CN106866438A - A kind of acrylate functional monomer and preparation method thereof - Google Patents

Abstract

The present invention provides a kind of acrylate functional monomer for the manufacture of self-polishing marine antifouling paint film-forming agent, which is characterized in that the chemical structure of the acrylate functional monomer contains quaternary ammonium cation or quaternary phosphonium cation and benzaldehyde function The group has a biocidal and antibacterial synergistic effect, which can effectively reduce the drug resistance of bacterial microorganisms. The acrylate functional monomer can undergo a hydrolysis reaction, and the newly formed organic acid and salicylaldehyde also have a biocidal and antibacterial effect, and the salicylaldehyde can also selectively chelate and absorb Cu ²⁺ , Zn ²⁺ , Ni ²⁺ , Hg ²⁺ , etc., produce new biocidal and antibacterial effects.

Description

A kind of acrylate functional monomer and preparation method thereof

technical field

The invention relates to an acrylate, in particular to an acrylate containing a quaternary ammonium cation or a quaternary phosphonium cation and benzaldehyde, which is used as an acrylate functional monomer and belongs to the field of functional polymer materials.

technical background

Since humans have engaged in marine activities, they have been continuously exploring technologies and methods for preventing and controlling biofouling of marine vessels and marine engineering facilities. So far, the most popular and effective antifouling method is the tributyltin acrylate polymer self-polishing antifouling coating that appeared in the 1970s. The antifouling mechanism of tributyltin acrylate polymer is to release tributyltin ions through the side chain hydrolysis reaction of polyacrylic acid organotin ester, which produces biological toxicity and poisons marine microorganisms; in addition, the remaining polyacrylic acid main chain is water-soluble, and when pro After the concentration of water-based groups reaches a critical value, the main chain of polyacrylic acid will dissolve in seawater to expose a new surface, thereby producing a self-cleaning effect, so that the coating surface is continuously renewed and kept smooth. Therefore, in the late last century, about 70% of the ships in the world used this kind of coating, which produced very huge economic benefits. However, this traditional biocide and antifouling agent is organotin, which produces marine bioaccumulation and then affects the marine food chain, which not only seriously endangers the marine ecological environment, but also affects human health. The International Marine Environmental Protection Committee stipulates that organotin antifouling The end-of-use period of paint is January 1, 2008.

Since then, countries all over the world have accelerated the research and development of new tin-free self-polishing antifouling coatings one after another. Copper or silicon-based biocide and antifouling agents have low efficacy, and it is necessary to compound some copper pyrithione, zinc, diuron, capsaicin, triclosan, nano-TiO ₂ or nano-SiO ₂ biocides to produce synergistic biocides Anti-fouling performance. However, many tin-free antifouling coatings that are widely used at present contain releasable low-toxicity copper-zinc antifouling agents that will also deposit in large quantities in harbors and cause seawater pollution, which is a potential hazard to marine ecological balance and human health. Some developed countries are now planning to formulate corresponding legal provisions to limit the use of copper and zinc. In view of the above situation, the development of environmentally friendly, non-toxic, broad-spectrum and efficient new self-polishing antifouling coatings has become the main development direction of marine antifouling coatings.

Quaternary ammonium salts or quaternary phosphonium salts are biocidal and antibacterial agents that have been used for nearly half a century. They have the characteristics of simple production process, safe and effective use, so in recent years, people have turned marine antifouling coatings to polyacrylates or quaternary ammonium salts modified Research on ammonium salt modified polyurethane coating. In 1992, US5084096 disclosed a high-performance marine antifouling coating of quaternary ammonium salt modified polyurethane coating; US6248806 disclosed the formulation of rosin auxiliary quaternary ammonium polyacrylate marine antifouling coating; WO0077103 disclosed olefin polymer sulfonic acid type quaternary ammonium salt It is effective as a slow-release marine antifouling coating; US2005070456 proposes a quaternary ammonium salt modified acrylate copolymer coating, and the antifouling effect is improved after adding a surfactant; US20080181862 reports a quaternary ammonium salt modified polysiloxane Excellent self-polishing and anti-marine fouling effects of alkane polyurethane coatings;

CN201110143379.8 and CN201110143380.0 also proposed antifouling multi-purpose of quaternary ammonium salt modified polysiloxane polyurethane coating. However, the above-mentioned technology has the defects of single biocidal and antibacterial effect, expensive raw materials and complicated production technology. Based on the above, the present invention designs an acrylic acid containing quaternary ammonium cations or quaternary phosphonium cations and benzaldehyde in a molecular structure according to the antifouling mechanism and chemical requirements of the self-polishing marine antifouling coating, and according to the principle of organic molecule design. Ester functional monomer for the preparation of self-polishing marine antifouling coatings.

Contents of the invention

The present invention provides a kind of acrylate functional monomer, it is characterized in that containing quaternary ammonium cation or quaternary phosphonium cation and benzaldehyde functional group in the chemical structure of described acrylate functional monomer, has general formula (I) or general formula ( II) The structure shown:

R ₁ in general formula (I) and general formula (II) is selected from H or CH ₃ , and R ₂ , R ₃ and R ₄ are respectively selected from C ₁ -C ₂₀ hydrocarbon groups.

The specific preparation method of the acrylate functional monomer provided by the invention is as follows:

Step 1: Preparation of quaternary ammonium salt or phosphonium salt containing salicylaldehyde

Take by weighing 5-chloromethyl salicylaldehyde and general formula (III) tertiary amine or general formula (IV) trihydrocarbyl phosphine and dissolve in organic solvent respectively, make 5-chloromethyl salicylaldehyde solution and tertiary amine solution or Trihydrocarbyl phosphine solution, temperature control 0-100°C, adding the 5-chloromethyl salicylaldehyde solution into the tertiary amine solution or the trihydrocarbyl phosphine solution, stirring and reacting for 2-20 hours, filtering, washing, Drying, the quaternary ammonium salt containing salicylaldehyde of structure shown in general formula (V) or the quaternary phosphonium salt containing salicylaldehyde of structure shown in general formula (VI):

Wherein the hydrocarbon group and R ₂ , R ₃ and R ₄ in the reaction formula ① are respectively selected from C ₁ -C ₂₀ hydrocarbon groups;

Described organic solvent is selected from ethanol, butanol, butanone, 1,4-dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, toluene, xylene, anisole, chlorobenzene, toluene , chloroform, carbon tetrachloride, 1,2-dichloroethane, tetrahydrofuran, ethyl acetate, methyl acetate, butyl acetate, N,N-dimethylformamide, dimethylsulfoxide or methylcyclohexyl One or more of alkanes;

The molar ratio of the 5-chloromethyl salicylaldehyde: tertiary amine or trihydrocarbyl phosphine: solvent is 1:0.8-2.0:5-50.

Step 2: Preparation of acrylates containing quaternary ammonium cations or quaternary phosphonium cations and benzaldehyde

The quaternary ammonium salt containing salicylaldehyde of the structure shown in the general formula (V) or the quaternary phosphonium salt containing salicylaldehyde of the structure shown in the general formula (VI) prepared in step 1 is dissolved in a solvent, and added to dry market Sales of weakly basic ion exchange resin, temperature control 20 ~ 80 ℃, stirring reaction for 2 hours, filter to remove the added resin, cool down to room temperature, then add acryloyl chloride or methacryloyl chloride, stirring reaction for 2 hours, rotary evaporation to concentrate and precipitate solid , filter, wash, dry, make the acrylic acid ester containing quaternary ammonium cation and benzaldehyde of structure shown in general formula (I) or the acrylate containing quaternary phosphonium cation and benzaldehyde of structure shown in general formula (II):

Wherein in the reaction formula ②, R ₁ is selected from H or CH ₃ , and R ₂ , R ₃ and R ₄ are selected from C ₁ -C ₂₀ hydrocarbon groups respectively.

Described solvent is selected from acetone, butanone, 1,4-dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, toluene, xylene, anisole, chlorobenzene, toluene, chloroform, tetra One of carbon chloride, 1,2-dichloroethane, tetrahydrofuran, ethyl acetate, methyl acetate, butyl acetate, N,N-dimethylformamide, dimethylsulfoxide or methylcyclohexane one or more species;

The mass ratio of the quaternary ammonium salt containing salicylaldehyde or the quaternary phosphonium salt containing salicylaldehyde: weakly basic ion exchange resin: solvent is 1:0.5～5:2～10;

The amount of the acryloyl chloride or methacryloyl chloride is 1.0-1.3 times the molar amount of the quaternary ammonium salt containing salicylaldehyde or the quaternary phosphonium salt containing salicylaldehyde.

The acrylate functional monomer containing quaternary ammonium cation and benzaldehyde or the acrylate functional monomer containing quaternary phosphonium cation and benzaldehyde provided by the invention has the following characteristics:

1. The method for preparing the acrylate containing quaternary ammonium cation and benzaldehyde or the acrylate functional monomer containing quaternary phosphonium cation and benzaldehyde provided by the present invention belongs to the classical organic chemical reaction, which is simple and easy to implement, with rich sources of raw materials and low cost.

② The molecular structure of the acrylate functional monomer of the present invention contains two kinds of biocidal and antibacterial substances with different mechanisms, which have a biocidal and antibacterial synergistic effect and can effectively reduce the drug resistance of bacteria and microorganisms.

③ The acrylate functional monomer described in the present invention can undergo hydrolysis reaction, and the regenerated organic acid and salicylaldehyde also have biocidal and antibacterial effects, and salicylaldehyde can also selectively chelate and absorb Cu ²⁺ and Zn in seawater ²⁺ , Ni ²⁺ , Hg ²⁺ , etc., produce new biocidal and antibacterial effects.

specific embodiment

The acrylate functional monomer provided by the present invention and the preparation method are further described through the following examples, the purpose of which is to better understand the content of the present invention. Therefore, acrylate functional monomers and preparation methods thereof not listed in the examples should not be considered as limiting the protection scope of the present invention. Any improvement aimed at the present invention is an act of infringement of intellectual property rights.

Embodiment 1 Acrylic acid-[3-formyl-4-(chloride N, N-dimethyl-N-benzyl ammonium methyl)] the preparation of phenyl ester

Acrylic acid-[3-formyl-4-(N,N-dimethyl-N-benzylammoniomethyl)]phenyl chloride

Step 1, the preparation of N, N-dimethyl-N-benzyl-N-(3-formyl-4-hydroxybenzyl) ammonium chloride

Weigh 20 grams of N, N-dimethylbenzylamine and 40 grams of 5-chloromethyl salicylaldehyde respectively, dissolve them in 80 grams of ethyl acetate respectively, and dissolve N, N-dimethylbenzylamine ethyl acetate at room temperature The ester solution was added to 5-chloromethyl salicylaldehyde ethyl acetate solution, stirred for 4 hours, the solid was filtered out, washed with ethyl acetate, and dried to obtain N,N-dimethyl-N-chloride Benzyl-N-(3-formyl-4-hydroxybenzyl)ammonium 42.8 g, yield 93.2%.

Step 2, the preparation of acrylic acid-[3-formyl-4-(chlorinated N, N-dimethyl-N-benzyl ammonium methyl)] phenyl ester

30 grams of N,N-dimethyl-N-benzyl-N-(3-formyl-4-hydroxybenzyl)ammonium chloride prepared in step 1 was dissolved in 80 grams of dimethyl sulfoxide, added to dry 50 grams of commercially available weakly basic ion-exchange resin D301, temperature controlled at 60°C, stirred and reacted for 2 hours, filtered to remove the resin, added 13 grams of acryloyl chloride to the filtrate, stirred and reacted for 2 hours, concentrated by rotary evaporation to precipitate solids, filtered , washed, and dried to obtain 37.3 grams of acrylic acid-[3-formyl-4-(chlorinated N,N-dimethyl-N-benzylammoniomethyl)]phenyl, with a yield of 92.8%.

The preparation of embodiment 2 methacrylic acid-[3-formyl-4-(chlorination N, N-dimethyl-N-n-octyl ammonium base methyl)] phenyl ester

Methacrylate-[3-formyl-4-(N,N-dimethyl-N-n-octylammoniomethyl)]phenyl chloride

According to the method and operation steps of Example 1, the N,N-dimethylbenzylamine in step 1 of Example 1 was replaced with N,N-dimethyl n-octylamine, and the acryloyl chloride in step 2 was replaced with methyl Acryloyl chloride to obtain [3-formyl-4-(N,N-dimethyl-N-n-octylammoniomethyl)]phenyl methacrylate.

Embodiment 3 The preparation of methacrylic acid-[3-formyl-4-(chlorinated N, N-dimethyl-N-allyl ammonium base methyl)] phenyl ester

[3-Formyl-4-(N,N-dimethyl-N-allylammoniomethyl)]phenyl methacrylate

According to the method and operation steps of Example 1, the N,N-dimethylbenzylamine in Step 1 of Example 1 was replaced with N,N-Dimethallylamine, and the acryloyl chloride in Step 2 was replaced with methacrylic Acyl chloride to obtain [3-formyl-4-(N,N-dimethyl-N-allylammoniomethyl)]phenyl methacrylate.

The preparation of embodiment 4 acrylic acid-[3-formyl-4-(chlorinated N-methyl-N, N-diallyl ammonium base methyl)] phenyl ester

Acrylic acid-[3-formyl-4-(N-methyl-N,N-diallylammoniomethyl)]phenyl chloride

According to the method and operation steps of Example 1, the N,N-dimethylbenzylamine in Step 1 of Example 1 was replaced with N-methyldiallylamine to obtain acrylic acid-[3-formyl-4-( N-Methyl-N,N-diallylammonomethyl)]phenyl chloride.

The preparation of embodiment 5 acrylic acid-[3-formyl-4-(chlorination P, P, P-triphenylphosphonium base methyl)] phenyl ester

Acrylic acid-[3-formyl-4-(P,P,P-triphenylphosphoniumylmethyl)]phenyl chloride

According to the method and operating steps of Example 1, the N,N-dimethyl-N-benzylamine in Step 1 of Example 1 was replaced with triphenylphosphine to obtain acrylic acid-[3-formyl-4-( P,P,P-Triphenylphosphonium (methyl)]phenyl chloride.

The preparation of embodiment 6 acrylic acid-[3-formyl-4-(chlorination P, P, P-tri-n-butylphosphonium base methyl)] phenyl ester

Acrylic acid-[3-formyl-4-(P,P,P-tri-n-butylphosphoniumylmethyl)]phenyl chloride

According to the method and operation steps of Example 1, the tri-n-butylphosphine in Step 1 of Example 1 was replaced with triphenylphosphine to obtain acrylic acid-[3-formyl-4-(chlorinated P, P, P- Tri-n-butylphosphonium methyl)]phenyl ester.

Acrylate hydrolysis reaction in embodiment 7 embodiment 1～6

Weigh 30 grams each of the acrylates in Examples 1 to 6, disperse them in 1000 grams of sodium chloride solution with a mass percent concentration of 3.5%, control the pH of the sodium chloride solution to 8.0-8.5, and stir at room temperature Carry out hydrolysis reaction, the result is shown in Table 1.

Acrylate functional monomer hydrolysis situation in table 1 embodiment 1～6

Claims (2)

1. a kind of acrylate functional monomer, it is characterised in that in described acrylate functional monomer structure containing quaternary ammonium sun from Son or quaternary phosphine cation and benzaldehyde functional group, with logical formula (I) or structure shown in logical formula (II)：

R in its formula of (I) or logical formula (II)₁Choose H or CH₃, R₂、R₃And R₄C is chosen respectively₁~C₂₀Alkyl.

2. according to the acrylate functional monomer described in claim 1, it is characterised in that its preparation method is as described below：

Step one：Prepare the quaternary ammonium salt Huo quaternary alkylphosphonium salts containing salicylide

5- chloromethyl salicylaldehydes and logical formula (III) tertiary amine or the dissolving of logical formula (IV) trihydrocarbyl phosphine are weighed respectively in organic solvent, 5- chloromethyl salicylaldehyde solutions and ertiary amine solution or trihydrocarbyl phosphine solution, 0~100 DEG C of temperature control, by 5- chloromethyl salicylaldehydes is obtained Solution is added in ertiary amine solution or trihydrocarbyl phosphine solution, stirring reaction 2~20 hours, filtering, washing, dry, prepared logical formula (V) The quaternary alkylphosphonium salt containing salicylide of the quaternary ammonium salt containing salicylide of shown structure or structure shown in logical formula (VI)：

Wherein described alkyl and reaction equation 1. in R₂、R₃And R₄C is chosen respectively₁~C₂₀Alkyl；

Described organic solvent be selected from ethanol, butanol, butanone, Isosorbide-5-Nitrae-dioxane, glycol dimethyl ether, ethylene glycol diethyl ether, Toluene, dimethylbenzene, methyl phenyl ethers anisole, chlorobenzene, toluene, chloroform, carbon tetrachloride, 1,2- dichloroethanes, tetrahydrofuran, ethyl acetate, second One or more in sour methyl esters, butyl acetate, DMF, dimethyl sulfoxide or hexahydrotoluene；

The 5- chloromethyl salicylaldehydes: tertiary amine or trihydrocarbyl phosphine: the consumption mol ratio of solvent is 1: 0.8~2.0: 5~50；

Step 2：Prepare the acrylate containing quaternary ammonium cation Huo quaternary phosphines cation and benzaldehyde

The quaternary ammonium salt containing salicylide of structure or containing for structure shown in logical formula (VI) shown in formula (V) will be led to obtained in step one The quaternary alkylphosphonium salt dissolving of salicylide in a solvent, adds dry commercially available weak-base ion-exchange resin, 20~80 DEG C of temperature control, stirring Reaction 2 hours, the filtrate after the filtering removal resin is cooled to room temperature, adds acryloyl chloride or methacrylic chloride, stirs Mix reaction 2 hours, concentrated by rotary evaporation separates out solid, filtering, washing, dry, be obtained structure shown in logical formula (I) containing quaternary ammonium sun from The acrylate or the acrylate containing quaternary phosphine cation and benzaldehyde of structure shown in logical formula (II) of son and benzaldehyde：

Wherein described reaction equation 2. in R₁Choose H or CH₃, R₂、R₃And R₄C is chosen respectively₁~C₂₀Alkyl；

Described solvent is selected from acetone, butanone, Isosorbide-5-Nitrae-dioxane, glycol dimethyl ether, ethylene glycol diethyl ether, toluene, diformazan Benzene, methyl phenyl ethers anisole, chlorobenzene, toluene, chloroform, carbon tetrachloride, 1,2- dichloroethanes, tetrahydrofuran, ethyl acetate, methyl acetate, second One or more in acid butyl ester, DMF, dimethyl sulfoxide or hexahydrotoluene；

The quaternary ammonium salt containing salicylide contains salicylide quaternary alkylphosphonium salts: weak-base ion-exchange resin: the consumption of solvent Mass ratio is 1: 0.5~5: 2~10；

The consumption of the acryloyl chloride or methacrylic chloride is the quaternary ammonium salt containing salicylide or the season containing salicylide 1.0~1.3 times of phosphonium salt mole dosage.