CN109021747A - A kind of marine antifouling coating and preparation method thereof for sterilizing anti-halobios adhersion - Google Patents
A kind of marine antifouling coating and preparation method thereof for sterilizing anti-halobios adhersion Download PDFInfo
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- CN109021747A CN109021747A CN201810704015.4A CN201810704015A CN109021747A CN 109021747 A CN109021747 A CN 109021747A CN 201810704015 A CN201810704015 A CN 201810704015A CN 109021747 A CN109021747 A CN 109021747A
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- talcum powder
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- lotion
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
-
- 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
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
- C09D5/1662—Synthetic film-forming substance
- C09D5/1668—Vinyl-type polymers
-
- 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
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1687—Use of special additives
Abstract
The invention discloses a kind of marine antifouling coatings and preparation method thereof for sterilizing anti-halobios adhersion, by the function of imitating shark skin surface mucilage secretion, utilize talcum powder modified methyl silicone oil modified twice, so that methyl-silicone oil hydrophobicity improves, surface tension reduces, lubricant effect is more prominent, it can be used as the substance of suitable simulation shark skin surface mucus, then Lauxite is chosen as wall material, carry out microencapsulation, it applies it in antifouling paint, preventing and kill off for marine organisms is realized using the slow releasing function of microcapsules, anti-fouling effect is good.
Description
Technical field
The invention belongs to technical field of coatings, and in particular to a kind of marine antifouling coating and its system for sterilizing anti-halobios adhersion
Preparation Method.
Background technique
Marine fouling organism easily increases boat trip resistance, and fuel consumption increases, and causes huge economic loss.It is antifouling
Agent plays critical effect to the prevention and treatment of marine fouling organism in marine antifouling coating.Traditional anti-fouling agent has generally included
Microbial inoculum and heavy metal etc. are killed, but poisonous anti-fouling agent can generate secondary pollution to marine ecosystems.In recent years, environmental-friendly
Bionical nonpolluting coating replaces organotin, gets the attention containing copper coating.In order to solve heavy metal pair in traditional antifouling paint
The pollution of environment studies the nontoxic bionical nonpolluting coating of one kind and has great importance.
Summary of the invention
In view of the above-mentioned problems, the present invention is intended to provide a kind of bactericidal effect is good, and anti-halobios adhersion, and it is environmental-friendly
Marine antifouling coating, and preparation method thereof.
The invention is realized by the following technical scheme:
A kind of marine antifouling coating for sterilizing anti-halobios adhersion, is made of raw material from the following weight:
Talcum powder 5-10, triethyl citrate 2-3, methyl-silicone oil 20-30, neopelex 2-3, urea 5-10, first
Aldehyde solution 15-30, ammonium chloride 0.5-0.8, resorcinol 0.1-0.2, antioxidant BHT 4-8, dimethicone 3-7, propylene
Acid resin 100-120；
The acrylic resin is thermoplastic acrylic resin, solid content 50-70%, viscosity 15-25；The formalin concentration
For 40-50%.
Further, preparation method includes the following steps:
(1) talcum powder is added into 6-10 times of methanol solution, is placed in Vltrasonic device, ultrasound 40-50min at 50-60 DEG C,
Triethyl citrate is added, after continuing ultrasound 10-20min, is cooled to 20-30 DEG C, is then transferred in grinder and grinds 2-3h
To 300-400 mesh, temperature is increased to 85-95 DEG C, solvent is evaporated, gains is put into drying box, 60-80 DEG C of dry 2-3h,
Regrinding gains are spare to 400-500 mesh；
(2) methyl-silicone oil is added in 5-10 times of deionized water, neopelex, step (1) gains is added,
In the emulsified dispersion 20-40 min of the mechanical stirring of 1500-1800 r/min, it is spare to obtain lotion；
(3) by lotion tune pH to 7-8 obtained by step (2), urea, formalin, ammonium chloride and isophthalic are then added into lotion
Diphenol carries out polycondensation reaction, and solution is warming up to 56-65 with the heating rate of 2-3 DEG C/min under 400-500r/min revolving speed
DEG C, 5-6h is kept the temperature, is cooled to room temperature, is filtered, it is dry at 30-50 DEG C, obtain microscapsule powder；
(4) step (3) gains, antioxidant BHT, dimethicone are added in acrylic resin, with 5000-6000 r
The rate high speed dispersion of/min is uniform.
Further, talcum powder described in step (1) passes through modification, specific method of modifying are as follows: talcum powder is added
Into ammonia spirit, ultrasound 5-10min at 10-20 DEG C is warming up to 20-30 DEG C, then magnetic agitation 5-10min, and then side is stirred
Silver nitrate solution is added dropwise in side, continues to stir 10-30min after being added dropwise, stands 3-5h, filters and vacuum is dry at 30-40 DEG C
It is dry.
Further, lotion pH is adjusted to 7-8 using the NaOH solution of 5-10% or the HCl solution of 5-10% by step (3).
Beneficial effects of the present invention: the present invention imitates the function of shark skin surface mucilage secretion, the cunning that utilization is modified twice
Mountain flour modified methyl silicone oil, so that methyl-silicone oil hydrophobicity improves, surface tension is reduced, and lubricant effect is more prominent, can be used as conjunction
Then the substance of suitable simulation shark skin surface mucus chooses Lauxite as wall material, carries out microencapsulation, applied
Into antifouling paint, preventing and kill off for marine organisms is realized using the slow releasing function of microcapsules, anti-fouling effect is good；With ammonium hydroxide nitric acid
Silver is modified talcum powder, in talcum powder Surface Creation nano-Ag particles, assigns the effect that talcum powder is persistently sterilized, then passes through
It is modified to cross secondary triethyl citrate, talcum compound powder can be evenly dispersed in methyl-silicone oil, common with methyl-silicone oil
As core material, microcapsules are formed, enhance the anti-halobios adhersion and sterilization persistence of antifouling paint, while pollution-free, environment
It is friendly.
Specific embodiment
Illustrate the present invention with specific embodiment below, but is not limitation of the present invention.
Embodiment 1
A kind of marine antifouling coating for sterilizing anti-halobios adhersion, is made of raw material from the following weight:
Talcum powder 5, triethyl citrate 2, methyl-silicone oil 20, neopelex 2, urea 5, formalin 15, chlorination
Ammonium 0.5, resorcinol 0.1, antioxidant BHT 4, dimethicone 3, acrylic resin 100；
The acrylic resin is thermoplastic acrylic resin, solid content 50%, viscosity 15；The formalin concentration is 40%.
Further, preparation method includes the following steps:
(1) talcum powder is added into 6 times of methanol solution, is placed in Vltrasonic device, lemon is added in ultrasound 40min at 50 DEG C
Triethylenetetraminehexaacetic acid ester is cooled to 20 DEG C after continuing ultrasound 10min, is then transferred in grinder and grinds 2h to 300 mesh, increases temperature
To 85 DEG C, solvent is evaporated, gains are put into drying box, 60 DEG C of dry 2h, regrinding gains are spare to 400 mesh；
(2) methyl-silicone oil is added in 5 times of deionized water, neopelex, step (1) gains is added,
1500 r/min mechanical stirring, 20 min of emulsified dispersion, it is spare to obtain lotion；
(3) by lotion tune pH to 7 obtained by step (2), urea, formalin, ammonium chloride and isophthalic two are then added into lotion
Phenol carries out polycondensation reaction, and solution is warming up to 56 DEG C with the heating rate of 2 DEG C/min under 400r/min revolving speed, keeps the temperature 5h,
It is cooled to room temperature, filters, it is dry at 30 DEG C, obtain microscapsule powder；
(4) step (3) gains, antioxidant BHT, dimethicone are added in acrylic resin, with 5000 r/min
Rate high speed dispersion it is uniform.
Further, talcum powder described in step (1) passes through modification, specific method of modifying are as follows: talcum powder is added
Into ammonia spirit, ultrasound 5min at 10 DEG C is warming up to 20 DEG C, then magnetic agitation 5min, silver nitrate is then added dropwise while stirring
Solution continues to stir 10min after being added dropwise, stands 3h, filters and be dried in vacuo at 30 DEG C.
Further, lotion pH is adjusted to 7 using 5% NaOH solution or 5% HCl solution by step (3).
Embodiment 2
A kind of marine antifouling coating for sterilizing anti-halobios adhersion, is made of raw material from the following weight:
Talcum powder 7, triethyl citrate 3, methyl-silicone oil 25, neopelex 3, urea 8, formalin 20, chlorination
Ammonium 0.6, resorcinol 0.1, antioxidant BHT 6, dimethicone 5, acrylic resin 110；
The acrylic resin is thermoplastic acrylic resin, solid content 60%, viscosity 20；The formalin concentration is 45%.
Further, preparation method includes the following steps:
(1) talcum powder is added into 8 times of methanol solution, is placed in Vltrasonic device, lemon is added in ultrasound 45min at 55 DEG C
Triethylenetetraminehexaacetic acid ester is cooled to 25 DEG C after continuing ultrasound 15min, is then transferred in grinder and grinds 3h to 350 mesh, increases temperature
To 90 DEG C, solvent is evaporated, gains are put into drying box, 70 DEG C of dry 3h, regrinding gains are spare to 400 mesh；
(2) methyl-silicone oil is added in 7 times of deionized water, neopelex, step (1) gains is added,
1700 r/min mechanical stirring, 30 min of emulsified dispersion, it is spare to obtain lotion；
(3) by lotion tune pH to 8 obtained by step (2), urea, formalin, ammonium chloride and isophthalic two are then added into lotion
Phenol carries out polycondensation reaction, and solution is warming up to 60 DEG C with the heating rate of 3 DEG C/min under 450r/min revolving speed, keeps the temperature 6h,
It is cooled to room temperature, filters, it is dry at 40 DEG C, obtain microscapsule powder；
(4) step (3) gains, antioxidant BHT, dimethicone are added in acrylic resin, with 6000 r/min
Rate high speed dispersion it is uniform.
Further, talcum powder described in step (1) passes through modification, specific method of modifying are as follows: talcum powder is added
Into ammonia spirit, ultrasound 8min at 15 DEG C is warming up to 25 DEG C, then magnetic agitation 8min, silver nitrate is then added dropwise while stirring
Solution continues to stir 20min after being added dropwise, stands 4h, filters and be dried in vacuo at 35 DEG C.
Further, lotion pH is adjusted to 8 using 8% NaOH solution or 8% HCl solution by step (3).
Embodiment 3
A kind of marine antifouling coating for sterilizing anti-halobios adhersion, is made of raw material from the following weight:
Talcum powder 10, triethyl citrate 3, methyl-silicone oil 30, neopelex 3, urea 10, formalin 30, chlorine
Change ammonium 0.8, resorcinol 0.2, antioxidant BHT -8, dimethicone 7, acrylic resin 120；
The acrylic resin is thermoplastic acrylic resin, solid content 70%, viscosity 25；The formalin concentration is 50%.
Further, preparation method includes the following steps:
(1) talcum powder is added into 10 times of methanol solution, is placed in Vltrasonic device, lemon is added in ultrasound 50min at 60 DEG C
Triethylenetetraminehexaacetic acid ester is cooled to 30 DEG C after continuing ultrasound 20min, is then transferred in grinder and grinds 3h to 400 mesh, increases temperature
To 95 DEG C, solvent is evaporated, gains are put into drying box, 80 DEG C of dry 3h, regrinding gains are spare to 500 mesh；
(2) methyl-silicone oil is added in 10 times of deionized water, neopelex, step (1) gains is added,
1800 r/min mechanical stirring, 40 min of emulsified dispersion, it is spare to obtain lotion；
(3) by lotion tune pH to 8 obtained by step (2), urea, formalin, ammonium chloride and isophthalic two are then added into lotion
Phenol carries out polycondensation reaction, and solution is warming up to 65 DEG C with the heating rate of 3 DEG C/min under 500r/min revolving speed, keeps the temperature 6h,
It is cooled to room temperature, filters, it is dry at 50 DEG C, obtain microscapsule powder；
(4) step (3) gains, antioxidant BHT, dimethicone are added in 120 parts of acrylic resins, with 6000 r
The rate high speed dispersion of/min is uniform.
Further, talcum powder described in step (1) passes through modification, specific method of modifying are as follows: talcum powder is added
Into ammonia spirit, ultrasound 10min at 20 DEG C is warming up to 30 DEG C, then magnetic agitation 10min, nitric acid is then added dropwise while stirring
Silver-colored solution continues to stir 30min after being added dropwise, stands 5h, filters and be dried in vacuo at 40 DEG C.
Further, lotion pH is adjusted to 8 using 10% NaOH solution or 10% HCl solution by step (3).
Comparative example 1
The operation processing step of step (1), method and step in addition to this is omitted compared to embodiment 1 in this comparative example
It is all the same.
Comparative example 2
This comparative example is compared to embodiment 1, the step of talcum powder ammonium hydroxide, silver nitrate processing is omitted, in addition to this
Method and step is all the same.
Antibacterial test: by sample obtained under the conditions of the above each group, weighing a certain amount of addition concentration is 106Cfu/mL's
Then shaken cultivation 1h in Escherichia coli bacteria liquid passes through sample elution, calculates antibiotic rate after count plate；
Anti-fouling effect test: will be coated with the coating of each embodiment and comparative example institute, and the fishing net that is completely dried carry out it is real extra large
Linked network, sea organism attachment area is less than 10%, it is believed that antifouling paint is effective；
The results are shown in Table 1 for it:
Table 1
| Antibiotic rate % | Antifouling phase effect | |
| Embodiment 1 | 99.1 | 14 months |
| Embodiment 2 | 98.4 | 13 months |
| Embodiment 3 | 98.7 | 13 months |
| Comparative example 1 | 71.5 | 8 months |
| Comparative example 2 | 0 | 5 months |
As can be seen from Table 1, antifouling paint good anti-bacterial effect produced by the present invention, and effect length of antifouling phase, antifouling capacity is strong, value
It must promote.
Claims (4)
1. a kind of marine antifouling coating for sterilizing anti-halobios adhersion, which is characterized in that be made of raw material from the following weight:
Talcum powder 5-10, triethyl citrate 2-3, methyl-silicone oil 20-30, neopelex 2-3, urea 5-10, first
Aldehyde solution 15-30, ammonium chloride 0.5-0.8, resorcinol 0.1-0.2, antioxidant BHT 4-8, dimethicone 3-7, propylene
Acid resin 100-120, ammonia spirit 50-80, silver nitrate solution 20-40；
The acrylic resin is thermoplastic acrylic resin, solid content 50-70%, viscosity 15-25；The formalin concentration
For 40-50%；The ammonia spirit concentration is 20-30%；The silver nitrate solution concentration is 0.2-0.5%, situ configuration.
2. a kind of marine antifouling coating for sterilizing anti-halobios adhersion according to claim 1, which is characterized in that its preparation side
Method the following steps are included:
(1) talcum powder is added into 6-10 times of methanol solution, is placed in Vltrasonic device, ultrasound 40-50min at 50-60 DEG C,
Triethyl citrate is added, after continuing ultrasound 10-20min, is cooled to 20-30 DEG C, is then transferred in grinder and grinds 2-3h
To 300-400 mesh, temperature is increased to 85-95 DEG C, solvent is evaporated, gains is put into drying box, 60-80 DEG C of dry 2-3h,
Regrinding gains are spare to 400-500 mesh；
(2) methyl-silicone oil is added in 5-10 times of deionized water, neopelex, step (1) gains is added,
In the emulsified dispersion 20-40 min of the mechanical stirring of 1500-1800 r/min, it is spare to obtain lotion；
(3) by lotion tune pH to 7-8 obtained by step (2), urea, formalin, ammonium chloride and isophthalic are then added into lotion
Diphenol carries out polycondensation reaction, and solution is warming up to 56-65 with the heating rate of 2-3 DEG C/min under 400-500r/min revolving speed
DEG C, 5-6h is kept the temperature, is cooled to room temperature, is filtered, it is dry at 30-50 DEG C, obtain microscapsule powder；
(4) step (3) gains, antioxidant BHT, dimethicone are added in acrylic resin, with 5000-6000 r
The rate high speed dispersion of/min is uniform.
3. a kind of marine antifouling coating preparation method for sterilizing anti-halobios adhersion according to claim 2, which is characterized in that
Talcum powder described in step (1) passes through modification, specific method of modifying are as follows: talcum powder is added in ammonia spirit, 10-20
Ultrasound 5-10min at DEG C, is warming up to 20-30 DEG C, then magnetic agitation 5-10min, silver nitrate solution is then added dropwise while stirring, drop
It adds and continues to stir 10-30min after finishing, stand 3-5h, filter and be dried in vacuo at 30-40 DEG C.
4. a kind of marine antifouling coating preparation method for sterilizing anti-halobios adhersion according to claim 2, which is characterized in that
Lotion pH is adjusted to 7-8 using the NaOH solution of 5-10% or the HCl solution of 5-10% by step (3).
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810704015.4A CN109021747A (en) | 2018-07-02 | 2018-07-02 | A kind of marine antifouling coating and preparation method thereof for sterilizing anti-halobios adhersion |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810704015.4A CN109021747A (en) | 2018-07-02 | 2018-07-02 | A kind of marine antifouling coating and preparation method thereof for sterilizing anti-halobios adhersion |
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| CN109021747A true CN109021747A (en) | 2018-12-18 |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101744003A (en) * | 2009-12-24 | 2010-06-23 | 浙江理工大学 | Compound type uvioresistant antibacterial agent and preparation method thereof |
| CN101845262A (en) * | 2010-05-07 | 2010-09-29 | 宁波海纳海洋生物科技有限公司 | Low surface energy liquid control release type marine anti-fouling paint |
| CN102807796A (en) * | 2012-06-25 | 2012-12-05 | 浙江省海洋开发研究院 | Novel environment-friendly anti-fouling coating paint for ocean |
| CN104403448A (en) * | 2014-10-23 | 2015-03-11 | 中油新星纳米工程技术有限公司 | Nano cuprous oxide and nano silver compounded sea anti-fouling paint |
| CN105820713A (en) * | 2016-05-03 | 2016-08-03 | 沈阳建筑大学 | Self-repairing coating for marine ships and preparation method thereof |
-
2018
- 2018-07-02 CN CN201810704015.4A patent/CN109021747A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101744003A (en) * | 2009-12-24 | 2010-06-23 | 浙江理工大学 | Compound type uvioresistant antibacterial agent and preparation method thereof |
| CN101845262A (en) * | 2010-05-07 | 2010-09-29 | 宁波海纳海洋生物科技有限公司 | Low surface energy liquid control release type marine anti-fouling paint |
| CN102807796A (en) * | 2012-06-25 | 2012-12-05 | 浙江省海洋开发研究院 | Novel environment-friendly anti-fouling coating paint for ocean |
| CN104403448A (en) * | 2014-10-23 | 2015-03-11 | 中油新星纳米工程技术有限公司 | Nano cuprous oxide and nano silver compounded sea anti-fouling paint |
| CN105820713A (en) * | 2016-05-03 | 2016-08-03 | 沈阳建筑大学 | Self-repairing coating for marine ships and preparation method thereof |
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