CN108794781A - The transparent rollable folding polysiloxane film of one kind and its preparation and self-repair method - Google Patents
The transparent rollable folding polysiloxane film of one kind and its preparation and self-repair method Download PDFInfo
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- 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
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- C08G77/04—Polysiloxanes
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- 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
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Abstract
The invention discloses a kind of transparent rollable folding polysiloxane film and its preparation and self-repair methods.2,2'-, bis- sulphur diethanols and diisocyanate are added in alkyl chloride, chain extending reaction obtains the isocyanates containing disulfide；Will be bis- (3- aminopropyls) sealing end dimethyl silicone polymer and diisocyanate be added alkyl chloride in, chain extending reaction obtains linear polydimethylsiloxane-；Linear polydimethylsiloxane- and the amino-containing hyperbranched polyorganosiloxane in end are dissolved in alkyl chloride, the isocyanates containing disulfide is added, mold is poured into after mixing, dries, obtains transparent rollable folding polysiloxane film.The present invention makes prepared polysiloxane film have both rigidity and toughness by the crosslinking of the dynamic physical of hydrogen bond at room temperature and the permanent chemical crosslinking of hyperbranched polyorganosiloxane, and hydrogen bond dissociation exchanges with disulfide and makes prepared polysiloxane film with good reversible self-healing properties in a heated condition.
Description
Technical field
The present invention relates to a kind of polymer film and preparation method thereof, more particularly to a kind of transparent rollable folding polysiloxanes
Film and its preparation and self-repair method, belong to technical field of polymer materials.
Background technology
With solar cell, sensor, flexible display, touch screen and flexible printed circuit board（FPCB）Etc. transparent light
The rapid development of electrical part, the flexible electronic device with high transmittance are increasingly becoming hot spot and the direction of research.Organic Electricity
Sub- device is usually multilayered structure, mainly by substrate（Such as silicon chip, glass or plastics）, dielectric, semiconductor（Or active layer）With
Conductive electrode forms.Wherein, it can cause device that there is prodigious rigidity as the organic electronic device of substrate using silicon chip or glass, only
Extremely limited bending can occur.Therefore current flexible and transparent electronic device is mainly with commercial polyimides（PI）Or it is poly- to benzene two
Formic acid glycol ester（PET）For substrate, it is fabricated by deposit functional layers on it.
Such as conditional electronic product, flexible and transparent electronic device also can be because of machineries such as overbending, unexpected scraping or cuttings
It damages and causes damage and failure, the thing followed also has a large amount of equipment waste, maintenance cost rise and raw material are lost etc.
Problem.In recent years, self healing impainnent of people's mimic biology body and the mechanism of survival probability is improved, by the molecule or molecule
Between introduce a variety of dynamic keys or interaction, be reversible self-healing properties, the machinery that effectively restorer is subjected to built in material
It damages and extends their service life.However, the PI or PET as flexible electronic device substrate do not have reversible selfreparing
Ability can not repair the fracture surprisingly occurred or cut.Meanwhile the development trend of micromation and portability does not require nothing more than flexibility thoroughly
Bright electronic device is flexible, and rollable folding requirement is more proposed to it, this is equally difficult to for PI or PET substrate
It realizes.Therefore, it is necessary to develop a kind of reversible self-repair material of flexibility of novel rollable folding to solve these problems.
In existing research, by groups such as the terminal modified pyridine of PDMS chains, triazoles, and and Co2+, Fe3+, Zn2+Metal
After ion forms dynamic coordinate bond, gained is modified the elongation at break of PDMS elastomers preferably and generally has 90% left side at room temperature
Right self-repair efficiency is highly suitable for preparing the Bionic flexibles devices such as electronic skin, wearable sensors and artificial-muscle.
But for the flexible and transparents electronic device such as solar cell, flexible display, capacitive touch screen and FPCB, above-mentioned report
These height stretch PDMS bases self-repair material and can not be but applicable in because poor intensity is with rigidity.In contrast, the prior art is logical
Cross and introduce the boroxine of three-functionality-degree and be used as crosslinking points, obtained a kind of rigidity PDMS base cross-linked networks, Young's modulus with
Tensile strength respectively reaches 182MPa and 9.46MPa, is the peak in current PDMS bases self-repair material, but this rigid
The elongation at break of property PDMS base cross-linked networks<10%, while the participation of water is needed in self-repair procedure, easily cause shorted devices
Danger thus while it has excellent mechanical property, but is not still suitable for flexible and transparent electronic device.
In conclusion a kind of PDMS base materials with high transmittance, excellent mechanical intensity and high tenacity of exploitation, overcome commercialization
The defect of PI and PET, the rollable folded substrate as reversible selfreparing flexible and transparent electronic device, which is one, has weight
The project of big application value.
Invention content
In view of the deficiencies of the prior art, the present invention provides a kind of transparent rollable folding polysiloxane film and its preparation and certainly
Restorative procedure.Polysiloxane film disclosed by the invention has the characteristics that flexible, transparent, inexpensive and easy processing and can be extensive
It uses, from chain structure, the Si-O ratios C-C of bond angle and bond distance's bigger is easier rotation in generation and realizes sub-chain motion, thus
Flexible more preferable, this feature meets requirement of the reversible self-repair material to polymer segment high movement property, using it as the soft of base material
Property transparent electronics have had both high stretch and good self-reparing capability.
In order to achieve the above objectives, the technical solution adopted in the present invention is：
A kind of transparent rollable preparation method for folding polysiloxane film, includes the following steps：
（1）After gamma-aminopropyl-triethoxy-silane, water and alcoholic solvent are mixed, the amino-containing hyperbranched poly in end is obtained by the reaction
Siloxanes；
（2）After 2,2'-, bis- sulphur diethanols, diisocyanate and alkyl chloride are mixed, the isocyanates containing disulfide is obtained by the reaction；
（3）Will be bis- (3- aminopropyls) sealing end dimethyl silicone polymer, diisocyanate and alkyl chloride mixing after, line is obtained by the reaction
Property dimethyl silicone polymer；
（4）By linear polydimethylsiloxane-, amino-containing hyperbranched polyorganosiloxane, the isocyanates containing disulfide and alkyl chloride
After mixing, mold is poured into, drying obtains transparent rollable folding polysiloxane film.
A kind of impaired transparent rollable self-repair method for folding polysiloxane film, includes the following steps, by what is be damaged
The transparent rollable impaired face paste for folding polysiloxane film is closed, the then heating 0.5~2 under conditions of temperature is 100~140 DEG C
Hour, complete the impaired transparent rollable selfreparing for folding polysiloxane film；The transparent rollable folding polysiloxane film
Preparation method include the following steps：
（1）After gamma-aminopropyl-triethoxy-silane, water and alcoholic solvent are mixed, the amino-containing hyperbranched poly in end is obtained by the reaction
Siloxanes；
（2）After 2,2'-, bis- sulphur diethanols, diisocyanate and alkyl chloride are mixed, the isocyanates containing disulfide is obtained by the reaction；
（3）Will be bis- (3- aminopropyls) sealing end dimethyl silicone polymer, diisocyanate and alkyl chloride mixing after, line is obtained by the reaction
Property dimethyl silicone polymer；
（4）By linear polydimethylsiloxane-, amino-containing hyperbranched polyorganosiloxane, the isocyanates containing disulfide and alkyl chloride
After mixing, mold is poured into, drying obtains transparent rollable folding polysiloxane film.
Gather the invention also discloses the amino-containing hyperbranched polyorganosiloxane in end, the isocyanates containing disulfide and linearly
Application of the dimethyl siloxane in preparing transparent rollable folding polysiloxane film, which is characterized in that end is amino-containing super
The preparation method of branched polysiloxane, the isocyanates containing disulfide and linear polydimethylsiloxane- is as follows：
After gamma-aminopropyl-triethoxy-silane, water and alcoholic solvent are mixed, the amino-containing hyperbranched poly silica in end is obtained by the reaction
Alkane；
After 2,2'-, bis- sulphur diethanols, diisocyanate and alkyl chloride are mixed, the isocyanates containing disulfide is obtained by the reaction；
Will be bis- after (3- aminopropyls) sealing end dimethyl silicone polymer, diisocyanate and alkyl chloride mixing, it is obtained by the reaction linear
Dimethyl silicone polymer.
The amino-containing hyperbranched polyorganosiloxane in specific end, the isocyanates containing disulfide and linear polydimethyl silica
Alkane prepares the transparent rollable method for folding polysiloxane film, by linear polydimethylsiloxane-, amino-containing hyperbranched poly
After siloxanes, the isocyanates containing disulfide and alkyl chloride mixing, mold is poured into, drying obtains the transparent rollable poly- silica of folding
Alkane film.
In above-mentioned technical proposal, the alcoholic solvent is in methanol, ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol, isobutanol
It is one or more of；The alkyl chloride is one or more of dichloromethane, chloroform, 1,2- dichloroethanes；Described two
Isocyanates is diisocyanate cpd or the di-isocyanate derivatives by diisocyanate cpd preparation；Described two
Isocyanate compound is toluene di-isocyanate(TDI)（TDI）, isophorone diisocyanate（IPDI）, two isocyanide of diphenyl methane
Acid esters（MDI）, dicyclohexyl methyl hydride diisocyanate（HMDI）, hexamethylene diisocyanate（HDI）, lysine diisocyanate
Ester（LDI）, benzene dimethylene diisocyanate（XDI）, naphthalene diisocyanate（NDI）, tetramethylxylene diisocyanate
Ester（TMXDI）, Methylcyclohexyl diisocyanate（HTDI）One or more of.It is preferred that bis- (3- aminopropyls) sealing end poly- two
Methylsiloxane molecular weight is 1000.
In above-mentioned technical proposal, step（1）In, the mass ratio of gamma-aminopropyl-triethoxy-silane, water and alcoholic solvent is
100:（10~15）:（100~200）；Step（2）In, 2,2'- bis- sulphur diethanols, diisocyanate and alkyl chloride mass ratio
For（75~80）:（160~270）:（1000~1500）；Step（3）In, bis- (3- aminopropyls) blocks polydimethylsiloxanes
The mass ratio of alkane, diisocyanate and alkyl chloride is 100:（10~25）:（1000~1500）；Step（4）In, linear poly- diformazan
Radical siloxane, amino-containing hyperbranched polyorganosiloxane, the isocyanates containing disulfide and alkyl chloride mass ratio be 50:（3~6）
:（10~15）:（100~150）.
In above-mentioned technical proposal, step（1）In, mixed temperature is room temperature, and the temperature of reaction is 60~80 DEG C, reaction
Time is 4~6h；Step（2）In, mixed temperature is room temperature, and the temperature of reaction is 60~80 DEG C, time of reaction is 2~
4h；Step（3）In, mixed temperature is room temperature, and the temperature of reaction is 60~80 DEG C, and the time of reaction is 4~6h；Step（4）
In, mixed temperature is room temperature.The room temperature refers to indoor temperature, preferably 20~30 DEG C.
In above-mentioned technical proposal, step（1）In, it removes solvent under reduced pressure after reaction, obtains the amino-containing over-expense in end
Change polysiloxanes；Step（2）In, it removes solvent under reduced pressure after reaction, obtains the isocyanates containing disulfide；Step（3）In,
It removes solvent under reduced pressure after reaction, obtains linear polydimethylsiloxane-.
It is described to be damaged to be broken in above-mentioned technical proposal, the plane of disruption is fixed into fitting with fixture, selfreparing is completed in heating.
The transparent rollable poly- silica of folding prepared according to the above-mentioned transparent rollable preparation method for folding polysiloxane film
Alkane film.
The transparent rollable preparation method for folding polysiloxane film disclosed by the invention is specific as follows：
（1）By mass, under conditions of temperature is 20~30 DEG C, by 100 parts of gamma-aminopropyl-triethoxy-silanes, 10~15
Part water and 100~200 parts of alcoholic solvents after mixing, rise to 60~80 DEG C and 4~6h of insulation reaction；Gained mixed liquor depressurizes
Alcoholic solvent is evaporated off, obtains the amino-containing hyperbranched polyorganosiloxane in end；
（2）By mass, temperature be 20~30 DEG C under conditions of, by 77 parts of 2,2'-, bis- sulphur diethanols, 169~264 part two it is different
Cyanate and 1000~1500 parts of alkyl chlorides after mixing, rise to 60~80 DEG C and 2~4h of insulation reaction；Gained mixed liquor
It removes alkyl chloride under reduced pressure, obtains the isocyanates containing disulfide；
（3）By mass, under conditions of temperature is 20~30 DEG C, 100 parts bis- (3- aminopropyls) is blocked into poly dimethyl silicon
Oxygen alkane（PDMS, Mn=1000）, 13~21 parts of diisocyanate and 1000~1500 parts of alkyl chlorides after mixing, rise to 60
~80 DEG C and 2~4h of insulation reaction；Gained mixed liquor removes alkyl chloride under reduced pressure, obtains linear polydimethylsiloxane-；
（4）By mass, under conditions of temperature is 20~30 DEG C, 50 parts of linear polydimethylsiloxane-s, 3~6 parts are contained into ammonia
The hyperbranched polyorganosiloxane of base, 10~15 parts of isocyanates and 100~150 parts of alkyl chlorides containing disulfide are uniformly mixed, and are poured into
Mold is dried, and transparent rollable folding polysiloxane film is obtained.
Compared with prior art, the advantageous effect that the present invention obtains is：
1, polysiloxane film provided by the invention is permanently chemically crosslinked by building dynamic hydrogen bond crosslinks and hyperbranched polyorganosiloxane
Multiple dimensioned cross-linked structure, not only there is high-modulus and high-tensile, while having had both high glass-transition temperature and high-ductility
Property.
2, polysiloxane film provided by the invention regulates and controls the exchange rate of hydrogen bond formation/dissociation and disulfide by temperature,
Realize the reversible selfreparing of high rigidity high intensity silicone materials, and self-repair efficiency（> 90%）With existing polysiloxanes
Elastomer phase is worked as.
3, compared with prior art, polysiloxane film provided by the invention can not only carry out while with high rigidity
Repeatedly bending folding can also be remained with curling and without folding line.
Description of the drawings
Fig. 1 is the amino-containing hyperbranched polyorganosiloxane in end prepared by the embodiment of the present invention 1（HPSi）Hydrogen nuclear magnetic resonance
Spectrum（1H-NMR）；
Fig. 2 is the amino-containing hyperbranched polyorganosiloxane in end prepared by the embodiment of the present invention 1（HPSi）Nuclear magnetic resonance silicon spectrum
（29Si-NMR）；
It is red with transparent rollable folding polysiloxane film that Fig. 3 is the isocyanates containing disulfide for preparing of the embodiment of the present invention 1
Outer spectrogram；
Fig. 4 is the transparent rollable thermogravimetric curve for folding polysiloxane film prepared by the embodiment of the present invention 1；
Fig. 5 is transparent rollable folding polysiloxane film dynamic mechanical curve prepared by the embodiment of the present invention 1；
Fig. 6 is the transparent rollable curling folding effect digital photograph for folding polysiloxane film prepared by the embodiment of the present invention 1；
Fig. 7 is the transparent rollable UV-Vis spectra for folding polysiloxane film prepared by the embodiment of the present invention 1.
Fig. 8 is the transparent rollable tensile stress-folded before and after polysiloxane film selfreparing prepared by the embodiment of the present invention 1
Strain curve；
Fig. 9 is the digital photograph of the transparent rollable selfreparing effect for folding polysiloxane film prepared by the embodiment of the present invention 1；
Figure 10 be prepared by the embodiment of the present invention 1 it is transparent it is rollable fold prepared by polysiloxane film and comparative example 1 without disulfide
The selfreparing effect polarized light microscopy photo of polysiloxane film.
Specific implementation mode
With reference to the accompanying drawings and examples, technical solution of the present invention will be further described.
Embodiment 1
1）The amino-containing hyperbranched polyorganosiloxane in end（It is denoted as HPSi）Preparation
By mass, under conditions of temperature is 20 DEG C, by 100g gamma-aminopropyl-triethoxy-silanes（KH550）, 10g water and
100g ethyl alcohol after mixing, rises to 60 DEG C and insulation reaction 4h；After gained mixed liquor removes ethyl alcohol under reduced pressure, obtains end and contain ammonia
The hyperbranched polyorganosiloxane of base（HPSi）, nuclear magnetic resonance spectroscopy is with nuclear magnetic resonance silicon spectrum respectively referring to attached Fig. 1 and 2.
2）The preparation of isocyanates containing disulfide
By mass, under conditions of temperature is 20 DEG C, by 77g 2, bis- sulphur diethanols of 2'-, 224g isophorone diisocyanates
Ester and 1000g dichloromethane after mixing, rise to 60 DEG C and insulation reaction 2h；Gained mixed liquor removes dichloromethane under reduced pressure
Afterwards, the isocyanates containing disulfide is obtained, infrared spectrum is shown in attached drawing 3.
3）The preparation of linear polydimethylsiloxane-
By mass, under conditions of temperature is 20 DEG C, 100g bis- (3- aminopropyls) is blocked into dimethyl silicone polymer
（PDMS, Mn=1000）, 17.7g isophorone diisocyanate and 1000g dichloromethane after mixing, rise to 60 DEG C and protect
Temperature reaction 2h；After gained mixed liquor removes dichloromethane under reduced pressure, linear polydimethylsiloxane- is obtained.
4）The transparent rollable preparation for folding polysiloxane film
By mass, under conditions of temperature is 20 DEG C, 50g linear polydimethylsiloxane-s, 3.6g HPSi, 10g are contained into two sulphur
The isocyanates and 100g dichloromethane of ether are uniformly mixed, and are poured into mold drying, are obtained transparent rollable folding polysiloxane film,
Its infrared spectrum, thermogravimetric curve, dynamic mechanical curve, digital photograph, UV-Vis spectra and the drawing for crimping folding effect
It stretches load-deformation curve and sees attached drawing 3,4,5,6,7 and 8 respectively.
5）The transparent rollable self-repair method for folding polysiloxane film
The impaired transparent rollable section for folding polysiloxane film is fixed and fitted closely with fixture, is then in temperature
It is heated 0.5 hour under conditions of 100 DEG C.Its repair after test load-deformation curve, selfreparing effect digital photograph with partially
Light microphoto is shown in attached drawing 8,9 and 10 respectively.
Preparation of the comparative example 1 without disulfide polysiloxane film
By mass, under conditions of temperature is 20 DEG C, by 50g linear polydimethylsiloxane-s, 3.6g HPSi, the different Fo Er of 4g
Ketone diisocyanate and 100g dichloromethane are uniformly mixed, and are poured into mold drying, are obtained no disulfide polysiloxane film.
The impaired section without disulfide polysiloxane film is fixed and fitted closely with fixture, is then 100 in temperature
It is heated 0.5 hour under conditions of DEG C, completes to repair.
Selfreparing effect polarized light microscopy photo of the comparative example 1 without disulfide polysiloxane film is shown in attached drawing 10.
Referring to attached drawing 1, it is the amino-containing hyperbranched polyorganosiloxane in end prepared by the embodiment of the present invention 1（HPSi）Core
Magnetic resonance hydrogen is composed（1H-NMR）.As seen from the figure, the characteristic peak at δ=1.21ppm is Si-O-CH2CH3Upper methyl（b）H, still
Arbitrary C in the number and aminopropyl of its H（C, d or e in figure）The ratio between number of upper H is 3:2, far smaller than KH550 corresponding 9:
2, hydrolytic condensation generates Si-O-Si between illustrating KH550.
Referring to attached drawing 2, it is the amino-containing hyperbranched polyorganosiloxane in end prepared by the embodiment of the present invention 1（HPSi）Core
Magnetic resonance silicon is composed（29Si-NMR）.Wherein D, L, T have respectively represented the branched chain link of hyperbranched siloxane, linear chain link and sealing end
Chain link.It can be found that the peaks D are significantly stronger than the peaks L and the peaks T from figure, illustrate branched chain link generally existing in HPSi, further demonstrate,proves
KH550 monomers are illustrated and have been fully hydrolyzed condensation.According to the corresponding integral areas of D in figure and L, using such as following formula（1）Formula meter
Calculate the value of degree of branching DB：
（1）
By calculating it is found that the DB of HPSi is 0.86, close to DB=1 of dendrimer, illustrate the molecular structure of HPSi with
Dendrimer is close, have lower viscosity and preferable dissolubility, and surface be rich in active amino, have high activity with
Reactivity.
Referring to attached drawing 3, it is that the isocyanates containing disulfide prepared by the embodiment of the present invention 1 gathers with transparent rollable fold
The infrared spectrum of silicone film.Bis- sulphur diethanols of 2,2'- generate carbamic acid after isophorone diisocyanate chain extension
Ester, there is 1720cm in the stretching vibration peak of C=O in infrared spectrum-1Place, and 2260cm-1Place is then the isocyanic acid containing disulfide
- NCO characteristic peaks in ester.
In the transparent rollable infrared spectrum for folding polysiloxane film, 3318cm-1With 1560cm-1The characteristic peak at place point
Not Wei-NH- stretching vibration and flexural vibrations peak, and 1630cm-1The characteristic peak at place is then the stretching vibration peak of C=O in urea groups,
This illustrate PDMS and isophorone diisocyanate chain extending reaction and then the isocyanates containing disulfide further with line
Property dimethyl silicone polymer or HPSi reaction generate a large amount of urea groups.PDMS and-the CH in isophorone3Stretching vibration with it is curved
Bent vibration peak respectively appears in 2960 cm-1With 1260cm-1Place；1080 and 1025cm-1The broad peak at place is then linear polydimethyl
The feature stretching vibration peak of Si-O-Si in siloxanes and HPSi, and 800cm-1The sharp absorption peak at place is then that the flexible of Si-C shakes
Dynamic peak；2260cm-1Place do not occur-NCO characteristic peaks then illustrate prepared by polysiloxane film-NCO with it is linear after chain extension
- NH in dimethyl silicone polymer and HPSi2The reaction was complete.
Referring to attached drawing 4, it is that the transparent rollable thermal weight loss for folding polysiloxane film prepared by the embodiment of the present invention 1 is bent
Line.It can be seen that the transparent rollable starting heat decomposition temperature for folding polysiloxane film（T di）It is 282 DEG C, there is good heat
Stability.
Referring to attached drawing 5, it is that transparent rollable folding polysiloxane film dynamic mechanical prepared by the embodiment of the present invention 1 is bent
Line.Wherein dielectric loss angle tangent（Tanδ）Peak temperature as glass transition temperature, single symmetrical Tan δ are presented
Peak.Therefore embodiment 1 prepare polysiloxane film glass transition temperature be 96 DEG C, higher than existing literature report it is reversible from
Repair silicone materials（Glass transition temperature is generally -120 ~ 65 DEG C）.
Referring to attached drawing 6, it is that the transparent rollable curling for folding polysiloxane film prepared by the embodiment of the present invention 1 folds effect
Fruit digital photograph.As shown, by the transparent rollable square for folding polysiloxane film and being cut to the mm sizes of 60 mm × 60
Afterwards, it can freely be converted between the shapes such as the bending of S types, positive inverse folding or curling, it was demonstrated that it is with excellent flexibility.It will be identical
The PI films of size with PET film as reference, equally twice to their positive inverse foldings, can be with to amplifying observation at their folding
See, PI film surfaces produce folding line that is transparent but can not restoring（In frame）, and the folding line on PET film can not only restore and shadow
Its transparency is rung, there are apparent white lines together in the letter C of background paper（In frame）.With them on the contrary, transparent rollable folding
It is remained without trace at the folding of folded polysiloxane film, the writing on background paper is still high-visible, illustrates that embodiment 1 is prepared poly-
Silicone film can effectively overcome the defect of PI and PET, be a kind of new material of foldable curling.
Referring to attached drawing 7, it is the transparent rollable ultraviolet-visible for folding polysiloxane film prepared by the embodiment of the present invention 1
Light spectrum.It can be seen that transparent rollable folding polysiloxane film has good transparency from photo, further pass through purple
Outside-visible light tests the transmitance of different film thickness under 200-800 nm.It can be seen that using air as baseline, different-thickness
Film the visible light regions 400-800 nm transmitance subtracting with film thickness of the transmitance at 80% or more, wherein 550nm
It is small from 86.09%（0.4mm）Rise to 88.63 %（0.2mm）.
Referring to attached drawing 8, before and after it is transparent rollable folding polysiloxane film selfreparing prepared by the embodiment of the present invention 1
Tensile stress-strain curve.It is by extension test it is found that the original transparent rollable tensile strength for folding polysiloxane film, disconnected
Split elongation, Young's modulus and toughness be respectively 9.25 ± 0.22MPa, 224.21 ± 2.79%, 214.89 ± 18.27MPa and
16.32 ± 0.18MPa has good rigidity and toughness.The tensile strength of polysiloxane film after reparation, elongation at break with it is tough
Property be respectively 8.16 ± 0.87MPa, 211.59 ± 5.63% and 14.91 ± 0.72MPa, corresponding remediation efficiency be 94.99%,
94.37% and 91.36%.As shown in the photo, by the polysiloxane film bending 180 after reparationoThe flawless appearance of upper and lower surface afterwards is protected
Good integrality is held；The present invention is while Young's modulus and tensile strength are more than state of the art, extension at break
Rate is 22.4 times of the prior art, not only realizes the attainable rigidity of prior art institute, has also taken into account excellent toughness.
Referring to attached drawing 9, it is the transparent rollable selfreparing effect for folding polysiloxane film prepared by the embodiment of the present invention 1
Digital photograph.As shown, complete transparent rollable folding polysiloxane film is cut, section, which fits closely, is positioned over heat
On platform 100 DEG C keep 30 min after, two parts film for being broken completely again fusion connection at an entirety.
Referring to attached drawing 10, it is that transparent rollable folding polysiloxane film prepared by the embodiment of the present invention 1 is made with comparative example 1
It is standby without disulfide polysiloxane film selfreparing effect polarized light microscopy photo.Using the transparent rollable folding of polarized light microscope observing
Polysiloxane film is damaged the surface topography at place after different repair times.As shown, in transparent rollable folding polysiloxanes
Film surface cut the cross section that a road width is 20 μm（Black region in figure）；Section is fixed with fixture then and is closely pasted
It closes, selfreparing is heated under conditions of temperature is 100 DEG C.As repair time extends, cross section becomes narrow gradually diminution, and from
Lighttight black region gradually becomes transparence；When repair time reaching 30 min, section is repaired completely.In contrast,
Cross section without disulfide polysiloxanes film surface fails to restore from lighttight black powder under the conditions of identical selfreparing
To transparence, section only width is become smaller, and after this illustrates that HPSi forms permanent crosslinking in film, has greatly fettered flexibility
The movement of PDMS segments, only rely on be heated to 100 DEG C make hydrogen bond dissociate and generate chain diffusion cannot complete selfreparing, because
And it is the key that transparent rollable folding polysiloxane film obtains good self-reparing capability to introduce disulfide.
Embodiment 2
1）The amino-containing hyperbranched polyorganosiloxane in end（It is denoted as HPSi）Preparation
By mass, under conditions of temperature is 25 DEG C, by 100g gamma-aminopropyl-triethoxy-silanes（KH550）, 12.5g water
After mixing with 150g methanol, 70 DEG C and insulation reaction 5h are risen to；After gained mixed liquor removes methanol under reduced pressure, obtains end and contain
The hyperbranched polyorganosiloxane of amino（HPSi）.
2）The preparation of isocyanates containing disulfide
By mass, under conditions of temperature is 25 DEG C, by 77g 2, bis- sulphur diethanols of 2'-, 169g hexa-methylene diisocyanates
Ester and 1100g chloroforms after mixing, rise to 70 DEG C and insulation reaction 2.5h；Gained mixed liquor removes chloroform under reduced pressure
Afterwards, the isocyanates containing disulfide is obtained.
3）The preparation of linear polydimethylsiloxane-
By mass, under conditions of temperature is 25 DEG C, 100g bis- (3- aminopropyls) is blocked into dimethyl silicone polymer
（PDMS, Mn=1000）, 13.4g hexamethylene diisocyanates and 1100g chloroforms after mixing, rise to 70 DEG C and protect
Temperature reaction 2.5h；After gained mixed liquor removes chloroform under reduced pressure, linear polydimethylsiloxane- is obtained.
4）The transparent rollable preparation for folding polysiloxane film
By mass, under conditions of temperature is 25 DEG C, 50g linear polydimethylsiloxane-s, 4g HPSi, 12g are contained into disulfide
Isocyanates and 125g chloroforms be uniformly mixed, pour into mold drying, obtain transparent rollable folding polysiloxane film.
5）The transparent rollable self-repair method for folding polysiloxane film
The impaired transparent rollable section for folding polysiloxane film is fixed and fitted closely with fixture, is then in temperature
It is heated 0.6 hour under conditions of 110 DEG C；The tensile strength of polysiloxane film, elongation at break are corresponding with toughness after reparation repaiies
Multiple efficiency is 92.89%, 92.17% and 91.06%.
Embodiment 3
1）The amino-containing hyperbranched polyorganosiloxane in end（It is denoted as HPSi）Preparation
By mass, under conditions of temperature is 30 DEG C, by 100g gamma-aminopropyl-triethoxy-silanes（KH550）, 15g water and
200g normal propyl alcohols after mixing, rise to 80 DEG C and insulation reaction 6h；After gained mixed liquor removes normal propyl alcohol under reduced pressure, end is obtained
Amino-containing hyperbranched polyorganosiloxane（HPSi）.
2）The preparation of isocyanates containing disulfide
By mass, under conditions of temperature is 30 DEG C, by 77g 2, bis- sulphur diethanols of 2'-, 264g dicyclohexyl methyl hydrides two are different
Cyanate and 1200g1,2- dichloroethanes after mixing, rise to 80 DEG C and insulation reaction 3h；Gained mixed liquor removes 1 under reduced pressure,
After 2- dichloroethanes, the isocyanates containing disulfide is obtained.
3）The preparation of linear polydimethylsiloxane-
By mass, under conditions of temperature is 30 DEG C, 100g bis- (3- aminopropyls) is blocked into dimethyl silicone polymer
（PDMS, Mn=1000）, 20.8g dicyclohexyl methyl hydride diisocyanates and 1200g1,2- dichloroethanes after mixing, rise to
80 DEG C and insulation reaction 3h；After gained mixed liquor removes 1,2- dichloroethanes under reduced pressure, linear polydimethylsiloxane- is obtained.
4）The transparent rollable preparation for folding polysiloxane film
By mass, under conditions of temperature is 30 DEG C, 50g linear polydimethylsiloxane-s, 5g HPSi, 15g are contained into disulfide
Isocyanates and 150g1,2- dichloroethanes be uniformly mixed, pour into mold drying, obtain transparent rollable folding polysiloxanes
Film.
5）The transparent rollable self-repair method for folding polysiloxane film
The impaired transparent rollable section for folding polysiloxane film is fixed and fitted closely with fixture, is then in temperature
It is heated 0.7 hour under conditions of 115 DEG C；The tensile strength of polysiloxane film, elongation at break are corresponding with toughness after reparation repaiies
Multiple efficiency is 93.01%, 92.67% and 90.86%.
Embodiment 4
1）The amino-containing hyperbranched polyorganosiloxane in end（It is denoted as HPSi）Preparation
By mass, under conditions of temperature is 22 DEG C, by 100g gamma-aminopropyl-triethoxy-silanes（KH550）, 11g water,
100g methanol after mixing, rises to 65 DEG C and insulation reaction 4.5h with 100g ethyl alcohol；Gained mixed liquor remove under reduced pressure methanol with
After ethyl alcohol, the amino-containing hyperbranched polyorganosiloxane in end is obtained（HPSi）.
2）The preparation of isocyanates containing disulfide
By mass, under conditions of temperature is 22 DEG C, by 77g 2, bis- sulphur diethanols of 2'-, two isocyanide of 125g diphenyl methanes
Acid esters, 106g naphthalene diisocyanates, 600g dichloromethane and 700g chloroforms after mixing, rise to 65 DEG C and insulation reaction
3.5h；Gained mixed liquor removes dichloromethane under reduced pressure with after chloroform, obtains the isocyanates containing disulfide.
3）The preparation of linear polydimethylsiloxane-
By mass, under conditions of temperature is 22 DEG C, 100g bis- (3- aminopropyls) is blocked into dimethyl silicone polymer
（PDMS, Mn=1000）, 10g methyl diphenylene diisocyanates, 8.4g naphthalene diisocyanates, 600g dichloromethane and 700g tri-
Chloromethanes after mixing, rises to 65 DEG C and insulation reaction 3.5h；Gained mixed liquor removes dichloromethane and chloroform under reduced pressure
Afterwards, linear polydimethylsiloxane- is obtained.
4）The transparent rollable preparation for folding polysiloxane film
By mass, under conditions of temperature is 22 DEG C, 50g linear polydimethylsiloxane-s, 6g HPSi, 11g are contained into disulfide
Isocyanates, 60g dichloromethane be uniformly mixed with 60g chloroforms, pour into mold drying, obtain it is transparent it is rollable fold it is poly-
Silicone film.
5）The transparent rollable self-repair method for folding polysiloxane film
The impaired transparent rollable section for folding polysiloxane film is fixed and fitted closely with fixture, is then in temperature
It is heated 0.8 hour under conditions of 120 DEG C.
Embodiment 5
1）The amino-containing hyperbranched polyorganosiloxane in end（It is denoted as HPSi）Preparation
By mass, under conditions of temperature is 24 DEG C, by 100g gamma-aminopropyl-triethoxy-silanes（KH550）, 13g water,
80g methanol after mixing, rises to 75 DEG C and insulation reaction 5.5h with 120g normal propyl alcohols；Gained mixed liquor remove under reduced pressure methanol with
After normal propyl alcohol, the amino-containing hyperbranched polyorganosiloxane in end is obtained（HPSi）.
2）The preparation of isocyanates containing disulfide
By mass, under conditions of temperature is 24 DEG C, by 77g 2, bis- sulphur diethanols of 2'-, 88g toluene di-isocyanate(TDI)s, 91g
Methylcyclohexyl diisocyanate, 300g dichloromethane and 1100g1,2- dichloroethanes after mixing, rise to 75 DEG C and keep the temperature
React 4h；Gained mixed liquor removes dichloromethane and 1 under reduced pressure, after 2- dichloroethanes, obtains the isocyanates containing disulfide.
3）The preparation of linear polydimethylsiloxane-
By mass, under conditions of temperature is 24 DEG C, 100g bis- (3- aminopropyls) is blocked into dimethyl silicone polymer
（PDMS, Mn=1000）, 7g toluene di-isocyanate(TDI)s, 7.2g Methylcyclohexyl diisocyanates, 300g dichloromethane with
1100g1,2- dichloroethanes after mixing, rise to 75 DEG C and insulation reaction 4h；Gained mixed liquor remove under reduced pressure dichloromethane with
After 1,2- dichloroethanes, linear polydimethylsiloxane- is obtained.
4）The transparent rollable preparation for folding polysiloxane film
By mass, under conditions of temperature is 24 DEG C, 50g linear polydimethylsiloxane-s, 3g HPSi, 13g are contained into disulfide
Isocyanates, 70g dichloromethane and 70g1,2- dichloroethanes be uniformly mixed, pour into mold drying, obtain transparent rollable folding
Folded polysiloxane film.
5）The transparent rollable self-repair method for folding polysiloxane film
The impaired transparent rollable section for folding polysiloxane film is fixed and fitted closely with fixture, is then in temperature
It is heated 1 hour under conditions of 125 DEG C.
Embodiment 6
1）The amino-containing hyperbranched polyorganosiloxane in end（It is denoted as HPSi）Preparation
By mass, under conditions of temperature is 28 DEG C, by 100g gamma-aminopropyl-triethoxy-silanes（KH550）, 14g water,
130g ethyl alcohol after mixing, rises to 60 DEG C and insulation reaction 5h with 70g n-butanols；Gained mixed liquor remove under reduced pressure ethyl alcohol with just
After butanol, the amino-containing hyperbranched polyorganosiloxane in end is obtained（HPSi）.
2）The preparation of isocyanates containing disulfide
By mass, under conditions of temperature is 28 DEG C, by 77g 2, bis- sulphur diethanols of 2'-, 114g lysine diisocyanates,
95g benzene dimethylene diisocyanate, 500g chloroforms and 800g1,2- dichloroethanes after mixing, rise to 73 DEG C and protect
Temperature reaction 3.5h；Gained mixed liquor removes chloroform and 1 under reduced pressure, after 2- dichloroethanes, obtains the isocyanates containing disulfide.
3）The preparation of linear polydimethylsiloxane-
By mass, under conditions of temperature is 28 DEG C, 100g bis- (3- aminopropyls) is blocked into dimethyl silicone polymer
（PDMS, Mn=1000）, 9g lysine diisocyanates, 7.5g benzene dimethylene diisocyanate, 500g chloroforms with
800g1,2- dichloroethanes after mixing, rise to 73 DEG C and insulation reaction 3.5h；Gained mixed liquor removes chloroform under reduced pressure
After 1,2- dichloroethanes, linear polydimethylsiloxane- is obtained.
4）The transparent rollable preparation for folding polysiloxane film
By mass, under conditions of temperature is 28 DEG C, 50g linear polydimethylsiloxane-s, 4.5g HPSi, 14g are contained into two sulphur
Isocyanates, 75g chloroforms and 75g1, the 2- dichloroethanes of ether are uniformly mixed, and are poured into mold drying, are obtained transparent rollable
Fold polysiloxane film.
5）The transparent rollable self-repair method for folding polysiloxane film
The impaired transparent rollable section for folding polysiloxane film is fixed and fitted closely with fixture, is then in temperature
It is heated 1.5 hours under conditions of 130 DEG C.
Embodiment 7
1）The amino-containing hyperbranched polyorganosiloxane in end（It is denoted as HPSi）Preparation
By mass, under conditions of temperature is 23 DEG C, by 100g gamma-aminopropyl-triethoxy-silanes（KH550）,11.5g
Water, 60g methanol, 60g isopropanols and 60g isobutanols after mixing, rise to 70 DEG C and insulation reaction 4h；Gained mixed liquor depressurizes
After methanol, isopropanol and isobutanol is evaporated off, the amino-containing hyperbranched polyorganosiloxane in end is obtained（HPSi）.
2）The preparation of isocyanates containing disulfide
By mass, under conditions of temperature is 21 DEG C, by 77g 2, bis- sulphur diethanols of 2'-, 75g isophorone diisocyanates
Ester, 56g hexamethylene diisocyanates, 82g tetramethylxylylene diisocyanates, 500g dichloromethane, 500g trichlorines
Methane and 500g1,2- dichloroethanes after mixing, rise to 62 DEG C and insulation reaction 3h；Gained mixed liquor removes dichloro under reduced pressure
Methane, chloroform and 1 after 2- dichloroethanes, obtain the isocyanates containing disulfide.
3）The preparation of linear polydimethylsiloxane-
By mass, under conditions of temperature is 21 DEG C, 100g bis- (3- aminopropyls) is blocked into dimethyl silicone polymer
（PDMS, Mn=1000）, 5.9g isophorone diisocyanate, 4.5g hexamethylene diisocyanates, 6.5g durols two
Methylene diisocyanate, 500g dichloromethane, 500g chloroforms and 500g1,2- dichloroethanes after mixing, rise to 62
DEG C and insulation reaction 3h；Gained mixed liquor removes dichloromethane, chloroform and 1 under reduced pressure, after 2- dichloroethanes, is linearly gathered
Dimethyl siloxane.
4）The transparent rollable preparation for folding polysiloxane film
By mass, under conditions of temperature is 21 DEG C, 50g linear polydimethylsiloxane-s, 5.5g HPSi, 12g are contained into two sulphur
Isocyanates, 50g dichloromethane, 50g chloroforms and 50g1, the 2- dichloroethanes of ether are uniformly mixed, and are poured into mold drying, are obtained
To transparent rollable folding polysiloxane film.
5）The transparent rollable self-repair method for folding polysiloxane film
The impaired transparent rollable section for folding polysiloxane film is fixed and fitted closely with fixture, is then in temperature
It is heated 2 hours under conditions of 140 DEG C.
Claims (10)
1. a kind of transparent rollable preparation method for folding polysiloxane film, which is characterized in that include the following steps：
（1）After gamma-aminopropyl-triethoxy-silane, water and alcoholic solvent are mixed, the amino-containing hyperbranched poly in end is obtained by the reaction
Siloxanes；
（2）After 2,2'-, bis- sulphur diethanols, diisocyanate and alkyl chloride are mixed, the isocyanates containing disulfide is obtained by the reaction；
（3）Will be bis- (3- aminopropyls) sealing end dimethyl silicone polymer, diisocyanate and alkyl chloride mixing after, line is obtained by the reaction
Property dimethyl silicone polymer；
（4）By linear polydimethylsiloxane-, amino-containing hyperbranched polyorganosiloxane, the isocyanates containing disulfide and alkyl chloride
After mixing, mold is poured into, drying obtains transparent rollable folding polysiloxane film.
2. a kind of impaired transparent rollable self-repair method for folding polysiloxane film, which is characterized in that include the following steps,
The impaired transparent rollable impaired face paste for folding polysiloxane film is closed, then heating 0.5~2 is small at 100~140 DEG C
When, complete the impaired transparent rollable selfreparing for folding polysiloxane film；The transparent rollable folding polysiloxane film
Preparation method includes the following steps：
（1）After gamma-aminopropyl-triethoxy-silane, water and alcoholic solvent are mixed, the amino-containing hyperbranched poly in end is obtained by the reaction
Siloxanes；
（2）After 2,2'-, bis- sulphur diethanols, diisocyanate and alkyl chloride are mixed, the isocyanates containing disulfide is obtained by the reaction；
（3）Will be bis- (3- aminopropyls) sealing end dimethyl silicone polymer, diisocyanate and alkyl chloride mixing after, line is obtained by the reaction
Property dimethyl silicone polymer；
（4）By linear polydimethylsiloxane-, amino-containing hyperbranched polyorganosiloxane, the isocyanates containing disulfide and alkyl chloride
After mixing, mold is poured into, drying obtains transparent rollable folding polysiloxane film.
3. according to claim 1 or claim 2, it is characterised in that：The alcoholic solvent is methanol, ethyl alcohol, normal propyl alcohol, different
One or more of propyl alcohol, n-butanol, isobutanol；The alkyl chloride is in dichloromethane, chloroform, 1,2- dichloroethanes
One or more；The diisocyanate is for diisocyanate cpd or by the two of diisocyanate cpd preparation
Isocyanate derivates；The diisocyanate cpd is toluene di-isocyanate(TDI), isophorone diisocyanate, diphenyl
Methane diisocyanate, dicyclohexyl methyl hydride diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, benzene
Dimethylene diisocyanate, naphthalene diisocyanate, tetramethylxylylene diisocyanate, methylcyclohexyl diisocyanate
One or more of ester.
4. according to claim 1 or claim 2, it is characterised in that：Step（1）In, gamma-aminopropyl-triethoxy silicon
The mass ratio of alkane, water and alcoholic solvent is 100:（10~15）:（100~200）；Step（2）In, it is 2,2'- bis- sulphur diethanols, two different
Cyanate and the mass ratio of alkyl chloride are（75~80）:（160~270）:（1000~1500）；Step（3）In, bis- (3- amino
Propyl) sealing end dimethyl silicone polymer, diisocyanate and alkyl chloride mass ratio be 100:（10~25）:（1000~
1500）；Step（4）In, linear polydimethylsiloxane-, amino-containing hyperbranched polyorganosiloxane, the isocyanates containing disulfide
Mass ratio with alkyl chloride is 50:（3~6）:（10~15）:（100~150）.
5. according to claim 1 or claim 2, it is characterised in that：Step（1）In, mixed temperature is room temperature, reaction
Temperature be 60~80 DEG C, time of reaction is 4~6h；Step（2）In, mixed temperature is room temperature, and the temperature of reaction is 60
~80 DEG C, the time of reaction is 2~4h；Step（3）In, mixed temperature is room temperature, and the temperature of reaction is 60~80 DEG C, reaction
Time be 4~6h；Step（4）In, mixed temperature is room temperature.
6. according to claim 1 or claim 2, it is characterised in that：Step（1）In, it removes under reduced pressure after reaction molten
Agent obtains the amino-containing hyperbranched polyorganosiloxane in end；Step（2）In, it removes solvent under reduced pressure after reaction, obtains containing two sulphur
The isocyanates of ether；Step（3）In, it removes solvent under reduced pressure after reaction, obtains linear polydimethylsiloxane-.
7. the impaired transparent rollable self-repair method for folding polysiloxane film according to claim 2, it is characterised in that：
It is described to be damaged as fracture.
8. the transparent rollable folding that according to claim 1 prepared by the transparent rollable preparation method for folding polysiloxane film
Polysiloxane film.
9. the amino-containing hyperbranched polyorganosiloxane in end, the isocyanates containing disulfide and linear polydimethylsiloxane- are being made
The standby transparent rollable application folded in polysiloxane film, which is characterized in that the amino-containing hyperbranched polyorganosiloxane in end contains two
The isocyanates of thioether and the preparation method of linear polydimethylsiloxane- are as follows：
After gamma-aminopropyl-triethoxy-silane, water and alcoholic solvent are mixed, the amino-containing hyperbranched poly silica in end is obtained by the reaction
Alkane；
After 2,2'-, bis- sulphur diethanols, diisocyanate and alkyl chloride are mixed, the isocyanates containing disulfide is obtained by the reaction；
Will be bis- after (3- aminopropyls) sealing end dimethyl silicone polymer, diisocyanate and alkyl chloride mixing, it is obtained by the reaction linear
Dimethyl silicone polymer.
10. application according to claim 9, it is characterised in that：The amino-containing hyperbranched polyorganosiloxane in end contains disulfide
Isocyanates and linear polydimethylsiloxane- prepare it is transparent it is rollable fold polysiloxane film method be linearly to gather
After dimethyl siloxane, amino-containing hyperbranched polyorganosiloxane, the isocyanates containing disulfide and alkyl chloride mixing, mould is poured into
Tool, drying obtain transparent rollable folding polysiloxane film.
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| CN112358620A (en) * | 2020-12-03 | 2021-02-12 | 苏州大学 | Preparation method of self-repairing material and application of self-repairing material |
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| CN110643058A (en) | 2020-01-03 |
| CN110643058B (en) | 2022-02-11 |
| CN110684220B (en) | 2022-04-15 |
| CN110684220A (en) | 2020-01-14 |
| CN108794781B (en) | 2019-11-22 |
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