Method to prepare three-dimensional transparent glass via polymer plasticity

Abstract

The present disclosure provides a method to fabricate three-dimensional transparent glass utilizing polymer plasticity, including the following steps. In step 1, synthesize polymer-glass powder composite containing dynamic chemical bonds, the bond exchange catalyst is added during the synthesis process, and then cure to obtain a two-dimensional sheet shape I, the bond exchange catalyst is used to activate a dynamic chemical bond in step 2. In step 2, shape the two-dimensional sheet shape I obtained in step 1 into a complex three-dimensional shape II under the conditions of the effect of an external force and the activable dynamic chemical bond. In step 3, pyrolyze the composite precursor at high temperature to obtain transparent glass with complex three-dimensional shape II. The present disclosure provides a method in shaping the transparent glass with complex geometries by unique polymer plasticity in lower temperature.

Claims

1. A method for preparing three-dimensional transparent glass through polymer plasticity, including the following steps: step 1: synthesizing a polymer-glass powder composite containing dynamic chemical bonds, wherein a bond exchange catalyst is added during the synthesis process, and then curing to obtain a two-dimensional sheet shape I; step 2: shaping the two-dimensional sheet shape I obtained in step 1 into a complex three-dimensional shape II; and using an external force and activating the dynamic chemical bonds via the bond exchange catalyst to fix a shape of the complex three-dimensional shape II; and step 3: pyrolyzing the complex three-dimensional shape II at a temperature ranging from 400° C.-1500° C. to obtain the transparent glass with the complex three-dimensional shape II.

2. The method for preparing three-dimensional transparent glass through polymer plasticity of claim 1, wherein the dynamic chemical bonds are one or more than one of dynamic covalent bonds or dynamic noncovalent bonds, wherein the dynamic covalent bonds include one or more than one of ester bonds, diene addition bonds, disulfide bonds, urethane bonds, alkoxyamine bonds, thioether, trithiocarbonate, carbon-carbon bonds, acylhydrazone bonds, oxime bonds, urea bonds, thiourea bonds, borate bonds, boroxine bonds, selenoether, and diselenide, and the dynamic non-covalent bonds include one or more than one of hydrogen bonds, ionic bonds, and delocalized π bonds.

3. The method for preparing three-dimensional transparent glass through polymer plasticity of claim 1, wherein the mass fraction of the bond exchange catalyst in the polymer-glass powder composite ranges from 0.01-5% in step 1.

4. The method for preparing three-dimensional transparent glass through polymer plasticity of claim 3, wherein the bond exchange catalyst includes one or more than one of calcium salts, magnesium salts, stannous octoate, dibutyltin dilaurate, titanates, zirconates, organic acids, organic bases, inorganic acids and inorganic bases in step 1.

5. The method for preparing three-dimensional transparent glass through polymer plasticity of claim 1, wherein the bond exchange catalyst includes one or more than one of calcium salts, magnesium salts, stannous octoate, dibutyltin dilaurate, titanates, zirconates, organic acids, organic bases, inorganic acids and inorganic bases in step 1.

6. The method for preparing three-dimensional transparent glass through polymer plasticity of claim 1, wherein a glass powder in the polymer-glass powder composite includes one or more than one of quartz glass powder, borosilicate glass powder, aluminosilicate glass powder, soda-lime glass powder, lead silica glass powder, and sodium boron glass powder, the particle size of the glass powder is in the range of 10 nm-100 μm, and the mass fraction of the glass powder in the total mass of the composite is 5%-80%.

7. The method for preparing three-dimensional transparent glass through polymer plasticity of claim 1, further adding functional components when synthesizing the polymer-glass powder composite in step 1, and the functional components include one or more than one of color-developing components, conductive components and magnetic components.

8. The method for preparing three-dimensional transparent glass through polymer plasticity of claim 1, wherein the method for shaping the two-dimensional sheet shape I obtained in step 1 into the three-dimensional shape II in step 2 includes one or more than one of origami and kirigami, the three-dimensional shape II includes sharp structures.

9. The method for preparing three-dimensional transparent glass through polymer plasticity of claim 8, wherein the process of origami includes one or more than one of valley fold, mountain fold, sinking, rolling, crimp fold, pleat fold, and reverse fold, the shape fabricated by origami includes one or more than one of Miura Fold, Yoshimura Mode, Triangle Helix, Torsion Box, sailboat base, frog base, windmill base, fish base, bird base and waterbomb base, and the process of kirigami includes one or more than one of folding, piercing, inkjet printing, and sketching.

10. The method for preparing three-dimensional transparent glass through polymer plasticity of claim 1, wherein a sintering aid is introduced in the synthesize process in step 1.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is a schematic diagram of the fabricating method of transparent glass with both sharp angles and complex three-dimensional structures through origami/kirigami techniques.

(2) FIG. 2 is the picture of the glass with three-dimensional structures.

DESCRIPTION OF THE EMBODIMENTS

(3) The examples below serve for further explanation of the present disclosure, with no restriction thereto.

Example 1 (Ester Bonds, the Dynamic Bond Contained in the Molecule which is Introduced into the Network)

(4) The reagent and the source thereof used in Example 1 is represented in Table 1 below.

(5) TABLE-US-00001 TABLE 1 used reagent molecular formula manufacturer poly(caprolactone) C.sub.4H.sub.8O.sub.3(C.sub.6H.sub.10O.sub.2).sub.n Sigma-Aldrich China diacrylate (PCL ) M.sub.n = 2000 2-isocyanatoethyl acrylate C.sub.6H.sub.7NO.sub.3 TCI shanghai dibutyltin dilaurate C.sub.32H.sub.64O.sub.4Sn J&K Scientific (DBTDL) butyl acrylate C.sub.7H.sub.12O.sub.3 TCI shanghai phenoxyethanol (POE) C.sub.8H.sub.10O.sub.2 Shanghai Aladdin Bio-Chem Technology silica powder R972 SiO.sub.2 EVONIK Irgacure 2959 C.sub.12H.sub.16O.sub.4 Sigma-Aldrich China

(6) Synthesis of Poly(Caprolactone) Diacrylate (PCLDA):

(7) 30 g of poly(caprolactone) diacrylate, 6.25 g of 2-isocyanatoethyl acrylate and 0.25 g of DBTDL were dissolved into 150 ml of toluene. Then the mixture was stirred for 6 h under N.sub.2 atmosphere at 80° C. After then, white precipitation was obtained by mixing the solution and 500 ml of methanol. Finally, the precipitation after suction filtration was vacuum dried for 24 h to obtain PCLDA.

(8) Synthesis of Polymer-Glass Powder Composite Containing Ester Bonds:

(9) 6 g PCLDA, 0.6 g of hydroxybutyl acrylate, 1 g of phenoxetol, 0.03 g of DBTDL, 0.06 g of Irgacure 2959 and 3.6 g of silica R972 were introduced into 10 g of N,N-dimethylformamide. Then the precursor liquid was poured into mold and treated for 1 min by UV light with 385 nm, so as to obtain the polymer-glass powder composite containing ester bonds.

(10) Origami/Kirigami Shaping and Thermal Treatment:

(11) Polymer-glass composite with original specific shape was prepared using laser cutting machine with programs set in advance. After origami/kirigami shaping (for example, performing the origami/kirigami shaping shown in FIG. 1), the shape was fixed by the external force then the composite was put into the oven of 120° C. for 3 h to prepare complex 3D permanent shape. The shaped precursor composite was thermally treated in muffle furnace. The thermal treatment program is heating up at a rate of 1° C./min to 600° C., keeping 600° C. for 2 h, then at a rate of 2° C./min to 1000° C., then keeping 1000° C. for 2 h, finally cooling naturally. After debinding, the green body was thermally treated in a vacuum furnace under −0.01 MPa. The thermal treatment program is heating up at a rate of 3° C./min to 1000° C., then at a rate of 1° C./min to 1200° C., then keeping 1200° C. for 2 h, finally cooling naturally.

(12) The transparency of the sample in present example is 85%.

Example 2 (Disulfide Bonds, the Dynamic Bond Contained in the Molecule which is Introduced into the Network)

(13) The reagent and the source thereof used in Example 2 is represented in Table 2 below.

(14) TABLE-US-00002 TABLE 2 used reagent molecular formula manufacturer 2,2′-dithiodiethanol C.sub.4H.sub.10O.sub.2S.sub.2 Shanghai Aladdin Bio-Chem Technology dibutyltin dilaurate C.sub.32H.sub.64O.sub.4Sn J&K Scientific (DBTDL) hexamethylene OCN(CH.sub.2).sub.6NCO Shanghai diisocyanate (HDI) Aladdin Bio-Chem Technology glycerol C.sub.3H.sub.8O.sub.3 J&K Scientific silica powder R972 SiO.sub.2 EVONIK

(15) Synthesis of Polymer-Glass Powder Composite Containing Disulfide Bonds:

(16) 4.62 g of 2,2′-dithiodiethanol, 5.04 g of hexamethylene diisocyanate, 1.84 g of glycerol, 0.05 g of DBTDL, 0.1 g of Irgacure 2959 and 6.6 g of silica R972 were introduced into a 50 ml glass beaker. Then the precursor liquid was poured into the mold and cured at 70° C. for 24 h, so as to obtain the polymer-glass powder composite containing disulfide bonds.

(17) Origami Shaping and Thermal Treatment:

(18) As Example 1 is shown.

(19) The transparency of the sample in present example is 85%.

Example 3 (D-A Bonds, the Dynamic Bond Introduced into the Network Through Chemical Reaction)

(20) The reagent and the source thereof used in Example 3 is represented in Table 3 below.

(21) TABLE-US-00003 TABLE 3 used reagent molecular formula manufacturer furfuramine C.sub.5H.sub.7NO TCI shanghai 2,2-bis C.sub.21H.sub.24O.sub.4 TCI shanghai (4-glycidoxyphenyl)- propane (BGPP) N,N′-(4,4′- C.sub.21H.sub.14N.sub.2O.sub.4 Sigma-Aldrich China methylenediphenyl) bismaleimide (BM) phenoxyethanol (POE) C.sub.8H.sub.10O.sub.2 Shanghai Aladdin Bio-Chem Technology silica powder R972 SiO.sub.2 EVONIK

(22) Synthesis of Polymer-Glass Powder Composite Containing D-A Bonds:

(23) 7.5 g of furfuramine and 7 g of 2,2-bis (4-glycidoxyphenyl)-propane and were dissolved into 30 ml of N,N-dimethylformamide at 120° C. and reacted for 12 h. Then 5.6 g of N, N′-(4,4′-methylenediphenyl) bismaleimide, 2.6 g of POE and 8.4 g of 8972 were added into the precursor. Then the liquid precursor was poured into the reaction cell and cured at 70° C. for 10 h. The composite was prepared after stoving at 80° C. for 24 h.

(24) Origami/Kirigami Shaping and Thermal Treatment:

(25) As Example 1 is shown.

(26) The transparency of the sample in present example is 90%.

Example 4 (Urethane Bonds, the Dynamic Bond Introduced into the Network Through Chemical Reaction)

(27) The reagent and the source thereof used in Example 4 is represented in Table 4 below.

(28) TABLE-US-00004 TABLE 4 used reagent molecular formula manufacturer 2-hydroxyethyl acrylate C.sub.5H.sub.8O.sub.3 Shanghai Aladdin Bio-Chem Technology dibutyltin dilaurate C.sub.32H.sub.64O.sub.4Sn J&K Scientific (DBTDL) hexamethylene diisocyanate OCN(CH.sub.2).sub.6NCO Shanghai (HDI) Aladdin Bio-Chem Technology Irgacure 2959 C.sub.12H.sub.16O.sub.4 Sigma-Aldrich China silica powder R972 SiO.sub.2 EVONIK

(29) Synthesis of Polyurethane Acrylate (PUA):

(30) 10 g of 2-hydroxyethyl acrylate, 3.7 g of hexaethylene diisocyanate and 0.4 g of DBTDL were mixed. Then the mixture was stirred at 70° C. for 4 h. The PUA was prepared then.

(31) Synthesis of Polymer-Glass Powder Composite Containing Urethane Bonds:

(32) 6 g PUA and 3.6 g of R972 were introduced into 10 g of N,N-dimethylformamide. Then the liquid transparent precursor was poured into the glass cell and treated for 1 min by UV light with 385 nm. The composite was prepared after stoving.

(33) Origami/Kirigami Shaping and Thermal Treatment:

(34) As Example 1 is shown.

(35) The transparency of the sample in present example is 85%.

Example 5 (Hydrogen Bonds)

(36) The reagent and the source thereof used in Example 5 is represented in Table 5 below.

(37) TABLE-US-00005 TABLE 5 used reagent molecular formula manufacturer 2-amino-4-hydroxy-6-methylpyrimidine C.sub.5H.sub.7N.sub.3O Sigma-Aldrich China (Upy) 2-isocyanatoethyl acrylate C.sub.6H.sub.7NO.sub.3 TCI shanghai polyethylene glycol diacrylate (C.sub.2H.sub.4O).sub.n (C.sub.3H.sub.2O.sub.2).sub.2 Sigma-Aldrich China (PEGDA, M.sub.n = 700) triethylamine C.sub.6H.sub.15N J&K Scientific pentaerythritol (C.sub.4H.sub.7O.sub.2S).sub.4C Sigma-Aldrich China tetrakis(3-mercaptopropionate) (PTME) silica powder OX50 SiO.sub.2 EVONIK

(38) Synthesis of 2-Amino-4-Hydroxy-6-Methylpyrimidine Acrylate (UPyA):

(39) 3.75 g of 2-amino-4-hydroxy-6-methylpyrimidine and 4.65 g of 2-isocyanatoethyl acrylate were dissolved into 30 ml of dimethyl sulfoxide at 150° C. Then the mixture was stirred at 150° C. for 15 min. After then, white precipitation was obtained by cooling at room temperature. Finally, the precipitation after suction filtration was vacuum dried for 24 h to obtain UPyA.

(40) Synthesis of Polymer-Glass Powder Composite Containing Hydrogen Bonds:

(41) 7.5 g of UPyA, 7 g of polyethylene glycol diacrylate (M.sub.n=700), 1.84 g of Pentaerythritol tetrakis(3-mercaptopropionate), 0.8 g of Triethylamine and 8.4 g of R972 were dissolved into 20 ml of N,N-Dimethylformamide at 80° C. Then the liquid precursor was poured into the reaction cell and cured at 80° C. for 6 h. The composite was prepared after stoving at 80° C. for 24 h.

(42) Origami/Kirigami Shaping and Thermal Treatment:

(43) As Example 1 is shown.

(44) The transparency of the sample in present example is 85%.

Example 6 (Hydrogel-Ionic Bonds)

(45) The reagent and the source thereof used in Example 6 is represented in Table 6 below.

(46) TABLE-US-00006 TABLE 6 used reagent molecular formula manufacturer sodium alginate (C.sub.6H.sub.7O.sub.6Na).sub.n Sigma-Aldrich China calcium dichloride CaCl.sub.2 TCI shanghai silica powder OX50 SiO.sub.2 EVONIK

(47) Synthesis of Hydrogel-Glass Powder Composite Containing Ionic Bonds:

(48) 5 g of sodium alginate, 10 g of water and 5 g of OX50 were mixed. Then 0.05 g of calcium dichloride was introduced to the solution. The obtained precursor was poured into mold and cured for 24 h.

(49) Origami/Kirigami Shaping and Thermal Treatment:

(50) Polymer-glass composite with original specific shape was prepared using a manual cutter. After origami/kirigami shaping, the shape was fixed then the composite was put into water for 24 h to prepare complex 3D permanent shape. Then the hydrogel was dried at 100° C. for 24 h. The shaped composite was thermally treated in muffle furnace. The thermal treatment program is heating up at a rate of 1° C./min to 600° C., keeping 600° C. for 2 h, then at a rate of 2° C./min to 1000° C., then keeping 1000° C. for 2 h, finally cooling naturally. After debinding, the green body was thermally treated in a vacuum furnace under −0.01 MPa. The thermal treatment program is heating up at a rate of 3° C./min to 1000° C., then at a rate of 1° C./min to 1200° C., then keeping 1200° C. for 2 h, finally cooling naturally.

(51) The transparency of the sample in present example is 80%.

Example 7 (Glass Powder with Low Melting Point)

(52) The reagent and the source thereof used in Example 7 is represented in Table 7 below.

(53) TABLE-US-00007 TABLE 7 used reagent molecular formula manufacturer poly(caprolactone) diacrylate (PCL) C.sub.4H.sub.8O.sub.3(C.sub.6H.sub.10O.sub.2).sub.n Sigma-Aldrich China 2-isocyanatoethyl acrylate C.sub.6H.sub.7NO.sub.3 TCI shanghai dibutyltin dilaurate (DBTDL) C.sub.32H.sub.64O.sub.4Sn J&K Scientific butyl acrylate C.sub.7H.sub.12O.sub.3 TCI shanghai phenoxyethanol (POE) C.sub.8H.sub.10O.sub.2 Shanghai Aladdin Bio-Chem Technology glass powder with low melting point SiO.sub.2 EVONIK (melting point of 600° C.) Irgacure 2959 C.sub.12H.sub.16O.sub.4 Sigma-Aldrich China

(54) Synthesis of Poly(Caprolactone) Diacrylate (PCLDA):

(55) As Example 1 is shown.

(56) Synthesis of Polymer-Glass Powder (Low Melting Point) Composite Containing Ester Bond:

(57) 6 g PCLDA, 0.6 g of hydroxybutyl acrylate, 1 g of phenoxetol, 0.03 g of DBTDL, 0.06 g of Irgacure 2959 and 3.6 g of glass powder with a low melting point were introduced into 10 g of N,N-dimethylformamide. Then the liquid transparent precursor was poured into the glass cell and treated for 1 min by UV light with 385 nm. The composite was prepared after stoving.

(58) Origami/Kirigami Shaping and Thermal Treatment:

(59) Polymer-glass composite with original specific shape was prepared using laser cutting with programs set in advance. After origami/kirigami shaping, the shape was fixed then the composite was put into the oven of 120° C. for 3 h to prepare complex 3D permanent shape. The shaped composite was thermally treated in a muffle furnace. The thermal treatment program is heating up at a rate of 1° C./min to 600° C., keeping 600° C. for 2 h, finally cooling naturally.

(60) The transparency of the sample in present example is 90%.

Example 8 (Glass Powder Obtained Through Sol-Gel)

(61) The reagent and the source thereof used in Example 8 is represented in Table 8 below.

(62) TABLE-US-00008 TABLE 8 used reagent molecular formula manufacturer poly(caprolactone) diacrylate (PCL) C.sub.4H.sub.8O.sub.3(C.sub.6H.sub.10O.sub.2).sub.n Sigma-Aldrich China 2-isocyanatoethyl acrylate C.sub.6H.sub.7NO.sub.3 TCI shanghai dibutyltin dilaurate (DBTDL) C.sub.32H.sub.64O.sub.4Sn J&K Scientific butyl acrylate C.sub.7H.sub.12O.sub.3 TCI shanghai phenoxyethanol (POE) C.sub.8H.sub.10O.sub.2 Shanghai Aladdin Bio-Chem Technology tetraethylorthosilicate Si(OC.sub.2H.sub.5).sub.4 J&K Scientific Irgacure 2959 C.sub.12H.sub.16O.sub.4 Sigma-Aldrich China

(63) Synthesis of Glass Powder by Sol-Gel:

(64) 9.62 g of tetraethylorthosilicate, 6.82 g of ethanol and 5.76 g of water were mixed and the pH of the solution was adjusted to 2 using hydrochloric acid. The reaction solution was then stirred at 30° C. for 12 h and dried at 80° C. for 24 h. Glass powder was obtained after grinding.

(65) Synthesis of Poly(Caprolactone) Diacrylate (PCLDA):

(66) As Example 1 is shown.

(67) Synthesis of Polymer-Glass Powder Composite Containing Ester Bond:

(68) 6 g PCLDA, 0.6 g of hydroxybutyl acrylate, 1 g of phenoxetol, 0.03 g of DBTDL, 0.06 g of Irgacure 2959 and 3.6 g of sol-gel glass powder were introduced into 10 g of N,N-dimethylformamide. Then the liquid transparent precursor was poured into the glass cell and treated for 1 min by UV light with 385 nm. The composite was prepared after stoving.

(69) Origami/Kirigami Shaping and Thermal Treatment:

(70) As Example 1 is shown.

(71) The transparency of the sample in present example is 95%.

Example 9 (Color-Developing Components is Added)

(72) The reagent and the source thereof used in Example 9 is represented in Table 9 below.

(73) TABLE-US-00009 TABLE 9 used reagent molecular formula manufacturer poly(caprolactone) diacrylate (PCL) C.sub.4H.sub.8O.sub.3(C.sub.6H.sub.10O.sub.2).sub.n Sigma-Aldrich China 2-isocyanatoethyl acrylate C.sub.6H.sub.7NO.sub.3 TCI shanghai dibutyltin dilaurate (DBTDL) C.sub.32H.sub.64O.sub.4Sn J&K Scientific butyl acrylate C.sub.7H.sub.12O.sub.3 TCI shanghai phenoxyethanol (POE) C.sub.8H.sub.10O.sub.2 Shanghai Aladdin Bio-Chem Technology silica powder R972 SiO.sub.2 EVONIK chromium nitrate nonahydrate Cr(NO.sub.3).sub.3•9H.sub.2O Shanghai Aladdin Bio-Chem Technology Irgacure 2959 C.sub.12H.sub.16O.sub.4 Sigma-Aldrich China

(74) Synthesis of Poly(Caprolactone) Diacrylate (PCLDA):

(75) As Example 1 is shown.

(76) Synthesis of Functional Polymer-Glass Powder Composite Containing Ester Bonds:

(77) 6 g PCLDA, 0.6 g of hydroxybutyl acrylate, 1 g of phenoxetol, 0.03 g of DBTDL, 0.06 g of Irgacure 2959, 3.6 g of R972 and 0.06 g of chromium nitrate nonahydrate were introduced into 10 g of N,N-dimethylformamide. Then the liquid transparent precursor was poured into the glass cell and treated for 1 min by UV light with 385 nm. The composite was prepared after stoving.

(78) Origami/Kirigami Shaping and Thermal Treatment:

(79) As Example 1 is shown.

(80) The final origami/kirigami glass is transparent and green. The transparency of the sample in present example is 75%.

(81) It will be apparent to those skilled in the art that various modifications and variations can be made to the disclosed embodiments without departing from the scope or spirit of the disclosure. In view of the foregoing, it is intended that the disclosure covers modifications and variations provided that they fall within the scope of the following claims and their equivalents.