CN110684220B - Transparent foldable polysiloxane membrane that curls - Google Patents
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Abstract
The invention discloses a transparent curlable folding polysiloxane film. Adding 2,2' -dithiodiethanol and diisocyanate into chloroalkane, and performing chain extension reaction to obtain disulfide-containing isocyanate; adding bis (3-aminopropyl) terminated polydimethylsiloxane and diisocyanate into chlorinated alkane, and performing chain extension reaction to obtain linear polydimethylsiloxane; dissolving linear polydimethylsiloxane and hyperbranched polysiloxane with amino at the tail end in chloroalkane, adding isocyanate containing disulfide, uniformly mixing, pouring into a mould, and drying to obtain the transparent curlable folding polysiloxane membrane. The invention enables the prepared polysiloxane film to have rigidity and toughness through dynamic physical crosslinking of hydrogen bonds at room temperature and permanent chemical crosslinking of hyperbranched polysiloxane, and enables the prepared polysiloxane film to have good reversible self-repairing performance through hydrogen bond dissociation and disulfide exchange under heating conditions.
Description
The invention belongs to a split application with the name of a transparent curlable folding polysiloxane film and a preparation and self-repairing method thereof, and belongs to the technical part of products, wherein the split application has the application number of 2018106547439 and the application date of invention application of 2018, 6 and 22.
Technical Field
The invention relates to a polymer film and a preparation method thereof, in particular to a transparent curly folding polysiloxane film and a preparation and self-repairing method thereof, belonging to the technical field of high polymer materials.
Background
With the rapid development of transparent photoelectric devices such as solar cells, sensors, flexible displays, touch panels, and Flexible Printed Circuit Boards (FPCBs), flexible electronic devices with high transmittance are becoming the focus and direction of research. Organic electronic devices are typically multilayer structures consisting essentially of a substrate (e.g., silicon wafer, glass or plastic), a dielectric, a semiconductor (or active layer), and a conductive electrode. Among them, organic electronic devices using silicon wafers or glass as substrates result in devices having a great rigidity and being capable of bending only to a very limited extent. At present, therefore, flexible transparent electronic devices are mainly manufactured by using commercially available Polyimide (PI) or polyethylene terephthalate (PET) as a substrate and depositing a functional layer thereon.
Like conventional electronic products, flexible transparent electronic devices are also damaged and broken due to mechanical damage such as excessive bending, accidental scratching or cutting, and the like, with the consequent problems of a large amount of equipment waste, increased maintenance cost, raw material loss and the like. In recent years, people imitate the mechanism of organism self-healing damage and increase survival probability, and introduce various dynamic bonds or interactions in molecules or among molecules to build reversible self-repairing performance in materials, thereby effectively recovering mechanical damage suffered by the materials and prolonging the service life of the materials. However, PI or PET, which is a substrate of a flexible electronic device, does not have reversible self-repairing capability, and cannot repair unexpected cracks or scratches. Meanwhile, the trend of miniaturization and portability not only requires that the flexible transparent electronic device be bendable, but also requires that the flexible transparent electronic device be foldable, which is also difficult to realize for PI or PET substrates. Therefore, a new flexible reversible self-repairing material capable of being rolled and folded is needed to solve the problems.
In the prior research, groups such as pyridine, triazole and the like are modified at the chain end of PDMS (polydimethylsiloxane), and are mixed with Co2+，Fe3+，Zn2+After the metal ions form dynamic valence-matching bonds, the obtained modified PDMS elastomer has good elongation at break and generally has self-repairing efficiency of about 90% at room temperature, and is very suitable for preparing bionic flexible devices such as electronic skins, wearable sensors, artificial muscles and the like. However, for flexible transparent electronic devices such as solar cells, flexible displays, capacitive touch screens, FPCBs, etc., the high tensile PDMS-based self-repairing materials reported above are not suitable for use due to their poor strength and rigidity. On the contrary, in the prior art, a rigid PDMS-based crosslinking network is obtained by introducing a trifunctional boron-oxygen hexacyclic ring as a crosslinking point, the Young modulus and the tensile strength of the rigid PDMS-based crosslinking network reach 182MPa and 9.46MPa respectively, and the Young modulus and the tensile strength of the rigid PDMS-based crosslinking network are the highest values in the current PDMS-based self-repairing materials, but the elongation at break of the rigid PDMS-based crosslinking network is the highest value<10 percent, and meanwhile, the water is needed in the self-repairing process, so that the danger of short circuit of the device is easily caused, and the flexible transparent electronic device is still not suitable for the flexible transparent electronic device although the flexible transparent electronic device has excellent mechanical properties.
In conclusion, the development of the PDMS substrate with high transmittance, excellent mechanical strength and high toughness overcomes the defects of commercial PI and PET, and the PDMS substrate serving as a novel flexible and foldable substrate of a reversible self-repairing flexible transparent electronic device is a subject with great application value.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a transparent curlable folding polysiloxane film and a preparation and self-repairing method thereof. The polysiloxane film disclosed by the invention has the characteristics of good flexibility, transparency, low cost, easiness in processing and the like, and can be widely used, in terms of chain structure, Si-O with larger bond angle and bond length is easier to rotate than C-C to realize chain motion, so that the flexibility is better, the characteristic meets the requirement of reversible self-repairing materials on high mobility of polymer chain segments, and a flexible transparent electronic device taking the polysiloxane film as a base material has high stretchability and good self-repairing capability.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a method of making a transparent, rollable, foldable silicone film comprising the steps of:
(1) mixing gamma-aminopropyltriethoxysilane, water and an alcohol solvent, and reacting to obtain hyperbranched polysiloxane with an amino group at the tail end;
(2) mixing 2,2' -dithiodiethanol, diisocyanate and chloroalkane, and reacting to obtain isocyanate containing disulfide;
(3) mixing bis (3-aminopropyl) terminated polydimethylsiloxane, diisocyanate and alkyl chloride, and reacting to obtain linear polydimethylsiloxane;
(4) mixing linear polydimethylsiloxane, amino-containing hyperbranched polysiloxane, disulfide-containing isocyanate and chloroalkane, pouring the mixture into a mold, and drying to obtain the transparent curlable folding polysiloxane film.
A self-repairing method of a damaged transparent curly foldable polysiloxane film comprises the following steps of attaching damaged surfaces of the damaged transparent curly foldable polysiloxane film, and then heating the damaged surfaces for 0.5-2 hours at the temperature of 100-140 ℃ to complete self-repairing of the damaged transparent curly foldable polysiloxane film; the preparation method of the transparent curly foldable polysiloxane film comprises the following steps:
(1) mixing gamma-aminopropyltriethoxysilane, water and an alcohol solvent, and reacting to obtain hyperbranched polysiloxane with an amino group at the tail end;
(2) mixing 2,2' -dithiodiethanol, diisocyanate and chloroalkane, and reacting to obtain isocyanate containing disulfide;
(3) mixing bis (3-aminopropyl) terminated polydimethylsiloxane, diisocyanate and alkyl chloride, and reacting to obtain linear polydimethylsiloxane;
(4) mixing linear polydimethylsiloxane, amino-containing hyperbranched polysiloxane, disulfide-containing isocyanate and chloroalkane, pouring the mixture into a mold, and drying to obtain the transparent curlable folding polysiloxane film.
The invention also discloses application of the hyperbranched polysiloxane with the amino group at the tail end, the isocyanate with the disulfide and the linear polydimethylsiloxane in preparing the transparent curlable folding polysiloxane membrane, which is characterized in that the preparation methods of the hyperbranched polysiloxane with the amino group at the tail end, the isocyanate with the disulfide and the linear polydimethylsiloxane are as follows:
mixing gamma-aminopropyltriethoxysilane, water and an alcohol solvent, and reacting to obtain hyperbranched polysiloxane with an amino group at the tail end;
mixing 2,2' -dithiodiethanol, diisocyanate and chloroalkane, and reacting to obtain isocyanate containing disulfide;
mixing bis (3-aminopropyl) terminated polydimethylsiloxane, diisocyanate and alkyl chloride, and reacting to obtain linear polydimethylsiloxane.
The method for preparing the transparent curlable folding polysiloxane membrane from the hyperbranched polysiloxane with the amino at the tail end, the isocyanate with the disulfide and the linear polydimethylsiloxane comprises the steps of mixing the linear polydimethylsiloxane, the hyperbranched polysiloxane with the amino, the isocyanate with the disulfide and the chloroalkane, pouring the mixture into a mold, and drying to obtain the transparent curlable folding polysiloxane membrane.
In the technical scheme, the alcohol solvent is one or more of methanol, ethanol, n-propanol, isopropanol, n-butanol and isobutanol; the chloralkane is one or more of dichloromethane, trichloromethane and 1, 2-dichloroethane; the diisocyanate is a diisocyanate compound or a diisocyanate derivative prepared from the diisocyanate compound; the diisocyanate compound is one or more of Toluene Diisocyanate (TDI), isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), dicyclohexylmethane diisocyanate (HMDI), Hexamethylene Diisocyanate (HDI), Lysine Diisocyanate (LDI), Xylylene Diisocyanate (XDI), Naphthalene Diisocyanate (NDI), tetramethylxylylene diisocyanate (TMXDI) and methylcyclohexyl diisocyanate (HTDI). Preferably, the bis (3-aminopropyl) terminated polydimethylsiloxane has a molecular weight of 1000.
In the technical scheme, in the step (1), the mass ratio of the gamma-aminopropyltriethoxysilane to the water to the alcohol solvent is 100 to (10-15) to (100-200); in the step (2), the mass ratio of the 2,2' -dithiodiethanol to the diisocyanate to the chloroalkane is (75-80) to (160-270) to (1000-1500); in the step (3), the mass ratio of the bis (3-aminopropyl) end-blocked polydimethylsiloxane to the diisocyanate to the chloroalkane is 100: 10-25: 1000-1500; in the step (4), the mass ratio of the linear polydimethylsiloxane to the amino-containing hyperbranched polysiloxane to the disulfide-containing isocyanate to the chloroalkane is 50 to (3-6) to (10-15) to (100-150).
In the technical scheme, in the step (1), the mixing temperature is room temperature, the reaction temperature is 60-80 ℃, and the reaction time is 4-6 hours; in the step (2), the mixing temperature is room temperature, the reaction temperature is 60-80 ℃, and the reaction time is 2-4 h; in the step (3), the mixing temperature is room temperature, the reaction temperature is 60-80 ℃, and the reaction time is 4-6 h; in the step (4), the mixing temperature is room temperature. The room temperature is indoor temperature, and preferably 20-30 ℃.
In the technical scheme, in the step (1), after the reaction is finished, the solvent is evaporated under reduced pressure to obtain the hyperbranched polysiloxane with the tail end containing amino; in the step (2), after the reaction is finished, the solvent is evaporated under reduced pressure to obtain isocyanate containing disulfide; and (3) after the reaction is finished, evaporating the solvent under reduced pressure to obtain the linear polydimethylsiloxane.
In the technical scheme, the damage is fracture, the fracture surface is fixedly attached by a clamp, and self-repairing is completed by heating.
A transparent rollable folding silicone film produced according to the above-described method for producing a transparent rollable folding silicone film.
The preparation method of the transparent curly foldable polysiloxane film disclosed by the invention comprises the following specific steps:
(1) uniformly mixing 100 parts by mass of gamma-aminopropyltriethoxysilane, 10-15 parts by mass of water and 100-200 parts by mass of an alcohol solvent at the temperature of 20-30 ℃, heating to 60-80 ℃, and carrying out heat preservation reaction for 4-6 hours; evaporating the alcohol solvent from the mixed solution under reduced pressure to obtain hyperbranched polysiloxane with amino at the tail end;
(2) uniformly mixing 77 parts of 2,2' -dithiodiethanol, 169-264 parts of diisocyanate and 1000-1500 parts of chloroalkane at the temperature of 20-30 ℃ by mass, raising the temperature to 60-80 ℃, and carrying out heat preservation reaction for 2-4 hours; decompressing and steaming the mixed solution to remove the chloralkane to obtain isocyanate containing disulfide;
(3) 100 parts by mass of bis (3-aminopropyl) terminated polydimethylsiloxane (PDMS, M) at a temperature of 20-30 DEG Cn= 1000), 13-21 parts of diisocyanate and 1000-1500 parts of alkyl chloride are mixed uniformly, heated to 60-80 ℃ and reacted for 2-4 hours under heat preservation; the obtained mixed solution is decompressed and steamed to remove the chloralkane, and linear polydimethylsiloxane is obtained;
(4) according to the mass percent, under the condition that the temperature is 20-30 ℃, 50 parts of linear polydimethylsiloxane, 3-6 parts of hyperbranched polysiloxane containing amino, 10-15 parts of isocyanate containing disulfide and 100-150 parts of chloroalkane are uniformly mixed, poured into a mold and dried, and the transparent curlable folding polysiloxane film is obtained.
Compared with the prior art, the invention has the beneficial effects that:
1. the polysiloxane membrane provided by the invention has high modulus and high tensile strength, and simultaneously has high glass transition temperature and high toughness by constructing a multi-scale crosslinking structure of dynamic hydrogen bond crosslinking and hyperbranched polysiloxane permanent chemical crosslinking.
2. The polysiloxane membrane provided by the invention realizes reversible self-repair of a high-rigidity and high-strength polysiloxane material by regulating and controlling the formation/dissociation of hydrogen bonds and the exchange rate of disulfide through temperature, and the self-repair efficiency (more than 90%) is equivalent to that of the existing polysiloxane elastomer.
3. Compared with the prior art, the polysiloxane film provided by the invention has high rigidity, can be bent for many times, can be repeatedly folded and curled, and has no crease residue.
Drawings
FIG. 1 shows Hyperbranched Polysiloxane (HPSi) having amino groups at the terminal prepared in example 1 of the present inventionNuclear magnetic resonance hydrogen spectrum of (1H-NMR）；
FIG. 2 is the NMR spectrum of a hyperbranched polysiloxane having an amino group at the end (HPSi) prepared in example 1 of the present invention: (29Si-NMR）；
FIG. 3 is an IR spectrum of a disulfide containing isocyanate with a transparent, crimpable polysiloxane film prepared according to example 1 of the present invention;
FIG. 4 is a graph of the thermogravimetric plot of a transparent crimpable polysiloxane film prepared in accordance with example 1 of the present invention;
FIG. 5 is a dynamic mechanical curve of a transparent crimpable polysiloxane film prepared according to example 1 of the present invention;
FIG. 6 is a digital photograph of the roll-fold effect of a transparent roll-foldable silicone film prepared in example 1 of the present invention;
FIG. 7 is a UV-VIS spectrum of a transparent crimpable polysiloxane film prepared according to example 1 of the present invention;
FIG. 8 is a tensile stress-strain curve before and after self-healing of a transparent crimpable polysiloxane film prepared in example 1 of this invention;
FIG. 9 is a digital photograph of the self-healing effect of a transparent, rollable, foldable silicone film made in accordance with example 1 of the present invention;
FIG. 10 is a polarizing photomicrograph of the self-healing effect of the transparent crimpable polysiloxane film prepared in example 1 of the present invention and the disulfide-free polysiloxane film prepared in comparative example 1.
Detailed Description
The technical solution of the present invention is further described with reference to the accompanying drawings and examples.
Example 1
1) Preparation of hyperbranched polysiloxanes containing amino groups at the ends (designated HPSi)
Uniformly mixing 100g of gamma-aminopropyltriethoxysilane (KH 550), 10g of water and 100g of ethanol by mass at the temperature of 20 ℃, heating to 60 ℃, and carrying out heat preservation reaction for 4 hours; and (3) distilling the mixed solution under reduced pressure to remove ethanol to obtain Hyperbranched Polysiloxane (HPSi) with amino at the tail end, wherein the nuclear magnetic resonance hydrogen spectrum and the nuclear magnetic resonance silicon spectrum of the hyperbranched polysiloxane are respectively shown in the attached figures 1 and 2.
2) Preparation of disulfide-containing isocyanates
According to the mass, 77g of 2,2' -dithiodiethanol, 224g of isophorone diisocyanate and 1000g of dichloromethane are uniformly mixed at the temperature of 20 ℃, heated to 60 ℃ and subjected to heat preservation reaction for 2 hours; the obtained mixed solution is decompressed and steamed to remove methylene dichloride, and the isocyanate containing disulfide is obtained, and the infrared spectrum of the isocyanate is shown in figure 3.
3) Preparation of Linear polydimethylsiloxane
100g of bis (3-aminopropyl) terminated polydimethylsiloxane (PDMS, M) was added by mass at a temperature of 20 ℃n= 1000), 17.7g of isophorone diisocyanate and 1000g of dichloromethane are mixed uniformly, heated to 60 ℃ and kept for reaction for 2 hours; and evaporating the dichloromethane from the mixed solution under reduced pressure to obtain the linear polydimethylsiloxane.
4) Preparation of transparent, rollable, foldable silicone films
According to the mass, under the condition that the temperature is 20 ℃, 50g of linear polydimethylsiloxane, 3.6g of HPSi, 10g of isocyanate containing disulfide and 100g of dichloromethane are uniformly mixed, poured into a mold and dried to obtain the transparent foldable polysiloxane film capable of being curled, and an infrared spectrogram, a thermal weight loss curve, a dynamic mechanical curve, a digital photo of a curling folding effect, an ultraviolet-visible light spectrum and a tensile stress-strain curve of the transparent foldable polysiloxane film are respectively shown in the attached figures 3, 4, 5, 6, 7 and 8.
5) Self-repairing method of transparent rollable folding polysiloxane film
The damaged section of the transparent rollable folded silicone film was fixed and closely attached with a jig, and then heated at a temperature of 100 ℃ for 0.5 hour. The stress-strain curve, the digital photo of the self-repairing effect and the polarized light micrograph of the repaired test are shown in the attached figures 8, 9 and 10 respectively.
Comparative example 1 preparation of disulfide-free polysiloxane membranes
By mass, 50g of linear polydimethylsiloxane, 3.6g of HPSi, 4g of isophorone diisocyanate and 100g of dichloromethane were uniformly mixed at a temperature of 20 ℃, poured into a mold and dried to obtain a disulfide-free polysiloxane film.
The cross section of the damaged disulfide-free polysiloxane film was fixed and closely attached with a jig, and then heated at 100 ℃ for 0.5 hour to complete the repair.
Comparative example 1 polarizing photomicrograph of the self-healing effect of a disulfide-free polysiloxane film is shown in figure 10.
Referring to the attached FIG. 1, it is the nuclear magnetic resonance hydrogen spectrum of the hyperbranched polysiloxane containing amino groups at the terminal (HPSi) prepared in example 1 of the invention (1H-NMR). As can be seen from the figure, the characteristic peak at δ =1.21ppm is Si-O-CH2CH3The ratio of the number of H in the methyl group (b) to the number of H in any C (C, d or e in the figure) in the aminopropyl group was 3:2, which is much smaller than 9:2 corresponding to KH550, indicating that Si-O-Si is formed by hydrolytic condensation between KH 550.
Referring to FIG. 2, it is the NMR spectrum of the hyperbranched polysiloxane having amino groups at the terminal (HPSi) prepared in example 1 of the present invention: (29Si-NMR). Wherein D, L and T respectively represent branched chain segments, linear chain segments and end-capping chain segments of the hyperbranched siloxane. From the figure, it can be found that the D peak is significantly stronger than the L peak and the T peak, indicating that the branched chain units are ubiquitous in HPSi, further proving that KH550 monomer has been fully hydrolyzed and condensed. From the integrated areas corresponding to D and L in the figure, the value of the degree of branching DB is calculated using the following formula (1):
it can be found by calculation that DB of HPSi is 0.86, which is close to DB =1 of dendrimer, indicating that molecular structure of HPSi is close to that of dendrimer, and has lower viscosity and better solubility, and surface is rich in active amino group, and has high activity and reactivity.
Referring to FIG. 3, there is shown an IR spectrum of a disulfide-containing isocyanate prepared in example 1 of the present invention with a transparent, crimpable, polysiloxane film. 2,2' -dithiodiethanol generates amino after chain extension of isophorone diisocyanateFormic ester, wherein the expansion vibration peak of C = O appears 1720cm in the infrared spectrum-12260cm above-1The peak is the characteristic peak of-NCO in the isocyanate containing disulfide.
3318cm in the IR spectrum of a transparent, crimpable, polysiloxane film-1And 1560cm-1The characteristic peaks are respectively the stretching vibration peak and the bending vibration peak of-NH-, and 1630cm-1The characteristic peak at (b) is then the C = O stretching vibration peak in the urea groups, which indicates that the chain extension reaction of PDMS with isophorone diisocyanate and the subsequent further reaction of the disulfide-containing isocyanate with linear polydimethylsiloxane or HPSi produces a large number of urea groups. -CH in PDMS and isophorone3Respectively appears at 2960 cm-1And 1260cm-1At least one of (1) and (b); 1080 and 1025cm-1The broad peak is the characteristic stretching vibration peak of Si-O-Si in linear polydimethylsiloxane and HPSi, and is 800cm-1The sharp absorption peak is the stretching vibration peak of Si-C; 2260cm-1The absence of the characteristic peak of-NCO indicates that-NCO in the prepared polysiloxane film has been reacted with-NH in the chain-extended linear polydimethylsiloxane and HPSi2The reaction was complete.
Referring to fig. 4, there is shown a thermogravimetric plot of a transparent, crimpable, folded silicone film made in accordance with example 1 of the present invention. From these, the initial thermal decomposition temperature of a transparent, rollable, foldable silicone film (C:)T di) Is 282 ℃ and has good thermal stability.
Referring to FIG. 5, a dynamic mechanical curve of a transparent rollable folded polysiloxane film prepared according to example 1 of the present invention is shown. The peak temperature of the dielectric loss tangent (Tan δ) is taken as the glass transition temperature, and the single symmetrical Tan δ peak is shown. Therefore, the glass transition temperature of the polysiloxane film prepared in example 1 is 96 ℃, which is higher than that of the reversible self-repairing polysiloxane material reported in the existing literature (the glass transition temperature is generally-120-65 ℃).
Referring to fig. 6, which is a digital photograph of the curl folding effect of the transparent curl foldable silicone film prepared in example 1 of the present invention. As shown in the figure, the transparent rollable silicone film was cut into a square of 60 mm by 60 mm, and then freely changed between S-bent, front-back folded or rolled shapes, thereby proving excellent flexibility. The PI film and the PET film with the same size are used as reference, the PI film and the PET film are folded in the positive and negative directions twice, and the folded positions of the PI film and the PET film are observed in an enlarged mode, so that transparent crease marks (in a frame) which cannot be recovered are generated on the surface of the PI film, the crease marks on the PET film cannot be recovered and influence the transparency of the PET film, and a clear white line (in the frame) is left on a letter C of background paper. In contrast, the transparent foldable silicone film has no trace residue at the folding position, and the writing on the background paper is still clear, which shows that the silicone film prepared in example 1 can effectively overcome the defects of PI and PET, and is a novel foldable and foldable material.
Referring to FIG. 7, the UV-Vis spectra of a transparent rollable folded polysiloxane film prepared according to example 1 of the present invention. From the photographs, it can be seen that the transparent foldable silicone film has good transparency, and further the transmittance of different film thicknesses at 200-800 nm was tested by ultraviolet-visible light. It can be seen that the transmittance of the films with different thicknesses in the visible light region of 400-800 nm is above 80% with air as a baseline, wherein the transmittance at 550nm increases from 86.09% (0.4 mm) to 88.63% (0.2 mm) with the decrease of the film thickness.
Referring to FIG. 8, there are shown the tensile stress-strain curves before and after self-healing of a transparent crimpable polysiloxane film prepared in example 1 of the present invention. Tensile tests show that the tensile strength, the elongation at break, the Young modulus and the toughness of the original transparent curly foldable polysiloxane film are respectively 9.25 +/-0.22 MPa, 224.21 +/-2.79%, 214.89 +/-18.27 MPa and 16.32 +/-0.18 MPa, and the original transparent curly foldable polysiloxane film has good rigidity and toughness. The tensile strength, the elongation at break and the toughness of the repaired polysiloxane film are respectively 8.16 +/-0.87 MPa, 211.59 +/-5.63 percent and 14.91 +/-0.72 MPa, and the corresponding repairing efficiencies are 94.99 percent, 94.37 percent and 91.36 percent. As shown in the photograph, the repaired silicone film was bent 180 degreesoNo crack appears on the upper and lower surfaces, so that good integrity is maintained; the invention can break the tensile strength and the Young's modulus of the product at the same timeThe elongation at break is 22.4 times of that of the prior art, and not only the rigidity achieved by the prior art is realized, but also the excellent toughness is considered.
Referring to FIG. 9, which is a digital photograph of the self-healing effect of the transparent rollable folded polysiloxane film prepared in example 1 of the present invention. As shown in the figure, the complete transparent curlable folding polysiloxane film is cut, the section is tightly attached and placed on a hot table at 100 ℃ for 30 min, and then the two parts of the completely broken film are fused and connected into a whole again.
Referring to FIG. 10, there are shown polarizing micrographs of the self-healing effect of the transparent crimpable polysiloxane film prepared in example 1 of the present invention and the disulfide-free polysiloxane film prepared in comparative example 1. And observing the surface appearance of the damaged part of the transparent curly folding polysiloxane film after different repairing times by adopting a polarizing microscope. As shown in the figure, a cross section (black area in the figure) with the width of 20 μm is cut on the surface of the transparent curly foldable polysiloxane film; and then fixing and tightly fitting the section by using a clamp, and heating to self-repair the section at the temperature of 100 ℃. Along with the prolonging of the repairing time, the cross section gradually narrows and shrinks and gradually changes from an opaque black area into a transparent state; and when the repairing time reaches 30 min, the cross section is completely repaired. In contrast, the cross section of the surface of the disulfide-free polysiloxane film cannot be recovered to be transparent from an opaque black shape under the same self-repairing condition, and only the width of the cross section is reduced, which shows that the movement of the flexible PDMS chain segment is greatly restricted after the HPSi forms permanent cross-linking in the film, and the self-repairing cannot be completed only by heating to 100 ℃ to dissociate the hydrogen bond, so that the introduction of the disulfide is the key of the good self-repairing capability of the transparent rollable folded polysiloxane film.
Example 2
1) Preparation of hyperbranched polysiloxanes containing amino groups at the ends (designated HPSi)
Uniformly mixing 100g of gamma-aminopropyltriethoxysilane (KH 550), 12.5g of water and 150g of methanol at 25 ℃, heating to 70 ℃, and carrying out heat preservation reaction for 5 hours; the mixed solution is decompressed and distilled to remove methanol, and Hyperbranched Polysiloxane (HPSi) with amino groups at the tail end is obtained.
2) Preparation of disulfide-containing isocyanates
According to the mass percent, 77g of 2,2' -dithiodiethanol, 169g of hexamethylene diisocyanate and 1100g of trichloromethane are uniformly mixed at the temperature of 25 ℃, heated to 70 ℃ and subjected to heat preservation reaction for 2.5 hours; and (3) evaporating the chloroform from the mixed solution under reduced pressure to obtain the disulfide-containing isocyanate.
3) Preparation of Linear polydimethylsiloxane
100g of bis (3-aminopropyl) terminated polydimethylsiloxane (PDMS, M) was added by mass at a temperature of 25 ℃n= 1000), 13.4g of hexamethylene diisocyanate and 1100g of chloroform are mixed uniformly, heated to 70 ℃ and kept for reaction for 2.5 hours; and (3) evaporating the chloroform from the mixed solution under reduced pressure to obtain the linear polydimethylsiloxane.
4) Preparation of transparent, rollable, foldable silicone films
By mass, 50g of linear polydimethylsiloxane, 4g of HPSi, 12g of disulfide-containing isocyanate and 125g of chloroform were mixed uniformly at a temperature of 25 ℃ and poured into a mold to be dried, thereby obtaining a transparent crimpable polysiloxane film.
5) Self-repairing method of transparent rollable folding polysiloxane film
Fixing and tightly attaching the damaged section of the transparent curly foldable polysiloxane film by using a clamp, and then heating for 0.6 hour at the temperature of 110 ℃; the tensile strength, elongation at break and toughness of the repaired polysiloxane film correspond to the repairing efficiency of 92.89%, 92.17% and 91.06%.
Example 3
1) Preparation of hyperbranched polysiloxanes containing amino groups at the ends (designated HPSi)
Uniformly mixing 100g of gamma-aminopropyltriethoxysilane (KH 550), 15g of water and 200g of n-propanol at the temperature of 30 ℃ by mass, heating to 80 ℃, and carrying out heat preservation reaction for 6 hours; the obtained mixed solution is decompressed and distilled to remove the normal propyl alcohol, and then the Hyperbranched Polysiloxane (HPSi) with the amino group at the end is obtained.
2) Preparation of disulfide-containing isocyanates
According to the mass, 77g of 2,2' -dithiodiethanol, 264g of dicyclohexylmethane diisocyanate and 1200g of 1, 2-dichloroethane are uniformly mixed at the temperature of 30 ℃, then the temperature is raised to 80 ℃, and the reaction is carried out for 3 hours under the condition of heat preservation; the obtained mixed solution is decompressed and distilled to remove 1, 2-dichloroethane, and then the isocyanate containing disulfide is obtained.
3) Preparation of Linear polydimethylsiloxane
100g of bis (3-aminopropyl) terminated polydimethylsiloxane (PDMS, M) was added by mass at a temperature of 30 ℃n= 1000), 20.8g dicyclohexylmethane diisocyanate and 1200g1, 2-dichloroethane are mixed uniformly, heated to 80 ℃ and reacted for 3 hours under the condition of heat preservation; and (3) evaporating the 1, 2-dichloroethane in the mixed solution under reduced pressure to obtain the linear polydimethylsiloxane.
4) Preparation of transparent, rollable, foldable silicone films
50g of linear polydimethylsiloxane, 5g of HPSi, 15g of disulfide-containing isocyanate and 150g of 1, 2-dichloroethane were mixed uniformly by mass at a temperature of 30 ℃ and poured into a mold to dry, and a transparent crimpable polysiloxane film was obtained.
5) Self-repairing method of transparent rollable folding polysiloxane film
Fixing and tightly attaching the damaged section of the transparent curly foldable polysiloxane film by using a clamp, and then heating for 0.7 hour at the temperature of 115 ℃; the tensile strength, elongation at break and toughness of the repaired polysiloxane film correspond to the repairing efficiency of 93.01%, 92.67% and 90.86%.
Example 4
1) Preparation of hyperbranched polysiloxanes containing amino groups at the ends (designated HPSi)
Uniformly mixing 100g of gamma-aminopropyltriethoxysilane (KH 550), 11g of water, 100g of methanol and 100g of ethanol by mass at the temperature of 22 ℃, heating to 65 ℃, and carrying out heat preservation reaction for 4.5 hours; and (3) evaporating the methanol and the ethanol from the mixed solution under reduced pressure to obtain the Hyperbranched Polysiloxane (HPSi) with the amino group at the tail end.
2) Preparation of disulfide-containing isocyanates
According to the mass percent, 77g of 2,2' -dithiodiethanol, 125g of diphenylmethane diisocyanate, 106g of naphthalene diisocyanate, 600g of dichloromethane and 700g of trichloromethane are uniformly mixed at the temperature of 22 ℃, then the mixture is heated to 65 ℃ and is subjected to heat preservation reaction for 3.5 hours; and (3) evaporating the dichloromethane and the trichloromethane from the mixed solution under reduced pressure to obtain the disulfide-containing isocyanate.
3) Preparation of Linear polydimethylsiloxane
100g of bis (3-aminopropyl) terminated polydimethylsiloxane (PDMS, M) was added by mass at a temperature of 22 ℃n= 1000), 10g of diphenylmethane diisocyanate, 8.4g of naphthalene diisocyanate, 600g of dichloromethane and 700g of trichloromethane are mixed uniformly, heated to 65 ℃ and kept for reaction for 3.5 hours; and evaporating the dichloromethane and the trichloromethane from the mixed solution under reduced pressure to obtain the linear polydimethylsiloxane.
4) Preparation of transparent, rollable, foldable silicone films
By mass, 50g of linear polydimethylsiloxane, 6g of HPSi, 11g of disulfide-containing isocyanate, 60g of dichloromethane and 60g of chloroform were mixed uniformly at a temperature of 22 ℃, poured into a mold and dried to obtain a transparent crimpable polysiloxane film.
5) Self-repairing method of transparent rollable folding polysiloxane film
The damaged section of the transparent rollable folded silicone film was fixed and tightly attached with a jig, and then heated at a temperature of 120 ℃ for 0.8 hour.
Example 5
1) Preparation of hyperbranched polysiloxanes containing amino groups at the ends (designated HPSi)
Uniformly mixing 100g of gamma-aminopropyltriethoxysilane (KH 550), 13g of water, 80g of methanol and 120g of n-propanol at the temperature of 24 ℃ by mass, raising the temperature to 75 ℃, and carrying out heat preservation reaction for 5.5 hours; and (3) evaporating the methanol and the n-propanol from the mixed solution under reduced pressure to obtain the Hyperbranched Polysiloxane (HPSi) with the amino group at the tail end.
2) Preparation of disulfide-containing isocyanates
According to the mass percent, 77g of 2,2' -dithiodiethanol, 88g of toluene diisocyanate, 91g of methylcyclohexyl diisocyanate, 300g of dichloromethane and 1100g of 1, 2-dichloroethane are uniformly mixed at the temperature of 24 ℃, then the mixture is heated to 75 ℃ and is subjected to heat preservation reaction for 4 hours; the obtained mixed solution is decompressed and distilled to remove dichloromethane and 1, 2-dichloroethane, and then the isocyanate containing disulfide is obtained.
3) Preparation of Linear polydimethylsiloxane
100g of bis (3-aminopropyl) terminated polydimethylsiloxane (PDMS, M) was added by mass at a temperature of 24 ℃n= 1000), 7g of toluene diisocyanate, 7.2g of methylcyclohexyl diisocyanate, 300g of dichloromethane and 1100g of 1, 2-dichloroethane are mixed uniformly, heated to 75 ℃ and reacted for 4 hours under the condition of heat preservation; and evaporating the dichloromethane and the 1, 2-dichloroethane from the mixed solution under reduced pressure to obtain the linear polydimethylsiloxane.
4) Preparation of transparent, rollable, foldable silicone films
50g of linear polydimethylsiloxane, 3g of HPSi, 13g of disulfide-containing isocyanate, 70g of methylene chloride and 70g of 1, 2-dichloroethane were mixed uniformly by mass at a temperature of 24 ℃ and poured into a mold to dry, and a transparent crimpable silicone film was obtained.
5) Self-repairing method of transparent rollable folding polysiloxane film
The damaged section of the transparent rollable folded silicone film was fixed and tightly attached with a jig, and then heated at 125 ℃ for 1 hour.
Example 6
1) Preparation of hyperbranched polysiloxanes containing amino groups at the ends (designated HPSi)
Uniformly mixing 100g of gamma-aminopropyltriethoxysilane (KH 550), 14g of water, 130g of ethanol and 70g of n-butanol by mass at the temperature of 28 ℃, heating to 60 ℃, and carrying out heat preservation reaction for 5 hours; and (3) evaporating the ethanol and the n-butanol from the mixed solution under reduced pressure to obtain the Hyperbranched Polysiloxane (HPSi) with the amino group at the tail end.
2) Preparation of disulfide-containing isocyanates
According to the mass percent, 77g of 2,2' -dithiodiethanol, 114g of lysine diisocyanate, 95g of xylylene diisocyanate, 500g of trichloromethane and 800g of 1, 2-dichloroethane are uniformly mixed at the temperature of 28 ℃, then the temperature is raised to 73 ℃, and the reaction is carried out for 3.5 hours under the condition of heat preservation; and (3) distilling the chloroform and the 1, 2-dichloroethane under reduced pressure to obtain the disulfide-containing isocyanate.
3) Preparation of Linear polydimethylsiloxane
100g of bis (3-aminopropyl) terminated polydimethylsiloxane (PDMS, M) was added by mass at a temperature of 28 ℃n= 1000), 9g of lysine diisocyanate, 7.5g of xylylene diisocyanate, 500g of chloroform and 800g of 1, 2-dichloroethane are mixed uniformly, heated to 73 ℃ and reacted for 3.5 hours under heat preservation; and distilling the obtained mixed solution under reduced pressure to remove the trichloromethane and the 1, 2-dichloroethane, thus obtaining the linear polydimethylsiloxane.
4) Preparation of transparent, rollable, foldable silicone films
50g of linear polydimethylsiloxane, 4.5g of HPSi, 14g of disulfide-containing isocyanate, 75g of chloroform and 75g of 1, 2-dichloroethane were mixed uniformly by mass at a temperature of 28 ℃ and poured into a mold to be dried, thereby obtaining a transparent crimpable polysiloxane film.
5) Self-repairing method of transparent rollable folding polysiloxane film
The damaged section of the transparent rollable folded silicone film was fixed and tightly attached with a jig, and then heated at a temperature of 130 ℃ for 1.5 hours.
Example 7
1) Preparation of hyperbranched polysiloxanes containing amino groups at the ends (designated HPSi)
Uniformly mixing 100g of gamma-aminopropyltriethoxysilane (KH 550), 11.5g of water, 60g of methanol, 60g of isopropanol and 60g of isobutanol by mass at the temperature of 23 ℃, heating to 70 ℃, and carrying out heat preservation reaction for 4 hours; the mixed solution is decompressed and distilled to remove methanol, isopropanol and isobutanol, and then Hyperbranched Polysiloxane (HPSi) with amino groups at the tail ends is obtained.
2) Preparation of disulfide-containing isocyanates
According to the mass, 77g of 2,2' -dithiodiethanol, 75g of isophorone diisocyanate, 56g of hexamethylene diisocyanate, 82g of tetramethylxylylene diisocyanate, 500g of dichloromethane, 500g of trichloromethane and 500g of 1, 2-dichloroethane are uniformly mixed at the temperature of 21 ℃, then the temperature is raised to 62 ℃, and the reaction is carried out for 3 hours under the condition of heat preservation; and (3) evaporating dichloromethane, trichloromethane and 1, 2-dichloroethane from the mixed solution under reduced pressure to obtain the disulfide-containing isocyanate.
3) Preparation of Linear polydimethylsiloxane
100g of bis (3-aminopropyl) terminated polydimethylsiloxane (PDMS, M) was added by mass at a temperature of 21 ℃n= 1000), 5.9g of isophorone diisocyanate, 4.5g of hexamethylene diisocyanate, 6.5g of tetramethylxylylene diisocyanate, 500g of dichloromethane, 500g of trichloromethane and 500g of 1, 2-dichloroethane are mixed uniformly, heated to 62 ℃ and reacted for 3 hours with heat preservation; and evaporating the dichloromethane, the trichloromethane and the 1, 2-dichloroethane from the mixed solution under reduced pressure to obtain the linear polydimethylsiloxane.
4) Preparation of transparent, rollable, foldable silicone films
50g of linear polydimethylsiloxane, 5.5g of HPSi, 12g of disulfide-containing isocyanate, 50g of dichloromethane, 50g of trichloromethane and 50g of 1, 2-dichloroethane are mixed uniformly by mass at a temperature of 21 ℃ and poured into a mold to be dried, so that a transparent crimpable polysiloxane film is obtained.
5) Self-repairing method of transparent rollable folding polysiloxane film
The damaged section of the transparent rollable folded silicone film was fixed and tightly attached with a jig, and then heated at a temperature of 140 ℃ for 2 hours.
Claims (5)
1. A transparent rollable foldable silicone film, characterized in that it is produced by a method comprising the steps of:
(1) mixing gamma-aminopropyltriethoxysilane, water and an alcohol solvent, and reacting to obtain hyperbranched polysiloxane with an amino group at the tail end;
(2) mixing 2,2' -dithiodiethanol, diisocyanate and chloroalkane, and reacting to obtain isocyanate containing disulfide;
(3) mixing bis (3-aminopropyl) terminated polydimethylsiloxane, diisocyanate and alkyl chloride, and reacting to obtain linear polydimethylsiloxane;
(4) mixing linear polydimethylsiloxane, hyperbranched polysiloxane with amino at the tail end, isocyanate containing disulfide and chloroalkane, pouring the mixture into a mold, and drying to obtain the transparent curlable folding polysiloxane film.
2. The transparent, rollable, foldable silicone film according to claim 1, wherein: the alcohol solvent is one or more of methanol, ethanol, n-propanol, isopropanol, n-butanol and isobutanol; the chloralkane is one or more of dichloromethane, trichloromethane and 1, 2-dichloroethane; the diisocyanate is a diisocyanate compound or a diisocyanate derivative prepared from the diisocyanate compound; the diisocyanate compound is one or more of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, xylylene diisocyanate, naphthalene diisocyanate, tetramethylxylylene diisocyanate and methylcyclohexyl diisocyanate.
3. The transparent, rollable, foldable silicone film according to claim 1, wherein: in the step (1), the mass ratio of the gamma-aminopropyltriethoxysilane to the water to the alcohol solvent is 100 to (10-15) to (100-200); in the step (2), the mass ratio of the 2,2' -dithiodiethanol to the diisocyanate to the chloroalkane is (75-80) to (160-270) to (1000-1500); in the step (3), the mass ratio of the bis (3-aminopropyl) end-blocked polydimethylsiloxane to the diisocyanate to the chloroalkane is 100: 10-25: 1000-1500; in the step (4), the mass ratio of the linear polydimethylsiloxane to the hyperbranched polysiloxane containing amino at the tail end to the isocyanate containing disulfide to the chloroalkane is 50 to (3-6) to (10-15) to (100-150).
4. The transparent, rollable, foldable silicone film according to claim 1, wherein: in the step (1), the mixing temperature is room temperature, the reaction temperature is 60-80 ℃, and the reaction time is 4-6 h; in the step (2), the mixing temperature is room temperature, the reaction temperature is 60-80 ℃, and the reaction time is 2-4 h; in the step (3), the mixing temperature is room temperature, the reaction temperature is 60-80 ℃, and the reaction time is 4-6 h; in the step (4), the mixing temperature is room temperature.
5. The transparent, rollable, foldable silicone film according to claim 1, wherein: in the step (1), after the reaction is finished, evaporating the solvent under reduced pressure to obtain hyperbranched polysiloxane with amino at the tail end; in the step (2), after the reaction is finished, the solvent is evaporated under reduced pressure to obtain isocyanate containing disulfide; and (3) after the reaction is finished, evaporating the solvent under reduced pressure to obtain the linear polydimethylsiloxane.
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