CN109233457A - A kind of graphene-based water paint of anti-freezing type for deep-sea engineering - Google Patents
A kind of graphene-based water paint of anti-freezing type for deep-sea engineering Download PDFInfo
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- CN109233457A CN109233457A CN201811174028.1A CN201811174028A CN109233457A CN 109233457 A CN109233457 A CN 109233457A CN 201811174028 A CN201811174028 A CN 201811174028A CN 109233457 A CN109233457 A CN 109233457A
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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
- C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
- C09D123/26—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers modified by chemical after-treatment
- C09D123/28—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers modified by chemical after-treatment by reaction with halogens or compounds containing halogen
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
-
- 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
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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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
- C09D7/63—Additives non-macromolecular organic
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
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- Wood Science & Technology (AREA)
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Abstract
The invention belongs to freeze proof technical field of coatings, it is formed more particularly to a kind of graphene-based water paint of the anti-freezing type for deep-sea engineering, including following raw material: 40-50 parts of hybrid resins, 10-14 parts of modified graphenes, 6-10 parts of freeze proof intermixtures, 3-5 parts of nano aluminium oxide ceramic powders, 7-13 parts of curing agent, 3-4 parts of defoaming agents, 6-8 parts of dispersing agents and 30-40 portions of reactive diluents.The present invention passes through addition modified graphene, and combine urea, propylene glycol and dimethyl sulfoxide, further improve the anti-freezing property of coating, it is ensured that in long-time cracking phenomena does not occur under low temperature for coating, and the graphene-based coating of anti-freezing type is made with high rigidity and resistance to medium.
Description
Technical field
The invention belongs to freeze proof technical field of coatings, and in particular to a kind of graphene-based water of anti-freezing type for deep-sea engineering
Property coating.
Background technique
The purpose of coating is that coating once applies obtained solid-state continuous film, is insulated to protect, decoration, coating
In metal, fabric, the plastic sheet on the matrixes such as plastics.Coating can be gaseous state, liquid, solid-state, generally according to needing to spray
Matrix determine coating type and state can be used for marine worker field although existing coating has certain anti-corrosion effect,
It is that coating is easy to that cracking phenomena occurs for a long time under deep sea low temperature, can not be used for a long time, and graphene is as a kind of at present
By carbon atom with sp2Hybridized orbit forms the two-dimentional carbon nanomaterial that hexangle type is in honeycomb lattice, has excellent optics, electricity
It learns, mechanical characteristic, is widely used in paint field.
Since its surface does not have oxygen-containing functional group, large specific surface area, interlayer model ylid bloom action stronger, graphene is in solvent type
Using in coating has two: (1) Investigation of stabilized dispersion of nano problem, the i.e. bad dispersibility in coating (solvent and component) are held
Easily occur to reunite, settle and be layered, is unfavorable for the formation of physical shielding structure and conductive network structure in coating；(2) interface is tied
Conjunction problem exists in the coating without forming chemical bonding that is, between coating composition compared with multiple solutions, between interface, interface with
Matrix combines poor.The present invention provides a kind of graphene-based water paint of the anti-freezing type for deep-sea engineering, can solve graphene
With the consistency problem of coating, and have excellent anti-freezing property.
Summary of the invention
The purpose of the present invention is to provide a kind of graphene-based water paint of the anti-freezing type for deep-sea engineering, systems of the present invention
Obtaining the graphene-based coating of anti-freezing type has high rigidity, resistance to medium and excellent anti-freezing property.
To achieve the above object, the present invention adopts the following technical scheme:
A kind of graphene-based water paint of anti-freezing type for deep-sea engineering, the raw material that the coating includes is by weight are as follows:
40-50 parts of hybrid resin, 10-14 parts of modified graphene, intermixture 6-10 parts freeze proof, 3-5 parts of nano aluminium oxide ceramic powder, solidification
7-13 parts of agent, 3-4 parts of defoaming agent, 6-8 parts of dispersing agent and 30-40 parts of reactive diluent.
Preferably, the hybrid resin is chlorinated polypropylene and polyurethane resin, mass ratio 3:(1-1.5).
Preferably, the freeze proof intermixture is urea, propylene glycol and dimethyl sulfoxide, mass ratio 2:1:0.8.
Preferably, the modified graphene preparation method the following steps are included:
(1) graphite, phosphorus pentoxide and potassium peroxydisulfate are added in the concentrated sulfuric acid, after reacting 2h at 70 DEG C, are cooled to room temperature
10min is stirred in ice-water bath afterwards, 1h is reacted in 35 DEG C of water-bath after being then slowly added into potassium permanganate, adds and centainly contain
The distilled water of amount is simultaneously warming up to 90 DEG C of reaction 10min, and hydrogen peroxide is finally added dropwise up to glassy yellow, then through centrifugation, dialysis, drying
Obtain graphene powder；
(2) graphene powder in step (2) is dissolved in dehydrated alcohol with neopelex, is ultrasonically treated
Centrifugal drying obtains modified graphene after 30min.
Preferably, graphite as described in step (1), phosphorus pentoxide, potassium peroxydisulfate, the concentrated sulfuric acid, potassium permanganate and distillation
The mass ratio of water is 1:2:2:55:2:40.
Preferably, the mass ratio of graphene powder described in step (2) and neopelex is 0.8:1.
A method of preparing the above-mentioned graphene-based water paint of anti-freezing type for deep-sea engineering: first by modified graphite
30min is mixed in alkene and freeze proof intermixture in ice-water bath, then sonicated 15min obtains mixed liquor A；Again by compound tree
1h is mixed in rouge and reactive diluent at 70-80 DEG C, and mixed liquor A is then added and continues to stir 2-3h, mixing speed is
400-500r/min；It finally sequentially adds dispersing agent and defoaming agent and stirs evenly, obtain the anti-freezing type stone for deep-sea engineering
Mertenyl water paint.
Remarkable advantage of the invention is: modified graphene prepared by the present invention has admirably compatible with hybrid resin
Property, disperse in coating ingredients more evenly, the hardness, corrosion resistance and anti-freezing property of coating can be greatlyd improve, the present invention
The frost resistance of coating is further improved in combination with urea, propylene glycol and dimethyl sulfoxide by addition modified graphene
It can, it is ensured that under low temperature cracking phenomena does not occur for coating in long-time.
Specific embodiment
Further to disclose rather than the present invention is limited, the present invention is described in further detail below in conjunction with example.
Embodiment 1
The raw material for including for the graphene-based water paint of anti-freezing type of deep-sea engineering of the present embodiment is by weight are as follows: mixing
40 parts of resin, 12 parts of modified graphene, 10 parts of freeze proof intermixture, 3 parts of nano aluminium oxide ceramic powder, 10 parts of curing agent, defoaming agent 3
Part, 6 parts of dispersing agent and 30 parts of reactive diluent.
Above-mentioned hybrid resin is chlorinated polypropylene and polyurethane resin, mass ratio 3:1.
Above-mentioned freeze proof intermixture is urea, propylene glycol and dimethyl sulfoxide, mass ratio 2:1:0.8.
The preparation method of above-mentioned modified graphene the following steps are included:
(1) graphite, phosphorus pentoxide and potassium peroxydisulfate are added in the concentrated sulfuric acid, after reacting 2h at 70 DEG C, are cooled to room temperature
10min is stirred in ice-water bath afterwards, 1h is reacted in 35 DEG C of water-bath after being then slowly added into potassium permanganate, adds and centainly contain
The distilled water of amount is simultaneously warming up to 90 DEG C of reaction 10min, and hydrogen peroxide is finally added dropwise up to glassy yellow, then through centrifugation, dialysis, drying
Obtain graphene powder；
(2) graphene powder in step (2) is dissolved in dehydrated alcohol with neopelex, is ultrasonically treated
Centrifugal drying obtains modified graphene after 30min.
Graphite described in above-mentioned steps (1), phosphorus pentoxide, potassium peroxydisulfate, the concentrated sulfuric acid, potassium permanganate and distilled water
Mass ratio is 1:2:2:60:2:50.
The mass ratio of graphene powder described in above-mentioned steps (2) and neopelex is 0.8:1.
The method for preparing the graphene-based coating of above-mentioned anti-freezing type: first by modified graphene and freeze proof intermixture in ice
30min is mixed in water-bath, then sonicated 15min obtains mixed liquor A；Again by hybrid resin and reactive diluent 70
1h is mixed at DEG C, mixed liquor A is then added and continues to stir 2h, mixing speed 400r/min；Finally sequentially add dispersion
Agent and defoaming agent simultaneously stir evenly, and obtain the graphene-based water paint of anti-freezing type for deep-sea engineering.
Embodiment 2
The raw material for including for the graphene-based water paint of anti-freezing type of deep-sea engineering of the present embodiment is by weight are as follows: mixing
50 parts of resin, 14 parts of modified graphene, 9 parts of freeze proof intermixture, 5 parts of nano aluminium oxide ceramic powder, 13 parts of curing agent, defoaming agent 4
Part, 8 parts of dispersing agent and 40 parts of reactive diluent.
Above-mentioned hybrid resin is chlorinated polypropylene and polyurethane resin, mass ratio 3:1.5.
Above-mentioned freeze proof intermixture is urea, propylene glycol and dimethyl sulfoxide, mass ratio 2:1:0.8.
The preparation method of above-mentioned modified graphene the following steps are included:
(1) graphite, phosphorus pentoxide and potassium peroxydisulfate are added in the concentrated sulfuric acid, after reacting 2h at 70 DEG C, are cooled to room temperature
10min is stirred in ice-water bath afterwards, 1h is reacted in 35 DEG C of water-bath after being then slowly added into potassium permanganate, adds and centainly contain
The distilled water of amount is simultaneously warming up to 90 DEG C of reaction 10min, and hydrogen peroxide is finally added dropwise up to glassy yellow, then through centrifugation, dialysis, drying
Obtain graphene powder；
(2) graphene powder in step (2) is dissolved in dehydrated alcohol with neopelex, is ultrasonically treated
Centrifugal drying obtains modified graphene after 30min.
Graphite described in above-mentioned steps (1), phosphorus pentoxide, potassium peroxydisulfate, the concentrated sulfuric acid, potassium permanganate and distilled water
Mass ratio is 1:2:2:60:2:50.
The mass ratio of graphene powder described in above-mentioned steps (2) and neopelex is 0.8:1.
The method for preparing the graphene-based coating of above-mentioned anti-freezing type: first by modified graphene and freeze proof intermixture in ice
30min is mixed in water-bath, then sonicated 15min obtains mixed liquor A；Again by hybrid resin and reactive diluent 80
1h is mixed at DEG C, mixed liquor A is then added and continues to stir 3h, mixing speed 450r/min；Finally sequentially add dispersion
Agent and defoaming agent simultaneously stir evenly, and obtain the graphene-based water paint of anti-freezing type for deep-sea engineering.
Embodiment 3
The raw material for including for the graphene-based water paint of anti-freezing type of deep-sea engineering of the present embodiment is by weight are as follows: mixing
46 parts of resin, 13 parts of modified graphene, 6 parts of freeze proof intermixture, 4 parts of nano aluminium oxide ceramic powder, 7 parts of curing agent, defoaming agent 3
Part, 7 parts of dispersing agent and 35 parts of reactive diluent.
Above-mentioned hybrid resin is chlorinated polypropylene and polyurethane resin, mass ratio 3:1.3.
Above-mentioned freeze proof intermixture is urea, propylene glycol and dimethyl sulfoxide, mass ratio 2:1:0.8.
The preparation method of above-mentioned modified graphene the following steps are included:
(1) graphite, phosphorus pentoxide and potassium peroxydisulfate are added in the concentrated sulfuric acid, after reacting 2h at 70 DEG C, are cooled to room temperature
10min is stirred in ice-water bath afterwards, 1h is reacted in 35 DEG C of water-bath after being then slowly added into potassium permanganate, adds and centainly contain
The distilled water of amount is simultaneously warming up to 90 DEG C of reaction 10min, and hydrogen peroxide is finally added dropwise up to glassy yellow, then through centrifugation, dialysis, drying
Obtain graphene powder；
(2) graphene powder in step (2) is dissolved in dehydrated alcohol with neopelex, is ultrasonically treated
Centrifugal drying obtains modified graphene after 30min.
Graphite described in above-mentioned steps (1), phosphorus pentoxide, potassium peroxydisulfate, the concentrated sulfuric acid, potassium permanganate and distilled water
Mass ratio is 1:2:2:60:2:50.
The mass ratio of graphene powder described in above-mentioned steps (2) and neopelex is 0.8:1.
The method for preparing the graphene-based coating of above-mentioned anti-freezing type: first by modified graphene and freeze proof intermixture in ice
30min is mixed in water-bath, then sonicated 15min obtains mixed liquor A；Again by hybrid resin and reactive diluent 75
1h is mixed at DEG C, mixed liquor A is then added and continues to stir 2h, mixing speed 500r/min；Finally sequentially add dispersion
Agent and defoaming agent simultaneously stir evenly, and obtain the graphene-based water paint of anti-freezing type for deep-sea engineering.
Comparative example 1
The raw material that the graphene-based water paint of the anti-freezing type of this comparative example includes is by weight are as follows: 40 parts of hybrid resin, graphite
12 parts of alkene powder, 10 parts of freeze proof intermixture, 3 parts of nano aluminium oxide ceramic powder, 10 parts of curing agent, 3 parts of defoaming agent, 6 parts of dispersing agent
With 30 parts of reactive diluent.Preparation method and other conditions are the same as the embodiment of the present invention 1.
Comparative example 2
The raw material that the anti-freezing type water paint of this comparative example includes is by weight are as follows: 40 parts of hybrid resin, freeze proof intermixture 10
Part, 3 parts of nano aluminium oxide ceramic powder, 10 parts of curing agent, 3 parts of defoaming agent, 6 parts of dispersing agent and 30 parts of reactive diluent.Preparation side
Method and other conditions are the same as the embodiment of the present invention 1.
Performance test: hardness test (referring to GB/T6739-2006), attached is carried out to embodiment 1-3 and comparative example 1,2 respectively
Put forth effort test (referring to GB/T9286-1998), resistance to medium test and anti-freezing property test.
Resistance to medium test: coating sample is produced referring to GB-T1727-1992, is separately immersed in 10wt% for the 2/3 of sample
Sulfuric acid solution, the sodium hydroxide solution of 10wt%, 3.5wt% NaCl solution, place for 24 hours, whether observation coating has loss of gloss, becomes
Color, vesicle, spot and obscission.
Anti-freezing property test: coating sample is produced referring to GB-T1727-1992, is then placed at -15 DEG C and carries out freeze proof examination
Test, every 10 days be a cycle, testing coating sample appearance (whether there is or not the variation of color, whether there is or not dusting, whether there is or not cracking), it is freeze proof
40 days.
The foregoing is merely presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with
Modification, is all covered by the present invention.
Claims (7)
1. a kind of graphene-based water paint of anti-freezing type for deep-sea engineering, it is characterised in that: the raw material that the coating includes
By weight are as follows: 40-50 parts of hybrid resin, 10-14 parts of modified graphene, intermixture 6-10 parts freeze proof, nano aluminium oxide pottery
3-5 parts of porcelain powder, 7-13 parts of curing agent, 3-4 parts of defoaming agent, 6-8 parts of dispersing agent and 30-40 parts of reactive diluent.
2. the graphene-based water paint of a kind of anti-freezing type for deep-sea engineering according to claim 1, it is characterised in that:
The hybrid resin is chlorinated polypropylene and polyurethane resin, mass ratio 3:(1-1.5).
3. the graphene-based water paint of a kind of anti-freezing type for deep-sea engineering according to claim 1, special
Sign is: the freeze proof intermixture is urea, propylene glycol and dimethyl sulfoxide, mass ratio 2:1:0.8.
4. the graphene-based water paint of a kind of anti-freezing type for deep-sea engineering according to claim 1, special
Sign is: the preparation method of the modified graphene the following steps are included:
(1) graphite, phosphorus pentoxide and potassium peroxydisulfate are added in the concentrated sulfuric acid, after reacting 2h at 70 DEG C, are cooled to room temperature
10min is stirred in ice-water bath afterwards, 1h is reacted in 35 DEG C of water-bath after being then slowly added into potassium permanganate, adds and centainly contain
The distilled water of amount is simultaneously warming up to 90 DEG C of reaction 10min, and hydrogen peroxide is finally added dropwise up to glassy yellow, then through centrifugation, dialysis, drying
Obtain graphene powder；
(2) graphene powder in step (2) is dissolved in dehydrated alcohol with neopelex, is ultrasonically treated
Centrifugal drying obtains modified graphene after 30min.
5. the graphene-based water paint of a kind of anti-freezing type for deep-sea engineering according to claim 4, special
Sign is: the quality of graphite as described in step (1), phosphorus pentoxide, potassium peroxydisulfate, the concentrated sulfuric acid, potassium permanganate and distilled water
Than for 1:2:2:55:2:40.
6. the graphene-based water paint of a kind of anti-freezing type for deep-sea engineering according to claim 4, special
Sign is: the mass ratio of graphene powder described in step (2) and neopelex is 0.8:1.
7. a kind of a kind of anti-freezing type for deep-sea engineering prepared as described in claim 1-4 any one is graphene-based aqueous
The method of coating, it is characterised in that: 30min is mixed in modified graphene and freeze proof intermixture in ice-water bath first, then
Sonicated 15min obtains mixed liquor A；1h is mixed at 70-80 DEG C in hybrid resin and reactive diluent again, then
Mixed liquor A is added to continue to stir 2-3h, mixing speed 400-500r/min；It finally sequentially adds dispersing agent and defoaming agent and stirs
It mixes uniformly, obtains the graphene-based water paint of anti-freezing type for deep-sea.
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| CN201811174028.1A CN109233457A (en) | 2018-10-09 | 2018-10-09 | A kind of graphene-based water paint of anti-freezing type for deep-sea engineering |
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| CN201811174028.1A CN109233457A (en) | 2018-10-09 | 2018-10-09 | A kind of graphene-based water paint of anti-freezing type for deep-sea engineering |
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2018
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Application publication date: 20190118 |