CN108610449B - Para-chloromethyl styrene/acrylic resin grafted methyl nicotinate pyridinium salt and novel marine antifouling paint prepared from same - Google Patents

Abstract

The invention discloses a p-chloromethyl styrene/acrylic resin grafted methyl nicotinate pyridinium salt and a novel marine antifouling coating prepared by using the same. The p-chloromethyl styrene/acrylic resin grafted methyl nicotinate pyridinium salt is prepared from the following components in percentage by mass: 0.1-1% of azodiisobutyronitrile, 0.1-1% of azoisobutyryl cyano formamide, 0.1-1% of benzoyl peroxide, 0.1-1% of isooctyl mercaptopropionate, 15-50% of p-xylene, 0.1-0.2% of o-dichlorobenzene, 3-10% of p-chloromethyl styrene, 40-65% of acrylic resin, 2-10% of methyl nicotinate and 4-15% of dimethylformamide; the total amount of the components is 100 percent.

Description

Para-chloromethyl styrene/acrylic resin grafted methyl nicotinate pyridinium salt and novel marine antifouling paint prepared from same

Technical Field

The invention relates to the technical field of marine corrosion and pollution prevention, in particular to a p-chloromethyl styrene/acrylic resin grafted methyl nicotinate pyridinium salt and a novel marine antifouling paint prepared from the same.

Background

The problem of marine fouling and adhesion continues to plague people during the development of marine economy and shipping industry. Marine fouling not only increases the resistance of the vessel in navigation and the consumption of fuel, accelerates the corrosion and degradation of the hull material, but also destroys the ecological balance of the water area. British international paint company has made statistics on fouling of the bottom of the ship and the increase in fuel consumption: if the bottom of the ship is polluted by 5%, the fuel consumption is increased by 10%; if the fouling of the ship bottom is more than 50%, the fuel consumption is increased by more than 40%. Since the organotin antifouling paint of 'special weapons' is completely forbidden in 1 month and 1 day in 2008, a compound paint system taking cuprous oxide as a main antifouling agent and an organic antifouling agent as an auxiliary antifouling agent is gradually formed. However, more and more researches show that even copper ions with low toxicity still slowly enrich in marine organisms and finally cause great harm to the marine organisms. Some countries have gradually started to restrict the use of cuprous oxide antifouling paints in some ports. International paint companies strive to develop environmentally friendly copper-free and tin-free antifouling paints. Such as: PPG company develops a copper-free tin-free self-polishing antifouling paint SIGMA NEXEONTM750 based on zinc acrylate resin.

Disclosure of Invention

The invention aims to provide a p-chloromethyl styrene/acrylic resin grafted methyl nicotinate pyridinium salt with excellent bactericidal effect.

The invention also provides a novel marine antifouling paint prepared by grafting methyl nicotinate pyridinium onto p-chloromethyl styrene/acrylic resin, and the paint has excellent sterilization antifouling property, good adhesive force and weather resistance.

The technical scheme adopted by the invention for solving the technical problems is as follows:

the p-chloromethyl styrene/acrylic resin grafted methyl nicotinate pyridinium salt is prepared from the following components in percentage by mass:

the total amount of the components is 100 percent.

Preferably, the p-chloromethyl styrene/acrylic resin grafted methyl nicotinate pyridinium salt is prepared from the following components in percentage by mass:

preferably, the acrylic resin is selected from one or more of butyl methacrylate, isobornyl methacrylate and 2-methoxyethyl 2-acrylate.

Further preferably, the acrylic resin is selected from one of the following combinations:

the combination is as follows:

butyl methacrylate and isobornyl methacrylate, the mass ratio of the butyl methacrylate to the isobornyl methacrylate is 1: 1.2-1.3;

combining two:

butyl methacrylate, isobornyl methacrylate and 2-acrylic acid-2-methoxyethyl ester, wherein the mass ratio of the butyl methacrylate to the isobornyl methacrylate to the 2-acrylic acid-2-methoxyethyl ester is 1: 1.2-1.3: 1.2-1.3.

The preparation method of the p-chloromethyl styrene/acrylic resin grafted methyl nicotinate pyridinium comprises the following three steps:

(1) adding 1/3 formula amount of azodiisobutyronitrile, and formula amount of isooctyl mercaptopropionate, p-xylene and o-dichlorobenzene into a reaction vessel, mixing, and heating to 100-110 ℃ to obtain a mixed solution I;

(2) weighing p-chloromethyl styrene, acrylic resin, benzoyl peroxide, azoisobutyryl cyano formamide with the formula amount of 1/3 and azobisisobutyronitrile with the formula amount of 2/3, mixing, dropwise adding into the mixed solution I at a constant speed for 3-4 hours by using a constant-pressure dropping funnel, heating to 120-130 ℃, and preserving heat for 1-2 hours to obtain a mixed solution II;

(3) and cooling the mixed solution II to 45-50 ℃, adding 2/3 formula amount of azo isobutyl cyano formamide and formula amount of methyl nicotinate and dimethyl formamide, reacting for 12-15 hours at a constant temperature, and cooling to room temperature to obtain the compound.

A novel marine antifouling paint is prepared by mixing the following raw materials in percentage by mass:

the total amount of the components is 100 percent.

Has the advantages that:

the invention synthesizes p-chloromethyl styrene/acrylic acid grafted methyl nicotinate pyridinium ester composite resin, and then an environment-friendly novel marine antifouling paint system is compounded.

Compared with the prior art, the invention is characterized in that:

(1) synthesizing a plurality of novel p-chloromethyl styrene/acrylic acid grafted methyl nicotinate pyridinium composite resins;

(2) acrylic resin containing trace biological bactericide, such as quaternary pyridinium or isoborneol, and the like is introduced into the main resin system, so that the resin matrix has a sterilization and antifouling effect;

(3) the pyridine quaternary ammonium salt bactericide is introduced with hydrophilic groups such as O atoms, ester groups and the like, so that the hydrophilic capacity is improved, bacteria in water are easier to adsorb on the surface of the resin, and the bactericidal activity is improved;

(4) the formula system has no copper and tin, and is a novel environment-friendly biological sterilization type antifouling coating;

(5) the adhesive force and the weather resistance of the resin are improved through the synergistic effect of the rosin resin and the silicone rubber adhesive;

(6) the novel marine antifouling paint disclosed by the invention has stronger antifouling capacity without adding an antifouling agent;

(7) the addition of the azo isobutyl cyano formamide is beneficial to adjusting the regulation of molecular weight and the narrow distribution of molecular weight;

(8) when the p-chloromethyl styrene/acrylic acid grafted methyl nicotinate pyridinium composite resin is prepared, the reaction solvent mainly comprises p-xylene and a small amount of o-dichlorobenzene, so that each reaction material, especially p-chloromethyl styrene, is fully dispersed in a reaction system, the reaction is fully carried out, the problems that reaction groups with sterilization antifouling effects are wound or groups cannot be added due to space crowding and the like are effectively avoided, and the sterilization antifouling effects of products are further ensured.

(9) For acrylic resins, the advantages of the combination one: butyl methacrylate provides proper hydrolysis performance, isobornyl methacrylate provides biological insecticidal and bacteriostatic performance, and the combination of the two is beneficial to release of the antifouling agent and stable polishing of resin. The advantage of the combination two: the addition of the soft monomer 2-acrylic acid-2-methoxyethyl ester can effectively reduce the viscosity, the hardness and the glass transition temperature of the resin, does not obviously reduce the polishing antifouling property of the resin, enlarges the application range of the resin, and can be used in particularly severe occasions such as: fishing nets, special equipment and the like can be applied.

Detailed Description

The present invention will be further illustrated by the following examples, which are intended to be merely illustrative and not limitative.

Example 1:

para-chloromethyl styrene/butyl methacrylate grafted methyl nicotinate pyridinium salt

The charge of the reaction materials is shown in Table 1, and the preparation method comprises the following three steps:

(1) adding 1/3 formula amount of azodiisobutyronitrile, and formula amount of isooctyl mercaptopropionate, p-xylene and o-dichlorobenzene to a reaction container, mixing, and heating to 100 ℃ to obtain a mixed solution I;

(2) weighing p-chloromethyl styrene, butyl methacrylate, benzoyl peroxide, azo isobutyl cyano formamide with the formula amount of 1/3 and azo diisobutyronitrile with the formula amount of 2/3 according to the formula amount, mixing, dropwise adding into the mixed solution I at a constant speed for 3 hours by using a constant-pressure dropping funnel, heating to 120 ℃, and preserving heat for 1 hour to obtain mixed solution II;

(3) and cooling the mixed solution II to 45 ℃, adding 2/3 formula amount of azo isobutyl cyano formamide and formula amount of methyl nicotinate and dimethyl formamide, reacting for 12 hours at a constant temperature, and cooling to room temperature to obtain the compound.

The resin had a number average molecular weight of 6848, a weight average molecular weight of 14531 and a dispersity of 3.12 by GPC. The reaction route is as follows:

example 2:

para-chloromethyl styrene/butyl methacrylate, isobornyl methacrylate graft methyl nicotinate pyridinium salt

The charge of the reaction materials is shown in Table 1, and the preparation method comprises the following three steps:

(1) adding 1/3 formula amount of azodiisobutyronitrile, and formula amount of isooctyl mercaptopropionate, p-xylene and o-dichlorobenzene to a reaction container, mixing, and heating to 110 ℃ to obtain a mixed solution I;

(2) weighing p-chloromethyl styrene, butyl methacrylate, isobornyl methacrylate, benzoyl peroxide, azo isobutyl cyano formamide in the formula amount of 1/3 and azo diisobutyronitrile in the formula amount of 2/3, mixing, dropwise adding into the mixed solution I at a constant speed for 4 hours by using a constant-pressure dropping funnel, heating to 130 ℃, and preserving heat for 2 hours to obtain a mixed solution II;

(3) and cooling the mixed solution II to 50 ℃, adding 2/3 formula amount of azo isobutyl cyano formamide and formula amount of methyl nicotinate and dimethyl formamide, reacting for 15 hours at a constant temperature, and cooling to room temperature to obtain the azoisobutyl cyano formamide.

The resin had a number average molecular weight of 6751, a weight average molecular weight of 14852 and a dispersity of 3.48 by GPC. The reaction scheme is as follows:

example 3:

p-chloromethyl styrene/butyl methacrylate, isobornyl methacrylate, 2-acrylic acid-2-methoxyethyl ester graft nicotinic acid methyl ester pyridinium salt

The charge of the reaction materials is shown in Table 1, and the preparation method comprises the following three steps:

(1) adding 1/3 formula amount of azodiisobutyronitrile, and formula amount of isooctyl mercaptopropionate, p-xylene and o-dichlorobenzene to a reaction vessel, mixing, and heating to 105 ℃ to obtain a mixed solution I;

(2) weighing p-chloromethyl styrene, butyl methacrylate, isobornyl methacrylate, 2-methoxyethyl acrylate, benzoyl peroxide, 1/3 formula amount of azoisobutyryl cyano formamide and 2/3 formula amount of azodiisobutyronitrile, mixing, dropwise adding into the mixed solution I at a constant speed for 3.5 hours by using a constant-pressure dropping funnel, heating to 125 ℃, and preserving heat for 1.5 hours to obtain a mixed solution II;

(3) and cooling the mixed solution II to 50 ℃, adding 2/3 formula amount of azo isobutyl cyano formamide and formula amount of methyl nicotinate and dimethyl formamide, reacting for 14 hours at a constant temperature, and cooling to room temperature to obtain the compound.

The resin had a number average molecular weight of 6723, a weight average molecular weight of 15193 and a dispersity of 3.98 by GPC. The reaction scheme is as follows:

comparative example 1

P-chloromethyl styrene/butyl methacrylate, isobornyl methacrylate, 2-acrylic acid-2-methoxyethyl ester graft nicotinic acid methyl ester pyridinium salt

The charge of the reaction materials is shown in Table 1, and the preparation method comprises the following three steps:

(1) adding 1/3 formula amount of azodiisobutyronitrile, and formula amount of isooctyl mercaptopropionate, p-xylene and o-dichlorobenzene to a reaction vessel, mixing, and heating to 105 ℃ to obtain a mixed solution I;

(2) weighing p-chloromethyl styrene, butyl methacrylate, isobornyl methacrylate, 2-acrylic acid-2-methoxyethyl ester, benzoyl peroxide and 2/3 azodiisobutyronitrile according to the formula amount, mixing, dropwise adding into the mixed solution I at a constant speed for 3.5 hours by using a constant-pressure dropping funnel, heating to 125 ℃, and preserving heat for 1.5 hours to obtain a mixed solution II;

(3) and cooling the mixed solution II to 50 ℃, adding methyl nicotinate and dimethylformamide according to the formula amount, keeping the temperature for reacting for 14 hours, and cooling to room temperature to obtain the compound.

The resin had a number average molecular weight of 6723, a weight average molecular weight of 15193 and a dispersity of 2.23 by GPC.

Comparative example 2

P-chloromethyl styrene/butyl methacrylate, isobornyl methacrylate, 2-acrylic acid-2-methoxyethyl ester graft nicotinic acid methyl ester pyridinium salt

The charge of the reaction materials is shown in Table 1, and the preparation method comprises the following three steps:

(1) adding 1/3 formula amount of azodiisobutyronitrile, and formula amount of isooctyl mercaptopropionate and p-xylene into a reaction vessel, mixing, and heating to 105 ℃ to obtain a mixed solution I;

(2) weighing p-chloromethyl styrene, butyl methacrylate, isobornyl methacrylate, 2-methoxyethyl acrylate, benzoyl peroxide, 1/3 formula amount of azoisobutyryl cyano formamide and 2/3 formula amount of azodiisobutyronitrile, mixing, dropwise adding into the mixed solution I at a constant speed for 3.5 hours by using a constant-pressure dropping funnel, heating to 125 ℃, and preserving heat for 1.5 hours to obtain a mixed solution II;

(3) and cooling the mixed solution II to 50 ℃, adding 2/3 formula amount of azo isobutyl cyano formamide and formula amount of methyl nicotinate and dimethyl formamide, reacting for 14 hours at a constant temperature, and cooling to room temperature to obtain the compound.

The resin had a number average molecular weight of 6723, a weight average molecular weight of 15193 and a dispersity of 1.28 by GPC.

It can be seen from the dispersion degree data that the dispersion degree is reduced to a certain extent when the azo-isobutyryl cyano formamide is not used, and the dispersion degree is obviously reduced when the reaction solvent is only p-xylene, which shows that the addition of the azo-isobutyryl cyano formamide and o-dichlorobenzene obviously improves the dispersion performance of the product.

TABLE 1 feed compositions for examples 1-3

And (3) testing the sterilization performance:

1. test strains:

representative strains, staphylococcus aureus, candida albicans, pseudomonas aeruginosa and pasteurella multocida are selected and purchased in the market.

2. And (3) strain culture medium:

nutrient agar medium and nutrient broth medium.

3. The specific test steps are as follows:

(1) preparing a bacterial liquid: the four strains are respectively inoculated on four agar culture media, cultured for 36 hours at 37 ℃, and typical colonies are respectively picked from the agar culture media and respectively inoculated in four fresh nutrient broth culture media, and cultured for 24 hours at the same temperature for standby.

(2) Subpackaging and marking strains: the strains cultured in the nutrient broth of step (1) for 24 hours were diluted 50-fold with sterile nutrient broth, and each strain was plated on 5 petri dishes.

(3) And (3) sterilization: each 1g of the resins obtained in examples 1 to 3 and comparative examples 1 to 2 was taken and placed in the petri dish in step (2).

5. And (3) test results:

four groups of strains are observed, the residual areas of the strains are measured, and the observation results are recorded and particularly shown in table 2.

TABLE 2 results of colony residual area

	Staphylococcus aureus	Candida albicans	Pseudomonas aeruginosa	Pasteurella multocida
					Example 1	0.5％	0.8％	0.7％	0.7％
Example 2	0.4％	0.6％	0.5％	0.4％
					Example 3	0.2％	0.4％	0.3％	0.1％
Comparative example 1	28.5％	23.5％	31.2％	30.5％
					Comparative example 2	27.6％	26.3％	36.3％	32.4％

As can be seen from Table 2, the resins of the present invention have significant synergistic bacteriostatic properties.

Example 4:

a novel marine antifouling paint is prepared by grafting methyl nicotinate pyridinium onto p-chloromethyl styrene/acrylic resin, and is prepared by uniformly mixing the components in the table 3. The antifouling times of examples 4 to 6 were all 5 years or more, and the antifouling times of comparative examples 3 to 4 were within two years.

TABLE 3 raw material compositions of examples 4-6 and comparative examples 3-4

	Example 4(kg)	Example 5(kg)	Example 6(kg)	COMPARATIVE EXAMPLE 3(kg)	COMPARATIVE EXAMPLE 4(kg)
						Example 1	10	0	0	0	0
Example 2	0	30	0	0	0
						Example 3	0	0	20	0	0
Comparative example 1	0	0	0	20	0
						Comparative example 2	0	0	0	0	20
Rosin resin	5	20	15	15	15
						Silicone rubberAdhesive agent	4	16	15	15	15
Zinc pyrithione	3	10	8	8	8
						Zineb	3	10	7	7	7
Pyridine triphenylboron	3	10	8	8	8
						Oleic acid amides	6	22	10	10	10
Phytic acid	0.5	2	1	1	1
						Zinc oxide	5	12	11	11	11
Iron oxide red	2	6	5	5	5

As a result of the tests, the results of the quality index tests of the novel marine antifouling paints of examples 4 to 6 and comparative examples 3 to 4 are shown in Table 4.

TABLE 4 quality index test results

Inspection item	Examples 4 to 6	Comparative examples 3 to 4	Inspection method
				Adhesion/grade	≤2	5-6	GB/T1720-79
Impact resistance/(kg. cm)	≥65	20-30	GB/T1732-93
				Flexibility/mm	≤2	4-5	GB/T1731-79
Oil resistance (Room temperature, 30d)	No change of paint	Foaming of the coating surface	GB/T1734-93
				2-year biofouling (%)	≤1	＞10	GB/T21805-2008
5-year-old biofouling (%)	≤5	＞50	GB/T21805-2008

As can be seen from Table 4, the coatings of examples 4-6 have adhesion, impact resistance, flexibility and oil resistance indexes that are significantly better than those of comparative examples 3-4; through the tests of 2 periods (2 years) and 5 periods (5 years) of the real sea hanging plate, the biological attachment amount of the examples 4-6 is obviously lower, which shows that the coating of the invention has better antifouling effect.

Although the present invention has been described with reference to the specific embodiments, it is not intended to limit the scope of the present invention, and various modifications and variations can be made by those skilled in the art without inventive changes based on the technical solution of the present invention.

Claims (1)

1. The preparation method of p-chloromethyl styrene/acrylic resin grafted methyl nicotinate pyridinium is characterized by comprising the following three steps:

(1) adding 1/3 formula amount of azodiisobutyronitrile, and formula amount of isooctyl mercaptopropionate, p-xylene and o-dichlorobenzene into a reaction vessel, mixing, and heating to 100-110 ℃ to obtain a mixed solution I;

(2) weighing p-chloromethyl styrene, acrylic resin, benzoyl peroxide, azoisobutyryl cyano formamide with the formula amount of 1/3 and azobisisobutyronitrile with the formula amount of 2/3, mixing, dropwise adding into the mixed solution I at a constant speed for 3-4 hours by using a constant-pressure dropping funnel, heating to 120-130 ℃, and preserving heat for 1-2 hours to obtain a mixed solution II;

(3) cooling the mixed solution II to 45-50 ℃, adding 2/3 formula amount of azo isobutyl cyano formamide and formula amount of methyl nicotinate and dimethyl formamide, reacting for 12-15 hours in a heat preservation manner, and cooling to room temperature to obtain the compound;

the p-chloromethyl styrene/acrylic resin grafted methyl nicotinate pyridinium salt is prepared from the following components in percentage by mass:

0.1 to 1 percent of azodiisobutyronitrile

0.1 to 1 percent of azo isobutyl cyano formamide

Benzoyl peroxide 0.1-1%

0.1 to 1 percent of isooctyl mercaptopropionate

15 to 50 percent of p-xylene

0.1 to 0.2 percent of o-dichlorobenzene

3 to 10 percent of p-chloromethyl styrene

40-65% of acrylic resin

2 to 10 percent of methyl nicotinate

4-15% of dimethylformamide;

the total amount of the components is 100 percent;

the acrylic resin is selected from one of the following combinations:

the combination is as follows:

butyl methacrylate and isobornyl methacrylate, the mass ratio of the butyl methacrylate to the isobornyl methacrylate is 1: 1.2-1.3;

combining two:

butyl methacrylate, isobornyl methacrylate and 2-acrylic acid-2-methoxyethyl ester, wherein the mass ratio of the butyl methacrylate to the isobornyl methacrylate to the 2-acrylic acid-2-methoxyethyl ester is 1: 1.2-1.3: 1.2-1.3.