CN107892855A - A kind of preparation method of the hydrophobic marine antifouling coating of low-surface-energy type - Google Patents
A kind of preparation method of the hydrophobic marine antifouling coating of low-surface-energy type Download PDFInfo
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Abstract
The present invention relates to technical field of paint preparation, and in particular to a kind of preparation method of the hydrophobic marine antifouling coating of low-surface-energy type.The present invention is modified jointly by silane coupler to nano titanium oxide and nano silicon, reduce the reunion of nano titanium oxide, be advantageous to dispersiveness and stability in acrylic resin, the addition of modified nano-titanium dioxide, improve the hydrophobicity of acrylic resin, so that fouling organism is not easy to adhere to or adhered to loosely on its surface, reduce the surface energy of marine antifouling coating, the present invention is by introducing Si O keys in resin, the micron order color stuffing and nano silicon of addition are after being blended, the hydrophobicity for being advantageous to resin is improved, continuously add chitosan, rosin and cuprous oxide, promote the caking property of resin and modified Nano level material or other fillers, further reduce the surface energy of marine antifouling coating, it is with a wide range of applications.
Description
Technical field
The present invention relates to technical field of paint preparation, and in particular to a kind of system of the hydrophobic marine antifouling coating of low-surface-energy type
Preparation Method.
Background technology
Hull is dirty or is stained and refers to that ship rode the sea after a period of time, and its under-water body surface can apposition growth one
A little marine organisms（Such as bacterium, algae, bryozoan）Phenomenon.The attachment of marine organisms is always one of shipping business and is difficult to solve
Certainly the problem of, it not only increases the weight of hull, increase resistance reduces shipping, causes the increase of operation cost, some attachments
The metabolite energy accelerated corrosion of biology, can also aggravate the corrosion of underwater installation.Application antifouling paint is most effective, universal at present
Method, while it is also that technology is most ripe, the simplest method of technique.
Antifouling paint relies primarily on oozing out for poisonous biocide in coating system, utilizes the toxicological effect of biocide to kill sea
Foreign fouling organism suppresses its growth and breeding.Wherein maximally efficient is organotin（TBT）Coating, yet with it in environment
The adverse side effect of aspect started to be prohibited from using in 2008.Then people develop cuprous oxide as biocide again
Low-toxicity anti-fouling coating, realize that the attachment for suppressing marine organisms is stained by the effect of killing livestock of cuprous oxide, but its effect of killing livestock is remote
Less than organotin biocide, a large amount of cupric oxide of addition need to be relied on just to meet antifouling demand.Therefore, use value can not also
Cause marine pollution matter.
Current most widely used low-toxicity anti-fouling coating is mainly using silicon Acrylote, copper and zinc as resin binder, then add
Tin-free Spc Anti-fouling Paint made from cuprous oxide and high-efficiency pollution-proof agent.The cuprous oxide of high content be present in this antifouling paint
Deng organo-metallic compound, very big pollution is caused to marine environment, the health of people can be caused to endanger by food chain
Evil.In addition, acrylic resin has good adhesive force because of it and turns into the preferred matrix of anti-corruption no coating from polishing performance,
But the defects of its modulus of elasticity is small, and matter is crisp, again limits its application.
It would therefore be highly desirable to develop the effective antifouling paint of a kind of not only nontoxic but also wide spectrum.
The content of the invention
The technical problems to be solved by the invention：Certain absorption affinity and parent be present for current common marine antifouling coating
It is water-based, its surface energy is improved, can adhere to marine organisms so as to result in under-water body surface, the defects of polluting hull,
Provide a kind of preparation method of the hydrophobic marine antifouling coating of low-surface-energy type.
In order to solve the above technical problems, the present invention is using technical scheme as described below：
A kind of preparation method of the hydrophobic marine antifouling coating of low-surface-energy type, it is characterised in that specifically preparation process is：
（1）100 mesh sieves are crossed after weighing 16~20g nano titanium oxides and the crushing of 12~16g nano silicons mixed grinding, are received
Collection sieving powder, sieving powder, distilled water, sesame oil and Silane coupling reagent KH-570 are mixed to be placed in 500mL flasks and stirred
Afterwards, then by the flask after stirring ultrasonic disperse in ultrasonic disperse machine is placed in, continues to be heated to reflux after scattered, obtain reaction solution, used
After absolute ethyl alcohol washing reaction liquid, natural air drying, grinding discharging, modified sieving powder is obtained；
（2）Measure 45~55mL dimethylbenzene, 12~16mL methyl methacrylates, 6~8mL butyl acrylates and 1~3mL propylene
Acid mixing, which is poured into the constant pressure funnel containing 2~4g azodiisobutyronitriles, rocks, and obtains Self-made mixture, then to equipped with cold
The stirring of 35~55mL dimethylbenzene is added in the four-hole boiling flask of condenser, agitator and thermometer, and self-control is added dropwise into four-hole boiling flask
Mixed liquor, insulated and stirred reaction, continue to add 1~3g azodiisobutyronitrile hybrid reactions into four-hole boiling flask, naturally cool to
Room temperature, discharging obtain making acrylic resin by oneself；
（3）After shrimp shell and crab shell mixed grinding, mixed shell powder is obtained, will be soaked in the beaker of mixed shell powder and hydrochloric acid,
Calcium carbonate in shell is removed, the mixed shell powder after being soaked, the mixed shell powder after immersion is put into the mixed shell after immersion
Boiled in the sodium hydroxide solution that 2~4 times of powder quality, remove protein in shell, continue the mixed shell powder poured into after immersion
Hydrolyzed in the sodium hydroxide solution that 1~3 times of quality, be put into baking oven and dry after hydrolysis, self-control chitosan is produced after drying, will be certainly
Dissolving is mixed in chitosan and acetum processed, obtains making chitosan solution by oneself；
（4）Count in parts by weight, weigh respectively self-control acrylic resin, modified sieving powder, self-control chitosan solution, rosin and
Deionized water mixing, which is placed in mixer, stirs, then adds chlorinated paraffin, cuprous oxide and dimethylbenzene, continues to mix, from
Room temperature so is cooled to, is discharged, you can the hydrophobic marine antifouling coating of low-surface-energy type is made.
Step（1）The described time that grinds is 8~10min, sieving powder, distilled water, sesame oil and silane coupled
Agent KH-570 mass ratio is 3：5：1：1, mixing time is 6~8min, and the ultrasonic disperse time is 16~20min, is heated to reflux
Temperature is 80~100 DEG C, and it is 2~4h to be heated to reflux the time, and wash time is 4~6min.
Step（2）The described time of rocking is 6~8min, and whipping temp is 60~80 DEG C, and mixing time is 4~6min,
The stirring reaction time is 1~2h, and the reaction time is 1~2h.
Step（3）Described shrimp shell and crab shell etc. mass ratio, milling time be 6~8min, mixed shell powder and hydrochloric acid
Mass ratio be 1：3, the mass fraction of hydrochloric acid is 5%, and soak time is 1~2h, and the mass fraction of sodium hydroxide solution is
10%, boiling time is 1~2h, and the mass fraction of sodium hydroxide solution is 35%, and hydrolysis temperature is 100~120 DEG C, during hydrolysis
Between be 2~4h, drying temperature is 80~100 DEG C, and drying time be 2~4h, the mass ratio 1 of self-control chitosan and acetum：
2, the mass fraction of acetum is 3%, and dissolution time is 1~2h.
Step（4）Described is in parts by weight meter, weigh respectively 24~32 parts of self-control acrylic resins, 16~20 parts change
Property sieving powder, 10~12 parts self-control chitosan solution, 6~8 parts of rosin, 8~10 parts of deionized waters, 3~5 parts of chlorinated paraffins, 1
~3 parts of cuprous oxide and 2~4 parts of dimethylbenzene, whipping temp are 45~55 DEG C, and mixing time is 16~20min, continue stirring temperature
Spend for 65~85 DEG C, continuation mixing time is 1~3h.
Compared with other method, advantageous effects are the present invention：
（1）The present invention is modified jointly by silane coupler to nano titanium oxide and nano silicon, even with silane first
Connection agent is hydrolyzed into side chain and contains-Si（OH）3Structure, it can chemically react with-the OH on nano titanium oxide surface, make
Lipophilic group in nano titanium oxide surface grafting sesame oil, enhance nano titanium oxide in dimethylbenzene dispersiveness and
Stability, so as to reduce the reunion of nano titanium oxide, be advantageous to dispersiveness of the nano titanium oxide in acrylic resin
And stability, when water contacts with hydrophobic micro nano structure, the micro-nano hole in part is closed by the globule and forms one layer of gas
Film, because acrylic resin has the characteristic of low-surface-energy in itself, under surface tension effects, the globule is more easy to Spontaneous Contraction, this
When contact angle increase, material hydrophobic improve, apply composite acrylic resin through silane coupler modified nano titanium oxide
Layer forms the rough surface of uniform micro-enzyme electrode, so as to reduce the surface energy of marine antifouling coating, while modified Nano
The addition of titanium dioxide, the hydrophobicity of acrylic resin is improved, additionally, due to modified nano-titanium dioxide in acrylic resin
In disperse evenly, the micron-nanometer surface texture of resin surface makes coating contact angle further increase, so as to reduce sea
The surface energy of foreign antifouling paint so that fouling organism is not easy to adhere to or adhered to loosely on its surface, avoids fouling organism pair
The pollution of hull；
（2）For the present invention by introducing Si-O keys into resin, the bond energy of Si-O keys is higher thus modified than the bond energy of C-C key
Resin there is relatively low surface energy in itself, the micron order color stuffing and nano silicon that are added in dope preparing process warp
After being blended, nano-micrometre structure is showed in film, roughness factor increase, makes the surface energy of film reduce, accordingly
Increase the contact angle of film and water, the hydrophobicity for being advantageous to resin is improved, the present invention continuously add chitosan, rosin and
Cuprous oxide, due to having sticking rosin, promote the caking property of resin and modified Nano level material or other fillers, and shell gathers
Sugar has the characteristic of certain hydrophobicity and bacteriostasis, can kill rudimentary marine animal with cuprous oxide and be combined, this
Sample will not produce water pollution, reduce further the surface energy of marine antifouling coating, be with a wide range of applications.
Embodiment
Weigh 16~20g nano titanium oxides and 12~16g nano silicons mixed grinding crushes mistake after 8~10min
100 mesh sieves, sieving powder is collected, is in mass ratio 3：5：1：1 will sieving powder, distilled water, sesame oil and silane coupler KH-
570 mixing are placed in 500mL flasks after 6~8min of stirring, then the flask after stirring are placed in into ultrasonic disperse in ultrasonic disperse machine
16~20min, continue to be heated to reflux 2~4h in the case where temperature is 80~100 DEG C after scattered, obtain reaction solution, washed with absolute ethyl alcohol
After washing 4~6min of reaction solution, natural air drying, grinding discharging, obtain modified sieving powder, measure 45~55mL dimethylbenzene, 12~
16mL methyl methacrylates, 6~8mL butyl acrylates and the mixing of 1~3mL acrylic acid are poured into containing the isobutyl of 2~4g azos two
6~8min is rocked in the constant pressure funnel of nitrile, obtains Self-made mixture, then to equipped with condenser, agitator and thermometer
35~55mL dimethylbenzene is added in four-hole boiling flask, stirs 4~6min at being 60~80 DEG C in temperature, and be added dropwise into four-hole boiling flask
Self-made mixture, insulated and stirred react 1~2h, continue to add into four-hole boiling flask 1~3g azodiisobutyronitriles hybrid reaction 1~
2h, naturally cools to room temperature, and discharging obtains making acrylic resin by oneself, by wait mass ratio by shrimp shell and crab shell mixed grinding 6~
After 8min, mixed shell powder is obtained, is in mass ratio 1：3 by the beaker of mixed shell powder and mass fraction for 5% hydrochloric acid
1~2h is soaked, calcium carbonate in shell is removed, the mixed shell powder after being soaked, the mixed shell powder after immersion is put into immersion
The mass fraction of 2~4 times of mixed shell powder quality afterwards is that 1~2h is boiled in 10% sodium hydroxide solution, removes egg in shell
White matter, the mass fraction for continuing to pour into 1~3 times of mixed shell powder quality after immersion be in 35% sodium hydroxide solution,
Temperature is that 2~4h is hydrolyzed at 100~120 DEG C, and 2~4h of drying in 80~100 DEG C of baking oven is put into after hydrolysis, is derived from after drying
Chitosan processed, in mass ratio 1：2 will make chitosan and mass fraction by oneself to mix 1~2h of dissolving in 3% acetum,
Obtain make by oneself chitosan solution, count in parts by weight, weigh respectively 24~32 parts self-control acrylic resins, 16~20 parts be modified
Sieve powder, 10~12 parts of self-control chitosan solutions, 6~8 parts of rosin and 8~10 parts of deionized water mixing are placed in mixer,
Temperature is that 16~20min is stirred at 45~55 DEG C, then adds 3~5 parts of chlorinated paraffins, 1~3 part of cuprous oxide and 2~4 parts of diformazans
Benzene, continue 1~3h of mixing at being 65~85 DEG C in temperature, naturally cool to room temperature, discharge, you can low-surface-energy type is made
Hydrophobic marine antifouling coating.
Example 1
100 mesh sieves are crossed after weighing 16g nano titanium oxides and 12g nano silicons mixed grinding crushing 8min, collect sieving
Powder, it is in mass ratio 3：5：1：Sieving powder, distilled water, sesame oil and Silane coupling reagent KH-570 mixing are placed in 500mL by 1
After stirring 6min in flask, then the flask after stirring is placed in ultrasonic disperse 16min in ultrasonic disperse machine, continued after disperseing in temperature
Spend to be heated to reflux 2h at 80 DEG C, obtain reaction solution, after absolute ethyl alcohol washing reaction liquid 4min, natural air drying, grinding discharging,
Modified sieving powder is obtained, 45mL dimethylbenzene, 12mL methyl methacrylates, 6mL butyl acrylates and 1mL acrylic acid is measured and mixes
Conjunction, which is poured into the constant pressure funnel containing 2g azodiisobutyronitriles, rocks 6min, obtains Self-made mixture, then to equipped with condensation
35mL dimethylbenzene is added in the four-hole boiling flask of device, agitator and thermometer, stirs 4min at being 60 DEG C in temperature, and burn to four mouthfuls
Self-made mixture is added dropwise in bottle, insulated and stirred reaction 1h, continues to add 1g azodiisobutyronitrile hybrid reactions into four-hole boiling flask
1h, naturally cools to room temperature, and discharging obtains making acrylic resin by oneself, by waiting mass ratio by shrimp shell and crab shell mixed grinding 6min
Afterwards, mixed shell powder is obtained, is in mass ratio 1：3 will soak in the beaker of mixed shell powder and mass fraction for 5% hydrochloric acid
1h, calcium carbonate in shell is removed, the mixed shell powder after being soaked, the mixed shell powder after immersion is put into the mixing after immersion
The mass fraction that 2 times of shell powder quality is that 1h is boiled in 10% sodium hydroxide solution, removes protein in shell, continues to pour into leaching
The mass fraction of 1 times of mixed shell powder quality after bubble is in 35% sodium hydroxide solution, is hydrolyzed at being 100 DEG C in temperature
2h, it is put into after hydrolysis in 80 DEG C of baking oven and dries 2h, self-control chitosan, in mass ratio 1 is produced after drying：2 will make chitosan by oneself
With mass fraction to mix dissolving 1h in 3% acetum, obtain making chitosan solution by oneself, count in parts by weight, divide
Also known as take 24 parts of self-control acrylic resins, 16 parts of modified sieving powder, 10 parts of self-control chitosan solutions, 6 parts of rosin and 8 parts go from
Sub- water mixing is placed in mixer, stirs 16min at being 45 DEG C in temperature, then add 3 parts of chlorinated paraffins, 1 part of cuprous oxide and 2
Part dimethylbenzene, continue to mix 1h at being 65 DEG C in temperature, naturally cool to room temperature, discharge, you can low-surface-energy type is made
Hydrophobic marine antifouling coating.
Example 2
100 mesh sieves are crossed after weighing 18g nano titanium oxides and 14g nano silicons mixed grinding crushing 9min, collect sieving
Powder, it is in mass ratio 3：5：1：Sieving powder, distilled water, sesame oil and Silane coupling reagent KH-570 mixing are placed in 500mL by 1
After stirring 7min in flask, then the flask after stirring is placed in ultrasonic disperse 18min in ultrasonic disperse machine, continued after disperseing in temperature
Spend to be heated to reflux 3h at 90 DEG C, obtain reaction solution, after absolute ethyl alcohol washing reaction liquid 5min, natural air drying, grinding discharging,
Modified sieving powder is obtained, 50mL dimethylbenzene, 14mL methyl methacrylates, 7mL butyl acrylates and 2mL acrylic acid is measured and mixes
Conjunction, which is poured into the constant pressure funnel containing 3g azodiisobutyronitriles, rocks 7min, obtains Self-made mixture, then to equipped with condensation
45mL dimethylbenzene is added in the four-hole boiling flask of device, agitator and thermometer, stirs 5min at being 70 DEG C in temperature, and burn to four mouthfuls
Self-made mixture is added dropwise in bottle, insulated and stirred reaction 1.5h, continues to add the mixing of 2g azodiisobutyronitriles into four-hole boiling flask instead
1.5h is answered, naturally cools to room temperature, discharging obtains making acrylic resin by oneself, by waiting mass ratio by shrimp shell and crab shell mixed grinding
After 7min, mixed shell powder is obtained, is in mass ratio 1：3 by the beaker of mixed shell powder and mass fraction for 5% hydrochloric acid
1.5h is soaked, removes calcium carbonate in shell, the mixed shell powder after being soaked, after the mixed shell powder after immersion is put into immersion
The mass fraction of 3 times of mixed shell powder quality be to boil 1.5h in 10% sodium hydroxide solution, remove protein in shell, after
The continuous mass fraction for pouring into 2 times of mixed shell powder quality after soaking is in 35% sodium hydroxide solution, is 110 DEG C in temperature
Lower hydrolysis 3h, is put into 90 DEG C of baking oven after hydrolysis and dries 3h, and self-control chitosan, in mass ratio 1 are produced after drying：2 will self-control
Dissolving 1.5h is mixed in chitosan and the acetum that mass fraction is 3%, obtains making chitosan solution by oneself, by weight
Number meter, weigh respectively 28 parts of self-control acrylic resins, 18 parts of modified sieving powder, 11 parts of self-control chitosan solutions, 7 parts of rosin and
9 parts of deionized water mixing are placed in mixer, and 18min is stirred at being 50 DEG C in temperature, then add 4 parts of chlorinated paraffins, 2 parts of oxidations
Cuprous and 3 parts of dimethylbenzene, continue to mix 2h at being 75 DEG C in temperature, naturally cool to room temperature, discharge, you can low table is made
Face can the hydrophobic marine antifouling coating of type.
Example 3
100 mesh sieves are crossed after weighing 20g nano titanium oxides and 16g nano silicons mixed grinding crushing 10min, collect sieving
Powder, it is in mass ratio 3：5：1：Sieving powder, distilled water, sesame oil and Silane coupling reagent KH-570 mixing are placed in 500mL by 1
After stirring 8min in flask, then the flask after stirring is placed in ultrasonic disperse 20min in ultrasonic disperse machine, continued after disperseing in temperature
Spend to be heated to reflux 4h at 100 DEG C, obtain reaction solution, after absolute ethyl alcohol washing reaction liquid 6min, natural air drying, be ground
Material, modified sieving powder is obtained, measures 55mL dimethylbenzene, 16mL methyl methacrylates, 8mL butyl acrylates and 3mL propylene
Acid mixing is poured into the constant pressure funnel containing 4g azodiisobutyronitriles and rocks 8min, obtains Self-made mixture, then to equipped with
55mL dimethylbenzene is added in the four-hole boiling flask of condenser, agitator and thermometer, 6min is stirred at being 80 DEG C in temperature, and to four
Self-made mixture is added dropwise in mouth flask, insulated and stirred reaction 2h, continues to add the mixing of 3g azodiisobutyronitriles into four-hole boiling flask
2h is reacted, naturally cools to room temperature, discharging obtains making acrylic resin by oneself, by waiting mass ratio by shrimp shell and crab shell mixed grinding
After 8min, mixed shell powder is obtained, is in mass ratio 1：3 by the beaker of mixed shell powder and mass fraction for 5% hydrochloric acid
2h is soaked, removes calcium carbonate in shell, the mixed shell powder after being soaked, after the mixed shell powder after immersion is put into immersion
The mass fraction that 4 times of mixed shell powder quality is that 2h is boiled in 10% sodium hydroxide solution, removes protein in shell, continues down
The mass fraction for entering 3 times of mixed shell powder quality after immersion is water at being 120 DEG C in temperature in 35% sodium hydroxide solution
4h is solved, is put into after hydrolysis in 100 DEG C of baking oven and dries 4h, self-control chitosan, in mass ratio 1 are produced after drying：2 gather self-control shell
Dissolving 2h is mixed in sugar and the acetum that mass fraction is 3%, obtains making chitosan solution by oneself, counts in parts by weight,
32 parts of self-control acrylic resins, 20 parts of modified sieving powder, 12 parts of self-control chitosan solutions, 8 parts of rosin and 10 parts are weighed respectively
Deionized water mixing is placed in mixer, and 20min is stirred at being 55 DEG C in temperature, then adds 5 parts of chlorinated paraffins, 3 parts of oxidation Asias
Copper and 4 parts of dimethylbenzene, continue to mix 3h at being 85 DEG C in temperature, naturally cool to room temperature, discharge, you can low surface is made
Can the hydrophobic marine antifouling coating of type.
Comparative example
With the marine antifouling coating of Shanghai City company production as a comparison case to the hydrophobic sea of low-surface-energy type produced by the present invention
Marine antifouling coating in foreign antifouling paint and comparative example is detected, and testing result is as shown in table 1, table 2：Method of testing
1st, contact angle is tested
Determined with contact angle instrument.
2nd, thickness is tested
According to the thickness of ASTMD1005 standard testing marine antifouling coatings.
3rd, abrasion resistance test
According to the abrasion resistance properties of GB/T13448-2005 standard testing marine antifouling coatings.
4th, solvent resistance test
According to the solvent resistance of the standard testing compound anti-fouling paints of GB/T13448-2005.
Table 1
| Test event | Example 1 | Example 2 | Example 3 | Comparative example |
| Thickness（mm） | 16 | 17 | 19 | 17 |
| Contact angle（°） | 121 | 123 | 125 | 93 |
| Wear weight loss（g） | 0.0126 | 0.0123 | 0.0120 | 0.0320 |
| Solvent resistance | Do not reveal base material | Do not reveal base material | Do not reveal base material | Expose a small amount of base material |
Table 2
| Sequence number | Spreading area（m2） | Test period（Year） | Marine organisms adhere to coverage rate（%） | Test marine site |
| Example 1 | 3 | 3 | Have no that marine organisms adhere to | Sunshine marine site |
| Example 2 | 3 | 3 | Have no that marine organisms adhere to | Sunshine marine site |
| Example 3 | 3 | 3 | Have no that marine organisms adhere to | Sunshine marine site |
| Comparative example | 3 | 3 | Marine organisms coverage rate reaches 48% | Sunshine marine site |
From table 1, the data of table 2, the hydrophobic marine antifouling coating of low-surface-energy type produced by the present invention has well to marine organisms
Anti-adhesion performance, and hydrophobicity is preferable, is avoided that and is corroded for a long time by water body, reduces the table of marine antifouling coating well
Face energy.Therefore, there is wide prospect of the application.
Claims (5)
1. a kind of preparation method of the hydrophobic marine antifouling coating of low-surface-energy type, it is characterised in that specifically preparation process is：
（1）100 mesh sieves are crossed after weighing 16~20g nano titanium oxides and the crushing of 12~16g nano silicons mixed grinding,
Sieving powder is collected, sieving powder, distilled water, sesame oil and Silane coupling reagent KH-570 are mixed to be placed in 500mL flasks and stirred
After mixing, then the flask after stirring is placed in ultrasonic disperse in ultrasonic disperse machine, continues to be heated to reflux after scattered, obtain reaction solution,
After absolute ethyl alcohol washing reaction liquid, natural air drying, grinding discharging, modified sieving powder is obtained；
（2）Measure 45~55mL dimethylbenzene, 12~16mL methyl methacrylates, 6~8mL butyl acrylates and 1~3mL propylene
Acid mixing, which is poured into the constant pressure funnel containing 2~4g azodiisobutyronitriles, rocks, and obtains Self-made mixture, then to equipped with cold
The stirring of 35~55mL dimethylbenzene is added in the four-hole boiling flask of condenser, agitator and thermometer, and self-control is added dropwise into four-hole boiling flask
Mixed liquor, insulated and stirred reaction, continue to add 1~3g azodiisobutyronitrile hybrid reactions into four-hole boiling flask, naturally cool to
Room temperature, discharging obtain making acrylic resin by oneself；
（3）After shrimp shell and crab shell mixed grinding, mixed shell powder is obtained, will be soaked in the beaker of mixed shell powder and hydrochloric acid,
Calcium carbonate in shell is removed, the mixed shell powder after being soaked, the mixed shell powder after immersion is put into the mixed shell after immersion
Boiled in the sodium hydroxide solution that 2~4 times of powder quality, remove protein in shell, continue the mixed shell powder poured into after immersion
Hydrolyzed in the sodium hydroxide solution that 1~3 times of quality, be put into baking oven and dry after hydrolysis, self-control chitosan is produced after drying, will be certainly
Dissolving is mixed in chitosan and acetum processed, obtains making chitosan solution by oneself；
（4）Count in parts by weight, weigh respectively self-control acrylic resin, modified sieving powder, self-control chitosan solution, rosin and
Deionized water mixing, which is placed in mixer, stirs, then adds chlorinated paraffin, cuprous oxide and dimethylbenzene, continues to mix, from
Room temperature so is cooled to, is discharged, you can the hydrophobic marine antifouling coating of low-surface-energy type is made.
A kind of 2. preparation method of hydrophobic marine antifouling coating of low-surface-energy type according to claim 1, it is characterised in that：
Step（1）The described time that grinds is 8~10min, sieving powder, distilled water, sesame oil and Silane coupling reagent KH-570
Mass ratio be 3：5：1：1, mixing time is 6~8min, and the ultrasonic disperse time is 16~20min, is heated to reflux temperature as 80
~100 DEG C, it is 2~4h to be heated to reflux the time, and wash time is 4~6min.
A kind of 3. preparation method of hydrophobic marine antifouling coating of low-surface-energy type according to claim 1, it is characterised in that：
Step（2）Described to rock the time be 6~8min, and whipping temp is 60~80 DEG C, and mixing time is 4~6min, stirring reaction
Time is 1~2h, and the reaction time is 1~2h.
A kind of 4. preparation method of hydrophobic marine antifouling coating of low-surface-energy type according to claim 1, it is characterised in that：
Step（3）Described shrimp shell and crab shell etc. mass ratio, milling time be 6~8min, mixed shell powder and hydrochloric acid mass ratio
For 1：3, the mass fraction of hydrochloric acid is 5%, and soak time is 1~2h, and the mass fraction of sodium hydroxide solution is 10%, when boiling
Between be 1~2h, the mass fraction of sodium hydroxide solution is 35%, and hydrolysis temperature is 100~120 DEG C, and hydrolysis time is 2~4h,
Drying temperature is 80~100 DEG C, and drying time is 2~4h, makes the mass ratio 1 of chitosan and acetum by oneself：2, acetum
Mass fraction be 3%, dissolution time is 1~2h.
A kind of 5. preparation method of hydrophobic marine antifouling coating of low-surface-energy type according to claim 1, it is characterised in that：
Step（4）Described is in parts by weight meter, weighs 24~32 parts of self-control acrylic resins, 16~20 parts of modified sieving powder respectively
End, 10~12 parts of self-control chitosan solutions, 6~8 parts of rosin, 8~10 parts of deionized waters, 3~5 parts of chlorinated paraffins, 1~3 part of oxygen
Change cuprous and 2~4 parts of dimethylbenzene, whipping temp is 45~55 DEG C, and mixing time is 16~20min, and it is 65 to continue whipping temp
~85 DEG C, continuation mixing time is 1~3h.
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| CN111500130A (en) * | 2020-04-10 | 2020-08-07 | 廊坊卡森清洗安装工程有限公司 | Environment-friendly super-hydrophobic antifouling paint |
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Application publication date: 20180410 |