CN103319827A

CN103319827A - Method for preparing organic-inorganic nano composite film

Info

Publication number: CN103319827A
Application number: CN2013102747518A
Authority: CN
Inventors: 徐安武; 刘睿旸
Original assignee: University of Science and Technology of China USTC
Current assignee: University of Science and Technology of China USTC
Priority date: 2013-07-02
Filing date: 2013-07-02
Publication date: 2013-09-25
Anticipated expiration: 2033-07-02
Also published as: CN103319827B

Abstract

The invention discloses a preparation method of an organic-inorganic nano material composite film material, which is characterized in that the colored ingredient graphene oxide, the colorless ingredient nano-based nano-montmorillonite and polyvinyl alcohol are respectively prepared into a mass percentage concentration of 1 to 2 % aqueous solution; then mix the colored batching liquid and polyvinyl alcohol solution, colorless batching liquid and polyvinyl alcohol solution according to the volume ratio 1: (0.5 ~ 1) and mix well; then mix the above two mixed solutions according to the volume ratio 1 : (0.25 ~ 4) Mix and stir evenly to obtain the film-making liquid; finally, the film-making liquid is evaporated to dry solution method or paper-making method to obtain the finished film. The film prepared by the method of the present invention has better mechanical properties, and at the same time has the advantage of transparency of the polymer film; by adjusting the ratio of the colored ingredients and the colorless ingredients, it can be adjusted without basically changing the mechanical properties. The purpose of transparency.

Description

The preparation method of the inorganic nano combined film of a kind of You Ji –

Technical field

The invention belongs to the inorganic nano combined thin-film material technical field of Ji –, be specifically related in the high-molecular polyivnyl alcohol base-material to add the method that batching graphene oxide and sodium-based montmorillonite prepare thin-film material.

Background technology

In recent years, very active for the research of You Ji – inorganic substances compound membrane.Particularly along with the rise of nanosecond science and technology, study inorganic nano material modified organic film material and caused increasing concern.Compare with traditional organic film material, nano-material modified organic film material is better than traditional organic membrane or composite film material at aspects such as mechanical property, optical property and thermotolerances.For example, " application chemical industry " (2011 the 40th volume fifth phases, the 807-813 page or leaf) preparation and the performance study thereof of polyvinyl alcohol/attapulgite clay nano composite membrane have been introduced, in polyvinyl alcohol (PVA)/attapulgite clay nano composite membrane, nano-attapulgite is combined with PVA by hydrogen bond, and is dispersed in the composite membrane.This composite membrane has improved thermal stability, mechanical property and the water tolerance of PVA.The preparation method of Chinese patent application number 201010214539.9 disclosed a kind of polyvinyl alcohol magnetic films has obtained having the PVA nano composite membrane of magnetic behavior.

At present, the research of nano material and PVA composite membrane also mainly concentrates on binary system compound between a kind of inorganic nano material and the PVA, and the research that two or more inorganic nano material and PVA are compound is also relatively more rare.Usually add a kind of character that a kind of inorganic materials generally can only be regulated and control composite membrane, for example magnetic.The PVA composite membrane that adds two or more inorganic nano material then can be realized the regulation and control of multiple performance, for example regulation and control of performance such as optics, mechanics.The PVA film of the above Attapulgite modification and the PVA film of magnetic nanoparticle modification all are only limited to a kind of doping of inorganic nano material, and tool is not regulated and control the feature that multiple performance is regulated and control simultaneously.

Summary of the invention

The preparation method who the purpose of this invention is to provide the inorganic nano combined film of a kind of You Ji – to overcome the above-mentioned defective of prior art, obtains transparent, lightweight, laminated film that physical strength is high.

The preparation method of the inorganic nano combined film of You Ji – of the present invention, it is characterized in that: organic polymer polyvinyl alcohol (PVA) base-material is evenly mixed obtaining preparation liquid with two kinds of inorganic nano material batching graphene oxides (GO) and sodium-based montmorillonite (MTM), adopt existing paper process or evaporate to dryness solution method film-forming process to prepare the inorganic nano combined film of You Ji – again; Technical process is as follows:

The first step: the preparation of each component solution:

It is 1～2% polyvinyl alcohol water solution that polyvinyl alcohol is mixed with mass percent concentration;

Coloured batching graphene oxide and colourless batching are received basic nano imvite, and to be mixed with mass percent concentration respectively be 1～2% the aqueous solution;

Second step: mixing raw material solution obtains preparation liquid:

The colourless batching batching of preparing in the first step is received the basic nano imvite aqueous solution and polyvinyl alcohol water solution according to volume ratio 1:(0.5～1) mix, stir; With coloured batching graphite oxide aqueous solution and polyvinyl alcohol solution according to volume ratio 1:(0.5～1) mix, stir; Subsequently with above-mentioned two kinds of mixing solutionss according to volume ratio 1:(0.25～4) mix, stir, obtain preparation liquid;

The 3rd step: film forming:

Adopt evaporate to dryness solution method or paper process to handle above-mentioned preparation liquid, film gets product.

Described evaporate to dryness solution method is: the preparation liquid for preparing is coated on the flat board, put into 40～60 ℃ baking oven oven dry moisture content after, laminated film is peeled off from container.

Described paper process is: the preparation liquid that uses mixed cellulose ester microporous membrane and sand core funnel suction filtration to prepare, subsequently filter membrane is taken off, and use the acetone washing by soaking to filter membrane is dissolved flush away, namely obtain laminated film.

Because the present invention has taked coloured proportion liquid and polyvinyl alcohol solution, colourless proportion liquid and polyvinyl alcohol solution are mixed respectively, and then with two kinds of mixing solutions remix, stirs, obtain preparation liquid; At last preparation liquid is adopted evaporate to dryness solution method or paper process handle finished films, prepared film has better mechanical property, has the transparent advantage of polymeric film simultaneously; Can be implemented in the purpose of regulating transparence under the prerequisite that does not change mechanical property substantially by regulating the ratio of coloured batching and two kinds of batchings of colourless batching.

The present invention has adopted two kinds of inorganic component graphene oxides and polynite as batching, compares with the pure polymers film, and its limit tensile strain and ultimate tensile stress have had significant raising, have better mechanical property; Simultaneously owing to controlled coloured batching graphene oxide and colourless batching and receive the add-on of basic nano imvite and be not more than 30%, can guarantee that it still has the transparent advantage of polymeric film; And if only use a kind of batching, the add-on of then adjusting batching can't be accomplished to regulate a kind of performance and do not influenced another performance, preparation method of the present invention has adopted coloured batching graphene oxide and colourless batching and has received two kinds of inorganic nano materials batchings of basic nano imvite, by regulating the ratio of coloured batching and colourless batching, can under changing less than 5% prerequisite, ultimate strain realize regulating the purpose of transparence.

Description of drawings

Fig. 1 is the photo in kind of the film of the embodiment of the invention 1 preparation;

Fig. 2 is the film of embodiment 1 preparation and the tensile property test data correlation curve of existing pure PVA (PVOH) FILM.

Fig. 3 is the photo in kind of three kinds of sample thin films of embodiment 2 preparations.

Fig. 4 is the tensile property test data correlation curve of three kinds of sample thin films of preparation among the embodiment 2.

Embodiment

Embodiment 1:

Be that to be formulated as mass percent concentration be 1% polyvinyl alcohol solution for the polyvinyl alcohol of 80000g/mol with average molecular mass: the 1g polyvinyl alcohol is added in 100 ml waters, stirring also is heated to 60 ℃, keep temperature to dissolve fully until polyvinyl alcohol, be cooled to room temperature subsequently, left standstill 12 hours;

It is 1% solution that graphene oxide and polynite are mixed with mass percent concentration respectively: get 1g graphene oxide and polynite, add respectively in 100 ml waters, stir, ultrasonic 30 minutes, continue subsequently to stir 2 hours; With the solution that obtains in whizzer with 3000 rpms speed centrifugal 3 minutes; Take out supernatant liquid;

Polynite solution 10ml, polyvinyl alcohol solution 10m are mixed, stir; Graphene oxide solution 10ml, polyvinyl alcohol solution 10ml mix, and stir; Subsequently above-mentioned two kinds of mixing solutionss are mixed according to volume ratio 1:1, stir, obtain preparation liquid;

Film-forming process adopts the evaporate to dryness solution method in the present embodiment: the 10ml preparation liquid is placed the culture dish of diameter 5cm, evaporate to dryness mixing solutions in 40-60 ℃ baking oven.Product film is attached on the culture dish, takes off to obtain product.

Coloured batching of using in the present embodiment is as follows as the preparation technology of graphene oxide:

0.5g Graphite Powder 99,3g potassium permanganate are mixed with 0.5g saltpetre, add the 23ml weight percent concentration subsequently and be 98% the vitriol oil; Stir, be heated to 35 ℃ and kept 30 minutes, solution becomes dark-brown; Add 40ml water subsequently, be warming up to 90 ℃ and kept 1 hour and continued stirring; Remove heating, treat the solution cooling, add 3ml 30% aqueous hydrogen peroxide solution; Stirred 10 minutes, suction filtration namely obtains the graphene oxide solid;

The graphite powder particle size that adopts in the present embodiment is 300 order to 400 orders.

Fig. 1 is the photo in kind of the film (PVA-GO-MTM) for preparing in the present embodiment, and this sample is the translucent film of light brown.Prepare in the present embodiment as can be seen film sample have the same with polymeric film transparent a bit.

Fig. 2 is the film sample of present embodiment preparation and the tensile property correlation curve of existing pure PVA (PVOH) FILM (the other mark of curve PVA reference).Pure PVA (PVOH) FILM (PVA reference) can be born the stress of 2.0 MPas, reaches 2.5% back fracture in strain; The film sample of present embodiment preparation can bear the stress of 3.8 MPas, reaches 5.5% back fracture in strain.The position of two curves more as can be seen from figure: the laminated film sample for preparing in the present embodiment has better intensity and ability of anti-deformation than pure polymeric film (PVA reference), and bigger ultimate deformation is arranged.

As seen the film product for preparing in the present embodiment has than the better mechanical property of straight polymer film, also has transparent advantage simultaneously concurrently.

Embodiment 2:

Each sample solution is carried out different mixing according to following table 1, prepares one group of sample:

The amount of the solution that each sample of table 1 uses

Sample number into spectrum	Sample 1	Sample 2	Sample 3
				Polynite solution clear liquid	5ml	15ml	25ml
Graphene oxide solution clear liquid	25ml	15ml	5ml
				Polyvinyl alcohol solution	30ml	30ml	30ml

With the polynite solution of volume as shown in table 1, mix with polyvinyl alcohol solution 15m, stir respectively; And respectively the graphene oxide solution of volume as shown in table 1 is mixed with polyvinyl alcohol solution 15ml, stir; Above-mentioned two kinds of mixing solutionss of each group that will obtain respectively subsequently mix according to volume ratio 1:1, stir, and obtain the preparation liquid of three samples;

The film-forming process of selecting for use in the present embodiment is paper process: use the filter membrane in 0.45um aperture and diameter to be the sand core funnel vacuum filtration preparation liquid of 46mm.Filter membrane is taken off, place culture dish, use acetone washing by soaking 5 times, each 15ml.The final product film that obtains.

Fig. 3 is the photo in kind of three kinds of film films of preparation in the present embodiment 2, is followed successively by sample 1 from left to right, sample 2, sample 3; According to the photo in kind of three kinds of film films as can be seen the color of each sample shoal along with the increase of the adding of graphene oxide.

Three kinds of film samples that Fig. 4 prepares for present embodiment 2 the tensile property correlation curve, the ultimate stress that can bear before each sample breakage is successively: sample 1 is 13, sample 2 is 35, sample 3 is 25 MPas, and ultimate strain is successively: sample 1 is 15%, sample 2 is 18%, sample 3 is 17%.By three kinds of film samples the tensile property correlation curve as can be seen, the sample that adopts the inventive method to prepare all has good stretch-proof ability, though their mechanical property changes to some extent along with the difference to some extent of prescription, but difference and not obvious still has similar mechanical property feature.

Therefore, the optical property that the film product that adopts the inventive method to prepare has changes along with the change of prescription, has Modulatory character; Adopting preparation method of the present invention can control prescription simultaneously remains unchanged mechanical property substantially.Therefore adopt the inventive method prepared film to have mechanical property preferably, have the transparent advantage of polymeric film simultaneously; Can be implemented in the purpose of regulating transparence under the prerequisite that does not change mechanical property substantially by regulating the ratio of coloured batching and two kinds of batchings of colourless batching.

Claims

1. A method for preparing an organic-inorganic nanocomposite film, characterized in that the technological process is as follows:

The first step: the preparation of each component solution:

The polyvinyl alcohol is formulated into a polyvinyl alcohol aqueous solution with a concentration of 1 to 2% by mass;

The colored ingredient graphene oxide and the colorless ingredient nano-montmorillonite are respectively prepared into aqueous solutions with a concentration of 1 to 2% by mass;

The second step: mixing the raw material solution to obtain the film-making solution:

Mix the colorless ingredients prepared in the first step with nano-based nano-montmorillonite aqueous solution and polyvinyl alcohol aqueous solution according to the volume ratio of 1: (0.5-1), and stir evenly; the colored ingredients graphene oxide aqueous solution and polyvinyl alcohol solution Mix according to the volume ratio 1: (0.5~1), and stir evenly; then mix the above two mixed solutions according to the volume ratio 1: (0.25~4), stir evenly, and obtain the film-forming solution;

The third step: film formation:

The above-mentioned film-making solution is treated by evaporation to dryness solution method or paper-making method to obtain the finished film.

2. The preparation method of organic-inorganic nanocomposite film as claimed in claim 1, characterized in that the evaporation solution method is as follows: apply the prepared film-making solution on a flat plate, and put it into an oven at 40-60°C to dry After drying, the composite film is peeled off from the container.

3. the preparation method of organic-inorganic nanocomposite film as claimed in claim 1, is characterized in that described papermaking method is: use mixed cellulose ester microporous filter membrane and sand core funnel suction filtration prepared film-making liquid, subsequently The filter membrane is removed, soaked and washed with acetone until the filter membrane is dissolved and washed away, and a composite membrane is obtained.