An ultra-flexible, ultra-thin hybrid glass and a low-temperature large-area preparation method thereof

Abstract

The application belongs to the field of advanced materials, and particularly relates to a super-flexible and super-thin hybrid glass and a low-temperature large-area preparation method thereof, raw materials of the hybrid glass comprising oligomeric silsesquioxane, inorganic nanoparticles and polymer porous film. The super-flexible and super-thin hybrid glass prepared by the application can be processed at room temperature or a lower temperature, compared with existing commercial super-thin glass, the flexibility of the super-thin hybrid glass is significantly improved, and a thinner thickness is achieved, the problem of easy breakage of traditional glass and technical challenges in the thinning process are overcome, which is conducive to the light and thin of electronic devices, and prolongs the service life of the electronic devices.

Description

Technical Field

[0001] This invention belongs to the field of advanced materials, specifically relating to an ultra-flexible, ultra-thin hybrid glass and its low-temperature large-area preparation method. Background Technology

[0002] In recent years, electronic devices have been gradually evolving from fixed designs to bendable, rollable, and foldable ones, which has placed new demands on cover materials for display devices. An ideal cover material not only needs to possess the high transparency and scratch resistance of glass, but also the flexibility of a polymer film. Currently, the mainstream solutions mainly include two types: one is the use of ultra-thin glass (UTG), which is typically prepared by melting and stretching silicate glass at high temperatures to reduce its thickness to 50μm or even 30μm, thus giving it bending properties; the other is coating polymer films, such as transparent polyimide (CPI) and polyethylene terephthalate (PET), with a hard coating to enhance their scratch resistance. However, polymer films exhibit poor creep resistance, easily developing wrinkles and creases, which seriously affect the display effect, premium feel, and reliability of the device during use. Therefore, UTG is gradually becoming the mainstream choice for flexible cover solutions.

[0003] Currently, commercially available ultrathin glass is mainly prepared by melting inorganic glass (such as sodium-calcium silicate, borosilicate, aluminosilicate, and lithium aluminosilicate glass) at temperatures above 1000℃ and then thinning it into shape. Although these materials possess excellent transparency, hardness, and bendability, their application still faces the following major problems: (1) Large thickness and high density. Existing commercially available ultrathin glass typically has a thickness exceeding 30 μm and a density greater than 2.2 g / cm³. 3 (1) It limits the design of thin and light end products; (2) It is brittle and has poor flexibility. The elongation at break of existing commercial ultra-thin glass is less than 0.5%, the elastic recovery is only 60%, and it is fragile. In addition, its large thickness results in a large bending radius, which restricts the bending performance and reliability of end products; (3) It has high processing temperature and high energy consumption. Existing commercial ultra-thin glass needs to be melted at a high temperature of over 1000℃ before it can be processed. This high-energy-consuming process is inconsistent with the concept of low-carbon economic development.

[0004] Therefore, developing new solutions to prepare more flexible and thinner ultrathin glass at low temperatures is an urgent problem to be solved. Summary of the Invention

[0005] To address the aforementioned problems, this invention provides an ultra-flexible, ultra-thin hybrid glass, wherein the raw materials of the hybrid glass include oligomeric silsesquioxane, inorganic nanoparticles, and porous polymer films.

[0006] In some embodiments, the oligomeric silsesquioxane, inorganic nanoparticles, and polymer porous films are cross-linked and cured to form an organic-inorganic hybrid cross-linked network.

[0007] In some embodiments, the crosslinking curing includes crosslinking curing within the porous polymer film.

[0008] In some embodiments, the raw materials for the hybrid glass also include an initiator.

[0009] In some embodiments, the mass ratio of oligomeric silsesquioxane to inorganic nanoparticles is 5-90:10-80, preferably 20-75:25-80.

[0010] In some embodiments, the oligomeric silsesquioxane includes at least one of random oligomeric silsesquioxane, ladder-shaped oligomeric silsesquioxane, or cage-shaped oligomeric silsesquioxane.

[0011] In some embodiments, the three-dimensional topological structures of the random oligomeric silsesquioxane, ladder-shaped oligomeric silsesquioxane, and cage-shaped oligomeric silsesquioxane are respectively shown in Formula I, Formula II, and Formula III:

[0012]

[0013] In the above formulas, R is either the same or different and is selected from... (When all R are of this structure, the corresponding compound is of formula I-1, II-1 or III-1) (When all R are of this structure, the corresponding compound is of formula I-2, II-2 or III-2) (When all R are of this structure, the corresponding compound is of formula I-3, II-3 or III-3) (When all R are of this structure, the corresponding compound is of formula I-4, II-4 or III-4) (When all R are of this structure, the corresponding compound is of formula I-5, II-5 or III-5) (When all R are of this structure, the corresponding compound is of formula I-6, II-6 or III-6) (When all R are of this structure, the corresponding compound is of formula I-7, II-7 or III-7) (When all R are of this structure, the corresponding compound is of formula I-8, II-8 or III-8) (When all R are of this structure, the corresponding compound is of formula I-9, II-9 or III-9) (When all R are of this structure, the corresponding compound is of formula I-10, II-10 or III-10) (When all R are of this structure, the corresponding compound is of formula I-11, II-11 or III-11) (When all R are of this structure, the corresponding compound is of formula I-12, II-12 or III-12) (When all R are of this structure, the corresponding compound is of formula I-13, II-13, or III-13) or (When all Rs are of this structure, the corresponding compounds are of formula I-4, II-4, or III-4), where R1s are the same or different and are selected from...

[0014] In some embodiments, the inorganic nanoparticles include at least one of silica particles, titanium dioxide particles, zirconium oxide particles, calcium carbonate particles, or zinc oxide particles.

[0015] In some embodiments, the inorganic nanoparticles are silicon dioxide particles.

[0016] In some embodiments, the inorganic nanoparticles have a size of 1–1000 nm.

[0017] In a preferred embodiment, the size of the inorganic nanoparticles is 20–500 nm; more preferably, it is 10–50 nm.

[0018] In some embodiments, the polymer porous film includes at least one of polyethylene, polypropylene, nylon, polyurethane, polytetrafluoroethylene, or polyvinylidene fluoride porous films.

[0019] In some embodiments, the porosity of the polymer porous film is 10% or more.

[0020] In a preferred embodiment, the porosity of the polymer porous film is 20-90%; more preferably 50-80%.

[0021] In some embodiments, the thickness of the polymer porous film is 20 nm to 100 μm.

[0022] In a preferred embodiment, the thickness of the porous polymer film is 0.5 μm to 50 μm; more preferably, it is 3 μm to 20 μm.

[0023] In some embodiments, the initiator is at least one of a thermal initiator, triethylamine, a platinum catalyst, or a photoinitiator.

[0024] In some embodiments, the thermal initiator includes azobisisobutyronitrile, azobisisobutyramidine hydrochloride, or azobisisopropylimidazoline hydrochloride.

[0025] In some embodiments, the photoinitiator includes 2-hydroxy-2-methylphenylacetone, 1-hydroxycyclohexylphenyl ketone, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]-1-propanone, benzoin dimethyl ether, triphenylthionium hexafluoroantimonate, or 2,2-diethoxyacetophenone.

[0026] In a preferred embodiment, the initiator is triphenylthionium hexafluoroantimonate.

[0027] In some implementations, the thickness of the ultra-flexible, ultra-thin hybrid glass is 0.8-50 μm.

[0028] In some implementations, the ultra-flexible, ultra-thin hybrid glass also has a light transmittance of more than 90%.

[0029] This invention also provides a method for preparing an ultra-flexible, ultra-thin hybrid glass as described herein, the method comprising the following steps:

[0030] (a) The oligomeric silsesquioxane and inorganic nanoparticles are thoroughly mixed in a solvent, and after the solvent is removed, an oligomeric silsesquioxane slurry containing inorganic nanoparticles is obtained.

[0031] (b) The oligomeric silsesquioxane slurry containing inorganic nanoparticles obtained in step (a) is coated onto a porous polymer film, allowing it to fully penetrate the interior of the porous polymer film and removing air, to obtain a porous polymer film composed of inorganic nanoparticles and oligomeric silsesquioxane.

[0032] (c) The porous polymer film containing inorganic nanoparticles and oligomeric silsesquioxane obtained in step (b) is cured to obtain an ultra-flexible and ultra-thin hybrid glass.

[0033] Further, the oligomeric silsesquioxane has a mass fraction of 5% or more in the hybrid glass raw material; preferably, the oligomeric silsesquioxane has a mass fraction of 50% or more in the hybrid glass raw material; more preferably, it has a mass fraction of 60-70%.

[0034] In some embodiments, the inorganic nanoparticles constitute 5-80% of the mass fraction of the hybrid glass raw material; preferably, the inorganic nanoparticles constitute 10% or more of the mass fraction of the hybrid glass raw material; more preferably, 20%-40%.

[0035] In some embodiments, the mass ratio of the oligomeric silsesquioxane to the inorganic nanoparticles is 5-90:10-80, preferably 20-75:25-80.

[0036] In some embodiments, the method further includes, in step (a), adding an initiator to the solvent and mixing thoroughly.

[0037] In some embodiments, the initiator has a mass fraction of 0.01 to 5% in the hybrid glass raw material; preferably, the initiator has a mass fraction of 0.5 to 3% in the hybrid glass raw material; more preferably, it has a mass fraction of 1 to 2%.

[0038] In some embodiments, the solvent includes at least one of the following substances: dichloromethane, trichloromethane, toluene, xylene, diethyl ether, tetrahydrofuran, acetone, methyl ethyl ketone, ethyl acetate, butyl acetate, N,N-dimethylformamide, N,N-dimethylacetamide, acetonitrile, benzonitrile, methanol, or ethanol.

[0039] In some implementations, the coating is performed by roller coating.

[0040] In some implementations, the curing includes light curing or heat curing.

[0041] In some implementations, the thickness of the prepared ultra-flexible, ultra-thin hybrid glass can be controlled by adjusting the mass ratio of the oligomeric silsesquioxane slurry containing inorganic nanoparticles to the porous polymer film and the roll coating pressure.

[0042] In some implementations, the thickness of the prepared ultra-flexible, ultra-thin hybrid glass is 0.8-50 μm.

[0043] The ultra-flexible, ultra-thin hybrid glass prepared by this invention can be processed and shaped at room temperature or lower temperatures, with a thickness of 0.8–50 μm, an elongation at break of 0.8–10%, a bending radius as low as 0.3–0.5 mm, a light transmittance of 92%, a hardness of 1.1–5 GPa, and a modulus of 5–30 GPa. Compared with existing commercially available ultra-thin glass, this ultra-thin hybrid glass exhibits significantly improved flexibility and achieves a thinner thickness, overcoming the fragility of traditional glass and the technical challenges in thinning processes. This is beneficial for the miniaturization of electronic devices and for extending their service life.

[0044] Compared with the prior art, the present invention has the following beneficial effects:

[0045] 1. This invention uses a porous polymer film as a support carrier, and combines it with a slurry composed of oligomeric silsesquioxane and inorganic nanoparticles to form an interconnected network. After cross-linking and curing, a mechanically interlocked organic-inorganic hybrid cross-linked material—ultrathin hybrid glass—is formed. The cross-linking of the oligomeric silsesquioxane and inorganic nanoparticles provides high hardness, while the polymer micro / nano film provides flexibility, resulting in an ultrathin hybrid glass that possesses the hardness of inorganic glass and the flexibility of polymer.

[0046] 2. Since the transmittance, hardness and function of the material can be controlled by adjusting the type and relative ratio of oligomeric silsesquioxane and nanoparticles, the flexible ultrathin hybrid glass of this invention not only has high transparency, but also has the advantages of adjustable mechanical properties and functionality.

[0047] 3. Existing ultrathin glasses are all thicker than 30 μm, and achieving large-area fabrication of even thinner ultrathin glasses remains a challenge. Since polymeric micro / nanoporous membranes can be processed over large areas, and their thickness and porosity can be controlled, the ultrathin hybrid glass of this invention can be fabricated over a wide range of areas within a thickness range of 20 nm to 100 μm.

[0048] 4. Existing ultra-thin glass processing requires melting the glass at temperatures above 1000℃ before thinning and shaping. The ultra-thin hybrid glass of this invention can be processed and shaped at room temperature or lower temperatures below 100℃, offering the advantage of low energy consumption.

[0049] In summary, this invention provides a simple and efficient method for the low-temperature, large-area fabrication of ultra-flexible, ultra-thin hybrid glass. The flexibility and thickness far exceed those of existing commercially available ultra-thin glass, overcoming the brittleness of traditional glass and the challenges of thinning processes, and can provide strong support for the development of flexible electronics. Attached Figure Description

[0050] Figure 1 The diagram shows the process of preparing ultra-flexible and ultra-thin hybrid glass according to the present invention. First, inorganic nanoparticles are mixed evenly with oligomeric silsesquioxane and an initiator is added. Then, the polysilsesquioxane monomer containing inorganic nanoparticles is roller coated and impregnated to fully penetrate into the porous film of the polymer. After curing, the target material, namely ultra-flexible and ultra-thin hybrid glass, can be obtained.

[0051] Figure 2 The results of continuous bending experiments are shown for the commercially available ultrathin glass of Comparative Example 1 and the ultra-flexible, ultrathin hybrid glass prepared in Example 2.

[0052] Figure 3 The results of the drop ball impact test are shown for the commercially available ultrathin glass of Comparative Example 1 and the ultra-flexible, ultrathin hybrid glass prepared in Example 2. Detailed Implementation

[0053] The present invention will be further illustrated below with reference to specific embodiments, but the embodiments do not limit the present invention in any way. Unless otherwise specified, the reagents, methods, and equipment used in the present invention are conventional reagents, methods, and equipment in this technical field.

[0054] Example 1

[0055] (1) By weight, 99 parts of 3-(2,3-epoxypropoxy)propyl cage-like oligomeric silsesquioxane (structural formula as shown in Formula III-1) and initiator (triphenylthionium hexafluoroantimonate, 1 part) are mixed evenly to form a transparent and viscous slurry A.

[0056] (2) Roller-coating slurry A onto a porous polyethylene film (thickness 3μm, porosity 70%) to allow it to fully penetrate the interior of the porous polyethylene film and remove air. After curing with ultraviolet light (365nm) for 3 minutes, the target material is obtained.

[0057] Example 2

[0058] (1) By mass, 75 parts of 3-(2,3-epoxypropoxy)propyl cage-like oligomeric silsesquioxane (structure shown in Formula III-1) and 25 parts of nano-silica (particle size ~20nm) were added to ethanol (20mL), mixed evenly under high speed stirring, and then the ethanol was removed to obtain transparent and viscous slurry A.

[0059] (2) Mix slurry A (99 parts) with initiator (triphenylthionium hexafluoroantimonate, 1 part) evenly to form transparent and viscous slurry B;

[0060] (3) Roller-coating slurry B onto a porous polyethylene film (thickness 3μm, porosity 70%) to allow it to fully penetrate the interior of the porous polyethylene film and remove air. After curing with ultraviolet light (365nm) for 3 minutes, the target material is obtained.

[0061] Example 3

[0062] The difference from Example 2 is:

[0063] In step 1, the number of parts of the nano-silica is replaced with 50 parts.

[0064] Example 4

[0065] The difference from Example 2 is:

[0066] In step 1, the number of parts of the nano-silica is replaced with 80 parts.

[0067] Example 5

[0068] The difference from Example 2 is:

[0069] In step 1, the particle size of the nano-silica is replaced with ~100nm.

[0070] Example 6

[0071] The difference from Example 2 is:

[0072] In step 1, the particle size of the nano-silica is replaced with ~200nm.

[0073] Example 7

[0074] The difference from Example 2 is:

[0075] In step 1, the particle size of the nano-silica is replaced with ~500nm.

[0076] Example 8

[0077] The difference from Example 2 is:

[0078] In step 1, the 3-(2,3-epoxypropoxy)propyl cage-like oligomeric silsesquioxane is replaced with 3-(2,3-epoxypropoxy)propyl ladder-like oligomeric silsesquioxane (structural formula shown in Formula II-1).

[0079] Example 9

[0080] The difference from Example 2 is:

[0081] In step 1, the 3-(2,3-epoxypropoxy)propyl cage-like oligomeric silsesquioxane is replaced with 3-(2,3-epoxypropoxy)propyl random oligomeric silsesquioxane (structural formula shown in Formula I-1).

[0082] Example 10

[0083] The difference from Example 2 is:

[0084] In step 1, the 3-(2,3-epoxypropoxy)propyl cage oligomeric silsesquioxane is replaced with 2-(3,4-epoxycyclohexyl)ethyl cage oligomeric silsesquioxane (structural formula shown in Formula III-2).

[0085] Example 11

[0086] The difference from Example 2 is:

[0087] In step 3, the thickness of the polyethylene porous film is replaced with 0.5 μm.

[0088] Example 12

[0089] The difference from Example 2 is:

[0090] In step 3, the thickness of the polyethylene porous film is replaced with 20 μm.

[0091] Example 13

[0092] The difference from Example 2 is:

[0093] In step 3, the thickness of the polyethylene porous film is replaced with 45 μm.

[0094] Example 14

[0095] The difference from Example 2 is:

[0096] In step 3, the thickness of the polyethylene porous film is replaced with 95 μm.

[0097] Example 15

[0098] The difference from Example 2 is:

[0099] In step 3, the polyethylene porous film is replaced with a polypropylene porous film.

[0100] Example 16

[0101] The difference from Example 2 is:

[0102] In step 3, the polyethylene porous film is replaced with a nylon porous film.

[0103] Example 17

[0104] The difference from Example 2 is:

[0105] In step 3, the polyethylene porous film is replaced with a polyurethane porous film.

[0106] Example 18

[0107] The difference from Example 2 is:

[0108] In step 3, the polyethylene porous film is replaced with a polymethyl methacrylate porous film.

[0109] Example 19

[0110] (1) By mass, 75 parts of 3-(methacryloyloxy)propyl cage oligomeric silsesquioxane (structure shown in formula III-3) and 25 parts of nano silica (particle size ~20nm) were added to ethanol (20mL), mixed evenly under high speed stirring, and then the ethanol was removed to obtain transparent and viscous slurry A.

[0111] (2) Mix slurry A (99 parts) with initiator (phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, 1 part) evenly to form transparent and viscous slurry B;

[0112] (3) The slurry B is roller coated onto a polyethylene porous film (thickness 3μm, porosity 70%), allowing it to fully penetrate into the polyethylene porous film and remove air. After curing under nitrogen atmosphere with ultraviolet light (365nm) for 5 minutes, the target material is obtained.

[0113] Example 20

[0114] Unlike Example 19:

[0115] In step 1, the 3-(methacryloyloxy)propyl cage oligomeric silsesquioxane is replaced with 3-(acryloyloxy)propyl cage oligomeric silsesquioxane (structural formula shown in Formula III-4).

[0116] Example 21

[0117] Unlike Example 19:

[0118] In step 1, the nano-silica is replaced with nano-titanium dioxide (particle size ~20nm).

[0119] Example 22

[0120] Unlike Example 19:

[0121] In step 1, the nano-silica is replaced with nano-zirconia (particle size ~20nm).

[0122] Example 23

[0123] Unlike Example 19:

[0124] In step 1, the nano-silica is replaced with nano-calcium carbonate (particle size ~20nm).

[0125] Example 24

[0126] Unlike Example 19:

[0127] In step 1, the nano-silica is replaced with nano-zinc oxide (particle size ~20nm).

[0128] Example 25

[0129] (1) By weight, 50 parts of vinyl ladder oligomeric silsesquioxane (structure shown in Formula II-5) and 50 parts of hydrogen-containing ladder oligomeric silsesquioxane (structure shown in Formula II-6) were added to toluene (20 mL) and dissolved. Then, the toluene was removed to obtain a transparent and viscous slurry A.

[0130] (2) Add slurry A (75 parts) and nano silica (25 parts, particle size ~20nm) to ethanol (20mL), mix evenly under high speed stirring, and then remove the ethanol to obtain transparent and viscous slurry B;

[0131] (3) Mix slurry B (99.99 parts) and initiator (platinum catalyst, 0.01 parts) evenly to form a transparent and viscous slurry C;

[0132] (4) The slurry C is roller coated onto the polytetrafluoroethylene porous film (thickness 3μm, porosity 70%), allowing it to fully penetrate into the interior of the polyethylene porous film and remove air. After curing at 80°C for 120 minutes under a nitrogen atmosphere, the target material is obtained.

[0133] Example 26

[0134] (1) By mass, 40 parts of 3-(2,3-epoxypropoxy)propyl cage oligomeric silsesquioxane (structure shown in Formula III-1), 3-mercaptopropyl cage oligomeric silsesquioxane (35 parts of 3-mercaptopropyl silsesquioxane (structure shown in Formula III-7)) and 25 parts of nano silica (particle size ~20nm) were added to ethanol (20mL), mixed evenly under high speed stirring, and then the ethanol was removed to obtain transparent and viscous slurry A.

[0135] (2) Cool slurry A (99.5 parts) and initiator (triethylamine, 0.5 parts) to 0°C respectively, and mix them evenly to form a transparent and viscous slurry B;

[0136] (3) Apply slurry B to a polyethylene porous film (thickness 3μm, porosity 70%), allowing it to fully penetrate the interior of the polyethylene porous film and remove air. After curing at 50°C for 120 minutes, the target material is obtained.

[0137] Example 27

[0138] Unlike Example 27:

[0139] In step 1, the 3-mercaptopropyl cage-like oligomeric silsesquioxane is replaced with 3-aminopropyl cage-like oligomeric silsesquioxane (structural formula shown in III-8).

[0140] Example 28

[0141] (1) By mass, alkoxy cage oligomeric silsesquioxane (75 parts, structural formula as shown in Formula III-9) and nano silica (25 parts, particle size ~20nm) were added to toluene (20mL), mixed evenly under high speed stirring, and then toluene was removed to obtain transparent and viscous slurry A.

[0142] (2) Roller-coating slurry A onto a polyvinylidene fluoride porous film (thickness 8μm, porosity 70%), allowing it to fully penetrate and wet the interior of the polyvinylidene fluoride porous film. After curing at 85°C for 120 minutes in an environment with 85% humidity, the target material is obtained.

[0143] Example 29

[0144] Unlike Example 28:

[0145] In step 1, the structural formula of the alkoxycage oligomeric silsesquioxane is replaced by formula III-9 with formula III-10.

[0146] Example 30

[0147] (1) By mass, alkoxy cage oligomeric silsesquioxane (40 parts, structural formula as shown in Formula III-9), trifluoropropyl cage oligomeric silsesquioxane (35 parts, structural formula as shown in Formula III-11) and nano silica (25 parts, particle size ~20nm) were added to toluene (20mL), mixed evenly under high speed stirring, and then the toluene was removed to obtain transparent and viscous slurry A;

[0148] (2) Roller-coating slurry A onto a polytetrafluoroethylene porous film (thickness 8μm, porosity 60%), allowing it to fully penetrate and wet the interior of the polyvinylidene fluoride porous film. After curing at 85°C for 120 minutes in an environment with 85% humidity, the target material is obtained.

[0149] Example 31

[0150] The difference from Example 30 is:

[0151] In step 1, the trifluoropropyl cage oligomeric silsesquioxane is replaced with 1H,1H,2H,2H-perfluorohexyl cage oligomeric silsesquioxane (structural formula shown in III-12).

[0152] Example 32

[0153] The difference from Example 30 is:

[0154] In step 1, the trifluoropropyl cage oligomeric silsesquioxane is replaced with 1H,1H,2H,2H-perfluorooctyl cage oligomeric silsesquioxane (structural formula shown in III-13).

[0155] Example 33

[0156] The difference from Example 30 is:

[0157] In step 1, the trifluoropropyl cage oligomeric silsesquioxane is replaced with 1H,1H,2H,2H-perfluorodecyl cage oligomeric silsesquioxane (structural formula shown in III-14).

[0158] Comparative Example 1

[0159] Commercially purchased ultrathin glass, 30μm thick.

[0160] Test case

[0161] The hybrid glasses prepared in Examples 1-33 and the ultrathin glass of Comparative Example 1 were subjected to performance tests. The specific performance test methods are as follows:

[0162] (1) Thickness test

[0163] Thickness characterization was performed using a Dektak XT step gauge from Bruker, USA.

[0164] (2) Transmission rate test

[0165] Transmittance was characterized using a Shimadzu UV-3600 UV-Vis meter.

[0166] (3) Hardness test

[0167] Hardness characterization was performed using a Bruker TI 980 nanoindenter.

[0168] (4) Modulus test

[0169] The modulus characterization comes from tensile testing, and the tensile stress-strain curves were tested using an EM6.501-W tensile testing machine from Shenzhen Tesmart Company in China.

[0170] (5) Elongation at break test

[0171] The elongation at break was characterized by tensile testing, and the tensile stress-strain curve was tested using an EM6.501-W tensile testing machine from Shenzhen Tesmart Company, China.

[0172] (6) Dynamic bending performance test

[0173] The continuous bending test was conducted using the KZ-FD2 small unidirectional folding cycle tester from China Science & Technology Co., Ltd.

[0174] (7) Minimum bending radius

[0175] The minimum bending radius of curvature was obtained through continuous bending experiments.

[0176] (8) Drop ball impact test

[0177] The ball drop impact test is conducted by adjusting the drop height of a 50g stainless steel ball.

[0178] (9) Water contact angle test

[0179] The water contact angle was characterized using a DSA25 instrument from KRUSS GmbH, Germany.

[0180] In the continuous bending test and the falling ball impact test, the ultra-flexible, ultra-thin hybrid glass prepared in Example 2 was compared with the commercially available ultra-thin glass of Comparative Example 1. The commercially available ultra-thin glass showed reliable bending stability at a bending radius of 1.5 mm, but under more demanding bending conditions (bending radius of curvature less than 1 mm), the ultra-thin glass broke after only one bend. Furthermore, due to the inherent brittleness of the glass and the compressive stress remaining inside the glass during high-temperature processing, the ultra-thin glass is extremely prone to shattering upon impact. Specific results are as follows... Figure 2 and Figure 3 As shown, Figure 2 In Comparative Example 1, the commercially available ultrathin glass was continuously bent with a bending radius of 0.5 mm and broke after only one bend. In Example 2, the ultra-flexible and ultra-thin hybrid glass remained intact after 500,000 consecutive bends under the same bending conditions, without any breakage or creases. This demonstrates that the ultra-flexible and ultra-thin hybrid glass of the present invention has excellent flexibility, far superior to existing commercially available ultra-thin glass. Figure 3 In Comparative Example 1, the commercially available ultrathin glass broke upon impact with a falling ball at a height of 14 cm, with the falling ball weighing 50 g. In the same falling ball impact test, the ultra-flexible, ultra-thin hybrid glass prepared in Example 2 showed only minor dents on its surface and did not break, even with a falling ball impact height of 150 cm. This demonstrates that the ultra-flexible, ultra-thin hybrid glass of this invention has excellent toughness, far superior to existing commercially available ultrathin glass.

[0181] The results of performance tests on the hybrid glasses prepared in Examples 1-33 are detailed in Table 1 below.

[0182] Table 1: Performance Test Results of Ultra-Flexible and Ultra-Thin Hybrid Glass

[0183]

[0184]

[0185]

[0186]

[0187] According to the performance test results of the ultra-flexible and ultra-thin hybrid glasses in Examples 1-33 of Table 1, the present invention uses oligomeric silsesquioxane and inorganic nanoparticles to form a transparent slurry, which is then poured into the interior of a porous polymer film. After curing, a mechanically interlocked organic-inorganic hybrid cross-linking network is formed, resulting in a hybrid glass that not only possesses transparency and high hardness but also excellent flexibility and hydrophobicity. The reasons are as follows: First, the slurry composed of oligomeric silsesquioxane and inorganic nanoparticles contains both organic and inorganic materials, which can form a nanoscale organic-inorganic hybrid network after curing, exhibiting excellent transparency, hardness, and modulus. Second, by adjusting the formulation, the refractive index of the slurry composed of oligomeric silsesquioxane and inorganic nanoparticles can be made comparable to that of the porous polymer film, avoiding the scattering of visible light by the porous polymer film, thus giving the composite hybrid glass high transparency. Third, the porous polymer film has... It has excellent flexibility and good mechanical strength, which can dissipate the energy of the material when it is bent or impacted, and avoid stress concentration, thus exhibiting excellent bending and impact resistance; Fourth, since the thickness and porosity of polymer micro-nano ultrathin films are easy to control and convenient for large-area preparation, the mechanical properties, thickness and width of the ultrathin hybrid glass involved in this invention can be prepared according to needs; Fifth, since there are many types of oligomeric silsesquioxanes and the surface functional groups are tunable, the surface hydrophilic and hydrophobic properties of the ultrathin hybrid glass involved in this invention can be adjusted within a certain range.

[0188] It should be noted that while the preferred embodiments of the present invention are given in the specification and accompanying drawings, the present invention can be implemented in many different forms and is not limited to the embodiments described herein. These embodiments are not intended to impose additional limitations on the content of the present invention; their purpose is to provide a more thorough and comprehensive understanding of the disclosure of the present invention. Furthermore, the above-described technical features can be combined with each other to form various embodiments not listed above, all of which are considered to be within the scope of the present invention specification. Moreover, those skilled in the art can make improvements or modifications based on the above description, and all such improvements and modifications should fall within the protection scope of the appended claims.

Claims

1. A type of ultra-flexible, ultra-thin hybrid glass, characterized in that, The raw materials for the hybrid glass include oligomeric silsesquioxanes, inorganic nanoparticles, and porous polymer films. The oligomeric silsesquioxane, inorganic nanoparticles, and polymer porous films are cross-linked and cured to form an organic-inorganic hybrid cross-linked network. The cross-linking curing includes cross-linking curing inside the porous polymer film; The polymer porous film includes at least one of polyethylene, polypropylene, nylon, polyurethane, polytetrafluoroethylene or polyvinylidene fluoride porous films. The hybrid glass has a thickness of 0.8~50 μm, an elongation at break of 0.8~10%, a bending radius as low as 0.3~0.5 mm, a light transmittance of 92%, a hardness of 1.1~5 GPa, and a modulus of 5~30 GPa.

2. The hybrid glass according to claim 1, characterized in that, The raw materials for the hybrid glass also include an initiator.

3. The hybrid glass according to claim 1, characterized in that, The mass ratio of oligomeric silsesquioxane to inorganic nanoparticles is 5-90:10-80.

4. The hybrid glass according to claim 1, characterized in that, The mass ratio of oligomeric silsesquioxane to inorganic nanoparticles is 20-75:25-80.

5. The hybrid glass according to any one of claims 1-4, characterized in that, The oligomeric silsesquioxane includes at least one of random oligomeric silsesquioxane, ladder-shaped oligomeric silsesquioxane, or cage-shaped oligomeric silsesquioxane.

6. The hybrid glass according to claim 5, characterized in that, The three-dimensional topological structures of the random oligomeric silsesquioxanes, ladder-shaped oligomeric silsesquioxanes, and cage-shaped oligomeric silsesquioxanes are shown in Formula I, Formula II, and Formula III, respectively: Formula I Formula II Formula III In the above formulas, R is either the same or different and is selected from... , , , , , , , , , , , , or Where R1 is the same or different and is selected from , or .

7. The hybrid glass according to any one of claims 1-4, characterized in that, The inorganic nanoparticles include at least one of silicon dioxide particles, titanium dioxide particles, zirconium oxide particles, calcium carbonate particles, or zinc oxide particles.

8. The hybrid glass according to claim 7, characterized in that, The inorganic nanoparticles are silicon dioxide particles.

9. The hybrid glass according to claim 8, characterized in that, The inorganic nanoparticles have a size of 1~1000 nm.

10. The hybrid glass according to claim 9, characterized in that, The inorganic nanoparticles have a size of 20~500nm.

11. The hybrid glass according to claim 9, characterized in that, The inorganic nanoparticles have a size of 10~50 nm.

12. The hybrid glass according to any one of claims 1-4, characterized in that, The porosity of the polymer porous film is 10% or more.

13. The hybrid glass according to claim 12, characterized in that, The porosity of the polymer porous film is 20-90%.

14. The hybrid glass according to claim 12, characterized in that, The porosity of the polymer porous film is 50-80%.

15. The hybrid glass according to any one of claims 1-4, characterized in that, The thickness of the porous polymer film is 20 nm to 100 μm.

16. The hybrid glass according to claim 15, characterized in that, The thickness of the porous polymer film is 0.5 μm to 50 μm.

17. The hybrid glass according to claim 15, characterized in that, The thickness of the porous polymer film is 3 μm to 20 μm.

18. The hybrid glass according to claim 2, characterized in that, The initiator is at least one of a thermal initiator, triethylamine, platinum catalyst, or photoinitiator.

19. The hybrid glass according to claim 18, characterized in that, The thermal initiator includes azobisisobutyronitrile, azobisisobutyramidine hydrochloride, or azobisisopropylimidazoline hydrochloride.

20. The hybrid glass according to claim 18, characterized in that, The photoinitiator includes 2-hydroxy-2-methylphenylpropanone, 1-hydroxycyclohexylphenyl ketone, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]-1-propanone, benzoin dimethyl ether, triphenylthionium hexafluoroantimonate, or 2,2-diethoxyacetophenone.

21. The hybrid glass according to claim 18, characterized in that, The initiator is triphenylthionium hexafluoroantimonate.

22. The method for preparing the ultra-flexible, ultra-thin hybrid glass according to any one of claims 1-21, characterized in that, The method includes the following steps: (a) The oligomeric silsesquioxane and inorganic nanoparticles are thoroughly mixed in a solvent, and after the solvent is removed, an oligomeric silsesquioxane slurry containing inorganic nanoparticles is obtained. (b) The oligomeric silsesquioxane slurry containing inorganic nanoparticles obtained in step (a) is coated onto a porous polymer film, allowing it to fully penetrate into the interior of the porous polymer film and removing air, to obtain a porous polymer film composited with inorganic nanoparticles and oligomeric silsesquioxane. (c) The porous polymer film containing inorganic nanoparticles and oligomeric silsesquioxane obtained in step (b) is cured to obtain an ultra-flexible and ultra-thin hybrid glass.

23. The preparation method according to claim 22, characterized in that, The oligomeric silsesquioxane has a mass fraction of 5% or more in the hybrid glass raw material.

24. The preparation method according to claim 22, characterized in that, The oligomeric silsesquioxane has a mass fraction of more than 50% in the hybrid glass raw material.

25. The preparation method according to claim 22, characterized in that, The oligomeric silsesquioxane has a mass fraction of 60-70% in the hybrid glass raw material.

26. The preparation method according to claim 22, characterized in that, The inorganic nanoparticles have a mass fraction of 5-80% in the hybrid glass raw material.

27. The preparation method according to claim 22, characterized in that, The inorganic nanoparticles constitute more than 10% of the mass fraction of the hybrid glass raw material.

28. The preparation method according to claim 22, characterized in that, The inorganic nanoparticles constitute 20% to 40% of the mass fraction of the hybrid glass raw material.

29. The preparation method according to claim 22, characterized in that, The mass ratio of the oligomeric silsesquioxane to the inorganic nanoparticles is 5-90:10-80.

30. The preparation method according to claim 22, characterized in that, The mass ratio of the oligomeric silsesquioxane to the inorganic nanoparticles is 20-75:25-80.

31. The preparation method according to claim 22, characterized in that, The method further includes, in step (a), adding an initiator to the solvent and mixing thoroughly.

32. The preparation method according to claim 31, characterized in that, The initiator has a mass fraction of 0.01-5% in the hybrid glass raw material.

33. The preparation method according to claim 31, characterized in that, The initiator has a mass fraction of 0.5-3% in the hybrid glass raw material.

34. The preparation method according to claim 31, characterized in that, The initiator has a mass fraction of 1-2% in the hybrid glass raw material.

35. The preparation method according to claim 22, characterized in that, The solvent includes at least one of the following substances: dichloromethane, trichloromethane, toluene, xylene, diethyl ether, tetrahydrofuran, acetone, methyl ethyl ketone, ethyl acetate, butyl acetate, N,N-dimethylformamide, N,N-dimethylacetamide, acetonitrile, benzonitrile, methanol, or ethanol.

36. The preparation method according to claim 22, characterized in that, The coating is applied using a roller coating method.

37. The preparation method according to claim 22, characterized in that, The curing process includes light curing or heat curing.

38. The preparation method according to claim 37, characterized in that, The heat curing is carried out at 50-90℃.

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