An antifouling, self-repairing non-isocyanate polyurethane coating and a method for preparing the same

Abstract

The application discloses a kind of antifouling, self-repairing non-isocyanate polyurethane coating and preparation method thereof, the preparation method includes the following steps: preparation of polybasic cyclic carbonate resin: add anhydride and polyol into organic solvent and mix uniformly, react under the condition of 100~150 DEG C for 3~5h until acid value is constant, cool to room temperature;Then add glycerol carbonate, adopt dimethylbenzene reflux, react until acid value is less than 3.0mgKOH / g at 180~210 DEG C, cool to room temperature, wash with water 2~3 times, remove solvent to obtain polybasic cyclic carbonate resin;Preparation of polyamine curing agent: polyamine, amino-terminated polydimethylsiloxane and amine compound containing disulfide bond are mixed, and polyamine curing agent is prepared after stirring uniformly.The preparation method of the application has the advantages of simple synthesis and low cost, and the non-isocyanate polyurethane coating prepared simultaneously has good self-repairing property, antifouling property and corrosion resistance.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of non-isocyanate polyurethane coatings, in particular to a non-isocyanate polyurethane coating with antifouling and self-repairing properties and a preparation method thereof. BACKGROUND

[0002] Polyurethane has many excellent properties and is widely used in electronic devices, transportation, biomedical, building materials, aerospace and other fields. The preparation of traditional polyurethane requires the use of isocyanate as raw material. Isocyanate itself contains certain toxicity, and its synthesis depends on the toxic gas phosgene, which is harmful to the human body and the environment. In addition, isocyanate is extremely sensitive to moisture, causing great difficulty in storage, transportation and preparation. It is easy to produce bubbles in the synthesis process, thereby affecting the material properties. Therefore, people strive to design and synthesize non-toxic and environmentally friendly non-isocyanate polyurethane materials to replace traditional polyurethane.

[0003] Non-isocyanate polyurethane is generally synthesized by reacting a polyamine with a polycyclic carbonate. In the preparation process, isocyanate is not involved, and it is not easily affected by moisture. The molecular chain structure contains a large number of hydroxyl groups, which helps to improve the chemical resistance and permeability resistance of the material. It is a kind of material with very broad application and development prospects. Therefore, non-isocyanate polyurethane has the potential to replace traditional polyurethane in the fields of adhesives, elastomers, coatings, foams and the like. However, the existing non-isocyanate polyurethane materials have a high water absorption rate and almost no self-repairing and staining properties. The most commonly used polycyclic carbonate is a polycyclic five-membered ring carbonate, which is usually generated by the addition reaction of an epoxy group and carbon dioxide under high pressure (1-20 MPa). High-pressure reaction not only has high generation cost, but also brings potential safety hazards. Therefore, the preparation of polycyclic five-membered ring carbonate under atmospheric pressure has become a research hotspot.

[0004] On the other hand, non-isocyanate polyurethane contains a large number of hydroxyl groups, and the chemical resistance of its coating film is not good, and the function is single. To solve this problem, Chinese patent application CN109593451A discloses a bisphenol AF-based hydrophobic and oleophobic non-isocyanate polyurethane coating, a preparation method and application thereof. Bisphenol AF and perfluorinated epoxy compound are used as raw materials to synthesize bisphenol AF and perfluorinated ring carbonate under carbon dioxide atmosphere, and further with different amine curing agents to prepare high-performance non-isocyanate polyurethane coating. The coating of non-isocyanate polyurethane prepared thereby has very good hydrophobic and oleophobic properties and corrosion resistance, and also has high hardness, excellent impact resistance and chemical resistance. Because fluorine-containing compounds are used to prepare hydrophobic and oleophobic polycyclic carbonates, not only the cost is high, but also the fluorine-containing compounds have physiological toxicity, and their commercial use is limited.

[0005] Self-repairing coating and antifouling coating have good application prospect and research significance due to their excellent physicochemical properties. The composite coating combining the two functions will have a broader application prospect. Siloxane is a kind of polymer containing siloxane bond. The polymer can be modified purposefully according to the different end structures. The tensile strength of the non-isocyanate polyurethane material can be enhanced, the water absorption can be reduced, and the thermal stability can be improved by modifying the non-isocyanate polyurethane with siloxane. However, it is difficult to simultaneously consider the self-repairing and self-cleaning functions of the non-isocyanate polyurethane material. For example, the Chinese invention patent application CN113088176A discloses a self-repairing scratch-resistant polyurethane coating and a preparation method thereof. The dynamic urea bond and the organic silicon segment are introduced into the polyurethane coating structure, and the prepared coating has excellent self-repairing performance, as well as basic properties such as scratch resistance, wear resistance, anti-graffiti, high tensile strength, and certain antifouling performance. However, the antifouling effect is not outstanding. SUMMARY

[0006] In order to overcome the above-mentioned defects and shortcomings of the prior art, the purpose of the present application is to provide a preparation method of antifouling and self-repairing non-isocyanate polyurethane coating, which has the advantages of simple synthesis and low cost. The prepared non-isocyanate polyurethane coating has good self-repairing property, antifouling property and corrosion resistance.

[0007] The purpose of the present application is achieved by the following technical solutions:

[0008] The present application provides a preparation method of antifouling and self-repairing non-isocyanate polyurethane coating, comprising the following steps:

[0009] Preparation of polybasic cyclic carbonate resin: add anhydride and polyol into an organic solvent and mix uniformly, react at 100-150℃ for 3-5h until the acid value is constant, cool to room temperature; then add glycerol carbonate, reflux with dimethylbenzene, react at 180-210℃ until the acid value is lower than 3.0mgKOH / g, cool to room temperature, wash with water for 2-3 times, and remove the solvent to obtain polybasic cyclic carbonate resin;

[0010] The acid anhydride is at least one of phthalic anhydride, trimellitic anhydride, methylhexahydrophthalic anhydride, succinic anhydride, maleic anhydride, glutaric anhydride and adipic anhydride;

[0011] The polyol is at least one of trimethylolpropane, pentaerythritol, ditrimethylolpropane and dipentaerythritol;

[0012] Preparation of polyamine curing agent: mix polyamine, amino-terminated polydimethylsiloxane and amine compound containing disulfide bond, stir uniformly to obtain polyamine curing agent;

[0013] The molecular weight of the terminal amino polydimethylsiloxane is 2000-8000, and has the following structural formula:

[0014]

[0015] Preparation of the non-isocyanate polyurethane coating: uniformly mix the polybasic cyclic carbonate resin with the amine curing agent, and cure at 120-150°C for 3-5h to obtain the antifouling and self-repairing non-isocyanate polyurethane coating.

[0016] Preferably, the polyamine is at least one of isophorone diamine, p-phenylenediamine, ethylenediamine, butylenediamine, pentanediamine, hexanediamine, octanediamine, decanediamine, polyethyleneimine, polyetherdiamine, diethylenetriamine, and tetraethylenepentamine.

[0017] Preferably, the disulfide bond-containing amine compound is at least one of 2,2'-diaminodiphenyl disulfide, dibenzocyclooctyne-bisulfide-amino, and cystamine dihydrochloride.

[0018] Preferably, the organic solvent is at least one of N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, and acetonitrile.

[0019] Preferably, the mass ratio of the acid anhydride, the polyol, and the glycerol carbonate is (25-45):(5-15):(25-45).

[0020] Preferably, the mass ratio of the polyamine, the terminal amino polydimethylsiloxane, and the disulfide bond-containing amine compound is (10-25):(1-10):(1-10).

[0021] Preferably, the mass ratio of the polybasic cyclic carbonate resin and the amine curing agent is (75-85):(18-30).

[0022] Preferably, the polybasic cyclic carbonate resin has a star structure.

[0023] Preferably, the molecular weight of the terminal amino polydimethylsiloxane is 2000-8000.

[0024] Preferably, the glycerol carbonate has the following structure:

[0025]

[0026] Preferably, the amount of the organic solvent added is 20%-50% of the total mass of the acid anhydride and the polyol.

[0027] The application also provides an antifouling and self-repairing non-isocyanate polyurethane coating prepared by the preparation method of the antifouling and self-repairing non-isocyanate polyurethane coating.

[0028] Compared with the prior art, the present application has the following advantages and beneficial effects:

[0029] (1) The preparation method of the anti-fouling and self-repairing non-isocyanate polyurethane coating of the present application uses one of trimethylolpropane, pentaerythritol, ditrimethylolpropane and dipentaerythritol as the polyol. The polyol is first reacted with an anhydride, and the product is then reacted with glycerol cyclic carbonate. The obtained polymeric cyclic carbonate has a star-shaped molecular structure, and each molecule contains 3 or more cyclic carbonate structures. This makes the prepared non-isocyanate polyurethane more dense and has a higher degree of polymerization, which can effectively improve the mechanical strength, heat resistance, hydrophobicity and corrosion resistance.

[0030] (2) The preparation method of the anti-fouling and self-repairing non-isocyanate polyurethane coating of the present application uses a polyamine, an amino-terminated polydimethylsiloxane and an amine compound containing a disulfide bond to prepare a polyamine curing agent. The polyamine curing agent further introduces functional groups: the amino-terminated polydimethylsiloxane provides the polyurethane material with low surface energy and low elastic modulus characteristics, so that liquid droplets do not spread and form spherical shapes, and contaminants are difficult to adhere to or adhere firmly to the material surface, thereby endowing the material with self-cleaning properties; the reaction of the cyclic carbonate group with the amino group containing a disulfide bond generates a urethane bond and introduces a disulfide bond. The disulfide bond has a low bond energy and can achieve bond rupture and bond reorganization at normal temperature and pressure, thereby completing the reconnection of the polymer chain segments and achieving the self-repairing effect of the material.

[0031] (3) The preparation method of the anti-fouling and self-repairing non-isocyanate polyurethane coating of the present application can be prepared at normal pressure, and the synthesis is simple. The method has the advantages of low cost, no fluorine and no toxicity, and can be widely used in the preparation of anti-fouling, self-cleaning, self-repairing and sustainable coatings or industrial paints. DETAILED DESCRIPTION

[0032] The present application will be further described in detail below with reference to the examples, but the embodiments of the present application are not limited thereto.

[0033] In the following examples, the test procedures are as follows:

[0034] Water contact angle test: tested according to the test standard GB / T 30447-2013.

[0035] Anti-fouling performance test: write words on the surface of the coating with an oily marker pen at room temperature, observe whether the oily marks shrink and deform, and then wipe the marks with a common paper towel after 3 minutes to observe whether there are traces left on the coating.

[0036] Self-cleaning performance test: sprinkle dust on the surface of the coating, let it stand for 24 hours, then drop water on the dusted part of the coating surface. If the dust completely falls off with the water, the self-cleaning performance is high.

[0037] Self-repairing efficiency determination: 5 min at 80°C, using 3D optical interference (profile) instrument to observe the self-repairing of the coating, the ratio of the repaired scratch depth (AC) to the scratch depth before repair (C1) is taken as the self-repairing efficiency (ε), i.e. ε = AC / C1.

[0038] Anticorrosion performance test: tested according to the test standard HGT 4077-2009.

[0039] Example 1

[0040] The present example provides a preparation method of a multi-ring carbonate resin and a non-isocyanate polyurethane coating, comprising the following steps:

[0041] (1) Preparation of multi-ring carbonate resin: benzene anhydride and pentaerythritol are added into a reaction kettle, then N,N-dimethylformamide is added, and the reaction is carried out at 100°C for 5h until the acid value remains constant, and then cooled to room temperature. Then add glycerol carbonate, and use xylene (20% of the total mass) to reflux, and react at 180°C until the acid value is less than 3.0 mgKOH / g, and then cool to room temperature, wash with water twice to remove unreacted glycerol carbonate, and finally remove the solvent to obtain the multi-ring carbonate resin. The reaction process is shown in formula (1)~(2).

[0042]

[0043] (2) Preparation of amine curing agent: isophorone diamine, amino-terminated polydimethylsiloxane-3000 and 2,2'-diamino diphenyl disulfide are mixed in proportion to obtain the amine curing agent.

[0044] (3) Preparation of non-isocyanate polyurethane coating: the multi-ring carbonate resin and the amine curing agent are mixed uniformly, and cured at 120°C for 5h to obtain the antifouling self-repairing non-isocyanate polyurethane coating.

[0045] Table 1 Formulation of non-isocyanate polyurethane coating of Example 1

[0046] No. Composition Weight fraction 1 Methylhexahydrophthalic anhydride 40.55 2 Pentaerythritol 8.45 3 Glycerol carbonate 28.15 4 N,N-dimethylformamide 20.00 5 Isophorone diamine 18.85 6 Amino-terminated polydimethylsiloxane-3000 1.00 7 2,2'-diaminodiphenyl disulfide 3.00 8 Total 120.00

[0047] Example 2

[0048] The present example provides a preparation method of a multi-ring carbonate resin and a non-isocyanate polyurethane coating, comprising the following steps:

[0049] (1) Preparation of the polycyclic carbonate resin: trimellitic anhydride and trimethylolpropane were added into a reaction kettle, then N,N-dimethylacetamide was added, and the reaction was carried out at 130°C for 5h until the acid value remained constant, and then cooled to room temperature. Then glycerol carbonate was added, and xylene (20% of the total mass) was used for refluxing, and the reaction was carried out at 180°C until the acid value was less than 3.0mgKOH / g, and then cooled to room temperature, washed with water for 3 times to remove the unreacted glycerol carbonate, and finally the solvent was removed to obtain the polycyclic carbonate resin.

[0050] The reaction process is shown in formula (3)-(4).

[0051]

[0052] (2) Preparation of the amine curing agent: isophorone diamine, amino-terminated polydimethylsiloxane-4000, 2,2'-diaminodiphenyl disulfide and cystamine dihydrochloride were mixed in proportion to obtain the amine curing agent.

[0053] (3) Preparation of the non-isocyanate polyurethane coating: the polycyclic carbonate resin and the amine curing agent were mixed uniformly, and cured at 150°C for 3h to obtain the antifouling self-repairing non-isocyanate polyurethane coating.

[0054] Table 2 Formulation of the non-isocyanate polyurethane coating of Example 2

[0055]

[0056]

[0057] Example 3

[0058] The present embodiment provides a preparation method of a polycyclic carbonate resin and a non-isocyanate polyurethane coating, comprising the following steps:

[0059] (1) Preparation of the polycyclic carbonate resin: succinic anhydride and dipentaerythritol were added into a reaction kettle in proportion, then dimethyl sulfoxide was added, and the reaction was carried out at 110°C for 4h until the acid value remained constant, and then cooled to room temperature. Then glycerol carbonate was added, and xylene (20% of the total mass) was used for refluxing, and the reaction was carried out at 200°C until the acid value was less than 3.0mgKOH / g, and then cooled to room temperature, washed with water for 2 times to remove the unreacted glycerol carbonate, and finally the solvent was removed to obtain the polycyclic carbonate resin. The reaction process is shown in formula (5)-(6).

[0060]

[0061] (2) Preparation of amine curing agent: pentanediamine, amino-terminated polydimethylsiloxane-5000 and dibenzocyclooctyne-bis-sulfur-amino were mixed in proportion to obtain the amine curing agent.

[0062] (3) Preparation of non-isocyanate polyurethane coating: the polycyclic carbonate resin was mixed with the amine curing agent, and cured at 130°C for 4h to obtain the antifouling self-repairing non-isocyanate polyurethane coating.

[0063] Table 3 Non-isocyanate polyurethane coating formula of Example 3

[0064]

[0065]

[0066] Example 4

[0067] The present embodiment provides a preparation method of polycyclic carbonate resin and non-isocyanate polyurethane coating, comprising the following steps:

[0068] (1) Preparation of polycyclic carbonate resin: glutaric anhydride and pentaerythritol were added into a reaction kettle in proportion, then N,N-dimethylformamide was added, and the reaction was carried out at 120°C for 5h until the acid value remained constant, and then cooled to room temperature. Then glycerol carbonate was added, and xylene (20% of the total mass) was refluxed, and the reaction was carried out at 200°C until the acid value was less than 3.0mgKOH / g, and then cooled to room temperature, washed with water twice to remove unreacted glycerol carbonate, and finally removed the solvent to obtain the polycyclic carbonate resin. The reaction process is shown in formula (7)-(8).

[0069]

[0070] (2) Preparation of amine curing agent: pentanediamine, diethylenetriamine, amino-terminated polydimethylsiloxane-5000 and 2,2'-diaminodiphenyl disulfide were mixed in proportion to obtain the amine curing agent.

[0071] (3) Preparation of non-isocyanate polyurethane coating: the polycyclic carbonate resin was mixed with the amine curing agent, and cured at 150°C for 4h to obtain the antifouling self-repairing non-isocyanate polyurethane coating.

[0072] Table 4 Non-isocyanate polyurethane coating formula of Example 4

[0073]

[0074]

[0075] Example 5

[0076] The embodiment provides a preparation method of a multi-ring carbonate resin and a non-isocyanate polyurethane coating, and comprises the following steps.

[0077] (1) Preparation of the multi-ring carbonate resin: adipic anhydride and double trimethylolpropane are added into a reaction kettle, then a proper amount of acetonitrile is added, and reaction is carried out at 150 DEG C for 5h until the acid value is constant, and then the reaction system is cooled to room temperature. Then glycerol carbonate is added, and reflux is carried out by using xylene (20% of the total mass), and reaction is carried out at 210 DEG C until the acid value is lower than 3.0 mgKOH / g, and then the reaction system is cooled to room temperature, washed with water twice to remove unreacted glycerol carbonate, and finally solvent is removed to obtain the multi-ring carbonate resin. The reaction process is shown in formula (9)-(10).

[0078]

[0079] (2) Preparation of the amine curing agent: decanediamine, amino-terminated polydimethylsiloxane-6000, 2,2'-diaminodiphenyl disulfide and dibenzocyclooctyne-bisulfide-amino are uniformly mixed in proportion to obtain the amine curing agent.

[0080] (3) Preparation of the non-isocyanate polyurethane coating: the multi-ring carbonate resin and the amine curing agent are uniformly mixed, and then curing is carried out at 150 DEG C for 5h to obtain the antifouling self-repairing non-isocyanate polyurethane coating.

[0081] Table 5 Formulation of the non-isocyanate polyurethane coating of Example 5

[0082]

[0083]

[0084] Example 6

[0085] The embodiment provides a preparation method of a multi-ring carbonate resin and a non-isocyanate polyurethane coating, and comprises the following steps.

[0086] (1) Preparation of the multi-ring carbonate resin: maleic anhydride and pentaerythritol are added into a reaction kettle, then N,N-dimethylformamide is added, and reaction is carried out at 150 DEG C for 5h until the acid value is constant, and then the reaction system is cooled to room temperature. Then glycerol carbonate is added, and reflux is carried out by using xylene (20% of the total mass), and reaction is carried out at 200 DEG C until the acid value is lower than 3.0 mgKOH / g, and then the reaction system is cooled to room temperature, washed with water twice to remove unreacted glycerol carbonate, and finally solvent is removed to obtain the multi-ring carbonate resin. The reaction process is shown in formula (11)-(12).

[0087]

[0088] (2) Preparation of amine curing agent: Hexanediamine, amino-terminated polydimethylsiloxane-8000, 2,2'-diaminodiphenyl disulfide were mixed in proportion to obtain the amine curing agent.

[0089] (3) Preparation of non-isocyanate polyurethane coating: The polyfunctional cyclic carbonate resin was mixed with the amine curing agent, and cured at 140℃ for 5h to obtain the antifouling self-repairing non-isocyanate polyurethane coating.

[0090] Table 6 Formulation of non-isocyanate polyurethane coating of Example 6

[0091] No. Composition Weight fraction 1 Maleic anhydride 26.50 2 Pentaerythritol 9.20 3 Glycerol carbonate 40.00 4 N,N-dimethylformamide 25.00 5 Hexamethylenediamine 9.80 6 Tetraethylenepentamine 11.70 7 Amino-terminated polydimethylsiloxane-8000 1.00 8 2,2'-diaminodiphenyl disulfide 6.80 9 Total 130.00

[0092] The non-isocyanate polyurethane coating after curing in Examples 1-6 was tested for performance, and a commercialized two-component polyurethane coating prepared by using Arcol Polyol 3553 polyester polyol (curing agent: HDI produced by Asahi Kasei Corporation) was used as a comparative example, and the test results are shown in Table 7.

[0093] Table 7 Test results of coating performance

[0094]

[0095] As shown in Table 7, the non-isocyanate polyurethane coating prepared by the present application has good self-repairing, antifouling and self-cleaning properties. The self-repairing efficiency of the non-isocyanate polyurethane coating in the present example can reach 70% after a short period of self-repairing. The static water contact angle of Examples 1-6 is greater than 95 degrees, which is greatly improved compared with the comparative example, and has strong self-cleaning and antifouling properties. Compared with the patent with publication number CN109593451A which uses biotoxic and expensive fluorine-containing substances for modification and the patent with publication number CN105504272A which uses a complicated preparation process of POSS modification, the present application uses chemically inert, moderately priced and environmentally friendly organic silicon and disulfide-containing materials to prepare non-isocyanate polyurethane coating, and the coating has good corrosion resistance, self-cleaning performance, self-repairing properties and other advantages, and can be widely used in the preparation of antifouling self-cleaning, self-repairing and sustainable coatings or industrial paints.

[0096] The above examples are the preferred embodiments of the present application, but the embodiments of the present application are not limited by the examples, and any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present application are equivalent replacement methods and are included in the protection scope of the present application.

Claims

1. A method for preparing a non-isocyanate polyurethane coating that is antifouling and self-healing, characterized in that, Includes the following steps: Preparation of polycyclic carbonate resin: Anhydride and polyol are added to an organic solvent and mixed evenly. The mixture is reacted at 100-150℃ for 3-5 h until the acid value is constant, and then cooled to room temperature. Glyceryl carbonate is then added, and the mixture is refluxed with xylene. The reaction is carried out at 180-210℃ until the acid value is below 3.0 mgKOH / g. The mixture is then cooled to room temperature, washed 2-3 times with water to remove the solvent, and the polycyclic carbonate resin is obtained. The polycyclic carbonate resin has a star-shaped structure. The acid anhydride is at least one of phthalic anhydride, trimellitic anhydride, methylhexahydrophthalic anhydride, succinic anhydride, maleic anhydride, glutaric anhydride, and adipic anhydride; The polyol is at least one of trimethylolpropane, pentaerythritol, bis(trimethylolpropane), and bis(pentaerythritol); Preparation of polyamine curing agents: Polyamines, amino-terminated polydimethylsiloxanes and disulfide-containing amine compounds are mixed and stirred evenly to prepare polyamine curing agents; The amino-terminated polydimethylsiloxane has a molecular weight of 2000-8000 and has the following structural formula: Preparation of non-isocyanate polyurethane coating: Polycyclic carbonate resin and polyamine curing agent are mixed evenly and cured at 120~150 ℃ for 3~5 h to obtain antifouling and self-healing non-isocyanate polyurethane coating.

2. The method for preparing the antifouling, self-healing non-isocyanate polyurethane coating according to claim 1, characterized in that, The polyamine is at least one of isophorone diamine, p-phenylenediamine, ethylenediamine, butanediamine, pentanediamine, hexanediamine, octanediamine, decanediamine, polyethyleneimine, polyetherdiamine, diethylenetriamine, and tetraethylenepentamine.

3. The method for preparing the antifouling, self-healing non-isocyanate polyurethane coating according to claim 1, characterized in that, The disulfide-containing amine compound is at least one of 2,2'-diaminodiphenyl disulfide, dibenzocyclooctyn-disulfide-amino, and cystamine dihydrochloride.

4. The method for preparing the antifouling, self-healing non-isocyanate polyurethane coating according to claim 1, characterized in that, The organic solvent is at least one of N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, and acetonitrile.

5. The method for preparing the antifouling, self-healing non-isocyanate polyurethane coating according to claim 1, characterized in that, The mass ratio of the acid anhydride, polyol, and glyceryl carbonate is (25~45):(5~15):(25~45).

6. The method for preparing the antifouling, self-healing non-isocyanate polyurethane coating according to claim 1, characterized in that, The mass ratio of the polyamine, the amino-terminated polydimethylsiloxane, and the disulfide-containing amine compound is (10~25):(1~10):(1~10).

7. The method for preparing the antifouling, self-healing non-isocyanate polyurethane coating according to claim 1, characterized in that, The mass ratio of the polycyclic carbonate resin to the polyamine curing agent is (75~85):(18~30).

8. A non-isocyanate polyurethane coating that is antifouling and self-healing, characterized in that, It is prepared by the method for preparing antifouling, self-healing non-isocyanate polyurethane coatings according to any one of claims 1 to 7.

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