CN106189418B - A kind of photocureable coating and preparation method thereof based on graphene - Google Patents
A kind of photocureable coating and preparation method thereof based on graphene Download PDFInfo
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- CN106189418B CN106189418B CN201610583532.1A CN201610583532A CN106189418B CN 106189418 B CN106189418 B CN 106189418B CN 201610583532 A CN201610583532 A CN 201610583532A CN 106189418 B CN106189418 B CN 106189418B
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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
- 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
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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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
Abstract
The present invention relates to photocureable coating technical fields, more specifically, be related to a kind of photocureable coating and preparation method thereof based on graphene, it is prepared by mass percentage by following raw materials: 30~70wt% oligomer, 20~60wt% active monomer diluent, 1~10wt% photoinitiator, 1~10wt% auxiliary agent and 0.01~10wt% graphene form.Photocureable coating mechanical performance produced by the present invention based on graphene is excellent, heat resistance and electrical property are good, external coating especially suitable for high-temperature resistant optical fiber, it is suitable for high speed fibre drawing process simultaneously, is also applied for other paint fields for needing quick-setting photoelectronic device.
Description
Technical field
The present invention relates to photocureable coating technical fields, apply more specifically to a kind of photocuring based on graphene
Material and preparation method thereof especially suitable for the external coating of high-temperature resistant optical fiber, while being suitable for high speed fibre drawing process, is also suitable
In the paint field that other need quick-setting photoelectronic device.
Background technique
Photocureable coating is a kind of energy saving, efficiently, environmentally friendly safe green coating, fast, no or low with solidification rate to have
Machine compound emission, solidification temperature be low, high production efficiency and the advantages that excellent protection and optical property, is widely used in moulding
The substrates such as material, metal, glass and ceramics.Photocureable coating mainly by homopolymer, photoactive monomer, photoinitiator etc. mainly at
Point, it is equipped with the auxiliary agents such as crosslinking agent, stabilizer and coupling agent composition.When coating is by ultraviolet light, photoinitiator absorbs energy
Volume production liveliness proof group, causes homopolymer and polymerization reaction occurs for monomer, thus film-forming.
The fast development of the communications industry, computer, printing and electronics industry etc., has pushed ultraviolet-curing paint significantly
Development, while also to the mechanical performance of coating and heat resistance etc., more stringent requirements are proposed.The mechanical strength of high molecular material takes
Certainly in the active force of backbone chemistry bonding force and molecule interchain, when active force is stronger, mechanical strength is higher.General increase material
Mechanical strength can be improved in polarity or formation hydrogen bond.But if polar group is overstocked or substituent group is excessive, unfavorable molecular motion is stretched
Although intensity improves, brittleness is presented.Common epoxy acrylic resin tensile strength is relatively high, but its elongation at break
It is low.The heat resistance of high molecular material depends on the flexibility of main chain, substituent group, geometry, relative molecular mass, molecule interchain
Active force etc..As, containing rigid phenyl ring, homopolymer heat resistance is higher in epoxy acrylic ester structure.
With the fast development of information age, the application field of optical fiber cable is more and more extensive, at present commercial common stone
English optical fiber uses ultra-violet curing acrylic resin coating, and use temperature range is -60 DEG C~85 DEG C, and it is special to have adapted to
The use condition of environment, especially in the high-temperature severe environments such as oil well and aircraft rocket engine, common ultra-violet curing
Heat ageing and thermo-oxidative ageing easily occur for coating, to reduce protective effect of the fibre coating to optical fiber, and then will affect light
The transmission performance of fine information.Currently, high-temperature resistant optical fiber coating mainly uses polyimides, a kind of macromolecule that comprehensive performance is splendid
Material, has excellent heat resistance, and low temperature resistant, anti-flammability, mechanical performance and biological friendly are widely used in aviation boat
It, laser, optical fiber pass can and the fields such as biological medicine.However as optical fiber coatings, the heat cure mode of polyimides is difficult
Realize rapid curing, temperature condition when not being able to satisfy the needs of the quick wire drawing of optical fiber, while solidifying will have a direct impact on optical fiber painting
The subsequent performance of layer.
Graphene is considered as the graphite of monoatomic layer, is the two-dimensional material of a carbon atom thickness, is not only known material
Most thin one kind in material also has the performances such as excellent mechanics, electricity, calorifics.Due to its unique structure and performance, and aoxidize
Graphene synthesis material is simple and easy to get, low in cost, has huge specific surface area and functional group abundant, by restoring or changing
Property after can form nano-dispersion in the polymer, graphene improve the calorifics of polymer, mechanics and in terms of
With sizable application value.The study found that Brinson and its colleague are in " Functionalized grapheme
Mass fraction is added for 1wt% functionalization graphene nanometer sheet in a sheets for polymer nanocomposites " text
Enter into polyacrylonitrile, glass transition temperature can be improved about 40 DEG C；Mass fraction is added into polymethacrylates
For the functionalization graphene nanometer sheet of 0.05wt%, glass transition temperature improves nearly 30 DEG C；It is about 1.0% by mass fraction
Graphene be added in PMMA, the elasticity modulus of composite material improves about 80%, and tensile strength improves about 20%.Graphene adds
Add the modulus, intensity and thermal stability for improving these polymer, greatly improved the hot property of polymer.Qiu et al. exists
By the graphene after removing in " Enhancing polymer performance through grapheme sheets " text
0.54% (volume ratio) is added in epoxy resin, and compared with the epoxy resin for being not added with graphene, graphene/epoxy resin is compound
The toughness of material improves 41%, and tensile strength and coefficient of elasticity enhance 10% and 25% respectively.Add suitable graphene
Or functionalization graphene can also make the mechanical property of matrix polymer be significantly improved, overcoming general inorganic filler makes
Dosage is big, and the shortcomings that cannot take into account rigidity, heat resistance, dimensional stability and toughness while improve.In consideration of it, the present invention provides
A kind of photocureable coating and preparation method thereof based on graphene, the composite coating tool prepared has excellent performance, heat resistance and
Electric property is good, is applicable to the adverse circumstances such as space flight, oil well, automobile engine cover and steel industry；Preparation method and mistake
Journey is simple, and the composite coating obtained based on graphene is solidified using ultraviolet light, is applicable to the external coating of high-temperature resistant optical fiber, together
When be suitable for high speed fibre drawing process.
Summary of the invention
The purpose of the present invention is to provide a kind of photocureable coating and preparation method thereof based on graphene.
Preparation method of the invention easy to carry out, the photocuring obtained based on graphene at low cost, environmental-friendly, simple
Paint machine is had excellent performance, heat resistance and electrical property are good, is applicable to space flight, oil well, automobile engine cover and steel industry
Etc. adverse circumstances, be especially suitable for high-speed wire-drawing technique in high-temperature resistant optical fiber preparation.
In order to achieve that object of the invention, the invention adopts the following technical scheme:
The present invention provides a kind of photocuring optical fiber coating based on graphene, oligomeric by 30~70wt% by mass percentage
Object, 20~60wt% active monomer diluent, 1~10wt% photoinitiator, 1~10wt% auxiliary agent and 0.01~10wt% graphite
Alkene composition.
The oligomer is that ultraviolet light solidifies oligomer, such as polyether acrylate, epoxy acrylate, polyester acrylic
The acrylatcs systems light such as ester, polyurethane acrylate, epoxy polyurethane acrylate, organic silicon modified epoxy acrylate are solid
Change one of oligomer or a variety of.
The optical fiber coatings of common Photocurable oligomers preparation can be solidified by ultraviolet light realizes rapid curing, but its is resistance to
Warm nature can be poor with heat resistance, and the present invention is improved its elasticity modulus, tensile strength and glass by the incorporation of graphene and turned
Change temperature, and then improves the mechanical performance and heat resistance of coating.When graphene oxide/graphene uniform is dispersed in coating resin
In, due to its special layer structure, the movement and thermal decomposition of molecular resin segment are hindered, so that it is solid to improve composite coating
Change the modulus of film, and then improves the heat resistance of composite coating；There are one between another aspect graphene oxide and coating resin
A little hydrogen bond actions and compatibility, so that the density of hard section increases in strand, crosslink density is improved.The crosslink density of coating and solid
Modulus after change is to influence the principal element of its heat resistance.The high-specific surface area of graphene makes it have stronger surface and inhales
Attached power can form reticular structure when coating is dry, to enhance the suction-operated of coating and substrate.Composite coating solidification simultaneously
Ultraviolet light photo catalytic reduction graphene oxide in the process increases the electric conductivity of system, helps to eliminate fiber drawing process
In electrostatic interaction, conducive to the receipts silk and winding displacement of production process optical fiber.
The graphene is the chemical modification/modification functionalization graphene or graphene prepared by chemical method, wherein
Chemical modification/modification function includes one of a variety of functional groups, such as hydroxyl, carboxyl, carbonyl, amino, sulfonic group or more
Kind.
The graphene be two-dimensional layered structure few layer of graphene, preferably the number of plies be one of 1~40 layer or/
With it is a variety of.
The addition mass percent of the graphene is preferably 0.01~10wt%.It is further preferred that of the invention
The additional amount mass percent of middle graphene is 0.01~5wt%.
The present invention also provides a kind of preparation method of photocureable coating based on graphene, the preparation method is a step
Or multistep blending method, one-step method i.e.: by graphene and dispersant at graphene solution, then by graphene solution with it is oligomeric
Object, active monomer diluent, photoinitiator and auxiliary agent are uniformly mixed according to a ratio, and obtain graphene composite coating, hybrid reaction temperature
It is 20~90 DEG C.Room temperature to be stood, composite coating is transferred in brown bottle, is placed in a vacuum drying oven and is gone at a certain temperature
Bubble removing and remaining graphene solvent are to get the photocureable coating based on graphene；Multistep processes are as follows: by graphene and dispersing agent
It is mixed into graphene solution, then graphene solution and oligomer are first sufficiently mixed uniformly according to the ratio, mixture A is obtained, will live
Property monomer diluent, photoinitiator and auxiliary agent are uniformly mixed according to a ratio to obtain mixture B, then by mixture A be added in arrive
Mixture B is uniformly mixed, and obtains graphene composite coating, and hybrid reaction temperature is 20~90 DEG C.Room temperature to be stood, by composite coating
It is transferred in brown bottle, is placed in a vacuum drying oven and removes bubble removing and remaining graphene solvent at a certain temperature, must be based on
The photocureable coating of graphene.
The dispersing agent is nonaqueous solvents, preferably acetone, ethyl alcohol, isopropanol, ethylene glycol, one in dimethylformamide
Kind is a variety of；More preferable ethyl alcohol and acetone according to mass ratio 1:1 mixed solution；Using above-mentioned solvent, the dissolubility of graphene
It can be preferably.
The auxiliary agent is the conven-tional adjuvants for preparing coating.
The active monomer diluent includes: alkoxide phenol acrylate, 2 (2- ethoxy ethoxy) ethyl propylenes
Acid esters, tetrahydrofuran acrylate, 2- phenoxyethyl acrylate, decyl acrylate, caprolactone, ethylization nonyl
Phenol acrylate, isobornyl acrylate, trimethylolpropane formal acrylate, neopentylglycol diacrylate, 1,
6- hexanediyl ester, tri (propylene glycol) diacrylate, trimethylolpropane trimethacrylate, pentaerythrite 3 third
One of olefin(e) acid ester or pentaerythritol tetraacrylate are a variety of.
The photoinitiator is selected from 2,4,6- trimethylbenzoy-dipheny phosphorous oxide, 2- hydroxy-2-methyl -1-
Bis- (2,4,6- trimethylbenzoyl) phosphine oxides of phenylacetone, 1- hydroxycyclohexyl phenylketone, benzoin dimethylether, phenyl,
The combination of one or more of 2- methyl-1-(4- methyl mercapto phenyl)-2- morpholine-1- acetone (IRGACURE 907).
A kind of photocureable coating and preparation method thereof based on graphene, the photocureable coating system based on graphene
Standby process hybrid reaction temperature is preferably 20~90 DEG C, it is further preferred that hybrid reaction temperature is 40~70 DEG C.
The compound photocureable coating mechanical performance of gained of the invention is excellent, heat resistance and electric property are good, is applicable to
The adverse circumstances such as space flight, oil well and automobile engine cover；Preparation process is simply easy to carry out, and at low cost, environmental-friendly, use is ultraviolet
Photocuring is particularly suitable for the outer coating of optical fiber, to optical fiber in harsh environment using playing a very good protection.
Detailed description of the invention
Fig. 1 is the mechanical performance cylindricality comparison diagram of each photocureable coating in various embodiments of the present invention and comparative example.
Specific embodiment
Of the invention for ease of understanding, it is as follows that the present invention enumerates embodiment.Those skilled in the art are it will be clearly understood that the implementation
Example is only to aid in the understanding present invention, should not be regarded as a specific limitation of the invention.
Embodiment 1
Graphene is evenly dispersed in acetone through ultrasound, according to mass percent polyurethane (methyl) acrylate
18wt%, epoxy acrylate 52wt%, alkoxide phenol acrylate 22.8wt%, benzoin dimethylether 3.9wt%, auxiliary agent
The proportion of 3.1wt% weighs material, sequentially adds in three-necked flask, quickly stirs at 60 DEG C 20 minutes, then by mass fraction
It is slowly added in flask for the graphene solution of 0.2wt%, continues to be protected from light quickly stirring 4h at 50 DEG C, fill material
Divide and be uniformly mixed, stands room temperature to it, composite coating is transferred in brown bottle, is placed in a vacuum drying oven and is removed at 50 DEG C
Bubble and remaining acetone are to get the photocureable coating based on graphene.On a glass by the graphene composite coating finally
It makes film by oneself, is solidified under ultraviolet lighting, then test the performance of graphene composite coating cured film.The graphene is compound
Elasticity modulus after paint solidification is 1.1GPa, and solvent resistance is greater than 200, and heat resistance is greater than 150 DEG C.
Embodiment 2
Graphene is dispersed in the mixed solution of ethyl alcohol and acetone according to mass ratio 1:1 through ultrasound, according to quality
Score polyurethane (methyl) acrylate 14wt%, epoxy acrylate 56wt%, caprolactone and ethylization nonyl benzene
Phenol acrylate mixture 22.7wt%, 2,4,6- trimethylbenzoy-dipheny phosphorous oxide 3.9wt%, auxiliary agent 3.1wt%
Proportion weigh material, sequentially add in three-necked flask, quickly stirred at 60 DEG C 20 minutes, be then by mass fraction
The graphene solution of 0.3wt% is slowly added in flask, continues to be protected from light quickly stirring 5h at 50 DEG C, keeps material abundant
It is uniformly mixed, composite coating is transferred in brown bottle by room temperature to be stood, and is placed in a vacuum drying oven in 50 DEG C of bubble removings that go down
With remaining acetone to get the photocureable coating based on graphene.Finally the graphene composite coating is made by oneself on a glass
Film is solidified under ultraviolet lighting, then tests the performance of graphene composite coating cured film.The graphene composite coating
Elasticity modulus after solidification is 1.35GPa, and solvent resistance is greater than 200, and heat resistance is greater than 200 DEG C.
Embodiment 3
Graphene is dispersed in the mixed solution of ethyl alcohol and acetone according to mass ratio 1:1 through ultrasound, according to quality
Score polyurethane (methyl) acrylate 15wt%, organic silicon modified epoxy acrylate 55wt%, the ratio of graphene 0.8%
Material is weighed, by each material be protected from light at 60 DEG C being sufficiently mixed and quickly stirs evenly to obtain mixture A.Tetrahydrofuran third is pressed again
The ratio of bis- (2,4,6- trimethylbenzoyl) the phosphine oxide 3.9wt% and auxiliary agent 3.1wt% of olefin(e) acid ester 22.2wt%, phenyl claims
Material is taken, each material and mixture A are protected from light quickly stirring 4h at 60 DEG C, are sufficiently mixed material uniformly, room temperature to be stood,
Composite coating is transferred in brown bottle, is placed in a vacuum drying oven the acetone of go down at 50 DEG C bubble removing and remnants to get base
In the photocureable coating of graphene.Finally make the graphene composite coating by oneself film on a glass, under ultraviolet lighting into
Row solidification, then tests the performance of graphene composite coating cured film.Elasticity modulus after the graphene composite coating solidifies is
2.1GPa, solvent resistance are greater than 200, and heat resistance is greater than 250 DEG C.
Embodiment 4
Graphene is dispersed in isopropanol through ultrasound, according to mass fraction polyurethane (methyl) acrylate
The ratio of 10wt%, organic silicon modified epoxy acrylate 56wt%, graphene 0.8% weigh material, by each object at 60 DEG C
Material, which be protected from light being sufficiently mixed, quickly stirs evenly to obtain mixture A.Pentaerythritol triacrylate 24.2wt%, 1- hydroxyl are pressed again
The ratio of cyclohexylbenzene ketone 4.9wt% and auxiliary agent 4.1wt% weigh material, are protected from light each material and mixture A at 60 DEG C
Quickly stirring 4h, is sufficiently mixed material uniformly, and composite coating is transferred in brown bottle by room temperature to be stood, and it is dry to be placed in vacuum
Go down bubble removing and remaining isopropanol at 50 DEG C in dry case to get the photocureable coating based on graphene.
Embodiment 5
Graphene is dispersed in isopropanol through ultrasound, according to mass fraction polyurethane (methyl) acrylate
10wt%, epoxy acrylate 56wt%, 1,6- hexanediyl ester 24.7wt%, 2- hydroxy-2-methyl -1- phenyl third
Ketone 4.7wt%, auxiliary agent 4.1wt% proportion weigh material, sequentially add in three-necked flask, quickly stirred at 60 DEG C 20 minutes,
Then the graphene solution that mass fraction is 0.5wt% is slowly added in flask, continues to be protected from light quickly at 50 DEG C
5h is stirred, is sufficiently mixed material uniformly, composite coating is transferred in brown bottle, is placed in vacuum oven by room temperature to be stood
In go down bubble removing and remaining acetone at 50 DEG C to get the photocureable coating based on graphene.
Comparative example 1
According to mass fraction polyurethane (methyl) acrylate 18wt%, epoxy acrylate 52wt%, activated monomer is dilute
Release agent 23wt%, photoinitiator 3.9wt%, auxiliary agent 3.1wt% proportion weigh material, sequentially add in three-necked flask, 50
Continue to be protected from light quickly stirring 4h at DEG C, is sufficiently mixed material uniformly, cold coating is transferred to brown by room temperature to be stood
Bottle in, be placed in a vacuum drying oven down at 50 DEG C bubble removing to get not containing graphene light-cured resin coating.Finally should
Coating makes film by oneself on a glass, is solidified under ultraviolet lighting, and the performance of paint solidification film is then tested.The coating is solid
Elasticity modulus after change is 0.7GPa, and solvent resistance is greater than 200, and heat resistance is greater than 85 DEG C." 0 " indicates this not in fig. 1
The coating of containing graphene.
It should be noted that and understand, in the feelings for not departing from the spirit and scope of the present invention required by appended claims
Under condition, various modifications and improvements can be made to the present invention of foregoing detailed description.It is therefore desirable to the model of the technical solution of protection
It encloses and is not limited by given any specific exemplary teachings.
The Applicant declares that the present invention is explained by the above embodiments detailed process equipment and process flow of the invention,
But the present invention is not limited to the above detailed process equipment and process flow, that is, it is above-mentioned detailed not mean that the present invention must rely on
Process equipment and process flow could be implemented.It should be clear to those skilled in the art, any improvement in the present invention,
Addition, selection of concrete mode of equivalence replacement and auxiliary element to each raw material of product of the present invention etc., all fall within of the invention
Within protection scope and the open scope.
Claims (3)
1. a kind of photocureable coating of suitable high speed fibre drawing process, it is prepared by mass percentage by following raw materials:
30 ~ 70wt% oligomer, 20 ~ 60wt% active monomer diluent, 1 ~ 10wt% photoinitiator, 1 ~ 10wt% auxiliary agent and 0.01 ~ 10wt%
Graphene composition；The oligomer is the mixture or polyurethane acroleic acid of urethane acrylate and epoxy acrylate
The mixture of ester and organic silicon modified epoxy acrylate；The graphene contains hydroxyl, carboxyl, carbonyl, amino, sulfonic group
One of or a variety of functional groups；The graphene is two-dimensional layered structure, and the number of plies is 1 ~ 40 layer；The activated monomer
Diluent includes: alkoxide phenol acrylate, 2(2- ethoxy ethoxy) ethyl propylene acid esters, tetrahydrofuran acrylate,
2- phenoxyethyl acrylate, isodecyl acrylate, caprolactone, ethylization nonyl phenol acrylate, acrylic acid are different
Norbornene ester, trimethylolpropane formal acrylate, neopentylglycol diacrylate, 1,6 hexanediol diacrylate, two
Contracting tripropylene glycol diacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate or pentaerythrite 4 third
One of olefin(e) acid ester is a variety of；It include dispersing agent in the auxiliary agent, dispersing agent is ethyl alcohol and acetone according to mass ratio 1:1
Mixed solution.
2. the preparation method of the photocureable coating of suitable high speed fibre drawing process as described in claim 1, it is characterised in that:
The preparation method is by graphene and dispersant into graphene solution, then according to the ratio by graphene solution and oligomer
It is first sufficiently mixed uniformly, obtains mixture A, active monomer diluent, photoinitiator and auxiliary agent are uniformly mixed according to a ratio to obtain
Then mixture A is added in mixture B and is uniformly mixed, obtains graphene photocureable coating, hybrid reaction temperature by mixture B
It is 20 ~ 90 DEG C, obtained graphene photocureable coating is placed in a vacuum drying oven down at 50 DEG C -60 DEG C bubble removing and remnants
Auxiliary agent, obtain be suitble to high speed fibre drawing process photocureable coating.
3. the preparation method of the photocureable coating of suitable high speed fibre drawing process as claimed in claim 2, it is characterised in that:
Gained coating is solidified using ultraviolet light.
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| CN107384224A (en) * | 2017-08-24 | 2017-11-24 | 深圳市国创珈伟石墨烯科技有限公司 | A kind of graphene thermal conductivity UV glue and preparation method thereof |
| CN108003756A (en) * | 2017-12-13 | 2018-05-08 | 厦门中凯新材石墨烯科技有限公司 | A kind of storage tank liner graphene photocureable coating and its application method and preparation method |
| CN107955519A (en) * | 2017-12-22 | 2018-04-24 | 恒力盛泰（厦门）石墨烯科技有限公司 | A kind of UV radiation curing heat radiation coatings containing graphene and preparation method thereof |
| CN108219377A (en) * | 2018-01-22 | 2018-06-29 | 厦门中凯新材石墨烯科技有限公司 | A kind of high tenacity graphene 3D printing photo-curing material and preparation method thereof |
| CN108288085A (en) * | 2018-02-09 | 2018-07-17 | 黄唏 | Graphene slurry, preparation method and applications |
| CN108690392A (en) * | 2018-06-20 | 2018-10-23 | 厦门祥福兴科技股份有限公司 | A kind of graphene coating and application thereof |
| CN109179394B (en) * | 2018-09-26 | 2021-03-23 | 长飞光纤光缆股份有限公司 | Direct transfer device and method for graphene film |
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| CN110698080B (en) * | 2019-10-22 | 2022-04-05 | 杭州富通通信技术股份有限公司 | Coating resin for optical fiber and preparation method and application thereof |
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| CN111471337A (en) * | 2019-12-16 | 2020-07-31 | 广东一纳科技有限公司 | Composition, preparation method and application in field of anticorrosive coating |
| CN111234682A (en) * | 2020-01-17 | 2020-06-05 | 成都迪泰化工有限公司 | Photosensitive graphene oxide UV (ultraviolet) photocuring building coating and preparation method thereof |
| CN112812682A (en) * | 2020-12-31 | 2021-05-18 | 惠州飞凯新材料有限公司 | Antistatic coating and preparation method and application thereof |
| CN112812252A (en) * | 2021-02-24 | 2021-05-18 | 陕西科技大学 | High-temperature-resistant functionalized graphene modified waterborne polyurethane and preparation method and application thereof |
| CN113004784A (en) * | 2021-03-29 | 2021-06-22 | 东莞市鹏威能源科技有限公司 | Graphene LCP composite material, preparation method and application thereof |
| CN114716905B (en) * | 2022-03-25 | 2022-12-23 | 浙江艾特普科技有限公司 | UV-cured conductive graphene coating and construction method thereof |
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| CN104371510A (en) * | 2014-11-24 | 2015-02-25 | 张家港保税区冠祥贸易有限公司 | Ultraviolet light curable metal anticorrosive paint and preparation method thereof |
| CN104830159A (en) * | 2014-12-17 | 2015-08-12 | 青岛科技大学 | Preparation method and application of photo-curing color paste containing graphene |
| CN104610871A (en) * | 2014-12-19 | 2015-05-13 | 长飞光纤光缆股份有限公司 | Radiation curing coating |
| CN105176326B (en) * | 2015-09-23 | 2017-09-08 | 常州大学 | A kind of photocuring repaired mouth coating of graphene filler and preparation method thereof |
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