A self-polishing antifouling paint and a method for its preparation

Abstract

The application relates to the technical field of marine paint, and particularly discloses a self-polishing antifouling paint and a preparation method thereof. The self-polishing antifouling paint comprises, by weight, 100 parts of capsaicin modified acrylic resin, 40-50 parts of rosin, 10-25 parts of chlorinated paraffin, 25-30 parts of dimethylbenzene, 110-150 parts of cuprous oxide, 35-50 parts of zinc oxide, 17-35 parts of copper pyrithione, 10-20 parts of talcum powder, 15-30 parts of red iron oxide and 10-15 parts of a dispersing agent. The self-polishing antifouling paint adopts the capsaicin modified acrylic resin as a base resin, the resin not only retains the excellent effect of capsaicin as an antifouling agent, reduces the use amount of cuprous oxide, but also greatly reduces the irritability of capsaicin in the production process.

Description

Technical Field

[0001] The invention relates to the technical field of marine coatings, in particular to a self-polishing antifouling paint and a preparation method thereof. Background Art

[0002] The marine environment is a complex environment of corrosion and fouling. Equipment immersed in seawater is inevitably affected by marine fouling organisms. Marine fouling organisms attach to the surface below the waterline of ships, not only affecting ship performance but also causing significant economic losses and waste of resources. Applying antifouling paint is currently the most important way to combat the impact of marine fouling organisms.

[0003] With growing environmental awareness, environmentally friendly antifouling agents have become a research focus. Capsaicin, a natural product, has been used as an antifouling agent. Currently, most capsaicin antifouling paints are prepared by directly adding capsaicin to the paint. For example, CN110484139A discloses a capsaicin antifouling paint that directly mixes capsaicin with other raw materials. However, relevant tests have shown that directly adding capsaicin to produce antifouling paints can cause strong irritation to workers during production and application due to its volatilization, which is detrimental to production and application. Summary of the Invention

[0004] In response to the above problems, the first object of the present invention is to provide a self-polishing antifouling paint that uses a capsaicin-modified acrylic resin as a base resin. This resin not only retains the excellent effect of capsaicin as an antifouling agent and reduces the amount of cuprous oxide used, but also greatly reduces the irritation of capsaicin during the production process.

[0005] The second object of the present invention is to provide a method for preparing the above-mentioned self-polishing antifouling paint. The antifouling paint prepared by this method has excellent antifouling ability and good physical properties, and can meet the antifouling requirements of various types of marine engineering equipment.

[0006] The first technical solution adopted by the present invention is: a self-polishing antifouling paint, comprising the following components in parts by weight:

[0007] 100 parts of capsaicin-modified acrylic resin;

[0008] 40-50 parts of rosin;

[0009] 10-25 parts of chlorinated paraffin;

[0010] 25-30 parts of xylene;

[0011] 110-150 parts of cuprous oxide;

[0012] 35-50 parts of zinc oxide;

[0013] 17-35 parts of copper pyrithione;

[0014] 10-20 parts of talcum powder;

[0015] 15-30 parts of red iron oxide;

[0016] 10-15 parts of dispersant;

[0017] Wherein, the capsaicin-modified acrylic resin is prepared by the following method:

[0018] S1: adding xylene to a reaction container; uniformly mixing the monomer mixture and the initiator to obtain a monomer and initiator mixture; dropwise adding the monomer and initiator mixture into the xylene to obtain an acrylic acid prepolymer; the monomer mixture comprises acrylic acid and an acrylate monomer;

[0019] S2: adding capsaicin to the acrylic prepolymer, grafting capsaicin to the acrylic prepolymer through an esterification reaction, and obtaining a capsaicin-modified acrylic resin.

[0020] Preferably, the mass ratio of xylene to the monomer mixture in step S1 is 1:1.

[0021] Preferably, the acrylic acid in step S1 accounts for 10% to 30% of the total mass of the monomer mixture.

[0022] Preferably, the acrylic acid ester monomer in step S1 is one or more of methyl acrylate, methyl methacrylate, ethyl acrylate, and ethyl methacrylate.

[0023] Preferably, the initiator in step S1 is azobisisobutyl cyanide, and the amount of the initiator used is 4% to 10% of the total mass of the monomer mixture.

[0024] Preferably, the step S1 includes:

[0025] Add xylene to a reaction container, stir and heat to 75° C. to 95° C.; uniformly mix the monomer mixture and the initiator to obtain a monomer and initiator mixture; dropwise add the monomer and initiator mixture into the xylene, add for 1 to 2 hours, and then continue to react for 1 to 4 hours to obtain an acrylic prepolymer.

[0026] Preferably, the mass ratio of capsaicin to acrylic acid in step S2 is 1:(1-5).

[0027] Preferably, step S2 includes:

[0028] Capsaicin is added to a reaction container, and capsaicin is grafted onto the acrylic prepolymer through an esterification reaction. After the reaction is completed until the solution becomes transparent, the temperature is raised to 140° C. to remove water. The reaction is stopped after no water is evaporated from the reaction container to obtain a capsaicin-modified acrylic resin.

[0029] The second technical solution adopted by the present invention is: a method for preparing the self-polishing antifouling paint as described in the first technical solution, comprising the following steps:

[0030] S10: weigh each component and set aside;

[0031] S20: capsaicin modified acrylic resin, rosin, chlorinated paraffin, xylene, cuprous oxide, zinc oxide, copper pyrithione, talc, red iron oxide, and a dispersant are mixed, dispersed, and filtered to prepare a self-polishing antifouling paint.

[0032] Beneficial effects of the above technical solution:

[0033] (1) The self-polishing antifouling paint disclosed in the present invention uses capsaicin-modified acrylic resin as a base resin. The resin not only retains the excellent effect of capsaicin as an antifouling agent and reduces the amount of cuprous oxide used, but also greatly reduces the irritation of capsaicin during the production process.

[0034] (2) The self-polishing antifouling paint provided by the present invention has excellent antifouling ability and good physical properties, and can meet the antifouling requirements of various types of marine engineering equipment.

[0035] (3) Currently commonly used zinc acrylate self-polishing resins and silicone acrylate self-polishing resins only have self-polishing properties but no antifouling properties. Although copper acrylate self-polishing resins release copper ions upon hydrolysis, the copper ion content is low and they also do not have antifouling properties. The capsaicin-modified acrylic resin used in the present invention not only has self-polishing properties, but also exhibits strong antifouling properties after the capsaicin on the side chains is hydrolyzed in seawater. Using capsaicin-modified acrylic resin as the base resin can effectively reduce the amount of cuprous oxide used.

[0036] (4) Compared with the existing method for preparing capsaicin-modified acrylic resin, the present invention not only retains the antifouling performance of capsaicin by grafting capsaicin onto acrylic resin, but also can significantly reduce the irritation during the antifouling paint coating process, thereby having better antifouling performance. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] Figure 1 The present invention is a process flow chart of a method for preparing a self-polishing antifouling paint. DETAILED DESCRIPTION

[0038] The present invention is further described below through specific embodiments. It should be pointed out that for ordinary technicians in this field, several modifications and improvements can be made without departing from the principles of the present invention, and these should also be regarded as falling within the scope of protection of the present invention.

[0039] The contents not described in detail in the specification of the present invention belong to the common knowledge of professionals in this field.

[0040] The present invention discloses a self-polishing antifouling paint, which comprises the following components in parts by weight:

[0041] 100 parts of capsaicin-modified acrylic resin;

[0042] 40-50 parts of rosin;

[0043] 10-25 parts of chlorinated paraffin;

[0044] 25-30 parts of xylene;

[0045] 110-150 parts of cuprous oxide;

[0046] 35-50 parts of zinc oxide;

[0047] 17-35 parts of copper pyrithione;

[0048] 10-20 parts of talcum powder;

[0049] 15-30 parts of red iron oxide;

[0050] 10-15 parts of dispersant.

[0051] Wherein, capsaicin modified acrylic resin is prepared by the following method:

[0052] S1: adding xylene to a reaction vessel, stirring and heating to 75° C. to 95° C.; uniformly mixing the monomer mixture and the initiator to obtain a monomer and initiator mixture; dropwise adding the monomer and initiator mixture to the xylene for 1 to 2 hours, and then continuing the reaction for 1 to 4 hours to obtain an acrylic prepolymer;

[0053] The mass ratio of xylene to monomer mixture is 1:1; the monomer mixture is composed of acrylic acid and acrylate monomers, the acrylic acid accounts for 10% to 30% of the total mass of the monomer mixture, and the acrylate monomer is one or more of methyl acrylate, methyl methacrylate, ethyl acrylate, and ethyl methacrylate; the initiator is azobisisobutyl cyanide, and the amount of the initiator is 4% to 10% of the total mass of the monomer mixture;

[0054] S2: adding capsaicin to a reaction vessel, grafting capsaicin to the acrylic acid prepolymer through an esterification reaction, reacting until the solution becomes transparent, then heating to 140° C. to remove water; stopping the reaction after no water is evaporated from the reaction vessel to obtain a capsaicin-modified acrylic resin; the mass ratio of capsaicin to acrylic acid is 1:(1-5).

[0055] like Figure 1 As shown, the self-polishing antifouling paint is prepared by the following steps:

[0056] S10: Accurately weigh each component in a dry environment and set aside;

[0057] S20: Capsaicin-modified acrylic resin, rosin, chlorinated paraffin, xylene, cuprous oxide, zinc oxide, copper pyrithione, talc, red iron oxide, and a dispersant are fully mixed, dispersed well, and filtered to prepare a self-polishing antifouling paint.

[0058] The prepared self-polishing antifouling paint was subjected to a shallow sea immersion test in sea areas in accordance with GB / T 5370.

[0059] Example 1

[0060] A self-polishing antifouling paint comprising the following components in parts by weight:

[0061] 100 parts of capsaicin-modified acrylic resin;

[0062] 50 parts of rosin;

[0063] 10 parts of chlorinated paraffin;

[0064] 30 parts of xylene;

[0065] 130 parts of cuprous oxide;

[0066] 40 parts of zinc oxide;

[0067] 20 parts of copper pyrithione;

[0068] 15 parts of talcum powder;

[0069] 20 parts of red iron oxide;

[0070] 10 parts of dispersant.

[0071] Capsaicin modified acrylic resin was prepared according to the following process:

[0072] Step 1: Add 250g of xylene to a reaction vessel, stir and heat to 75°C; mix 25g of acrylic acid, 75g of methyl methacrylate, 150g of ethyl acrylate monomer mixture and 10g of initiator azobisisobutylcyanide, and then add dropwise to the xylene for 2h. After the addition is completed, continue the reaction for 4h to obtain an acrylic acid prepolymer;

[0073] Step two: 25g capsaicin is added to the reaction vessel, and capsaicin is grafted with acrylic acid prepolymer through esterification reaction, and the temperature is raised to 140℃ to remove water after the solution is transparent; the reaction is stopped after no water vapor is out of the reaction vessel, and a capsaicin modified acrylic resin is obtained.

[0074] The capsaicin modified acrylic resin, rosin, chlorinated paraffin, xylene, cuprous oxide, zinc oxide, copper pyrithione, talc, red iron oxide, and dispersant are mixed and dispersed well and filtered to obtain the self-polishing antifouling paint.

[0075] The prepared self-polishing antifouling paint is subjected to shallow sea immersion test, and after 24 months, there is no obvious marine organism attachment in the effective area of the test plate surface.

[0076] Example 2

[0077] A self-polishing antifouling paint, comprising the following components by weight:

[0078] 100 parts of capsaicin modified acrylic resin;

[0079] 40 parts of rosin;

[0080] 25 parts of chlorinated paraffin;

[0081] 25 parts of xylene;

[0082] 110 parts of cuprous oxide;

[0083] 50 parts of zinc oxide;

[0084] 35 parts of copper pyrithione;

[0085] 20 parts of talc;

[0086] 30 parts of red iron oxide;

[0087] 15 parts of dispersant.

[0088] The capsaicin modified acrylic resin is prepared by the following process:

[0089] Step one: 250g of xylene is added to the reaction vessel, stirred and heated to 85℃; 75g of acrylic acid, 75g of methyl acrylate, and 100g of methyl methacrylate monomer mixture are mixed with 20g of initiator azobisisobutyronitrile, and then added dropwise into the xylene, the dropping time is 2h, and the reaction is continued for 1h after the dropping is completed to obtain an acrylic acid prepolymer;

[0090] Step two: 50g of capsaicin is added to the reaction vessel, and capsaicin is grafted with acrylic acid prepolymer through esterification reaction, and the temperature is raised to 140℃ to remove water after the solution is transparent; the reaction is stopped after no water vapor is out of the reaction vessel, and a capsaicin modified acrylic resin is obtained.

[0091] Capsaicin modified acrylic resin, rosin, chlorinated paraffin, xylene, cuprous oxide, zinc oxide, copper pyrithione, talcum powder, red iron oxide and dispersant are fully mixed, well dispersed and filtered to prepare the self-polishing antifouling paint.

[0092] The prepared self-polishing antifouling paint was subjected to a shallow sea immersion test. After 24 months, no obvious marine organisms were found to be attached to the effective area of ​​the test plate surface.

[0093] Example 3

[0094] A self-polishing antifouling paint comprising the following components in parts by weight:

[0095] 100 parts of capsaicin-modified acrylic resin;

[0096] 45 parts of rosin;

[0097] 20 parts of chlorinated paraffin;

[0098] 25 parts of xylene;

[0099] 130 parts of cuprous oxide;

[0100] 40 parts of zinc oxide;

[0101] 20 parts of copper pyrithione;

[0102] 15 parts of talcum powder;

[0103] 20 parts of red iron oxide;

[0104] 13 parts of dispersant.

[0105] Capsaicin modified acrylic resin was prepared according to the following process:

[0106] Step 1: Add 250g of xylene to a reaction vessel, stir and heat to 95°C; mix 50g of acrylic acid, 50g of methyl methacrylate, 150g of ethyl acrylate monomer mixture and 15g of initiator azobisisobutylcyanide, and then add dropwise to the xylene for 1 hour. After the addition is completed, continue the reaction for 2 hours to obtain an acrylic acid prepolymer;

[0107] Step 2: Add 20g of capsaicin to a reaction vessel, graft capsaicin with an acrylic acid prepolymer through an esterification reaction, react until the solution becomes transparent, then heat to 140°C to remove water; stop the reaction when no water is evaporated from the reaction vessel to obtain a capsaicin-modified acrylic resin.

[0108] Capsaicin modified acrylic resin, rosin, chlorinated paraffin, xylene, cuprous oxide, zinc oxide, copper pyrithione, talcum powder, red iron oxide and dispersant are fully mixed, well dispersed and filtered to prepare the self-polishing antifouling paint.

[0109] The prepared self-polishing antifouling paint was subjected to a shallow sea immersion test. After 24 months, no obvious marine organisms were found to be attached to the effective area of ​​the test plate surface.

[0110] Example 4

[0111] A self-polishing antifouling paint comprising the following components in parts by weight:

[0112] 100 parts of capsaicin-modified acrylic resin;

[0113] 50 parts of rosin;

[0114] 10 parts of chlorinated paraffin;

[0115] 30 parts of xylene;

[0116] 150 parts of cuprous oxide;

[0117] 35 parts of zinc oxide;

[0118] 17 parts of copper pyrithione;

[0119] 10 parts of talcum powder;

[0120] 15 parts of red iron oxide;

[0121] 12 parts of dispersant.

[0122] Capsaicin modified acrylic resin was prepared according to the following process:

[0123] Step 1: Add 250g of xylene to a reaction vessel, stir and heat to 80°C; mix 50g of acrylic acid, 175g of methyl acrylate, 25g of ethyl methacrylate monomer mixture and 25g of initiator azobisisobutylcyanide, and then add dropwise to the xylene for 1 hour. After the addition is completed, continue the reaction for 1 hour to obtain an acrylic acid prepolymer;

[0124] Step 2: Add 10g of capsaicin to a reaction vessel, graft capsaicin with an acrylic acid prepolymer through an esterification reaction, react until the solution becomes transparent, then heat to 140°C to remove water; stop the reaction when no water is evaporated from the reaction vessel to obtain a capsaicin-modified acrylic resin.

[0125] Capsaicin modified acrylic resin, rosin, chlorinated paraffin, xylene, cuprous oxide, zinc oxide, copper pyrithione, talcum powder, red iron oxide and dispersant are fully mixed, well dispersed and filtered to prepare the self-polishing antifouling paint.

[0126] The prepared self-polishing antifouling paint was subjected to a shallow sea immersion test. After 24 months, no obvious marine organisms were found to be attached to the effective area of ​​the test plate surface.

[0127] Example 5

[0128] A self-polishing antifouling paint comprising the following components in parts by weight:

[0129] 100 parts of capsaicin-modified acrylic resin;

[0130] 50 parts of rosin;

[0131] 10 parts of chlorinated paraffin;

[0132] 30 parts of xylene;

[0133] 120 parts of cuprous oxide;

[0134] 45 parts of zinc oxide;

[0135] 20 parts of copper pyrithione;

[0136] 13 parts of talc;

[0137] 17 parts of red iron oxide;

[0138] 13 parts of dispersant.

[0139] Capsaicin modified acrylic resin was prepared according to the following process:

[0140] Step 1: Add 250g of xylene to a reaction vessel, stir and heat to 75°C; mix 75g of acrylic acid, 100g of methyl methacrylate, 75g of ethyl acrylate monomer mixture and 25g of initiator azobisisobutylcyanide, and then add dropwise to the xylene for 1 hour. After the addition is completed, continue the reaction for 1 hour to obtain an acrylic acid prepolymer;

[0141] Step 2: Add 25g of capsaicin to a reaction vessel, graft capsaicin with an acrylic acid prepolymer through an esterification reaction, react until the solution becomes transparent, then heat to 140°C to remove water; stop the reaction when no water is evaporated from the reaction vessel to obtain a capsaicin-modified acrylic resin.

[0142] Capsaicin modified acrylic resin, rosin, chlorinated paraffin, xylene, cuprous oxide, zinc oxide, copper pyrithione, talcum powder, red iron oxide and dispersant are fully mixed, well dispersed and filtered to prepare the self-polishing antifouling paint.

[0143] The prepared self-polishing antifouling paint was subjected to a shallow sea immersion test. After 24 months, no obvious marine organisms were found to be attached to the effective area of ​​the test plate surface.

[0144] Comparative Example 1

[0145] The capsaicin-modified acrylic resin is prepared by the following process:

[0146] Step one: 250g of xylene is added to a reaction vessel, stirred and heated to 75°C; 25g of acrylic acid, 75g of methyl methacrylate, 150g of an ethyl acrylate monomer mixture and 5g of an initiator azobisisobutyronitrile are mixed uniformly and then added dropwise to the xylene, the dropping time is 2h, after the dropping is completed, the reaction is continued for 4h to obtain an acrylic acid prepolymer;

[0147] Step two: 25g of capsaicin is added to the reaction vessel, the capsaicin is grafted with the acrylic acid prepolymer through esterification, after the solution becomes transparent, the temperature is raised to 140°C to remove water; after no water vapor is generated in the reaction vessel, the reaction is stopped to obtain a capsaicin-modified acrylic resin.

[0148] The capsaicin-modified acrylic resin is in a gel state and has no flowability and cannot be used.

[0149] Comparative Example 2

[0150] The capsaicin-modified acrylic resin is prepared by the following process:

[0151] Step one: 250g of xylene is added to a reaction vessel, stirred and heated to 75°C; 25g of acrylic acid, 75g of methyl methacrylate, 150g of an ethyl acrylate monomer mixture and 5g of an initiator azobisisobutyronitrile are mixed uniformly and then added dropwise to the xylene, the dropping time is 2h, after the dropping is completed, the reaction is continued for 4h to obtain an acrylic acid prepolymer;

[0152] Step two: 25g of capsaicin is added to the reaction vessel, the capsaicin is grafted with the acrylic acid prepolymer through esterification, after the solution becomes transparent, the temperature is raised to 140°C to remove water; after no water vapor is generated in the reaction vessel, the reaction is stopped to obtain a capsaicin-modified acrylic resin.

[0153] Comparative Example 3

[0154] A self-polishing antifouling paint comprises the following components by weight parts:

[0155] Capsaicin-modified acrylic resin 100 parts;

[0156] Rosin 50 parts;

[0157] Chlorinated paraffin 10 parts;

[0158] Xylene 30 parts;

[0159] Cuprous oxide 130 parts;

[0160] Zinc oxide 40 parts;

[0161] Copper pyrithione 20 parts;

[0162] 15 parts of talcum powder;

[0163] 20 parts of red iron oxide;

[0164] 10 parts of dispersant.

[0165] Capsaicin modified acrylic resin is prepared according to the process disclosed in CN108341909A; capsaicin modified acrylic resin, rosin, chlorinated paraffin, xylene, cuprous oxide, zinc oxide, copper pyrithione, talc, red iron oxide, and a dispersant are fully mixed, well dispersed, and filtered to obtain a self-polishing antifouling paint.

[0166] The self-polishing antifouling paint prepared in Comparative Example 3 was subjected to a shallow sea immersion test. After 24 months, obvious marine organisms were found to be attached to the effective area of ​​the test plate surface.

[0167] By comparing the shallow sea hanging boards in Examples 1 to 5 and Comparative Example 3, there is no obvious marine organism attachment within the effective area of ​​the test boards in Examples 1 to 5, and the results are better; while there is obvious marine organism attachment on the surface of the test board in Comparative Example 3; this shows that the capsaicin-modified acrylic resin prepared by the method disclosed in the present invention has a better anti-fouling effect.

[0168] The present invention has been described in detail. The above description is illustrative and not exhaustive, and is not limited to the disclosed embodiments; the above description should not be construed as limiting the present invention. Those skilled in the art will appreciate that various equivalent substitutions, modifications, or improvements may be made to the technical solutions and implementations of the present invention without departing from the spirit and scope of the present invention, all of which fall within the scope of the present invention; the scope of protection of the present invention shall be determined by the appended claims.

Claims

1. A self-polishing antifouling paint, characterized in that: The following components are included in parts by weight: 100 parts of capsaicin-modified acrylic resin; 40-50 parts of rosin; 10-25 parts of chlorinated paraffin; 25-30 parts of xylene; 110-150 parts of cuprous oxide; 35-50 parts of zinc oxide; 17-35 parts of copper pyrithione; 10-20 parts of talcum powder; 15-30 parts of red iron oxide; 10-15 parts of dispersant; Wherein, the capsaicin-modified acrylic resin is prepared by the following method: S1: adding xylene to a reaction vessel; uniformly mixing a monomer mixture and an initiator to obtain a monomer and initiator mixture; and dropwise adding the monomer and initiator mixture into the xylene to obtain an acrylic acid prepolymer; the monomer mixture comprises acrylic acid and an acrylate monomer; the acrylic acid accounts for 10% to 30% of the total weight of the monomer mixture; the initiator is azobisisobutyl cyanide, and the amount of the initiator used is 4% to 10% of the total weight of the monomer mixture; S2: adding capsaicin to the acrylic acid prepolymer, grafting capsaicin to the acrylic acid prepolymer through an esterification reaction, and obtaining a capsaicin-modified acrylic resin; the mass ratio of the capsaicin to the acrylic acid is 1:(1-5).

2. The self-polishing antifouling paint according to claim 1, characterized in that The mass ratio of xylene to the monomer mixture in step S1 is 1:

1.

3. The self-polishing antifouling paint according to claim 1, characterized in that The acrylic acid ester monomer in step S1 is one or more of methyl acrylate, methyl methacrylate, ethyl acrylate, and ethyl methacrylate.

4. The self-polishing antifouling paint according to claim 1, characterized in that The step S1 comprises: Add xylene to a reaction container, stir and heat to 75° C. to 95° C.; uniformly mix the monomer mixture and the initiator to obtain a monomer and initiator mixture; dropwise add the monomer and initiator mixture to the xylene, add for 1 to 2 hours, and then continue to react for 1 to 4 hours to obtain an acrylic prepolymer.

5. The self-polishing antifouling paint according to claim 1, characterized in that The step S2 comprises: Capsaicin is added to a reaction container, and capsaicin is grafted onto the acrylic prepolymer through an esterification reaction. After the reaction is completed until the solution becomes transparent, the temperature is raised to 140° C. to remove water. The reaction is stopped after no water is evaporated from the reaction container to obtain a capsaicin-modified acrylic resin.

6. A method for preparing a self-polishing antifouling paint according to any one of claims 1 to 5, characterized in that: The following steps are involved: S10: weigh each component and set aside; S20: capsaicin modified acrylic resin, rosin, chlorinated paraffin, xylene, cuprous oxide, zinc oxide, copper pyrithione, talc, red iron oxide, and a dispersant are mixed, dispersed, and filtered to prepare a self-polishing antifouling paint.

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