CN111574654B

CN111574654B - Structure and preparation method of acrylate antifouling resin containing benzo [ d ] isothiazoline-3-ketone-triazine-based monomer

Info

Publication number: CN111574654B
Application number: CN201910997833.2A
Authority: CN
Inventors: 杨建新; 董苗; 王雪梅; 林强; 王向辉
Original assignee: Hainan University
Current assignee: Hainan University
Priority date: 2019-10-21
Filing date: 2019-10-21
Publication date: 2021-09-17
Anticipated expiration: 2039-10-21
Also published as: CN111574654A

Abstract

The invention relates to the field of marine antifouling, and uses 1,2-benzo[d]isothiazoline-3-ketone (BIT) and cyanuric chloride (CNC) as raw materials to prepare a BIT-allyloxy The triazine monomer was copolymerized with acrylate monomer to prepare an acrylate antifouling resin grafted with BIT active structural unit. The method for preparing a BIT-triazine-based antifouling resin monomer comprises: at a temperature of 0-25° C., firstly reacting CNC and propenyl alcohol to obtain alkenyloxytriazine, and then reacting with BIT to obtain BIT-triazine base antifouling resin monomer. The invention also discloses the structure and method of the BIT-triazine-based marine antifouling resin prepared by the copolymerization reaction of the above-mentioned monomer and acrylate. The BIT-triazine-based antifouling resin monomer provided by the present invention has excellent polymerizability, and can be self-polymerized or copolymerized with other monomers, and the obtained BIT-triazine-based antifouling resin has a relatively high molecular weight. The active substance is not easy to diffuse and lose, and at the same time, the release rate can be controlled by the hydrolysis of the ester bond, so that the antifouling active substance can be efficiently utilized, and it is expected to become a green and efficient new marine antifouling coating.

Description

Structure and preparation method of acrylate antifouling resin containing benzo [ d ] isothiazoline-3-ketone-triazine-based monomer

Technical Field

The invention relates to the field of marine antifouling paint, in particular to benzo [ d ] isothiazoline-3-ketone-triazine antifouling resin monomer and a structure of copolymer type acrylate antifouling resin thereof, and preparation methods of the benzo [ d ] isothiazoline-3-ketone-triazine antifouling resin monomer and the copolymer type acrylate antifouling resin. The antifouling resin copolymer contains benzo [ d ] isothiazoline-3-ketone structural units, and can be used for marine antifouling coatings, industrial bactericidal coatings and the like.

Background

The ocean is used as a treasury of human living resources and energy, creates abundant material wealth and convenient traffic for the development of the human society, and the reasonable development and utilization of the ocean resources become development strategies of various countries. China has a wide sea area, the ocean area is about more than 300 ten thousand square kilometers, and the development and utilization of ocean resources become a necessary way for the development of economic society. The marine biofouling refers to the phenomenon of biofouling formed by the adhesion and growth of marine microorganisms, animals and plants on the surface of a ship body or an underwater solid facility. Marine biofouling can increase the roughness of hull bottom surface and even destroy hull surface, increases the resistance that boats and ships navigation in-process received, and then causes a series of problems such as boats and ships navigation speed slowdown, fuel use increase. In addition, the marine fouling organisms also generate acidic organic matters in the growth process, corrode ships, block pipeline systems, reduce the service life and influence marine transportation and production activities. According to incomplete statistics, the economic loss due to marine fouling worldwide reaches billions of dollars each year.

In order to prevent marine biofouling, many techniques and methods for marine biofouling have been developed, and the most effective method at present is to paint a functional marine antifouling paint. The early-appearing organic tin antifouling paint generates serious marine organism accumulated toxicity and harms marine ecological environment due to continuous release of tributyl tin compounds, and the international marine environment protection committee forbids the organic tin antifouling paint in 2008. The released copper ions of the organic copper-containing antifouling paint which is widely used at present can be gathered in estuary, and the ecological balance of the ocean is damaged. Therefore, the development of a novel non-toxic or low-toxic and environmentally friendly marine antifouling paint has become an urgent problem to be solved in the field.

Benzo [ d ] isothiazolin-3-ketone (BIT) compound is a high-efficiency bactericidal and algae-inhibiting compound, belongs to a biosynthesis inhibitor, and an active part on a heterocycle forms a hydrogen bond with a base in a protein in a bacterium body and is adsorbed on a cell of the bacterium, so that the structure of DNA in the cell is damaged, the replication capacity of the DNA is lost, and finally an organism is killed. The BIT compounds have high antibacterial activity and very low toxicity, and are particularly useful for killing bacteria and fungi. In recent years, more intensive research on BIT has been carried out, and certain research results have been obtained when BIT is used for marine antifouling paint. However, in terms of structure, BIT belongs to a small molecular compound, so that the use mainly depends on physical addition and mixing, and in the actual application process, the defects of poor water solubility, serious dialysis, short duration of drug effect and the like occur, so that the use range of the BIT is limited to a certain extent.

The invention provides a BIT-triazine structure grafted acrylic antifouling resin and a preparation method thereof, and the prepared BIT-triazine antifouling resin monomer can be used as a bactericide and can be subjected to copolymerization reaction with other double-bond-containing functional monomers to prepare the BIT-triazine antifouling resin with antifouling property. The BIT is connected to the main chain of the acrylic resin in a chemical bond mode, so that the BIT is not easy to diffuse and run away in the using process, and active substances such as the BIT and the like can be slowly and uniformly released through hydrolysis of a C-N bond and a C-O bond. The use effect is improved, the use time is prolonged, and the defects of the micromolecule antifouling paint are overcome.

Disclosure of Invention

The invention provides a structure of a monomer containing a BIT-triazine system and antifouling resin and a preparation method thereof, and an antifouling paint prepared from the resin has good antifouling performance and self-polishing performance.

A structure of BIT-triazinyl monomer represented by the following formula 1, wherein R is propylenoxy, 2-methylallyloxy, 2-butenyloxy, 2-methyl-2-butenyloxy, 3-butenyloxy or 3-methyl-3-butenyloxy.

BIT-triazine-based antifouling resin monomer, characterized in thatThe method is implemented by the following steps: adding allyl alcohol or its derivative into flask, stirring while cooling, controlling temperature below 5 deg.C, adding cyanuric chloride and acid-binding agent, respectively, and adding N₂The reaction was stirred for 4 h under protection and stopped. Mixing the reaction solution with ethyl acetate, extracting and washing the mixture for three times, drying the mixture for 12 hours by using anhydrous magnesium sulfate, and filtering the mixture to obtain filtrate, wherein the filtrate is a solution containing 2-propenyloxy-4, 6-dichloro-1, 3, 5-triazine. Then, continuously adding BIT, stirring at room temperature for 8 h, and adjusting the pH to be neutral by using an acid-binding agent in the reaction process. And (4) carrying out suction filtration, extracting the filtrate by using ethyl acetate, washing the filtrate by using deionized water for three times, and drying the filtrate for 12 hours by using anhydrous magnesium sulfate. Filtering, distilling the filtrate to remove the solvent to obtain the BIT-triazine base antifouling resin monomer 2-propylene oxy-4, 6-dibit-1, 3, 5-triazine. The allyl alcohol or the derivative thereof includes but is not limited to allyl alcohol, 2-butenol, 3-butenol, 2-methylbutenol and the like.

An acrylate antifouling resin containing BIT-triazine functional monomer, which is characterized in that the structure is shown in figure 2.

The preparation method of the BIT-triazine acrylate antifouling resin is characterized by comprising the following steps: adding a solvent into a three-necked bottle, heating to 80-85 ℃, uniformly mixing an initiator, a BIT-triazine-based monomer and an acrylate monomer according to a mass ratio, dropwise adding at a dropping speed of within 3-4 seconds per drop, adding a small amount of initiator after 3 hours of dropwise adding, reacting for 10-12 hours, and cooling to room temperature to obtain red transparent resin, namely the acrylate antifouling resin containing the BIT-triazine-based functional monomer.

The BIT-triazine monomer accounts for 5-50 wt% of the total amount of the mixed monomer, the acrylate monomer is at least one of methyl methacrylate, methyl acrylate, ethyl acrylate, hydroxyethyl acrylate, butyl acrylate and butyl methacrylate, and the amount of the acrylate monomer accounts for 50-95 wt% of the total amount of the mixed monomer. The solvent is toluene, xylene, n-butanol or n-pentanol, or a mixture thereof. The initiator is azobisisobutyronitrile or benzoyl peroxide or a mixture thereof. The resin prepared by the method is used as the base resin of the antifouling paint to prepare the antifouling paint, and the antifouling paint has good film forming performance and physical and mechanical properties, and has excellent self-polishing performance and marine antifouling performance.

The innovation points and advantages of the invention are as follows: the compound BIT has the advantages of strong antibacterial ability, low toxicity and easy compatibility with other additives, but can only be added physically, and in the practical application process, the compound BIT has poor water solubility, can cause serious dialysis and is difficult to maintain the drug effect for a long time. The invention firstly carries out structural modification on the BIT molecule to obtain the BIT monomer structure containing alkenyl. The prepared BIT-monomer has good polymerizability, and the antifouling resin with higher molecular weight and grafted BIT active groups can be obtained through copolymerization, so that the antifouling agent is not easy to diffuse and run off in the use process, and the release rate can be controlled through hydrolysis of ester bonds, so that the antifouling agent is efficiently utilized.

The preparation method provided by the invention has the advantages of simple synthetic route, mild conditions, low cost and suitability for large-scale production, and the antifouling resin has good development prospect in the field of marine antifouling paint.

The invention is described in more detail below by way of example.

Example 1

Synthesis of BIT-triazine-based antifouling resin monomer 1 (FIG. 1-a): adding 10 mL of propylene alcohol into a two-neck flask with a stirring device, controlling the temperature below 5 ℃ under the condition of ice-water bath, sequentially adding 1.85 g of cyanuric chloride and 1.05 g of sodium bicarbonate, reacting for 0.5 h, naturally heating to room temperature, continuously stirring for reacting for 2h, and stopping the reaction. Mixing the reaction solution with ethyl acetate, extracting and washing with water, repeating the operation for three times, drying with anhydrous magnesium sulfate for 12h, and filtering to obtain filtrate, namely the 2-propenyloxy-4, 6-dichloro-1, 3, 5-triazine. Then, 3.02 g of BIT is added continuously, the pH value is adjusted by triethylamine in the reaction process, the mixture is stirred for 8 hours at room temperature, and the reaction is stopped. Filtering and separating to obtain filtrate, extracting with ethyl acetate, washing with deionized water for three times, and drying with anhydrous magnesium sulfate for 12 h. And distilling the filtered filtrate under reduced pressure to remove the solvent to obtain the 2-propenyloxy-4, 6-bis (benzisothiazolin-3-one) -1,3, 5-triazine, namely the BIT-triazine antifouling resin monomer 1.

Example 2

Synthesis of BIT-triazine-based antifouling resin monomer 2 (FIG. 1-b): adding 10 mL of methallyl alcohol into a two-neck flask with a stirring device, controlling the temperature below 5 ℃ under the condition of ice-water bath, sequentially adding 1.85 g of cyanuric chloride and 1.05 g of sodium bicarbonate, reacting for 0.5 h, naturally heating to room temperature, continuously stirring for reacting for 3h, and stopping the reaction. Mixing the reaction solution with ethyl acetate, extracting and washing with water, repeating the operation for three times, drying for 12h by using anhydrous magnesium sulfate, and obtaining filtered filtrate, namely the 2- (2-methacryloxy) -4, 6-dichloro-1, 3, 5-triazine. Then, 3.02 g of BIT is added continuously, the pH value is adjusted by triethylamine in the reaction process, the mixture is stirred for 8 hours at room temperature, and the reaction is stopped. Filtering and separating to obtain filtrate, extracting with ethyl acetate, washing with deionized water for three times, and drying with anhydrous magnesium sulfate for 12 h. And distilling the filtered filtrate under reduced pressure to remove the solvent to obtain the 2- (2-methyl propylene oxyl) -4, 6-bis (benzisothiazolin-3-one) -1,3, 5-triazine, namely the BIT-triazine antifouling resin monomer 2.

Example 3

Synthesis of BIT-triazine-based antifouling resin monomer 3 (FIG. 1-c): adding 10 mL of 3-butenol into a two-neck flask with a stirring device, controlling the temperature below 5 ℃ under the condition of ice-water bath, sequentially adding 1.85 g of cyanuric chloride and 1.05 g of sodium bicarbonate, reacting for 0.5 h, naturally heating to room temperature, continuously stirring for reacting for 5 h, and stopping the reaction. Mixing the reaction solution with ethyl acetate, extracting and washing with water, repeating the operation for three times, drying for 12h by using anhydrous magnesium sulfate, and obtaining filtered filtrate, namely the 2- (3-butenyloxy) -4, 6-dichloro-1, 3, 5-triazine. Then 3.32 g of BIT is added, the pH value is adjusted by triethylamine in the reaction process, and the reaction is stopped after stirring for 6 hours at room temperature. Filtering and separating to obtain filtrate, extracting with ethyl acetate, washing with deionized water for three times, and drying with anhydrous magnesium sulfate for 12 h. And distilling the filtered filtrate under reduced pressure to remove the solvent to obtain the 2- (3-butenyloxy) -4, 6-bis (benzisothiazolin-3-one) -1,3, 5-triazine, namely the BIT-triazine antifouling resin monomer 3.

Example 4

Synthesis of BIT-triazine based antifouling resin a (fig. 2, R = H, n = 1): in a 100 mL three-neck flask equipped with a stirring device, 40 parts of xylene and 5 parts of n-butanol were sequentially added, and the temperature was raised to 85 ℃. Adding 20 parts of BIT-triazine antifouling resin monomer 1 (firstly dissolved by DMF), 3 parts of AIBN, 20 parts of methyl methacrylate and 20 parts of butyl acrylate into a constant-pressure dropping funnel, continuously preserving heat for 3 hours after dropping for 2-3 hours, adding the rest 1.5 parts of AIBN, continuously preserving heat for 7-8 hours, and cooling to room temperature to obtain BIT-triazine antifouling resin A.

Example 5

BIT-TRIAZINE BASED ANTI-FOULING RESIN B (FIG. 2, R = CH)₃N = 1) synthesis: in a 100 mL three-neck flask equipped with a stirring device, 40 parts of xylene and 5 parts of n-butanol were sequentially added, and the temperature was raised to 85 ℃. Adding 20 parts of BIT-triazine antifouling resin monomer 2 (firstly dissolved by DMF), 3 parts of AIBN, 20 parts of methyl methacrylate and 20 parts of butyl acrylate into a constant-pressure dropping funnel, continuously preserving heat for 3 hours after dropping for 2-3 hours, adding the rest 1.5 parts of AIBN, continuously preserving heat for 7-8 hours, and cooling to room temperature to obtain BIT-triazine antifouling resin B.

Example 6

Synthesis of BIT-triazine based antifouling resin C (fig. 2, R = H, n = 2): in a 100 mL three-neck flask equipped with a stirring device, 40 parts of xylene and 5 parts of n-butanol were sequentially added, and the temperature was raised to 85 ℃. Adding 20 parts of BIT-triazine antifouling resin monomer 3 (firstly dissolved by DMF), 3 parts of AIBN, 20 parts of methyl methacrylate and 20 parts of butyl acrylate into a constant-pressure dropping funnel, continuously preserving heat for 3 hours after dropping for 2-3 hours, adding the rest 1.5 parts of AIBN, continuously preserving heat for 7-8 hours, and cooling to room temperature to obtain BIT-triazine antifouling resin C.

The main properties of the antifouling resins prepared in examples 4, 5 and 6 were characterized as follows: molecular weight (GPC) test the molecular weight and molecular weight distribution of a polymer are measured using gel permeation chromatography. The bacteriostatic and algae inhibiting performance of the polymer is tested by adopting an absorbance method; the antifouling performance of the prepared antifouling paint is evaluated according to the national standard 'antifouling paint sample plate shallow sea immersion test method'.

Example 7

And (3) testing the molecular weight of the BIT-triazine antifouling resin A-C. The molecular weight data were determined as follows:

the synthesized copolymer acrylic resin has the number average molecular weight (Mn) of 9999-11357 and the weight average molecular weight (Mw) of 10207-11545, which are not greatly different. The Polymer Dispersion Index (PDI) was 1.02, indicating a relatively uniform molecular weight distribution.

Example 8

And (3) testing the bacteriostatic performance of the BIT-triazine antifouling resin. The 12h inhibition data for the three resins A-C were as follows:

the resins were tested for their bacteriostatic properties against staphylococcus aureus, vibrio coralliilyticus and vibrio parahaemolyticus. The results show that the number of strains in the well plate coated with the BIT-triazine-based antifouling resin sample is obviously less, and the BIT-triazine-based antifouling resin prepared in examples 4, 5 and 6 has good capability of inhibiting the growth of marine bacteria.

Example 9

And (3) testing the algae inhibition performance of the BIT-triazine antifouling resin A-C. The inhibition data for the following seaweeds for the 7 day three resins are as follows:

the three resins were tested for their algal-inhibitory properties against chlorella, dinoflagellate such as chlorella, coccobanchum, and chaetoceros spinulosum. The results show that the number of algae in the plastic cup with the BIT-triazine antifouling resin sample plate is obviously less, and the BIT-triazine antifouling resin prepared in the examples 4, 5 and 6 has good capability of inhibiting the growth of marine algae.

Example 10

And (3) testing the marine antifouling performance of the BIT-triazine antifouling resin A-C. The marine fouling organisms in the sea area are mainly tested by barnacles, mussels, limestans, oysters, various seaweeds and the like. After a test of the shallow sea hanging plate for 30 days, the blank sample plate has obvious barnacle, mussel, lima and other organisms, and the sample plate coated with the BIT-triazine-based antifouling resin has no obvious marine animal and plant attachment; after the shallow sea hanging plate is tested for 60 days, the blank sample plate is full of organisms such as barnacles, mussels and the like, but the sample plate coated with the BIT-triazine-based antifouling resin only has a very small amount of attached marine animals and plants, which shows that the BIT-triazine-based antifouling resin prepared in the examples 4, 5 and 6 has very good antifouling performance.

The above description is not intended to limit the present invention, and the present invention is not limited to the above examples, and those skilled in the art can make structural changes, additions or substitutions of substituted groups within the spirit of the present invention, and fall within the protection scope of the present invention.

Drawings

FIG. 1 is a schematic diagram of the structure of a BIT-triazine-based monomer.

FIG. 2 is a schematic view of the structure of a BIT-triazine-based antifouling resin.

Claims

1. a BIT-triazine-based antifouling resin monomer, is characterized in that, the structure of this monomer is as shown in formula (I):

aR=OCH ₂ CH=CH ₂ ;

bR=OCH ₂ C(CH ₃ )=CH ₂ ;

cR=OCH ₂ CH ₂ CH=CH ₂ ;

dR=OCH ₂ C(CH ₃ )=CHCH ₃ ;

eR=OCH ₂ CH=CHCH ₃ ;

fR=OCH ₂ CH ₂ C(CH ₃ )=CH ₂ ;

2. the preparation method of BIT-triazine-based antifouling resin monomer according to claim 1, is characterized in that, comprises: first use alkenyl alcohol and cyanuric chloride in the presence of sodium bicarbonate, carry out monosubstitution reaction to obtain Alkenyloxytriazine, and then the alkenyloxytriazine and BIT are subjected to a double substitution reaction in the presence of triethylamine to obtain the BIT-triazine-based antifouling resin monomer (Formula I).

3. the preparation method of BIT-triazine-based antifouling resin monomer (I) according to claim 2, is characterized in that, the ratio of cyanuric chloride and alkenyl alcohol is 1: 1～1: 10, hydrogen carbonate The amount of sodium added is 2 to 5 times that of cyanuric chloride; the molar ratio of alkenoxytriazine to BIT is 1:1 to 1:5, and the amount of triethylamine added is 2 to 4 times that of alkenyloxytriazine .

4. a BIT-triazine-based antifouling resin, adopts the BIT-triazine-based antifouling resin monomer (I) of claim 1 to carry out a copolymerization reaction with butyl acrylate, methyl methacrylate to prepare, and its It is characterized in that its copolymer structural formula (II) is as follows:

Wherein, R=H, CH ₃ , n=1, 2.

5. the preparation method of BIT-triazine-based antifouling resin copolymer (II) according to claim 4, is characterized in that, described preparation reaction raw material comprises initiator, BIT-triazine-based antifouling resin monomer ( 1), butyl acrylate, methyl methacrylate, after mixing by mass ratio, add dropwise to the mixed solvent of xylene and n-butanol, react 6-12h at 60-120 DEG C, cool to room temperature, obtain red transparent The resin is the BIT-triazine-based antifouling resin copolymer.

6. according to claim 5 and the preparation method of described BIT-triazine-based antifouling resin, it is characterized in that, the mass ratio of solvent xylene and n-butanol is 1: 5～5: 1, accounts for 40～50% of total mass 85%.