Biobased degradable epoxy resin precursor and marine antifouling coating and method of making same

Abstract

The application discloses a kind of biobased degradable epoxy resin precursor and marine antifouling coating and its preparation method.The biobased epoxy resin precursor has any one of structures shown in the following formula: wherein R is selected from any one of H, CH3, CHCH3CH3, CH2CHCH3CH3, CHCH3CH2CH3, CH2C6H5, CH2CH2SCH3;n is selected from 1 to 5.The biobased degradable marine antifouling coating prepared by the application has the characteristics of slow degradation in seawater environment, and has the advantages of low processing viscosity, excellent heat resistance and the like, and has potential practical application value in the field of marine antifouling.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of coatings, and particularly relates to a bio-based degradable epoxy resin precursor and a marine antifouling coating and a preparation method thereof. BACKGROUND

[0002] One of the most direct, effective and relatively economical methods for preventing and controlling marine biofouling is to apply various types of antifouling coatings. However, most of the traditional dominant antifouling technologies are based on self-polishing antifouling coatings of zinc polyacrylate, copper or silane ester, which have achieved relatively ideal antifouling effects. However, they have exposed many problems affecting the development of marine antifouling coatings and marine environmental protection, which hinder the further development of marine antifouling coatings. For example, the traditional metal antifouling agent has a high content (Cu2O≥40%), an unstable release and an unsatisfactory antifouling effect, and also shows toxicity to organisms; the self-polishing antifouling resin prepared from traditional polyacrylate and epoxy resin has a permanent covalent bond in the main chain and is generally non-degradable or broken into microplastic particles and long-term exists in the marine environment, which brings serious microplastic pollution and biological chain crisis; the molecular composition and structure of the general antifouling paint are quite different from those of the epoxy resin in the primer, the interlayer adhesion is poor, and the antifouling coating has defects such as short effective time, unsatisfactory antifouling effect and the like; the promising antifouling market is waiting for development. Therefore, it is particularly important to independently develop a degradable epoxy resin-based marine antifouling coating with good compatibility with the primer layer. At the same time, due to the higher requirements of the international community for green environmental protection and sustainable development of epoxy resin, it has become one of the very important development directions to explore the greenization and sustainability of degradable epoxy resin for marine antifouling.

[0003] The existing linear polyester-based coatings cannot be applied in the strong wet and high salt marine environment, and also cannot be well interfacially compatible with the primer, so it is an urgent problem to provide a marine antifouling coating with the functions of protection and self-polishing antifouling. SUMMARY

[0004] The main purpose of the present application is to provide a bio-based degradable marine antifouling coating and a preparation method and application thereof to overcome the deficiencies of the prior art.

[0005] To achieve the foregoing purposes of the application, the technical solutions adopted by the present application include:

[0006] The bio-based epoxy resin precursor provided by the embodiments of the present application has a structure as shown in formula (I) and / or formula (II):

[0007]

[0008] Wherein, R is selected from any one of H, CH3, CHCH3CH3, CH2CHCH3CH3, CHCH3CH2CH3, CH2C6H5, CH2CH2SCH3; n is selected from 1-5.

[0009] The embodiment of the present application also provides a preparation method of the aforementioned bio-based epoxy resin precursor, which comprises the following steps:

[0010] Michael addition reaction and dehydration condensation reaction are performed on the amino acid compound and itaconic acid to obtain a bio-based multifunctional precursor;

[0011] Allylation reaction and oxidation reaction are performed on the bio-based multifunctional precursor to obtain the bio-based epoxy resin precursor shown in formula (I); or, epoxidation reaction is performed on the bio-based multifunctional precursor to obtain the bio-based epoxy resin precursor shown in formula (II).

[0012] The bio-based multifunctional precursor has a structure shown in formula (III):

[0013]

[0014] The embodiment of the present application also provides an application of the aforementioned bio-based epoxy resin precursor in the field of marine antifouling.

[0015] The embodiment of the present application also provides a bio-based degradable marine antifouling coating, and raw materials of the bio-based degradable marine antifouling coating comprise the aforementioned bio-based epoxy resin precursor and a curing agent and / or an accelerator.

[0016] The embodiment of the present application also provides a preparation method of the aforementioned bio-based degradable marine antifouling coating, which comprises the following step: reacting the bio-based epoxy resin precursor shown in formula (I) and / or formula (II) with a curing agent and / or an accelerator to obtain the bio-based degradable marine antifouling coating.

[0017] The embodiment of the present application also provides a marine antifouling method, which comprises the following steps: coating the aforementioned bio-based degradable marine antifouling coating on a surface of a substrate and curing to form a coating layer.

[0018] Compared with the prior art, the embodiment of the present application has the following beneficial effects:

[0019] (1) The bio-based epoxy resin precursor in the present application directly uses itaconic acid and amino acid compounds which are rich in biological sources and cheap as raw materials, has the advantages of simple and efficient preparation method, simple operation, good controllability of reaction conditions, large-scale production by using existing chemical equipment, high yield, simple process, and is suitable for large-scale industrial production, and can reduce the dependence of existing petroleum-based epoxy resins on petrochemical resources and the pollution to the environment;

[0020] (2) The biobased degradable marine antifouling coating cured product obtained by the present application has more hydrogen bond interactions and exhibits excellent thermodynamic properties; at the same time, the biobased degradable marine antifouling coating cured product obtained by the present application has more pyrrolidone rings and ester group structures and has the characteristics of slow degradation in seawater environment;

[0021] (3) The biobased degradable marine antifouling coating cured product prepared by the present application has good self-polishing performance and degradable performance, and at the same time has the advantages of low processing viscosity, excellent heat resistance, etc., and has potential practical application value in the field of marine antifouling;

[0022] (4) The present application uses biomass raw material sources of itaconic acid and amino acid compounds, therefore, the development of this type of biobased epoxy resin product based on biomass sources can promote the development of biobased polymer materials, and at the same time has the characteristics of degradable into small molecules, promotes the sustainability of the resin cured product in the entire life cycle, and has very important significance for promoting the sustainable development of the entire field of material science, and is a biobased, green and environmentally friendly product, which has multiple effects of saving petroleum resources and protecting the environment. BRIEF DESCRIPTION OF DRAWINGS

[0023] In order to more clearly illustrate the technical solutions in the embodiments of the present application or the prior art, the drawings needed to be used in the embodiments or prior art description will be briefly introduced below. Obviously, the drawings in the following description are only some embodiments described in the present application, and other drawings can also be obtained by those skilled in the art without creative labor.

[0024] Figure 1 The nuclear magnetic resonance hydrogen spectrum 1H-NMR diagram of 1-carboxymethyl pyrrolidone carboxylic acid (IG) prepared by itaconic acid and glycine in Example 1 of the present application;

[0025] Figure 2 The nuclear magnetic resonance hydrogen spectrum 1H-NMR diagram of epoxy precursor (DIGE) prepared by 1-carboxymethyl pyrrolidone carboxylic acid (IG) in Example 4 of the present application. DETAILED DESCRIPTION

[0026] In view of the defects of the prior art, the present inventors have long-term research and a large number of practices, and have come up with the technical solutions of the present application, which mainly combine itaconic acid and amino acid to provide degradable sites for epoxy resin-pyrrolidone ring and ester group structure, and give the epoxy resin the characteristics of slow degradation into small molecules in a specific environment, to overcome the difficulty of thermosetting resin to completely degrade into small molecules, and at the same time expand the application of biobased epoxy resin in marine degradable, self-polishing and antifouling coatings for ships.

[0027] The technical solutions of the present application will be described clearly and completely below. Obviously, the described embodiments are part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application.

[0028] Specifically, as one aspect of the technical solutions of the present application, the bio-based epoxy resin precursor has a structure as shown in formula (I) and / or formula (II):

[0029]

[0030] wherein R is selected from any one of H, CH3, CHCH3CH3, CH2CHCH3CH3, CHCH3CH2CH3, CH2C6H5, CH2CH2SCH3; n is selected from 1-5.

[0031] In some preferred embodiments, in formula (I), the amino acid part where R is located can be glycine, alanine, valine, leucine, isoleucine, phenylalanine, methionine; wherein the amino acid part where R is located can have a side group or no side group, wherein the side group substituent group contains one benzene ring or more than one methyl group.

[0032] In some preferred embodiments, in formula (II), the amino acid part where R is located can be glycine, alanine, valine, leucine, isoleucine, phenylalanine, methionine; wherein the amino acid part where R is located can have a side group or no side group, wherein the side group substituent group contains one benzene ring or more than one methyl group.

[0033] Specifically, R includes -CH- with or without branching, wherein the non-branched R is H, and the branched substituent group contains -CH3, -CH-(CH3)2, -CH2-CH(CH3)2, -CH-(CH3)CH2CH3, -CH2-C6H5, and -(CH2)2-S-CH3, etc.

[0034] Another aspect of the embodiments of the present application also provides a preparation method of the aforementioned bio-based epoxy resin precursor, which comprises:

[0035] Michael addition reaction and dehydration condensation reaction are performed on the amino acid compound and itaconic acid to obtain the bio-based multifunctional precursor;

[0036] The bio-based multifunctional precursor is subjected to an allylation reaction and an oxidation reaction to obtain a bio-based epoxy resin precursor represented by Formula (I); or the bio-based multifunctional precursor is subjected to an epoxidation reaction to obtain a bio-based epoxy resin precursor represented by Formula (II).

[0037] The bio-based multifunctional precursor has a structure represented by Formula (III):

[0038]

[0039] In some preferred embodiments, the preparation method comprises: mixing and heating an amino acid compound to dissolve, then adding itaconic acid and performing a Michael addition reaction at 40-160°C for 12-36h, and then performing a dehydration condensation reaction at 80-160°C for 5-12h to obtain the bio-based multifunctional precursor.

[0040] Further, the amino acid compound comprises any one or a combination of two or more of glycine, alanine, valine, leucine, isoleucine, phenylalanine, and methionine, and is not limited thereto.

[0041] In some preferred embodiments, the preparation method comprises:

[0042] The bio-based multifunctional precursor is subjected to an allylation reaction with an allyl halide under the action of an acid-binding agent to obtain a bio-based multifunctional allylation intermediate;

[0043] The bio-based multifunctional allylation intermediate is subjected to an oxidation reaction with an organic peracid epoxidation agent to obtain a bio-based epoxy resin precursor represented by Formula (I).

[0044] Further, the acid-binding agent comprises any one or a combination of two or more of potassium carbonate, sodium carbonate, calcium carbonate, and magnesium carbonate, and is not limited thereto.

[0045] Still further, the acid-binding agent comprises sodium carbonate and / or calcium carbonate, and is not limited thereto.

[0046] Further, the allyl halide comprises any one or a combination of two or more of allyl chloride, allyl bromide, and allyl iodide, and is not limited thereto.

[0047] Still further, the allyl halide comprises allyl chloride and / or allyl bromide, and is not limited thereto.

[0048] Further, the organic peracid epoxidation agent comprises any one or a combination of two or more of peroxoacetic acid, peroxobenzoic acid, meta-chloroperoxybenzoic acid, and trifluoroperacetic acid, and is not limited thereto.

[0049] More specifically, the organic peracid epoxidizing agent includes peroxyacetic acid and / or meta-chloroperoxybenzoic acid, and is not limited thereto.

[0050] Further, the molar ratio of the allyl-type halogenated hydrocarbon, the acid binding agent, the organic peracid epoxidizing agent, and the carboxyl group in the bio-based multifunctional precursor is 2-50:1-30:1-10:1.

[0051] More specifically, 2-30:3-15:0.9-1.2:0.005-0.25:1.

[0052] Further, the molar ratio of the bio-based multifunctional allyl-type intermediate and the organic peracid epoxidizing agent is 1:2-10.

[0053] In some preferred embodiments, the preparation method comprises: performing an epoxidation reaction on a mixture comprising the bio-based multifunctional precursor, an aqueous solution of the epoxide halopropane, and the basic metal compound in the presence of a phase transfer catalyst to obtain a bio-based epoxy resin precursor represented by formula (II).

[0054] Further, the pressure of the epoxidation reaction is 0.01-0.5 MPa.

[0055] More specifically, the pressure of the epoxidation reaction is 0.1-0.2 MPa.

[0056] Further, the temperature of the epoxidation reaction is 40-120°C.

[0057] More specifically, the temperature of the epoxidation reaction is 50-70°C.

[0058] More specifically, the temperature of the epoxidation reaction is 50-100°C.

[0059] Further, the time of the epoxidation reaction is 1-10 h.

[0060] More specifically, the time of the epoxidation reaction is 3-8 h.

[0061] More specifically, the time of the epoxidation reaction is 4-5 h.

[0062] Further, the phase transfer catalyst comprises a quaternary ammonium salt, wherein the quaternary ammonium salt comprises any one or a combination of two or more of tetramethylammonium chloride, tetraethylammonium chloride, tetramethylammonium bromide, tetraethylammonium bromide, benzyltriethylammonium bromide, and is not limited thereto.

[0063] More specifically, the quaternary ammonium salt comprises tetrabutylammonium bromide and / or benzyltriethylammonium bromide, and is not limited thereto.

[0064] Further, the epoxy halopropane includes any one or a combination of two or more of an epoxy chloropropane, an epoxy bromopropane, and an epoxy iodopropane, and is not limited thereto.

[0065] Further, the epoxy halopropane includes any one or a combination of two or more of an epoxy chloropropane, an epoxy bromopropane, and an epoxy iodopropane, and is not limited thereto.

[0066] Further, the basic metal compound in the aqueous solution of the basic metal compound includes any one or a combination of two or more of potassium hydroxide, sodium hydroxide, lithium hydroxide, magnesium hydroxide, calcium hydroxide, potassium hydride, sodium hydride, and calcium hydride, and is not limited thereto.

[0067] Further, the basic metal compound in the aqueous solution of the basic metal compound includes any one or a combination of two or more of potassium hydroxide, sodium hydroxide, lithium hydroxide, magnesium hydroxide, calcium hydroxide, potassium hydride, sodium hydride, and calcium hydride, and is not limited thereto.

[0068] Further, the aqueous solution of the basic metal compound has a mass percentage concentration of 10-48%.

[0069] Further, the aqueous solution of the basic metal compound has a mass percentage concentration of 30-48%.

[0070] Further, the aqueous solution of the basic metal compound has a mass percentage concentration of 30-36%, 33-48%, or 36-48%.

[0071] Further, the epoxy halopropane, the basic metal compound, the phase transfer catalyst, and the carboxyl in the bio-based multifunctional precursor have a molar ratio of 1-50:0.8-1.4:0.001-1.0:1.

[0072] Further, the epoxy halopropane, the basic metal compound, the phase transfer catalyst, and the carboxyl in the bio-based multifunctional precursor have a molar ratio of 3-15:0.9-1.2:0.005-0.25:1.

[0073] The present application uses abundant and inexpensive itaconic acid as a main raw material, and uses the carboxyl on the structure and various amino acids to perform a Michael addition reaction, and further dehydrates to prepare a bio-based multifunctional precursor containing both a carboxyl and a rigid pyrrolidone ring in the structure, and further prepares a bio-based epoxy resin precursor with high curing activity and low viscosity, as shown in formula (I) and / or (II).

[0074] Another aspect of the embodiment of the present application also provides a bio-based degradable marine antifouling coating, and raw materials of the bio-based degradable marine antifouling coating include the aforementioned bio-based epoxy resin precursor and a curing agent and / or an accelerator.

[0075] Another aspect of the embodiments of the present application also provides a preparation method of the aforementioned biobased degradable marine antifouling coating, which comprises: reacting the biobased epoxy resin precursor represented by the formula (I) and / or the formula (II) with a curing agent and / or an accelerator to prepare the biobased degradable marine antifouling coating.

[0076] In some preferred embodiments, the preparation method comprises: heating and curing the biobased epoxy resin precursor represented by the formula (I) and / or the formula (II) with the curing agent and / or the accelerator at 25-250°C for 1-24h to prepare the biobased degradable marine antifouling coating.

[0077] Further, the curing agent comprises an organic acid anhydride and / or an organic amine; wherein the organic acid anhydride comprises any one or a combination of two or more of phthalic anhydride, methyl phthalic anhydride, tetrahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl hexahydrophthalic anhydride, norbornene anhydride; and the organic amine comprises any one or a combination of two or more of diethylene triamine, triethylene tetramine, dicyandiamide, diaminodiphenyl methane, diaminodiphenyl sulfone.

[0078] Still further, the organic acid anhydride comprises methyl tetrahydrophthalic anhydride and / or methyl hexahydrophthalic anhydride, and is not limited thereto.

[0079] Still further, the organic amine comprises dicyandiamide and / or diaminodiphenyl methane, and is not limited thereto.

[0080] Further, the accelerator comprises any one or a combination of two or more of a Lewis acid, an imidazole compound, an organic phosphine compound, and is not limited thereto.

[0081] Still further, the Lewis acid comprises boron trifluoride and / or boron trifluoride-ethanol complex, and is not limited thereto.

[0082] Still further, the imidazole compound comprises 2-ethyl imidazole and / or 2-ethyl-4-methyl imidazole, and is not limited thereto.

[0083] Still further, the organic phosphine compound comprises triphenyl phosphine and / or tri(p-methylphenyl) phosphine, and is not limited thereto.

[0084] The present application prepares non-ionic water-soluble dicarboxylic acid compounds containing rigid pyrrolidone ring by Michael addition reaction and dehydration cyclization based on the amino group on various amino acids and the carbon-carbon double bond on the structure of itaconic acid, and prepares a series of bio-based epoxy resin precursors by epoxidation. After curing the epoxy resin precursors with different epoxy curing agents and / or accelerators, a series of bio-based degradable marine antifouling coatings are obtained. Due to the compact three-dimensional cross-linked network structure of these bio-based degradable marine antifouling coatings, the progress of seawater corrosion can be slowed down in the strong wet and high salt marine environment, and excellent thermodynamic properties and protective properties as well as strong adhesion with epoxy primer are provided, prolonging the service time and protecting the primer. At the same time, a large number of pyrrolidone and ester structures are contained in the cross-linked network, among which the pyrrolidone structure is easy to open ring in alkaline environment, and a large number of hydrophilic glyceride structures also exist in the epoxy resin, which can promote the degradation of ester bond by improving hydrophilicity and affecting the electron cloud density of adjacent ester bond. However, the degradation behavior only occurs on the surface of the coating during the erosion process and cannot penetrate into the interior of the cross-linked network, so that the antifouling coating can perform slow self-polishing antifouling behavior and degradation into small molecules in weak alkaline seawater environment. The present application combines the compact three-dimensional cross-linked network and the degradable pyrrolidone ring and ester structure, and achieves the purpose of combining protection and self-polishing antifouling functions. At the same time, it has the advantages of low processing viscosity, excellent interlayer adhesion and heat resistance, etc., and has potential practical application value in the field of marine antifouling.

[0085] The biobased epoxy resin precursor contains a large number of pyrrolidone rings and ester groups, and the biobased degradable marine antifouling coating based on the precursor has improved thermodynamic performance, degradation performance and self-polishing performance in seawater compared with traditional epoxy resins. The biobased degradable marine antifouling coating has a compact and compact network structure, which can provide excellent thermodynamic performance and protective performance. In addition, the epoxy resin has the advantages of antifouling coating: the solubility parameter of the epoxy primer is close to that of the epoxy resin, so the adhesion is strong due to strong diffusion. At the same time, the cross-linked network contains a large number of pyrrolidone and ester groups. The pyrrolidone structure is prone to ring opening in an alkaline environment, and a large number of hydrophilic glyceride structures exist in the epoxy resin. By improving the hydrophilicity of the epoxy resin and affecting the electron cloud density of the adjacent ester bond, the degradation of the ester bond is promoted. However, the degradation behavior only occurs on the surface of the coating during the erosion process and cannot penetrate into the cross-linked network, thereby enabling the antifouling coating to slowly self-polish and degrade into small molecules in a weakly alkaline seawater environment. Especially the self-polishing performance and complete degradation characteristics in seawater can be used as a candidate for self-polishing marine antifouling coatings. Due to the difference in R in the structure, the glass transition temperature, heat resistance and degradation performance also have great differences. R includes a side group or no side group, the side group substituent group contains a benzene ring or more than one methyl group, and the cured epoxy resin cured product has good glass transition temperature and heat resistance. The non-side group substituent group has good self-polishing performance and degradation performance.

[0086] Another aspect of the embodiment of the present application also provides a marine antifouling method, which comprises: applying the biobased degradable marine antifouling coating to the surface of the substrate and curing to form a coating.

[0087] The technical solutions of the present application will be further described in detail below in combination with several preferred embodiments and drawings. The embodiments are implemented on the premise of the technical solutions of the present application, and detailed implementation modes and specific operation processes are given, but the protection scope of the present application is not limited to the following embodiments.

[0088] The experimental materials used in the following examples are commercially available from conventional biochemical reagent companies unless otherwise specified.

[0089] In the examples, the nuclear magnetic resonance hydrogen spectrum 1 H-NMR was measured by a 400AVANCE III type spectrometer (Spectrometer) of Bruker company, 400MHz, heavy water and deuterated acetone.

[0090] The yield of the biobased epoxy resin precursor is calculated by the following formula:

[0091] Yield = (Mass number of bio-based epoxy resin precursors) / (Moles of bio-based multifunctional precursors containing pyrrolidone rings × Molar mass of bio-based multifunctional precursors) × 100%

[0092] Example 1

[0093] 130.1 g (1.0 mol) of itaconic acid and 75.1 g (1.0 mol) of L-glycine were placed in a 500 mL round flask and reacted continuously with stirring at 40 °C for 36 hours under a nitrogen atmosphere. The mixture was then heated to 130 °C and reacted for 3 hours. The reaction system was then evacuated under vacuum for 2 hours, followed by cooling to room temperature. Acetone was added to the reaction system to dissolve the product. The product was then poured into petroleum ether and allowed to settle overnight. The resulting white precipitate was dispersed by stirring, filtered, and the resulting white solid was washed three times with ethyl acetate and dried. Finally, a white powdery product, 1-carboxymethylpyrrolidone carboxylic acid (IG), was collected and dried under vacuum with a yield of 98%.

[0094]

[0095] 1H NMR spectrum 1 H-NMR such as Figure 1 As shown in the figure, each peak corresponds one-to-one with an atom in the structure of 1-carboxymethylpyrrolidone carboxylic acid (IG).

[0096] Example 2

[0097] 130.1 g (1.0 mol) of itaconic acid and 89.1 g (1.0 mol) of L-alanine were placed in a 500 mL round flask and reacted continuously with stirring at 80 °C for 20 hours under a nitrogen atmosphere. The mixture was then heated to 135 °C and reacted for 6 hours. The reaction system was then evacuated under vacuum for 2 hours, followed by cooling to room temperature. An acetone-petroleum ether solvent (1:1) was added to the reaction system, and the mixture was allowed to stand overnight, forming a white precipitate. The resulting white solid was washed three times with ethyl acetate, then filtered under vacuum and dried. Finally, a white powdery product, 1-carboxymethylmethylpyrrolidone carboxylic acid (IA), was collected and dried under vacuum, with a yield of 88%.

[0098]

[0099] Example 3

[0100] Itaconic acid 130.1 grams (1.0 mol), 131.2 grams (1.0 mol) L-Isoleucine were placed in a 500 mL round bottom flask, 100 ml of deionized water was added, and the mixture was heated to 160°C for 12 hours. The mixture was then heated to 160°C for 3 hours, after which the reaction was vacuumed for 2 hours using a vacuum pump, and then cooled to room temperature. Ethyl acetate was added to the yellow reaction mixture, which was allowed to sit overnight. A white precipitate formed, which was vacuum filtered. The resulting solid was washed with ether three times, filtered, and oven dried. The white powdery product, 1-carboxymethyl sec-butyl pyrrolidone carboxylic acid (I-isoL), was collected and vacuum dried, with a yield of 72%.

[0101]

[0102] Example 4

[0103] Itaconic acid 130.1 grams (1.0 mol), 131.2 grams (1.0 mol) L-Isoleucine were placed in a 500 mL round bottom flask, 100 ml of deionized water was added, and the mixture was heated to 160°C for 12 hours. The mixture was then heated to 160°C for 3 hours, after which the reaction was vacuumed for 2 hours using a vacuum pump, and then cooled to room temperature. Ethyl acetate was added to the yellow reaction mixture, which was allowed to sit overnight. A white precipitate formed, which was vacuum filtered. The resulting solid was washed with ether three times, filtered, and oven dried. The white powdery product, 1-carboxymethyl sec-butyl pyrrolidone carboxylic acid (I-isoL), was collected and vacuum dried, with a yield of 72%.

[0104]

[0105] Example 5

[0106] Itaconic acid 130.1 grams (1.0 mol), 131.2 grams (1.0 mol) L-Isoleucine were placed in a 500 mL round bottom flask, 100 ml of deionized water was added, and the mixture was heated to 160°C for 12 hours. The mixture was then heated to 160°C for 3 hours, after which the reaction was vacuumed for 2 hours using a vacuum pump, and then cooled to room temperature. Ethyl acetate was added to the yellow reaction mixture, which was allowed to sit overnight. A white precipitate formed, which was vacuum filtered. The resulting solid was washed with ether three times, filtered, and oven dried. The white powdery product, 1-carboxymethyl sec-butyl pyrrolidone carboxylic acid (I-isoL), was collected and vacuum dried, with a yield of 72%.

[0107]

[0108] Example 6

[0109] Into a 250 mL three-necked round bottom flask, 130.1 g (1.0 mol) of itaconic acid and 165.2 g (1.0 mol) of L-phenylalanine were charged, the mixture was heated to 130°C and continuously stirred under nitrogen atmosphere for 16 hours. After the reaction was completed, the reaction system was vacuumed for 2 hours by vacuum pump, and then cooled to room temperature. Ethyl acetate was added to the yellow crude product and stirred overnight. The white precipitate formed was suction filtered and washed with ether three times. The white powder product, 1-carboxyphenethyl pyrrolidone carboxylic acid (IP), was finally collected and dried under vacuum with a yield of 72%.

[0110]

[0111] Example 7

[0112] Into a 250 mL three-necked round bottom flask, 130.1 g (1.0 mol) of itaconic acid and 165.2 g (1.0 mol) of L-phenylalanine were charged, the mixture was heated to 130°C and continuously stirred under nitrogen atmosphere for 16 hours. After the reaction was completed, the reaction system was vacuumed for 2 hours by vacuum pump, and then cooled to room temperature. Ethyl acetate was added to the yellow crude product and stirred overnight. The white precipitate formed was suction filtered and washed with ether three times. The white powder product, 1-carboxyphenethyl pyrrolidone carboxylic acid (IP), was finally collected and dried under vacuum with a yield of 72%.

[0113]

[0114] Example 8

[0115] First, 0.1 mol of 1-carboxymethyl pyrrolidone carboxylic acid precursor (IG) and 2.5 mol of allyl bromide were heated to 65°C in the presence of 3 mol of anhydrous calcium carbonate, stirring was started, 200 mL of acetonitrile was used as solvent, and the reaction was carried out for 10 hours. After the reaction was completed, the system was cooled to room temperature, the filtrate was obtained by filtration, and the solvent was removed by rotary evaporation under reduced pressure, maintaining the system pressure at 0.12-0.15 MPa. Then the obtained allyl intermediate was oxidized with peracetic acid to prepare 1-carboxymethyl pyrrolidone carboxylic acid epoxy precursor (DIGE) with a yield of 78%.

[0116] The obtained 1-carboxymethyl pyrrolidone carboxylic acid epoxy precursor (DIGE) was mixed with diamino diphenyl methane (DDM) in a molar ratio of one to one of epoxy and NH in acetone, then pre-cured in a blast oven, and finally post-cured at 250°C for 5 hours to obtain the cured product of 1-carboxymethyl pyrrolidone carboxylic acid epoxy-DDM epoxy resin. The glass transition temperature of the obtained cured product was 138°C, and the T d10％339.7°C, tensile strength 89.8 MPa, Young's modulus 3.22 GPa.

[0117] The obtained cured product was put into a 1M NaOH aqueous solution mixed with the same volume ratio of DMF degradation solution, and the degradation system was placed at 80°C for degradation test. The cured product could be completely degraded and dissolved in the degradation solution system after 38 hours.

[0118] The sample plate for the real sea hanging plate experiment was a steel plate of 300 mm x 150 mm x 3 mm, which was polished with 240 grit sandpaper and then coated with 1 pass of epoxy zinc-rich primer (dry film thickness 15 μm) and 2 passes of epoxy resin anticorrosive paint (dry film thickness 2 x 100 μm) before use. The antifouling paint was coated on the sample plate treated as above, and the dry film thickness was about 150 μm. After the real sea hanging plate experiment period (three months), the antifouling coating thickness was about 130 μm, and no peeling, biofilm or other marine organism load occurred.

[0119] Example 9

[0120] First, 0.1 mol of 1-carboxymethyl pyrrolidone carboxylic acid precursor (IG) and 2 mol of epichlorohydrin were heated to 75°C in the presence of 0.05 mol of quaternary ammonium salt tetrabutylammonium bromide, stirring was started, and the solid was completely dissolved to form a homogeneous liquid, and the reaction was carried out for 6 hours. After the reaction was completed, 8.8 grams of 30% aqueous solution of sodium hydroxide was added dropwise at room temperature for 0.5 hours, and the reaction was continued for 3 hours. After the reaction was completed, the solvent was removed by rotary evaporation under reduced pressure while continuously vacuumizing, and the water was removed, and the system pressure was maintained at 0.12-0.15 MPa. After the salt was removed by filtration and dried, 1-carboxymethyl pyrrolidone carboxylic acid epoxy precursor (DIGE) was obtained with a yield of 85%. The nuclear magnetic resonance hydrogen spectrum 1 H-NMR as shown in Figure 2 Each peak on the graph corresponds to an atom on the structure of 1-carboxymethyl pyrrolidone carboxylic acid epoxy precursor (DIGE).

[0121] The obtained 1-carboxymethyl pyrrolidone carboxylic acid epoxy precursor (DIGE) was mixed with diamino diphenyl sulfone (DDS) in acetone at a molar ratio of 1:1, and then pre-cured in a blast oven, and finally post-cured at 250°C for 5h to obtain 1-carboxymethyl pyrrolidone carboxylic acid epoxy-DDS epoxy resin cured product. The glass transition temperature of the obtained cured product was 135°C, T d10％ 345.4°C, tensile strength 75.5 MPa, Young's modulus 3.45 GPa.

[0122] The obtained cured product was put into a degradation solution of 1 M NaOH aqueous solution mixed with the same volume ratio of DMF, and the degradation system was placed at 80°C for degradation test. The cured product could be completely degraded and dissolved in the degradation solution system after 30 hours. The sample was prepared according to the operation requirements of the real sea panel experiment described in Example 8. After the real sea panel experiment period (three months), the antifouling coating had a thickness of about 120 μm, no peeling occurred, and there was no biofilm and other marine organism load.

[0123] Example 10

[0124] First, 0.1 mol of 1-carboxymethyl methyl pyrrolidone carboxylic acid (IA) and 2 mol of allyl bromide were heated to 65°C in the presence of 0.5 mol of anhydrous calcium carbonate, stirring was started, 200 mL of acetonitrile was used as solvent, and the reaction was carried out for 10 hours. After the reaction was completed, it was cooled to room temperature, the filtrate was obtained by filtration, and the solvent was removed by rotary evaporation under reduced pressure, maintaining the system pressure at 0.12-0.15 MPa. Then the obtained allyl intermediate was oxidized by an epoxidizing agent to prepare 1-carboxymethyl methyl pyrrolidone carboxylic acid epoxy precursor (DIAE), with a yield of 75%.

[0125] The obtained 1-carboxymethyl methyl pyrrolidone carboxylic acid epoxy precursor (DIAE) was mixed with diamino diphenyl methane (DDM) in a 1:1 molar ratio of epoxy and NH in acetone, then pre-cured in a blast oven, and finally post-cured at 250°C for 5 hours to obtain the cured product of 1-carboxymethyl methyl pyrrolidone carboxylic acid epoxy-DDM epoxy resin. The glass transition temperature of the obtained cured product was 141°C, T d10％ 334.2°C, the tensile strength was 85.8 MPa, and the Young's modulus was 3.24 GPa.

[0126] The obtained cured product was put into a degradation solution of 1 M NaOH aqueous solution mixed with the same volume ratio of DMF, and the degradation system was placed at 80°C for degradation test. The cured product could be completely degraded and dissolved in the degradation solution system after 30 hours. The sample was prepared according to the operation requirements of the real sea panel experiment described in Example 8. After the real sea panel experiment period (three months), the antifouling coating had a thickness of about 120 μm, no peeling occurred, and there was no biofilm and other marine organism load.

[0127] Example 11

[0128] First, 0.1 mol of 1-carboxymethyl methyl pyrrolidone carboxylic acid (IA) and 2 mol of epichlorohydrin were heated to 90°C in the presence of 0.5 mol of quaternary ammonium salt tetraethyl ammonium bromide, stirring was started to make the solid completely dissolved to form a homogeneous liquid, and the reaction was carried out for 6 hours. After the reaction was completed, 9.0 g of a 35% aqueous solution of sodium hydroxide was added dropwise at room temperature for 0.5 hours, and the reaction was continued for 4 hours. After the reaction was completed, the solvent was removed by vacuum rotary evaporation, maintaining the system pressure at 0.12-0.15 MPa, and the product was washed with water for 3 times. After drying, 1-carboxymethyl methyl pyrrolidone carboxylic acid epoxy precursor (DIAE) was obtained with a yield of 89%.

[0129] The obtained 1-carboxymethyl methyl pyrrolidone carboxylic acid epoxy precursor (DIGE) was mixed with diamino diphenyl sulfone (DDS) in acetone at a molar ratio of epoxy to NH of 1:1, and then pre-cured in a blast oven and finally post-cured at 250°C for 5 hours to obtain a 1-carboxymethyl methyl pyrrolidone carboxylic acid epoxy-DDS epoxy resin cured product. The glass transition temperature of the obtained cured product was 138°C, the T d10％ was 336.2°C, the tensile strength was 73.5 MPa, and the Young's modulus was 3.56 GPa.

[0130] The obtained cured product was placed in a 1M NaOH aqueous solution mixed with the same volume ratio of DMF degradation solution, and the degradation system was placed at 80°C for degradation test. The cured product was completely degraded and dissolved in the degradation solution system after 28 hours. The sample was prepared according to the operation requirements of the real sea hanging plate experiment described in Example 8. After the real sea hanging plate experiment period (three months), the antifouling coating had a thickness of about 120 μm, no peeling occurred, and no biofilm and other marine biological loadings were observed.

[0131] Example 12

[0132] The 1-carboxymethyl methyl pyrrolidone carboxylic acid epoxy precursor (DIGE) was mixed with methyl tetrahydrophthalic anhydride at a molar ratio of epoxy to anhydride of 1:0.75, and 1 wt.% of 2-ethyl imidazole was added as a curing reaction promoter, and then the mixture was placed in a vacuum oven to remove bubbles, pre-cured in a blast oven, and finally post-cured at 160°C for 5 hours to obtain a 1-carboxymethyl methyl pyrrolidone carboxylic acid epoxy-methyl tetrahydrophthalic anhydride epoxy resin cured product. The glass transition temperature of the obtained cured product was 120°C, the T d10％ was 334.7°C, the tensile strength was 94.5 MPa, and the Young's modulus was 3.44 GPa.

[0133] The obtained cured product was put into a degradation solution of 1M NaOH aqueous solution mixed with DMF in the same volume ratio, and the degradation system was placed at 80°C for degradation test. The cured product could be completely degraded and dissolved in the degradation solution system after 10 hours. The sample was prepared according to the operation requirements of the real sea panel experiment described in Example 8. After the real sea panel experiment period (three months), the antifouling coating had a thickness of about 80 μm, no peeling occurred, and there was no biofilm and other marine organism load.

[0134] Example 13

[0135] The 1-carboxymethyl pyrrolidone carboxylic acid epoxy precursor (DIGE) was uniformly mixed with methyl hexahydrophthalic anhydride at a molar ratio of epoxy to anhydride of 1:0.75, and 1 wt.% 2-ethyl-4-methyl imidazole was added as a curing reaction promoter and uniformly mixed, then after removing the bubbles in a vacuum oven, pre-curing was performed in a forced air oven, and finally post-curing was performed at 180°C for 2 hours to obtain a 1-carboxymethyl pyrrolidone carboxylic acid epoxy-methyl hexahydrophthalic anhydride epoxy resin cured product. The glass transition temperature of the obtained cured product was 115°C, T d10％ was 344.6°C, the tensile strength was 87.1 MPa, and the Young's modulus was 3.12 GPa.

[0136] The obtained cured product was put into a degradation solution of 1M NaOH aqueous solution mixed with DMF in the same volume ratio, and the degradation system was placed at 80°C for degradation test. The cured product could be completely degraded and dissolved in the degradation solution system after 10 hours. The sample was prepared according to the operation requirements of the real sea panel experiment described in Example 8. After the real sea panel experiment period (three months), the antifouling coating had a thickness of about 80 μm, no peeling occurred, and there was no biofilm and other marine organism load.

[0137] Example 14

[0138] First, 0.1 mol of 1-carboxymethyl isopropyl pyrrolidone carboxylic acid (IV) and 2 mol of epoxy bromopropane were heated to 80°C in the presence of 0.02 mol of quaternary ammonium salt benzyl triethyl ammonium bromide, stirring was started, and the solid was completely dissolved to form a homogeneous liquid, and the reaction was allowed to proceed for 8 hours. After the reaction was completed, 9.2 grams of a 40% aqueous solution of sodium hydroxide was added dropwise at room temperature for 0.5 hours, and the reaction was continued for 3 hours. After the reaction was completed, the salt was removed by filtration, washed with water 3 times, and the solvent was removed by vacuum and reduced pressure rotary evaporation, maintaining the system pressure at 0.12-0.15 MPa. After drying, 1-carboxymethyl isopropyl pyrrolidone carboxylic acid epoxy precursor (DIVE) was obtained with a yield of 84%.

[0139] The obtained 1-carboxymethyl isopropyl pyrrolidone carboxylic acid epoxy precursor (DIVE) was mixed with methyltetrahydrophthalic anhydride uniformly according to the molar ratio of epoxy and anhydride 1:0.75, and 1 wt.% 2-ethyl imidazole was added as a curing reaction promoter and mixed uniformly, then after removing bubbles in a vacuum oven, it was placed in a forced air oven for pre-curing, and finally post-cured at 180°C for 2 hours to obtain a 1-carboxymethyl isopropyl pyrrolidone carboxylic acid epoxy-methyltetrahydrophthalic anhydride epoxy resin cured product. The glass transition temperature of the obtained cured product was 114°C, T d10％ 340.1°C, the tensile strength was 88.4 MPa, and the Young's modulus was 3.21 GPa.

[0140] The obtained cured product was placed in a 1M NaOH aqueous solution mixed with the same volume ratio of DMF degradation solution, and the degradation system was placed at 80°C for degradation test. The cured product can be completely degraded and dissolved in the degradation solution system after 12 hours. The sample was prepared according to the requirements of the real sea hanging plate experiment operation described in Example 8. After the real sea hanging plate experiment period (three months), the antifouling coating thickness was about 80μm, no peeling phenomenon occurred, and there was no biofilm and other marine organism load.

[0141] Example 15

[0142] The obtained 1-carboxymethyl isopropyl pyrrolidone carboxylic acid epoxy precursor (DIVE) was mixed with methyltetrahydrophthalic anhydride uniformly according to the molar ratio of epoxy and anhydride 1:0.75, and 1 wt.% 2-ethyl imidazole was added as a curing reaction promoter and mixed uniformly, then after removing bubbles in a vacuum oven, it was placed in a forced air oven for pre-curing, and finally post-cured at 180°C for 2 hours to obtain a 1-carboxymethyl isopropyl pyrrolidone carboxylic acid epoxy-methyltetrahydrophthalic anhydride epoxy resin cured product. The glass transition temperature of the obtained cured product was 114°C, T d10％ 340.1°C, the tensile strength was 88.4 MPa, and the Young's modulus was 3.21 GPa.

[0143] The obtained cured product was placed in a 1M NaOH aqueous solution mixed with the same volume ratio of DMF degradation solution, and the degradation system was placed at 80°C for degradation test. The cured product can be completely degraded and dissolved in the degradation solution system after 12 hours. The sample was prepared according to the requirements of the real sea hanging plate experiment operation described in Example 8. After the real sea hanging plate experiment period (three months), the antifouling coating thickness was about 80μm, no peeling phenomenon occurred, and there was no biofilm and other marine organism load.

[0144] Example 16

[0145] The 1-carboxymethyl isopropyl pyrrolidone carboxylic acid epoxy precursor (DIVE) was mixed with 0.1 wt.% boron trifluoride-etherate complex, and then placed in a vacuum oven to remove air bubbles, and then placed in a forced air oven to pre-cure, and finally post-cured at 120°C for 10 hours to obtain a 1-carboxymethyl isopropyl pyrrolidone carboxylic acid epoxy resin cured product. The glass transition temperature of the obtained cured product was 76.5°C, T d10％ 340.7°C, the tensile strength was 64.3 MPa, and the Young's modulus was 2.44 GPa.

[0146] The obtained cured product was placed in a 1M aqueous hydrochloric acid solution mixed with the same volume ratio of DMF degradation solution, and the degradation system was placed at 80°C for degradation test. The cured product can be completely degraded and dissolved in the degradation solution system after 22 hours. The sample was prepared according to the operation requirements of the real sea hanging plate experiment described in Example 8. After the real sea hanging plate experiment period (three months), the antifouling coating had a thickness of about 110 μm, no shedding phenomenon occurred, and no biofilm and other marine biological loadings were present.

[0147] Example 17

[0148] First, 0.1 mol of 1-carboxymethyl isobutyl pyrrolidone carboxylic acid (IL) and 3 mol of epoxy chloropropane were heated to 50°C in the presence of 0.01 mol of quaternary ammonium salt tetrabutylammonium bromide, stirring was started, and the solid was completely dissolved to form a homogeneous liquid, and the reaction was carried out for 10 hours. After the reaction was completed, 9.2 grams of a 48% aqueous solution of sodium hydroxide was added dropwise at room temperature for 0.5 hours, and the reaction was continued for 2 hours. After the reaction was completed, the salt was removed by filtration, washed with water 3 times, and then the solvent was removed by vacuum and reduced pressure rotary evaporation, maintaining the system pressure at 0.12-0.2 MPa. After drying, 1-carboxymethyl isobutyl pyrrolidone carboxylic acid epoxy precursor (DILE) was obtained with a yield of 77%.

[0149] The obtained 1-carboxymethyl isobutyl pyrrolidone carboxylic acid epoxy precursor (DILE) was mixed with methyl tetrahydrophthalic anhydride according to a molar ratio of epoxy to anhydride of 1:0.75, and 1 wt.% 2-ethyl-4-methyl imidazole was added as a curing reaction promoter, and then mixed uniformly, and then placed in a vacuum oven to remove air bubbles, and then placed in a forced air oven to pre-cure, and finally post-cured at 180°C for 2 hours to obtain a 1-carboxymethyl isobutyl pyrrolidone carboxylic acid epoxy-methyl tetrahydrophthalic anhydride epoxy resin cured product. The glass transition temperature of the obtained cured product was 118°C, T d10％ 364.5°C, the tensile strength was 83.9 MPa, and the Young's modulus was 3.18 GPa.

[0150] The obtained cured product was put into a degradation solution of 1 M NaOH aqueous solution mixed with DMF in the same volume ratio, and the degradation system was placed at 80°C for degradation test. The cured product could be completely degraded and dissolved in the degradation solution system after 10 hours. The sample was prepared by the operation requirement of the real sea panel experiment described in Example 8. After the real sea panel experiment period (three months), the antifouling coating thickness was about 80 μm, no peeling phenomenon occurred, and no biofilm and other marine organism load.

[0151] Example 18

[0152] The obtained 1-carboxymethyl isobutyl pyrrolidone carboxylic acid epoxy precursor (DILE) was mixed with methyl hexahydrophthalic anhydride uniformly in a molar ratio of epoxy and anhydride 1:0.75, and 1 wt.% 2-ethyl-4-methyl imidazole was added as a curing reaction promoter and mixed uniformly, then after removing bubbles in a vacuum oven, pre-cured in a forced air oven, and finally post-cured at 160°C for 6 hours, a 1-carboxymethyl isobutyl pyrrolidone carboxylic acid epoxy-methyl hexahydrophthalic anhydride epoxy resin cured product was obtained. The glass transition temperature of the obtained cured product was 117°C, T d10％ 352.2°C, the tensile strength was 78.9 MPa, and the Young's modulus was 3.01 GPa.

[0153] The obtained cured product was put into a degradation solution of 1 M NaOH aqueous solution mixed with DMF in the same volume ratio, and the degradation system was placed at 80°C for degradation test. The cured product could be completely degraded and dissolved in the degradation solution system after 10 hours. The sample was prepared by the operation requirement of the real sea panel experiment described in Example 8. After the real sea panel experiment period (three months), the antifouling coating thickness was about 80 μm, no peeling phenomenon occurred, and no biofilm and other marine organism load.

[0154] Example 19

[0155] The obtained 1-carboxymethyl isobutyl pyrrolidone carboxylic acid epoxy precursor (DILE) was mixed with 0.1 wt.% boron trifluoride uniformly, then after removing bubbles in a vacuum oven, pre-cured in a forced air oven, and finally post-cured at 140°C for 8 hours, a 1-carboxymethyl isobutyl pyrrolidone carboxylic acid epoxy resin cured product was obtained. The glass transition temperature of the obtained cured product was 79.2°C, T d10％ 346.9°C, the tensile strength was 69.2 MPa, and the Young's modulus was 2.58 GPa.

[0156] The obtained cured product was put into a 1M hydrochloric acid aqueous solution mixed with the same volume ratio of DMF mixed degradation solution, and the degradation system was placed at 80°C for degradation test. The cured product can be completely degraded and dissolved in the degradation solution system after 25 hours. The sample was prepared according to the operation requirements of the real sea hanging plate experiment described in Example 8. After the real sea hanging plate experiment period (three months), the antifouling coating thickness was about 100 μm, no peeling phenomenon occurred, and there was no biofilm and other marine organism load.

[0157] Example 20

[0158] First, 0.1 mol of 1-carboxymethylthioethyl pyrrolidone carboxylic acid (IM) and 0.6 mol of epichlorohydrin were heated to 100°C in the presence of 0.5 mol of quaternary ammonium salt benzyl triethyl ammonium bromide, and stirring was started to make the solid completely dissolved to form a homogeneous liquid, and the reaction was carried out for 3 hours. After the reaction was completed, 9.2 grams of 30% aqueous solution of sodium hydroxide was added dropwise at room temperature for 0.5 hours, and the reaction was continued for 3 hours. After the reaction was completed, the salt was removed by filtration, washed with water for 3 times, and then the solvent was removed by vacuum and reduced pressure rotary evaporation, and the system pressure was maintained at 0.12-0.2 MPa. After drying, 1-carboxymethylthioethyl pyrrolidone carboxylic acid epoxy precursor (DIME) was obtained with a yield of 74%.

[0159] The obtained 1-carboxymethylthioethyl pyrrolidone carboxylic acid epoxy precursor (DIME) was mixed with dicyandiamide in a molar ratio of 1:1 in acetone, and 1 wt.% 2-ethyl imidazole was added as a curing reaction promoter and mixed uniformly, then the bubbles were removed in a vacuum oven, and then placed in a forced air oven for pre-curing, and finally post-cured at 140°C for 6 hours to obtain a 1-carboxymethylthioethyl pyrrolidone carboxylic acid epoxy-dicyandiamide epoxy resin cured product. The glass transition temperature of the obtained cured product was 126°C, T d10％ 360.4°C, the tensile strength was 72.5 MPa, and the Young's modulus was 3.46 GPa.

[0160] The obtained cured product was put into a 1M NaOH aqueous solution mixed with the same volume ratio of DMF mixed degradation solution, and the degradation system was placed at 80°C for degradation test. The cured product can be completely degraded and dissolved in the degradation solution system after 30 hours. The sample was prepared according to the operation requirements of the real sea hanging plate experiment described in Example 8. After the real sea hanging plate experiment period (three months), the antifouling coating thickness was about 110 μm, no peeling phenomenon occurred, and there was no biofilm and other marine organism load.

[0161] Example 21

[0162] The 1-carboxymethylthioethyl pyrrolidone carboxylic acid epoxy precursor (DIME) was mixed with 2 wt.% triphenylphosphine uniformly, and then pre-cured in a forced air oven after removing the air bubbles in a vacuum oven, and finally post-cured at 180 °C for 5 hours to obtain the 1-carboxymethylthioethyl pyrrolidone carboxylic acid epoxy resin cured product. The glass transition temperature of the obtained cured product was 82 °C, T d10％ 337.2 °C, the tensile strength was 65.8 MPa, and the Young's modulus was 2.43 GPa.

[0163] The obtained cured product was placed in a 1 M NaOH aqueous solution mixed with the same volume ratio of DMF degradation solution, and the degradation system was placed at 80 °C for degradation test. The cured product could be completely degraded and dissolved in the degradation solution system after 34 hours. The sample was prepared according to the operation requirements of the real sea hanging plate experiment described in Example 8. After the real sea hanging plate experiment period (three months), the antifouling coating had a thickness of about 120 μm, no peeling phenomenon occurred, and no biofilm and other marine organism load was observed.

[0164] Example 22

[0165] First, 0.1 mol of 1-carboxyphenethyl pyrrolidone carboxylic acid (IP) and 1 mol of epichlorohydrin were heated to 80 °C in the presence of 0.3 mol of quaternary ammonium salt tetraethylammonium chloride, and stirring was started to make the solid completely dissolved to form a homogeneous liquid, and the reaction was carried out for 10 hours. After the reaction was completed, 9.2 grams of a 35% aqueous solution of sodium hydroxide was added dropwise at room temperature for 0.5 hours, and the reaction was continued for 3 hours. After the reaction was completed, the salt was removed by filtration, washed with water for 3 times, and then the solvent was removed by vacuum and reduced pressure rotary evaporation, and the system pressure was maintained at 0.12-0.2 MPa. After drying, 1-carboxyphenethyl pyrrolidone carboxylic acid epoxy precursor (DIPE) was obtained with a yield of 79%.

[0166] Example 23

[0167] The 1-carboxymethylthioethyl pyrrolidone carboxylic acid epoxy precursor (DIME) was mixed with 2 wt.% triphenylphosphine uniformly, and then pre-cured in a forced air oven after removing the air bubbles in a vacuum oven, and finally post-cured at 180 °C for 5 hours to obtain the 1-carboxymethylthioethyl pyrrolidone carboxylic acid epoxy resin cured product. The glass transition temperature of the obtained cured product was 82 °C, T d10％ 350.5 °C, the tensile strength was 75.6 MPa, and the Young's modulus was 2.88 GPa.

[0168] The obtained cured product was placed in a degradation solution of 1M NaOH aqueous solution mixed with the same volume ratio of DMF, and the degradation system was placed at 80°C for degradation test. The cured product could be completely degraded and dissolved in the degradation solution system after 35 hours. The sample preparation was required by the operation of the real sea panel experiment described in Example 8. After the real sea panel experiment period (three months), the antifouling coating had a thickness of about 120 μm, no peeling phenomenon occurred, and no biofilm and other marine organism load existed.

[0169] It can be found from Examples 1-23 that the bio-based epoxy resin precursor containing a pyrrolidone ring and an ester group structure obtained by the above technical solutions of the present application directly uses the abundant and inexpensive itaconic acid and amino acid compound as raw materials, has a simple and efficient preparation method, is easy to operate, has good controllability of reaction conditions, can be produced on a large scale using existing chemical equipment, can reduce the dependence of existing petroleum-based epoxy resins on petrochemical resources and the pollution to the environment, has the advantages of high yield and simple process, and is suitable for large-scale industrial production.

[0170] Comparative Example 1

[0171] First, 0.1 mol of succinic acid and 2.5 mol of allyl bromide were heated to 65°C in the presence of 3 mol of anhydrous calcium carbonate, stirring was started, 200 mL of acetonitrile was used as a solvent, and the reaction was carried out for 10 hours. After the reaction was completed, the system was cooled to room temperature, the filtrate was obtained by filtration, and the solvent was removed by rotary evaporation under reduced pressure, maintaining the system pressure at 0.12-0.15 MPa. Then, the obtained allyl intermediate was subjected to epoxidation with peracetic acid to prepare a succinic acid epoxy precursor, and the yield was 72%.

[0172] The obtained succinic acid epoxy precursor was mixed with diamino diphenyl methane (DDM) in a molar ratio of 1:1 in acetone, then pre-cured in a blast oven, and finally post-cured at 200°C for 5 hours to obtain a succinic acid epoxy-DDM epoxy resin cured product. The glass transition temperature of the obtained cured product was 112°C, the T d10％ g was 322.4°C, the tensile strength was 78.1 MPa, and the Young's modulus was 2.10 GPa.

[0173] The obtained cured product was placed in a degradation solution of 1M NaOH aqueous solution mixed with the same volume ratio of DMF, and the degradation system was placed at 80°C for degradation test. The cured product could be completely degraded and dissolved in the degradation solution system after 35 hours. The sample preparation was required by the operation of the real sea panel experiment described in Example 8. After the real sea panel experiment period (three months), the antifouling coating had a thickness of about 120 μm, no peeling phenomenon occurred, and no biofilm and other marine organism load existed.

[0174] Comparative Example 2

[0175] Itaconic acid 260.2 g (2.0 mol), 60.1 g (1.0 mol) ethylenediamine were placed in a 500 mL round bottle flask, continuously stirred under nitrogen atmosphere and reacted at 40°C for 24 hours. Subsequently, the mixture was heated to 130°C, vacuumed for 2 hours after reaction for 3 hours, and then cooled to room temperature. Acetone was added to the reaction system and the product was dissolved. Then pour into petroleum ether to settle overnight, the white precipitate formed was stirred and dispersed, filtered and the white solid obtained was washed with ethyl acetate three times, and the white powder of the di-functional pyrrolidone ring-containing dicarboxylic acid product was collected by drying.

[0176] Firstly, 0.1 mol of the above product and 2.5 mol of allyl bromide were heated to 65°C in the presence of 3 mol of anhydrous calcium carbonate, stirred, 200 mL of acetonitrile was used as solvent, and reacted for 10 hours. After the reaction was completed, it was cooled to room temperature, filtered to obtain the filtrate, and the solvent was removed by rotary evaporation under reduced pressure, maintaining the system pressure at 0.12-0.15 MPa. Then the obtained allyl intermediate was epoxidized with peracetic acid to prepare an epoxy precursor containing a di-functional pyrrolidone ring.

[0177] The obtained epoxy precursor containing a di-functional pyrrolidone ring was mixed with diamino diphenyl methane (DDM) in a molar ratio of one to one of epoxy and NH in acetone, then pre-cured in a blast oven, and finally post-cured at 200°C for 5 hours to obtain an epoxy-DDM epoxy resin cured product containing a di-functional pyrrolidone ring. The glass transition temperature of the obtained cured product was 101°C, T d10％ 314.2°C, the tensile strength was 71.2 MPa, and the Young's modulus was 2.80 GPa.

[0178] The obtained cured product was placed in a 1M NaOH aqueous solution mixed with the same volume ratio of DMF degradation solution, and the degradation system was placed at 80°C for degradation test. The cured product can be completely degraded and dissolved in the degradation solution system after 4 hours. The sample was prepared according to the operation requirements of the real sea hanging plate experiment described in Example 8. After the real sea hanging plate experiment period (three months), the antifouling coating was peeled off, the primer had no coating protection, and there were a large amount of biofilm and some other marine organisms.

[0179] Comparative Example 3

[0180] The 1-carboxymethyl pyrrolidone carboxylic acid (IG) obtained in Example 1 was prepared into a polyester system containing a pyrrolidone structure by polycondensation reaction with a diol. It was found in actual application that the polyester system containing a pyrrolidone structure could not be processed into a coating by coating, and had no good interfacial compatibility with the epoxy primer, and at the same time, in the real sea hanging plate experiment, the polyester system was easy to peel off, and could not be applied to the marine self-polishing coating.

[0181] In addition, the inventors of the present application have also carried out tests with reference to the aforementioned examples, other raw materials, process operations and process conditions described in the present specification, and all have obtained relatively ideal results.

[0182] It should be understood that the technical solutions of the present application are not limited to the specific implementation cases described above, and any technical modification made according to the technical solutions of the present application without departing from the purpose of the present application and the scope protected by the claims falls within the protection scope of the present application.

Claims

1. A biobased degradable marine antifouling coating, characterized in that, The raw material of the biobased degradable marine antifouling coating comprises a biobased epoxy resin precursor and a curing agent or an accelerator; The biobased epoxy resin precursor has a structure as shown in formula (I): ； R is selected from any one of CH3, CHCH3CH3, CH2CHCH3CH3, CHCH3CH2CH3, CH2C6H5, and CH2CH2SCH3.

2. The method for preparing a bio-based degradable marine antifouling paint according to claim 1, characterized in that, The biobased epoxy resin precursor as shown in formula (I) is reacted with a curing agent or an accelerator to obtain the biobased degradable marine antifouling coating. The biobased epoxy resin precursor as shown in formula (I) is reacted with a curing agent or an accelerator to obtain the biobased degradable marine antifouling coating.

3. The production method according to claim 2, characterized by, The biobased epoxy resin precursor as shown in formula (I) is reacted with a curing agent or an accelerator to obtain the biobased degradable marine antifouling coating. The curing agent comprises an organic acid anhydride or an organic amine; the organic acid anhydride comprises any one or a combination of two or more of phthalic anhydride, methyl phthalic anhydride, tetrahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl hexahydrophthalic anhydride, and norbornene anhydride; the organic amine comprises any one or a combination of two or more of diethylene triamine, triethylene tetramine, dicyandiamide, and diamino diphenyl methane.

4. The method of claim 3, wherein: The accelerator comprises any one or a combination of two or more of a Lewis acid, an imidazole compound, and an organic phosphine compound; the Lewis acid comprises any one or a combination of two or more of boron trifluoride, boron trifluoride-ether complex, and tin octoate; the imidazole compound comprises any one or a combination of two or more of 2-methyl imidazole, 2-ethyl imidazole, and 2-ethyl-4-methyl imidazole; the organic phosphine compound comprises any one or a combination of two or more of tributyl phosphine, triphenyl phosphine, tri (p-methyl phenyl) phosphine, tri (nonyl phenyl) phosphine, triphenyl phosphine benzoquinone adduct, and tetraphenyl phosphine tetraphenyl borate. The organic acid anhydride comprises methyl tetrahydrophthalic anhydride or methyl hexahydrophthalic anhydride; the organic amine comprises dicyandiamide or diamino diphenyl methane.

5. The method of claim 4, wherein: The Lewis acid comprises boron trifluoride or boron trifluoride-ether complex; the imidazole compound comprises 2-ethyl imidazole or 2-ethyl-4-methyl imidazole; the organic phosphine compound comprises triphenyl phosphine or tri (p-methyl phenyl) phosphine. The biobased degradable marine antifouling coating is coated on a substrate surface and cured to form a coating layer.

6. A method for marine antifouling, characterized by, ​ ​

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