CN105181891A - Method for construction of polypyrrole membrane with hierarchical morphology based on in-situ wrinkling and solvent swelling - Google Patents

Abstract

The invention discloses a method for construction of a polypyrrole membrane with hierarchical morphology based on in-situ wrinkling and solvent swelling. The method includes: mixing a PDMS prepolymer and a crosslinking agent in a mass ratio of 10:1 to form a uniform prepolymer; subjecting the prepolymer to degassing for 1h, then performing heating at 70DEG C for 4h to conduct curing so as to obtain a PDMS elastomer; shearing the PDMS elastomer into sheets, and placing the sheets vertically in a container; preparing a pyrrole hydrochloric acid water solution and a ferric chloride hydrochloric acid water solution, carrying out ultrasonic dispersion evenly, then adding the solutions into the container according to a mole ratio of pyrrole to ferric chloride of 1:2, carrying out reaction for 4-60min, and then taking out the sample; and subjecting the sample to swelling under THF steam for 6h to construct the polypyrrole membrane with hierarchical morphology. The method provided by the invention employs a simple operation mode to obtain the hierarchical morphology of the conductive polymer, and avoids the disadvantages of complex operation, high cost, nonuniform pattern, small area and the like in previous photoetching and other patterning methods.

Description

Based on the wrinkling method building the polypyrrole film of hierarchical morphology with solvent swell of original position

Technical field

The present invention is specifically related to a kind of based on the wrinkling process obtaining the homogeneous hierarchical morphology of large area with solvent swell of original position.

Background technology

The method that researcher adopts photoetching, electron beam lithography etc. to combine with electrochemical deposition mostly prepares the polypyrrole film of patterning, and this conducting film has potential application prospect in various fields such as sensor, ultracapacitor, biological medicine, optics, hydrophilic and hydrophobics.Existing patterning film of poly pyrrole has the deficiency that poor repeatability, preparation process are loaded down with trivial details and yield poorly.Particularly to need research further in size and homogeneity preparing.And utilize the wrinkling method combined of solvent swell and original position to obtain the homogeneous polypyrrole film hierarchical morphology of large area, due to the attention of feature is more and more the subject to academia such as it is applied widely, obtain the good area of pattern homogeneity is large.

Summary of the invention

For above-mentioned prior art, the invention provides a kind of based on the wrinkling method building the polypyrrole film of hierarchical morphology with solvent swell of original position, prepare the polypyrrole film of homogeneous multistage wrinkle pattern.The present invention selects PDMS (10:1) to be substrate, utilizes the method for oxidative polymerization to obtain wrinkle pattern, the more swelling 6h under THF steam of the sample containing wrinkle pattern is obtained multistage wrinkle pattern.And accomplished, by changing oxidative polymerization sedimentation time, to realize the regulation and control to wrinkle pattern.This process avoids the use of expensive instrument and the operation steps of very complicated.

In order to solve the problems of the technologies described above, it is a kind of based on the wrinkling method building the polypyrrole film of hierarchical morphology with solvent swell of original position that the present invention proposes, and comprises the following steps:

Step one, by PDMS performed polymer and crosslinking chemical in mass ratio for after 10:1 mixing, pour in double dish, fully stir with glass bar and form uniform prepolymer;

Step 2, prepolymer obtained for step one after degassed 1h, is heated 4h and is cured in the multiplex vacuum pump of circulating water type at 70 DEG C, obtained PDMS elastic body;

Step 3, PDMS elastomeric shear obtained for step 2 is become sheet material, be vertically put in a container;

Step 4, preparation pyrroles's aqueous hydrochloric acid solution and iron chloride salt aqueous acid, be uniformly dispersed under ultrasonic, then join in said vesse according to the mol ratio of pyrroles and iron chloride 1:2, takes out sample after reaction 4 ~ 60min;

Step 5, the sample swelling 6h under THF steam step 4 obtained, so far build the polypyrrole film obtaining hierarchical morphology.

Compared with prior art, the invention has the beneficial effects as follows:

Method of the present invention has fast, simply, and reproducible feature.The wrinkling method be combined with solvent swell of original position can be utilized to prepare the homogeneous hierarchical morphology of large area.Avoid the shortcoming of preparation process complexity, the little homogeneity difference of patterned area.

Accompanying drawing explanation

Fig. 1 is the optical microscope picture of the original position wrinkle pattern that the embodiment of the present invention 1 step 4 obtains

Fig. 2 is the optical microscope picture of the multistage wrinkle pattern of polypyrrole film that the embodiment of the present invention 1 obtains;

Fig. 3 is the SEM picture of the multistage wrinkle pattern of polypyrrole film that the embodiment of the present invention 1 obtains;

Fig. 4 is the SEM picture that polypyrrole that the embodiment of the present invention 2 obtains touches multistage wrinkle pattern;

Fig. 5 is the SEM picture that polypyrrole that the embodiment of the present invention 3 obtains touches multistage wrinkle pattern.

Embodiment

Be described in further detail technical solution of the present invention below in conjunction with the drawings and specific embodiments, described specific embodiment only explains the present invention, not in order to limit the present invention.

Embodiment 1:

Based on the wrinkling method building the polypyrrole film of hierarchical morphology with solvent swell of original position, comprise the following steps:

Step one, by PDMS performed polymer and crosslinking chemical in mass ratio for after 10:1 mixing, pour in double dish, fully stir with glass bar and form uniform prepolymer;

Step 2, prepolymer obtained for step one after degassed 1h, is heated 4h and is cured in the multiplex vacuum pump of circulating water type at 70 DEG C, obtained PDMS elastic body;

Step 3, PDMS elastomeric shear obtained for step 2 is become the rectangle of 14mm × 7mm, be vertically put in 2ml plastic tube;

Step 4, preparation pyrroles's aqueous hydrochloric acid solution and iron chloride salt aqueous acid, be uniformly dispersed under ultrasonic, then join in above-mentioned 2ml plastic tube according to the mol ratio of pyrroles and iron chloride 1:2, reaction 60min (i.e. in-situ oxidation sedimentation time) takes out sample afterwards; The original position wrinkle pattern obtained is as shown in light microscopic figure in Fig. 1.

Step 5, the sample swelling 6h under THF steam step 4 obtained, the multistage wrinkle pattern obtained is as shown in the SEM figure in light microscopic figure and Fig. 3 in Fig. 2.

Embodiment 2:

A kind of based on the wrinkling method building the polypyrrole film of hierarchical morphology with solvent swell of original position, embodiment 2 and step one in embodiment 1 are identical to three, five, just in step 4, change in-situ oxidation sedimentation time into 4min, the multistage wrinkle pattern finally obtained is as shown in scintigram in Fig. 4.

Embodiment 3:

A kind of based on the wrinkling method building the polypyrrole film of hierarchical morphology with solvent swell of original position, embodiment 3 and step one in embodiment 1 are identical to three, five, just in step 4, change in-situ oxidation sedimentation time into 20min, the multistage wrinkle pattern finally obtained is as shown in scintigram in Fig. 5.

The invention provides a kind of based on the wrinkling method building the polypyrrole film of hierarchical morphology with solvent swell of original position, prepare the multistage wrinkle pattern of homogeneous polypyrrole.The present invention selects PDMS (10:1) to be substrate, utilizes the method for oxidative polymerization to obtain wrinkle pattern, then will have sample swelling 6h under THF steam of wrinkle pattern.And accomplished the increase along with the oxide deposition time, the cycle of solvent swell wrinkle pattern increases.The operation steps of the use and very complicated that this process avoids expensive instrument inventive process avoids the shortcoming of preparation process complexity, the little homogeneity difference of patterned area.

Although invention has been described by reference to the accompanying drawings above; but the present invention is not limited to above-mentioned embodiment; above-mentioned embodiment is only schematic; instead of it is restrictive; those of ordinary skill in the art is under enlightenment of the present invention; when not departing from present inventive concept, can also make a lot of distortion, these all belong within protection of the present invention.

Claims (1)

1., based on the wrinkling method building the polypyrrole film of hierarchical morphology with solvent swell of original position, comprise the following steps:

Step one, by PDMS performed polymer and crosslinking chemical in mass ratio for after 10:1 mixing, pour in double dish, fully stir with glass bar and form uniform prepolymer;

Step 2, prepolymer obtained for step one after degassed 1h, is heated 4h and is cured in the multiplex vacuum pump of circulating water type at 70 DEG C, obtained PDMS elastic body;

Step 3, PDMS elastomeric shear obtained for step 2 is become sheet material, be vertically put in a container;

Step 4, preparation pyrroles's aqueous hydrochloric acid solution and iron chloride salt aqueous acid, be uniformly dispersed under ultrasonic, then join in said vesse according to the mol ratio of pyrroles and iron chloride 1:2, takes out sample after reaction 4 ~ 60min;

Step 5, the sample swelling 6h under THF steam step 4 obtained, so far build the polypyrrole film obtaining hierarchical morphology.