CN110272680A - A kind of graphene conductive coating and preparation method thereof - Google Patents
A kind of graphene conductive coating and preparation method thereof Download PDFInfo
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- CN110272680A CN110272680A CN201910527508.XA CN201910527508A CN110272680A CN 110272680 A CN110272680 A CN 110272680A CN 201910527508 A CN201910527508 A CN 201910527508A CN 110272680 A CN110272680 A CN 110272680A
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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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/06—Polyurethanes from polyesters
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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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/24—Electrically-conducting paints
Abstract
The invention discloses a kind of graphene conductive coating and preparation method thereof, and conductive coating includes following components by weight: 2-5 parts of surface carboxylation graphene, 120-160 parts of polyester polyol, 50-80 parts of diisocyanate, 0.5-1.5 parts of catalyst, 200-260 parts of diluent；The preparation method of the graphene conductive coating, comprising: (1) preparation of surface carboxylation graphene；(2) preparation of carboxylated graphene dispersing solution；(3) preparation of graphene conductive coating；The present invention is by the surface carboxylation of graphene, more active sites are provided with reacting for basis material for graphene base body, it is chemically reacted using carboxyl (- COOH) and the isocyanate groups (- NCO) of terminal isocyanate group performed polymer, terminal isocyanate group performed polymer is grafted on to the surface of graphene, reagency between isocyanate group and carboxyl greatly increases the binding force between graphene and polyurethane, dispersibility of the graphene in basis material is enhanced, makes graphene conductive coating that there is better intensity, toughness and electric conductivity.
Description
Technical field
The present invention relates to a kind of graphene conductive coating and preparation method thereof.
Background technique
Conductive coating refers to that conductivity is greater than 10-12S/m is coated on non-conductive substrate, with conduction electric current and row
Except a kind of functional paint of accumulation electrostatic charge ability；Conductive coating, which has, eliminates electrostatic, anti-electromagnetic shielding and Anticorrosive Character, can be wide
It is applied to petrochemical industry, space flight and aviation, telecommunications, building and war industry field generally；It is conductive according to conductive mechanism
Coating can be divided into Intrinsical and two kinds of admixing type；Wherein, intrinsically conducting coating mainly has polyaniline, polypyrrole electromagnetic shielding
Coating etc., but it is larger in the presence of difficulty in synthesis, work progress, the development of intrinsically conducting coating is limited to a certain extent；
Admixing type conductive coating, which refers to, itself does not have conductive conductive filler incorporation in the coating of electric conductivity, conductive filler
Particle is interconnected to conductive path inside system and conductive；Addition type conductive coating have equipment be simple and convenient to operate, at
The advantages that this is cheap and can be coated on various surfaces of complex shape, market application range is wider.
Graphene is a kind of obform body that hexagonal lattice is arranged in by single layer of carbon atom, has carbon atom sp2Hydridization rail
Road makes it have excellent electricity according to honeycomb crystal arrangement, the thickness of only one carbon atom, unique two-dimensional structure
The performances such as conductance, thermal conductivity, electron mobility, mechanical strength, due to being incorporated into often as filler with good electric conductivity
In conductive coating, for example, graphene is entrained in polyurethane coating, using the excellent mechanics of graphene, thermodynamic property with
And good electronic transmission performance improves the electric conductivity and electromagnetic wave shielding of addition type conductive coating, and then widens conductive material
Application field；But graphene has biggish surface area, easily occurs reuniting and influencing its electric conductivity in conductive material
And translucency.
Summary of the invention
The purpose of the present invention is to solve the above the deficiencies in the prior art, propose a kind of graphene conductive coating and its
Preparation method, the conductive coating includes following components by weight: 2-5 parts of surface carboxylation graphene, polyester polyols
120-160 parts of alcohol, 50-80 parts of diisocyanate, 0.5-1.5 parts of catalyst, 200-260 parts of diluent；
The surface carboxylation graphene the preparation method comprises the following steps: prepare graphene oxide with Hummers method, stone will be aoxidized
Then black alkene ultrasonic disperse is added NaOH and peroxysuccinic acid continues ultrasound in DMF, control reaction temperature is 75-90 DEG C,
Reaction time is 2-3h, is filtered, washed, is dried to obtain carboxylated graphite oxide；Wherein, graphene oxide, NaOH, peroxidating fourth
Ratio between diacid and DMF are as follows: 1mmol:(10-13) mmol:(10-13) mmol:(15-20) ml；Stone is aoxidized in carboxylated
Surfactant is added in ink, then diazonium salt solution is added in ultrasonic 10-20min, keep being added 2-2.5ml's at 0-4 DEG C
The concentrated hydrochloric acid of 35-38wt% stirs 8-10h, and 5-8h is then stirred at room temperature, and washing filters, obtains surface carboxyl groups after drying
Graphite alkene；Wherein, the ratio between carboxylated graphite oxide and diazonium salt solution is 1g:(0.8-0.9) ml；
The preparation method of the graphene conductive coating, includes the following steps:
S1: the diluent for measuring part and surface carboxylation graphene high-speed uniform being dispersed, ball-milling treatment 90-200min,
Then ultrasonic treatment 90-200min obtains stable carboxylated graphene dispersing solution；
S2: the polyester polyol, diisocyanate of metering part are added in the carboxylated graphene dispersing solution in step (1)
And catalyst, it is warming up to 70-90 DEG C under nitrogen atmosphere, stops reaction after reacting 2-3.5h, vacuum distillation obtains graphene conductive painting
Material.
Wherein, polyaddition reaction occurs in the presence of a catalyst for the polyester polyol of stoichiometric number and diisocyanate, raw
Surface grafting polymerization is carried out at the performed polymer containing isocyanate group, then with the carboxylated graphene of high degree of dispersion, obtains graphene
Conductive coating.
Preferably, the diisocyanate is 4,4'- methyl diphenylene diisocyanate.
Preferably, the diluent is one of methanol, ethyl alcohol, propyl alcohol, butanol or a variety of.
Preferably, the catalyst is one in stannous octoate, dibutyl tin dilaurate and organo-bismuth class catalyst
Kind.
Beneficial effects of the present invention are as follows: the present invention is graphene base body and matrix material by the surface carboxylation of graphene
The reaction of material provides more active sites, utilizes the isocyanate groups of carboxyl (- COOH) and terminal isocyanate group performed polymer
(- NCO) is chemically reacted, and terminal isocyanate group performed polymer grafts on to the surface of graphene, isocyanate group and carboxyl it
Between reagency the binding force between graphene and polyurethane is greatly increased, enhance graphene in basis material point
Property is dissipated, so that the graphene conductive coating of preparation has better intensity, toughness and electric conductivity.
Specific embodiment
In order to deepen the understanding of the present invention, the present invention will be described in further detail with reference to the examples below, the embodiment
For explaining only the invention, it is not intended to limit the scope of the present invention..
Embodiment 1
A kind of graphene conductive coating and preparation method thereof, the conductive coating includes following components by weight:
5 parts of surface carboxylation graphene, 140 parts of polyester polyol, 60 parts of 4,4'- methyl diphenylene diisocyanate, tin dilaurate two
1.2 parts of butyl tin, 220 parts of methanol；
The preparation method of the graphene conductive coating, includes the following steps:
(1) graphene oxide is prepared with Hummers method, by graphene oxide ultrasonic disperse in DMF, NaOH is then added
Continue ultrasound with peroxysuccinic acid, control reaction temperature is 80 DEG C, and reaction time 2.5h is filtered, washed, is dried to obtain carboxylic
Base graphite oxide；Wherein, the ratio between graphene oxide, NaOH, peroxysuccinic acid and DMF are as follows: 1mmol:12mmol:
12mmol:16ml；Surfactant is added in carboxylated graphite oxide, then diazonium salt solution is added in ultrasonic 15min, protect
The concentrated hydrochloric acid that the 35-38wt% of 2ml is added at 0-4 DEG C is held, 8h is stirred, 5-8h is then stirred at room temperature, washing filters, is dry
Surface carboxylation graphene is obtained after dry；Wherein, the ratio between carboxylated graphite oxide and diazonium salt solution is 1g:0.8ml；
(2) methanol for measuring part and surface carboxylation graphene high-speed uniform are dispersed, then ball-milling treatment 150min surpasses
Sonication 150min obtains stable carboxylated graphene dispersing solution；
(3) polyester polyol, diisocyanate of metering part are added in the carboxylated graphene dispersing solution in step (1)
And catalyst, it is warming up to 85 DEG C under nitrogen atmosphere, stops reaction after reacting 2.5h, vacuum distillation obtains graphene conductive coating.
Embodiment 2
A kind of graphene conductive coating and preparation method thereof, the conductive coating includes following components by weight:
3 parts of surface carboxylation graphene, 160 parts of polyester polyol, 80 parts of 4,4'- methyl diphenylene diisocyanate, tin dilaurate two
1.5 parts of butyl tin, 260 parts of methanol；
The preparation method of the graphene conductive coating, includes the following steps:
(1) graphene oxide is prepared with Hummers method, by graphene oxide ultrasonic disperse in DMF, NaOH is then added
Continue ultrasound with peroxysuccinic acid, control reaction temperature is 90 DEG C, and reaction time 3h is filtered, washed, is dried to obtain carboxyl
Change graphite oxide；Wherein, the ratio between graphene oxide, NaOH, peroxysuccinic acid and DMF are as follows: 1mmol:10mmol:
10mmol:20ml；Surfactant is added in carboxylated graphite oxide, then diazonium salt solution is added in ultrasonic 15min, protect
The concentrated hydrochloric acid that the 35-38wt% of 2.5ml is added at 0-4 DEG C is held, 10h is stirred, 8h is then stirred at room temperature, washing filters, is dry
Surface carboxylation graphene is obtained after dry；Wherein, the ratio between carboxylated graphite oxide and diazonium salt solution is 1g:0.9ml；
(2) methanol for measuring part and surface carboxylation graphene high-speed uniform are dispersed, then ball-milling treatment 200min surpasses
Sonication 150min obtains stable carboxylated graphene dispersing solution；
(3) polyester polyol, diisocyanate of metering part are added in the carboxylated graphene dispersing solution in step (1)
And catalyst, it is warming up to 90 DEG C under nitrogen atmosphere, stops reaction after reacting 2h, vacuum distillation obtains graphene conductive coating.
After tested, the graphene conductive coating property test index of Examples 1 and 2 is as shown in table 1:
Table 1
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Within mind and principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (5)
1. a kind of graphene conductive coating and preparation method thereof, which is characterized in that the conductive coating includes by weight
Following components: 2-5 parts of surface carboxylation graphene, 120-160 parts of polyester polyol, 50-80 parts of diisocyanate, catalyst
0.5-1.5 parts, 200-260 parts of diluent；
The surface carboxylation graphene the preparation method comprises the following steps: graphene oxide is prepared with Hummers method, by graphene oxide
Then ultrasonic disperse is added NaOH and peroxysuccinic acid continues ultrasound, control reaction temperature is 75-90 DEG C, reaction in DMF
Time is 2-3h, is filtered, washed, is dried to obtain carboxylated graphite oxide；Wherein, graphene oxide, NaOH, peroxysuccinic acid
Ratio between DMF are as follows: 1mmol:(10-13) mmol:(10-13) mmol:(15-20) ml；In carboxylated graphite oxide
Surfactant is added, then diazonium salt solution is added in ultrasonic 10-20min, keep the 35- that 2-2.5ml is added at 0-4 DEG C
The concentrated hydrochloric acid of 38wt% stirs 8-10h, and 5-8h is then stirred at room temperature, and washing filters, obtains surface carboxylation after drying
Graphene；Wherein, the ratio between carboxylated graphite oxide and diazonium salt solution is 1g:(0.8-0.9) ml.
2. a kind of graphene conductive coating according to claim 1, which is characterized in that the diisocyanate is 4,
4'- methyl diphenylene diisocyanate.
3. a kind of graphene conductive coating according to claim 1, which is characterized in that the diluent is methanol, second
One of alcohol, propyl alcohol, butanol are a variety of.
4. a kind of graphene conductive coating according to claim 1, which is characterized in that the catalyst is that octanoic acid is sub-
One of tin, dibutyl tin dilaurate and organo-bismuth class catalyst.
5. a kind of preparation method of graphene conductive coating as described in claim 1, which comprises the steps of:
S1: the diluent for measuring part and surface carboxylation graphene high-speed uniform are dispersed, ball-milling treatment 90-200min, then
Ultrasonic treatment 90-200min obtains stable carboxylated graphene dispersing solution；
S2: the polyester polyol for measuring part, diisocyanate are added in the carboxylated graphene dispersing solution in step (1) and urges
Agent is warming up to 70-90 DEG C under nitrogen atmosphere, stops reaction after reacting 2-3.5h, vacuum distillation obtains graphene conductive coating.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102272253A (en) * | 2008-11-05 | 2011-12-07 | Posco公司 | Resin composition for surface treatment of steel sheet and surface-treated steel sheet using the same |
| WO2014144352A2 (en) * | 2013-03-15 | 2014-09-18 | Mackinac Polymers Llc | Polymeric composition with electroactive characteristics |
| CN105153905A (en) * | 2015-07-03 | 2015-12-16 | 泰山玻璃纤维有限公司 | Preparation method and application of graphene modified polyurethane film-forming agent |
| CN105860064A (en) * | 2016-06-17 | 2016-08-17 | 西北师范大学 | Preparation method of polyaniline/carboxylated graphene composite material |
| CN106220826A (en) * | 2016-08-04 | 2016-12-14 | 中海油常州涂料化工研究院有限公司 | The preparation method of the water solublity isocyanate curing agent that a kind of Graphene is modified |
| CN106400506A (en) * | 2016-09-21 | 2017-02-15 | 东莞市联洲知识产权运营管理有限公司 | Waterborne polyurethane textile size based on graphene modification and preparation method thereof |
-
2019
- 2019-06-18 CN CN201910527508.XA patent/CN110272680A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102272253A (en) * | 2008-11-05 | 2011-12-07 | Posco公司 | Resin composition for surface treatment of steel sheet and surface-treated steel sheet using the same |
| WO2014144352A2 (en) * | 2013-03-15 | 2014-09-18 | Mackinac Polymers Llc | Polymeric composition with electroactive characteristics |
| CN105153905A (en) * | 2015-07-03 | 2015-12-16 | 泰山玻璃纤维有限公司 | Preparation method and application of graphene modified polyurethane film-forming agent |
| CN105860064A (en) * | 2016-06-17 | 2016-08-17 | 西北师范大学 | Preparation method of polyaniline/carboxylated graphene composite material |
| CN106220826A (en) * | 2016-08-04 | 2016-12-14 | 中海油常州涂料化工研究院有限公司 | The preparation method of the water solublity isocyanate curing agent that a kind of Graphene is modified |
| CN106400506A (en) * | 2016-09-21 | 2017-02-15 | 东莞市联洲知识产权运营管理有限公司 | Waterborne polyurethane textile size based on graphene modification and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 胡泽艺等: "氧化石墨烯的表面羧基化与表征", 《包装学报》 * |
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Application publication date: 20190924 |