WO2020006720A1 - 一种透明可卷曲折叠聚硅氧烷膜及其制备与自修复方法 - Google Patents

一种透明可卷曲折叠聚硅氧烷膜及其制备与自修复方法 Download PDF

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WO2020006720A1
WO2020006720A1 PCT/CN2018/094572 CN2018094572W WO2020006720A1 WO 2020006720 A1 WO2020006720 A1 WO 2020006720A1 CN 2018094572 W CN2018094572 W CN 2018094572W WO 2020006720 A1 WO2020006720 A1 WO 2020006720A1
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diisocyanate
polysiloxane
foldable
transparent
chloroalkane
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French (fr)
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梁国正
张又豪
顾嫒娟
袁莉
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Suzhou University
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Suzhou University
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Priority to PCT/CN2018/094572 priority Critical patent/WO2020006720A1/zh
Priority to US16/759,328 priority patent/US11479671B2/en
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/775—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C08L83/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/61—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/38—Polysiloxanes modified by chemical after-treatment
    • C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
    • C08G77/388—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/38—Polysiloxanes modified by chemical after-treatment
    • C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
    • C08G77/392—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/08—Heat treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/32—Compounds containing nitrogen bound to oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/37—Thiols
    • C08K5/372—Sulfides, e.g. R-(S)x-R'
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/02—Polyureas
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/02—Polyureas
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2383/04—Polysiloxanes
    • C08J2383/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2475/02—Polyureas
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2483/04—Polysiloxanes
    • C08J2483/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/10—Transparent films; Clear coatings; Transparent materials

Definitions

  • the invention relates to a polymer film and a preparation method thereof, in particular to a transparent rollable and foldable polysiloxane film, and a preparation and self-repairing method thereof, and belongs to the technical field of polymer materials.
  • Organic electronic devices usually have a multilayer structure and are mainly composed of a substrate (such as a silicon wafer, glass or plastic), a dielectric, a semiconductor (or an active layer), and a conductive electrode.
  • a substrate such as a silicon wafer, glass or plastic
  • dielectric such as a silicon wafer, glass or plastic
  • semiconductor or an active layer
  • a conductive electrode such as a silicon electrode
  • an organic electronic device using a silicon wafer or glass as a substrate will cause the device to have great rigidity and can only undergo extremely limited bending. Therefore, currently, flexible transparent electronic devices are mainly manufactured by using a commercial polyimide (PI) or polyethylene terephthalate (PET) as a substrate and depositing a functional layer thereon.
  • PI polyimide
  • PET polyethylene terephthalate
  • a rigid PDMS-based crosslinking network was obtained by introducing a trifunctional boron-oxane as a crosslinking point, and its Young's modulus and tensile strength reached 182 MPa and 9.46 MPa, respectively. It is the highest value among current PDMS-based self-healing materials, but the elongation at break of this rigid PDMS-based cross-linked network is less than 10%. At the same time, the participation of water during the self-healing process is likely to cause the risk of short circuit of the device. Has excellent mechanical properties, but still not suitable for flexible transparent electronic devices.
  • the rollable folding substrate is a This project has significant application value.
  • the invention aims at the shortcomings of the prior art, and provides a transparent roll-foldable polysiloxane film and a method for preparing and self-repairing the same.
  • the disclosed polysiloxane film has the characteristics of good flexibility, transparency, low cost, and easy processing, and can be widely used.
  • Si-O with a larger bond angle and bond length is more likely to occur than CC.
  • Internal rotation realizes chain movement, so it is more flexible.
  • This feature meets the requirements of polymer chains for reversible self-healing materials.
  • Flexible transparent electronic devices based on it have both high stretchability and good performance. Self-healing ability.
  • a method for preparing a transparent roll-foldable polysiloxane film includes the following steps:
  • a self-repairing method for a damaged transparent roll-foldable polysiloxane film includes the steps of bonding the damaged surface of the damaged transparent roll-foldable polysiloxane film, and then at a temperature of 100-140 Heating at 0.5 ° C for 2 hours to complete the self-repair of the damaged transparent roll-foldable polysiloxane film;
  • the preparation method of the transparent roll-foldable polysiloxane film includes the following steps:
  • the invention also discloses the application of a hyperbranched polysiloxane containing an amino group at the terminal, an isocyanate containing a disulfide, and a linear polydimethylsiloxane in the preparation of a transparent roll-foldable polysiloxane film, which is characterized in that:
  • the preparation method of hyperbranched polysiloxane containing amino group at the terminal, isocyanate containing disulfide and linear polydimethylsiloxane is as follows:
  • a specific method for preparing a transparent, roll-foldable polysiloxane film by using a hyperbranched polysiloxane containing an amino group at the end, a disulfide-containing isocyanate, and a linear polydimethylsiloxane is as follows: 2. Amino-containing hyperbranched polysiloxane, disulfide-containing isocyanate and chloroalkane are mixed, poured into a mold, and dried to obtain a transparent, curly and foldable polysiloxane film.
  • the alcohol solvent is one or more of methanol, ethanol, n-propanol, isopropanol, n-butanol, and isobutanol; and the chloroalkane is dichloromethane and chloroform One or more of 1,2-dichloroethane;
  • the diisocyanate is a diisocyanate compound or a diisocyanate derivative prepared from a diisocyanate compound;
  • the diisocyanate compound is toluene diisocyanate (TDI) , Isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), dicyclohexylmethane diisocyanate (HMDI), hexamethylene diisocyanate (HDI), lysine diisocyanate (LDI), One or more of xylylene diisocyanate (XDI), naphthalene diisocyanate (NDI),
  • step (1) the mass ratio of ⁇ -aminopropyltriethoxysilane, water and alcohol solvent is 100: (10-15): (100-200); in step (2), The mass ratio of 2,2'-dithiodiethanol, diisocyanate and chloroalkane is (75-80): (160-270): (1000-1500); in step (3), the bis (3-aminopropyl) Group) The mass ratio of the blocked polydimethylsiloxane, diisocyanate and chloroalkane is 100: (10-25): (1000-1500); in step (4), the linear polydimethylsiloxane The mass ratio of amino-containing hyperbranched polysiloxane, disulfide-containing isocyanate and chloroalkane is 50: (3-6): (10-15): (100-150).
  • step (1) the mixing temperature is room temperature, the reaction temperature is 60 to 80 ° C, and the reaction time is 4 to 6 hours; in step (2), the mixing temperature is room temperature and the reaction temperature is 60 to 80 ° C, the reaction time is 2 to 4h; in step (3), the mixing temperature is room temperature, the reaction temperature is 60 to 80 ° C, and the reaction time is 4 to 6h; in step (4), the mixed The temperature is room temperature.
  • the room temperature refers to an indoor temperature, and preferably 20 to 30 ° C.
  • step (1) the solvent is distilled off under reduced pressure after the reaction is completed to obtain a hyperbranched polysiloxane containing an amino group at the terminal; in step (2), the solvent is distilled off under reduced pressure after the reaction is completed to obtain a solvent containing Isocyanate of thioether; in step (3), after the reaction is completed, the solvent is distilled off under reduced pressure to obtain linear polydimethylsiloxane.
  • the damage is fracture.
  • the fracture surface is fixed and bonded with a clamp, and self-repair is completed by heating.
  • the transparent roll-foldable polysiloxane film prepared according to the above preparation method of the transparent roll-foldable polysiloxane film.
  • the method for preparing the transparent and rollable folding polysiloxane film disclosed in the present invention is as follows:
  • the polysiloxane film provided by the present invention has not only a high modulus and a high tensile strength, but also a multi-scale cross-linked structure by constructing a dynamic hydrogen bond cross-linking and a permanent chemical cross-linking of a hyperbranched polysiloxane. It has high glass transition temperature and high toughness.
  • the polysiloxane film provided by the present invention regulates the exchange rate of hydrogen bond formation / dissociation and disulfide through temperature, and realizes the reversible self-repair of high-rigidity and high-strength polysiloxane materials, and the self-repair efficiency (> 90%) is comparable to existing silicone elastomers.
  • the polysiloxane film provided by the present invention has high rigidity, can not only be bent multiple times, but also can be repeatedly folded and curled without creases remaining.
  • Example 1 is a nuclear magnetic resonance hydrogen spectrum ( 1 H-NMR) of a terminally-containing amino-containing hyperbranched polysiloxane (HPSi) prepared in Example 1 of the present invention
  • Example 2 is a nuclear magnetic resonance silicon spectrum ( 29 Si-NMR) of a terminally-containing amino-containing hyperbranched polysiloxane (HPSi) prepared in Example 1 of the present invention;
  • Example 3 is an infrared spectrum of a disulfide-containing isocyanate and a transparent roll-foldable polysiloxane film prepared in Example 1 of the present invention
  • FIG. 4 is a thermal weight loss curve of the transparent rollable and folded polysiloxane film prepared in Example 1 of the present invention
  • FIG. 5 is a dynamic mechanical curve of a transparent roll-foldable polysiloxane film prepared in Example 1 of the present invention
  • FIG. 6 is a digital photograph of the curl-folding effect of the transparent roll-foldable polysiloxane film prepared in Example 1 of the present invention.
  • FIG. 7 is an ultraviolet-visible light spectrum of the transparent roll-foldable polysiloxane film prepared in Example 1 of the present invention.
  • FIG. 8 is a tensile stress-strain curve of the transparent rollable folding silicone film prepared in Example 1 of the present invention before and after self-repair;
  • Example 9 is a digital photograph of the self-repairing effect of the transparent roll-foldable polysiloxane film prepared in Example 1 of the present invention.
  • FIG. 10 is a polarization photomicrograph of the self-healing effect of the transparent roll-foldable polysiloxane film prepared in Example 1 of the present invention and the disulfide-free polysiloxane film prepared in Comparative Example 1.
  • FIG. 10 is a polarization photomicrograph of the self-healing effect of the transparent roll-foldable polysiloxane film prepared in Example 1 of the present invention and the disulfide-free polysiloxane film prepared in Comparative Example 1.
  • the section of the damaged transparent roll-foldable polysiloxane film was fixed with a clamp and closely adhered, and then heated at a temperature of 100 ° C. for 0.5 hours.
  • the stress-strain curves, digital photos of the self-repair effect, and polarized photomicrographs of the stress-strain curves tested after repair are shown in Figures 8, 9, and 10, respectively.
  • the cross section of the damaged disulfide-free polysiloxane film was fixed with a jig and tightly adhered, and then heated at a temperature of 100 ° C for 0.5 hours to complete the repair.
  • FIG. 1 it is a nuclear magnetic resonance ( 1 H-NMR) spectrum of a hyperbranched polysiloxane (HPSi) containing an amino group at the terminal prepared in Example 1 of the present invention.
  • HPSi hyperbranched polysiloxane
  • FIG. 2 it is a nuclear magnetic resonance silicon spectrum ( 29 Si-NMR) of an amino-terminated hyperbranched polysiloxane (HPSi) prepared in Example 1 of the present invention.
  • D, L, and T respectively represent branched, linear, and capped links of hyperbranched siloxane. From the figure, it can be found that the D peak is significantly stronger than the L and T peaks, indicating that branched chains are ubiquitous in HPSi, which further proves that the KH550 monomer has been fully hydrolyzed and condensed.
  • the value of the degree of branching DB is calculated using the following formula (1):
  • FIG. 3 it is an infrared spectrum of a disulfide-containing isocyanate and a transparent roll-foldable polysiloxane film prepared in Example 1 of the present invention.
  • 2,2'-dithio diethanol through isophorone diisocyanate chain extender epigenetic became urethane
  • C O stretching vibration which occurs in the infrared spectrum at 1720cm -1, 2260cm -1 and at the It is the characteristic peak of -NCO in isocyanate containing disulfide.
  • FIG. 4 it is a thermal weight loss curve of the transparent roll-foldable foldable polysiloxane film prepared in Example 1 of the present invention. It can be seen from this that the initial thermal decomposition temperature ( T di ) of the transparent roll-foldable polysiloxane film is 282 ° C, which has good thermal stability.
  • FIG. 5 it is a dynamic mechanical curve of a transparent and rollable folded polysiloxane film prepared in Example 1 of the present invention.
  • the peak temperature of the dielectric loss tangent (Tan ⁇ ) is taken as the glass transition temperature, which shows a single symmetrical Tan ⁇ peak. Therefore, the glass transition temperature of the polysiloxane film prepared in Example 1 is 96 ° C, which is higher than the reversible self-repairing polysiloxane materials reported in the existing literature (the glass transition temperature is generally -120 ⁇ 65 ° C).
  • FIG. 6 it is a digital photograph of the curl-folding effect of the transparent roll-foldable silicone film prepared in Example 1 of the present invention.
  • the transparent roll-foldable polysiloxane film As shown in the figure, after cutting the transparent roll-foldable polysiloxane film into 60 mm ⁇ 60 mm squares, it can be freely transformed between S-shaped bends, forward and reverse folds, or curls, which proves that it has excellent Flexible.
  • PI film and PET film of the same size as a reference they were also folded back and forth twice, and when they were magnified and observed, we could see that the surface of the PI film had transparent but unrecoverable creases (inside the frame). The crease on the PET film is not only irrecoverable but also affects its transparency.
  • FIG. 7 it is an ultraviolet-visible light spectrum of the transparent roll-foldable polysiloxane film prepared in Example 1 of the present invention. It can be seen from the photos that the transparent roll-foldable polysiloxane film has good transparency, and further tested the transmittance of different film thicknesses at 200-800 nm by UV-visible light. It can be seen that with air as the baseline, the thickness of the film is between 400-800 The transmittance in the visible region of nm is more than 80%, and the transmittance at 550nm increases from 86.09% (0.4mm) to 88.63% (0.2mm) as the film thickness decreases.
  • FIG. 8 it is a tensile stress-strain curve before and after self-healing of the transparent roll-foldable polysiloxane film prepared in Example 1 of the present invention.
  • the tensile strength, elongation at break, Young's modulus, and toughness of the original transparent roll-foldable polysiloxane film were 9.25 ⁇ 0.22MPa, 224.21 ⁇ 2.79%, 214.89 ⁇ 18.27MPa, and 16.32, respectively. ⁇ 0.18MPa, with good rigidity and toughness.
  • the tensile strength, elongation at break and toughness of the silicone film after repair were 8.16 ⁇ 0.87MPa, 211.59 ⁇ 5.63%, and 14.91 ⁇ 0.72MPa, respectively, and the corresponding repair efficiency was 94.99%, 94.37%, and 91.36%.
  • the polysiloxane film is bent after the repairing of the surface without cracks appeared after 180 o, maintained good integrity; in the present invention are Young's modulus and tensile strength than the prior art at the same level
  • the elongation at break is 22.4 times of the existing technology, which not only achieves the rigidity that can be achieved by the existing technology, but also takes into account excellent toughness.
  • FIG. 9 it is a digital photograph of the self-healing effect of the transparent roll-foldable polysiloxane film prepared in Example 1 of the present invention.
  • the complete transparent rollable and foldable polysiloxane film is cut open, and the cross section is closely attached to the hot stage and kept at 100 ° C for 30 minutes, and the completely broken two parts of the film are re-fused to form a whole.
  • FIG. 10 it is a polarized photomicrograph of the self-healing effect of the transparent roll-foldable polysiloxane film prepared in Example 1 of the present invention and the disulfide-free polysiloxane film prepared in Comparative Example 1.
  • a polarized light microscope was used to observe the surface morphology of the transparent and rollable folded silicone film after different repair times.
  • a cross section black area in the figure
  • a width of 20 ⁇ m was cut on the surface of the transparent and rollable folded polysiloxane film; the section was then fixed with a clamp and closely attached, at a temperature of 100 ° C. Self-healing under heating.
  • the section of the damaged transparent roll-foldable polysiloxane film was fixed with a jig and closely adhered, and then heated at a temperature of 120 ° C. for 0.8 hours.

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Abstract

本发明公开了一种透明可卷曲折叠聚硅氧烷膜及其制备与自修复方法。将2,2'-二硫二乙醇和二异氰酸酯加入氯代烷中，扩链反应得到含二硫醚的异氰酸酯；将双(3-氨基丙基)封端聚二甲基硅氧烷和二异氰酸酯加入氯代烷中，扩链反应得到线性聚二甲基硅氧烷；将线性聚二甲基硅氧烷与末端含氨基的超支化聚硅氧烷溶于氯代烷中，加入含二硫醚的异氰酸酯，混匀后倒入模具，烘干，得到透明可卷曲折叠聚硅氧烷膜。本发明通过室温下氢键的动态物理交联与超支化聚硅氧烷的永久化学交联使所制备的聚硅氧烷膜兼具了刚性与韧性，而在加热条件下氢键解离与二硫醚交换使所制备的聚硅氧烷膜具有良好的可逆自修复性能。

Description

一种透明可卷曲折叠聚硅氧烷膜及其制备与自修复方法 技术领域
本发明涉及一种聚合物膜及其制备方法，特别涉及一种透明可卷曲折叠聚硅氧烷膜及其制备与自修复方法，属于高分子材料技术领域。
 背景技术
随着太阳能电池、传感器、柔性显示器、触控屏与柔性印刷电路板（FPCB）等透明光电器件的飞速发展，具有高透过率的柔性电子器件正逐渐成为研究的热点与方向。有机电子器件通常为多层结构，主要由衬底（如硅片、玻璃或塑料）、电介质、半导体（或活性层）和导电电极组成。其中，以硅片或玻璃为衬底的有机电子器件会导致器件具有很大的刚性，只能发生极为有限的弯曲。因此目前柔性透明电子器件主要以商用聚酰亚胺（PI）或聚对苯二甲酸乙二醇酯（PET）为衬底，通过在其上沉积功能层制造而成。
如同传统电子产品，柔性透明电子器件也会因过度弯曲、意外刮擦或切削等机械损伤而引起损坏与故障，随之而来的还有大量的器材浪费、维护成本上升和原材料损耗等问题。近年来，人们模仿生物体自我愈合损伤并提高生存机率的机制，通过在分子内或分子间引入多种动态键或相互作用，为材料内置可逆自修复性能，有效地恢复材料遭受的机械损伤并延长它们的使用寿命。然而，作为柔性电子器件衬底的PI或PET并不具备可逆自修复能力，无法修复意外发生的断裂或划痕。同时，微型化和便携化的发展趋势不仅要求柔性透明电子器件可弯曲，更对其提出了可卷曲可折叠的要求，这对于PI或PET衬底来说同样难以实现。因此，需要开发一种新型可卷曲折叠的柔性可逆自修复材料来解决这些问题。
在现有研究中，通过在PDMS链端修饰吡啶、三氮唑等基团，并与Co 2+，Fe 3+，Zn 2+金属离子形成动态配价键后，所得改性PDMS弹性体的断裂伸长率较好且室温下普遍具有90％左右的自修复效率，非常适合用于制备电子皮肤、可穿戴传感器与人工肌肉等仿生柔性器件。但是对于太阳能电池、柔性显示器、电容式触摸屏和FPCB等柔性透明电子器件，上述报道的这些高拉伸PDMS基自修复材料却因较差的强度与刚性而无法适用。与之相反，现有技术通过引入三官能度的硼氧六环作为交联点，得到了一种刚性PDMS基交联网络，其杨氏模量和拉伸强度分别达到182MPa和9.46MPa，均为目前PDMS基自修复材料中的最高值，但是这种刚性PDMS基交联网络的断裂伸长率<10%，同时自修复过程中需水的参与，易造成器件短路的危险，因此虽然它具有优异的力学性能，但是仍然不适用于柔性透明电子器件。
综上所述，开发一种具有高透过率、优异力学强度和高韧性的PDMS基材，克服商用PI与PET的缺陷，作为新型可逆自修复柔性透明电子器件的可卷曲折叠衬底是一项具有重大应用价值的课题。
 技术问题
本发明针对现有技术的不足，提供一种透明可卷曲折叠聚硅氧烷膜及其制备与自修复方法。本发明公开的聚硅氧烷膜具有柔性好、透明、低成本和易加工等特点而可被广泛使用，从链结构上讲，键角与键长更大的Si-O比C-C更容易发生内旋转实现链段运动，因而柔性更好，这一特点符合可逆自修复材料对聚合物链段高运动性的要求，以其为基材的柔性透明电子器件兼具了高拉伸性和良好的自修复能力。
 技术解决方案
为达到上述目的，本发明所采用的技术方案是：
一种透明可卷曲折叠聚硅氧烷膜的制备方法，包括如下步骤：
（1）将γ-氨丙基三乙氧基硅烷、水和醇溶剂混合后，反应得到末端含氨基的超支化聚硅氧烷；
（2）将2,2'-二硫二乙醇、二异氰酸酯和氯代烷混合后，反应得到含二硫醚的异氰酸酯；
（3）将双(3-氨基丙基)封端聚二甲基硅氧烷、二异氰酸酯和氯代烷混合后，反应得到线性聚二甲基硅氧烷；
（4）将线性聚二甲基硅氧烷、含氨基的超支化聚硅氧烷、含二硫醚的异氰酸酯和氯代烷混合后，倒入模具，烘干得到透明可卷曲折叠聚硅氧烷膜。
一种受损的透明可卷曲折叠聚硅氧烷膜的自修复方法，包括如下步骤，将受损的透明可卷曲折叠聚硅氧烷膜的受损面贴合，然后在温度为100～140℃的条件下加热0.5～2小时，完成受损的透明可卷曲折叠聚硅氧烷膜的自修复；所述透明可卷曲折叠聚硅氧烷膜的制备方法包括以下步骤：
（1）将γ-氨丙基三乙氧基硅烷、水和醇溶剂混合后，反应得到末端含氨基的超支化聚硅氧烷；
（2）将2,2'-二硫二乙醇、二异氰酸酯和氯代烷混合后，反应得到含二硫醚的异氰酸酯；
（3）将双(3-氨基丙基)封端聚二甲基硅氧烷、二异氰酸酯和氯代烷混合后，反应得到线性聚二甲基硅氧烷；
（4）将线性聚二甲基硅氧烷、含氨基的超支化聚硅氧烷、含二硫醚的异氰酸酯和氯代烷混合后，倒入模具，烘干得到透明可卷曲折叠聚硅氧烷膜。
本发明还公开了末端含氨基的超支化聚硅氧烷、含二硫醚的异氰酸酯以及线性聚二甲基硅氧烷在制备透明可卷曲折叠聚硅氧烷膜中的应用，其特征在于，末端含氨基的超支化聚硅氧烷、含二硫醚的异氰酸酯以及线性聚二甲基硅氧烷的制备方法如下：
将γ-氨丙基三乙氧基硅烷、水和醇溶剂混合后，反应得到末端含氨基的超支化聚硅氧烷；
将2,2'-二硫二乙醇、二异氰酸酯和氯代烷混合后，反应得到含二硫醚的异氰酸酯；
将双(3-氨基丙基)封端聚二甲基硅氧烷、二异氰酸酯和氯代烷混合后，反应得到线性聚二甲基硅氧烷。
具体末端含氨基的超支化聚硅氧烷、含二硫醚的异氰酸酯以及线性聚二甲基硅氧烷制备透明可卷曲折叠聚硅氧烷膜的方法为，将线性聚二甲基硅氧烷、含氨基的超支化聚硅氧烷、含二硫醚的异氰酸酯和氯代烷混合后，倒入模具，烘干得到透明可卷曲折叠聚硅氧烷膜。
上述技术方案中，所述醇溶剂为甲醇、乙醇、正丙醇、异丙醇、正丁醇、异丁醇中的一种或几种；所述氯代烷为二氯甲烷、三氯甲烷、1,2-二氯乙烷中的一种或几种；所述的二异氰酸酯为二异氰酸酯化合物或者由二异氰酸酯化合物制备的二异氰酸酯衍生物；所述二异氰酸酯化合物为甲苯二异氰酸酯（TDI）、异佛尔酮二异氰酸酯（IPDI）、二苯基甲烷二异氰酸酯（MDI）、二环己基甲烷二异氰酸酯（HMDI）、六亚甲基二异氰酸酯（HDI）、赖氨酸二异氰酸酯（LDI）、苯二亚甲基二异氰酸酯（XDI）、萘二异氰酸酯（NDI）、四甲基苯二亚甲基二异氰酸酯（TMXDI）、甲基环己基二异氰酸酯（HTDI）中的一种或几种。优选双(3-氨基丙基)封端聚二甲基硅氧烷分子量为1000。
上述技术方案中，步骤（1）中，γ-氨丙基三乙氧基硅烷、水和醇溶剂的质量比为100∶（10～15）∶（100～200）；步骤（2）中，2,2'-二硫二乙醇、二异氰酸酯和氯代烷的质量比为（75～80）∶（160～270）∶（1000～1500）；步骤（3）中，双(3-氨基丙基)封端聚二甲基硅氧烷、二异氰酸酯和氯代烷的质量比为100∶（10～25）∶（1000～1500）；步骤（4）中，线性聚二甲基硅氧烷、含氨基的超支化聚硅氧烷、含二硫醚的异氰酸酯和氯代烷的质量比为50∶（3～6）∶（10～15）∶（100～150）。
上述技术方案中，步骤（1）中，混合的温度为室温，反应的温度为60～80℃，反应的时间为4～6h；步骤（2）中，混合的温度为室温，反应的温度为60～80℃，反应的时间为2～4h；步骤（3）中，混合的温度为室温，反应的温度为60～80℃，反应的时间为4～6h；步骤（4）中，混合的温度为室温。所述室温是指室内温度，优选20～30℃。
上述技术方案中，步骤（1）中，反应结束后减压蒸除溶剂，得到末端含氨基的超支化聚硅氧烷；步骤（2）中，反应结束后减压蒸除溶剂，得到含二硫醚的异氰酸酯；步骤（3）中，反应结束后减压蒸除溶剂，得到线性聚二甲基硅氧烷。
上述技术方案中，所述受损为断裂，将断裂面用夹具固定贴合，加热完成自修复。
根据上述透明可卷曲折叠聚硅氧烷膜的制备方法制备的透明可卷曲折叠聚硅氧烷膜。
本发明公开的透明可卷曲折叠聚硅氧烷膜的制备方法具体如下：
（1）按质量计，在温度为20～30℃的条件下，将100份γ-氨丙基三乙氧基硅烷、10～15份水和100～200份醇溶剂混合均匀后，升至 60～80℃并保温反应4～6h；所得混合液减压蒸除醇溶剂，得到末端含氨基的超支化聚硅氧烷；
（2）按质量计，在温度为20～30℃的条件下，将77份2,2'-二硫二乙醇、169～264份二异氰酸酯和1000～1500份氯代烷混合均匀后，升至 60～80℃并保温反应2～4h；所得混合液减压蒸除氯代烷，得到含二硫醚的异氰酸酯；
（3）按质量计，在温度为20～30℃的条件下，将100份双(3-氨基丙基)封端聚二甲基硅氧烷（PDMS, M n=1000）、13～21份二异氰酸酯和1000～1500份氯代烷混合均匀后，升至 60～80℃并保温反应2～4h；所得混合液减压蒸除氯代烷，得到线性聚二甲基硅氧烷；
（4）按质量计，在温度为20～30℃的条件下，将50份线性聚二甲基硅氧烷、3～6份含氨基的超支化聚硅氧烷、10～15份含二硫醚的异氰酸酯和100～150份氯代烷混合均匀，倒入模具烘干，得到透明可卷曲折叠聚硅氧烷膜。
 有益效果
与现有技术相比，本发明取得的有益效果是：
1、 本发明提供的聚硅氧烷膜通过构建动态氢键交联与超支化聚硅氧烷永久化学交联的多尺度交联结构，不仅具有高模量与高抗拉强度，同时兼具了高玻璃化转变温度和高韧性。
2、本发明提供的聚硅氧烷膜通过温度调控氢键形成/解离与二硫醚的交换速率，实现了高刚性高强度聚硅氧烷材料的可逆自修复，且自修复效率（＞90%）与现有聚硅氧烷弹性体相当。
3、相比现有技术，本发明提供的聚硅氧烷膜在具有高刚性的同时，不仅可以进行多次弯曲，还可反复折叠与卷曲且无折痕残留。
 附图说明
图1是本发明实施例1制备的末端含氨基的超支化聚硅氧烷（HPSi）的核磁共振氢谱（ 1H-NMR）；
图2是本发明实施例1制备的末端含氨基的超支化聚硅氧烷（HPSi）的核磁共振硅谱（ 29Si-NMR）；
图3是本发明实施例1制备的含二硫醚的异氰酸酯与透明可卷曲折叠聚硅氧烷膜的红外谱图；
图4是本发明实施例1制备的透明可卷曲折叠聚硅氧烷膜的热失重曲线；
图5是本发明实施例1制备的透明可卷曲折叠聚硅氧烷膜动态力学曲线；
图6是本发明实施例1制备的透明可卷曲折叠聚硅氧烷膜的卷曲折叠效果数码照片；
图7是本发明实施例1制备的透明可卷曲折叠聚硅氧烷膜的紫外-可见光光谱。
图8是本发明实施例1制备的透明可卷曲折叠聚硅氧烷膜自修复前后的拉伸应力-应变曲线；
图9是本发明实施例1制备的透明可卷曲折叠聚硅氧烷膜的自修复效果的数码照片；
图10是本发明实施例1制备的透明可卷曲折叠聚硅氧烷膜与比较例1制备的无二硫醚聚硅氧烷膜的自修复效果偏光显微照片。
 本发明的实施方式
下面结合附图和实施例，对本发明技术方案作进一步的描述。
实施例1
1）末端含氨基的超支化聚硅氧烷（记作HPSi）的制备
按质量计，在温度为20℃的条件下，将100g γ-氨丙基三乙氧基硅烷（KH550）、10g水和100g乙醇混合均匀后，升至60℃并保温反应4h；所得混合液减压蒸除乙醇后，得到末端含氨基的超支化聚硅氧烷（HPSi），其核磁共振氢谱与核磁共振硅谱分别参见附图1和2。
2）含二硫醚的异氰酸酯的制备
按质量计，在温度为20℃的条件下，将77g 2,2'-二硫二乙醇、224g异佛尔酮二异氰酸酯和1000g二氯甲烷混合均匀后，升至60℃并保温反应2h；所得混合液减压蒸除二氯甲烷后，得到含二硫醚的异氰酸酯，其红外光谱见附图3。
3）线性聚二甲基硅氧烷的制备
按质量计，在温度为20℃的条件下，将100g 双(3-氨基丙基)封端聚二甲基硅氧烷（PDMS, M n=1000）、17.7g异佛尔酮二异氰酸酯和1000g二氯甲烷混合均匀后，升至60℃并保温反应2h；所得混合液减压蒸除二氯甲烷后，得到线性聚二甲基硅氧烷。
4）透明可卷曲折叠聚硅氧烷膜的制备
按质量计，在温度为20℃的条件下，将50g线性聚二甲基硅氧烷、3.6g HPSi、10g含二硫醚的异氰酸酯和100g二氯甲烷混合均匀，倒入模具烘干，得到透明可卷曲折叠聚硅氧烷膜，其红外谱图、热失重曲线、动态力学曲线、卷曲折叠效果的数码照片、紫外-可见光光谱和拉伸应力-应变曲线分别见附图3、4、5、6、7和8。
5）透明可卷曲折叠聚硅氧烷膜的自修复方法
将受损的透明可卷曲折叠聚硅氧烷膜的断面用夹具固定并紧密贴合，然后在温度为100℃的条件下加热0.5小时。其修复后测试的应力-应变曲线、自修复效果的数码照片与偏光显微照片分别见附图8、9和10。
比较例1 无二硫醚聚硅氧烷膜的制备
按质量计，在温度为20℃的条件下，将50g线性聚二甲基硅氧烷、3.6g HPSi、4g异佛尔酮二异氰酸酯和100g二氯甲烷混合均匀，倒入模具烘干，得到无二硫醚聚硅氧烷膜。
将受损的无二硫醚聚硅氧烷膜的断面用夹具固定并紧密贴合，然后在温度为100℃的条件下加热0.5小时，完成修复。
比较例1无二硫醚聚硅氧烷膜的自修复效果偏光显微照片见附图10。
参见附图1，它是本发明实施例1制备的末端含氨基的超支化聚硅氧烷（HPSi）的核磁共振氢谱（ 1H-NMR）。由图可知，δ=1.21ppm处的特征峰为Si-O-CH 2CH 3上甲基（b）的H，但是其H的个数与氨丙基上任意C（图中c,d或e）上H的个数之比为3:2，远远小于KH550对应的9:2，说明KH550之间水解缩合生成了Si-O-Si。
参见附图2，它是本发明实施例1制备的末端含氨基的超支化聚硅氧烷（HPSi）的核磁共振硅谱（ 29Si-NMR）。其中D，L，T分别代表了超支化硅氧烷的支化链节，线性链节和封端链节。从图中可以发现D峰明显强于L峰和T峰，说明支化链节在HPSi中普遍存在，进一步证明了KH550单体已经充分水解缩合。根据图中D和L对应的积分面积，采用如下式（1）公式计算支化度DB的值：
Figure dest_path_image001a
   （1）
通过计算可知，HPSi的DB为0.86，接近于树枝状分子的DB= 1，说明HPSi的分子结构与树枝状分子相近，具有较低的粘度和较好的溶解性，并且表面富含活泼氨基，具有高活性与反应性。
参见附图3，它是本发明实施例1制备的含二硫醚的异氰酸酯与透明可卷曲折叠聚硅氧烷膜的红外谱图。2,2'-二硫二乙醇经过异佛尔酮二异氰酸酯扩链后生成了氨基甲酸酯，其红外谱图中C=O的伸缩振动峰出现1720cm -1处，而2260cm -1处则是含二硫醚的异氰酸酯中-NCO特征峰。
在透明可卷曲折叠聚硅氧烷膜的红外谱图中，3318cm -1与1560cm -1处的特征峰分别为-NH-的伸缩振动与弯曲振动峰，而1630cm -1处的特征峰则是脲基中C=O的伸缩振动峰，这说明PDMS与异佛尔酮二异氰酸酯的扩链反应以及随后含二硫醚的异氰酸酯进一步与线性聚二甲基硅氧烷或HPSi反应生成了大量脲基。PDMS与异氟尔酮中的-CH 3的伸缩振动与弯曲振动峰分别出现在2960 cm -1 与1260cm -1处；1080与1025cm -1处的宽峰则是线性聚二甲基硅氧烷和HPSi中Si-O-Si的特征伸缩振动峰，而800cm -1处的尖锐吸收峰则是Si-C的伸缩振动峰；2260cm -1处未出现-NCO特征峰则说明所制备聚硅氧烷膜中-NCO已经与扩链后的线性聚二甲基硅氧烷和HPSi中的-NH 2反应完全。
参见附图4，它是本发明实施例1制备的透明可卷曲折叠聚硅氧烷膜的热失重曲线。从中可知，透明可卷曲折叠聚硅氧烷膜的起始热分解温度（ T di）为282℃，具有良好的热稳定性。
参见附图5，它是本发明实施例1制备的透明可卷曲折叠聚硅氧烷膜动态力学曲线。其中介质损耗角正切（Tanδ）的峰值温度作为玻璃化转变温度，其呈现单一对称的Tanδ峰。因此实施例1制备的聚硅氧烷膜的玻璃化转变温度为96℃，高于现有文献报道的可逆自修复聚硅氧烷材料（玻璃化转变温度一般为-120~65℃）。
参见附图6，它是本发明实施例1制备的透明可卷曲折叠聚硅氧烷膜的卷曲折叠效果数码照片。如图所示，将透明可卷曲折叠聚硅氧烷膜裁剪为60 mm×60 mm大小的正方形后，可在S型弯曲、正反折叠或卷曲等形状之间自由变换，证明其具有优异的柔韧性。将相同大小的PI膜与PET膜作为参照，同样对它们正反折叠两次，对它们的折叠处放大观察，可以看到，PI膜表面产生了透明但无法恢复的折痕（框内），而PET膜上的折痕不但无法恢复且影响其透明性，在背景纸的字母C上留有一道明显的白线（框内）。与它们相反，透明可卷曲折叠聚硅氧烷膜的折叠处无痕迹残留，背景纸上的字迹依然清晰可见，说明实施例1制备的聚硅氧烷膜可有效克服PI与PET的缺陷，是一种可折叠卷曲的新型材料。
参见附图7，它是本发明实施例1制备的透明可卷曲折叠聚硅氧烷膜的紫外-可见光光谱。从照片中可以看出透明可卷曲折叠聚硅氧烷膜具有良好的透明度，进一步通过紫外-可见光测试了200-800 nm下不同膜厚的透过率。可以看到，以空气作为基线，不同厚度的膜在400-800 nm可见光区域的透过率均在80%以上，其中550nm处的透过率随着膜厚的减小从86.09% （0.4mm）上升至88.63 % （0.2mm）。
参见附图8，它是本发明实施例1制备的透明可卷曲折叠聚硅氧烷膜自修复前后的拉伸应力-应变曲线。通过拉伸测试可知，原始透明可卷曲折叠聚硅氧烷膜的抗拉强度、断裂伸长率、杨氏模量与韧性分别为9.25±0.22MPa、224.21±2.79%、214.89±18.27MPa和16.32±0.18MPa，具有良好的刚性与韧性。修复后聚硅氧烷膜的抗拉强度、断裂伸长率与韧性分别为8.16±0.87MPa、211.59±5.63%和14.91±0.72MPa，对应的修复效率为94.99%，94.37%和91.36%。如照片所示，将修复后的聚硅氧烷膜弯曲180 o后上下表面无裂痕出现，保持了良好的完整性；本发明在杨氏模量与抗拉强度均超过现有技术水平的同时，断裂伸长率为现有技术22.4倍，不仅实现了现有技术所能达到的刚性，也兼顾了优异的韧性。
参见附图9，它是本发明实施例1制备的透明可卷曲折叠聚硅氧烷膜的自修复效果的数码照片。如图所示，将完整的透明可卷曲折叠聚硅氧烷膜切开，断面紧密贴合放置于热台上100℃保持30 min后，完全断裂的两部分膜重新融合连接成一个整体。
参见附图10，它是本发明实施例1制备的透明可卷曲折叠聚硅氧烷膜与比较例1制备的无二硫醚聚硅氧烷膜自修复效果偏光显微照片。采用偏光显微镜观察透明可卷曲折叠聚硅氧烷膜在不同修复时间后受损处的表面形貌。如图所示，在透明可卷曲折叠聚硅氧烷膜表面切割了一道宽为20μm的十字断面（图中黑色区域）；随后将断面用夹具固定并紧密贴合，在温度为100℃的条件下加热自修复。随着修复时间延长，十字断面逐渐变窄缩小，并从不透光的黑色区域逐渐变为透明状；在修复时间达到30 min时，断面完全修复。与之相反，无二硫醚聚硅氧烷膜表面的十字断面在相同的自修复条件下，未能从不透光的黑色状恢复至透明状，断面仅宽度有所变小，这说明HPSi在膜中形成永久交联后，极大地束缚了柔性PDMS链段的运动，仅依靠加热至100℃使氢键解离而产生的链扩散是不能完成自修复的，因而引入二硫醚是透明可卷曲折叠聚硅氧烷膜获得良好自修复能力的关键。
实施例2
1）末端含氨基的超支化聚硅氧烷（记作HPSi）的制备
按质量计，在温度为25℃的条件下，将100g γ-氨丙基三乙氧基硅烷（KH550）、12.5g水和150g甲醇混合均匀后，升至70℃并保温反应5h；所得混合液减压蒸除甲醇后，得到末端含氨基的超支化聚硅氧烷（HPSi）。
2）含二硫醚的异氰酸酯的制备
按质量计，在温度为25℃的条件下，将77g 2,2'-二硫二乙醇、169g六亚甲基二异氰酸酯和1100g三氯甲烷混合均匀后，升至70℃并保温反应2.5h；所得混合液减压蒸除三氯甲烷后，得到含二硫醚的异氰酸酯。
3）线性聚二甲基硅氧烷的制备
按质量计，在温度为25℃的条件下，将100g 双(3-氨基丙基)封端聚二甲基硅氧烷（PDMS, M n=1000）、13.4g六亚甲基二异氰酸酯和1100g三氯甲烷混合均匀后，升至70℃并保温反应2.5h；所得混合液减压蒸除三氯甲烷后，得到线性聚二甲基硅氧烷。
4）透明可卷曲折叠聚硅氧烷膜的制备
按质量计，在温度为25℃的条件下，将50g线性聚二甲基硅氧烷、4g HPSi、12g含二硫醚的异氰酸酯和125g三氯甲烷混合均匀，倒入模具烘干，得到透明可卷曲折叠聚硅氧烷膜。
5）透明可卷曲折叠聚硅氧烷膜的自修复方法
将受损的透明可卷曲折叠聚硅氧烷膜的断面用夹具固定并紧密贴合，然后在温度为110℃的条件下加热0.6小时；修复后聚硅氧烷膜的抗拉强度、断裂伸长率与韧性对应的修复效率为92.89%，92.17%和91.06%。
实施例3
1）末端含氨基的超支化聚硅氧烷（记作HPSi）的制备
按质量计，在温度为30℃的条件下，将100g γ-氨丙基三乙氧基硅烷（KH550）、15g水和200g正丙醇混合均匀后，升至80℃并保温反应6h；所得混合液减压蒸除正丙醇后，得到末端含氨基的超支化聚硅氧烷（HPSi）。
2）含二硫醚的异氰酸酯的制备
按质量计，在温度为30℃的条件下，将77g 2,2'-二硫二乙醇、264g二环己基甲烷二异氰酸酯和1200g1,2-二氯乙烷混合均匀后，升至80℃并保温反应3h；所得混合液减压蒸除1,2-二氯乙烷后，得到含二硫醚的异氰酸酯。
3）线性聚二甲基硅氧烷的制备
按质量计，在温度为30℃的条件下，将100g 双(3-氨基丙基)封端聚二甲基硅氧烷（PDMS, M n=1000）、20.8g二环己基甲烷二异氰酸酯和1200g1,2-二氯乙烷混合均匀后，升至80℃并保温反应3h；所得混合液减压蒸除1,2-二氯乙烷后，得到线性聚二甲基硅氧烷。
4）透明可卷曲折叠聚硅氧烷膜的制备
按质量计，在温度为30℃的条件下，将50g线性聚二甲基硅氧烷、5g HPSi、15g含二硫醚的异氰酸酯和150g1,2-二氯乙烷混合均匀，倒入模具烘干，得到透明可卷曲折叠聚硅氧烷膜。
5）透明可卷曲折叠聚硅氧烷膜的自修复方法
将受损的透明可卷曲折叠聚硅氧烷膜的断面用夹具固定并紧密贴合，然后在温度为115℃的条件下加热0.7小时；修复后聚硅氧烷膜的抗拉强度、断裂伸长率与韧性对应的修复效率为93.01%，92.67%和90.86%。
实施例4
1）末端含氨基的超支化聚硅氧烷（记作HPSi）的制备
按质量计，在温度为22℃的条件下，将100g γ-氨丙基三乙氧基硅烷（KH550）、11g水、100g甲醇与100g乙醇混合均匀后，升至65℃并保温反应4.5h；所得混合液减压蒸除甲醇与乙醇后，得到末端含氨基的超支化聚硅氧烷（HPSi）。
2）含二硫醚的异氰酸酯的制备
按质量计，在温度为22℃的条件下，将77g 2,2'-二硫二乙醇、125g二苯基甲烷二异氰酸酯、106g萘二异氰酸酯、600g二氯甲烷与700g三氯甲烷混合均匀后，升至65℃并保温反应3.5h；所得混合液减压蒸除二氯甲烷与三氯甲烷后，得到含二硫醚的异氰酸酯。
3）线性聚二甲基硅氧烷的制备
按质量计，在温度为22℃的条件下，将100g 双(3-氨基丙基)封端聚二甲基硅氧烷（PDMS, M n=1000）、10g二苯基甲烷二异氰酸酯、8.4g萘二异氰酸酯、600g二氯甲烷与700g三氯甲烷混合均匀后，升至65℃并保温反应3.5h；所得混合液减压蒸除二氯甲烷与三氯甲烷后，得到线性聚二甲基硅氧烷。
4）透明可卷曲折叠聚硅氧烷膜的制备
按质量计，在温度为22℃的条件下，将50g线性聚二甲基硅氧烷、6g HPSi、11g含二硫醚的异氰酸酯、60g二氯甲烷与60g三氯甲烷混合均匀，倒入模具烘干，得到透明可卷曲折叠聚硅氧烷膜。
5）透明可卷曲折叠聚硅氧烷膜的自修复方法
将受损的透明可卷曲折叠聚硅氧烷膜的断面用夹具固定并紧密贴合，然后在温度为120℃的条件下加热0.8小时。

Claims (10)

  1. 一种透明可卷曲折叠聚硅氧烷膜的制备方法，其特征在于，包括如下步骤：
    （1）将γ-氨丙基三乙氧基硅烷、水和醇溶剂混合后，反应得到末端含氨基的超支化聚硅氧烷；
    （2）将2,2'-二硫二乙醇、二异氰酸酯和氯代烷混合后，反应得到含二硫醚的异氰酸酯；
    （3）将双(3-氨基丙基)封端聚二甲基硅氧烷、二异氰酸酯和氯代烷混合后，反应得到线性聚二甲基硅氧烷；
    （4）将线性聚二甲基硅氧烷、含氨基的超支化聚硅氧烷、含二硫醚的异氰酸酯和氯代烷混合后，倒入模具，烘干得到透明可卷曲折叠聚硅氧烷膜。
  2. 一种受损的透明可卷曲折叠聚硅氧烷膜的自修复方法，其特征在于，包括如下步骤，将受损的透明可卷曲折叠聚硅氧烷膜的受损面贴合，然后于100～140℃下加热0.5～2小时，完成受损的透明可卷曲折叠聚硅氧烷膜的自修复；所述透明可卷曲折叠聚硅氧烷膜的制备方法包括以下步骤：
    （1）将γ-氨丙基三乙氧基硅烷、水和醇溶剂混合后，反应得到末端含氨基的超支化聚硅氧烷；
    （2）将2,2'-二硫二乙醇、二异氰酸酯和氯代烷混合后，反应得到含二硫醚的异氰酸酯；
    （3）将双(3-氨基丙基)封端聚二甲基硅氧烷、二异氰酸酯和氯代烷混合后，反应得到线性聚二甲基硅氧烷；
    （4）将线性聚二甲基硅氧烷、含氨基的超支化聚硅氧烷、含二硫醚的异氰酸酯和氯代烷混合后，倒入模具，烘干得到透明可卷曲折叠聚硅氧烷膜。
  3. 根据权利要求1或者2所述的方法，其特征在于：所述醇溶剂为甲醇、乙醇、正丙醇、异丙醇、正丁醇、异丁醇中的一种或几种；所述氯代烷为二氯甲烷、三氯甲烷、1,2-二氯乙烷中的一种或几种；所述的二异氰酸酯为二异氰酸酯化合物或者由二异氰酸酯化合物制备的二异氰酸酯衍生物；所述二异氰酸酯化合物为甲苯二异氰酸酯、异佛尔酮二异氰酸酯、二苯基甲烷二异氰酸酯、二环己基甲烷二异氰酸酯、六亚甲基二异氰酸酯、赖氨酸二异氰酸酯、苯二亚甲基二异氰酸酯、萘二异氰酸酯、四甲基苯二亚甲基二异氰酸酯、甲基环己基二异氰酸酯中的一种或几种。
  4. 根据权利要求1或者2所述的方法，其特征在于：步骤（1）中，γ-氨丙基三乙氧基硅烷、水和醇溶剂的质量比为100∶（10～15）∶（100～200）；步骤（2）中，2,2'-二硫二乙醇、二异氰酸酯和氯代烷的质量比为（75～80）∶（160～270）∶（1000～1500）；步骤（3）中，双(3-氨基丙基)封端聚二甲基硅氧烷、二异氰酸酯和氯代烷的质量比为100∶（10～25）∶（1000～1500）；步骤（4）中，线性聚二甲基硅氧烷、含氨基的超支化聚硅氧烷、含二硫醚的异氰酸酯和氯代烷的质量比为50∶（3～6）∶（10～15）∶（100～150）。
  5. 根据权利要求1或者2所述的方法，其特征在于：步骤（1）中，混合的温度为室温，反应的温度为60～80℃，反应的时间为4～6h；步骤（2）中，混合的温度为室温，反应的温度为60～80℃，反应的时间为2～4h；步骤（3）中，混合的温度为室温，反应的温度为60～80℃，反应的时间为4～6h；步骤（4）中，混合的温度为室温。
  6. 根据权利要求1或者2所述的方法，其特征在于：步骤（1）中，反应结束后减压蒸除溶剂，得到末端含氨基的超支化聚硅氧烷；步骤（2）中，反应结束后减压蒸除溶剂，得到含二硫醚的异氰酸酯；步骤（3）中，反应结束后减压蒸除溶剂，得到线性聚二甲基硅氧烷。
  7. 根据权利要求2所述受损的透明可卷曲折叠聚硅氧烷膜的自修复方法，其特征在于：所述受损为断裂。
  8. 根据权利要求1所述透明可卷曲折叠聚硅氧烷膜的制备方法制备的透明可卷曲折叠聚硅氧烷膜。
  9. 末端含氨基的超支化聚硅氧烷、含二硫醚的异氰酸酯以及线性聚二甲基硅氧烷在制备透明可卷曲折叠聚硅氧烷膜中的应用，其特征在于，末端含氨基的超支化聚硅氧烷、含二硫醚的异氰酸酯以及线性聚二甲基硅氧烷的制备方法如下：
    将γ-氨丙基三乙氧基硅烷、水和醇溶剂混合后，反应得到末端含氨基的超支化聚硅氧烷；
    将2,2'-二硫二乙醇、二异氰酸酯和氯代烷混合后，反应得到含二硫醚的异氰酸酯；
    将双(3-氨基丙基)封端聚二甲基硅氧烷、二异氰酸酯和氯代烷混合后，反应得到线性聚二甲基硅氧烷。
  10. 根据权利要求9所述的应用，其特征在于：末端含氨基的超支化聚硅氧烷、含二硫醚的异氰酸酯以及线性聚二甲基硅氧烷制备透明可卷曲折叠聚硅氧烷膜的方法为，将线性聚二甲基硅氧烷、含氨基的超支化聚硅氧烷、含二硫醚的异氰酸酯和氯代烷混合后，倒入模具，烘干得到透明可卷曲折叠聚硅氧烷膜。
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113150232A (zh) * 2021-05-11 2021-07-23 太原工业学院 一种mdi基高透明聚氨酯弹性体的制备方法
CN114380980A (zh) * 2021-12-01 2022-04-22 西北工业大学 自修复有机硅弹性体材料及其制备方法
CN114874604A (zh) * 2022-06-06 2022-08-09 贵州民族大学 一种可回收的动态共价聚二甲基硅氧烷膜的制备方法
CN116396480A (zh) * 2023-03-02 2023-07-07 无锡海特新材料研究院有限公司 一种高介电常数低模量室温自愈合的介电弹性体及其制备方法
CN116554430A (zh) * 2023-05-11 2023-08-08 青岛格林沃德新材料科技有限公司 一种含动态二硫键的高性能聚氨酯阻尼材料及其制备方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104140675A (zh) * 2014-07-23 2014-11-12 苏州大学 一种环状对苯二甲酸丁二醇酯齐聚物/热固性树脂及其制备方法
CN105400405A (zh) * 2015-10-30 2016-03-16 华南理工大学 一种自修复有机硅聚氨酯/聚脲防污材料及其方法与应用
CN106928797A (zh) * 2017-04-10 2017-07-07 苏州大学 一种可逆自修复抗菌丙烯酸涂层、制备及自修复方法
CN107082862A (zh) * 2017-05-18 2017-08-22 中国科学院深圳先进技术研究院 自修复有机硅改性聚氨酯弹性体及其制备方法
CN107814937A (zh) * 2017-11-17 2018-03-20 四川大学 一种自修复可重复加工的聚硅氧烷弹性体及制备方法和应用
CN108003317A (zh) * 2017-12-22 2018-05-08 四川大学 一种聚硅氧烷弹性体及其制备方法和应用
CN108102531A (zh) * 2018-01-12 2018-06-01 邯郸市富奥新材料有限公司 一种高强度可自修复型防污闪涂料及其制备方法
WO2018108950A1 (en) * 2016-12-13 2018-06-21 Repsol, S.A. Disulfide-containing self-healing polymer blend
CN108794781A (zh) * 2018-06-22 2018-11-13 苏州大学 一种透明可卷曲折叠聚硅氧烷膜及其制备与自修复方法

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105482065B (zh) * 2015-12-10 2018-05-15 东华大学 一种含有双硫键的自愈合聚氨酯树脂及其制备方法

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104140675A (zh) * 2014-07-23 2014-11-12 苏州大学 一种环状对苯二甲酸丁二醇酯齐聚物/热固性树脂及其制备方法
CN105400405A (zh) * 2015-10-30 2016-03-16 华南理工大学 一种自修复有机硅聚氨酯/聚脲防污材料及其方法与应用
WO2018108950A1 (en) * 2016-12-13 2018-06-21 Repsol, S.A. Disulfide-containing self-healing polymer blend
CN106928797A (zh) * 2017-04-10 2017-07-07 苏州大学 一种可逆自修复抗菌丙烯酸涂层、制备及自修复方法
CN107082862A (zh) * 2017-05-18 2017-08-22 中国科学院深圳先进技术研究院 自修复有机硅改性聚氨酯弹性体及其制备方法
CN107814937A (zh) * 2017-11-17 2018-03-20 四川大学 一种自修复可重复加工的聚硅氧烷弹性体及制备方法和应用
CN108003317A (zh) * 2017-12-22 2018-05-08 四川大学 一种聚硅氧烷弹性体及其制备方法和应用
CN108102531A (zh) * 2018-01-12 2018-06-01 邯郸市富奥新材料有限公司 一种高强度可自修复型防污闪涂料及其制备方法
CN108794781A (zh) * 2018-06-22 2018-11-13 苏州大学 一种透明可卷曲折叠聚硅氧烷膜及其制备与自修复方法

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113150232A (zh) * 2021-05-11 2021-07-23 太原工业学院 一种mdi基高透明聚氨酯弹性体的制备方法
CN114380980A (zh) * 2021-12-01 2022-04-22 西北工业大学 自修复有机硅弹性体材料及其制备方法
CN114874604A (zh) * 2022-06-06 2022-08-09 贵州民族大学 一种可回收的动态共价聚二甲基硅氧烷膜的制备方法
CN114874604B (zh) * 2022-06-06 2024-04-19 贵州民族大学 一种可回收的动态共价聚二甲基硅氧烷膜的制备方法
CN116396480A (zh) * 2023-03-02 2023-07-07 无锡海特新材料研究院有限公司 一种高介电常数低模量室温自愈合的介电弹性体及其制备方法
CN116554430A (zh) * 2023-05-11 2023-08-08 青岛格林沃德新材料科技有限公司 一种含动态二硫键的高性能聚氨酯阻尼材料及其制备方法
CN116554430B (zh) * 2023-05-11 2024-04-19 青岛格林沃德新材料科技有限公司 一种含动态二硫键的高性能聚氨酯阻尼材料及其制备方法

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