CN106590179B - A kind of CNC/PEG composite coating and preparation method thereof - Google Patents
A kind of CNC/PEG composite coating and preparation method thereof Download PDFInfo
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- CN106590179B CN106590179B CN201610913213.2A CN201610913213A CN106590179B CN 106590179 B CN106590179 B CN 106590179B CN 201610913213 A CN201610913213 A CN 201610913213A CN 106590179 B CN106590179 B CN 106590179B
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D101/00—Coating compositions based on cellulose, modified cellulose, or cellulose derivatives
- C09D101/02—Cellulose; Modified cellulose
- C09D101/04—Oxycellulose; Hydrocellulose
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Abstract
The invention discloses a kind of CNC/PEG composite coatings, including Cellulose nanocrystal and polyethylene glycol, the mass percentage that polyethylene glycol accounts for Cellulose nanocrystal is 0~50%, and the particle size length of the Cellulose nanocrystal is 151~167nm, diameter 48-52nm.The invention also discloses the preparation methods of CNC/PEG composite coating.The present invention is using native cellulose as raw material, and using nontoxic and pollution-free PEG as coating color regulator and plasticizer, the coloured coating environment-friendly degradable being prepared, mechanical performance is substantially improved, and structural color is bright-coloured controllable；On the other hand, by composite, simple drop coating can be prepared by substrate surface, and preparation process is simple, easily controllable, at low cost.
Description
Technical field
The invention belongs to coatings arts, and in particular to a kind of CNC/PEG composite coating and preparation method thereof.
Background technique
The method for being commonly prepared with color coating is to be made by chemically reacting, for example pass through inorganic salts and tristearin mostly
Sour sodium reaction, or the fluorine-containing nitrogen dyestuff of grafting, these methods can generate many pollution problems, and preparation cost is higher；And
Typical commercial polyurethane class coating at present, the organic solvent content used in it is high, will cause serious VOC pollution；Existing skill
The color of color coating in art is single unadjustable.
Cellulose nanocrystal is a kind of novel liquid crystal material of cholesteric phase, and anisotropy can occur in higher concentrations for crystal to respectively
Transformation to the same sex, until forming liquid crystalline phase.Cellulose nanocrystal is light, excellent in mechanical performance, translucency are good, good from group
Performance is filled, makes it that there is huge application potential in the high-end technical field such as liquid crystal material, precision optics, medical material.
The application both at home and abroad to Cellulose nanocrystal on coating is rarely reported at present, and this liquid crystal coatings have high-crystallinity and regular
Structural arrangement, there is bright-coloured bright and beautiful structural color, and cannot be replicated by common pigments, if the internal structure of this coating is arranged
Column be not modified, then this structural color can long sustaining, no common pigments fade the problems such as, this be more in line with modern society energy conservation
Environmental protection theory, make its building material surface decoration, in terms of have wider application.
Summary of the invention
Goal of the invention: the purpose of the present invention is to solve the color of color coating in the prior art it is single it is unadjustable,
There is the problems such as environmental pollution, a kind of composite coating of environment-friendly degradable, and Color tunable are provided.
Technical solution: a kind of CNC/PEG composite coating, including Cellulose nanocrystal and polyethylene glycol, polyethylene glycol account for fibre
The nanocrystalline mass percentage of dimension element is 0~50%, and the particle size length of the Cellulose nanocrystal is 151~167nm,
Diameter is 48-52nm.
A kind of preparation method of CNC/PEG composite coating, comprises the following steps:
1) preparation of Cellulose nanocrystal (CNC) suspension: cellulose is prepared using the method for sulphuric acid hydrolysis cellulose and is received
Rice crystalline suspension liquid；The preparation method is using the prior art, and details are not described herein；
2) preparation of polyethylene glycol (PEG) solution: polyethylene glycol is dissolved in water, polyglycol solution is obtained；
3) polyglycol solution in step (2) is added dropwise in the Cellulose nanocrystal suspension in step (1), is stirred
It is uniformly mixed, obtains CNC/PEG composite suspension liquid；CNC/PEG composite suspension liquid is concentrated by evaporation, then carries out deaeration processing, is obtained
To CNC/PEG composite coating stoste.
Further, it is ultrasonically treated in ultrasonic washing instrument again after being uniformly mixed in the step 3)；Institute
The ultrasonic power for stating ultrasonic treatment is 200W, ultrasonic time 2min.
Cellulose nanocrystal has a high-crystallinity, high elastic modulus, the characteristics such as high intensity, due to its excessively high cohesive force,
Adhesion strength between the nanocrystalline coloured coating of pure cellulose and common plastic substrates is too low.And the amphiphilic macromoleculars such as PEG have very
Good plasticising performance, therefore, using Cellulose nanocrystal as host matrix, the high molecular polymers such as compound PEG retain cellulose
It while nanocrystalline liquid crystal characteristic, can also improve its mechanical property, expand it in the application of coatings art.
CNC/PEG coating designed by the present invention can be coated on various plastic plates, such as POM, PC, ABS, PA plastics
Plate.
Compared with the prior art, the invention has the following advantages: the present invention utilizes nothing using native cellulose as raw material
The free of contamination PEG of poison is as coating color regulator and plasticizer, the coloured coating environment-friendly degradable being prepared, mechanical performance
It is substantially improved, and structural color is bright-coloured controllable；On the other hand, by composite, simple drop coating is in substrate surface
It can be made, preparation process is simple, easily controllable, at low cost.
Detailed description of the invention
Fig. 1 is the polarization microscope photo of CNC/PEG composite coating film in the embodiment of the present invention 1；
Fig. 2 is the SEM photograph of CNC/PEG composite coating film cross section in the embodiment of the present invention 1；
Fig. 3 tests for the tensile property of CNC/PEG composite coating film obtained in the embodiment of the present invention；
Fig. 4 is the adhesion strength test for the CNC/PEG composite coating that the embodiment of the present invention is coated on ABS plate.
Specific embodiment
In order to deepen the understanding of the present invention, below in conjunction with embodiment and attached drawing, the invention will be further described, this
A little the examples are only for explaining the invention, is not intended to limit the scope of the present invention..
Embodiment 1
1) preparation of Cellulose nanocrystal suspension: 4.0g microcrystalline cellulose is mixed with 80ml concentration for 64wt% sulfuric acid
It closes, in 50 DEG C of water-baths after mechanical stirring 2h, the distilled water for adding 5 times of amounts stops hydrolysis, and the suspension after dilution falls
Enter bag filter, dialyse in the distilled water extra acid of removal in several days, the carbohydrate of small-molecular-weight and other water-solubility impurities；?
The nanocrystalline CNC suspension of aqueous fiber element for being about 6.0 to pH value, concentration 0.5wt%.(Cellulose nanocrystal suspends herein
The bibliography of liquid and preparation method thereof is Liu, D.；Wang,S；Ma,Z.；Tian,D.；Gu,M.；Lin,F.Structure-color
mechanism of iridescent cellulose nanocrystal films.RSC Adv.2014,4,39322-
39331.)
2) prepared by PEG solution: 5gPEG20000 being dispersed in 100ml distilled water, stirring makes it after completely dissolution, stands
Bubble in system of going out, obtaining PEG solution concentration is 5%.
3) preparation of CNC/PEG composite coating: being that 5%PEG solution is added separately to 50ml cellulose by 0.25ml concentration
In nanocrystal suspension, stirs and be ultrasonically treated 2min under 200W power in ultrasonic washing instrument, obtain after mixing
CNC/PEG composite suspension liquid；CNC/PEG composite suspension liquid is evaporated concentration at ambient conditions, then carries out deaeration processing,
Obtain the CNC/PEG composite coating stoste that concentration is 2wt%.
Embodiment 2
0.5ml concentration is that 5%PEG solution is separately added into difference from example 1 is that step 3) by the present embodiment
It into 50ml Cellulose nanocrystal suspension, stirs and is ultrasonically treated 2min under 200W power in ultrasonic washing instrument, mix
CNC/PEG composite suspension liquid is obtained after uniformly；CNC/PEG composite suspension liquid is evaporated concentration at ambient conditions, then into
Row deaeration processing, obtains CNC/PEG composite coating stoste.
Embodiment 3
0.75ml concentration is that 5%PEG solution adds respectively difference from example 1 is that step 3) by the present embodiment
Enter into 50ml Cellulose nanocrystal suspension, stir and be ultrasonically treated 2min under 200W power in ultrasonic washing instrument, mixes
CNC/PEG composite suspension liquid is obtained after closing uniformly；CNC/PEG composite suspension liquid is evaporated concentration at ambient conditions, then
Deaeration processing is carried out, CNC/PEG composite coating stoste is obtained.
Embodiment 4
1.0ml concentration is that 5%PEG solution is separately added into difference from example 1 is that step 3) by the present embodiment
It into 50ml Cellulose nanocrystal suspension, stirs and is ultrasonically treated 2min under 200W power in ultrasonic washing instrument, mix
CNC/PEG composite suspension liquid is obtained after uniformly；CNC/PEG composite suspension liquid is evaporated concentration at ambient conditions, then into
Row deaeration processing, obtains CNC/PEG composite coating stoste.
Embodiment 5
1.5ml concentration is that 5%PEG solution is separately added into difference from example 1 is that step 3) by the present embodiment
It into 50ml Cellulose nanocrystal suspension, stirs and is ultrasonically treated 2min under 200W power in ultrasonic washing instrument, mix
CNC/PEG composite suspension liquid is obtained after uniformly；CNC/PEG composite suspension liquid is evaporated concentration at ambient conditions, then into
Row deaeration processing, obtains CNC/PEG composite coating stoste.
Embodiment 6
2.0ml concentration is that 5%PEG solution is separately added into difference from example 1 is that step 3) by the present embodiment
It into 50ml Cellulose nanocrystal suspension, stirs and is ultrasonically treated 2min under 200W power in ultrasonic washing instrument, mix
CNC/PEG composite suspension liquid is obtained after uniformly；CNC/PEG composite suspension liquid is evaporated concentration at ambient conditions, then into
Row deaeration processing, obtains CNC/PEG composite coating stoste.
Embodiment 7
2.5ml concentration is that 5%PEG solution is separately added into difference from example 1 is that step 3) by the present embodiment
It into 50ml Cellulose nanocrystal suspension, stirs and is ultrasonically treated 2min under 200W power in ultrasonic washing instrument, mix
CNC/PEG composite suspension liquid is obtained after uniformly；CNC/PEG composite suspension liquid is evaporated concentration at ambient conditions, then into
Row deaeration processing, obtains CNC/PEG composite coating stoste.
The preparation of pure CNC coated film:
The preparation of Cellulose nanocrystal suspension: 4.0g microcrystalline cellulose is mixed with 80ml concentration for 64wt% sulfuric acid,
In 50 DEG C of water-baths after mechanical stirring 2h, the distilled water for adding 5 times of amounts stops hydrolysis, and the suspension after dilution pours into
Bag is analysed, dialyse in the distilled water extra acid of removal in several days, the carbohydrate of small-molecular-weight and other water-solubility impurities；Obtain pH
The nanocrystalline CNC suspension of aqueous fiber element of value about 6.0, concentration 0.5wt%.By CNC composite suspension liquid in environmental condition
Under be evaporated concentration, then carry out deaeration processing, obtain CNC coating stoste.
Performance test embodiment
CNC/PEG composite suspension liquid mixed in embodiment 1 is placed in the polytetrafluoroethylene (PTFE) diaphragm capsule that diameter is 9mm,
The CNC/PEG colour composite coating film that self-supporting can be opened is dried into 30 DEG C of baking ovens, the polarisation for obtaining composite coating film is aobvious
Micro mirror photo is shown in that Fig. 1 and the SEM photograph of composite coating film cross section are shown in Fig. 2.
As shown in Figure 1, CNC/PEG composite coating film remains the cholesteric liquid crystal structure of pure fiber nanocrystalline coating film,
It can be seen that fingerprint screw pitch constantly increases, while film color is also changing under petrographic microscope with the increase of PEG content,
Become orange from blue；Fig. 2 is as it can be seen that be a layer structure inside pure cellulose nanocrystalline coating film, and the addition of PEG retains
Layer structure, while increasing distance between layers.But when the PEG content being added is excessively high, after 30%, due to
PEG assembles in system, and the cholesteric liquid crystal of Cellulose nanocrystal is destructurized, and coated film color is thin out or even disappears
It loses.The maximum reflection wavelength that ultraviolet spectra testing result pure cellulose nanocrystalline coating film measures be 425nm, CNC/PEG2.5,
CNC/PEG5, CNC/PEG7.5, CNC/PEG10, CNC/PEG15, CNC/PEG20, CNC/PEG30, CNC/PEG40 coated film
Maximum reflection wavelength is respectively 435nm, and 442nm, 443nm, 460nm, 475nm, 481nm, 545nm, 494nm is with PEG content
Increase (be no more than 30%), integrally show a red shift.
Tensile property test is carried out to CNC/PEG composite coating film prepared by embodiment 2,4,5,6,7, as a result such as Fig. 3 institute
Show.Compared to pure cellulose nanocrystalline coating film, in the present invention by PEG and Cellulose nanocrystal it is compound after, with PEG content
Increase, the flexibility of coated film obviously increases.
CNC/PEG composite coating stoste prepared by embodiment 1,3,4,5,6,7 is respectively coated on ABS plastic with drop-coating
It is dry under environmental condition on plate, adhesive force test is then carried out, as shown in figure 4, the visible continuous increasing with PEG content of result
Adding (be no more than 30%), coating is also continuously improved in the adhesive force of ABS plastic plate surface, and it is amphiphilic due to PEG, it is on the one hand more
Hydroxyl structure, making its hydroxyl with Cellulose nanocrystal, there are stronger hydrogen bond actions, are readily dispersed between CNC layers；Simultaneously
PEG main chain has hydrophobicity again, makes between the plastic plates such as itself and ABS that there are compatibilities, increases CNC/PEG coating and ABS etc.
Adhesive force between substrate.
Claims (4)
1. a kind of CNC/PEG composite coating, which is characterized in that including Cellulose nanocrystal and polyethylene glycol, polyethylene glycol accounts for fibre
The nanocrystalline mass percentage of dimension element is 5 ~ 50%, and the particle size length of the Cellulose nanocrystal is 151 ~ 167nm, directly
Diameter is 48-52nm；
Preparation method comprises the following steps:
1) it the preparation of Cellulose nanocrystal suspension: is suspended using the method preparation Cellulose nanocrystal of sulphuric acid hydrolysis cellulose
Liquid；
2) preparation of polyglycol solution: polyethylene glycol is dissolved in water, polyglycol solution is obtained；
3) polyglycol solution in step (2) is added dropwise in the Cellulose nanocrystal suspension in step (1), stirring is mixed
It closes uniformly, obtains CNC/PEG composite suspension liquid: CNC/PEG composite suspension liquid being concentrated by evaporation, then carries out deaeration processing, is obtained
CNC/PEG composite coating stoste.
2. a kind of preparation method of CNC/PEG composite coating, which is characterized in that comprise the following steps:
1) it the preparation of Cellulose nanocrystal suspension: is suspended using the method preparation Cellulose nanocrystal of sulphuric acid hydrolysis cellulose
Liquid；
2) preparation of polyglycol solution: polyethylene glycol is dissolved in water, polyglycol solution is obtained；
3) polyglycol solution in step (2) is added dropwise in the Cellulose nanocrystal suspension in step (1), stirring is mixed
It closes uniformly, obtains CNC/PEG composite suspension liquid: CNC/PEG composite suspension liquid being concentrated by evaporation, then carries out deaeration processing, is obtained
CNC/PEG composite coating stoste.
3. the preparation method of CNC/PEG composite coating according to claim 2, which is characterized in that stirred in the step 3)
It mixes and is ultrasonically treated in ultrasonic washing instrument again after mixing.
4. the preparation method of CNC/PEG composite coating according to claim 3, which is characterized in that the ultrasonic treatment
Ultrasonic power is 200W, ultrasonic time 2min.
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| CN112759982A (en) * | 2020-12-24 | 2021-05-07 | 南京信息工程大学 | PVA/CNC composite coating and preparation method and application thereof |
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Effective date of registration: 20221222 Address after: No. 88-2, pubin Avenue, Jiangpu street, Pukou District, Nanjing, Jiangsu 210000 Patentee after: Nanjing ruiniu Nenghuan New Material Technology Co.,Ltd. Address before: 210044 No. 219, Ning six road, Nanjing, Jiangsu Patentee before: Nanjing University of Information Science and Technology |