Optical resin, preparation method thereof and optical lens containing optical resin

Abstract

The invention provides optical resin, a preparation method thereof and an optical lens containing the optical resin, and belongs to the technical field of optical materials. The optical resin comprises reticular polyurethane and chain-shaped fluorine-containing polyurethane; the reticular polyurethane is selected from at least one of polymers as shown in a formula I; the chain fluorine-containing polyurethane is selected from at least one of a polymer shown in a formula II and a polymer shown in a formula III. The optical resin provided by the invention has good heat resistance, mechanical strength, toughness, flame retardant property, refractive index and light transmittance, and can improve the heat resistance and flame retardant property of the optical lens and reduce the risk of thermal deformation or burning of the optical lens while meeting the optical performance of the optical lens.

Description

Technical Field

[0001] The present invention belongs to the technical field of optical materials, and in particular relates to an optical resin, a preparation method thereof and an optical lens containing the same. Background Art

[0002] Optical lenses are lenses made of optical materials with special optical properties (such as refractive index, dispersion, transmittance, spectral transmittance, light absorptivity, etc.). Optical lenses can be used to change the direction of light propagation, change the relative spectral distribution, focus, and other purposes. They are widely used in optical equipment such as photography, display, and microscopes.

[0003] Optical lenses include inorganic optical lenses and organic optical lenses according to the type of materials. The materials of inorganic optical lenses are usually oxides of silicon, boron, sodium, potassium, zinc, lead, magnesium, calcium, barium, etc. The materials of organic optical lenses are polymer resins.

[0004] Compared with inorganic optical lenses, organic optical lenses have the advantages of light weight, strong impact resistance and not easy to break, but at the same time they also have disadvantages such as high thermal expansion coefficient and low softening temperature. Most organic optical lenses are close to some electronic components. During use, the electronic components may heat up, which may cause the optical lenses to deform due to heat and affect the optical performance. In some cases, the optical lenses may heat up and burn due to untimely heat dissipation. Therefore, this type of organic optical lens needs to have certain heat resistance and flame retardancy to improve its reliability and safety. Summary of the invention

[0005] In view of the shortcomings of the prior art, the object of the present invention is to provide an optical resin, a preparation method thereof and an optical lens containing the same. The optical resin has good heat resistance, mechanical strength, toughness, flame retardancy, refractive index and light transmittance, and can improve the heat resistance and flame retardancy of the optical lens while meeting the optical properties of the optical lens, and reduce the risk of deformation or burning of the optical lens due to heat.

[0006] To achieve this object, the present invention adopts the following technical solutions:

[0007] In a first aspect, the present invention provides an optical resin, the optical resin comprising a network polyurethane and a chain fluorine-containing polyurethane;

[0008] The reticulated polyurethane is selected from at least one of the polymers of formula I;

[0009] The chain-like fluorine-containing polyurethane is selected from at least one of a polymer of formula II and a polymer of formula III;

[0010]

[0011] wherein R1 and R3 are each independently a residue of a diisocyanate;

[0012] R2 and R4 are each independently a residue of a polymer diol;

[0013] m1 is 6-10, m2 is 10-30, m3 is 10-30, q is 2-7;

[0014] -* represents the connection key.

[0015] In some embodiments of the present invention, the diisocyanate is xylylene diisocyanate (XDI), tetramethyl-m-xylylene diisocyanate (TMXDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), dicyclohexylmethane diisocyanate (HMDI), diphenylmethane diisocyanate (MDI) or toluene diisocyanate (TDI). Preferably, it is xylylene diisocyanate (XDI), tetramethyl-m-xylylene diisocyanate (TMXDI) or toluene diisocyanate (TDI).

[0016] In some embodiments of the present invention, the polymer diol is polyethylene glycol, polypropylene glycol, polytetramethylene glycol or polycarbonate diol, preferably polycarbonate diol.

[0017] In some embodiments of the present invention, the weight average molecular weight of the polymer diol is 500-2000.

[0018] In some embodiments of the present invention, the mass ratio of the network polyurethane to the chain fluorine-containing polyurethane is (10-20):1, preferably (10-15):1.

[0019] In a second aspect, the present invention provides a method for preparing the optical resin as described in the first aspect, the preparation method comprising the following steps:

[0020] Synthesis of the polymer of formula I: (1) reacting diisocyanate OCN-R1-NCO under the action of a first catalyst, and terminating the reaction when the number of isocyanate groups decreases to 1 / 2 of the initial value to obtain an isocyanate trimer;

[0021]

[0022] (2) subjecting the isocyanate trimer to a polymerization reaction with a polymer diol HO-R2-OH under the action of a second catalyst to obtain the polymer of formula I;

[0023] Synthesis of the polymer of formula II or III: (a) polymerizing diisocyanate OCN-R3-NCO and polymer diol HO-R4-OH to obtain a polyurethane prepolymer;

[0024]

[0025] (b) subjecting the polyurethane prepolymer to a polymerization reaction with a fluorinated diol to obtain the polymer of formula II or the polymer of formula III;

[0026] The fluorinated diol is

[0027] The polymer of formula I, the polymer of formula II and / or the polymer of formula III are mixed according to a proportion to obtain the optical resin.

[0028] In some embodiments of the present invention, the first catalyst is selected from one or more of sodium methoxide, triethylamine, methylene-bis(3,3',5,5'-tetrakis(dimethylaminomethyl)-2,2'-phenol, 2,4,6-tris(dimethylaminomethyl)phenol, pentamethyldiethylenetriamine and tri-n-butylphosphine.

[0029] In some embodiments of the present invention, the amount of the first catalyst used is 500-1000 ppm of the mass of the diisocyanate OCN-R1-NCO.

[0030] In some embodiments of the present invention, the reaction temperature in step (1) is 60-140°C.

[0031] In some embodiments of the present invention, the reaction in step (1) is carried out in an organic solvent.

[0032] In some embodiments of the present invention, the organic solvent is selected from one or more of N,N-dimethylformamide (DMF) and dimethyl sulfoxide (DMSO).

[0033] In some embodiments of the present invention, the second catalyst is selected from one or more of dibutyltin dilaurate and stannous octoate.

[0034] In some embodiments of the present invention, the dosage of the second catalyst is 500-1000 ppm based on the mass of the isocyanate trimer.

[0035] In some embodiments of the present invention, the molar ratio of the isocyanate trimer to the polymer diol HO-R2-OH in step (2) is 2:(3-3.1).

[0036] In some embodiments of the present invention, the polymerization reaction process in step (2) is: first, stirring the reaction at room temperature and reduced pressure for 30 to 60 minutes, standing to degas; and then reacting at 50 to 80° C. for 6 to 8 hours.

[0037] In some embodiments of the present invention, the molar ratio of the diisocyanate OCN-R3-NCO to the polymer diol HO-R4-OH in step (a) is (2 to 2.05):1.

[0038] In some embodiments of the present invention, the polymerization reaction in step (a) is carried out at a temperature of 50 to 70° C. and for a time of 4 to 6 hours.

[0039] In some embodiments of the present invention, the molar ratio of the polyurethane prepolymer to the fluorinated diol in step (b) is 1:(1-1.05).

[0040] In some embodiments of the present invention, the polymerization reaction in step (b) is carried out at a temperature of 70 to 140° C. and for a time of 4 to 6 hours.

[0041] In a third aspect, the present invention provides an optical lens, wherein the material of the optical lens includes the optical resin as described in the first aspect, or the optical resin prepared by the preparation method as described in the second aspect.

[0042] Compared with the prior art, the present invention has the following beneficial effects:

[0043] In the optical resin provided by the present invention, the reticular polyurethane and the chain-shaped fluorine-containing polyurethane have the effect of synergistically improving the flame retardant properties and refractive index of the material. The present invention compounded the reticular polyurethane and the chain-shaped fluorine-containing polyurethane to obtain an optical resin having good heat resistance, mechanical strength, toughness, light transmittance, and higher flame retardant properties and refractive index than a single component. The optical resin is used for optical lenses, which can improve the heat resistance and flame retardant properties of the optical lenses while meeting the optical properties of the optical lenses, and reduce the risk of thermal deformation or burning of the optical lenses. DETAILED DESCRIPTION

[0044] In order to more clearly understand the above-mentioned objectives, features and advantages of the present invention, the scheme of the present invention will be further described below. It should be noted that the embodiments of the present invention and the features in the embodiments can be combined with each other without conflict.

[0045] In the following description, many specific details are set forth to facilitate a full understanding of the present invention, but the present invention may also be implemented in other ways different from those described herein; it is obvious that the embodiments in the specification are only part of the embodiments of the present invention, rather than all of the embodiments.

[0046] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by technicians in the technical field to which this application belongs; the terms used herein are only for the purpose of describing specific embodiments and are not intended to limit this application.

[0047] In a first aspect, an embodiment of the present invention provides an optical resin, wherein the optical resin comprises a network polyurethane and a chain fluorine-containing polyurethane;

[0048] The reticulated polyurethane is selected from at least one of the polymers of formula I;

[0049] The chain-like fluorine-containing polyurethane is selected from at least one of a polymer of formula II and a polymer of formula III;

[0050]

[0051] wherein R1 and R3 are each independently a residue of a diisocyanate;

[0052] R2 and R4 are each independently a residue of a polymer diol;

[0053] m1 is 6-10 (for example, 6, 7, 8, 9, 10, etc.), m2 is 10-30 (for example, 10, 12, 15, 18, 20, 22, 25, 28, 30, etc.), m3 is 10-30 (for example, 10, 12, 15, 18, 20, 22, 25, 28, 30, etc.), and q is 2-7 (for example, 2, 3, 4, 5, 6, 7, etc.);

[0054] -* represents the connection key.

[0055] It should be noted that the residue of the diisocyanate in the embodiment of the present invention refers to the portion remaining after two isocyanate groups (-NCO) are removed from the diisocyanate (which can be expressed as OCN-R-NCO), and the residue of the polymer diol refers to the portion remaining after two hydroxyl groups (-OH) are removed from the polymer diol (which can be expressed as HO-R-OH).

[0056] m1, m2, m3, q, n1, n2, n3 represent the average value of repeating units, which can be an integer or a non-integer. Among them, n1 can be 1-5 (for example, 1, 2, 3, 4, 5, etc.), n2 can be 5-15 (for example, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, etc.), and n3 can be 1-8 (for example, 1, 2, 3, 4, 5, 6, 7, 8, etc.).

[0057] In the optical resin provided by the embodiment of the present invention, the reticular polyurethane has good heat resistance, mechanical strength, flame retardancy, and light transmittance, and the chain-shaped fluorine-containing polyurethane has good heat resistance, flame retardancy, toughness, light transmittance and demoulding performance. Through research, it is found that the two have the effect of synergistically improving the flame retardancy and refractive index of the material. By compounding the reticular polyurethane and the chain-shaped fluorine-containing polyurethane, the obtained optical resin has good heat resistance, mechanical strength, toughness, light transmittance, and higher flame retardancy and refractive index than a single component.

[0058] In some embodiments of the present invention, the diisocyanate is xylylene diisocyanate (XDI), tetramethyl metaxylylene diisocyanate (TMXDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), dicyclohexylmethane diisocyanate (HMDI), diphenylmethane diisocyanate (MDI) or toluene diisocyanate (TDI). Preferably, it is xylylene diisocyanate (XDI), tetramethyl metaxylylene diisocyanate (TMXDI) or toluene diisocyanate (TDI), which contain benzene ring structures, and are helpful to further improve the heat resistance and refractive index of the final optical resin.

[0059] In some embodiments of the present invention, the polymer diol is polyethylene glycol, polypropylene glycol, polytetramethylene glycol or polycarbonate diol, preferably polycarbonate diol. Among them, the polyurethane synthesized from polycarbonate diol has higher cohesive energy, which can further improve the heat resistance, weather resistance and mechanical strength of the optical resin.

[0060] In some embodiments of the present invention, the weight average molecular weight of the polymer diol is 500-2000; for example, it can be 500, 800, 1000, 1200, 1500, 1800 or 2000.

[0061] In some embodiments of the present invention, the mass ratio of the reticulated polyurethane to the chain-like fluorinated polyurethane is (10-20):1, for example, 10:1, 11:1, 12:1, 13:1, 14:1, 15:1, 16:1, 17:1, 18:1, 19:1 or 20:1, etc. Preferably, it is (10-15):1, and more preferably, it is 12:1.

[0062] In the embodiment of the present invention, by controlling the mass ratio of the network polyurethane to the chain fluorine-containing polyurethane within the above range, the synergistic effect of the two can be fully exerted to further improve the flame retardant property and refractive index of the optical resin.

[0063] In a second aspect, the present invention provides a method for preparing the optical resin as described in the first aspect, the preparation method comprising the following steps:

[0064] Synthesis of polymers of formula I:

[0065]

[0066] (1) reacting diisocyanate OCN-R1-NCO under the action of a first catalyst, and terminating the reaction when the number of isocyanate groups decreases to 1 / 2 of the initial value to obtain an isocyanate trimer;

[0067]

[0068] (2) subjecting the isocyanate trimer to a polymerization reaction with a polymer diol HO-R2-OH under the action of a second catalyst to obtain the polymer of formula I;

[0069] Synthesis of polymer of formula II or polymer of formula III:

[0070]

[0071] (a) polymerizing diisocyanate OCN-R3-NCO and polymer diol HO-R4-OH to obtain a polyurethane prepolymer;

[0072]

[0073] (b) subjecting the polyurethane prepolymer to a polymerization reaction with a fluorinated diol to obtain the polymer of formula II or the polymer of formula III;

[0074] The fluorinated diol is

[0075] The polymer of formula I, the polymer of formula II and / or the polymer of formula III are mixed according to a proportion to obtain the optical resin.

[0076] In the embodiment of the present invention, the reaction process in the above preparation method is carried out in a protective atmosphere, and the protective atmosphere may be, for example, a nitrogen atmosphere, an argon atmosphere, or the like.

[0077] In the embodiment of the present invention, the method for terminating the reaction in the above step (1) is not particularly limited, and those skilled in the art can routinely select. Exemplarily, the reaction can be terminated by adding a terminator, which includes but is not limited to hydroquinone, p-tert-butylcatechol, p-hydroxyanisole, and methyl toluenesulfonate.

[0078] In some embodiments of the present invention, the first catalyst is selected from one or more of sodium methoxide, triethylamine, methylene-bis(3,3',5,5'-tetrakis(dimethylaminomethyl)-2,2'-phenol, 2,4,6-tris(dimethylaminomethyl)phenol, pentamethyldiethylenetriamine and tri-n-butylphosphine.

[0079] In some embodiments of the present invention, the amount of the first catalyst used is 500-1000 ppm of the mass of the diisocyanate OCN-R1-NCO.

[0080] In some embodiments of the present invention, the reaction temperature in step (1) is 60-140°C; for example, it can be 60°C, 70°C, 80°C, 90°C, 100°C, 110°C, 120°C, 130°C or 140°C, etc.

[0081] In some embodiments of the present invention, the reaction in step (1) is carried out in an organic solvent.

[0082] In some embodiments of the present invention, the organic solvent is selected from one or more of N,N-dimethylformamide (DMF) and dimethyl sulfoxide (DMSO).

[0083] In some embodiments of the present invention, the second catalyst is selected from one or more of dibutyltin dilaurate and stannous octoate.

[0084] In some embodiments of the present invention, the dosage of the second catalyst is 500-1000 ppm based on the mass of the isocyanate trimer.

[0085] In some embodiments of the present invention, the molar ratio of the isocyanate trimer to the polymer diol HO-R2-OH in step (2) is 2:(3-3.1).

[0086] In some embodiments of the present invention, the process of the polymerization reaction in step (2) is: first, stirring the reaction at room temperature and reduced pressure for 30 to 60 minutes (for example, it can be 30 minutes, 35 minutes, 40 minutes, 45 minutes, 50 minutes, 55 minutes or 60 minutes, etc.), and standing for degassing; then, reacting at 50 to 80°C (for example, it can be 50°C, 52°C, 55°C, 58°C, 60°C, 62°C, 65°C, 68°C, 70°C, 72°C, 73°C, 75°C, 76°C, 78°C or 80°C, etc.) for 6 to 8 hours (for example, it can be 6 hours, 6.5 hours, 7 hours, 7.5 hours or 8 hours, etc.).

[0087] In some embodiments of the present invention, the molar ratio of the diisocyanate OCN-R3-NCO to the polymer diol HO-R4-OH in step (a) is (2 to 2.05):1.

[0088] In some embodiments of the present invention, the polymerization reaction in step (a) is carried out at a temperature of 50 to 70°C (for example, 50°C, 52°C, 53°C, 55°C, 56°C, 58°C, 60°C, 62°C, 63°C, 65°C, 66°C, 68°C or 70°C, etc.), and the reaction time is 4 to 6h (for example, 4h, 4.5h, 5h, 5.5h or 6h, etc.).

[0089] In some embodiments of the present invention, the molar ratio of the polyurethane prepolymer to the fluorinated diol in step (b) is 1:(1-1.05).

[0090] In some embodiments of the present invention, the polymerization reaction in step (b) is carried out at a temperature of 70 to 140°C (for example, 70°C, 75°C, 80°C, 85°C, 90°C, 95°C, 100°C, 105°C, 110°C, 115°C, 120°C, 125°C, 130°C, 135°C or 140°C, etc.), and the reaction time is 4 to 6 h (for example, 4 h, 4.5 h, 5 h, 5.5 h or 6 h, etc.).

[0091] In a third aspect, the present invention provides an optical lens, wherein the material of the optical lens includes the optical resin as described in the first aspect, or the optical resin prepared by the preparation method as described in the second aspect.

[0092] In order to make the technical problems, technical solutions and beneficial effects solved by the present invention clearer, the present invention will be further described in detail in conjunction with the embodiments below. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than all of the embodiments. The following description of at least one exemplary embodiment is actually only illustrative and is by no means intended to limit the present invention and its applications. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work belong to the scope of protection of the present invention.

[0093] If no specific techniques or conditions are specified in the examples, the conventional techniques or conditions in the art, or the techniques or conditions described in the literature, or the product instructions are used. If no manufacturer is specified for the reagents or instruments used, they are all conventional products that can be purchased commercially.

[0094] In the embodiments of the present invention, all the raw materials used are dry raw materials after dehydration treatment.

[0095] Synthesis of polyurethane I-1:

[0096] (1) Under nitrogen protection, 0.6 mol of XDI and 100 mL of organic solvent DMF were added to the reactor, heated under stirring, 0.12 g of tri-n-butylphosphine was added, and the reaction was carried out at 80° C. During the reaction, the -NCO mass fraction was sampled and measured (di-n-butylamine titration method). When the -NCO mass fraction dropped to half of the initial -NCO mass fraction, methyl toluenesulfonate, a terminator, was added, and the reaction was continued for 0.5 h. Free XDI was removed under reduced pressure, the temperature was lowered, toluene was added, and the residual catalyst was removed by filtration to obtain an XDI trimer;

[0097] (2) Under nitrogen protection, add 75g PPG500 (polypropylene glycol, M w =500), 0.13 g of dibutyltin dilaurate and 0.1 mol of XDI trimer, control the reaction pressure to 0.05 MPa, stir at room temperature for 30 min, stop stirring, maintain the pressure, and stand for degassing for 60 min; then heat and cure the material at 70°C for 5 h to obtain polyurethane I-1. The number average molecular weight measured by GPC is 28145.4.

[0098] Synthesis of polyurethane I-2:

[0099] (1) Under nitrogen protection, 0.6 mol of IPDI monomer and 100 mL of organic solvent DMF were added to the reactor, heated under stirring, 0.13 g of tri-n-butylphosphine was added, and the reaction was carried out at 70° C. During the reaction, the -NCO mass fraction was sampled and measured (di-n-butylamine titration method). When the -NCO mass fraction dropped to half of the initial -NCO mass fraction, methyl toluenesulfonate, a terminator, was added, and the reaction was continued for 0.5 h. Free IPDI was removed under reduced pressure, the temperature was lowered, toluene was added, and the residual catalyst was removed by filtration to obtain IPDI trimer;

[0100] (2) Under nitrogen protection, add 75g PPG500 (polypropylene glycol, M w =500), 0.16 g of dibutyltin dilaurate and 0.1 mol of IPDI trimer, control the reaction pressure to 0.05 MPa, stir at room temperature for 30 min, stop stirring, maintain pressure, and stand for degassing for 60 min; then heat and cure the material at 70°C for 5 h to obtain polyurethane I-2. The number average molecular weight measured by GPC is 29168.7.

[0101] Synthesis of polyurethane I-3:

[0102] (1) Under nitrogen protection, 0.6 mol of TDI and 100 mL of an organic solvent DMSO were added to a reactor, the temperature was raised while stirring, 0.1 g of triethylamine was added, and the reaction was carried out at 80° C. During the reaction, the -NCO mass fraction was sampled and measured (di-n-butylamine titration method). When the -NCO mass fraction dropped to half of the initial -NCO mass fraction, a terminator benzoyl chloride was added, the reaction was continued for 0.5 h, free TDI was removed under reduced pressure, the temperature was lowered, toluene was added, and the residual catalyst was removed by filtration to obtain a TDI trimer;

[0103] (2) Under nitrogen protection, add 75 g PTMG500 (polybutylene glycol, M w =500), 0.13g of dibutyltin dilaurate and 0.1mol of TDI trimer, control the reaction pressure to 0.05Mpa, stir at room temperature for 30min, stop stirring, maintain the pressure, and stand for degassing for 60min; then heat and cure the material at 70°C for 5h to obtain polyurethane I-3. The number average molecular weight measured by GPC is 27724.7.

[0104] Synthesis of polyurethane II-1:

[0105] (a) Under nitrogen protection, 0.2 mol (33.6 g) HDI was added to the three-necked flask. The temperature was controlled at 60 °C. Under stirring, 0.1 mol (100 g) PTMG (M w =1000), controlling the molar ratio of OH to NCO in the raw material to be 1:2, the addition was completed in 0.5h, and the reaction was continued for 4h to obtain a polyurethane prepolymer, and the molar amount of NCO in the polyurethane prepolymer was measured by titration using di-n-butylamine method;

[0106] (b) Add 0.1 mol (46.2 g) of hexafluoro-1,10-decanediol to the three-necked flask, control the molar ratio of NCO in the polyurethane prepolymer to OH in hexafluoro-1,10-decanediol to be 1:1, gradually raise the temperature to 90° C., and stop the reaction after reacting for 5 hours to obtain polyurethane II-1. The number average molecular weight measured by GPC is 17985.2.

[0107] Synthesis of polyurethane II-2:

[0108] (a) Under nitrogen protection, 0.2 mol (37.6 g) of XDI was added to a three-necked flask. The temperature was controlled at 60°C. Under stirring, 0.1 mol (100 g) of PCDL (polycarbonate diol, M w =1000), controlling the molar ratio of OH to NCO in the raw material to be 1:2, the addition was completed in 0.5h, and the reaction was continued for 4h to obtain a polyurethane prepolymer, and the molar amount of NCO in the polyurethane prepolymer was measured by titration using di-n-butylamine method;

[0109] (b) Add 0.1 mol (46.2 g) of hexafluoro-1,10-decanediol to the three-necked flask, control the molar ratio of NCO in the polyurethane prepolymer to OH in hexafluoro-1,10-decanediol to be 1:1, gradually raise the temperature to 90° C., and stop the reaction after reacting for 5 hours to obtain polyurethane II-2. The number average molecular weight measured by GPC is 18383.6.

[0110] Synthesis of polyurethane III-1:

[0111] (a) Under nitrogen protection, 0.2 mol (44.5 g) IPDI was added to a three-necked flask. The temperature was controlled at 60 °C. Under stirring, 0.1 mol (100 g) PTMG (M w =1000), controlling the molar ratio of OH to NCO in the raw material to be 1:2, the addition was completed in 0.5h, and the reaction was continued for 4h to obtain a polyurethane prepolymer, and the molar amount of NCO in the polyurethane prepolymer was measured by titration using di-n-butylamine method;

[0112] (b) Add 0.1 mol of fluorinated diol into the three-necked flask Wherein, q=3, m2 is 10-30, m3 is 10-30, m2:m3=0.94:1, and the number average molecular weight of the fluorinated diol is 9800; the molar ratio of NCO in the polyurethane prepolymer to OH in the oxetane fluorinated branched diol is controlled to be 1:1, the temperature is gradually raised to 90°C, and the reaction is stopped after 5 hours to obtain polyurethane III-1. The number average molecular weight measured by GPC is 67599.5.

[0113] Example 1

[0114] This embodiment provides an optical resin, which is composed of 8 parts by weight of polyurethane I-1 and 1 part by weight of polyurethane II-1.

[0115] The preparation method of the optical resin in this embodiment is:

[0116] The above synthesized polyurethane is stirred in a clean container according to the proportion, and after stirring evenly, it is put into the extruder, and the operating parameters of the extruder are set and the operation is started. When the material at the outlet of the extruder becomes a uniform transparent semi-flowing liquid, it is connected to the injection mold. After the injection is completed, the temperature is naturally lowered and the test sample is demoulded to obtain.

[0117] Embodiment 2-9

[0118] Examples 2-9 respectively provide an optical resin, the preparation steps of which are the same as those of Example 1, and the component types and contents (parts by weight) are shown in Table 1.

[0119] Table 1

[0120]

[0121] Performance Testing

[0122] The performance of the optical resins provided in the above embodiments and comparative examples was tested, and the testing method was as follows:

[0123] Tensile strength: Plastic parts tensile test-fracture tensile strain test national standard GB / T 1040.2-2006;

[0124] Drop ball test: GB 14866-2006 Technical requirements for personal eye protection;

[0125] Refractive index: GB / T 39691-2020 Determination of refractive index of plastics;

[0126] Light transmittance: GB / T 2410-2008 "Determination of light transmittance and haze of transparent plastics";

[0127] Glass transition temperature (T g ): GB / T 11998-1989 Determination of glass transition temperature of plastics - Thermomechanical analysis method;

[0128] Flame retardant grade: UL94 vertical burning test.

[0129] The results of the above performance tests are shown in Table 2 below.

[0130] Table 2

[0131]

[0132] It can be seen from the test results in Table 1 that the optical resin provided by the embodiment of the present invention has good heat resistance, mechanical strength, toughness, flame retardancy, refractive index and light transmittance.

[0133] Among them, by comparing Examples 1-6 with Comparative Examples 1 and 4, it can be seen that the flame retardant grade and refractive index of the optical resin provided by Examples 1-6 are higher than any of its components; similarly, by comparing Examples 7-9 with Comparative Examples 2, 4 and 6, it can be seen that the flame retardant grade and refractive index of the optical resin provided by Examples 7-9 are higher than any of its components; by comparing Examples 10-12 with Comparative Examples 3 and 5, it can be seen that the flame retardant grade and refractive index of the optical resin provided by Examples 10-12 are higher than any of its components. This shows that the reticular polyurethane and chain fluorine-containing polyurethane provided by the embodiments of the present invention have the effect of synergistically improving the flame retardancy and refractive index of the material.

[0134] Among them, when the mass ratio of the network polyurethane to the chain fluorinated polyurethane is 12:1, the tensile strength, refractive index, transmittance, T gIt is significantly higher than the performance at other ratios, and the performance of optical resin is the best at this time.

[0135] The above description is only a specific embodiment of the present disclosure, so that those skilled in the art can understand or implement the present disclosure. Various modifications to these embodiments will be apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the present disclosure. Therefore, the present disclosure will not be limited to the embodiments described herein, but will conform to the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. An optical resin, characterized in that: The optical resin includes a network polyurethane and a chain fluorine-containing polyurethane; The reticulated polyurethane is selected from at least one of the polymers of formula I; The chain-like fluorine-containing polyurethane is selected from at least one of a polymer of formula II and a polymer of formula III; wherein R1 and R3 are each independently a residue of a diisocyanate; R2 and R4 are each independently a residue of a polymer diol; m1 is 6-10, m2 is 10-30, m3 is 10-30, q is 2-7; -* represents the connection key.

2. The optical resin according to claim 1, characterized in that: The diisocyanate is xylylene diisocyanate, tetramethyl-m-xylylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, diphenylmethane diisocyanate or toluene diisocyanate; preferably xylylene diisocyanate, tetramethyl-m-xylylene diisocyanate or toluene diisocyanate.

3. The optical resin according to claim 1 or 2, characterized in that: The polymer diol is polyethylene glycol, polypropylene glycol, polytetramethylene glycol or polycarbonate diol, preferably polycarbonate diol; Preferably, the weight average molecular weight of the polymer diol is 500-2000.

4. The optical resin according to any one of claims 1 to 3, characterized in that: The mass ratio of the network polyurethane to the chain fluorine-containing polyurethane is (10-20):1, preferably (10-15):

1.

5. A method for preparing an optical resin according to any one of claims 1 to 4, characterized in that: The preparation method comprises the following steps: Synthesis of polymers of formula I: (1) reacting diisocyanate OCN-R1-NCO under the action of a first catalyst, and terminating the reaction when the number of isocyanate groups decreases to 1 / 2 of the initial value to obtain an isocyanate trimer; (2) subjecting the isocyanate trimer to a polymerization reaction with a polymer diol HO-R2-OH under the action of a second catalyst to obtain the polymer of formula I; Synthesis of the polymer of formula II or III: (a) polymerizing diisocyanate OCN-R3-NCO and polymer diol HO-R4-OH to obtain a polyurethane prepolymer; (b) subjecting the polyurethane prepolymer to a polymerization reaction with a fluorinated diol to obtain the polymer of formula II or the polymer of formula III; The fluorinated diol is The polymer of formula I, the polymer of formula II and / or the polymer of formula III are mixed according to a proportion to obtain the optical resin.

6. The preparation method according to claim 5, characterized in that: The first catalyst is selected from one or more of sodium methoxide, triethylamine, methylene-bis(3,3',5,5'-tetrakis(dimethylaminomethyl)-2,2'-phenol, 2,4,6-tris(dimethylaminomethyl)phenol, pentamethyldiethylenetriamine and tri-n-butylphosphine; Preferably, the first catalyst is used in an amount of 500-1000 ppm of the mass of the diisocyanate OCN-R1-NCO; Preferably, the reaction temperature in step (1) is 60-140°C; Preferably, the reaction in step (1) is carried out in an organic solvent; Preferably, the organic solvent is selected from one or more of N,N-dimethylformamide and dimethyl sulfoxide.

7. The preparation method according to claim 5 or 6, characterized in that: The second catalyst is selected from one or more of dibutyltin dilaurate and stannous octoate; Preferably, the amount of the second catalyst is 500-1000 ppm of the mass of the isocyanate trimer; Preferably, in step (2), the molar ratio of the isocyanate trimer to the polymer diol HO-R2-OH is 2:(3-3.1); Preferably, the polymerization reaction process in step (2) is: first, stirring the reaction at room temperature and reduced pressure for 30 to 60 minutes, standing to degas; and then reacting at 50 to 80° C. for 6 to 8 hours.

8. The preparation method according to any one of claims 5 to 7, characterized in that: The molar ratio of the diisocyanate OCN-R3-NCO to the polymer diol HO-R4-OH in step (a) is (2 to 2.05):1; Preferably, the polymerization reaction in step (a) is carried out at a temperature of 50 to 70° C. and for a time of 4 to 6 hours.

9. The preparation method according to any one of claims 5 to 8, characterized in that: The molar ratio of the polyurethane prepolymer to the fluorinated diol in step (b) is 1:(1-1.05); Preferably, the polymerization reaction in step (b) is carried out at a temperature of 70 to 140° C. and for a time of 4 to 6 hours.

10. An optical lens, characterized in that: The material of the optical lens includes the optical resin described in any one of claims 1-4, or the optical resin prepared by the preparation method described in any one of claims 5-9.

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