well as a preparation method and application thereof. The optical component is prepared from a thermoplastic polyurethane material, and the raw materials comprise an isocyanate component, a polymer with a terminal group containing multi-element reactive hydrogen and a chain extender; the optical component can be bonded to a base material of a terminal product through an adhesive, and the bonding strength of the optical component and the base material of the terminal product is high, so that the practical application of the thermoplastic polyurethane flexible optical component is realized; in addition, the effect that the bonding area of the optical component can be bonded to the product base material through the adhesive without being polished is achieved.

Description

Technical Field

[0001] The present invention belongs to the field of public safety protection products, and particularly relates to an adhesive thermoplastic polyurethane flexible optical component, a preparation method thereof, and an application thereof. Background Art

[0002] Polyurethane (including polyurea) is a polymer obtained by the reaction polymerization of -NCO groups with active -H. Due to its good comprehensive properties, this polymer can be used to prepare new flexible optical components. For example, the lens material disclosed in CN107383328B, but the subsequent bonding problem was not involved at that time.

[0003] The optical component prepared from polyurethane has good flexibility, and other product bases such as the rubber cover body matched with it also have good flexibility. If the two are combined by bonding, they can be combined into protective products such as bendable and portable protective masks.

[0004] However, TPU components generally do not adopt a bonding form to combine with products. Therefore, the adhesiveness of TPU pellets after being prepared into components is generally not considered. An attempt was made to prepare flexible optical components from thermoplastic polyurethane (TPU). However, when bonding TPU to prepare flexible optical components, because the TPU granulation process undergoes twin-screw reactive extrusion, and when preparing products, it is necessary to pressurize and fill the mold through a single screw, the raw material system contains a large number of process aids such as lubricants, mold release agents, defoaming agents, plasticizers, leveling agents, diluents, water removers, etc., and functional aids such as ultraviolet absorbers / light stabilizers, anti-yellowing agents, hydrolysis stabilizers, wetting agents, reinforcing agents, covering agents, etc. Most of these aids are low-polarity substances, and their compatibility with the polar polyurethane main raw material is poor, and they are extremely likely to continuously precipitate or migrate to the surface of the optical component. This precipitation or migration can last for several years or even more than ten years. Especially at the bonding interface, because there is a barrier of the adhesive layer here, the inert aids will accumulate in large quantities at the bonding interface, resulting in the continuous weakening of the bonding strength at the bonding interface over time. Therefore, after a certain period of storage, the bonded parts are difficult to resist external force damage. Therefore, current TPU components generally do not combine with other parts of the product in a bonding form, and are only used as non-bonded products such as mobile phone cases, desktop pads, cable sheaths, etc. Therefore, whether the optical component can be bonded to the substrate of the product with high strength has become a prerequisite for the practical application of such optical components.

[0005] CN110982251A discloses some blend products containing polyurethane components, and CN 114578459 A discloses fluorinated polyurethane blend materials. The above are all blend materials containing polyurethane, and neither of them involves subsequent bonding and assembly problems such as bonding.

[0006] Therefore, obtaining a thermoplastic polyurethane flexible optical component with high bonding strength has become a technical problem that urgently needs to be solved in this field for the application of thermoplastic polyurethane flexible optical components. Summary of the Invention

[0007] One of the objectives of the present invention is to provide a thermoplastic polyurethane flexible optical component. After this optical component is bonded to a base through an adhesive, the bonding property of the bonding surface can maintain a relatively high bonding strength, so that such optical components can be practically applied. Further, before bonding the products, it is often necessary to roughen the surfaces of the two materials to be bonded to remove the surface layers. However, the present invention also achieves the unexpected technical effect that the bonding area of the optical component can be bonded to the product substrate with an adhesive without grinding.

[0008] The optical component is prepared by melting TPU pellets and injecting them into a mold through a screw extruder. The granular TPU raw material, after being melted at a high temperature, is molded into various products with the target shape. The inventors found that due to the high temperature of the extruder and the shear force of the screw that the TPU pellets experience during the processing, the heat and external force cause significant changes in the molecular weight and its distribution of the polyurethane long chains of the optical component compared with those of the polyurethane long chains of the TPU pellets. During the processing of TPU pellets through high temperature and screw shear, complex changes will occur in the polyurethane system of the TPU raw material: thermal degradation and screw shear lead to a decrease in the molecular weight of TPU and a broadening of the distribution; at the same time, the high temperature will also cause some unfinished TPU chain growth reactions to continue, and the molecular weight of some chains will continue to increase; new disproportionation / grafting structures may also be formed at this time. Therefore, it becomes very difficult to completely control various actual properties of the optical component, such as the bonding property, from the raw material end and the process end.

[0009] The inventors found in their research that after the TPU pellets are processed into products, the bonding property of the formed optical component is not directly related to the molecular weight and its distribution of the TPU raw material, but is related to the actual molecular weight and its distribution of the polyurethane long chains of the optical component of the product. Furthermore, through a large amount of research, the inventors determined that excellent bonding performance of the optical component can be obtained by controlling the molecular weight characteristics of the polyurethane long chains of the optical component, especially the molecular weight distribution, within a specific range. It is speculated that the principle may be that in the molecular weight and its distribution of the polyurethane long chains of the optical component, the influence of the molecular weight distribution on the processing process may be more obvious than the change in the molecular weight. It is speculated that this structure may provide some suitable opportunities for the infiltration or crystallization of the adhesive. The above description is only a speculation, and the changes caused by the action of the high-temperature field and the shear force of the screw during the processing of the optical component, as well as their combined action, are actually more complex.

[0010] Different from the pursuit of a narrower molecular weight distribution for TPU pellets / raw materials to obtain good mechanical properties of products, the optical components of the present invention do not pursue a narrow molecular weight distribution. Instead, a molecular weight distribution within a specific limited range is determined based on the actual bonding effect, with the aim of obtaining good bonding properties.

[0011] The inventors found that the optical components obtained in the present invention do not point to specific raw materials and processing methods and the combination of the two. The raw material end groups of TPU containing polyfunctional active hydrogen polymers will have relevant molecular weights and molecular weight distributions. However, after polymerization into TPU pellets and extrusion and injection molding into products, the influence of the polymer-related molecular weight and molecular weight distribution has been completely diluted. For TPU pellets, in fact, TPU pellet suppliers do not provide or measure the specific molecular weight and its distribution. Instead, it is often a "hardness" that can summarize the general properties of the obtained products as the first index, as well as mechanical property indexes and processing conditions. That is, it is also difficult to infer the molecular weight and its distribution after processing into products from the TPU pellets / raw materials and the process end. Although the parameters such as the molecular weight distribution of TPU pellets and the processing parameters cannot point to the parameters such as the molecular weight distribution of optical products, after the hardness index of the target optical component is determined, those skilled in the art can select TPU raw materials suitable for the processing process of optical component products in combination with various specific performance requirements and further confirm by actually evaluating the molecular weight distribution of the optical components.

[0012] For the selection of TPU pellets, process conditions (temperature, rotation speed, etc.) that do not significantly affect the properties of the products can be selected according to the raw material type (polyester / polyether type, aromatic isocyanate / aliphatic isocyanate, etc.). The above selection methods are known to those skilled in the art, and the specific methods are not unique. For example, TPU prepared from polyether polyol with the same molecular weight has a low hardness, while TPU pellets prepared from polycarbonate polyol have a high hardness. At the same time, similar product parameters may also be obtained by different methods. For example, a higher temperature in each section combined with a higher rotation speed may have a similar preparation effect to a lower temperature in each section combined with a lower rotation speed. Such general process principles for preparing products are known to those skilled in the art.

[0013] Therefore, to obtain a bondable thermoplastic polyurethane flexible optical component with a target bonding strength, it is necessary to screen thermoplastic polyurethane raw materials according to the processing process of the thermoplastic polyurethane flexible optical component and ensure that the molecular weight distribution of the optical component products prepared therefrom meets the requirements through actual characterization.

[0014] A thermoplastic polyurethane flexible optical component, the optical component is prepared from a thermoplastic polyurethane material, and the raw materials of the polyurethane material include an isocyanate component, a polymer with multiple active hydrogens at the end group, and an optional chain extender; the optical component can be combined with the substrate of the terminal product in the form of adhesive bonding; the peel strength of the bonding between the optical component and the substrate of the terminal product is ≥1.15 kN / m, preferably ≥1.75 kN / m, more preferably ≥2.45 kN / m.

[0015] In one embodiment of the present invention, the Shore A hardness of the optical component is 78-99A, preferably the Shore A hardness is 80-99A.

[0016] In one embodiment of the present invention, the light transmittance of the optical component is ≥80.0%, preferably the light transmittance is ≥82.5%.

[0017] In one embodiment of the present invention, the haze of the optical component is ≤8.6%, preferably the haze is ≤6.7%.

[0018] In one embodiment of the present invention, in the polyurethane structure of the optical component, the molecular weight distribution coefficient is F, 1.32 ≤ F ≤ 8.85, preferably 1.55 ≤ F ≤ 7.45, more preferably 1.78 ≤ F ≤ 5.65.

[0019] In one embodiment of the present invention, in the polyurethane structure of the optical component, the weight average molecular weight is Mw, 18,200 ≤ Mw ≤ 228,000, preferably 22,100 ≤ Mw ≤ 185,000, more preferably 32,200 ≤ Mw ≤ 144,000.

[0020] In one embodiment of the present invention, the isocyanate component is a component containing an isocyanate group, preferably one or more of an isocyanate monomer, an isocyanate oligomer, an isocyanate adduct, and a modified isocyanate.

[0021] In one embodiment of the present invention, the raw material isocyanate of the isocyanate component is an aromatic isocyanate and / or an aliphatic isocyanate, and the aliphatic isocyanate includes an isocyanate having an alicyclic structure; wherein, preferably, the aromatic isocyanate is one or more of diphenylmethane diisocyanate, toluene diisocyanate, p-phenylene diisocyanate, dimethyldiphenylmethane diisocyanate, and benzylidene diisocyanate; wherein, preferably, the aliphatic isocyanate is one or more of hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, methylcyclohexyl diisocyanate, 1,4-cyclohexane diisocyanate, trimethyl-1,6-hexamethylene diisocyanate, and cyclohexyl dimethylene diisocyanate; more preferably, the raw material isocyanate of the isocyanate component is one or more of diphenylmethane diisocyanate, benzylidene diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, and cyclohexyl dimethylene diisocyanate.

[0022] In one embodiment of the present invention, the NCO content of the isocyanate component is 17.5% - 64.2%, preferably 18.2% - 52.9%, more preferably 20.4% - 48.4%, based on the total mass of the isocyanate component; preferably, the functionality of the isocyanate component is 2.

[0023] In one embodiment of the present invention, the polymer with multiple active hydrogens at the end groups is a polymer with one or more of hydroxyl, amino, and thiol as end groups, preferably one or more of polyether polyol, polyester polyol, bio-based polyol, polyolefin polyol, urethane polyol, polyether ester polyol, polythiol, and polyether with terminal amino groups; more preferably one or more of polypropylene oxide polyol, polymer polyol, polytetrahydrofuran polyol (PTMG), poly(tetrahydrofuran - propylene oxide) copolymer polyether, conventional polyester polyol, polycaprolactone polyol, polycarbonate polyol, and polyether with terminal amino groups; preferably, the molecular weight of the polymer with multiple active hydrogens at the end groups is 600 - 5000, preferably 800 - 4000, more preferably 1000 - 2800; preferably, the functionality of the polymer with multiple active hydrogens at the end groups is 2.

[0024] In one embodiment of the present invention, the chain extender is one or more of small molecule polyols, polyamines, polyol amines, polythiols, and polycarboxylic acids, preferably one or more of small molecule polyols, polyamines, polyol amines, and polythiols, more preferably one or more of small molecule polyols, polyamines, and polythiols; preferably, the functionality of the chain extender is 2.

[0025] For other raw materials, a functionality of 2 for the chain extender is also a preferred option. This is because thermoplastic polyurethanes can be prepared even when there are trace amounts of raw materials with a functionality higher than 2. However, when preparing products with a relatively high molecular weight, it will lead to high viscosity and great difficulty in the preparation process. Therefore, raw materials with a functionality other than 2 cannot be completely excluded. In fact, due to the complexity of the reaction, even if only bifunctional raw materials are used, a very small amount of non-linear structures such as biurets will be formed by the NCO groups.

[0026] In one embodiment of the present invention, the molar ratio of the sum of the active -H groups in the end - group - containing polyactive hydrogen polymer and the chain extender to the -NCO groups of the isocyanate component is (0.70 - 1.40):1, preferably (0.80 - 1.35):1, and more preferably (0.90 - 1.25):1.

[0027] The above - mentioned isocyanate component, end - group - containing polyactive hydrogen polymer, and chain extender are all common raw materials for preparing isocyanates, and their selection, dosage, and proportional relationship are known to those skilled in the art.

[0028] The polyurethane described in the present invention refers to a polymer in which the main chain contains repeating urethane groups and / or allophanate groups formed by the reaction of an isocyanate compound and a compound containing active hydrogen, that is, polyurethane in a broad sense. Its definition includes narrow - sense polyurethane (polyurethane), polyurea (polyure), polyurethane - urea (poly(urethane - urea)), biuret, and other polymers containing such groups.

[0029] During the preparation process of TPU pellets, high - pressure injection of materials through a casting machine and reactive extrusion through a twin - screw extruder are required. Therefore, a large number of process aids such as lubricants, mold release agents, defoaming agents, plasticizers, leveling agents, diluents, etc., and functional aids such as ultraviolet absorbers / light stabilizers, anti - yellowing agents, hydrolysis stabilizers, wetting agents, reinforcing agents, etc. are also added to the above - mentioned raw material system. The selection and dosage of the above - mentioned aids are well - known to those skilled in the art.

[0030] Another object of the present invention is to provide a method for preparing a thermoplastic polyurethane flexible optical component.

[0031] A method for preparing a thermoplastic polyurethane flexible optical component, wherein the thermoplastic polyurethane flexible optical component is the above - mentioned optical component. The method melts and injects one or more of thermoplastic polyurethane pellets, powders, crushed materials, cut materials, and broken materials into a mold and then thermo - forms them, and demolds to obtain the optical component.

[0032] Another object of the present invention is to provide a thermoplastic polyurethane material.

[0033] A thermoplastic polyurethane material, which is used to prepare the above-mentioned optical components or in the above-mentioned preparation method, and the optical components prepared from the polyurethane material can be adhered to the product substrate with an adhesive.

[0034] In one embodiment of the present invention, the polyurethane material is obtained by metering and mixing an isocyanate component, a polymer with multiple active hydrogens at the end group, and an optional chain extender, and reacting them by one of the prepolymer method, semi-prepolymer method, one-step method, and multi-step method, and then extruding and pelletizing.

[0035] In one embodiment of the present invention, the form of the polyurethane material is one or more of thermoplastic polyurethane pellets, powders, crushed materials, cut materials, and broken materials, preferably thermoplastic polyurethane pellets.

[0036] The thermoplastic polyurethane raw material described in the present invention includes pure thermoplastic and semi-thermoplastic. The former has a linear structure without chemical cross-linking bonds, and the latter may contain a very small amount of various cross-linking bonds such as ureido groups.

[0037] The thermoplastic polyurethane raw material described in the present invention can be obtained by the prepolymer method or the one-step method, and can be obtained by a continuous synthesis process or an intermittent synthesis process. The methods and processes for preparing TPU raw materials / pellets have no obvious influence on parameters such as the molecular weight and its distribution of the optical components processed in the present invention.

[0038] Another object of the present invention is to provide an application of a thermoplastic polyurethane flexible optical component.

[0039] An application of a thermoplastic polyurethane flexible optical component, where the optical component is the above-mentioned optical component, or an optical component prepared by the above-mentioned preparation method, or an optical component prepared from the above-mentioned polyurethane material. The optical component is used as an optical component of a product with optical performance requirements, preferably for an optical component adhered to the product substrate with an adhesive, and more preferably for an optical component that can be adhered to the product substrate with an adhesive without grinding in the bonding area.

[0040] In one embodiment of the present invention, the application form of the optical component is an optical component of a protective mask, face mask, transparent window, goggles, protective cover, or equipment, or is used as an optical plate, optical sheet, or optical profile that can be processed into an optical component.

[0041] Another object of the present invention is to provide a product containing a thermoplastic polyurethane flexible optical component.

[0042] A product comprising a thermoplastic polyurethane flexible optical component, wherein the optical component is the above-mentioned optical component, or an optical component prepared by the above-mentioned preparation method, or an optical component prepared by the above-mentioned polyurethane material, and the product is a protective article adhered with a thermoplastic polyurethane flexible optical component. Preferably, the product is a protective article adhered with a thermoplastic polyurethane flexible optical component, and the adhesion area of the optical component is not polished; preferably, the form of the product is one or more of a protective mask, a face shield, a viewing window, goggles, a protective cover, and an equipment; preferably, the product can protect one or more of chemical, biological, radioactive, and irritating agents or pollutants.

[0043] Another object of the present invention is to provide a use of a product comprising a thermoplastic polyurethane flexible optical component.

[0044] A use of a product comprising a thermoplastic polyurethane flexible optical component, wherein the optical component used in the product is the above-mentioned optical component, or an optical component prepared by the above-mentioned preparation method, or an optical component prepared by the above-mentioned polyurethane material, or the above-mentioned product, and the product is used for protecting chemical, biological, radioactive, or irritating agents or pollutants in the civilian or military / police field.

[0045] In the present invention, to solve the problem of the adhesion performance of TPU components, the inventor did not start from the adhesive, but changed the idea and started from the perspective of TPU optical components. It was found that there is a relationship between the molecular weight distribution coefficient of the adhesive substrate optical component and the adhesion performance. Furthermore, through a large number of studies, their specific relationship was obtained, thus solving the above technical problems. Therefore, the positive effects of the present invention are as follows:

[0046] (1) Solved the problem of whether the thermoplastic polyurethane flexible optical component can be adhered firmly;

[0047] (2) Further achieved the unexpected technical effect that the adhesion area of the optical component can be adhered to the product substrate with an adhesive without polishing, and simplified the adhesion process;

[0048] (3) The optical component can not only be adhered with a polyurethane adhesive but also be applicable to many other adhesives including epoxy resin adhesives and acrylic adhesives. Detailed Embodiments

[0049] To better understand the technical solution of the present invention, the content of the present invention will be further elaborated below in conjunction with embodiments, but the content of the present invention is not limited to the following embodiments only.

[0050] Testing and Characterization:

[0051] Molecular weight and molecular weight distribution were determined using Lubrizol's classic method: Molecular weight distribution was measured on a Waters Gel Permeation Chromatograph (GPC) maintained at 40 °C, equipped with a Waters Model 515 pump, a Waters Model 717 autosampler, and a Waters Model 2414 refractive index detector. The GPC conditions were a temperature of 40 °C, a set of Phenogel Guard + 2x Mixed D (5u), 300×7.5 mm, a mobile phase of tetrahydrofuran (THF) stabilized with 250 ppm butylated hydroxytoluene, a flow rate of 1.0 ml / min, an injection volume of 50 μl, a sample concentration of 0.12%, and data acquisition was performed using Waters Empower Pro Software. Typically, a small amount (usually about 0.05 g of polymer) was dissolved in 20 ml of stabilized HPLC-grade THF, filtered through a 0.45 micron PTFE disposable filter (Whatman), and injected into the GPC. The molecular weight calibration curve was established using polystyrene standards from Polymer Laboratories.

[0052] Adhesion test: T-peel strength test, according to GB / T 2791-1995, using a New Sansi CMT4104 electronic tensile testing machine. The bonding length of the T-shaped specimen was 150 mm, and the bonding width was 25 mm. The sample preparation steps were as follows:

[0053] Sample surface treatment: The chlorobutyl rubber cover material was cut after surface grinding and chip removal, with a width of 25 mm, and dried after treatment with a trichloroacetocyanuric acid and ethyl acetate treatment solution; the TPU lens material surface was not ground, cut after drying after treatment with the treatment solution, with a width of 25 mm;

[0054] Coating the adhesive: Coat the adhesive on the surfaces of the cover material specimen and the TPU lens material specimen respectively;

[0055] Bonding and curing: Stack and flatten the specimens coated with the adhesive, and let it stand naturally for more than 48 h to complete curing.

[0056] Shore hardness was measured according to the current national standard GB / T 531.1-2008.

[0057] Transmittance was measured according to the current national standard GB / T 2410-2008.

[0058] Main equipment:

[0059] Two-component casting machine from Burel, France, with a mixing head speed of 3600 RPM and a maximum casting volume of 30 kg / min;

[0060] Berstorff twin-screw extruder, model ZE40A, with 10 barrel segments;

[0061] Arburg 420C screw injection molding machine, maximum closing force = 100 kN, screw geometric dimensions: D = 30 mm, L / D = 25 (three-zone screw), thread depth ratio: 2.2:1.

[0062] Raw material information:

[0063] The main raw material information is shown in Table 1.

[0064] Auxiliary agent 1: lubricant distearamide, silicone defoamer BYK-A506, leveling agent BYK-S706, reactive diluent γ-butyrolactone, with a mass ratio of 9.4:2.5:3.6:3.5. Auxiliary agent 1 is added in the third zone of the twin-screw extruder, and the addition amount is 5.95% of the total mass of the raw material isocyanate component, end-group containing polyactive hydrogen polymer, and chain extender.

[0065] Auxiliary agent 2: catalyst dibutyltin dilaurate, hydrolysis stabilizer carbodiimide, benzotriazole ultraviolet absorber, ultraviolet absorber UV-327, antioxidant 1010, antioxidant 168, with a mass ratio of 0.4:2.6:1.2:1.2:2.4:1.2. Auxiliary agent 2 is added to the B tank, and the addition amount is 1.32% of the total mass of the raw material isocyanate component, end-group containing polyactive hydrogen polymer, and chain extender.

[0066] Although the above-mentioned auxiliary agent system is significantly lower than the actual usage in industrial production, it can basically meet the requirements for preparing TPU pellets in small batches and slow processes.

[0067] Raw material treatment:

[0068] Raw material drying treatment: The end-group containing polyactive hydrogen polymer is vacuum dehydrated for 1 hour under heating and stirring at 115 °C, and the chain extender is vacuum dehydrated for 0.5 hour under heating and stirring at 110 °C. It is confirmed that the water content is less than 500 ppm.

[0069] Preparation Example 1

[0070] Prepared by the prepolymer method. The isocyanate and the end-group containing polyactive hydrogen polymer are reacted at 75 °C for 45 minutes to obtain a prepolymer. The prepolymer is added to the A tank of the casting machine, and the temperature is controlled at 75 °C. The chain extender is added to the B tank, and the temperature is controlled at 85 °C. The casting machine is used to meter and mix and feed it into the twin-screw extruder. The flow rate of the A tank and the discharge amount of the B tank make the H / NCO the set ratio in Table 2.

[0071] The first zone of the twin-screw extruder is 90 ± 3 °C, the second zone is 160 ± 3 °C, the third zone is 180 ± 3 °C, the fourth zone is 185 ± 3 °C, the fifth zone is 190 ± 3 °C, the sixth zone is 192 ± 3 °C, the seventh zone is 185 ± 3 °C, the eighth zone is 180 ± 3 °C, the ninth zone is 180 ± 3 °C, and the tenth zone is 175 ± 3 °C. The screw speed is 15 Hz. The extruded product enters an underwater pelletizer for pelletizing to obtain TPU pellets M1.

[0072] Preparation Example 2

[0073] The isocyanate reacts with the multi-active hydrogen-containing polymer at the end group at 75 °C for 45 min to obtain a prepolymer. The prepolymer is added to the A tank of the casting machine, and the temperature is controlled at 75 °C. The chain extender is added to the B tank, and the temperature is controlled at 85 °C. The casting machine is used for metering and mixing and feeding into the twin-screw extruder. The flow rate of the A tank and the discharge amount of the B tank make H / NCO the set ratio in Table 2.

[0074] The first zone of the twin-screw extruder is 85 ± 3 °C, the second zone is 160 ± 3 °C, the third zone is 180 ± 3 °C, the fourth zone is 185 ± 3 °C, the fifth zone is 190 ± 3 °C, the sixth zone is 195 ± 3 °C, the seventh zone is 185 ± 3 °C, the eighth zone is 180 ± 3 °C, the ninth zone is 180 ± 3 °C, and the tenth zone is 175 ± 3 °C. The screw speed is 17 Hz. The extruded product enters an underwater pelletizer for pelletizing to obtain TPU pellets M2.

[0075] Preparation Example 3

[0076] The isocyanate reacts with the multi-active hydrogen-containing polymer at the end group at 75 °C for 45 min to obtain a prepolymer. The prepolymer is added to the A tank of the casting machine, and the temperature is controlled at 75 °C. The chain extender is added to the B tank, and the temperature is controlled at 85 °C. The casting machine is used for metering and mixing and feeding into the twin-screw extruder. The flow rate of the A tank and the discharge amount of the B tank make H / NCO the set ratio in Table 2.

[0077] The first zone of the twin-screw extruder is 85 ± 3 °C, the second zone is 160 ± 3 °C, the third zone is 180 ± 3 °C, the fourth zone is 185 ± 3 °C, the fifth zone is 188 ± 3 °C, the sixth zone is 192 ± 3 °C, the seventh zone is 185 ± 3 °C, the eighth zone is 182 ± 3 °C, the ninth zone is 180 ± 3 °C, and the tenth zone is 175 ± 3 °C. The screw speed is 15 Hz. The extruded product enters an underwater pelletizer for pelletizing to obtain TPU pellets M3.

[0078] Preparation Example 4

[0079] The isocyanate reacts with the multi-active hydrogen-containing polymer at the end group at 76 °C for 45 min to obtain a prepolymer. The prepolymer is added to the A tank of the casting machine, and the temperature is controlled at 76 °C. The chain extender is added to the B tank, and the temperature is controlled at 86 °C. The casting machine is used for metering and mixing and feeding into the twin-screw extruder. The flow rate of the A tank and the discharge amount of the B tank make H / NCO the set ratio in Table 2.

[0080] The first zone of the twin-screw extruder is 90 ± 3 °C, the second zone is 160 ± 3 °C, the third zone is 180 ± 3 °C, the fourth zone is 185 ± 3 °C, the fifth zone is 190 ± 3 °C, the sixth zone is 192 ± 3 °C, the seventh zone is 185 ± 3 °C, the eighth zone is 182 ± 3 °C, the ninth zone is 180 ± 3 °C, and the tenth zone is 172 ± 3 °C. The screw speed is 19 Hz. The extruded product enters an underwater pelletizer for pelletization to obtain TPU pellets M4.

[0081] Preparation Example 5

[0082] The isocyanate and the multi-active hydrogen-containing polymer with terminal groups are reacted at 90 °C for 45 min to obtain a prepolymer. The prepolymer is added to the A tank of the casting machine, and the temperature is controlled at 75 °C. The chain extender is added to the B tank, and the temperature is controlled at 86 °C. The casting machine is used for metering and mixing and feeding into the twin-screw extruder. The flow rate of the A tank and the discharge amount of the B tank make H / NCO the set ratio in Table 2.

[0083] The first zone of the twin-screw extruder is 90 ± 3 °C, the second zone is 160 ± 3 °C, the third zone is 180 ± 3 °C, the fourth zone is 185 ± 3 °C, the fifth zone is 190 ± 3 °C, the sixth zone is 192 ± 3 °C, the seventh zone is 185 ± 3 °C, the eighth zone is 180 ± 3 °C, the ninth zone is 180 ± 3 °C, and the tenth zone is 175 ± 3 °C. The screw speed is 18 Hz. The extruded product enters an underwater pelletizer for pelletization to obtain TPU pellets M5.

[0084] Preparation Example 6

[0085] The isocyanate and the multi-active hydrogen-containing polymer with terminal groups are reacted at 92 °C for 45 min to obtain a prepolymer. The prepolymer is added to the A tank of the casting machine, and the temperature is controlled at 75 °C. The chain extender is added to the B tank, and the temperature is controlled at 85 °C. The casting machine is used for metering and mixing and feeding into the twin-screw extruder. The flow rate of the A tank and the discharge amount of the B tank make H / NCO the set ratio in Table 2.

[0086] The first zone of the twin-screw extruder is 90 ± 3 °C, the second zone is 160 ± 3 °C, the third zone is 180 ± 3 °C, the fourth zone is 185 ± 3 °C, the fifth zone is 188 ± 3 °C, the sixth zone is 192 ± 3 °C, the seventh zone is 185 ± 3 °C, the eighth zone is 180 ± 3 °C, the ninth zone is 180 ± 3 °C, and the tenth zone is 175 ± 3 °C. The screw speed is 18 Hz. The extruded product enters an underwater pelletizer for pelletization to obtain TPU pellets M6.

[0087] Preparation Example 7

[0088] The isocyanate and the multi-active hydrogen-containing polymer with terminal groups are reacted at 90 °C for 45 min to obtain a prepolymer. The prepolymer is added to the A tank of the casting machine, and the temperature is controlled at 75 °C. The chain extender is added to the B tank, and the temperature is controlled at 85 °C. The casting machine is used for metering and mixing and feeding into the twin-screw extruder. The flow rate of the A tank and the discharge amount of the B tank make H / NCO the set ratio in Table 2.

[0089] The temperature of the first zone of the twin-screw extruder is 90 ± 3 °C, the second zone is 160 ± 3 °C, the third zone is 180 ± 3 °C, the fourth zone is 185 ± 3 °C, the fifth zone is 190 ± 3 °C, the sixth zone is 192 ± 3 °C, the seventh zone is 185 ± 3 °C, the eighth zone is 180 ± 3 °C, the ninth zone is 180 ± 3 °C, and the tenth zone is 175 ± 3 °C. The screw speed is 15 Hz. The extruded product enters an underwater pelletizer for pelletization to obtain TPU pellets M7.

[0090] Preparation Example 8

[0091] Prepared by a one-step method. The isocyanate is added to the A tank of the casting machine, and the temperature is controlled at 90 °C. The chain extender and the multi-active hydrogen-containing polymer at the end group are added to the B tank, and the temperature is controlled at 90 °C. They are metered and mixed by the casting machine and fed into the twin-screw extruder. The flow rate of the A tank and the discharge amount of the B tank make the H / NCO ratio the set ratio in Table 2.

[0092] The temperature of the first zone of the twin-screw extruder is 90 ± 3 °C, the second zone is 160 ± 3 °C, the third zone is 180 ± 3 °C, the fourth zone is 185 ± 3 °C, the fifth zone is 190 ± 3 °C, the sixth zone is 192 ± 3 °C, the seventh zone is 185 ± 3 °C, the eighth zone is 180 ± 3 °C, the ninth zone is 180 ± 3 °C, and the tenth zone is 175 ± 3 °C. The screw speed is 15 Hz. The extruded product enters an underwater pelletizer for pelletization to obtain TPU pellets M8.

[0093] Preparation Example 9

[0094] The isocyanate is added to the A tank of the casting machine, and the temperature is controlled at 90 °C. The chain extender and the multi-active hydrogen-containing polymer at the end group are added to the B tank, and the temperature is controlled at 90 °C. They are metered and mixed by the casting machine and fed into the twin-screw extruder. The flow rate of the A tank and the discharge amount of the B tank make the H / NCO ratio the set ratio in Table 2.

[0095] The temperature of the first zone of the twin-screw extruder is 90 ± 3 °C, the second zone is 160 ± 3 °C, the third zone is 180 ± 3 °C, the fourth zone is 185 ± 3 °C, the fifth zone is 190 ± 3 °C, the sixth zone is 195 ± 3 °C, the seventh zone is 185 ± 3 °C, the eighth zone is 182 ± 3 °C, the ninth zone is 180 ± 3 °C, and the tenth zone is 175 ± 3 °C. The screw speed is 15 Hz. The extruded product enters an underwater pelletizer for pelletization to obtain TPU pellets M9.

[0096] Preparation Example 10

[0097] The isocyanate is added to the A tank of the casting machine, and the temperature is controlled at 90 °C. The chain extender and the multi-active hydrogen-containing polymer at the end group are added to the B tank, and the temperature is controlled at 90 °C. They are metered and mixed by the casting machine and fed into the twin-screw extruder. The flow rate of the A tank and the discharge amount of the B tank make the H / NCO ratio the set ratio in Table 2.

[0098] The first zone of the twin-screw extruder is 90 ± 3 °C, the second zone is 160 ± 3 °C, the third zone is 180 ± 3 °C, the fourth zone is 185 ± 3 °C, the fifth zone is 190 ± 3 °C, the sixth zone is 192 ± 3 °C, the seventh zone is 185 ± 3 °C, the eighth zone is 180 ± 3 °C, the ninth zone is 180 ± 3 °C, and the tenth zone is 175 ± 3 °C. The screw speed is 18 Hz. The extruded product enters an underwater pelletizer for pelletizing to obtain TPU pellets M10.

[0099] Preparation Example 11

[0100] The isocyanate is added to the A tank of the casting machine, and the temperature is controlled at 85 °C. The chain extender and the multi-active hydrogen-containing polymer at the end group are added to the B tank, and the temperature is controlled at 85 °C. They are metered and mixed by the casting machine and fed into the twin-screw extruder. The flow rate of the A tank and the discharge amount of the B tank make H / NCO the set ratio in Table 2.

[0101] The first zone of the twin-screw extruder is 85 ± 3 °C, the second zone is 160 ± 3 °C, the third zone is 180 ± 3 °C, the fourth zone is 185 ± 3 °C, the fifth zone is 190 ± 3 °C, the sixth zone is 192 ± 3 °C, the seventh zone is 185 ± 3 °C, the eighth zone is 180 ± 3 °C, the ninth zone is 180 ± 3 °C, and the tenth zone is 172 ± 3 °C. The screw speed is 20 Hz. The extruded product enters an underwater pelletizer for pelletizing to obtain TPU pellets M11.

[0102] Preparation Example 12

[0103] The isocyanate is added to the A tank of the casting machine, and the temperature is controlled at 85 °C. The chain extender and the multi-active hydrogen-containing polymer at the end group are added to the B tank, and the temperature is controlled at 85 °C. They are metered and mixed by the casting machine and fed into the twin-screw extruder. The flow rate of the A tank and the discharge amount of the B tank make H / NCO the set ratio in Table 2.

[0104] The first zone of the twin-screw extruder is 90 ± 3 °C, the second zone is 160 ± 3 °C, the third zone is 180 ± 3 °C, the fourth zone is 185 ± 3 °C, the fifth zone is 190 ± 3 °C, the sixth zone is 192 ± 3 °C, the seventh zone is 185 ± 3 °C, the eighth zone is 180 ± 3 °C, the ninth zone is 180 ± 3 °C, and the tenth zone is 175 ± 3 °C. The screw speed is 20 Hz. The extruded product enters an underwater pelletizer for pelletizing to obtain TPU pellets M3.

[0105] Preparation Example 13

[0106] The isocyanate is added to the A tank of the casting machine, and the temperature is controlled at 85 °C. The chain extender and the multi-active hydrogen-containing polymer at the end group are added to the B tank, and the temperature is controlled at 85 °C. They are metered and mixed by the casting machine and fed into the twin-screw extruder. The flow rate of the A tank and the discharge amount of the B tank make H / NCO the set ratio in Table 2.

[0107] The temperature of the first zone of the twin-screw extruder is 90 ± 3 °C, the second zone is 160 ± 3 °C, the third zone is 180 ± 3 °C, the fourth zone is 185 ± 3 °C, the fifth zone is 190 ± 3 °C, the sixth zone is 192 ± 3 °C, the seventh zone is 185 ± 3 °C, the eighth zone is 180 ± 3 °C, the ninth zone is 180 ± 3 °C, and the tenth zone is 175 ± 3 °C. The screw speed is 15 Hz. The extruded product enters an underwater pelletizer for pelletizing to obtain TPU pellets M13.

[0108] Preparation Example 14

[0109] The isocyanate is added to the A tank of the casting machine, and the temperature is controlled at 86 °C. The chain extender and the multi-active hydrogen polymer containing terminal groups are added to the B tank, and the temperature is controlled at 86 °C. They are metered and mixed by the casting machine and sent into the twin-screw extruder. The flow rate of the A tank and the discharge amount of the B tank make H / NCO the set ratio in Table 2.

[0110] The temperature of the first zone of the twin-screw extruder is 75 ± 3 °C, the second zone is 160 ± 3 °C, the third zone is 180 ± 3 °C, the fourth zone is 185 ± 3 °C, the fifth zone is 190 ± 3 °C, the sixth zone is 192 ± 3 °C, the seventh zone is 185 ± 3 °C, the eighth zone is 180 ± 3 °C, the ninth zone is 180 ± 3 °C, and the tenth zone is 170 ± 3 °C. The screw speed is 15 Hz. After the extruded product solidifies, it is crushed to obtain crushed material, and TPU crushed material M14 is obtained.

[0111] Preparation Example 15

[0112] Prepared by the semi-prepolymer method. The isocyanate is added to the A tank of the casting machine, and the temperature is controlled at 85 °C. The chain extender and the multi-active hydrogen polymer containing terminal groups are added to the B tank and mixed for 30 min, and the temperature is controlled at 85 °C. They are metered and mixed by the casting machine and sent into the twin-screw extruder. The flow rate of the A tank and the discharge amount of the B tank make H / NCO the set ratio in Table 2.

[0113] The temperature of the first zone of the twin-screw extruder is 75 ± 3 °C, the second zone is 160 ± 3 °C, the third zone is 180 ± 3 °C, the fourth zone is 185 ± 3 °C, the fifth zone is 190 ± 3 °C, the sixth zone is 195 ± 3 °C, the seventh zone is 185 ± 3 °C, the eighth zone is 180 ± 3 °C, the ninth zone is 180 ± 3 °C, and the tenth zone is 170 ± 3 °C. The screw speed is 16 Hz. The extruded product enters an underwater pelletizer for pelletizing to obtain TPU pellets M15.

[0114] Preparation Example 16

[0115] The isocyanate is added to the A tank of the casting machine, and the temperature is controlled at 88 °C. The chain extender and the multi-active hydrogen polymer containing terminal groups are added to the B tank and mixed for 30 min, and the temperature is controlled at 88 °C. They are metered and mixed by the casting machine and sent into the twin-screw extruder. The flow rate of the A tank and the discharge amount of the B tank make H / NCO the set ratio in Table 2.

[0116] The temperature of the first zone of the twin-screw extruder is 75 ± 3 °C, the second zone is 160 ± 3 °C, the third zone is 180 ± 3 °C, the fourth zone is 185 ± 3 °C, the fifth zone is 190 ± 3 °C, the sixth zone is 200 ± 3 °C, the seventh zone is 185 ± 3 °C, the eighth zone is 180 ± 3 °C, the ninth zone is 180 ± 3 °C, and the tenth zone is 175 ± 3 °C. The screw speed is 15 Hz. The extruded product enters an underwater pelletizer for pelletization to obtain TPU pellets M16.

[0117] Preparation Example 17

[0118] The isocyanate is added to the A tank of the casting machine, and the temperature is controlled at 89 °C. The chain extender and the multi-active hydrogen polymer containing terminal groups are added to the B tank and mixed for 30 min, and the temperature is controlled at 89 °C. Then, they are metered and mixed by the casting machine and fed into the twin-screw extruder. The flow rate of the A tank and the discharge rate of the B tank make the H / NCO ratio the set ratio in Table 2.

[0119] The temperature of the first zone of the twin-screw extruder is 80 ± 3 °C, the second zone is 150 ± 3 °C, the third zone is 180 ± 3 °C, the fourth zone is 185 ± 3 °C, the fifth zone is 190 ± 3 °C, the sixth zone is 200 ± 3 °C, the seventh zone is 195 ± 3 °C, the eighth zone is 180 ± 3 °C, the ninth zone is 180 ± 3 °C, and the tenth zone is 175 ± 3 °C. The screw speed is 15 Hz. The extruded product enters an underwater pelletizer for pelletization to obtain TPU pellets M17.

[0120] Preparation Example 18

[0121] The isocyanate is added to the A tank of the casting machine, and the temperature is controlled at 89 °C. The chain extender and the multi-active hydrogen polymer containing terminal groups are added to the B tank and mixed for 35 min, and the temperature is controlled at 89 °C. Then, they are metered and mixed by the casting machine and fed into the twin-screw extruder. The flow rate of the A tank and the discharge rate of the B tank make the H / NCO ratio the set ratio in Table 2.

[0122] The temperature of the first zone of the twin-screw extruder is 80 ± 3 °C, the second zone is 160 ± 3 °C, the third zone is 180 ± 3 °C, the fourth zone is 185 ± 3 °C, the fifth zone is 190 ± 3 °C, the sixth zone is 197 ± 3 °C, the seventh zone is 185 ± 3 °C, the eighth zone is 180 ± 3 °C, the ninth zone is 180 ± 3 °C, and the tenth zone is 175 ± 3 °C. The screw speed is 15 Hz. The extruded product enters an underwater pelletizer for pelletization to obtain TPU pellets M18.

[0123] Preparation Example 19

[0124] The isocyanate is added to the A tank of the casting machine, and the temperature is controlled at 88 °C. The chain extender and the multi-active hydrogen polymer containing terminal groups are added to the B tank and mixed for 40 min, and the temperature is controlled at 88 °C. Then, they are metered and mixed by the casting machine and fed into the twin-screw extruder. The flow rate of the A tank and the discharge rate of the B tank make the H / NCO ratio the set ratio in Table 2.

[0125] The first zone of the twin-screw extruder is 80 ± 3 °C, the second zone is 160 ± 3 °C, the third zone is 180 ± 3 °C, the fourth zone is 185 ± 3 °C, the fifth zone is 190 ± 3 °C, the sixth zone is 195 ± 3 °C, the seventh zone is 185 ± 3 °C, the eighth zone is 180 ± 3 °C, the ninth zone is 180 ± 3 °C, and the tenth zone is 180 ± 3 °C. The screw speed is 16 Hz. The extruded product enters an underwater pelletizer for pelletizing to obtain TPU pellets M19.

[0126] Preparation Example 20

[0127] The isocyanate is added to the A tank of the casting machine, and the temperature is controlled at 88 °C. The chain extender and the terminal group-containing polyactive hydrogen polymer are added to the B tank and mixed for 30 min, and the temperature is controlled at 88 °C. They are metered and mixed by the casting machine and sent into the twin-screw extruder. The flow rate of the A tank and the discharge rate of the B tank make the H / NCO ratio the set ratio in Table 2.

[0128] The first zone of the twin-screw extruder is 85 ± 3 °C, the second zone is 160 ± 3 °C, the third zone is 180 ± 3 °C, the fourth zone is 185 ± 3 °C, the fifth zone is 190 ± 3 °C, the sixth zone is 196 ± 3 °C, the seventh zone is 185 ± 3 °C, the eighth zone is 180 ± 3 °C, the ninth zone is 180 ± 3 °C, and the tenth zone is 180 ± 3 °C. The screw speed is 16 Hz. The extruded product enters an underwater pelletizer for pelletizing to obtain TPU pellets M20.

[0129] Preparation Example 21

[0130] The method is the same as that in Example 2, using the raw materials in Table 1 to obtain TPU pellets M21.

[0131] Preparation Example 22

[0132] The method is the same as that in Example 10, using the raw materials in Table 1 to obtain TPU pellets M22.

[0133] Preparation Example 23

[0134] The method is the same as that in Example 17, using the raw materials in Table 1 to obtain TPU pellets M23.

[0135] Preparation of optical components:

[0136] Example 1

[0137] The M1 pellets are dried at 120 °C for 2 h and added to the hopper of the injection molding machine. The screw temperatures in the three zones are: the first zone is 90 ± 3 °C, the second zone is 195 ± 3 °C, the third zone is 180 ± 3 °C, the pressure is 350 Bar, and the injection flow rate is 25 cm 3 / s, and the mold temperature is 73 °C.

[0138] Example 2

[0139] Dry the M2 pellets at 120 °C for 2 h, add them to the hopper of the injection molding machine. The temperature of the three-zone screw is as follows: the first zone is 92 ± 3 °C, the second zone is 195 ± 3 °C, the third zone is 180 ± 3 °C, the pressure is 350 Bar, and the injection flow rate is 25 cm 3 / s, and the mold temperature is 76 °C.

[0140] Example 3

[0141] Dry the M3 pellets at 120 °C for 2 h, add them to the hopper of the injection molding machine. The temperature of the three-zone screw is as follows: the first zone is 90 ± 3 °C, the second zone is 195 ± 3 °C, the third zone is 180 ± 3 °C, the pressure is 320 Bar, and the injection flow rate is 22 cm 3 / s, and the mold temperature is 74 °C.

[0142] Example 4

[0143] Dry the M4 pellets at 120 °C for 2 h, add them to the hopper of the injection molding machine. The temperature of the three-zone screw is as follows: the first zone is 85 ± 3 °C, the second zone is 198 ± 3 °C, the third zone is 180 ± 3 °C, the pressure is 340 Bar, and the injection flow rate is 26 cm 3 / s, and the mold temperature is 80 °C.

[0144] Example 5

[0145] Dry the M5 pellets at 120 °C for 2 h, add them to the hopper of the injection molding machine. The temperature of the three-zone screw is as follows: the first zone is 90 ± 3 °C, the second zone is 196 ± 3 °C, the third zone is 180 ± 3 °C, the pressure is 340 Bar, and the injection flow rate is 25 cm 3 / s, and the mold temperature is 65 °C.

[0146] Example 6

[0147] Dry the M6 pellets at 120 °C for 2 h, add them to the hopper of the injection molding machine. The temperature of the three-zone screw is as follows: the first zone is 92 ± 3 °C, the second zone is 195 ± 3 °C, the third zone is 180 ± 3 °C, the pressure is 350 Bar, and the injection flow rate is 26 cm 3 / s, and the mold temperature is 68 °C.

[0148] Example 7

[0149] Dry the M7 pellets at 120 °C for 2 h, add them to the hopper of the injection molding machine. The temperature of the three-zone screw is as follows: the first zone is 90 ± 3 °C, the second zone is 195 ± 3 °C, the third zone is 180 ± 3 °C, the pressure is 350 Bar, and the injection flow rate is 25 cm 3 / s, and the mold temperature is 69 °C.

[0150] Example 8

[0151] Dry the M8 pellets at 120 °C for 2 hours, add them to the hopper of the injection molding machine. The temperature of the three-zone screw is: the first zone 90 ± 3 °C, the second zone 205 ± 3 °C, the third zone 180 ± 3 °C, the pressure is 360 Bar, and the injection flow rate is 25 cm 3 / s, and the mold temperature is 71 °C.

[0152] Example 9

[0153] Dry the M9 pellets at 120 °C for 2 hours, add them to the hopper of the injection molding machine. The temperature of the three-zone screw is: the first zone 90 ± 3 °C, the second zone 195 ± 3 °C, the third zone 180 ± 3 °C, the pressure is 350 Bar, and the injection flow rate is 25 cm 3 / s, and the mold temperature is 62 °C.

[0154] Example 10

[0155] Dry the M10 pellets at 120 °C for 2 hours, add them to the hopper of the injection molding machine. The temperature of the three-zone screw is: the first zone 90 ± 3 °C, the second zone 195 ± 3 °C, the third zone 180 ± 3 °C, the pressure is 350 Bar, and the injection flow rate is 25 cm 3 / s, and the mold temperature is 72 °C.

[0156] Example 11

[0157] Dry the M12 pellets at 120 °C for 2 hours, add them to the hopper of the injection molding machine. The temperature of the three-zone screw is: the first zone 90 ± 3 °C, the second zone 197 ± 3 °C, the third zone 180 ± 3 °C, the pressure is 350 Bar, and the injection flow rate is 25 cm 3 / s, and the mold temperature is 74 °C.

[0158] Example 12

[0159] Dry the M12 pellets at 120 °C for 2 hours, add them to the hopper of the injection molding machine. The temperature of the three-zone screw is: the first zone 92 ± 3 °C, the second zone 198 ± 3 °C, the third zone 180 ± 3 °C, the pressure is 320 Bar, and the injection flow rate is 25 cm 3 / s, and the mold temperature is 71 °C.

[0160] Example 13

[0161] Dry the M3 pellets at 120 °C for 2 hours, add them to the hopper of the injection molding machine. The temperature of the three-zone screw is: the first zone 90 ± 3 °C, the second zone 195 ± 3 °C, the third zone 180 ± 3 °C, the pressure is 350 Bar, and the injection flow rate is 25 cm 3 / s, and the mold temperature is 68 °C.

[0162] Example 14

[0163] Dry the M14 crushed material at 120 °C for 2 hours, add it to the hopper of the injection molding machine. The temperature of the three-zone screw: the first zone is 90 ± 3 °C, the second zone is 198 ± 3 °C, the third zone is 180 ± 3 °C, the pressure is 350 Bar, and the injection flow rate is 25 cm 3 / s, and the mold temperature is 77 °C.

[0164] Example 15

[0165] Dry the M15 pellets at 120 °C for 2 hours, add it to the hopper of the injection molding machine. The temperature of the three-zone screw: the first zone is 90 ± 3 °C, the second zone is 195 ± 3 °C, the third zone is 180 ± 3 °C, the pressure is 350 Bar, and the injection flow rate is 25 cm 3 / s, and the mold temperature is 68 °C.

[0166] Example 16

[0167] Dry the M16 pellets at 120 °C for 2 hours, add it to the hopper of the injection molding machine. The temperature of the three-zone screw: the first zone is 90 ± 3 °C, the second zone is 195 ± 3 °C, the third zone is 180 ± 3 °C, the pressure is 345 Bar, and the injection flow rate is 25 cm 3 / s, and the mold temperature is 69 °C.

[0168] Example 17

[0169] Dry the M17 pellets at 120 °C for 2 hours, add it to the hopper of the injection molding machine. The temperature of the three-zone screw: the first zone is 90 ± 3 °C, the second zone is 195 ± 3 °C, the third zone is 180 ± 3 °C, the pressure is 350 Bar, and the injection flow rate is 25 cm 3 / s, and the mold temperature is 72 °C.

[0170] Example 18

[0171] Dry the M18 pellets at 120 °C for 2 hours, add it to the hopper of the injection molding machine. The temperature of the three-zone screw: the first zone is 90 ± 3 °C, the second zone is 195 ± 3 °C, the third zone is 180 ± 3 °C, the pressure is 300 Bar, and the injection flow rate is 25 cm 3 / s, and the mold temperature is 72 °C.

[0172] Example 19

[0173] Dry the M19 pellets at 120 °C for 2 hours, add it to the hopper of the injection molding machine. The temperature of the three-zone screw: the first zone is 85 ± 3 °C, the second zone is 195 ± 3 °C, the third zone is 180 ± 3 °C, the pressure is 340 Bar, and the injection flow rate is 26 cm 3 / s, and the mold temperature is 70 °C.

[0174] Example 20

[0175] Dry M20 pellets at 120 °C for 2 hours, add them to the hopper of the injection molding machine. The temperature of the three-zone screw is as follows: the first zone is 90 ± 3 °C, the second zone is 195 ± 3 °C, the third zone is 180 ± 3 °C, the pressure is 350 Bar, and the injection flow rate is 25 cm 3 / s, and the mold temperature is 70 °C.

[0176] Comparative Example 1

[0177] Use M21 pellets, and the process is the same as that in Example 2.

[0178] Comparative Example 2

[0179] Use M22 pellets, and the process is the same as that in Example 10.

[0180] Comparative Example 3

[0181] Use M23 pellets, and the process is the same as that in Example 17.

[0182] Table 1 Raw material information of examples and comparative examples

[0183] Isocyanate Polymers containing multiple active hydrogen at the end groups Chain extender (mass ratio) Example 1 MDI diphenylmethane diisocyanate, NCO%=33.5%, BASF Daicel, polycarbonate diol CD220, M=2000 1,4-Butanediol BDO Example 2 MDI, NCO%=33.5%, BASF Polyester diol, PBA2000, CMA-44, M=2000 BDO Example 3 MDI, NCO%=33.5%, BASF Polyester diol, PEA1000, CMA-1024, M=1000 BDO Example 4 MDI, NCO%=33.5%, BASF BASF, PTMEG PolyTHF1800, M=1800 BDO: ethylene glycol EG = 5:5 Example 5 MDI, NCO%=33.5%, BASF BASF, PTMEG PolyTHF650, M=650 BDO Example 6 Dicyclohexylmethane diisocyanate HMDI, NCO%=32%, Wanhua Polyester diol, PBA2000, CMA-44, M=2000 BDO Example 7 HMDI, NCO%=32%, Wanhua Polyester diol, PEA1000, CMA-1024, M=1000 BDO Example 8 HMDI, NCO%=32%, Wanhua Polyester diol, PBA3000, PE-230, M=3000 BDO:Hexanediol HDO=8:2 Example 9 HMDI, NCO%=32%, Wanhua Daicel, polycarbonate diol CD220, M=2000 BDO Example 10 HMDI, NCO%=32%, Wanhua Polyether diol, Diol-1000, M=1000, Mitsui BDO:HDO=9:1 Embodiment 11 Isophorone diisocyanate IPDI, NCO%=37.6%, Wanhua Polyether diol, Diol-3000, M=3000, Mitsui BDO:EG=5:5 Example 12 IPDI, NCO%=37.6%, Wanhua PTMEG, PolyTHF1800, M=1800, BASF BDO:EG=5:5 Embodiment 13 IPDI, NCO%=37.6%, Wanhua PTMEG, PolyTHF650, M=650, BASF BDO Embodiment 14 IPDI, NCO% = 37.6% Polycarbonate diol CD210PL, M=1000, Daicel BDO:isophorone diamine = 95:5 Embodiment 15 IPDI, NCO%=37.6%, Wanhua PTMG3000, M=3000, Mitsubishi BDO Example 16 Hexamethylene diisocyanate HDI, NCO%=49.8%, Meirui Polycaprolactone diol, 240, M=4000, Daicel BDO:HDO=9:1 Embodiment 17 HDI, NCO%=49.8%, Meirui Polycaprolactone diol, 220N, M=2000, Daicel BDO:HDO=9:1 Embodiment 18 HDI, NCO%=49.8%, Meirui Polycarbonate diol CD210PL, M=1000, Daicel BDO Embodiment 19 HDI, NCO%=49.8%, Meirui Polyether diol, Diol-1000, M=1000, Mitsui BDO:HDO=9:1 Embodiment 20 HDI, NCO%=24.4%, Wanhua dimer Polyether diol, Diol-3000, M=3000, Mitsui BDO:EG=5:5 Comparative Example 1 MDI, NCO%=33.5%, BASF Polyester diol, POL-156, M=2000, Uda BDO Comparative Example 2 HMDI, NCO%=32%, Wanhua Polyether diol, TDiol-1000, M=1000, Tianjin Petrochemical BDO:HDO=9:1 Comparative Example 3 HDI, NCO%=49.8%, Meirui Polycaprolactone diol, CAPA2200, M=2000, PERSTRO BDO:HDO=9:1

[0184] In the above table, M is the molecular weight.

[0185] Table 2 Raw material usage of examples and comparative examples (unit: kg)

[0186] Isocyanate Polymers containing multiple active hydrogen at the end groups Chain Extender H / NCO Example 1 100 131.35 29.96 1 Example 2 100 143.30 29.73 1.01 Example 3 100 117.19 25.35 1 Example 4 100 133.40 23.78 0.99 Example 5 100 73.23 25.52 0.997 Example 6 100 138.36 27.79 0.99 Example 7 100 119.77 23.76 0.995 Example 8 100 113.31 33.72 1.01 Example 9 100 123.64 29.01 1.01 Example 10 100 108.43 25.82 1.01 Embodiment 11 100 181.95 28.39 1 Example 12 100 166.65 26.03 0.995 Example 13 100 87.08 28.04 1 Embodiment 14 100 125.58 25.49 0.88 Embodiment 15 100 210.04 33.86 1 Example 16 100 359.41 53.25 1.15 Embodiment 17 100 246.27 42.14 1 Embodiment 18 100 200.15 35.36 1 Embodiment 19 100 178.60 38.81 1 Embodiment 20 100 226.99 42.78 0.995 Comparative Example 1 100 143.30 29.73 1.01 Comparative Example 2 100 108.43 25.82 1.01 Comparative Example 3 100 246.27 42.14 1

[0187] Table 3 Characterization results of examples and comparative examples

[0188] Bond strength (kN / m) hardness Light transmittance(%) Haze(%) F M Example 1 3.76, Epoxy Adhesive ‌3M Scotch-Weld DP100plus 98A 87 6.2 2.8 122,000 Example 2 3.05, Epoxy Adhesive ‌3M Scotch-Weld DP100plus 92A 92 5.4 3.9 35,700 Example 3 3.88, Epoxy Adhesive ‌3M Scotch-Weld DP100plus 94A 91 5.3 4.3 24,000 Example 4 3.77, Epoxy Adhesive ‌3M Scotch-Weld DP100plus 93A 90 4.2 5.2 23,300 Example 5 3.52 Polyurethane Adhesive ‌3M DP6310NS 98A 90 3.1 4.6 20,100 Example 6 3.08 Polyurethane Adhesive ‌3M DP6310NS 93A 91 4.1 5.2 32,400 Example 7 3.45 Polyurethane Adhesive ‌3M DP6310NS 96A 88 4.3 6.6 28,300 Example 8 2.33, Acrylic Adhesive Henkel LOCTITE AA H8000 97A 86 4.0 7.1 64,300 Example 9 3.77, Epoxy Adhesive ‌3M Scotch-Weld DP100plus 99A 81 5.1 6.2 164,000 Example 10 3.24, Polyurethane Adhesive ‌3M DP6310NS 88A 87 3.2 4.4 34,300 Embodiment 11 3.65 Polyurethane Adhesive ‌3M DP6310NS 85A 89 3.6 7.2 34,700 Example 12 4.02, Epoxy Adhesive ‌3M Scotch-Weld DP100plus 91A 91 4.1 5.3 43,000 Example 13 3.79, Polyurethane Adhesive ‌3M DP6310NS 96A 90 3.6 5.1 23,600 Embodiment 14 3.71, Polyurethane Adhesive ‌3M DP6310NS 98A 89 5.9 3.5 28,000 Embodiment 15 2.89 Polyurethane Adhesive ‌3M DP6310NS 83A 87 3.7 6.7 113,000 Example 16 1.43, Henkel LOCTITE AA H8000 acrylic adhesive 80A 88 3.9 6.1 187,000 Example 17 2.98, Henkel LOCTITE AA H8000 acrylic adhesive 87A 91 3.1 6.0 135,000 Example 18 3.44, 3M DP6310NS polyurethane adhesive 98A 84 5.1 3.5 113,000 Example 19 3.77, 3M DP6310NS polyurethane adhesive 85A 87 3.3 5.8 45,200 Example 20 3.14, Henkel LOCTITE AA H8000 acrylic adhesive 82A 90 3.5 6.3 48,400 Comparative Example 1 1.14, 3M Scotch-Weld DP100plus epoxy resin adhesive 90A 87 4.4 8.9 34,700 Comparative Example 2 1.08, 3M DP6310NS polyurethane adhesive 87A 83 4.3 9.1 17,500 Comparative Example 3 0.94, Henkel LOCTITE AA H8000 acrylic adhesive 88A 82 3.9 1.2 29,400

[0189] In the above table, when comparing Comparative Example 1 with Example 2, Comparative Example 2 with Example 10, and Comparative Example 3 with Example 17, the raw materials selected in these comparative examples result in a molecular weight distribution that does not meet the requirements when testing the lens components, thereby leading to poor bonding performance. Among them, for Comparative Example 1, the F value measured using the pellets of Preparation Example 21 is 8.40, but the F of the optical component is too wide at 8.9, resulting in still poor bonding performance. For Comparative Example 3, the F value measured using the pellets of Preparation Example 23 is 1.36, but the F of the optical component is too narrow at 1.2, also resulting in poor bonding performance.

[0190] The solutions provided from the perspective of optical components as described above solve the bonding performance problem existing in the art.

Claims

1. A thermoplastic polyurethane flexible optical component, characterized in that: The optical component is prepared from a thermoplastic polyurethane material, the raw materials of which include an isocyanate component, a terminal-containing multi-active hydrogen polymer, and an optional chain extender; the optical component can be bonded to the substrate of the terminal product by means of an adhesive; The peel strength between the optical component and the substrate of the terminal product is ≥1.15 kN / m, preferably ≥1.75 kN / m, and more preferably ≥2.45 kN / m.

2. The optical component according to claim 1, characterized in that The Shore A hardness of the optical component is 78-99A, preferably the Shore A hardness is 80-99A; and / or the transmittance of the optical component is ≥80.0%, preferably the transmittance is ≥82.5%; and / or the haze of the optical component is ≤8.6%, preferably the haze is ≤6.7%; and / or the molecular weight distribution coefficient in the polyurethane structure of the optical component is F, 1.32≤F≤8.85, preferably 1.55≤F≤7.45, more preferably 1.78≤F≤5.65; and / or the weight average molecular weight in the polyurethane structure of the optical component is Mw, 18,200≤Mw≤228,000, preferably 22,100≤Mw≤185,000, more preferably 32,200≤Mw≤144,000.

3. The optical component according to claim 1 or 2, characterized in that: The isocyanate component is a component containing an isocyanate group, preferably one or more of an isocyanate monomer, an isocyanate oligomer, an isocyanate adduct, and a modified isocyanate; and / or, the raw material isocyanate of the isocyanate component is an aromatic isocyanate and / or an aliphatic isocyanate, and the aliphatic isocyanate contains an isocyanate with an alicyclic structure; wherein the aromatic isocyanate is preferably one or more of diphenylmethane diisocyanate, toluene diisocyanate, p-phenylene diisocyanate, dimethyl diphenylmethane diisocyanate, and xylylene diisocyanate; wherein the aliphatic isocyanate is preferably hexamethylene diisocyanate. The isocyanate component is preferably one or more of diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, methylcyclohexyl diisocyanate, 1,4-cyclohexane diisocyanate, trimethyl-1,6-hexamethylene diisocyanate and cyclohexyl dimethylene diisocyanate; more preferably, the raw material isocyanate of the isocyanate component is one or more of diphenylmethane diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate and cyclohexyl dimethylene diisocyanate; and / or the NCO content of the isocyanate component is 17.5%-64.2%, preferably 18.2%-5 2.9%, more preferably 20.4%-48.4%, based on the total mass of the isocyanate component; preferably, the functionality of the isocyanate component is 2; and / or, the terminal group-containing polyvalent active hydrogen polymer is a polymer with one or more of hydroxyl, amino, and thiol as terminal groups, preferably one or more of polyether polyols, polyester polyols, bio-based polyols, polyolefin polyols, urethane polyols, polyether ester polyols, polythiol, and amino-terminated polyethers, more preferably polyoxypropylene polyols, polymer polyols, polytetramethylene glycol polyols, polytetramethylene glycol-oxypropylene copolymer polyether polyols, conventional polyester polyols, polycaprolactone polyols, poly One or more of carbonate polyols, terminal amino polyethers; preferably, the molecular weight of the terminal group-containing polyvalent active hydrogen polymer is 600-5000, preferably 800-4000, more preferably 1000-2800; preferably, the functionality of the terminal group-containing polyvalent active hydrogen polymer is 2; and / or, the chain extender is one or more of small molecule polyols, polyamines, polyol amines, polythiols, and polycarboxylic acids, preferably one or more of small molecule polyols, polyamines, polyol amines, and polythiols, more preferably one or more of small molecule polyols, polyamines, and polythiols; preferably, the functionality of the chain extender is 2.

4. The optical component according to any one of claims 1 to 3, characterized in that: The molar ratio of the sum of the terminal group-containing polyvalent active hydrogen polymer and the active -H group in the chain extender to the -NCO group of the isocyanate component is (0.70-1.40):1, preferably (0.80-1.35):1, and more preferably (0.90-1.25):

1.

5. A method for preparing a thermoplastic polyurethane flexible optical component, wherein the thermoplastic polyurethane flexible optical component is the optical component according to any one of claims 1 to 4, characterized in that: The method melts and injects one or more of thermoplastic polyurethane granules, powders, crushed materials, cut materials and broken materials into a mold for thermoplastic molding, and then demolds to obtain an optical component.

6. A thermoplastic polyurethane material, which is used to prepare the optical component according to any one of claims 1 to 4, or used in the preparation method according to claim 5, characterized in that: The optical component prepared from the polyurethane material can be bonded to the product substrate with an adhesive; and / or, the polyurethane material is obtained by metering, mixing and reacting an isocyanate component, a terminal polyvalent active hydrogen polymer, and an optional chain extender through a prepolymerization method, a semi-prepolymerization method, a one-step method, and a multi-step method, and then extruding and granulating; and / or, the polyurethane material is in the form of one or more of thermoplastic polyurethane pellets, powders, crushed materials, cut materials, and broken materials, preferably thermoplastic polyurethane pellets.

7. An application of a thermoplastic polyurethane flexible optical component, wherein the optical component is the optical component according to any one of claims 1 to 4, or is an optical component prepared by the preparation method according to claim 5, or is an optical component prepared by the polyurethane material according to claim 6, characterized in that: The optical component is used as an optical component of a product with optical performance requirements, preferably as an optical component bonded to a product substrate with an adhesive, and more preferably as an optical component that can be bonded to a product substrate with an adhesive without polishing the bonding area; and / or, the optical component is applied in the form of an optical component of a protective mask, a face shield, a transparent window, goggles, a protective cover, an optical component of an appliance, or is used as an optical plate, an optical sheet, or an optical profile that can be processed into an optical component.

8. A product comprising a thermoplastic polyurethane flexible optical component, wherein the optical component is the optical component according to any one of claims 1 to 4, or is an optical component prepared by the preparation method according to claim 5, or is an optical component prepared by the polyurethane material according to claim 6, characterized in that: The product is a protective article bonded with a thermoplastic polyurethane flexible optical component, preferably the product is a protective article bonded with a thermoplastic polyurethane flexible optical component, and the bonding area of ​​the optical component is not polished; preferably, the product is in the form of one or more of a protective mask, a face shield, a window, goggles, a protective cover, and a harness; preferably, the product can protect against one or more of chemical, biological, radioactive, irritating toxic agents or pollutants.

9. Use of a product comprising a thermoplastic polyurethane flexible optical component, wherein the optical component used in the product is the optical component according to any one of claims 1 to 4, or an optical component prepared by the preparation method according to claim 5, or an optical component prepared by the polyurethane material according to claim 6, or a product according to claim 8, characterized in that: The product is used in the civilian or military / police fields to protect against chemical, biological, radioactive or irritating toxic agents or pollutants.