A composite material for impact-resistant and explosion-proof protective glasses and its preparation method

Abstract

This invention discloses an impact-resistant and explosion-proof protective eyewear composite material and its preparation method, belonging to the field of protective eyewear technology. The impact-resistant and explosion-proof protective eyewear composite material of this invention comprises the following components by weight: 70-100 parts of modified UV-resistant polycarbonate, 2-8 parts of modified inorganic nanoparticles, and 8-20 parts of Ph-PBS-HR. The rigid modified inorganic nanoparticles, together with the modified UV-resistant polycarbonate and the flexible Ph-PBS-HR, work synergistically to give the protective eyewear high impact and explosion-proof capabilities. The symmetrical benzene rings in the main chain of the modified UV-resistant polycarbonate and Ph-PBS-HR reduce self-scattering and interface scattering, reducing haze and improving the light transmittance of the protective eyewear. The introduction of UV-resistant functional components into the modified UV-resistant polycarbonate reduces the risk of yellowing due to UV aging.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of protective eyewear, in particular to an anti-impact and anti-explosion protective eyewear composite material and a preparation method thereof. BACKGROUND

[0002] Protective eyewear is an important role in our daily life, which can deal with various risks that may cause damage to the eyes in work and life, and protect the vision safety of the user. For example, it can prevent debris and dust from splashing into the eyes in construction scenes to cause eye scratches or infections; it can also prevent toxic or corrosive chemical reagents from splashing out of the eyes in laboratories and chemical plants; and it can also reduce the direct radiation of strong light to the eyes. In daily work scenes, ordinary protective eyewear can be worn to reduce the risk of eye damage, while in higher risk scenes such as high-speed fragments generated during metal processing and explosion fragments during blasting operations, the impact force is extremely high due to the high speed and high energy, so ordinary protective eyewear cannot withstand the impact and is easily broken, and the fragments of the protective eyewear can further splash into the eyes, causing more harm to the eyes. Therefore, it is necessary to develop anti-impact and anti-explosion protective eyewear that can resist high impact.

[0003] Common methods for improving the anti-impact and anti-explosion performance of protective eyewear are to add a layer of flexible anti-impact protective material such as polyurethane foam, Kevlar fiber, and the new generation of intelligent high-molecular anti-impact protective material polyborosiloxane to the polymethyl methacrylate (PMMA) or polycarbonate (PC) high-molecular material used to prepare the lens or coat the lens surface. These materials can absorb and disperse impact energy to play a protective role. Among them, polyborosiloxane has outstanding advantages. Polyborosiloxane is a supermolecular polymer formed by introducing boron elements into the siloxane structure to form chemical cross-linking and physical cross-linking centered on boron. Polyborosiloxane has a rate response characteristic, is soft in normal state, and exhibits liquid or liquid-like properties, but exhibits solid-like properties when impacted, and this strain rate response is reversible, which can greatly extend the service life. Common polyborosiloxane materials are obtained by reacting double-end hydroxyl polydimethylsiloxane and boric acid or boric ester derivatives, but they have the disadvantages of easy creep and easy hydrolysis, poor stability, reduced reversible strain response, and thus reduced service life. SUMMARY

[0004] To overcome the shortcomings of the existing technology, this invention provides an impact-resistant and explosion-proof protective eyewear composite material and its preparation method. The impact-resistant and explosion-proof protective eyewear composite material is obtained by mixing modified UV-resistant polycarbonate, modified inorganic nanoparticles, and Ph-PBS-HR. The modified UV-resistant polycarbonate is prepared by transesterification of product D with a diol structure, which is obtained by modifying (1,1'-binaphthyl)-2,2'-diamine with the UV-resistant functional component 4-propenoxy-2-hydroxybenzophenone. The Ph-PBS-HR is obtained by polymerizing hydroxyl-terminated diphenyl dimethyl (siloxane and polysiloxane) with boric acid. The modified inorganic nanoparticles are prepared by coating the surface of inorganic nanoparticles with a silane coupling agent, and the inorganic nanoparticles are one or a combination of SiO2, ZnO, TiO2, and Al2O3. Among them, the (1,1'-binaphthyl)-2,2'-diamine of product D has high symmetry and rigidity, which can not only reduce scattering and improve light transmittance, but also improve the rigidity of the glasses to enhance impact resistance. At the same time, product D is also grafted with the anti-ultraviolet functional component 4-propenoxy-2-hydroxybenzophenone, which can improve the glasses' anti-ultraviolet ability and prevent aging and yellowing under ultraviolet irradiation, thus affecting the performance. In addition, diphenyldimethyl (siloxane and polysiloxane) with hydroxyl-terminated phenyl groups was selected to prepare polyborosiloxane with boric acid. Compared with polydimethylsiloxane, firstly, the introduction of benzene rings increases the rigidity of the molecular chain and reduces chain segment slip, thereby significantly reducing the creep rate. Secondly, the hydrophobicity of benzene rings is better than that of methyl groups, which can reduce the penetration of water molecules into the material interior, reduce the risk of hydrolysis of borate bonds (BO), and further improve the structural stability of polyborosiloxane. Finally, the symmetrical benzene rings have strong π-π stacking, and the π-π interaction surface will slip and disperse the force during impact, which can further reduce the impact force. At the same time, the refractive index of the symmetrical benzene rings is similar to that of the naphthalene rings in modified UV-resistant polycarbonate, which can reduce interfacial scattering and improve the transparency of glasses.

[0005] The purpose of this invention is to provide an impact-resistant and explosion-proof protective eyewear composite material and its preparation method.

[0006] This invention is achieved through the following technical solution:

[0007] A composite material for impact-resistant and explosion-proof protective glasses, comprising, by weight, the following components: 70-100 parts of modified UV-resistant polycarbonate, 2-8 parts of modified inorganic nanoparticles, and 8-20 parts of Ph-PBS-HR; the structural formula of the modified UV-resistant polycarbonate is shown in Formula 1.

[0008]

[0009] In one specific embodiment, the preparation of the modified UV-resistant polycarbonate includes the following steps:

[0010] S1. Phenolic hydroxyl group activation

[0011] Under a nitrogen atmosphere, 4-propenoxy-2-hydroxybenzophenone was dissolved in anhydrous DCM and placed in an ice bath. Anhydrous pyridine and trifluoromethanesulfonic anhydride were added dropwise in sequence, and the reaction was allowed to proceed. The reaction was then brought to room temperature and quenched with ice water. The organic phase was extracted with DCM, concentrated, and purified by column chromatography to obtain product A.

[0012] S2.CN coupling

[0013] Under a nitrogen atmosphere, product A, (1,1'-binaphthyl)-2,2'-diamine, base, and ligand Xphos were dissolved in toluene; Pd(OAc)2 was added as a catalyst and the temperature was raised to 100-110℃. The reaction was stopped after 24-36 hours; the product B was obtained by cooling, column chromatography purification, concentration, and drying.

[0014] S3. Double bond epoxidation

[0015] Product B was dissolved in anhydrous dichloromethane in an ice bath; m-chloroperoxybenzoic acid was added in portions; the reaction was carried out at room temperature; after the reaction was completed, the product was washed with 10% sodium bicarbonate, and the organic phase was dried and concentrated. The product C was then purified by short silica gel column chromatography.

[0016] S4. Epoxy ring-opening

[0017] Product C was dissolved in THF solution, then methanol was added, and the mixture was placed in an ice bath. Concentrated sulfuric acid was added dropwise. The mixture was brought to room temperature and stirred for 4-8 hours until the reaction was complete. Saturated NaHCO3 was added to neutralize the pH to 7-8. The reaction solution was concentrated, extracted, the organic phase was concentrated, and recrystallized to obtain product D.

[0018] S5. Modified UV-resistant polycarbonate

[0019] Product D was dehydrated in a vacuum drying oven at 100-120℃ for 18-24 hours and then placed in a reaction vessel. Under nitrogen protection, diphenyl carbonate and Ti(OBu)4 were added and mixed, and the mixture was heated to 175-180℃ and stirred until melted. The temperature was increased to carry out transesterification. The temperature was increased and the vacuum was reduced to 0.133 kPa to carry out high-temperature polycondensation. Heating was stopped, nitrogen was introduced and phosphite was added to terminate the reaction. The product was cooled and dissolved in THF, and purified by precipitation with anhydrous ethanol. The product was dried to obtain modified UV-resistant polycarbonate.

[0020] In a specific embodiment, in step S1, the amount of anhydrous pyridine used is 2.5-3 times the molar amount of 4-propenoxy-2-hydroxybenzophenone; the amount of trifluoromethanesulfonic anhydride used is 1.2-1.5 times the molar amount of 4-propenoxy-2-hydroxybenzophenone; the ice bath reaction time is 1-1.5 hours; and the room temperature reaction time is 2-3 hours with stirring.

[0021] In one specific embodiment, in step S2, the amount of product A is 2.01-2.1 times the molar amount of (1,1'-binaphthyl)-2,2'-diamine; the base is one of cesium carbonate, sodium tert-butoxide, and sodium hydride, and the amount is 3-5 times the molar amount of (1,1'-binaphthyl)-2,2'-diamine; the amount of ligand Xphos is 0.1 wt% of (1,1'-binaphthyl)-2,2'-diamine.

[0022] In one specific embodiment, in step S3, the amount of m-chloroperoxybenzoic acid used is 1.2 times the molar amount of product B; and the room temperature reaction time is 8-10 hours.

[0023] In one specific embodiment, in step S4, the amount of THF solution used is 1.2-1.5 times the molar amount of product C; the amount of methanol used is 10-20 times the molar amount of product C; and the amount of concentrated sulfuric acid used is 0.1-0.2 times the molar amount of product C.

[0024] In a specific embodiment, in step S5, the amount of product D is 2.05-2.1 times the molar amount of diphenyl carbonate; the amount of Ti(OBu)4 is 0.05 wt% of diphenyl carbonate; the transesterification temperature is 180-220℃ and the time is 4-5 hours; the polycondensation temperature is 200-220℃ and the time is 4-6 hours; and the number-average molecular weight of the modified UV-resistant polycarbonate is 30,000-80,000.

[0025] In one specific embodiment, the highly reactive phenyl polyborosiloxane (Ph-PBS-HR) is prepared as follows:

[0026] S1. Preprocessing

[0027] Grind boric acid and filter it through a 100-mesh aluminum sieve. Then dry it in a vacuum drying oven at 120℃ for 28-24 hours.

[0028] S2. Boronization

[0029] At room temperature, boric acid and hydroxyl-terminated diphenyldimethyl (siloxane and polysiloxane) silicone oil are mixed and stirred for 1-2 hours; the reaction is heated to obtain a crude product; the crude product is dissolved in n-hexane, filtered, rotary evaporated, and vacuum dried at 60-70℃ for 20-24 hours to finally obtain transparent Ph-PBS-HR.

[0030] In one specific embodiment, in step S2, the hydroxyl-terminated diphenyldimethyl (siloxane and polysiloxane) silicone oil and boric acid are fed in an equimolar ratio of -OH (stoichiometric coefficient r = 1:1); the reaction temperature is 110-120℃ and the time is 6-48 hours; the filter membrane is a polyvinylidene fluoride membrane with an average pore size of 0.22μm.

[0031] In one specific embodiment, the modified inorganic nanoparticles are silane coupling agent modified inorganic nanoparticles, wherein the inorganic nanoparticles are one or a combination of SiO2, ZnO, TiO2, and Al2O3; the silane coupling agent is 3-aminopropyltriethoxysilane, and the amount used is 2-5 wt% of the inorganic nanoparticles. The modified inorganic nanoparticles are prepared by dispersing the inorganic nanoparticles in ethanol and sonicating them for 30-45 minutes; adding the silane coupling agent and heating to 70-80℃ for 6-8 hours; and centrifuging and washing to obtain the modified inorganic nanoparticles.

[0032] Another object of the present invention is to protect a method for preparing an impact-resistant and explosion-proof protective eyewear composite material, comprising the following steps:

[0033] Modified UV-resistant polycarbonate, modified inorganic nanoparticles, and Ph-PBS-HR are placed in a mixer, heated, and kneaded at 50-80 rpm. The mixture is then transferred to an extruder for extrusion molding. The molded material is cooled by water and cut into granules by a granulator to obtain the impact-resistant and explosion-proof protective eyewear composite material.

[0034] In one specific embodiment, the mixing temperature is 180-200℃; the time is 5-10 minutes.

[0035] Beneficial effects

[0036] This invention provides an impact-resistant and explosion-proof protective eyewear composite material and its preparation method. The impact-resistant and explosion-proof protective eyewear composite material is obtained by mixing modified UV-resistant polycarbonate, modified inorganic nanoparticles, and Ph-PBS-HR. The modified UV-resistant polycarbonate is prepared by transesterification of diol-structured product D, which is obtained by modifying (1,1'-binaphthyl)-2,2'-diamine with the UV-resistant functional component 4-propenoxy-2-hydroxybenzophenone, with diphenyl carbonate. The Ph-PBS-HR is obtained by polymerizing hydroxyl-terminated diphenyldimethyl (siloxane and polysiloxane) with boric acid. The modified inorganic nanoparticles are prepared by coating the surface of inorganic nanoparticles with a silane coupling agent, and the inorganic nanoparticles are one or a combination of SiO2, ZnO, TiO2, and Al2O3. Among them, the (1,1'-binaphthyl)-2,2'-diamine of product D has high symmetry and rigidity, which reduces scattering and improves light transmittance while giving the glasses high impact resistance; at the same time, product D is also grafted with the anti-ultraviolet functional component 4-propenoxy-2-hydroxybenzophenone, which greatly improves the glasses' anti-ultraviolet ability, and the performance decline is small after one week of ultraviolet irradiation. In addition, diphenyldimethyl (siloxane and polysiloxane) with hydroxyl-terminated phenyl groups was selected to prepare polyborosiloxane with boric acid. Compared with polydimethylsiloxane, firstly, the introduction of benzene rings increases the rigidity of the molecular chain and reduces chain segment slippage, thereby significantly reducing the creep rate. Secondly, the hydrophobicity of benzene rings is better than that of methyl groups, which can reduce the penetration of water molecules into the material interior, reduce the risk of hydrolysis of borate ester bonds (BO), and further improve the structural stability of polyborosiloxane. Finally, the symmetrical benzene rings have strong π-π stacking, and the π-π interaction surface generates slip dispersion force during impact, which can effectively disperse the impact force of the material and avoid lens breakage. At the same time, the refractive index of the symmetrical benzene rings is similar to that of the naphthalene rings in modified UV-resistant polycarbonate, which can reduce interfacial scattering and give the glasses a light transmittance of up to 91%. Attached Figure Description

[0037] Figure 1 Synthetic routes for modified UV-resistant polycarbonate and Ph-PBS-HR;

[0038] Figure 2 The 1H NMR spectrum of product D;

[0039] Figure 3 Infrared spectra of product D, modified UV-resistant polycarbonate, Ph-PDMS, and Ph-PBS-HR; Detailed Implementation

[0040] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0041] Unless otherwise specified, the experimental methods used in the embodiments are conventional methods, and the materials and reagents used are commercially available unless otherwise specified.

[0042] The raw materials used in the examples and comparative examples are described below:

[0043] Anti-UV functional component: 4-propenoxy-2-hydroxybenzophenone, 99%, product number A800611, purchased from Shanghai Maclean Biochemical Technology Co., Ltd.

[0044] Trifluoromethanesulfonic anhydride (Tf2O): 98%, product number T819101, purchased from Shanghai Maclean Biochemical Technology Co., Ltd.

[0045] Pyridine (Py): 99.5%, product number P816288, purchased from Shanghai Maclean Biochemical Technology Co., Ltd.

[0046] (1,1'-binaphthyl)-2,2'-diamine: 97%, product number B803445, purchased from Shanghai Maclean Biochemical Technology Co., Ltd.

[0047] Palladium acetate (Pd(OAc)2): Product number P815382, purchased from Shanghai Maclean Biochemical Technology Co., Ltd.

[0048] 2-Dicyclohexylphosphine-2,4,6-triisopropylbiphenyl (XPhos): 97%, product number D806579, purchased from Shanghai Maclean Biochemical Technology Co., Ltd.

[0049] Oxidizing agent: m-chloroperoxybenzoic acid (mCPBA), 75%, product number C804779, purchased from Shanghai Maclean Biochemical Technology Co., Ltd.

[0050] Tetrabutyl titanate (Ti(OBu)4): 98%, product number CP38330, purchased from Jiaxing Zhejia Biotechnology Co., Ltd.

[0051] Diphenyl carbonate: 99%, purchased from Shanghai Maclean Biochemical Technology Co., Ltd.

[0052] Hydroxyl-terminated diphenyl dimethyl (siloxane and polysiloxane) (Ph-PDMS): 98%, catalog number 1765183, purchased from Tianjin Xiens Biochemical Technology Co., Ltd.

[0053] Dihydroxyl-terminated poly(dimethylsiloxane) (PDMS): 65 cst, purchased from Sigma-Aldrich, USA;

[0054] Boric acid (BA): 99.5%, product number B802844, purchased from Shanghai Maclean Biochemical Technology Co., Ltd.

[0055] Silane coupling agent: 3-aminopropyltriethoxysilane, 99%, product number A800523, purchased from Shanghai Maclean Biochemical Technology Co., Ltd.

[0056] Inorganic nanoparticles: SiO2 nanoparticles, 100-150nm, purchased from Shanghai Yingxin Laboratory Equipment Co., Ltd.

[0057] Modified UV-resistant polycarbonate: self-made, preparation method as follows:

[0058] S1. Phenolic hydroxyl group activation

[0059] Under a nitrogen atmosphere, 4-propenoxy-2-hydroxybenzophenone (1 equivalent) was dissolved in anhydrous DCM and placed in an ice bath; anhydrous pyridine (2.5 equivalents) was slowly added dropwise while stirring for 10 minutes; trifluoromethanesulfonic anhydride (1.3 equivalents) was slowly added dropwise while reacting for 1.5 hours; the reaction was brought to room temperature and stirred for 3 hours until the reaction was complete; the reaction was quenched with ice water, the organic phase was extracted with DCM, concentrated, and purified by column chromatography to obtain product A;

[0060] S2.CN coupling

[0061] Under a nitrogen atmosphere, product A (2.05 equivalents), (1,1'-binaphthyl)-2,2'-diamine (1 equivalent), sodium tert-butoxide (3 equivalents), and ligand Xphos (0.1 wt%) were dissolved in toluene and bubbled under aeration for 30 minutes. Catalyst Pd(OAc)2 was added and bubbled under aeration for another 10 minutes. The temperature was raised to 110°C, and the reaction was stirred for 24 hours until the reaction was complete. The reaction mixture was cooled to room temperature, purified by column chromatography, concentrated, and dried to obtain product B.

[0062] S3. Double bond epoxidation

[0063] Product B (1 equivalent) was dissolved in anhydrous dichloromethane in an ice bath; m-chloroperoxybenzoic acid (mCPBA) (1.2 equivalent) was added in portions; the reaction was stirred at room temperature for 10 hours until the reaction was complete; the product was washed with 10% sodium bicarbonate, the organic phase was dried and concentrated, and purified by rapid chromatography using a short silica gel column to obtain product C.

[0064] S4. Epoxy ring-opening

[0065] Product C (1 equivalent) was dissolved in THF solution (1.3 equivalent), and methanol (15 equivalent) was added. The mixture was kept in an ice bath. A small amount of concentrated sulfuric acid (0.1 equivalent) was slowly added dropwise. The mixture was brought to room temperature and stirred for 6 hours until the reaction was complete. A small amount of saturated NaHCO3 was added to neutralize the pH to 7-8. The reaction solution was concentrated, extracted with ethyl acetate / water, the organic phase was concentrated, and the mixture was recrystallized from ethyl acetate and n-hexane to obtain product D.

[0066] S5. Modified UV-resistant polycarbonate

[0067] Product D (2.1 equivalents) was dehydrated in a vacuum drying oven at 120°C for 24 hours and then placed in a reaction vessel. Under nitrogen protection, diphenyl carbonate (1 equivalent) and Ti(OBu)4 (0.05 wt%) were added and mixed. The mixture was heated to 175°C and stirred until melted. The mixture was then heated to 215°C for low-temperature transesterification for 5 hours. The mixture was then heated to 220°C and the vacuum was reduced to 0.133 kPa for high-temperature polycondensation for 6 hours. Heating was stopped, nitrogen was introduced, and phosphite was added to terminate the reaction. The product was cooled, dissolved in THF, and purified by precipitation with anhydrous ethanol. The product was dried to obtain modified UV-resistant polycarbonate with a number average molecular weight of 35,000.

[0068] The modified polycarbonate is prepared in a similar manner to the modified UV-resistant polycarbonate, except that (1,1'-binaphthyl)-2,2'-diamine is used to modify propylene oxide, which has no UV-resistant function.

[0069] Highly reactive phenyl-type polyborosiloxane (Ph-PBS-HR): In-house prepared according to the following method:

[0070] S1. Preprocessing

[0071] Grind boric acid and filter it through a 100-mesh aluminum sieve. Then dry it in a vacuum drying oven at 120℃ for 28-24 hours.

[0072] S2. Boronization

[0073] Boric acid and hydroxyl-terminated diphenyldimethyl (siloxane and polysiloxane) silicone oil (Ph-PDMS) were added at an equimolar ratio of -OH (stoichiometric coefficient r = 1:1), and stirred at room temperature for 1 hour. The mixture was then heated to 120°C and stirred for 48 hours to obtain a crude product with a high degree of reaction, denoted as Ph-PBS-HR. The crude product was dissolved in hexane and filtered through a polyvinylidene fluoride membrane with an average pore size of 0.22 μm to obtain a clear solution. The hexane was removed by rotary evaporation, and the solution was dried under vacuum at 60°C for 24 hours to finally obtain transparent Ph-PBS-HR.

[0074] The preparation method for low-reactivity phenyl polyborosiloxane (Ph-PBS-LR) is the same as that for Ph-PBS-HR, except that the stirring time is 6 hours.

[0075] The highly reactive polydimethylsiloxane-polyborosiloxane PBS-HR is prepared using the same method as Ph-PBS-HR, the difference being that the silicone oil is polydimethylsiloxane (PDMS).

[0076] Modified inorganic nanoparticles: SiO2 nanoparticles were dispersed in ethanol and sonicated for 30 minutes; 3 wt% silane coupling agent was added, and the mixture was heated to 80℃ and reacted for 6 hours; modified inorganic nanoparticles were obtained by centrifugation and washing.

[0077] It should be noted that the term "equivalent" used in this invention refers to "molar equivalent".

[0078] Unless otherwise specified, all components and raw materials used in the embodiments and comparative examples of this invention are commercially available, and the same type of components and raw materials are used in each parallel experiment.

[0079] Examples and Comparative Examples

[0080] A composite material for impact-resistant and explosion-proof protective glasses, the weight parts of which are shown in Table 1, is prepared as follows:

[0081] Modified UV-resistant polycarbonate, modified inorganic nanoparticles, and Ph-PBS-HR are placed in a mixer, heated to 180°C, and kneaded at 50-80 rpm for 5 minutes. The mixture is then transferred to an extruder for extrusion molding. The molded material is cooled by water and cut into granules by a granulator to obtain the impact-resistant and explosion-proof protective eyewear composite material.

[0082] The resulting composite material was placed in a 180℃ flat vulcanizing machine and cured at a pressure of 10MPa for 10 minutes, and then cold-pressed at room temperature for 3 minutes to obtain a transparent protective eyewear strip with a thickness of 4mm used in the experiment.

[0083] Table 1. Composite materials for impact-resistant and explosion-proof protective glasses (parts by weight)

[0084] Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Modified ultraviolet resistant polycarbonate 95 95 95 95 95 95 Modified polycarbonate 95 Modified inorganic nanoparticles 3 6 3 3 3 3 3 Ph-PBS-HR 10 10 16 10 0 Ph-PBS-LR 10 PBS-HR 10

[0085] The impact-resistant and explosion-proof protective eyewear composite material prepared in the examples and comparative examples was subjected to the following performance tests, and the results are shown in the attached figures and Table 2, respectively.

[0086] 1. Proton NMR Spectroscopy: The synthesized product D sample was dissolved in deuterated DMSO to prepare a 1.0 wt% solution. The NMR spectrum of the sample was measured using a proton NMR spectrometer at 400 MHz. The results are as follows: Figure 2 As shown.

[0087] 2. Infrared Spectroscopy: Modified UV-resistant polycarbonate, product D, Ph-PDMS, and Ph-PBS-HR were mixed with potassium bromide at a ratio of 1:50 to prepare a pellet. An Avatar 380 spectrometer was used for this test. Before testing, a blank background scan was performed, followed by the placement of the pelleted sample for analysis. The scanning range was 500-4000 cm⁻¹. -1 The result is as follows Figure 1 As shown.

[0088] 3. Impact test: Using a drop hammer impact tester and in accordance with EN 166 standard, the transparent protective eyewear sample strip was cut into a sample strip of 5cm*5cm*2cm. The impact energy was 15J. A steel ball was dropped from a height of 1.3m and hit the center of the sample strip vertically. The test was repeated multiple times. The average impact force and average energy loss that the sample strip could withstand were recorded, and it was observed whether cracks appeared in the sample strip.

[0089] 4. Light transmittance: According to ASTM D1003 standard, a transparent protective eyewear sample strip with a smooth, scratch-free surface and a length of 50mm × width of 50mm × thickness was prepared and wiped with alcohol. A CIE standard light source D65 was used as the light source, and the test was conducted at 23℃±2℃ and a relative humidity of 50%±10%. The incident, transmitted, and scattered light flux were recorded, and the transmittance (Tt) and haze (H) were calculated according to the following formulas: Φt: Luminous flux transmitted through the material; Φi: Luminous flux of incident light; Φd: Luminous flux of scattered light that deviates from the incident direction by more than 2.5° after passing through the material.

[0090] 5. Abrasion Resistance: Tested according to ASTM D4060 standard under conditions of 50% ± 10% relative humidity. Prepare a transparent protective eyewear strip with a smooth, scratch-free surface, measuring 100mm in length × 100mm in width × 2mm in thickness. Select a CS-10 wheel with a 500g load, a rotation speed of 60 ± 5 rpm, and a total rotation speed of 500 rpm. Weigh the mass difference (Δm) before and after wear. Determine the abrasion resistance using the following formula: For protective eyewear: it is considered qualified when Δm < 10mg / 500r.

[0091] 6. Anti-aging properties: Take a transparent protective eyewear sample strip cut to 1×1×0.22cm and place it in an ultraviolet aging test chamber. Set the temperature to room temperature and humidity to 55% and irradiate for one week. Measure the percentage decrease in performance.

[0092] Table 2 Performance test results of impact-resistant and explosion-proof protective eyewear composite materials

[0093]

[0094]

[0095] From the appendix Figure 2 The 1H NMR spectrum shows that twice the integral number corresponds to the number of hydrogen atoms in the molecule, and the shifts of each hydrogen atom in the spectrum are consistent with their chemical environment, indicating that product D was successfully synthesized.

[0096] From the appendix Figure 3 It can be seen that the peak value appears between 2940-2850 cm. -1 The stretching vibrations attributed to CH peak at 3070-3000 cm⁻¹ -1 This is attributed to the stretching vibration of CH in the benzene ring. In the spectrum of modified UV-resistant polycarbonate, it does not show a vibration at 3450 cm⁻¹. -1 A -OH signal peak belonging to product D was observed near the signal, but the characteristic signal of product D was still retained at 1666 cm⁻¹. -1 A characteristic peak belonging to the ketone carbonyl group was observed at 1289 cm⁻¹. -1 and 1100-1053cm -1 Ph-O- absorption was observed at 1755 cm⁻¹. -1 The presence of a characteristic absorption peak attributable to the stretching vibration of the C=O group on the ester carbonyl group indicates that product D successfully reacted with diphenyl carbonate to produce a modified UV-resistant polycarbonate. In the Ph-PDMS spectrum, the peak appeared at 3610 cm⁻¹. -1 The stretching vibrations, attributed to free Si-OH, peak at 3300-3200 cm⁻¹. -1 The stretching vibrations attributed to Si-OH peak at 3000-1700 cm⁻¹. -1 Attributable to the stretching vibration of CH on a monosubstituted benzene ring, 1261 cm⁻¹ -1 and 804cm -1 The nearby signal peaks are due to the bending vibrations of Si-(CH3)2, 1071-1023 cm⁻¹. -1 Characteristic stretching vibrations in the Si-O-Si range, at 1127 cm⁻¹ -1 and 844cm -1 The signal at this location is a characteristic stretching vibration of Si-Ph. In the Ph-PBS-HR spectrum, the signal at 3200 cm⁻¹ is not observed. -1 The above observations pertain to the stretching vibrations of Si-OH at 1340 cm⁻¹. -1 A new signal peak appears at the point, which is the characteristic stretching vibration of BO. At the same time, the signal of Ph-PDMS is retained, indicating that boric acid has successfully reacted with hydroxyl-terminated diphenyldimethyl (siloxane and polysiloxane) silicone oil and the reaction is complete.

[0097] As shown in Table 2, Comparative Example 3, without the addition of polyborosiloxane, exhibited poor impact resistance, with the sample rupturing on the second impact to dissipate energy, making it unsuitable as an impact-resistant and explosion-proof material. For Comparative Example 2 and Example 1, the addition of Ph-PBS-HR significantly improved the impact resistance of the materials, and they did not rupture after 10 impacts. This is because, upon impact, the polyborosiloxane behaves as a solid-like substance, undergoing impact hardening and increasing the material's stress-bearing area to dissipate energy and reduce the average transmitted impact force. Example 1, using Ph-PBS-HR, showed a lower average transmitted impact force and higher energy loss, indicating superior impact resistance. This is attributed to its regular benzene rings and strong π-π stacking, which causes slippage and dispersion forces on the π-π interaction surface during impact, further reducing the impact force. However, excessive addition can lead to a decrease in light transmittance.

[0098] As can be seen from the data in Table 2, Example 1 has higher light transmittance. Meanwhile, compared with Comparative Example 1, it can be seen that the introduction of anti-UV functional components can improve the anti-aging ability to a limited extent, and the performance decline remains below 2.5% even after one week of aging.

[0099] The preferred embodiments of the present invention disclosed above are merely illustrative of the invention. These preferred embodiments do not exhaustively describe all details, nor do they limit the invention to the specific implementations described. Clearly, many modifications and variations can be made based on the content of this specification. This specification selects and specifically describes these embodiments to better explain the principles and practical applications of the invention, thereby enabling those skilled in the art to better understand and utilize the invention. The invention is limited only by the claims and their full scope and equivalents.

Claims

1. A composite material for impact-resistant and explosion-proof protective glasses, characterized in that, By weight, it comprises the following components: 70-100 parts modified UV-resistant polycarbonate, 2-8 parts modified inorganic nanoparticles, and 8-20 parts Ph-PBS-HR; the structural formula of the modified UV-resistant polycarbonate is shown in Formula 1: Formula 1; The preparation steps of the Ph-PBS-HR are as follows: S1. Preprocessing Grind boric acid and filter it through a 100-mesh aluminum sieve. Then dry it in a vacuum drying oven at 120 ℃ for 28-24 hours. S2. Boronization At room temperature, boric acid and hydroxyl-terminated diphenyldimethyl (siloxane and polysiloxane) silicone oil were mixed and stirred for 1-2 hours; the reaction was heated to obtain a crude product; the crude product was dissolved in n-hexane, filtered, rotary evaporated, and vacuum dried at 60-70 °C for 20-24 hours to finally obtain transparent Ph-PBS-HR. The modified inorganic nanoparticles are silane coupling agent modified inorganic nanoparticles, and the inorganic nanoparticles are one or a combination of SiO2, ZnO, TiO2, and Al2O3; the silane coupling agent is 3-aminopropyltriethoxysilane, and the amount used is 2-5 wt% of the inorganic nanoparticles.

2. The impact-resistant and explosion-proof protective eyewear composite material as described in claim 1, characterized in that, The preparation of the modified UV-resistant polycarbonate includes the following steps: S1. Phenolic hydroxyl group activation Under a nitrogen atmosphere, 4-propenoxy-2-hydroxybenzophenone was dissolved in anhydrous DCM and placed in an ice bath. Anhydrous pyridine and trifluoromethanesulfonic anhydride were added dropwise sequentially, and the reaction was carried out at room temperature. After the reaction was completed, the reaction was quenched with ice water, and the organic phase was extracted with DCM, concentrated, and purified by column chromatography to obtain product A. S2.CN coupling Under a nitrogen atmosphere, product A, (1,1'-binaphthyl)-2,2'-diamine, base, and ligand Xphos were dissolved in toluene; Pd(OAc)2 was added as a catalyst and the temperature was raised to 100-110 °C. The reaction was stopped after 24-36 hours; the product B was obtained by cooling, column chromatography purification, concentration, and drying. S3. Double bond epoxidation Product B was dissolved in anhydrous dichloromethane in an ice bath; m-chloroperoxybenzoic acid was added in portions; the reaction was carried out at room temperature; after the reaction was completed, the product was washed with 10% sodium bicarbonate, and the organic phase was dried and concentrated. The product C was then purified by short silica gel column chromatography. S4. Epoxy ring-opening Product C was dissolved in THF solution, then methanol was added, and the mixture was placed in an ice bath. Concentrated sulfuric acid was added dropwise. The mixture was brought to room temperature and stirred for 4-8 hours until the reaction was complete. Saturated NaHCO3 was added to neutralize the pH to 7-8. The reaction solution was concentrated, extracted, the organic phase was concentrated, and recrystallized to obtain product D. S5. Modified UV-resistant polycarbonate Product D was dehydrated in a vacuum drying oven at 100-120 °C for 18-24 hours and then placed in a reaction vessel. Under nitrogen protection, diphenyl carbonate and Ti(OBu)4 were added and mixed, and the mixture was heated to 175-180 °C and stirred until melted. The temperature was increased to carry out transesterification. The temperature was increased and the vacuum was reduced to 0.133 kPa to carry out high-temperature polycondensation. Heating was stopped, nitrogen was introduced and phosphite was added to terminate the reaction. The product was cooled and dissolved in THF, and purified by precipitation with anhydrous ethanol. The product was dried to obtain modified UV-resistant polycarbonate.

3. The impact-resistant and explosion-proof protective eyewear composite material as described in claim 2, characterized in that, In step S1, the amount of anhydrous pyridine used is 2.5-3 times the molar amount of 4-propenoxy-2-hydroxybenzophenone; the amount of trifluoromethanesulfonic anhydride used is 1.2-1.5 times the molar amount of 4-propenoxy-2-hydroxybenzophenone; the ice bath reaction time is 1-1.5 hours; and the room temperature reaction time is 2-3 hours with stirring.

4. The impact-resistant and explosion-proof protective eyewear composite material as described in claim 2, characterized in that, In step S2, the amount of product A is 2.01-2.1 times the molar amount of (1,1'-binaphthyl)-2,2'-diamine; the base is one of cesium carbonate, sodium tert-butoxide, and sodium hydride, and the amount is 3-5 times the molar amount of (1,1'-binaphthyl)-2,2'-diamine; the amount of ligand Xphos is 0.1 wt% of (1,1'-binaphthyl)-2,2'-diamine; in step S3, the amount of m-chloroperoxybenzoic acid is 1.2 times the molar amount of product B; the reaction time at room temperature is 8-10 hours; in step S4, the amount of THF solution is 1.2-1.5 times the molar amount of product C; the amount of methanol is 10-20 times the molar amount of product C; and the amount of concentrated sulfuric acid is 0.1-0.2 times the molar amount of product C.

5. The impact-resistant and explosion-proof protective eyewear composite material as described in claim 2, characterized in that, In step S5, the amount of product D is 2.05-2.1 times the molar amount of diphenyl carbonate; the amount of Ti(OBu)4 is 0.05 wt% of diphenyl carbonate; the transesterification temperature is 180-220 ℃ and the time is 4-5 hours; the polycondensation temperature is 200-220 ℃ and the time is 4-6 hours; the number-average molecular weight of the modified UV-resistant polycarbonate is 30,000-80,000.

6. The impact-resistant and explosion-proof protective eyewear composite material as described in claim 1, characterized in that, In step S2, the hydroxyl-terminated diphenyldimethyl (siloxane and polysiloxane) silicone oil and boric acid are fed in an equimolar ratio of -OH (stoichiometric coefficient r = 1:1); the reaction temperature is 110-120 ℃ and the time is 6-48 hours; the filter membrane is a polyvinylidene fluoride membrane with an average pore size of 0.22 μm.

7. The impact-resistant and explosion-proof protective eyewear composite material as described in claim 1, characterized in that, The modified inorganic nanoparticles are prepared by dispersing inorganic nanoparticles in ethanol and sonicating them for 30-45 minutes; adding a silane coupling agent and heating to 70-80 ℃ for 6-8 hours; and centrifuging and washing to obtain the modified inorganic nanoparticles.

8. A method for preparing an impact-resistant and explosion-proof protective eyewear composite material as described in any one of claims 1 to 7, characterized in that, Includes the following steps: Modified UV-resistant polycarbonate, modified inorganic nanoparticles, and Ph-PBS-HR are placed in a mixer and kneaded at 180-200 ℃ and 50-80 rpm for 5-10 minutes. The mixture is then transferred to an extruder for extrusion molding. The molded material is cooled by water and cut into granules by a granulator to obtain the impact-resistant and explosion-proof protective eyewear composite material.

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