阅读说明：本技术 一种具有自修复功能的聚乳酸聚碳酸酯基聚氨酯及其制备方法、用途 (Polylactic acid polycarbonate-based polyurethane with self-repairing function and preparation method and application thereof ) 是由 王文焕 王鹏 张盾 于 2021-08-18 设计创作，主要内容包括：本发明属于海洋防污技术领域,涉及一种具有自修复功能的聚乳酸聚碳酸酯基聚氨酯基底材料及其制备方法、用途。一种具有自修复功能的聚乳酸聚碳酸酯基聚氨酯,其软段组分为双羟基封端的聚乳酸聚碳酸酯聚合物大分子二元醇；其硬段组分为二苯甲基二异氰酸酯、异佛尔酮二异氰酸酯、1,6-己基二异氰酸酯中的任一种。采用本发明提供的具有自修复功能的聚乳酸聚碳酸酯基聚氨酯材料可以制备出自修复仿生超滑涂层和具有防污剂温敏控释功能的自修复海洋防污涂层,自修复功能和防污剂温敏控释功能赋予涂层更长久的防治生物污损的性能。同时该聚乳酸聚碳酸酯基聚氨酯材料及涂层的制备方法简单,反应条件温和高效。(The invention belongs to the technical field of marine antifouling, and relates to a polylactic acid polycarbonate based polyurethane base material with a self-repairing function, and a preparation method and application thereof. A self-repairing polylactic acid polycarbonate polyurethane comprises a soft segment component of dihydroxy-terminated polylactic acid polycarbonate polymer macrodiol; the hard segment component is any one of diphenyl methyl diisocyanate, isophorone diisocyanate and 1, 6-hexyl diisocyanate. The polylactic acid polycarbonate-based polyurethane material with the self-repairing function can be used for preparing self-repairing bionic super-smooth coatings and self-repairing marine antifouling coatings with the antifouling agent temperature-sensitive controlled-release function, and the self-repairing function and the antifouling agent temperature-sensitive controlled-release function endow the coatings with longer biofouling prevention performance. Meanwhile, the preparation method of the polylactic acid polycarbonate-based polyurethane material and the coating is simple, and the reaction conditions are mild and efficient.)

1. A polylactic acid polycarbonate-based polyurethane having a self-repairing function, characterized in that: the soft segment component of the polylactic acid polycarbonate-based polyurethane is dihydroxy-terminated polylactic acid polycarbonate polymer macrodiol; the hard segment component is any one of diphenyl methyl diisocyanate, isophorone diisocyanate and 1, 6-hexyl diisocyanate.

2. The self-repairing polylactic acid polycarbonate-based polyurethane according to claim 1, wherein: the initiator of the macrodiol is any one of ethylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol and diethylene glycol.

3. A preparation method of polylactic acid polycarbonate polyurethane with self-repairing function is characterized by comprising the following steps:

under the protection of inert gas, adding a stirrer and an initiator into a round-bottom flask, and simultaneously adding lactide and trimethylene carbonate, wherein the molar ratio of the lactide to the trimethylene carbonate to the hydroxyl in the initiator is 10-200; stirring at room temperature until the two components of solid monomers are in a eutectic state;

quickly adding an organic base catalyst, wherein the molar ratio of the organic base catalyst to hydroxyl in the initiator is 0.1-5, continuously stirring at room temperature for 1 min, quickly raising the reaction temperature, and continuously reacting for 20 hours;

adding a chloroform solvent to dissolve after the reaction is finished, removing the catalyst and unreacted monomers from the obtained product, and drying to constant weight to obtain a polylactic acid polycarbonate copolymer;

adding a polylactic acid polycarbonate copolymer, diisocyanate and an organic solvent into a dry reactor under the protection of inert gas, and reacting for 4 hours at 90 ℃; slowly dripping a chain extender and an organic tin catalyst, wherein the molar ratio of amino of the chain extender to the organic tin catalyst is 0.1-10;

reacting at 110 ℃ for 2 hours, cooling to room temperature, and continuing to react for a period of time; after the reaction is finished, the polylactic acid polycarbonate polyurethane with the self-repairing function is obtained.

4. The method for producing a polylactic acid polycarbonate-based polyurethane having a self-repairing function according to claim 3, wherein: the diisocyanate is any one of diphenyl methyl diisocyanate, isophorone diisocyanate and 1, 6-hexyl diisocyanate.

5. The method for producing a polylactic acid polycarbonate-based polyurethane having a self-repairing function according to claim 3, wherein: the organic base catalyst is one or a mixture of more than two of 1,5, 7-triazabicyclo [4.4.0] dec-5-ene (TBD), aminomethyl-1, 5, 7-triazabicyclo [4.4.0] dec-5-ene (MTBD) and 1, 8-diazabicyclo [5.4.0] undec-7-ene (DBU) in any proportion.

6. The method for producing a polylactic acid polycarbonate-based polyurethane having a self-repairing function according to claim 3, wherein: the organic tin catalyst is one or a mixture of more than two of stannous octoate and dibutyltin dilaurate in any proportion.

7. Use of the polylactic acid polycarbonate-based polyurethane having a self-repairing function according to claim 1 or 2, wherein: the polylactic acid polycarbonate polyurethane is used as a substrate material for preparing the self-repairing bionic super-smooth coating.

8. Use of the polylactic acid polycarbonate-based polyurethane having a self-repairing function according to claim 1 or 2, wherein: the polylactic acid polycarbonate-based polyurethane is used as a substrate material for preparing the self-repairing marine antifouling coating with the temperature-sensitive controlled-release function of the antifouling agent.

9. A self-repairing bionic super-smooth coating is characterized in that: the polylactic acid polycarbonate-based polyurethane having a self-repairing function according to claim 1 or 2, which is used as a base material, wherein a lubricating oil is added to the base material.

10. A self-repairing marine antifouling coating with an antifouling agent temperature-sensitive controlled-release function is characterized in that: the polylactic acid polycarbonate-based polyurethane having a self-repairing function according to claim 1 or 2, which is used as a base material, wherein an antifouling agent is added to the base material.

Technical Field

The invention belongs to the technical field of marine antifouling, and relates to a polylactic acid polycarbonate based polyurethane base material with a self-repairing function, and a preparation method and application thereof.

Background

In recent years, with the rapid development of the marine industry, the problem of biofouling has received increasing attention. The main reason for the occurrence of marine biofouling is that marine organisms in the sea water adhere to the surfaces of ships and underwater structures, thereby causing corrosion damage to the surfaces of ship hulls and structures, and seriously affecting the safety of the ships and underwater structures. Inhibition of biofouling becomes a key to preventing marine corrosion and fouling, and the simplest and most straightforward way to prevent biofouling is to use antifouling coatings.

With the continuous progress of research, various types of antifouling coating materials continuously appear, various novel efficient environment-friendly antifouling coatings are developed in succession, but with the increasingly high use requirements of people on antifouling coating design, the defects of the existing antifouling coatings are gradually revealed, such as difficult maintenance and construction operation, short antifouling service cycle and the like after the coatings are damaged. The bionic (pitcher plant) super-smooth surface receives extensive attention because of having good antifouling property, and a large amount of studies show that this type of coating does not contain toxic substance and can effectively prevent the adhesion of marine microorganism, but when this bionic surface's lubricating oil film or solid base material suffered to destroy, the antifouling ability on surface also can receive very big influence, and how to ensure antifouling ability's long-term effect is the technological problem that bionical super-smooth coating needs to solve in the middle of practical.

In the actual marine ecological environment, microorganisms usually do not have activity of being attached to the surface of a ship body in a low-temperature state, and the anti-fouling coating can continuously release the bactericide to cause certain waste and reduce the service time of the coating. In water at higher temperatures, however, it is desirable to deliver a sufficient amount of antimicrobial agent to provide good soil resistance. When the antifouling coating is damaged by the outside, the antifouling capability of the surface is greatly influenced. Therefore, the self-repairing marine antifouling coating with the temperature-sensitive controlled-release function of the bactericide has certain practical significance for improving the antifouling performance of the coating and enriching the types of antifouling coatings.

Disclosure of Invention

Aiming at the defects of the existing marine antifouling coating, the invention provides polylactic acid polycarbonate-based polyurethane with a self-repairing function and a preparation method thereof.

The invention solves the technical problem by adopting the technical scheme that the polylactic acid polycarbonate-based polyurethane with the self-repairing function is provided, and the soft segment component of the polylactic acid polycarbonate-based polyurethane is dihydroxy-terminated polylactic acid polycarbonate polymer macromolecular dihydric alcohol; the hard segment component is any one of diphenyl methyl diisocyanate, isophorone diisocyanate and 1, 6-hexyl diisocyanate.

Further preferably, the initiator of the macrodiol is any one of ethylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, and diethylene glycol.

The invention further provides a preparation method of the polylactic acid polycarbonate-based polyurethane with the self-repairing function, which comprises the following steps:

under the protection of inert gas, adding a stirrer and an initiator into a round-bottom flask, and simultaneously adding lactide and trimethylene carbonate, wherein the molar ratio of the lactide to the trimethylene carbonate to the hydroxyl in the initiator is 10-200; stirring at room temperature until the two components of solid monomers are in a eutectic state;

quickly adding an organic base catalyst, wherein the molar ratio of the organic base catalyst to hydroxyl in the initiator is 0.1-5, continuously stirring at room temperature for 1 min, quickly raising the reaction temperature, and continuously reacting for 20 hours;

adding a chloroform solvent to dissolve after the reaction is finished, removing the catalyst and unreacted monomers from the obtained product, and drying to constant weight to obtain a polylactic acid polycarbonate copolymer;

adding a polylactic acid polycarbonate copolymer, diisocyanate and an organic solvent into a dry reactor under the protection of inert gas, and reacting for 4 hours at 90 ℃; slowly dripping a chain extender and an organic tin catalyst, wherein the molar ratio of amino of the chain extender to the organic tin catalyst is 0.1-10;

reacting at 110 ℃ for 2 hours, cooling to room temperature, and continuing to react for a period of time; after the reaction is finished, the polylactic acid polycarbonate polyurethane with the self-repairing function is obtained.

More preferably, the lactide monomer is one or a mixture of more than two of levorotatory lactide, dextrorotatory lactide, racemic lactide and meso-lactide in any proportion.

More preferably, the diisocyanate is any one of benzhydryl diisocyanate, isophorone diisocyanate, and 1, 6-hexyl diisocyanate.

Further preferably, the organic base catalyst is one or a mixture of more than two of 1,5, 7-triazabicyclo [4.4.0] dec-5-ene (TBD), aminomethyl-1, 5, 7-triazabicyclo [4.4.0] dec-5-ene (MTBD) and 1, 8-diazabicyclo [5.4.0] undec-7-ene (DBU) in any proportion.

More preferably, the organic tin catalyst is one or a mixture of two or more of stannous octoate and dibutyltin dilaurate in any proportion.

More preferably, the organic solvent is one or a mixture of two or more of dichloromethane, chloroform, pentane, hexane, heptane, cyclohexane, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, N-dimethylformamide and N, N-dimethyl sulfoxide in any proportion.

The invention further provides application of the polylactic acid polycarbonate-based polyurethane with the self-repairing function, which is used as a substrate material for preparing a self-repairing bionic super-smooth coating or a self-repairing marine antifouling coating with an antifouling agent temperature-sensitive controlled-release function.

The invention further provides a self-repairing bionic super-smooth coating, which adopts polylactic acid polycarbonate-based polyurethane with a self-repairing function as a substrate material, and lubricating oil is added into the substrate material.

The invention also provides a self-repairing marine antifouling coating with the temperature-sensitive controlled-release function of the antifouling agent, the coating adopts polylactic acid polycarbonate polyurethane with the self-repairing function as a substrate material, and the antifouling agent is added into the substrate material.

The invention has the following beneficial effects:

(1) the bionic super-smooth coating prepared from the polylactic acid polycarbonate-based polyurethane with the self-repairing function has the function of realizing self-repairing of a substrate material through the action of hydrogen bonds in polyurethane molecules, so that the coating has the performance of preventing and treating biofouling for a longer time;

(2) the self-repairing marine antifouling coating prepared by adopting the polylactic acid polycarbonate-based polyurethane with the self-repairing function has the temperature-sensitive controlled-release function of the bactericide, and the release rate of the bactericide is increased or reduced when the water temperature is increased or reduced, so that the technical effect of bactericide slow release is achieved, and the problem of excessive loss caused by the continuous release of the bactericide of the traditional antifouling coating under the low-temperature condition is solved;

(3) the polylactic acid polycarbonate-based polyurethane with the self-repairing function provided by the invention has the advantages of simple preparation method, mild and efficient reaction conditions, and long-acting marine organism fouling prevention capability of an antifouling coating prepared from the material.

Drawings

FIG. 1 is a nuclear magnetic spectrum of a polylactic acid-polycarbonate polymer-based polyurethane with self-repairing function prepared in example 1 of the present invention;

FIG. 2 is a graph of the dynamic wettability of a self-healing bionic super-slip coating surface provided in example 3 of the present invention by a droplet (10 μ l), wherein the tilt angle of the bionic super-slip coating surface is 10 °;

fig. 3 is an image comparison of the self-repair process of the self-repair bionic super-slip coating provided in embodiment 3 of the present invention: (a) a photograph of a polylactic acid polycarbonate based polyurethane self-healing process; (b) a laser confocal image of a self-repairing process of the bionic super-smooth coating prepared by taking the polyurethane as a base material; (c) a laser confocal 3D image (scale bar is 500 mu m) of the bionic super-smooth coating self-repairing process prepared by taking the polyurethane as a base material;

FIG. 4 is a comparison of the super-lubricity before and after self-repairing of the self-repairing bionic super-lubricity coating provided in embodiment 3 of the invention;

fig. 5 is a comparison of the cumulative release rates of the drugs of the self-repairing marine antifouling coating with temperature-sensitive controlled-release function of the antifouling agent provided by embodiment 4 of the invention under different temperature conditions.

Detailed Description

In order to facilitate an understanding of the invention, the invention is described in more detail below with reference to the accompanying drawings and specific examples. Preferred embodiments of the present invention are shown in the drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.

The self-repairing of the substrate and the lubricating oil film is realized through the action of hydrogen bonds in polyurethane molecules and intermolecular osmotic pressure, and a solution is provided for the long-acting problem of the coating in marine biofouling protection.

Example 1 the polylactic acid polycarbonate based polyurethane with self-repairing function provided in this example was prepared by the following steps:

(1) preparation of polylactic acid polycarbonate copolymer: first, a round-bottomed flask, previously subjected to three repeated vacuum-bake-nitrogen purges, was charged with a stir bar and 1, 4-butanediol initiator (0.0375 g, 0.6 mmol), while adding levolactide (L-LA, 2.88 g, 0.02 mol.) and trimethylene carbonate (TMC, 2.04 g, 0.02 mol.). Then, the mixture was stirred at 25 ℃ for 30 min until the two components of the solid monomer were in a eutectic state. After this time, catalyst DBU (0.023 g, 0.21 mmol) was added quickly. The reaction was started by stirring at room temperature for 20 s, about 40After s (1 min total), the polylactic acid component formed first begins to crystallize out. At this point the reaction was rapidly warmed to 61 ℃ (above the glass transition temperature of polylactic acid) and continued for 20 hours. Adding chloroform solvent to dissolve after the reaction is finished, adding metered benzoic acid solution (polymerization reaction terminator), removing catalyst and unreacted monomer from the obtained product by using excessive anhydrous methanol precipitation glue, and drying at 40 ℃ in vacuum to constant weight. The product was tested by organogel chromatography (GPC)M _n9200 and PDI of 1.07.

(2) Preparation of polylactic acid polycarbonate based polyurethane: at normal temperature and normal pressure, under the protection of inert gas argon, 4.5g of the polylactic acid polycarbonate copolymer synthesized in the example 1 and 0.222g of isophorone diisocyanate are added into 20 mL of N, N-dimethylformamide, and reacted for 4 hours at 90 ℃ to obtain NCO-terminated polyurethane prepolymer, then heated to 110 ℃, 0.037g of chain extender 1, 3-propylene diamine and a small amount of stannous octoate catalyst are added into a flask, and the temperature is reduced to room temperature after the reaction is continued for 2 hours and the reaction is continued for 10 hours. The final product was dried in a vacuum oven at 80 ℃ for 12 hours after settling with deionized water. The product was tested by organogel chromatography (GPC)M _nIs 3.55 multiplied by 10⁴And PDI is 1.21.

Molecular structure characterization was performed on the polyurethane prepared in example 1 as shown in fig. 1, where δ e =2.89 ppm and δ h =1.05 ppm correspond to characteristic peaks of methylene and methyl groups on the IPDI ring. δ f =3.66 ppm and δ g =3.70ppm correspond to methyl and methylene groups attached to urethane bonds. The methylene groups in the chain extender were then assigned δ i =1.88 ppm and δ j =2.77 ppm, respectively. In conclusion, the results of the 1H-NMR spectroscopy of the polyurethane confirm the successful preparation of the polylactic acid polycarbonate based polyurethane.

Example 2 the polylactic acid polycarbonate based polyurethane with self-repairing function provided in this example was prepared by the following steps: (1) preparation of polylactic acid polycarbonate copolymer: first, a round-bottomed flask, which had been subjected to vacuum-bake-nitrogen purging repeatedly three times in advance, was charged with a stirrer and a diethylene glycol initiator (0.0368 g, 0.5 mmol), while adding levolactide (L-LA, 7.20 g, 0.05 mol.) and trimethylene carbonate (TMC, 5.10 g, 0.05 mol.). Then, the mixture was stirred at 25 ℃ for 30 min until the two components of the solid monomer were in a eutectic state. Thereafter, catalyst DBU (0.0575 g, 0.525 mmol) was added rapidly. The reaction was started by stirring at room temperature for 20 seconds, and after about 40 seconds (1 min total), the polylactic acid component formed first began to crystallize out. At this point the reaction was rapidly warmed to 61 ℃ (above the glass transition temperature of polylactic acid) and continued for 20 hours. Adding chloroform solvent to dissolve after the reaction is finished, adding metered benzoic acid solution (polymerization reaction terminator), removing catalyst and unreacted monomer from the obtained product by using excessive anhydrous methanol precipitation glue, and drying at 40 ℃ in vacuum to constant weight. The product Mn was 26200 and PDI was 1.12 as determined by organogel chromatography (GPC).

(2) Preparation of polylactic acid polycarbonate polymer based polyurethane: adding 5.24g of the synthesized polylactic acid polycarbonate copolymer and 0.0888g of isophorone diisocyanate into 20 mL of N, N-dimethylformamide at normal temperature and normal pressure under the protection of inert gas argon, reacting at 90 ℃ for 4 hours to obtain an NCO-terminated polyurethane prepolymer, heating to 110 ℃, adding 0.015g of chain extender 1, 3-propane diamine and a small amount of dibutyltin dilaurate catalyst into a flask, reacting for 2 hours, cooling to room temperature, and reacting for 12 hours. The final product was dried in a vacuum oven at 80 ℃ for 12 hours after settling with deionized water. The product Mn was 7.55X 104 and PDI was 1.31 as determined by organogel chromatography (GPC).

Embodiment 3 the self-repairing biomimetic super-smooth coating based on polylactic acid polycarbonate based polyurethane with self-repairing function provided in this example has a molecular structure of polylactic acid polycarbonate based polyurethane, and the substrate material is mixed with silicone oil.

The self-repairing bionic super-smooth coating based on the polylactic acid polycarbonate-based polyurethane with the self-repairing function is prepared by the following method:

(1) a polylactic acid polycarbonate-based polyurethane having a self-repairing function was prepared by the method of example 1;

(2) dissolving the dried polylactic acid polycarbonate-based polyurethane and silicone oil with the kinematic viscosity of 200cst in tetrahydrofuran according to a proper proportion, stirring and heating to volatilize part of solvent, then coating the solvent on the surface of Q235 steel, and completely drying at room temperature to obtain the bionic super-smooth coating with the self-repairing function.

The method comprises the following steps of measuring the sliding property of a water drop on the surface of the inclined super-smooth coating by a contact angle measuring instrument, specifically: a drop of water (10. mu.l) was dropped on the surface of the ultra-smooth coating prepared in example 3 with a gradient of less than 10 °, and then the distance of the drop after sliding on the surface for a certain period of time was recorded with a contact angle meter.

It can be seen from fig. 2 that the liquid drops can automatically slide off the surface of the super-slip coating prepared in example 3, and the liquid drops can stably and quickly slide, indicating that the surface of the bionic super-slip coating has excellent super-slip performance.

The repairing condition of the scratched ultra-smooth surface scratch is observed through a laser confocal microscope, and specifically comprises the following steps: and scratching the surface of the prepared sample by using a scalpel which is vertical to the surface, and taking a picture by using a laser confocal microscope for recording. And then placing the scratched sample in an environment of 40 ℃ for standing and repairing for 20 minutes, and taking a picture by using a laser confocal microscope and recording a 3D image.

As can be seen from (a), (b), and (c) in fig. 3, the bionic super-smooth coating with self-repairing function has reliable self-repairing performance at room temperature. Based on the good flexibility of the molecular chain and the combined action of hydrogen bonds among molecules, the sample can be completely repaired within 20 minutes until the trace disappears at 40 ℃.

Fig. 4 shows that the bionic super-slip coating with the self-repairing function prepared in example 3 regains good super-slip performance after self-repairing, which indicates that the bionic super-slip coating has reliable self-repairing performance.

Embodiment 4 the self-repairing marine antifouling coating having a temperature-sensitive controlled-release function of an antifouling agent provided in this embodiment has a molecular structure of a base material of polylactic acid polycarbonate based polyurethane having a self-repairing function, and a bactericide is mixed in the base material.

The self-repairing marine antifouling coating with the temperature-sensitive controlled-release function of the antifouling agent is prepared by the following steps:

(1) a polylactic acid polycarbonate-based polyurethane having a self-repairing function was prepared by the method of example 2;

(3) dissolving the dried polylactic acid polycarbonate-based polyurethane and the bactericide capsaicin in dichloromethane according to a proper proportion, stirring and heating to volatilize part of the solvent, then coating the solvent on the surface of Q235 steel, and completely drying at room temperature to obtain the self-repairing marine antifouling coating with the bactericide temperature-sensitive controlled-release function.

The cumulative release rates of the biocides at different temperatures in the coatings prepared in example 4 were measured, and the cumulative release rates of the biocides in the coatings tended to increase with increasing temperature as shown in fig. 5. By utilizing the characteristic, the effect of controlling the slow release of the medicine in the coating in a low-temperature environment can be achieved, and the problem of excessive loss caused by the continuous release of the bactericide under the low-temperature condition is avoided. Meanwhile, when the coating material is damaged, self-repairing can be realized through the internal acting force of molecules.