CN109825167A - A kind of corrosion resistant coating and preparation method thereof for navigation mark - Google Patents
A kind of corrosion resistant coating and preparation method thereof for navigation mark Download PDFInfo
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Abstract
The corrosion resistant coating and preparation method thereof that the present invention relates to a kind of for navigation mark, its raw material includes: 24~32 parts of epoxy resin, 14~22 parts of polyester, 1~3 part of titanate coupling agent, 6~15 parts of graphene, 10~20 parts of zinc powder, 35~45 parts of siloxane oligomer, 4~12 parts of antimicrobial by weight, the preparation method is easy to operate, and graphene, zinc powder is evenly dispersed in the mixture；The present invention solve the problems, such as the film of navigation mark coating in the prior art it is not fine and close enough, it is waterproof and permeability resistant it is poor, antiseptic property is bad, poor adhesive force, the synergistic effect that the present invention passes through each component, corrosion resistance, rub resistance, water resistance, weatherability and impact resistance of the coating in briny environment are improved, while extending the service life of navigation mark.
Description
Technical field
The present invention relates to technical field of coatings, and in particular to a kind of corrosion resistant coating and preparation method thereof for navigation mark.
Background technique
Marine environment is a kind of corrosive environment of complexity, and in this environment, seawater itself is a kind of strong corrosive medium,
Wave, wave, tide, stream generate low frequency toward combined stress and impact to navigation mark again simultaneously, and navigation mark is chronically at the higher marine environment of salinity
In, corrosion is extremely serious, and corrosion not only reduces the structural strength of navigation mark, shortens the working life, in addition marine organisms can also adhere to
On its surface, marine microorganism, aufwuch and their metabolite etc. all generate direct or indirect add to corrosion process
Speed effect.
Existing coating is still difficult to cope with asking for seawater corrosion, the mutation of marine climate and marine organisms attachment well
Topic, at present coating film it is not fine and close enough, it is waterproof and permeability resistant it is poor, antiseptic property is bad, poor adhesive force, prepare a kind of waterproof performance
It is excellent, adhesive force is strong, antiseptic property is excellent, navigation mark coating with long service life is a technical problem to be solved urgently.
Graphene is the most thin most hard substance of mankind's discovery so far, graphite as a kind of Novel Carbon Nanomaterials
Alkene be a kind of single layer being made of carbon atom it is tightly packed at two dimension (2D) honeycomb lattice material, the carbon atom arrangement of graphene
It is identical as the monoatomic layer of graphite, it be the hexangle type that is formed with sp2 hybridized orbit of carbon atom is in the list that honeycomb lattice is arranged to make up
Stratification thinks two dimensional crystal, its structure is closely and in neat formation, and British scientist is found for the first time can be with individualism, because of its uniqueness
Performance is paid close attention to by various countries researcher, and becomes research hotspot.
Chinese patent application CN106398402A discloses a kind of anticorrosive marine paint, which includes that polymerization is adjacent
To 3-11 parts of base toluidines, 15-23 parts of organobentonite, 3.5-5.6 parts of aldehyde ketone resin, 1.8-3.2 parts of polytrifluorochloroethylene, hydrogen
Nitrile rubber 5-14 parts of change, 12-18 parts of diene base imidodicarbonic diamide, 4.8-6.5 parts of alkyl acid imide, glass microballoon 4-10
Part；The hydrophobic and lyophobic property of the invention coating, waterproofness and corrosion resistance are limited.
Chinese patent application CN105238157A discloses a kind of anticorrosive marine paint and preparation method thereof, and the invention is logical
Cross chlorinated rubber is miscible with furane resins, nano barium titanate calcium and other auxiliary agent of the addition through coupling agent coating modification, each ingredient
Between be uniformly dispersed, constitute the biggish C-Cl key of polarity, improve the corrosion resistance of coating, but the compactness of coating, to substrate
Adhesive force is limited, and coating is only applicable to metal base, and then effect is undesirable for other substrates.
Summary of the invention
In order to overcome the shortcomings in the prior art, the purpose of the present invention is to provide a kind of high adhesion force, good weatherability, resistance to punchings
Hitting property is strong, rub resistance is good, good corrosion resistance, long service life, coating are fine and close and what marine organisms were difficult to adhere to is used for navigation mark
Corrosion resistant coating and preparation method thereof, its technical solution is as follows:
A kind of corrosion resistant coating for navigation mark, raw material include: by weight 24~32 parts of epoxy resin, polyester 14~
22 parts, 1~3 part of titanate coupling agent, 6~15 parts of graphene, 10~20 parts of zinc powder, 35~45 parts of siloxane oligomer, resist it is micro-
4~12 parts of biological agent.
Preferably, the preparation step of the siloxane oligomer is as follows:
(1) divalent metal is added in the aqueous solution containing organic carboxyl acid, adds silicon dioxide gel, prepared
Mixed aqueous solution；
(2) methyltrimethoxysilane is mixed with isopropanol, prepares silanol solution；
(3) under the conditions of stirring is slow, silanol solution prepared by step (2) is added to the mixed of step (1) preparation
It in Heshui solution, stirs evenly, adds polytetrafluoroethylene (PTFE), be sufficiently stirred, siloxane oligomer is made.
Preferably, the organic carboxyl acid is one of acetic acid, glacial acetic acid, propionic acid, maleic acid, oxalic acid or any combination.
Preferably, the divalent metal is one of calcium ion, manganese ion, copper ion, zinc ion or any
Combination.
Preferably, the antimicrobial is that diiodomethyl is sub- to toluene sulfone, the different phthalonitrile of tetrachloro, phthalyl
One of amine or any combination.
Preferably, the graphene is the graphene oxide of micro sheet structure, and with a thickness of 3~8 μm, diameter is 6~9 μm.
Preferably, the graphene, zinc powder, antimicrobial weight ratio be 8~12:12~18:6~10.
Preferably, the epoxy resin, polyester, siloxane oligomer weight ratio be 25~30:16~20:38~43.
A kind of preparation method of the corrosion resistant coating for navigation mark, comprising the following steps:
(1) epoxy resin, polyester are added in blender in proportion, 40~60 DEG C of whipping temp, mixing time 10~
20min；
(2) first titanate coupling agent is added in blender in proportion, 70~80 DEG C of whipping temp, mixing time 15~
Then 20min is added graphene, zinc powder, is sufficiently stirred, 10~20min of mixing time；
(3) antimicrobial is added in blender in proportion, 10~15min of mixing time；
(4) siloxane oligomer is added in blender in proportion, 10~15min of mixing time.
Preferably, the stirring rate of blender described in step (1) is 1000~1300rpm, is stirred described in step (2)
The stirring rate of machine is 900~1100rpm, the stirring rate of blender described in step (3) and step (4) for 1200~
1500rpm。
Present invention advantageous effects obtained:
1) present invention solves not fine and close, waterproof and permeability resistant enough the poor, antiseptic property of navigation mark coating film in the prior art
It is corrosion-resistant in briny environment to improve coating by the synergistic effect of each component by the problem of bad, poor adhesive force, the present invention
Property, rub resistance, water resistance, weatherability and impact resistance, and then extend the service life of navigation mark；
2) present invention adds graphene on the basis of corrosion-resistant epoxy paint and prepares new coating, and graphene and resin are crosslinked
It is compound, one layer of fine and close protective film is formed in coating, has the function of obstructing air, not only with the yin of epoxy zinc-enriched paint
Pole protective effect, the screen effect of glass-flake coating make coating have good toughness, adhesive force strong, water-tolerant, with high hardness
Advantage；
3) by adding graphene in coating the additive amount of zinc powder can be greatly reduced, while greatly mentioning in the present invention
The corrosion resistance of high coating, the anti-corrosion mode for overcoming epoxy zinc-enriched paint to sacrifice zinc powder as cost, the high ratio of graphene
Surface area keeps its superficial attractive forces strong, forms reticular structure when coating is dry, so that the absorption for enhancing coating and substrate is made
With, keep coating finer and close, improves coating to the adhesive force of substrate, meanwhile, help to improve impact resistance, the antifriction of coating
Wipe performance, thermal conductivity, weatherability and corrosion resistance；
4) present invention makes marine organisms be difficult to be attached to navigation mark by addition microorganism agent in conjunction with the low-surface-energy of coating
Surface growth and breeding makes coating that " lotus leaf " be presented and keeps away water effect；By adding siloxane oligomer, coating is made to be not only suitable for metal
Substrate is suitable for the surface treatment of non-metallic substrate again, further increases coating to the adhesive force of substrate, improves the densification of coating
Property, preparation method of the invention is easy to operate, and graphene, zinc powder is evenly dispersed in the mixture, improve the resistance to of coating surface
Friction, impact resistance, corrosion resistance.
Detailed description of the invention
The drawings described herein are used to provide a further understanding of the present invention, constitutes part of this application, this hair
Bright illustrative embodiments and their description are used to explain the present invention, and are not constituted improper limitations of the present invention.In the accompanying drawings:
Fig. 1 is a kind of process flow chart of the corrosion resistant coating preparation method for navigation mark of the present invention.
Specific embodiment
Hereinafter reference will be made to the drawings, describes technical solution of the present invention in detail by way of example.It needs to illustrate herein
, the descriptions of the manners of these embodiments are used to facilitate the understanding of the present invention, but and does not constitute a limitation of the invention.
The terms "and/or", only a kind of incidence relation for describing affiliated partner, indicates that there may be three kinds of passes
System, for example, A and/or B, can indicate: individualism A, individualism B exist simultaneously tri- kinds of situations of A and B, the terms
"/and " it is to describe another affiliated partner relationship, indicate may exist two kinds of relationships, for example, A/ and B, can indicate: individually depositing
In A, two kinds of situations of individualism A and B, in addition, character "/" herein, typicallying represent forward-backward correlation object is a kind of "or" pass
System.
Embodiment 1
A kind of corrosion resistant coating for navigation mark, raw material include: 32 parts of epoxy resin, 14 parts of polyester, match by weight
The different adjacent benzene of 3 parts of bit-type titanate coupling agent, 15 parts of graphene, 10 parts of zinc powder, 35 parts of siloxane oligomer, antimicrobial tetrachloro
12 parts of dimethoxy nitrile, graphene is microplate mealy structure, and with a thickness of 3 μm, diameter is 6 μm, and zinc powder is sclay texture, average diameter
It is 2 μm.
Wherein, the preparation step of siloxane oligomer is as follows:
(1) manganese oxide is added in the aqueous solution containing glacial acetic acid, adds silicon dioxide gel, preparation mixing is water-soluble
Liquid；
(2) by mass percentage 1:1 parts weigh methyltrimethoxysilane and mixed with isopropanol, prepare silanol solution；
(3) under the conditions of stirring is slow, silanol solution prepared by step (2) is added to the mixed of step (1) preparation
It in Heshui solution, stirs evenly, adds polytetrafluoroethylene (PTFE), be sufficiently stirred, siloxane oligomer is made.
A kind of preparation method of the corrosion resistant coating for navigation mark, comprising the following steps:
(1) 32:14 by weight parts weigh epoxy resin, polyester be added blender in, 60 DEG C of whipping temp, mixing time
20min, stirring rate 1300rpm；
(2) it first weighs 3 parts of corrdination type titanate coupling agents by weight to be added in blender, 80 DEG C of whipping temp, stirring
Then time 20min is added 15 parts of graphenes, 10 parts of zinc powders, is sufficiently stirred, mixing time 20min, stirring rate is
1100rpm；
(3) the different phthalonitrile of 12 parts of antimicrobial tetrachloros is added in blender, mixing time 15min, stirring speed
Rate is 1500rpm；
(4) 35 parts of siloxane oligomers are added in blender, mixing time 15min, stirring rate 1500rpm.
Embodiment 2
A kind of corrosion resistant coating for navigation mark, raw material include: 24 parts of epoxy resin, 22 parts of polyester, titanium by weight
1 part of acid esters coupling agent, 6 parts of graphene, 20 parts of zinc powder, 45 parts of siloxane oligomer, antimicrobial diiodomethyl are to toluene sulfone 4
Part, graphene is microplate mealy structure, and with a thickness of 8 μm, diameter is 9 μm, and zinc powder is sclay texture, and average diameter is 9 μm.
Wherein, the preparation step of siloxane oligomer is as follows:
(1) calcium oxide is added in the aqueous solution containing acetic acid, adds silicon dioxide gel, prepare mixed aqueous solution；
(2) by mass percentage 1:1 parts weigh methyltrimethoxysilane and mixed with isopropanol, prepare silanol solution；
(3) under the conditions of stirring is slow, silanol solution prepared by step (2) is added to the mixed of step (1) preparation
It in Heshui solution, stirs evenly, adds polytetrafluoroethylene (PTFE), be sufficiently stirred, siloxane oligomer is made.
A kind of preparation method of the corrosion resistant coating for navigation mark, comprising the following steps:
(1) 24:22 by weight parts weigh epoxy resin, polyester be added blender in, 40 DEG C of whipping temp, mixing time
10min, stirring rate 1000rpm；
(2) it first weighs 1 part of titanate coupling agent by weight to be added in blender, 70 DEG C of whipping temp, mixing time
Then 15min is added 6 parts of graphenes, 20 parts of zinc powders, is sufficiently stirred, mixing time 10min, stirring rate 900rpm；
(3) toluene sulfone is added in blender in 4 parts of antimicrobial diiodomethyls, mixing time 10min, stirring rate
For 1200rpm；
(4) 45 parts of siloxane oligomers are added in blender, mixing time 10min, stirring rate 1200rpm.
Embodiment 3
A kind of corrosion resistant coating for navigation mark, raw material include: 25 parts of epoxy resin, 20 parts of polyester, match by weight
2 parts of bit-type titanate coupling agent, 12 parts of graphene oxide, 12 parts of zinc powder, 38 parts of siloxane oligomer, antimicrobial neighbour benzene two
6 parts of carboximide, graphene oxide is microplate mealy structure, and with a thickness of 4 μm, diameter is 7 μm, and zinc powder is chondritic, average
Diameter is 2 μm.
Wherein, the preparation step of siloxane oligomer is as follows:
(1) zinc oxide is added in the aqueous solution containing propionic acid, adds silicon dioxide gel, prepare mixed aqueous solution；
(2) methyltrimethoxysilane and phenyl silane are mixed in proportion, is then mixed with isopropanol, prepare silanol
Solution, wherein methyltrimethoxysilane and phenyl silane mass percent 70:30, methyltrimethoxysilane and phenyl silane
Mixture and isopropanol mass percent 1:1；
(3) under the conditions of stirring is slow, silanol solution prepared by step (2) is added to the mixed of step (1) preparation
It in Heshui solution, stirs evenly, adds polytetrafluoroethylene (PTFE), be sufficiently stirred, siloxane oligomer is made.
A kind of preparation method of the corrosion resistant coating for navigation mark, comprising the following steps:
(1) 25:20 by weight parts weigh epoxy resin, polyester be added blender in, 50 DEG C of whipping temp, mixing time
18min, stirring rate 1200rpm；
(2) it first weighs 2 parts of titanate coupling agents by weight to be added in blender, 75 DEG C of whipping temp, mixing time
Then 15min is added 12 parts of graphene oxides, 12 parts of zinc powders, is sufficiently stirred, mixing time 18min, stirring rate is
1000rpm；
(3) 6 parts of antimicrobial phthalimides are added in blender, mixing time 14min, stirring rate is
1400rpm；
(4) 38 parts of siloxane oligomers are added in blender, mixing time 14min, stirring rate 1400rpm.
Embodiment 4
A kind of corrosion resistant coating for navigation mark, raw material include: 30 parts of epoxy resin, 16 parts of polyester, titanium by weight
2 parts of acid esters coupling agent, 8 parts of graphene oxide, 18 parts of zinc powder, 43 parts of siloxane oligomer, antimicrobial diiodomethyl are to first
5 parts of the different phthalonitrile of 5 parts of benzene sulfone, antimicrobial tetrachloro, graphene oxide is microplate mealy structure, with a thickness of 6 μm, diameter
It is 8 μm, zinc powder is chondritic, and average diameter is 4 μm.
Wherein, the preparation step of siloxane oligomer is as follows:
(1) Cu oxide is added in the aqueous solution containing maleic acid and oxalic acid, adds silicon dioxide gel, preparation is mixed
Heshui solution；
(2) methyltrimethoxysilane and phenyl silane are mixed in proportion, is then mixed with isopropanol, prepare silanol
Solution, wherein methyltrimethoxysilane and phenyl silane mass percent 80:20, methyltrimethoxysilane and phenyl silane
Mixture and isopropanol mass percent 1:1；
(3) under the conditions of stirring is slow, silanol solution prepared by step (2) is added to the mixed of step (1) preparation
It in Heshui solution, stirs evenly, adds polytetrafluoroethylene (PTFE), be sufficiently stirred, siloxane oligomer is made.
A kind of preparation method of the corrosion resistant coating for navigation mark, comprising the following steps:
(1) 30:16 by weight parts weigh epoxy resin, polyester be added blender in, 50 DEG C of whipping temp, mixing time
18min, stirring rate 1200rpm；
(2) it first weighs 2 parts of titanate coupling agents by weight to be added in blender, 75 DEG C of whipping temp, mixing time
Then 15min is added 8 parts of graphene oxides, 12 parts of zinc powders, is sufficiently stirred, mixing time 18min, stirring rate is
1000rpm；
(3) toluene sulfone, the different phthalonitrile of 5 parts of antimicrobial tetrachloros is added in 5 parts of antimicrobial diiodomethyls
In blender, mixing time 14min, stirring rate 1400rpm；
(4) 43 parts of siloxane oligomers are added in blender, mixing time 14min, stirring rate 1400rpm.
Corrosion resistant coating made from above-described embodiment is mainly used for navigation mark, and has high adhesion force, good weatherability, impact resistance
Property it is strong, rub resistance is good, good corrosion resistance, long service life, coating are fine and close and marine organisms are difficult to the characteristic adhered to.
Embodiment 5
The present embodiment is comparative example, and a kind of corrosion resistant coating for navigation mark, raw material includes: epoxy resin by weight
30 parts, 20 parts of polyester, 3 parts of titanate coupling agent, 20 parts of zinc powder.
A kind of preparation method of the corrosion resistant coating for navigation mark, comprising the following steps:
(1) epoxy resin, polyester are added in blender in proportion, 40 DEG C of whipping temp, mixing time 10min, stirring
Rate is 1000rpm；
(2) titanate coupling agent is added in blender again, 70 DEG C of whipping temp, then zinc is added in mixing time 15min
Powder is sufficiently stirred, mixing time 10min, stirring rate 900rpm.
It is compared using corrosion resistant coating end properties index analysis made from above-described embodiment 1-5, is shown in Table 1:
Table 1
As shown in Table 1, the present invention is by the synergistic effect of each component, improve corrosion resistance of the coating in briny environment,
Rub resistance, water resistance, weatherability and impact resistance, and then extend the service life of navigation mark.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field
For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, made any to repair
Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of corrosion resistant coating for navigation mark, which is characterized in that its raw material includes: epoxy resin 24~32 by weight
Part, 14~22 parts of polyester, 1~3 part of titanate coupling agent, 6~15 parts of graphene, 10~20 parts of zinc powder, siloxane oligomer 35
~45 parts, 4~12 parts of antimicrobial.
2. the corrosion resistant coating according to claim 1 for navigation mark, which is characterized in that the system of the siloxane oligomer
It is standby that steps are as follows:
(1) divalent metal is added in the aqueous solution containing organic carboxyl acid, adds silicon dioxide gel, preparation mixing
Aqueous solution；
(2) methyltrimethoxysilane is mixed with isopropanol, prepares silanol solution；
(3) under the conditions of stirring is slow, silanol solution prepared by step (2) is added to the mixing water of step (1) preparation
It in solution, stirs evenly, adds polytetrafluoroethylene (PTFE), be sufficiently stirred, siloxane oligomer is made.
3. the corrosion resistant coating according to claim 2 for navigation mark, which is characterized in that the organic carboxyl acid be acetic acid,
One of glacial acetic acid, propionic acid, maleic acid, oxalic acid or any combination.
4. the corrosion resistant coating according to claim 2 for navigation mark, which is characterized in that the divalent metal is
One of calcium ion, manganese ion, copper ion, zinc ion or any combination.
5. the corrosion resistant coating according to claim 1-4 for navigation mark, which is characterized in that described antimicrobial
Agent is diiodomethyl to one of toluene sulfone, the different phthalonitrile of tetrachloro, phthalimide or any combination.
6. the corrosion resistant coating according to claim 1-4 for navigation mark, which is characterized in that the graphene is
The graphene oxide of micro sheet structure, with a thickness of 3~8 μm, diameter is 6~9 μm.
7. the corrosion resistant coating according to claim 1-4 for navigation mark, which is characterized in that graphene, zinc powder,
The weight ratio of antimicrobial is 8~12:12~18:6~10.
8. the corrosion resistant coating according to claim 1-4 for navigation mark, which is characterized in that epoxy resin gathers
Ester, siloxane oligomer weight ratio be 25~30:16~20:38~43.
9. a kind of preparation method of the corrosion resistant coating according to claim 1-8 for navigation mark, feature exist
In, comprising the following steps:
(1) epoxy resin, polyester are added in blender in proportion, 40~60 DEG C of whipping temp, 10~20min of mixing time；
(2) first titanate coupling agent is added in blender in proportion, 70~80 DEG C of whipping temp, 15~20min of mixing time,
Then graphene, zinc powder is added, is sufficiently stirred, 10~20min of mixing time；
(3) antimicrobial is added in blender in proportion, 10~15min of mixing time；
(4) siloxane oligomer is added in blender in proportion, 10~15min of mixing time.
10. the preparation method of the corrosion resistant coating according to claim 9 for navigation mark, which is characterized in that in step (1)
The stirring rate of the blender is 1000~1300rpm, the stirring rate of blender described in step (2) is 900~
The stirring rate of blender described in 1100rpm, step (3) and step (4) is 1200~1500rpm.
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| CN114752298A (en) * | 2022-03-31 | 2022-07-15 | 山东天盾矿用设备有限公司 | Embedded channel sealing coating and preparation method and application thereof |
| CN115612329A (en) * | 2022-09-08 | 2023-01-17 | 江苏科技大学 | Anticorrosive paint containing two-dimensional metal coordination polymer and preparation method thereof |
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| CN112592631A (en) * | 2020-12-02 | 2021-04-02 | 湖南翰坤实业有限公司 | Ocean corrosion-resistant nano aviation coating and preparation method thereof |
| CN114752298A (en) * | 2022-03-31 | 2022-07-15 | 山东天盾矿用设备有限公司 | Embedded channel sealing coating and preparation method and application thereof |
| CN115612329A (en) * | 2022-09-08 | 2023-01-17 | 江苏科技大学 | Anticorrosive paint containing two-dimensional metal coordination polymer and preparation method thereof |
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