CN110819293A - Antifouling adhesive, preparation method and application thereof - Google Patents
Antifouling adhesive, preparation method and application thereof Download PDFInfo
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- CN110819293A CN110819293A CN201911181179.4A CN201911181179A CN110819293A CN 110819293 A CN110819293 A CN 110819293A CN 201911181179 A CN201911181179 A CN 201911181179A CN 110819293 A CN110819293 A CN 110819293A
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/36—Hydroxylated esters of higher fatty acids
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3045—Sulfates
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
The invention relates to an antifouling adhesive, a preparation method and application thereof, wherein the antifouling adhesive is composed of a component A and a component B according to the weight ratio of 3-5:1, and the component A comprises the following raw material components: 500 parts of castor oil 450-one, 35-45 parts of molecular sieve, 10-20 parts of silicon dioxide, 50-70 parts of dipropylene glycol, 40-60 parts of neopentyl glycol, 2-4 parts of defoaming agent, 350 parts of barite powder 250-one, 15-25 parts of glycerol, 10-18 parts of surfactant, 2-4 parts of triethylene diamine and 15-25 parts of pepper essential oil; the component B is isocyanate. The antifouling adhesive disclosed by the invention can generate a lasting stimulation effect on marine fouling organisms, so that the marine fouling organisms are not easy to approach, and meanwhile, the antifouling adhesive has the characteristics of strong adhesion, good adhesion, water resistance, acid resistance and alkali resistance, is a friendly antifouling material, and is very suitable for antifouling on the surface of a sea ship.
Description
Technical Field
The invention belongs to the technical field of marine biofouling prevention and control, and particularly relates to an antifouling adhesive, and a preparation method and application thereof.
Background
Marine biofouling refers to biofouling formed by the adsorption growth of marine microorganisms and animals and plants on the surface of ship hulls or marine facilities, and brings many adverse effects on marine shipping and the exploration, development and utilization of marine resources. With the rapid development of marine economy, the adverse effect of marine biofouling on further development and utilization of marine resources is more obvious, and therefore, the prevention and treatment of marine biofouling also becomes a hot spot to be solved urgently by scientific research at present.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides an antifouling adhesive and a preparation method thereof. The antifouling adhesive can generate a lasting stimulation effect on marine fouling organisms, so that the marine fouling organisms are not easy to approach, has the characteristics of strong adhesion, good adhesion, water resistance, acid resistance and alkali resistance, is a friendly antifouling material, and is very suitable for antifouling on the surface of a marine vessel.
The technical scheme of the invention is as follows:
an antifouling adhesive comprises a component A and a component B according to the weight ratio of 3-5:1, wherein the component A comprises the following raw material components: 500 parts of castor oil 450-one, 35-45 parts of molecular sieve, 10-20 parts of silicon dioxide, 50-70 parts of dipropylene glycol, 40-60 parts of neopentyl glycol, 2-4 parts of defoaming agent, 350 parts of barite powder 250-one, 15-25 parts of glycerol, 10-18 parts of surfactant, 2-4 parts of triethylene diamine and 15-25 parts of pepper essential oil; the component B is isocyanate.
Preferably, the raw material components of the A component comprise: 480 parts of castor oil, 40 parts of molecular sieve, 15 parts of silicon dioxide, 60 parts of dipropylene glycol, 50 parts of neopentyl glycol, 3 parts of defoaming agent, 300 parts of barite powder, 18 parts of glycerol, 14 parts of surfactant, 3 parts of triethylene diamine and 20 parts of pepper essential oil.
Preferably, the defoaming agent is a silicone defoaming agent, and the surfactant is a low-foaming nonionic surfactant.
The preparation method of the antifouling adhesive comprises the following steps:
(1) placing castor oil in a stirring kettle, heating to 50-70 ℃, then sequentially adding a molecular sieve and silicon dioxide, and uniformly stirring to obtain a first mixture;
(2) continuously heating the first mixture to 75-85 ℃, then sequentially adding dipropylene glycol, neopentyl glycol and a defoaming agent, and uniformly stirring to obtain a second mixture;
(3) cooling the second mixture to 55-65 ℃, then sequentially adding barite powder, glycerol, a surfactant and triethylene diamine, and uniformly stirring to obtain a third mixture;
(4) continuously cooling the third mixture to below 40 ℃, then adding the pepper essential oil, and uniformly stirring to obtain a component A;
(5) and (3) mixing and stirring the component A and the component B uniformly to obtain the antifouling adhesive.
Preferably, in the step (1), the stirring speed is 40-60r/min, and the stirring time is 20-40 min.
Preferably, in the step (2), the stirring speed is 60-80r/min, and the stirring time is 100-150 min.
Preferably, in the step (3), the barite powder is added firstly, and stirred for 50-70min at a stirring speed of 100-200r/min, after the adhesion is formed, the glycerol, the surfactant and the triethylene diamine are sequentially added, and the stirring is continued for 50-70min at the stirring speed.
Preferably, in the step (4), the stirring speed is 100-120r/min, and the stirring time is 30-50 min.
The method for preventing fouling on the surface of the marine vessel based on the antifouling adhesive comprises the following specific steps: cleaning dirt on the surface of a ship body, spraying an antifouling adhesive on the surface of the ship body, and then carrying out electrostatic spraying flocking on the surface of the antifouling adhesive to obtain the antifouling adhesive.
The antifouling adhesive is applied to surface antifouling materials.
The invention has the beneficial effects that:
the anti-fouling adhesive is a synthetic two-component high-viscosity polyurethane adhesive, the adhesive takes castor oil and pepper essential oil as anti-fouling active ingredients, and can generate obvious and lasting irritation effect on marine fouling organisms by using the castor oil and the pepper essential oil simultaneously, so that the castor oil and the pepper essential oil are not easy to approach. On the other hand, the physical and mechanical properties are also improved, so that the adhesive disclosed by the invention is strong in bonding degree, good in adhesive force, water-resistant, acid-resistant and alkali-resistant. The invention is environment-friendly and pollution-free, is a friendly antifouling material, and is very suitable for antifouling use on the surface of a sea ship.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below. It is to be understood that the described embodiments are merely a few embodiments of the invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the examples given herein without any inventive step, are within the scope of the present invention. In the following examples, 1 part by weight represents 1 g.
Example 1
The embodiment provides an antifouling adhesive, which consists of a component A and a component B in a weight ratio of 3:1, wherein the component A comprises the following raw material components: 450 parts of castor oil, 35 parts of molecular sieve, 10 parts of silicon dioxide, 50 parts of dipropylene glycol, 40 parts of neopentyl glycol, 2 parts of organic silicon defoamer (XP205XPG100, Nanjing Huaxing defoamer Co., Ltd.), 250 parts of barite powder, 15 parts of glycerol, 10 parts of low-foam nonionic surfactant (LF-221, Nanjing Heian petrochemical plant), 2 parts of triethylene diamine and 15 parts of pepper essential oil; the component B is isocyanate.
Further, a method for preparing the antifouling adhesive is provided, which comprises the following steps:
(1) placing castor oil in a stirring kettle, heating to 50 ℃, then sequentially adding a molecular sieve and silicon dioxide, and stirring at a stirring speed of 40r/min for 40min to obtain a first mixture;
(2) continuously heating the first mixture to 75 ℃, then sequentially adding dipropylene glycol, neopentyl glycol and a defoaming agent, and stirring at a stirring speed of 60r/min for 150min to obtain a second mixture;
(3) cooling the second mixture to 55 ℃, adding barite powder, stirring at a stirring speed of 100r/min for 70min, sequentially adding glycerol, a surfactant and triethylene diamine after forming adhesion, and continuously stirring at the stirring speed for 50min to obtain a third mixture;
(4) continuously cooling the third mixture to 40 ℃, adding the pepper essential oil, and stirring at the stirring speed of 100r/min for 50min to obtain a component A;
(5) and (3) mixing and stirring the component A and the component B uniformly to obtain the antifouling adhesive.
Example 2
The embodiment provides an antifouling adhesive, which consists of a component A and a component B in a weight ratio of 5:1, wherein the component A comprises the following raw material components: 500 parts of castor oil, 45 parts of molecular sieve, 20 parts of silicon dioxide, 70 parts of dipropylene glycol, 60 parts of neopentyl glycol, 4 parts of organic silicon defoamer (XP205XPG100, Nanjing Huaxing defoamer Co., Ltd.), 350 parts of barite powder, 25 parts of glycerol, 18 parts of low-foam nonionic surfactant (LF-221, Nanjing Heian petrochemical plant), 4 parts of triethylene diamine and 25 parts of pepper essential oil; the component B is isocyanate.
Further, a method for preparing the antifouling adhesive is provided, which comprises the following steps:
(1) placing castor oil in a stirring kettle, heating to 70 ℃, then sequentially adding a molecular sieve and silicon dioxide, and stirring at a stirring speed of 60r/min for 20min to obtain a first mixture;
(2) continuously heating the first mixture to 85 ℃, then sequentially adding dipropylene glycol, neopentyl glycol and a defoaming agent, and stirring at a stirring speed of 80r/min for 100min to obtain a second mixture;
(3) cooling the second mixture to 65 ℃, adding barite powder, stirring for 50min at a stirring speed of 200r/min, sequentially adding glycerol, a surfactant and triethylene diamine after forming adhesion, and continuously stirring for 70min at the stirring speed to obtain a third mixture;
(4) continuously cooling the third mixture to 40 ℃, adding pepper essential oil, and stirring at a stirring speed of 120r/min for 30min to obtain a component A;
(5) and (3) mixing and stirring the component A and the component B uniformly to obtain the antifouling adhesive.
Example 3
The embodiment provides an antifouling adhesive which comprises a component A and a component B in a weight ratio of 4:1, wherein the component A comprises the following raw material components: 480 parts of castor oil, 40 parts of molecular sieve, 15 parts of silicon dioxide, 60 parts of dipropylene glycol, 50 parts of neopentyl glycol, 3 parts of organic silicon defoamer (XP205XPG100, Nanjing Huaxing defoamer Co., Ltd.), 300 parts of barite powder, 18 parts of glycerol, 14 parts of low-foam nonionic surfactant (LF-221, Nanjing Haian petrochemical plant), 3 parts of triethylene diamine and 20 parts of pepper essential oil; the component B is isocyanate.
Further, a method for preparing the antifouling adhesive is provided, which comprises the following steps:
(1) placing castor oil in a stirring kettle, heating to 60 ℃, then sequentially adding a molecular sieve and silicon dioxide, and stirring for 30min at a stirring speed of 40r/min to obtain a first mixture;
(2) continuously heating the first mixture to 80 ℃, then sequentially adding dipropylene glycol, neopentyl glycol and a defoaming agent, and stirring at a stirring speed of 80r/min for 120min to obtain a second mixture;
(3) cooling the second mixture to 60 ℃, adding barite powder, stirring at a stirring speed of 150r/min for 60min, sequentially adding glycerol, a surfactant and triethylene diamine after adhesion is formed, and continuously stirring at the stirring speed for 60min to obtain a third mixture;
(4) continuously cooling the third mixture to 40 ℃, adding the pepper essential oil, and stirring at the stirring speed of 100r/min for 40min to obtain a component A;
(5) and (3) mixing and stirring the component A and the component B uniformly to obtain the antifouling adhesive.
Comparative example 1
The difference from the example 3 lies in the different raw material proportion of the component A, and specifically, the raw material component of the component A in the comparative example comprises: 480 parts of castor oil, 30 parts of molecular sieve, 30 parts of silicon dioxide, 80 parts of dipropylene glycol, 75 parts of neopentyl glycol, 4 parts of organic silicon defoamer (XP205XPG100, Nanjing Huaxing defoamer Co., Ltd.), 220 parts of barite powder, 30 parts of glycerol, 30 parts of low-foaming nonionic surfactant (LF-221, Nanjing Heian petrochemical plant), 4 parts of triethylene diamine and 20 parts of pepper essential oil; the component B is isocyanate.
Comparative example 2
The difference from the example 3 is that the pepper essential oil in the raw material of the component A is replaced by pepper oil.
In order to verify the antifouling effect of the antifouling adhesive, the inventor of the application conducts a test study on the antifouling of the surface of the marine vessel, and the specific test process is as follows:
6 square steel plates 50cm × 50cm in size are respectively numbered A, B, C, D, E, F, after the surfaces are cleaned, the antifouling adhesives of examples 1-3 of the invention, the antifouling adhesives of comparative examples 1-2 and the commercial adhesives are respectively and uniformly sprayed on the surfaces of the steel plates, black fuzz blended by nylon is planted on the steel plates coated with the adhesives by using an electrostatic spraying flocking technology (the length of the fuzz is 3mm), holes are punched on each flocking sample plate, a string is threaded through the flocking sample plate and is fixed in the sea water to a depth of 2m for sample hanging, and the attachment conditions of fouling organisms on the plates at the end of the sea water soaking of 3 months, 6 months and 12 months are respectively observed.
Test results show that various plates containing the antifouling adhesives of the examples 1 to 3 of the invention have smooth and clean surfaces and no obvious attachment of fouling organisms at the end of seawater immersion in the 12 th month; the samples containing the commercially available adhesives showed adhesion of fouling organisms such as algae and crustaceans at the end of the 3 rd month immersion, and showed an increasing tendency in the amount of adhesion with time; the sample containing the antifouling adhesive of comparative example 1 had no significant adhesion of fouling organisms such as algae and crustaceans at the end of the 6 th month immersion, but algae adhered at the end of the 12 th month immersion; the flocking sample plate containing the antifouling adhesive of comparative example 2 showed excellent antifouling effect without significant adhesion of fouling organisms at the end of the 3 rd month immersion, but the antifouling effect began to decrease sharply thereafter, and the amount of adhesion of fouling organisms at the end of the 6 th month immersion was comparable to that of the commercially available adhesive.
According to the test results, the analysis shows that the specific raw material ratio of the invention enables the antifouling effect of the invention to be excellent, and the invention is very suitable for being combined with the electrostatic flocking technology to be used for antifouling on the surface of a sea vessel, and pepper oil is adopted to replace pepper essential oil in the component A of the invention, although the antifouling effect is excellent in a short period, the lasting force is insufficient, and the commercially available adhesive has almost no antifouling effect.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (10)
1. The antifouling adhesive is characterized by comprising a component A and a component B according to the weight ratio of 3-5:1, wherein the component A comprises the following raw material components: 500 parts of castor oil 450-one, 35-45 parts of molecular sieve, 10-20 parts of silicon dioxide, 50-70 parts of dipropylene glycol, 40-60 parts of neopentyl glycol, 2-4 parts of defoaming agent, 350 parts of barite powder 250-one, 15-25 parts of glycerol, 10-18 parts of surfactant, 2-4 parts of triethylene diamine and 15-25 parts of pepper essential oil; the component B is isocyanate.
2. The antifouling adhesive of claim 1 wherein the raw material component of the A component comprises: 480 parts of castor oil, 40 parts of molecular sieve, 15 parts of silicon dioxide, 60 parts of dipropylene glycol, 50 parts of neopentyl glycol, 3 parts of defoaming agent, 300 parts of barite powder, 18 parts of glycerol, 14 parts of surfactant, 3 parts of triethylene diamine and 20 parts of pepper essential oil.
3. The antifouling adhesive of claim 1 wherein the defoamer is a silicone defoamer and the surfactant is a low foaming nonionic surfactant.
4. A method for preparing an antifouling adhesive according to any of claims 1 to 3, comprising the steps of:
(1) placing castor oil in a stirring kettle, heating to 50-70 ℃, then sequentially adding a molecular sieve and silicon dioxide, and uniformly stirring to obtain a first mixture;
(2) continuously heating the first mixture to 75-85 ℃, then sequentially adding dipropylene glycol, neopentyl glycol and a defoaming agent, and uniformly stirring to obtain a second mixture;
(3) cooling the second mixture to 55-65 ℃, then sequentially adding barite powder, glycerol, a surfactant and triethylene diamine, and uniformly stirring to obtain a third mixture;
(4) continuously cooling the third mixture to below 40 ℃, then adding the pepper essential oil, and uniformly stirring to obtain a component A;
(5) and (3) mixing and stirring the component A and the component B uniformly to obtain the antifouling adhesive.
5. The method for preparing the antifouling adhesive according to claim 4, wherein in the step (1), the stirring speed is 40-60r/min, and the stirring time is 20-40 min.
6. The method for preparing an antifouling adhesive according to claim 4, wherein in the step (2), the stirring speed is 60-80r/min, and the stirring time is 100-150 min.
7. The method for preparing an antifouling adhesive according to claim 4, wherein in the step (3), the barite powder is added, the mixture is stirred at a stirring speed of 100-200r/min for 50-70min, after the adhesion is formed, the glycerol, the surfactant and the triethylene diamine are sequentially added, and the stirring is continued at the stirring speed for 50-70 min.
8. The method for preparing an antifouling adhesive according to claim 4, wherein in the step (4), the stirring speed is 100-120r/min, and the stirring time is 30-50 min.
9. The method for antifouling the surface of a marine vessel based on the antifouling adhesive according to any one of claims 1 to 3, which comprises the following specific steps: cleaning dirt on the surface of a ship body, spraying an antifouling adhesive on the surface of the ship body, and then carrying out electrostatic spraying flocking on the surface of the antifouling adhesive to obtain the antifouling adhesive.
10. Use of an antifouling adhesive according to any of claims 1 to 3 in surface antifouling materials.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911181179.4A CN110819293A (en) | 2019-11-27 | 2019-11-27 | Antifouling adhesive, preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201911181179.4A CN110819293A (en) | 2019-11-27 | 2019-11-27 | Antifouling adhesive, preparation method and application thereof |
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| CN110819293A true CN110819293A (en) | 2020-02-21 |
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Application publication date: 20200221 |