CN106280911A - A kind of Cellulose nanocrystal strengthens composite coating and preparation method thereof - Google Patents
A kind of Cellulose nanocrystal strengthens composite coating and preparation method thereof Download PDFInfo
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- CN106280911A CN106280911A CN201610721511.1A CN201610721511A CN106280911A CN 106280911 A CN106280911 A CN 106280911A CN 201610721511 A CN201610721511 A CN 201610721511A CN 106280911 A CN106280911 A CN 106280911A
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- cellulose nanocrystal
- composite coating
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- oligomer
- cellulose
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Classifications
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- C—CHEMISTRY; METALLURGY
- 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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
- C09D163/10—Epoxy resins modified by unsaturated compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- 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
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Organic Chemistry (AREA)
- Wood Science & Technology (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Polymerisation Methods In General (AREA)
- Paints Or Removers (AREA)
Abstract
The invention discloses a kind of Cellulose nanocrystal and strengthen composite coating and preparation method thereof, the Cellulose nanocrystal that the present invention provides strengthens the preparation method of composite coating, including: step one, Cellulose nanocrystal is carried out surface modification；Step 2, modified Cellulose nanocrystal is purified；Step 3, mixed and modified after Cellulose nanocrystal and other material prepared needed for coating.Paint solidification temperature can be reduced by technical scheme, improve coating intensity.
Description
Technical field
The invention belongs to Biological nanocomposite field, particularly to a kind of Cellulose nanocrystal strengthen composite coating and
Its preparation method.
Background technology
In modern society, coating has been applied more and more extensive as surface preservative.Most traditional coating, as
Woodwork furniture coating, all based on nitrate paint, polyurethane, unsaturated polyester (UP), aminoacid equal solvent type coating, and these are coated with
In material, containing substantial amounts of volatile organic matter.Some solvent based coating even contains the strong carcinogens such as benzene,toluene,xylene,
In these coating curing processes, the material of volatilization seriously compromises the health of natural environment and the mankind；So environmentally friendly type
Coating creates demand.
Ultraviolet-curing paint is due to the ageing-resistant performance of its brilliance, chemical resistance, anti-staining and working (machining) efficiency
High, machining tool is easy to use and receives much concern without chemical contamination performance.Ultraviolet light polymerization molding has become as macromolecule
An important forming method outside the heat cure molding of field.The method is that the short wavelength's optical energy utilizing radiation source excites
Active component in material, thus cause the fast-growth of strand and ultimately result in the curing molding of material.But it is existing
The solidification temperature of ultraviolet-curing paint is the lowest, intensity is low.
Summary of the invention
The problem that the present invention solves is that existing ultraviolet-curing paint solidification temperature is the lowest, and coating intensity is low；For solving
Certainly described problem, the present invention provides a kind of Cellulose nanocrystal to strengthen composite coating and preparation method thereof.
The Cellulose nanocrystal that the present invention provides strengthens composite coating and includes: acrylate quasi-oligomer, esters of acrylic acid
Monomer, defoamer, modified cellulose are nanocrystalline, light trigger.
The present invention also provides for Cellulose nanocrystal and strengthens the preparation method of composite coating, including:
Step one, Cellulose nanocrystal is carried out surface modification；
Step 2, modified Cellulose nanocrystal is purified；
Step 3, mixed and modified after Cellulose nanocrystal and other material prepared needed for coating.
Further, described cationic surfactant uses ammonium salt class or quaternary ammonium salt, cationic surfactant
Concentration is 10 ~ 20%.
Further, described step one includes: with the deionized waters of 45 ~ 55 DEG C as dispersion liquid, in the condition of electromagnetic agitation
Under, soak Cellulose nanocrystal 1.5 ~ 2.5 h with cationic surfactant.
Further, described step 2 removes the cationic surfactant on modified Cellulose nanocrystal surface.
Further, described step 3 includes:
Step 3.1, acrylate quasi-oligomer is joined in acrylic ester monomer；
Step 3.2, under agitation, is sequentially added into that defoamer, modified cellulose be nanocrystalline, light trigger.
Further, described acrylic ester monomer selects trimethylol-propane trimethacrylate, propoxylation new
Any one or two kinds in pentanediol double methacrylate；Described acrylate quasi-oligomer selects bisphenol-A epoxy propylene
One or two kinds of in acid esters and the mixed system of tri (propylene glycol) diacrylate, mono-acrylate oligomer；Described
Defoamer select the one or two kinds of in polyoxyethylene polyoxypropylene tetramethylolmethane ether, polyoxyethylene polyoxy propanol amidogen ether；
Described light trigger selects 2-hydroxy-2-methyl phenylacetone, 2-hydroxy-2-methyl-1-[4-(2-hydroxyl-oxethyl) benzene
Base] one or two kinds of in-1-acetone.
In the present invention, by being reactant with acrylic ester monomer and oligomer, at ultraviolet excitation and cellulose
Nanocrystalline reinforcement, other auxiliary agents assosting effect under, it is possible to prepare without chemical contamination with faster rate generation radical polymerization
And the novel nano composite coating that solidification is rapid, mechanical property, adhesive property are excellent.
Detailed description of the invention
Hereinafter, spirit and substance of the present invention are further elaborated in conjunction with the embodiments.
Embodiment 1
The present embodiment is directed to cetyl trimethylammonium bromide as surfactant, to cellulose nanometer at 45 DEG C
Brilliant immersion treatment 1.5 h in the dispersion liquid of deionized water, modified, it is single with trimethylol-propane trimethacrylate
Body, the oligomer with the mixed system of bisphenol A epoxy acrylate and tri (propylene glycol) diacrylate as reaction system, with
Polyoxyethylene polyoxypropylene tetramethylolmethane ether is defoamer, and the mixing with 2-hydroxy-2-methyl phenylacetone as light trigger is molten
After liquid stirs, solution is 600 mJ/cm through intensity2Ultraviolet irradiate curing molding after 1 min.
In the present embodiment, Cellulose nanocrystal content is 2 %, prepared enhancing nano composite dope glass transition temperature
Degree is 38 DEG C, reduces by 3 DEG C than the most plain nanocrystalline coating, and water absorption is 0.0001 g/cm2* min, light transmission
Rate is 89 %.
Embodiment 2
The present embodiment is directed to quaternary ammonium salt as surfactant, to Cellulose nanocrystal at deionized water at 48 DEG C
In dispersion liquid, immersion treatment 2.5 h, modified, is monomer with ethoxylated neopentylglycol double methacrylate, with mono acrylic ester
Oligomer is the oligomer of reaction system, with polyoxyethylene polyoxy propanol amidogen ether as defoamer, with 2-hydroxy-2-methyl-1-[4-
(2-hydroxyl-oxethyl) phenyl]-1-acetone is that after the mixed solution of light trigger stirs, solution is 800 through intensity
mJ/cm2Ultraviolet irradiate curing molding after 0.5 min.
In the present embodiment, Cellulose nanocrystal content is 1 %, prepared enhancing nano composite dope glass transition temperature
Degree is 37 DEG C, reduces by 4 DEG C than the most plain nanocrystalline coating, and water absorption is 0.00011 g/cm2* min, light is saturating
The rate of mistake is 90 %.
Embodiment 3
The present embodiment is directed to quaternary ammonium salt as surfactant, divides Cellulose nanocrystal at deionized water at 50 DEG C
Dissipate immersion treatment 2.2 h in liquid, modified, it is monomer with trimethylol-propane trimethacrylate, low with mono acrylic ester
Polymers is the oligomer of reaction system, with polyoxyethylene polyoxypropylene tetramethylolmethane ether as defoamer, with 2-hydroxy-2-methyl benzene
Benzylacetone is that after the mixed solution of light trigger stirs, solution is 700 mJ/cm through intensity2Ultraviolet irradiate
Curing molding after 0.8 min.
In the present embodiment, Cellulose nanocrystal content is 1.5 %, prepared enhancing nano composite dope glass transition
Temperature is 37.5 DEG C, reduces by 3.5 DEG C than the most plain nanocrystalline coating, and water absorption is 0.00013 g/cm2*min,
Light transmission rate is 88 %.
Embodiment 4
The present embodiment is directed to cetyl trimethylammonium bromide as surfactant, to cellulose nanometer at 45 DEG C
Brilliant immersion treatment 2.0 h in the dispersion liquid of deionized water, modified, it is single with ethoxylated neopentylglycol double methacrylate
Body, the oligomer with mono-acrylate oligomer as reaction system, with polyoxyethylene polyoxypropylene tetramethylolmethane ether as defoamer,
After mixed solution with 2-hydroxy-2-methyl phenylacetone as light trigger stirs, solution is 700 mJ/ through intensity
cm2Ultraviolet irradiate curing molding after 2.5 min.
In the present embodiment, Cellulose nanocrystal content is 2.0 %, prepared enhancing nano composite dope glass transition
Temperature is 37 DEG C, reduces by 4 DEG C than the most plain nanocrystalline coating, and water absorption is 0.0001g/cm2* min, light is saturating
The rate of mistake is 88 %.
Embodiment 5
The present embodiment is directed to alkyl trimethyl ammonium salt as surfactant, is going Cellulose nanocrystal at 52 DEG C
In the dispersion liquid of ionized water, immersion treatment 1.2 h, modified, is monomer with trimethylol-propane trimethacrylate, with list
Acrylate oligomer is the oligomer of reaction system, with polyoxyethylene polyoxy propanol amidogen ether as defoamer, with 2-hydroxyl-2-first
Base-1-[4-(2-hydroxyl-oxethyl) phenyl]-1-acetone is after the mixed solution of light trigger stirs, and solution is through strong
Degree is 650 mJ/cm2Ultraviolet irradiate curing molding after 2.5 min.
In the present embodiment, Cellulose nanocrystal content is 2.5 %, prepared enhancing nano composite dope glass transition
Temperature is 38 DEG C, reduces by 3 DEG C than the most plain nanocrystalline coating, and water absorption is 0.00012 g/cm2* min, light
Transmitance is 88 %.
Embodiment 6
The present embodiment is directed to alkyl trimethyl ammonium salt as surfactant, is going Cellulose nanocrystal at 55 DEG C
In the dispersion liquid of ionized water, immersion treatment 2.5 h, modified, is monomer with ethoxylated neopentylglycol double methacrylate, with double
Phenol A epoxy acrylate oligomer is the oligomer of reaction system, with polyoxyethylene polyoxypropylene tetramethylolmethane ether as defoamer,
It is sufficiently stirred for all with 2-hydroxy-2-methyl-1-[4-(2-hydroxyl-oxethyl) the phenyl]-1-acetone mixed solution as light trigger
After even, solution is 800 mJ/cm through intensity2Ultraviolet irradiate curing molding after 1.5 min.
In the present embodiment, Cellulose nanocrystal content is 2.5 %, prepared enhancing nano composite dope glass transition
Temperature is 37.2 DEG C, reduces by 3.8 DEG C than the most plain nanocrystalline coating, and water absorption is 0.00013 g/cm2*min,
Light transmission rate is 88 %.
Compared with existing solvent based coating, the new coating prepared by the present invention by ultraviolet light polymerization mode molding,
Do not have any chemical substance to volatilize, there is environment friendly, and harmless to human body, meet current people for improving life
The demand of quality；Compared with current existing green coating, the present invention passes through ultraviolet light polymerization method molding, and operating procedure is simple,
And owing to introducing cellulose wadding, while material cost is greatly lowered, resistance to water, the transparency, mechanical performance are all carried
High.To sum up, the present invention has obvious commercial Application advantage.
Although the present invention is open as above with preferred embodiment, but it is not for limiting the present invention, any this area
Technical staff without departing from the spirit and scope of the present invention, may be by the method for the disclosure above and technology contents to this
Bright technical scheme makes possible variation and amendment, therefore, every content without departing from technical solution of the present invention, according to the present invention
Technical spirit any simple modification, equivalent variations and modification that above example is made, belong to technical solution of the present invention
Protection domain.
Claims (7)
1. a Cellulose nanocrystal strengthens composite coating, it is characterised in that including: acrylate quasi-oligomer, acrylate
Class monomer, defoamer, modified cellulose are nanocrystalline, light trigger.
2. the preparation method of a Cellulose nanocrystal enhancing composite coating, it is characterised in that including:
Step one, Cellulose nanocrystal is carried out surface modification；
Step 2, modified Cellulose nanocrystal is purified；
Step 3, mixed and modified after Cellulose nanocrystal and other material prepared needed for coating.
3. strengthen the preparation method of composite coating according to the Cellulose nanocrystal described in claim 2, it is characterised in that step one
Including: with the deionized waters of 45 ~ 55 DEG C as dispersion liquid, under conditions of electromagnetic agitation, soak fibre with cationic surfactant
Dimension nanocrystalline 1.5 ~ 2.5 h of element.
4. strengthen the preparation method of composite coating according to the Cellulose nanocrystal described in claim 2, it is characterised in that described sun
Ionic surface active agent uses ammonium salt class or quaternary ammonium salt, and the concentration of cationic surfactant is 10 ~ 20%.
5. strengthen the preparation method of composite coating according to the Cellulose nanocrystal described in claim 2, it is characterised in that described step
Rapid two cationic surfactants removing modified Cellulose nanocrystal surface.
6. strengthen the preparation method of composite coating according to the Cellulose nanocrystal described in claim 2, it is characterised in that described step
Rapid three include:
Step 3.1, acrylate quasi-oligomer is joined in acrylic ester monomer；
Step 3.2, under agitation, is sequentially added into that defoamer, modified cellulose be nanocrystalline, light trigger.
7. strengthen the preparation method of composite coating according to the Cellulose nanocrystal described in claim 6, it is characterised in that described
Acrylic ester monomer selects appointing in trimethylol-propane trimethacrylate, ethoxylated neopentylglycol double methacrylate
Meaning one or two kinds of；Described acrylate quasi-oligomer selects bisphenol A epoxy acrylate and tripropylene glycol dipropyl
One or two kinds of in the mixed system of olefin(e) acid ester, mono-acrylate oligomer；Described defoamer selects polyoxyethylene to gather
One or two kinds of in oxypropylene tetramethylolmethane ether, polyoxyethylene polyoxy propanol amidogen ether；Described light trigger selects 2-hydroxyl
One or two in base-2-methylpropiophenone, 2-hydroxy-2-methyl-1-[4-(2-hydroxyl-oxethyl) phenyl]-1-acetone
Kind.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610721511.1A CN106280911A (en) | 2016-08-25 | 2016-08-25 | A kind of Cellulose nanocrystal strengthens composite coating and preparation method thereof |
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| CN201610721511.1A CN106280911A (en) | 2016-08-25 | 2016-08-25 | A kind of Cellulose nanocrystal strengthens composite coating and preparation method thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107254002A (en) * | 2017-08-01 | 2017-10-17 | 张振 | Nano-cellulose containing cinnamyl functional groups and its preparation method and application |
| CN107459852A (en) * | 2017-09-02 | 2017-12-12 | 佛山市北朝源科技服务有限公司 | A kind of water-soluble anti-rust nano composite dope |
| CN109486297A (en) * | 2018-11-24 | 2019-03-19 | 上海凯虹特种材料科技有限公司 | A kind of white fluorine carbon finishing paint and its preparation process |
| CN110218360A (en) * | 2019-05-31 | 2019-09-10 | 华南理工大学 | A kind of flexible waterproof CNC/PEGDA photon crystal material and preparation method thereof |
| CN111944067A (en) * | 2019-05-14 | 2020-11-17 | 中国科学技术大学 | Biomass environment-friendly water-based paint and preparation method and application thereof |
| CN112144316A (en) * | 2020-09-30 | 2020-12-29 | 广东福美新材料科技有限公司 | Nano-cellulose modified acrylic resin, preparation method thereof and decorative paper |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107254002A (en) * | 2017-08-01 | 2017-10-17 | 张振 | Nano-cellulose containing cinnamyl functional groups and its preparation method and application |
| CN107459852A (en) * | 2017-09-02 | 2017-12-12 | 佛山市北朝源科技服务有限公司 | A kind of water-soluble anti-rust nano composite dope |
| CN109486297A (en) * | 2018-11-24 | 2019-03-19 | 上海凯虹特种材料科技有限公司 | A kind of white fluorine carbon finishing paint and its preparation process |
| CN111944067A (en) * | 2019-05-14 | 2020-11-17 | 中国科学技术大学 | Biomass environment-friendly water-based paint and preparation method and application thereof |
| CN111944067B (en) * | 2019-05-14 | 2022-05-17 | 中国科学技术大学 | Biomass environment-friendly water-based paint and preparation method and application thereof |
| CN110218360A (en) * | 2019-05-31 | 2019-09-10 | 华南理工大学 | A kind of flexible waterproof CNC/PEGDA photon crystal material and preparation method thereof |
| CN110218360B (en) * | 2019-05-31 | 2021-05-14 | 华南理工大学 | Flexible water-resistant CNC/PEGDA photonic crystal material and preparation method thereof |
| CN112144316A (en) * | 2020-09-30 | 2020-12-29 | 广东福美新材料科技有限公司 | Nano-cellulose modified acrylic resin, preparation method thereof and decorative paper |
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