CN106672895A - Preparation method of patterning of azo based supramolecular polymer - Google Patents
Preparation method of patterning of azo based supramolecular polymer Download PDFInfo
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- CN106672895A CN106672895A CN201710013896.0A CN201710013896A CN106672895A CN 106672895 A CN106672895 A CN 106672895A CN 201710013896 A CN201710013896 A CN 201710013896A CN 106672895 A CN106672895 A CN 106672895A
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- B81C1/00—Manufacture or treatment of devices or systems in or on a substrate
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Abstract
The invention disclosed a preparation method of patterning of azo based supramolecular polymer. A single-layer membrane system taking PDMS (Polydimethylsiloxane) as a substrate and P4VP and a supramolecular polymer of azo micromolecule 4-hydroxy-4'-dimethylaminoazobenzene (OH-DMA) as a surface layer is utilized to regulate and control technological method of a wrinkle period by means of the advantage that a supramolecular system is easy to regulate and control relative content between the azo and a macromolecule. As hydroxyl is contained in the OH-DMA molecule, the OH-DMA molecule can be bonded with the P4VP through a hydrogen bond, so that conventional complicated synthesizing processes of realizing bonding through covalent bonds, and the defect of phase separation in a doping is overcome. According to the preparation method disclosed by the invention, wrinkle patterns of different periods are prepared by regulating and controlling molar ratio between an azobenzene molecule and a high-molecular polymer by means of interaction of the hydrogen bond between the azobenzene molecule and the high-molecular polymer. The preparation method disclosed by the invention is quick and simple, and the method for regulating and controlling surface patterns by means of the supramolecular system has a wide application in surface wettability and microfluidic devices.
Description
Technical field
The present invention relates to the surface micro-structure process technology of polymer, and in particular to the regulation and control wrinkle in supramolecular complex system
The process of stricture of vagina.
Background technology
As supramolecular chemistry and the cross discipline of polymer chemistry --- --- supermolecule polymer chemistry, just it is increasingly subject to
People's pays high attention to supermolecule polymer as an emerging subject, is characterized in combining weight using non-covalent bond effect
Complex radical unit, and the structure orderly to we show many novelties.It is many in traditional method for preparing azobenzene polymer
People is employed the method for general polymer and azobenzene molecule blending.But only in the case where content is relatively low, Cai Nengshi
The preferable dispersion of existing azobenzene molecule, this just makes such mixed system have significant limitations in performance and design aspect.In addition, being permitted
Many researcheres are connected to azobenzene molecule on polymer chain by the form of covalent bond, although ensure that good dispersibility,
But preparation process very complicated.In domestic and international research in recent years, azo-compound is constructed into poly- with non-covalent bond effect
Compound system, obtains supermolecule azobenzene polymer.This supermolecule azobenzene polymer system is easily prepared, structural controllability
By force, good dispersion, component is easily controllable, and structure diversity and machinability are provided as functional material for it.
The content of the invention
For prior art, the present invention provides a kind of preparation method of azo-based supermolecule polymer patterning, will be super
Molecularly Imprinted Polymer thin film is used for surface wrinkling, prepares the patterned surface with different-shape.This azo supermolecule polymerization
Thing thin film is simple due to its preparation, and good stability is widely used in surface micro-structure manufacture field.
In order to solve above-mentioned technical problem, a kind of preparation of azo-based supermolecule polymer patterning proposed by the present invention
Method, step is as follows：
Step one, PDMS performed polymers and cross-linking agent are pressed into 10:1 mass ratio mixing, in pouring culture dish into, is filled with Glass rod
Stirring is divided to form prepolymer；
Step 2, with multiplex vavuum pump of circulating water type by the prepolymer for mixing deaerate 2 hours after, be put into constant temperature air blast
Drying baker, solidifies 4 hours at 70 DEG C；
Step 3, the N-dimethylformamide solution for preparing the P4VP that mass fraction is 6% and the OH- that mass fraction is 6%
The N-dimethylformamide solution of DMA, then according to mol ratio is 1:0.0625~1.0 is mixed both, obtains P4VP
(OH-DMA) the supermolecule composite solution of x, wherein, x=0.0625~1.0；
Step 4, the PDMS films that step 2 is cured cut into 1cm × 1cm as substrate, and plasma treatment 30s makes it
Surface hydrophilic, then using the method for spin-coating film by the supermolecule composite solution of P4VP obtained in step 3 (OH-DMA) x
It is coated onto in the PDMS substrates of surface hydrophilic and prepares supermolecule polymer single thin film；
Step 5, the supermolecule polymer single thin film for preparing step 4 are in multiplex vavuum pump of circulating water type evacuation 2
Then hour is transferred to the supermolecule polymer single thin film in baking oven with removing excess of solvent, is heated 1 hour at 90 DEG C
After close baking oven, make supermolecule polymer single thin film Slow cooling obtain reticulation patterns.
Further, in preparation method of the present invention, the mol ratio of the supermolecule composite solution of P4VP (OH-DMA) x is different,
It is final to obtain the chill mark pattern with different cycles.
Compared with prior art, the invention has the beneficial effects as follows：
The method of the present invention has quickly, the characteristics of easy, can simply and easily regulate and control macromolecule and azo small molecule
Between ratio, and also will not be separated in very high mol ratio.The invention provides a kind of new wrinkle regulation and control
Method.
Description of the drawings
Fig. 1 is the optical microscope picture of the crepe structure that supermolecule polymer film prepared by the embodiment of the present invention 1 is formed；
Fig. 2 is the optical microscope picture of the crepe structure that supermolecule polymer film prepared by the embodiment of the present invention 2 is formed；
Fig. 3 is the optical microscope picture of the crepe structure that supermolecule polymer film prepared by the embodiment of the present invention 3 is formed；
Fig. 4 is the optical microscope picture of the crepe structure that supermolecule polymer film prepared by the embodiment of the present invention 4 is formed；
Fig. 5 is the optical microscope picture of the crepe structure that supermolecule polymer film prepared by the embodiment of the present invention 5 is formed；
The wrinkle mechanical periodicity figure that Fig. 6 is formed for the supermolecule polymer film of embodiment 1-5 different mol ratio.
Specific embodiment
Below in conjunction with the accompanying drawings technical solution of the present invention is described in further detail with specific embodiment, described is concrete
Embodiment is only explained to the present invention, not to limit the present invention.
A kind of preparation method of the patterning of azo-based supermolecule polymer thin film proposed by the present invention, discloses with poly-
Dimethyl siloxane (PDMS) is substrate, poly- (4-vinylpyridine) (P4VP) and azo small molecule 4- hydroxyl -4'- dimethylamino idols
The supermolecule polymer of pyridine (OH-DMA) is the monolayer film system on top layer, is easy to regulate and control azo and high score using supramolecular system
The advantage of relative amount is regulating and controlling the process in wrinkle cycle between son.Contain in 4- hydroxyl -4'- dimethyl amino-azo-benzene molecules
There is hydroxyl, such that it is able to connect by hydrogen bond and polyvinylpyridine between, it is to avoid in the past by covalently bonded
Complicated synthesis procedure, while also overcoming the drawbacks of being separated in doping system.The present invention is using azobenzene molecule and height
Interaction of hydrogen bond between Molecularly Imprinted Polymer, by regulation and control molar ratio therebetween, prepares the wrinkle of different cycles
Pattern.The method of the present invention have it is quick, the characteristics of simple, it is to avoid complicated process conditions.It is this by supramolecular system
Method to regulate and control picture on surface has very big application in terms of surface wettability, micro-fluidic device
Embodiment 1：
A kind of preparation method of the patterning of azo-based supermolecule polymer thin film, comprises the following steps：
Step one, polydimethylsiloxane (PDMS) performed polymer and cross-linking agent are pressed into 10:1 mass ratio mixing, pours training into
In foster ware, it is sufficiently stirred for forming prepolymer with Glass rod；
Step 2, with multiplex vavuum pump of circulating water type by the prepolymer for mixing deaerate 2 hours after, be put into constant temperature air blast
Drying baker, solidifies 4 hours at 70 DEG C；
Step 3, prepare poly- (4-vinylpyridine) N-dimethylformamide solution (P4VP) and matter that mass fraction is 6%
Amount fraction is the N-dimethylformamide solution of 6% azo small molecule 4- hydroxyl -4'- dimethyl amino-azo-benzenes (OH-DMA), so
It is afterwards 1 according to mol ratio:0.0625 is mixed both, obtains the P4VP (OH-DMA) that mol ratio is 0.06250.0625It is super
Molecule composite solution；
Step 4, the PDMS films that step 2 is cured cut into 1cm × 1cm as substrate, and plasma treatment 30s makes it
Surface hydrophilic, then using the method for spin-coating film by P4VP obtained in step 3 (OH-DMA)0.0625Supermolecule be combined it is molten
Liquid is coated onto in the PDMS substrates of surface hydrophilic and prepares supermolecule polymer single thin film；
Step 5, the supermolecule polymer single thin film for preparing step 4 are in multiplex vavuum pump of circulating water type evacuation 2
Then hour is transferred to the supermolecule polymer single thin film in baking oven with removing excess of solvent, is heated 1 hour at 90 DEG C
After close baking oven, make supermolecule polymer single thin film Slow cooling obtain reticulation patterns, Fig. 1 shows the light of its crepe structure
Learn microscope photograph.
Embodiment 2：
A kind of preparation method of azo-based supermolecule polymer patterning, its preparation process is substantially the same manner as Example 1,
Difference is only：Step 3 obtains the P4VP (OH-DMA) that mol ratio is 0.250.25Supermolecule composite solution, Fig. 2 shows reality
Apply the optical microscope picture of the reticulation patterns that example 2 is finally obtained.
Embodiment 3：
A kind of preparation method of azo-based supermolecule polymer patterning, its preparation process is substantially the same manner as Example 1,
Difference is only：Step 3 obtains the P4VP (OH-DMA) that mol ratio is 0.50.5Supermolecule composite solution, Fig. 3 shows enforcement
The optical microscope picture of the reticulation patterns that example 3 is finally obtained.
Embodiment 4：
A kind of preparation method of azo-based supermolecule polymer patterning, its preparation process is substantially the same manner as Example 1,
Difference is only：Step 3 obtains the P4VP (OH-DMA) that mol ratio is 0.750.75Supermolecule composite solution, Fig. 4 shows reality
Apply the optical microscope picture of the reticulation patterns that example 4 is finally obtained.
Embodiment 5：
A kind of preparation method of azo-based supermolecule polymer patterning, its preparation process is substantially the same manner as Example 1,
Difference is only：Step 3 obtains the P4VP (OH-DMA) that mol ratio is 1.01.0Supermolecule composite solution, Fig. 5 shows enforcement
The optical microscope picture of the reticulation patterns that example 5 is finally obtained.
Can show that the supermolecule in preparation method of the present invention due to P4VP (OH-DMA) x is answered by above-described embodiment 1-5
(embodiment 1 to 5 is respectively to close solution mol ratio：0.0625,0.25,0.5,0.75, difference 1.0), final acquisition has not
Synperiodic chill mark pattern.With the increase of molar ratio, the wrinkle cycle of chill mark pattern is on a declining curve, Fig. 6
Show the wrinkle mechanical periodicity trend that the supermolecule polymer film of the different mol ratio of embodiment 1 to 5 is formed.
Although above in conjunction with accompanying drawing, invention has been described, the invention is not limited in above-mentioned being embodied as
Mode, above-mentioned specific embodiment is only schematic, rather than restricted, and one of ordinary skill in the art is at this
Under the enlightenment of invention, without deviating from the spirit of the invention, many variations can also be made, these belong to the present invention's
Within protection.
Claims (2)
1. the preparation method that a kind of azo-based supermolecule polymer is patterned, it is characterised in that step is as follows：
Step one, PDMS performed polymers and cross-linking agent are pressed into 10:1 mass ratio mixing, in pouring culture dish into, is fully stirred with Glass rod
Mix to form prepolymer；
Step 2, with multiplex vavuum pump of circulating water type by the prepolymer for mixing deaerate 2 hours after, be put into constant temperature forced air drying
Case, solidifies 4 hours at 70 DEG C；
Step 3, the N-dimethylformamide solution for preparing the P4VP that mass fraction is 6% and the OH-DMA that mass fraction is 6%
N-dimethylformamide solution, then according to mol ratio be 1:0.0625~1.0 is mixed both, obtains P4VP (OH-
DMA) the supermolecule composite solution of x, wherein, x=0.0625~1.0；
Step 4, the PDMS films that step 2 is cured cut into 1cm × 1cm as substrate, and plasma treatment 30s makes its surface
Hydrophiling, is then coated onto the supermolecule composite solution of P4VP obtained in step 3 (OH-DMA) x using the method for spin-coating film
Supermolecule polymer single thin film is prepared in the PDMS substrates of surface hydrophilic；
Step 5, the supermolecule polymer single thin film for preparing step 4 were in multiplex vavuum pump of circulating water type evacuation 2 hours
To remove excess of solvent, then the supermolecule polymer single thin film is transferred in baking oven, is closed after heating 1 hour at 90 DEG C
Baking oven is closed, makes supermolecule polymer single thin film Slow cooling obtain reticulation patterns.
2. the preparation method that according to claim 1 azo-based supermolecule polymer is patterned, it is characterised in that wherein,
The mol ratio of the supermolecule composite solution of P4VP (OH-DMA) x is different, final to obtain the chill mark pattern with different cycles.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107342374A (en) * | 2017-08-10 | 2017-11-10 | 青岛海信电器股份有限公司 | A kind of flexible base board, preparation method and applications |
| CN107367426A (en) * | 2017-07-06 | 2017-11-21 | 天津大学 | Regulate and control the method for supermolecular film light softening degree by azobenzene guest molecules |
| CN107501583A (en) * | 2017-07-06 | 2017-12-22 | 天津大学 | Regulate and control the method for PAAB PMMA hybrid films light softening degrees by adjusting aminoazabenzol content |
| CN109054074A (en) * | 2018-07-24 | 2018-12-21 | 天津大学 | A kind of preparation method of the complete light-operated reversible wrinkle micro-structure of azobenzene film surface |
| CN116751394A (en) * | 2023-05-16 | 2023-09-15 | 杭州师范大学 | PH/light dual-response polymer material with reversible shape transformation, and preparation method and application thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107367426A (en) * | 2017-07-06 | 2017-11-21 | 天津大学 | Regulate and control the method for supermolecular film light softening degree by azobenzene guest molecules |
| CN107501583A (en) * | 2017-07-06 | 2017-12-22 | 天津大学 | Regulate and control the method for PAAB PMMA hybrid films light softening degrees by adjusting aminoazabenzol content |
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| CN109054074A (en) * | 2018-07-24 | 2018-12-21 | 天津大学 | A kind of preparation method of the complete light-operated reversible wrinkle micro-structure of azobenzene film surface |
| CN109054074B (en) * | 2018-07-24 | 2021-04-20 | 天津大学 | Preparation method of all-optical control azobenzene film surface reversible wrinkle microstructure |
| CN116751394A (en) * | 2023-05-16 | 2023-09-15 | 杭州师范大学 | PH/light dual-response polymer material with reversible shape transformation, and preparation method and application thereof |
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