CN109553787A - A kind of graphene oxide modified polyvinylalcohol film and its preparation and application - Google Patents
A kind of graphene oxide modified polyvinylalcohol film and its preparation and application Download PDFInfo
- Publication number
- CN109553787A CN109553787A CN201811560084.9A CN201811560084A CN109553787A CN 109553787 A CN109553787 A CN 109553787A CN 201811560084 A CN201811560084 A CN 201811560084A CN 109553787 A CN109553787 A CN 109553787A
- Authority
- CN
- China
- Prior art keywords
- film
- graphene oxide
- solution
- pva
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
- C09J7/24—Plastics; Metallised plastics based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/245—Vinyl resins, e.g. polyvinyl chloride [PVC]
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2429/00—Presence of polyvinyl alcohol
- C09J2429/006—Presence of polyvinyl alcohol in the substrate
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Carbon And Carbon Compounds (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
A kind of graphene oxide modified polyvinylalcohol film and its preparation and application, belong to water soluble polymer Material Field.The preparation of graphene oxide: graphene oxide and water 1:250~1:1000 in mass ratio solution has been configured into；Graphene oxide modified PVA film forming: (1) it takes PVA to be increased to 95 DEG C using water bath temperature and is heated, and stirring melts PVA, on choose no colloidal solid, then press PVA: the modified solution that step 2) has dissolved is added in mass ratio 1:1~1:5 of graphene modified solution, it is stirred well to and is uniformly dispersed, water temperature in water-bath is dropped to 85 DEG C at this time, and stands 16~20 hours under 85 DEG C of constant temperature, bubble in solution is discharged thoroughly；It is film-made if being generated without precipitating after standing.The functional groups such as a large amount of carboxyls existing for the surface of graphene oxide can form condensation reaction with the hydroxyl in PVA, and technological feasibility is good.
Description
Technical field
The invention belongs to water soluble polymer Material Field, in particular to a kind of graphene oxide modified poly ethylene
The preparation method of alcohol solubility adhesive tape.
Background technique
Polyvinyl alcohol is water-soluble polymer, can be used for manufacturing adhesive, emulsifier, glue, film, fiber etc., is weight
The industrial chemicals wanted.In addition, it can be used as carbon source, degraded by the effect of enzyme and bacterium, and non-petroleum can be passed through
Route large-scale production.And PVA is outstanding in terms of oil resistant, solvent resistant, also possesses good barrier properties for gases.In order to make poly- second
Enol is adapted to the market demand, needs to be modified PVA, to achieve the purpose that change or the certain properties of addition.PVA's
Modification can be divided into four kinds of methods: (1) modification by copolymerization, introduce weaker unit by copolyreaction to reduce PVA fusing point；(2) altogether
Mixed modification forms powerful hydrogen bond by hydroxyl in modified material and PVA to destroy between polyvinyl alcohol molecule active force and reduce
It reduces fusing point or improves water solution temperature；(3) reaction modifying reduces regularity or raising thermostabilization by introducing to polyvinyl alcohol
The unit of property improves its thermoplastic processability；(4) plasticization and modification reduces PVA fusing point by the way that plasticization modifier is added.
Graphene is a kind of single layer of carbon atom layer of 2D plane, and thickness only has 0.34nm, and the carbon between graphene is former
Son is closely connected, and the carbon atomic layer of plane, which can distort, under external force prevents from being broken, and thereby may be ensured that the steady of its structure
Determine, referred to as material most thin in universe.Graphene oxide (GO) is the important derivatives of graphene, and structure and graphene are substantially
Identical, difference is to be connected with the functional groups such as carboxyl, hydroxyl on the edge and face of carbon atomic layer.
Summary of the invention
To solve the problems, such as polyvinyl alcohol modification, the present invention provides a kind of graphene oxide modified polyvinylalcohol solubility glue
Preparation method with substrate, the preparation method comprise the steps of:
The preparation of step 1) graphene oxide:
It is preferred that: the concentrated sulfuric acid of 60ml is added in beaker, puts it into and puts well in the cold bath of ice bag in advance, be cooled to
0 DEG C, 5g natural graphite is added slowly in the concentrated sulfuric acid, 1 hour is persistently stirred in ice-water bath, slowly added by several times later
Enter 3.8gKNO3With 9g KMnO4, 2 hours of stirring are maintained in ice-water bath；Remove ice-water bath, continues stirring 2 at normal temperature
Temperature is increased to 35 DEG C after hour to be stirred for 2 hours, reacts it sufficiently, temperature is increased to 98 DEG C later, is added certain
The deionized water of amount, while suitable 30%H is added2O2, continue to stir 2h, the mixture that stirring is completed poured into dry beaker
In, test tube is dispensed, is centrifuged, a certain amount of deionized water is added in centrifugation every time, is repeatedly centrifuged, it is detected with pH test paper, until
The waste liquid being centrifuged out no longer is in acidity；
Step 2) prepares graphene oxide modified solution, and graphene oxide and water 1:250~1:1000 in mass ratio are matched
Solution is set；
Step 3) graphene oxide modified PVA film forming: (1) taking PVA to be increased to 95 DEG C using water bath temperature and heated,
And stirring melts PVA, above chooses no colloidal solid, then presses PVA: mass ratio 1:1~1 of graphene modified solution:
5 modified solutions that have dissolved of addition steps 2), are stirred well to and are uniformly dispersed, and water temperature in water-bath is dropped to 85 DEG C at this time, and
16~20 hours are stood under 85 DEG C of constant temperature, bubble in solution is discharged thoroughly；It is made if being generated without precipitating after standing
Film.
If step 3) has precipitating after standing, takes upper clear supernate to abandon lower part precipitating and carry out lower step film.
Step 3) film is preferred: casting drum being heated to 100 DEG C, pulls up heating pin later, opens favourable turn, rotation makes
Its roller is integrally heated evenly, and starts to operate after 5~10min.Solution is slowly poured into pallet along side, hand rest is placed on roller
Lower section, holding up the level of immerses roller lower edge in solution, and roller rotation, solution forms one layer of solution film, solution in cylinder surface
It is stained with and puts down pallet after a week, after standing and drying solution 10min, film is torn from cylinder surface, with scissors by four Bian Xiuqi, i.e.,
At a PVA film.
In the present invention, the concentrated sulfuric acid is mixed sufficiently with graphite and potassium nitrate is added and should stirred immediately with after potassium permanganate by step 1)
It mixes
In the present invention, PVA model 1799 used in step 2) can also add various defoaming agents, film forming in modified solution
The additives such as agent.
In the present invention, modified solution used in step 2 is graphene oxide solution, to make graphene oxide be uniformly dispersed,
Preceding dissolution in PVA solution is added, PVA and modified solution mass ratio are 1:1~1:5.
The application of graphene oxide modified polyvinylalcohol film of the present invention, is used to prepare soluble tape substrate.
The present invention selects blending and modifying to carry out modified polyvinylalcohol, and selection modified material is graphene oxide.Graphene oxide
Surface existing for the functional groups such as a large amount of carboxyls can form condensation reaction with the hydroxyl in PVA, graphene oxide solution can be made
The solution of standby stable dispersion, therefore technological feasibility is good.Simultaneously because polyvinyl alcohol can form a film and can be led to the characteristic of glue
Cross the modified role that can serve as tape substrate completely.If certain rubber belt material is same material, then what recycling was got up
Efficiency can be obviously improved.
Detailed description of the invention
Fig. 1 is the modified PVA film light transmittance test chart that embodiment 1-4 is provided.
Fig. 2 is that 0.5g GO sample 1-3 different stretch strains corresponding tensile stress figure；
Fig. 3 is that 1.0g GO sample 1-3 different stretch strains corresponding tensile stress figure；
Fig. 4 is that 1.5g GO sample 1-4 different stretch strains corresponding tensile stress figure；
Fig. 5 is that 2.0g GO sample 1-3 different stretch strains corresponding tensile stress figure；
Fig. 6 is X-ray diffraction.
Specific embodiment
The present invention is further illustrated below by embodiment, but the present invention is not limited to following embodiments.
Embodiment 1
A kind of graphene oxide modified PVA film provided in this embodiment, preparation process are as follows:
The PVA of 500ml is taken to be added in beaker, water bath temperature is increased to 95 DEG C, and the beaker equipped with PVA is placed in water-bath
Stirring makes its thawing in pot, until above choosing no colloidal solid when being stirred for, oxidation stone is added in 1:1 in mass ratio at this time
Black alkene and water quality are stirred well to it and are uniformly dispersed than the modified solution for 1:1000, at this time drop to water temperature in water-bath
It 85 DEG C, needs solution standing 16~20 hours under 85 DEG C of constant temperature, bubble in solution is discharged thoroughly, and seen whether
Precipitating generates.It stands, has no precipitating.
Casting drum is heated to 100 DEG C, pulls up heating pin later, opens favourable turn, rotation makes its roller integrally be heated
Uniformly, 5~start to operate after ten minutes.Solution is slowly poured into pallet along side, hand rest is placed below roller, level support
Rising immerses roller lower edge in solution, and roller rotation, solution forms one layer of solution film in cylinder surface, and solution is stained with to be put after a week
After standing and drying solution 10min, film is torn from cylinder surface for lower tray, with scissors by four Bian Xiuqi, a modification
PVA film.It is 0.5g GO with added graphene oxide quality status stamp.
Embodiment 2
A kind of graphene oxide modified PVA film provided in this embodiment, preparation process are as follows:
The PVA of 500ml is taken to be added in beaker, water bath temperature is increased to 95 DEG C, and the beaker equipped with PVA is placed in water-bath
Stirring makes its thawing in pot, until above choosing no colloidal solid when being stirred for, oxidation stone is added in 1:1 by volume at this time
Black alkene and water quality are stirred well to it and are uniformly dispersed than the modified solution for 1:500, and water temperature in water-bath is dropped to 85 at this time
DEG C, need solution standing 16~20 hours under 85 DEG C of constant temperature, bubble in solution be discharged thoroughly, and seen whether it is heavy
It forms sediment and generates.It stands, has no precipitating.
Casting drum is heated to 100 DEG C, pulls up heating pin later, opens favourable turn, rotation makes its roller integrally be heated
Uniformly, 5~start to operate after ten minutes.Solution is slowly poured into pallet along side, hand rest is placed below roller, level support
Rising immerses roller lower edge in solution, and roller rotation, solution forms one layer of solution film in cylinder surface, and solution is stained with to be put after a week
After standing and drying solution 10min, film is torn from cylinder surface for lower tray, with scissors by four Bian Xiuqi, a modification
PVA film.It is 1g GO with added graphene oxide quality status stamp.
Embodiment 3
A kind of graphene oxide modified PVA film provided in this embodiment is manufactured in this way:
The PVA of 500ml is taken to be added in beaker, water bath temperature is increased to 95 DEG C, and the beaker equipped with PVA is placed in water-bath
Stirring makes its thawing in pot, until above choosing no colloidal solid when being stirred for, oxidation stone is added in 1:1 in mass ratio at this time
Black alkene and water quality are stirred well to it and are uniformly dispersed than the modified solution for 1:333, and water temperature in water-bath is dropped to 85 at this time
DEG C, need solution standing 16~20 hours under 85 DEG C of constant temperature, bubble in solution be discharged thoroughly, and seen whether it is heavy
It forms sediment and generates.It standing, there is volume precipitating to generate, the amount that graphene oxide is added is greater than maxima solubility, to prevent film forming from failing, bottom
Portion's solution is abandoned, only with top without precipitation solution.
Casting drum is heated to 100 DEG C, pulls up heating pin later, opens favourable turn, rotation makes its roller integrally be heated
Uniformly, start to operate after 5~10min.Solution is slowly poured into pallet along side, hand rest is placed below roller, is held up the level of
Immerse roller lower edge in solution, roller rotation, solution forms one layer of solution film in cylinder surface, and solution is stained with to be put down after a week
After standing and drying solution 10min, film is torn from cylinder surface for pallet, with scissors by four Bian Xiuqi, a modified PVA
Film.It is 1.5g GO with added graphene oxide quality status stamp.
Embodiment 4
A kind of graphene oxide modified PVA film provided in this embodiment is manufactured in this way:
The PVA of 500ml is taken to be added in beaker, water bath temperature is increased to 95 DEG C, and the beaker equipped with PVA is placed in water-bath
Stirring makes its thawing in pot, until above choosing no colloidal solid when being stirred for, oxidation stone is added in 1:1 by volume at this time
Black alkene and water quality are stirred well to it and are uniformly dispersed than the modified solution for 1:250, and water temperature in water-bath is dropped to 85 at this time
DEG C, need solution standing 16~20 hours under 85 DEG C of constant temperature, bubble in solution be discharged thoroughly, and seen whether it is heavy
It forms sediment and generates.
It stands, solution bottom has micro floccule to generate, and the amount that graphene oxide is added is greater than maxima solubility, pours into support
Bottom solution goes out at plume when in disk, is chosen the floccule in pallet with spoon.
Casting drum is heated to 100 DEG C, pulls up heating pin later, opens favourable turn, rotation makes its roller integrally be heated
Uniformly, start to operate after 5~10min.Solution is slowly poured into pallet along side, hand rest is placed below roller, is held up the level of
Immerse roller lower edge in solution, roller rotation, solution forms one layer of solution film in cylinder surface, and solution is stained with to be put down after a week
Pallet, standing and drying solution are torn from cylinder surface after ten minutes, by film, with scissors by four Bian Xiuqi, a modified PVA
Film.It is 2g GO with added graphene oxide quality status stamp.
Comparative example
Workshop Production PVA film, identical as PVA model used in embodiment, property is identical.It is denoted as PVA.
Experimental example:
1, the PVA film provided the modified PVA film of embodiment 1-4 offer, comparative example carries out water solution temperature test.Knot
Fruit is as follows.
①PVA
D:35 μm of thickness
Area S:10cm*5cm
T:65 DEG C of solution temperature (starts 62 DEG C -63 DEG C of temperature of scattering)
Dissolution time t:1.5min
②2g Go
D:36 μm of thickness
Area S:10cm*5cm
T:65 DEG C of solution temperature (starts 62 DEG C -63 DEG C of temperature of scattering)
Dissolution time t:1.5min
③1.5g Go
D:35 μm of thickness
Area S:10cm*5cm
T:63 DEG C of solution temperature (starts -61 DEG C of the temperature 60 C that scatters)
Dissolution time t:1.5min
④1.0g Go
D:36 μm of thickness
Area S:10cm*5cm
T:65 DEG C of solution temperature (starts 63 DEG C -64 DEG C of temperature of scattering)
Dissolution time t:1.4min
⑤0.5g Go
D:50 μm of thickness
Area S:10cm*5cm
T:66 DEG C of solution temperature (starts 63 DEG C -64 DEG C of temperature of scattering)
Dissolution time t:1.5min
It is slightly changed that the water solution temperature that GO forms a film to PVA is added, can be adjusted when 1.5gGO is added to 60 DEG C.
2, the PVA film provided the modified PVA film of embodiment 1-4 offer, comparative example uses TU-1900/TU-1901
Dual-beam UV, visible light spectrophotometric photometer carries out light transmittance test.As a result such as Fig. 1.
Firstly the need of the sample that film is cut into 1cm × 3cm size, it is put into laboratory apparatus by several times and is tested, final benefit
With data at figure.It is followed successively by factory's PVA film, the PVA film of 0.5g GO is mixed into and the PVA for being mixed into 1.0g, 1.5g, 2.0g is thin
The light transmittance of film is tested.
It can be seen from the figure that the PVA laminated film light transmittance of graphene oxide, which is added, will be lower than the pure PVA film of factory.
The film outline for being mixed into 1.5g graphene oxide is several better than other, and the graphene oxide that volume is added is saturating in low wavelength
The variation of light rate is little, and when wavelength is more than 250, light transmittance curve starts to occur significantly fluctuating.But it is mixed into 0.5g graphite oxide
The PVA film of alkene, that is, when concentration is 0.09%, the light transmittance of film is far below the pure PVA film of comparative example.
3, the PVA film provided 4 kinds of modified PVA films of embodiment 1-4 offer, comparative example uses high and low temperature environment electricity
The Mechanics Performance Testing that sub- tensile testing machine forms a film, it is as a result as follows.
The film became uneven provided by embodiment, it is difficult to measure thickness, experimental sample selects same specification different materials
Each 3 parts of sample testings of film and take its average value to be analyzed, size of sample 100mm × 25mm, tensile speed 300mm/
Min is recorded the data variation in drawing process, is carried out being processed into curve to data using bluehill.Test data includes drawing
Stretch intensity, elongation at break and young's modulus in tension.Wherein Young's modulus is the physical quantity that film resists deformability, belongs to elasticity
One kind of modulus.
1. the tension failure data of 1 resulting materials of 0.5g GO table
Table 1
As shown in Figure 2, sample 1-3 different stretch strains corresponding tensile stress, and film became uneven keeps experimental data poor
Away from larger, it is averaged and calculates variance and analyzed.
2. the tension failure data of 2 resulting materials of 1.0g GO table
Table 2
From the figure 3, it may be seen that sample 1-3 different stretch strains corresponding tensile stress, film became uneven keeps experimental data poor
Away from larger, it is averaged and calculates variance and analyzed.
3. the tension failure data of 3 resulting materials of 1.5g GO table
Table 3
As shown in Figure 4, sample 1-4 different stretch strains corresponding tensile stress, and film became uneven keeps experimental data poor
Away from larger, it is averaged and calculates variance and analyzed.
4. the tension failure data of 4 resulting materials of 2.0g GO table
Table 4
As shown in Figure 5, sample 1-3 different stretch strains corresponding tensile stress, and film became uneven keeps experimental data poor
Away from larger, it is averaged and calculates variance and analyzed.
After tested, the tensile strength of comparative example PVA film is in 45MPa or so, and elongation at break is 127% or so, Young
Modulus is 1300MPa or so.500mlPVA containing 0.5gGO at average film tensile strength be 85MPa or so, average fracture is stretched
Long rate 15.7%, average Young's modulus is 2960MPa, finds out that the PVA film tensile strength containing 0.5gGO is stretched with fracture from data
Long rate differs greatly with pure PVA film, but because of manual film, not can guarantee the consistent of the thickness of film, the thickness of comparative example PVA film
It is 33 μm, the thickness of the film containing 0.5gGO has been greater than 50 μm, and thickness effect factor of going out, rough estimate tensile strength is in Young mould
Amount is only slightly larger than workshop PVA film, and elongation at break is less than workshop PVA film.GO content is the average drawing of the laminated film of 1.0g
Stretching intensity is 58MPa or so, and 55% or so, average Young's modulus relatively compares average elongation at break in 2000MPa or so
Example PVA film has biggish variation.GO content is the average tensile strength of the PVA/GO film of 1.5g in 56MPa or so, averagely
Elongation at break is 70% or so, and for average Young's modulus 2150 or so, rigidity is the film of 1.0gGO slightly larger than content.Contain
The average tensile strength of the PVA/GO film of 2.0g is 58MPa or so, and average elongation at break is 55% or so, average tensile poplar
1960 or so, the whole laminated film with 1.5g content is not much different family name's modulus.
It can be obtained from different sample mean data with coarse analysis, a certain amount of graphite oxide is added in PVA material
Alkene can increase its mechanical strength, and as the concentration of graphene oxide is increasing, film strength is also increasing, but in 1.0g
The data of~2.0g analyze it can be concluded that, when in the PVA solution and modified solution of the 500ml concentration 17% of volume ratio 1:1 mixing
The quality of middle graphene oxide content of graphene oxide in 1.2g or so, solution reaches saturation.
In PVA/GO composite material, the oxygen-containing functional group such as carboxyl and the-OH in PVA strand on the surface GO are formd very
Strong condensation reaction, so that composite material shows rigidity more stronger than pure PVA material when facing external force.Simultaneous oxidation stone
Also should can have interaction between black alkene and graphene oxide, the content of GO affects the mechanical strength of film, when GO content compared with
When low, graphene oxide is uniformly distributed in PVA, can be only present in PVA and be formed hydrogen bond, when GO content is higher, graphite oxide
Mutually overlap between alkene and graphene oxide also can cause the mechanical strength of film higher there is interaction, so just can be
It is higher by when graphene oxide content reaches saturation than the Young's modulus of workshop polyvinyl alcohol film more.Opposite, it joined oxygen
After graphite alkene, intermolecular force enhancing becomes hard and brittle film after increasing tensile strength, so that film is disconnected
Elongation is split to be lower.
4, the PVA film provided the modified PVA film of embodiment 1-4 offer, comparative example carries out surface tension test.Knot
Fruit is as follows.
Surface tension test is tested according to laboratory in factory using surface tension test pen.It is surveyed using surface tension
Pen is tried, the minor changes such as the surface energy of different materials film, hydrophily, degree of wetting is can analyze out, predominantly detects its surface
Tension.The surface tension test pen of selection is 40 dynes per centimeters.Judge that film tension needs to be drawn with test pen in film surface
One line observes ink state.Setting-out is evenly distributed and not beading up point, then illustrates that the film surface tension is higher than institute on test pen
The index marked.Setting-out shrink at leisure, illustrate the film surface tension be slightly less than on test pen labelled in index.Setting-out
It shrinks immediately and ink forms pearl point, then illustrate that the film surface tension is lower than index labelled in test pen very much.Pass through sight
Examine that skilled worker helps that we are detected as a result, finding that the surface tension of all films is all larger than 40.
5, table correspond to surface tension test data for each material modification solution
Table 55, the PVA film provided the modified PVA film of embodiment 1-4 offer, comparative example carry out X-ray diffraction point
Analysis test.
1. preparation
First by protective switch, recirculated water power supply opening, booting needs to wait, and machine has 5 display lamps behind, is waiting
After a period of time, 5, machine back indicator light, which all lights, indicates that machine can run well.Since detection article is thin
Film, unlike solids such as glass, metals, thin-film material is soft and thin, needs to be laid in sample plate face.Plasticine is filled in the window of hole,
Film is mounted in sky window, is compressed it with flat and smooth glass plate, guarantees that film is concordant smooth as sample plate face.
2. calibrating
Sample stage is put into according to prompt, it may appear that is started to carry out θ calibration, is put into film sample according to prompt.Film sample
Adjustment need open the door adjustment, as long as when enabling pain to instrument ring 3 sound more than can just open the door, two hand of enabling city be sky, act
It is light, it cannot shake, be otherwise automatically closed since the shock of door causes X-ray leakage to will cause instrument.Calibration is reached until numerical value
It is clicked again in range and saves save key.
3. measuring
It needs to set angle, termination point, surface sweeping speed etc. in fact when measurement, Fixed angle when testing film
It is set greater than 0.5 °, Scan Axis will be set as 2Theta single action.Since this test is tests for the first time, so test
Range is wider, therefore the testing time can also increase.
Fig. 6 is above-mentioned experiment X-ray diffraction interpretation of result.Consulting literatures post analysis, the diffraction maximum of PVA/GO laminated film
It is 2Theta=20 ° or so.After GO is dispersed substantially in polyvinyl alcohol matrix, the X-ray of PVA/GO laminated film is spread out
Penetrate the diffraction maximum in peak entirely without GO.This indicates that graphene oxide has been completely exfoliated, and is dispersed in the state of monolithic layer
In PVA.
Graphene oxide can form condensation reaction with polyvinyl alcohol, allow GO and PVA perfect compatible, spread out from XRD
It penetrates open country in figure and can analyze GO and be fully dispersed in PVA.GO's is suitably added the light transmittance that can also improve PVA film, to PVA film
Melting temperature have certain adjustment effect, some changes can occur for surface tension.The addition of graphene oxide is so that PVA film
Mechanical strength greatly increases, and in low concentration, effect is unobvious, but when concentration reaches saturation, and tensile strength soon reaches former
One times of PVA film tensile strength.
Polyvinyl alcohol itself can be with glue, and polyvinyl alcohol passes through the modified role that can serve as tape substrate completely.Glue
Band is used as a kind of material, and the efficiency of recycling can be promoted adequately.
Claims (8)
1. a kind of method of graphene oxide modified polyvinylalcohol film, which comprises the following steps:
The preparation of step 1) graphene oxide:
Step 2) prepares graphene oxide modified solution, and graphene oxide and water 1:250~1:1000 in mass ratio are configured
Solution；
Step 3) graphene oxide modified PVA film forming: (1) it takes PVA to be increased to 95 DEG C using water bath temperature and is heated, and stir
Mixing melts PVA, above chooses no colloidal solid, and then press PVA: mass ratio 1:1~1:5 of graphene modified solution is added
The modified solution that step 2) has dissolved, is stirred well to and is uniformly dispersed, and water temperature in water-bath is dropped to 85 DEG C at this time, and at 85 DEG C
16~20 hours are stood under constant temperature, bubble in solution is discharged thoroughly；It is film-made if being generated without precipitating after standing.
2. a kind of method of graphene oxide modified polyvinylalcohol film described in accordance with the claim 1, which is characterized in that step
1) preparation of graphene oxide: the concentrated sulfuric acid is added in beaker, is put it into and is put well in the cold bath of ice bag in advance, is cooled to
0 DEG C, 5g natural graphite is added slowly in the concentrated sulfuric acid, 1 hour is persistently stirred in ice-water bath, slowly added by several times later
Enter KNO3And KMnO4, 2 hours of stirring are maintained in ice-water bath；Remove ice-water bath, it will be warm after continuing stirring at normal temperature 2 hours
Degree is increased to 35 DEG C and is stirred for 2 hours, reacts it sufficiently, and temperature is increased to 98 DEG C later, and deionized water is added, and adds simultaneously
Enter 30%H2O2, continue to stir 2h, the mixture that stirring is completed poured into dry beaker, dispense test tube, be centrifuged, every time
Deionized water is added in centrifugation, is repeatedly centrifuged, and is detected with pH test paper, until the waste liquid being centrifuged out no longer is in acidity.
3. a kind of method of graphene oxide modified polyvinylalcohol film described in accordance with the claim 1, which is characterized in that step
3) film is preferred: casting drum is heated to 100 DEG C, pulls up heating pin later, opens favourable turn, rotation make its roller integrally by
It is hot uniform, start to operate after 5~10min.Solution is slowly poured into pallet along side, hand rest is placed below roller, level support
Rising immerses roller lower edge in solution, and roller rotation, solution forms one layer of solution film in cylinder surface, and solution is stained with to be put after a week
After standing and drying solution 10min, film is torn from cylinder surface for lower tray, with scissors by four Bian Xiuqi, a PVA film.
4. a kind of method of graphene oxide modified polyvinylalcohol film described in accordance with the claim 1, which is characterized in that in step
If having precipitating after rapid 3) standing, takes upper clear supernate to abandon lower part precipitating and carry out lower step film.
5. a kind of method of graphene oxide modified polyvinylalcohol film described in accordance with the claim 1, which is characterized in that step
2) PVA model 1799 used in.
6. a kind of method of graphene oxide modified polyvinylalcohol film described in accordance with the claim 1, which is characterized in that modified
The additives such as various defoaming agents, film forming agent are also added in solution.
7. the graphene oxide modified polyvinylalcohol film being prepared according to method described in any one of claims 1-6.
8. the graphene oxide modified polyvinylalcohol film being prepared according to method described in any one of claims 1-6 is answered
With being used to prepare soluble tape substrate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811560084.9A CN109553787A (en) | 2018-12-19 | 2018-12-19 | A kind of graphene oxide modified polyvinylalcohol film and its preparation and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811560084.9A CN109553787A (en) | 2018-12-19 | 2018-12-19 | A kind of graphene oxide modified polyvinylalcohol film and its preparation and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109553787A true CN109553787A (en) | 2019-04-02 |
Family
ID=65870581
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811560084.9A Pending CN109553787A (en) | 2018-12-19 | 2018-12-19 | A kind of graphene oxide modified polyvinylalcohol film and its preparation and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109553787A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112280073A (en) * | 2020-10-30 | 2021-01-29 | 哈尔滨工业大学 | Preparation method of multifunctional film |
| WO2022056974A1 (en) * | 2020-09-18 | 2022-03-24 | 华侨大学 | Insulating polyvinyl alcohol composite heat-conducting film and preparation method therefor |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106006616A (en) * | 2016-05-25 | 2016-10-12 | 江苏科技大学 | Preparation method of high-adsorbability graphene aerogel |
| CN108819067A (en) * | 2018-07-25 | 2018-11-16 | 扬州亿斯特新材料科技有限公司 | A kind of process producing polyvinyl alcohol film |
-
2018
- 2018-12-19 CN CN201811560084.9A patent/CN109553787A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106006616A (en) * | 2016-05-25 | 2016-10-12 | 江苏科技大学 | Preparation method of high-adsorbability graphene aerogel |
| CN108819067A (en) * | 2018-07-25 | 2018-11-16 | 扬州亿斯特新材料科技有限公司 | A kind of process producing polyvinyl alcohol film |
Non-Patent Citations (3)
| Title |
|---|
| MUHAMMAD ASLAM: ""Graphene oxides nanosheets mediation of poly(vinyl alcohol) films in tuning their structural and opto-mechanical attributes"", 《JOURNAL OF MATERIALS SCIENCE-MATERIALS IN ELECTRONICS》 * |
| 王鑫婷 等: ""PVA胶带的制备及力学性能研究"", 《包装工程》 * |
| 马国富 等: ""层状聚乙烯醇/氧化石墨烯纳米复合膜的制备及性能研究"", 《西北师范大学学报(自然科学版)》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022056974A1 (en) * | 2020-09-18 | 2022-03-24 | 华侨大学 | Insulating polyvinyl alcohol composite heat-conducting film and preparation method therefor |
| CN112280073A (en) * | 2020-10-30 | 2021-01-29 | 哈尔滨工业大学 | Preparation method of multifunctional film |
| CN112280073B (en) * | 2020-10-30 | 2022-05-06 | 哈尔滨工业大学 | Preparation method of multifunctional film |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI267664B (en) | Enhanced K-type polarizer | |
| CN109553787A (en) | A kind of graphene oxide modified polyvinylalcohol film and its preparation and application | |
| CN100549739C (en) | Polarizer protection film, polaroid and image display device | |
| CN101900851A (en) | Polarizer, the optical thin film that has used polarizer, and image display device | |
| CN101086539B (en) | Adhesive for polarizing filter, polarizing filter and manufacturing method thereof, optical film and image display device | |
| CN102193133B (en) | Polarizing plate, method of manufacturing same, optical film and image display apparatus | |
| CN100472253C (en) | Optical compensation layer-carrying polarizing plate, liquid crystal panel, liquid crystal display unit, image display unit and production method of optical compensation layer-carrying polarizing plat | |
| Wang et al. | Energy-transfer study of polymer diffusion in melt-pressed films of poly (methyl methacrylate) | |
| CN101183157B (en) | Polarizing plate, manufacturing method therefor, optical film and image display | |
| Dalnoki‐Veress et al. | Phase separation morphology of thin films of polystyrene/polyisoprene blends | |
| CN114889268B (en) | Quantum dot light diffusion plate and preparation method and application thereof | |
| CN101107547A (en) | Pressure-sensitive adhesive composition for optical member, pressure-sensitive adhesive layer for optical member, pressure-sensitive adhesion type optical member, and image display device | |
| Tsugawa et al. | Effect of lithium salt addition on the structure and optical properties of PMMA/PVB blends | |
| Wang et al. | Understanding morphology evolution and roughening in phase-separating thin-film polymer blends | |
| CN109666208A (en) | A kind of graphene oxide@SiO2The method of modified poly ethylene film | |
| JPS60134204A (en) | Polarizing film | |
| US5958596A (en) | Composite material | |
| CN101960339A (en) | Retardation film with pressure-sensitive adhesive layer and elliptical polarizer and liquid-crystal display both employing the same | |
| CN103080782A (en) | Film for improving viewing angle, liquid crystal display device, and viewing angle improvement method | |
| CN110945393B (en) | Polarizing plate and display device | |
| Guselnikova et al. | Multiresponsive wettability switching on polymer surface: Effect of surface chemistry and/or morphology tuning | |
| CN106590179A (en) | CNC/PEG composite coating and preparation method thereof | |
| Akrman et al. | The coloration of polypropylene fibres with acid dyes | |
| CN109735040A (en) | A kind of film super-hydrophobic antifogging master batch and its preparation | |
| Ogawa et al. | Composition fluctuations before dewetting in polystyrene/poly (vinyl methyl ether) blend thin films |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190402 |