KR100535950B1 - Biocatalytic synthesis of polyphenolics and its application - Google Patents

Abstract

The present invention relates to a method for producing a phenolic polymer using a biocatalyst and its use. More particularly, the phenolic monomer derived from a plant is effectively polymerized in an organic solvent by the action of a redox enzyme, which is a biocatalyst. When the polymer is prepared and applied to the antifouling paint after curing, the surface energy of the phenolic polymer coating film formed by coating the antifouling paint is small to inhibit adhesion of physical marine organisms, and also consumes antifouling functional groups. The present invention relates to a method for producing a phenolic polymer using a biocatalyst which exhibits excellent characteristics of chemical antifouling action that continuously expresses durability, and a use thereof.

Description

Method for producing phenolic polymer using biocatalyst and use thereof {Biocatalytic synthesis of polyphenolics and its application}

The present invention relates to a method for producing a phenolic polymer using a biocatalyst and its use. More particularly, the phenolic monomer derived from a plant is effectively polymerized in an organic solvent by the action of a redox enzyme, which is a biocatalyst. When the polymer is prepared and applied to the antifouling paint after curing, the surface energy of the phenolic polymer coating film formed by coating the antifouling paint is small to inhibit adhesion of physical marine organisms, and also consumes antifouling functional groups. The present invention relates to a method for producing a phenolic polymer using a biocatalyst which exhibits excellent characteristics of chemical antifouling action that continuously expresses durability, and a use thereof.

"Anti-fouling action" described in the specification of the present invention, when applied as a coating material on the bottom of the ship to maintain the shape of the ship and increase the durability of the ship by inhibiting the adhesion of marine organisms, especially barnacles, mussels, algae, microorganisms, etc. It means to act.

Conventional antifouling paints are manufactured by blending a polymer of a tin-containing material monomer such as tributyltin, a copper-based compound such as copper nitrous oxide, and the like to have antifouling action on a petrochemical resin. Although such heavy metal antifouling compounds are known to have good antifouling ability, the toxic effects of heavy metal antifouling compounds have been known in recent years. In particular, tin-based compounds have been banned in Korea since 2003, and all developed countries have banned the use of them five years ago [Trentin, I., etc.]. Progress In Organic Coatings, 42, 15, 2001].

As another type of antifouling coating material that does not use heavy metal antifouling materials, a compound of a silicone polymer has been developed. Such silicone-based polymers significantly reduce the free energy of the surface and physically inhibit the adhesion of marine organisms. However, since the silicone-based polymer does not have a chemical antifouling ability, adhesion of marine organisms is observed when the ship's traveling speed is below a certain range. In addition, the silicone-based polymer has a high cost of the resin itself, and at the same time has a disadvantage in that the coating work is difficult due to the small coating adhesion in painting the silicone-based polymer on the ship. In addition, the physical strength is lower than that of heavy metal-containing antifouling paints, which may be easily damaged by impacts that may occur when the ship is in operation (Wynne, K.J., etc., Biofouling, 11, 277, 2000).

Since ancient times, paints called lacquer have been used. The main component of the lacquer is characterized in that it is polymerized by racase present together as catechol lipids derived from plants to form a coating material. Such a lacquer coating material is known to be very excellent in rust prevention, anticorrosion, moisture proof and durability, but the production of the main raw material is limited, there is a limit to use for industrial use. In addition, the polymerization of lacquer is an enzyme called laccase, which acts as a catalyst. In this case, since the reaction occurs until the crosslinking process in addition to the polymerization, a highly skilled coating technique is required for use as a paint. In particular, because the laccase enzyme requires oxygen in the air during the reaction, it is difficult to supply oxygen when the coating film thickness exceeds a predetermined level. This difficulty in oxygen supply is a major obstacle to the coating film as a result, it is very difficult to form a uniform coating coating film (Tsujimot, T. etc., Macromol. Chem. Phys. 202, 3420-3425, 2001).

When polymerizing a phenolic compound without using an enzymatic reaction, hexamethylenetetraamine, which is a condensation reaction between formaldehyde and ammonia, or formalin may be used. In this case, due to the polymerization of the phenolic monomer, it is possible to synthesize an organic solvent soluble polyphenolics, but the use of a toxic substance such as formalin used there is a problem. In addition, when synthesizing a phenolic polymer using a chemical such as formalin, there is a disadvantage in that a double bond of a lipid group attached to the side chain of a phenolic monomer is consumed, which makes it difficult to cure the phenolic polymer thus formed by radical reaction. have.

Accordingly, the inventors of the present invention have made efforts to solve the problems caused by the toxicity of the heavy metal-containing antifouling paints and the problems of chemical antifouling action of the silicone polymer-containing antifouling paints. By using a redox enzyme derived from natural products as a catalyst, the phenolic polymer can be easily prepared under milder conditions than the conventional polymerization method by polymerizing in an organic solvent. When applied, the surface energy of the formed coating film is lowered, so that the physical antifouling action is excellent, and at the same time, the durability and protein resolution of the coating film are improved, thereby discovering that the chemical antifouling ability is excellent.

Accordingly, an object of the present invention is to provide a method for efficiently preparing a phenolic polymer which simultaneously exhibits physical antifouling action and chemical antifouling action and its use thereof.

The present invention is characterized by a method for producing a phenolic polymer and its use for polymerizing a vegetable phenolic monomer using an oxidoreductase in an alcoholic organic solvent to which an oxidizing agent is added.

The present invention also includes a method of curing the polymerized phenolic polymer described above using a transition metal and an organic ligand complex as a curing catalyst and the use of the cured phenolic polymer.

The present invention will be described in detail as follows.

The present invention can effectively polymerize phenolic polymers under milder conditions compared to the conventional method for preparing phenolic polymers by polymerizing phenolic monomers derived from plants in organic solvents under the action of oxidoreductase, a biocatalyst. have. In addition, the polymerized phenolic polymer exhibits excellent antifouling action on its own, and in particular, when it is cured using a specific curing catalyst and applied to antifouling paints, the surface energy of the coating film formed by coating the antifouling paint is small so that the physical marine Since it effectively inhibits the adhesion of organisms and also maintains durability because antifouling agents are not consumed, the resolution of proteins secreted by adherents lasts for a long time, resulting in excellent chemical antifouling effects. .

Hereinafter, a phenolic polymer is formed in an organic solvent using a vegetable phenolic monomer as a starting material, and the preparation method of the present invention using a redox enzyme as a biocatalyst will be described in detail according to the components and the preparation steps.

Specific examples of the vegetable phenol-based monomers used in the present invention include those selected from cardanol, cardol, anacardic acid, zinc high-ic acid, methylcardol, urushiol, thitsiol, langool and lacol. Currently, about 1 million tons or more of the above-mentioned vegetable phenolic monomers are produced as a by-product of food, and a considerable amount thereof is used as a simple fuel, and there is no problem in the supply thereof.

An oxidoreductase is used as a biocatalyst in the process of polymerizing the above-mentioned vegetable phenolic monomer of the present invention. As the oxidoreductase, polyphenol oxidase, peroxidase and laccase are used. In particular, peroxidase is preferable among the above-described oxidoreductases, and as the peroxidase, natural peroxidases such as plant-derived, bacterial-derived, and fungal-derived can be used. Among the peroxidases described above, the most preferable result can be obtained when a fungal-derived peroxidase, in particular Aspergillus peroxidase, is used in terms of stability and yield of enzymatic activity. Conditions such as temperature and pH applied to the reaction is adjusted according to the physiological characteristics of the enzyme used.

The amount of the oxidoreductase as described above is 0.1 to 1.0% by weight relative to the amount of the phenolic monomers used. If the amount is less than 0.1% by weight, the reaction rate is too small, so that the time required for the reaction is long, and 1.0 weight is used. In case of exceeding%, there is a problem in that a stable phenolic polymer cannot be obtained due to the economical problem and the phenomenon in which the polymerized product crosslinks itself.

In order to polymerize vegetable phenolic monomers using redox enzymes, an oxidizing agent is required. Examples of the oxidizing agent include hydrogen peroxide, organic hydrogen peroxide such as t-butyl hydroperoxide and t-ethyl hydroperoxide, and the like, and are used in a molar ratio of 0.1 to 1.0 with respect to the vegetable phenol monomer. At this time, if the amount of the oxidizing agent is less than 0.1 molar ratio, there is a problem that the polymerization yield is reduced, and when the amount exceeds 1.0 molar ratio, there is a problem that the activity of the oxidoreductase is rapidly reduced.

The above-mentioned vegetable phenolic monomer is polymerized in an organic solvent using the biocatalyst described above, and the organic solvent has a stable activity according to the type of vegetable phenolic monomer to be polymerized and the type of redox enzyme used. You must choose something that can last.

In the present invention, an alcohol-based organic solvent, which is a polar solvent, is used among various organic solvents. Specifically, for example, isopropanol, methanol, ethanol, t-butanol, or the like may be used. In addition to the alcohol-based organic solvent, other solvents tend to significantly reduce the activity and stability of the oxidoreductase used as a biocatalyst, and as a result, the yield of the polymer tends to be greatly reduced.

The alcohol-based organic solvent is used by mixing with 30 to 70% by volume of the buffer, the alcohol-based organic solvent used is 30 to 70% by volume of the total reactant. At this time, when the amount of the organic solvent is less than 30% by volume, there is a problem in that the monomer of a high concentration cannot be reacted due to the layer separation phenomenon caused by the decrease in the solubility of the vegetable phenolic monomer. In addition, when the amount of the organic solvent used exceeds 70% by volume, the activity of the oxidoreductase used as a biocatalyst tends to decrease rapidly, so that there is a problem in that the reaction cannot be continued.

As described above, in the present invention, by using a oxidoreductase in the process of preparing a phenolic polymer by polymerizing a vegetable phenolic monomer, mild conditions, such as a high temperature and a high pressure at the time of manufacturing a conventional phenolic polymer, are not mild. It can be carried out in, and can be obtained a higher molecular weight phenolic polymer than the conventional manufacturing method while making improvements in production, such as not using toxic compounds such as formalin.

In addition, in the present invention, in order to increase the characteristics of chemical antifouling action, compounds such as oxsaicin, nonibamide, hydroxyquinone, ferulic acid, and gallic acid, which are known to have antifouling action, are especially phenolic monomers. It can be added during the polymerization process to form a complete polymer, the amount of the used may be used 5 to 20% by weight based on the total weight of the reactants, when the amount exceeds 20% by weight is a disadvantage that the copolymerization of the phenolic polymer is not smooth have. In the case of using a compound known to have an antifouling functional group as described above, the antifouling functional group of the formed phenolic polymer is not consumed further and remains durable and consequently can maintain the antifouling effect for a longer period of time.

The phenolic polymer prepared by the method as described above can be applied to various fields that require antioxidant capacity because it shows excellent antioxidant properties by itself, and specifically, for example, internal coating materials of food storage containers and devices, It can be used as a material for marine coating compositions requiring antifouling action. In addition, it is generally applicable to the industrial field in which phenolic polymers have been used.

In order to apply the phenolic polymer polymerized by the oxidoreductase to the coating material as described above, it is required to undergo a curing process utilizing the radical crosslinking reaction of the alkenyl group attached to the side of the phenolic polymer. As a curing catalyst that can be used for curing, a complex of a transition metal and an organic ligand is used. Specifically, for example, cobalt naphthenate, manganese naphthenate, or the like can be used. The amount of the curing catalyst used is 0.05 to 0.3% by weight relative to the amount of the phenolic polymer. When the amount of the curing catalyst is less than 0.05% by weight, it takes a long time to cure and the strength of the coating film coated with the cured phenolic polymer is increased. When the amount of the curing catalyst used exceeds 0.3% by weight, the curing process proceeds too fast and the pot life is rapidly shortened, which makes it difficult to coat and causes problems such as wrinkles during coating.

As described above, a phenolic polymer is prepared in an organic solvent using a vegetable phenolic monomer as a starting material and an oxidoreductase as a biocatalyst, and then a transition metal and an organic radical generating material in the curing process of forming a coating film. By controlling the curing action using the complex of the ligand solves the problem caused in the practical application of the coating material.

The coating film coated with the phenolic polymer obtained by the above method has a very small surface energy, so that the adhesion of marine organisms is physically suppressed similarly to the silicone antifouling paint.

Although this invention is demonstrated concretely based on an Example, this invention is not limited by the following Example.

Example 1

In general, cardanol (Palmer International, USA) isolated from cashew nut extracts has a purity of 90-95%, which contains about 3-6% by weight of cadol.

0.6 g of cardanol (2 mmol) was dissolved in a mixed solution of 12.5 ml of isopropanol and 12.5 ml of phosphate buffer (0.1 M, pH 7.0) followed by 20 mg of peroxidase (soybean peroxidase, Sigma, USA). Was added, and 300 ?? of 30% hydrogen peroxide solution were added continuously and evenly over 6 hours. The reaction temperature is carried out at room temperature and the mixing degree is carried out so that the entire solution can be uniformly mixed. After the reaction, the reaction solution is concentrated under reduced pressure, and 20 ml of ethyl acetate is added thereto. The portion dissolved in the ethyl acetate solvent was recovered and concentrated by removing the solvent under reduced pressure.

Figure 1a shows the cardanol before the reaction, and Figure 1b shows the nuclear magnetic resonance spectrum of the polycardanol after the reaction. Looking at Figures 1a and 1b it can be seen that the overall hydrogen peak is widened after the reaction between 6 ~ 7.2 ppm, especially the hydrogen peak located in the benzene ring is mainly disappeared by the peroxidase benzene ring and benzene ring It was confirmed that the reaction is connected directly.

Examples 2-3 and Comparative Examples 1-3

While reacting under the same conditions as in Example 1, the polymerization characteristics of cardanol by using another organic solvent instead of isopropanol as a solvent were examined, and the polymerization characteristics of cardanol according to the type of organic solvent are shown in Table 1 below. .

Remarks Cardanol (mmol) Organic solvent Biocatalyst yield(%) Mw Mn Example 1 2.0 Isopropanol SBP 72.5 8,221 3,400 Example 2 2.0 Methanol SBP 42.5 12,808 3,540 Example 3 2.0 ethanol SBP 50.4 10,974 4,096 Comparative Example 1 2.0 t-butanol SBP 0 - - Comparative Example 2 2.0 1,4-dioxane SBP 0 - - Comparative Example 3 2.0 Isopropanol HRP 0 - - SBP: Soybean peroxidase HRP: Horse radish peroxidase

As can be seen in Table 1, when the soybean peroxylase is used as a biocatalyst, polycardanol is synthesized when alcohol is used as an organic solvent, but polycardanol is hardly obtained when other organic solvents are used (Comparative Example 1 2). In addition, when horseradishperoxidase is used in addition to soybean peroxidase, polycardanol was not synthesized at all under isopropanol solvent conditions (Comparative Example 3).

The peroxidase activity during the reaction was measured using a colorimetric method using ABTS (azinobisethylbenzothiazolinesulfonate), and the molecular weight of the product was measured using GPC (Gel permeation chromatography) equipped with a refractive index sensor. As a result, average molecular weights ranged from 8,000 to 12,000, with average yields of over 70%.

Peroxidase activity remaining during the reaction is shown in FIG. 2. As can be seen in Figure 2 it can be seen that under the isopropanol solvent conditions relatively stable activity is maintained up to 2 hours after the start of the reaction. Similar trends can be seen under ethanol and methanol conditions, but the activity of peroxidase can be rapidly reduced in solvents without polymer synthesis of cardanol (Comparative Examples 1 and 2).

In view of the above results, it can be seen that an appropriate organic solvent should be selected according to the type of peroxidase to be used to keep the activity of the peroxidase stable.

Example 4

6 g cardanol was dissolved in a mixed solution of 17.5 ml isopropanol and 7.5 ml phosphate buffer (0.1 M, pH 7.0), followed by a peroxidase (aspergillus peroxidase, Novozyme, Denmark) was added, and 3000 [mu] l of 15% hydrogen peroxide solution was continuously added evenly over 5 hours. The reaction temperature was carried out at room temperature and the degree of mixing was performed so that the entire solution could be uniformly mixed. After the reaction, the reaction solution was concentrated under reduced pressure, and then 20 ml of ethyl acetate was added thereto, and the portion dissolved in the ethyl acetate solvent was recovered, and then the solvent was removed by concentration under reduced pressure. The average molecular weight of the product was 8,000 to 12,000, and the average yield was determined to be 90% or more.

The change in the degree of ringing of aspergillus peroxidase according to the type of solvent is shown in FIG. 3, and when the 1,4-dioxane and t-butanol are used, the peroxidase activity is maintained for a certain period of time. However, it was observed that delamination occurred under these solvent conditions. Therefore, it can be seen that it is advantageous to use isopropanol when synthesizing polycardanol using aspergillus peroxidase. In addition, when aspergillus peroxidase was used, the reaction proceeded in a yield of more than 90% even in an environment where the concentration of cardanol was about 24% (w / v).

It is thought that the higher the concentration of the monomer in the synthesis of general polymers, the more economical the productivity in the process and the monomer concentration of 24% (w / v) in the present invention is sufficiently economical. Therefore, it is possible that the process of synthesizing the polymer using Asrugillsperperoxidase is very commercially feasible.

Example 5

Cadol was isolated from cashew nut extracts (AF6155, Palmer International, USA) in the following manner. 50 g of cashew nut extract was dissolved in 467 ml of methanol, and 200 ml of aqueous ammonia solution (25%) was added and stirred. After adding n-hexane four times to extract impurities, this n-hexane solvent layer was separated and discarded. The aqueous methanol layer containing ammonia was neutralized with 17.5% hydrochloric acid, and then extracted by adding 200 ml of ethyl acetate / hexane (8: 1) solvent. 15 ml of 2.5% hydrochloric acid was added to the extracted solvent to remove impurities. Finally, the remaining water was removed using anhydrous sodium sulfate. Finally, pure kadol was obtained by concentration under reduced pressure, which was confirmed using high performance liquid chromatography and hydrogen magnetic resonance spectroscopy.

To synthesize polycardol, 0.6 g of cardol and 2 mg of aspergillus peroxidase were added to a mixed solution of 12.5 ml of t-butanol and 12.5 ml of phosphate buffer (0.1 M, pH 7.0). The reaction was proceeded at room temperature (25 ° C.) while injecting 0.34 ml of 10% hydrogen peroxide at a constant rate for 5 hours using a syringe pump. After 24 hours, the reaction mixture was concentrated under reduced pressure, and 30 ml of ethyl acetate and 10 ml of distilled water were added thereto to separate a portion dissolved in an ethyl acetate solvent. The ethyl acetate layer was concentrated under reduced pressure and low temperature methanol was added to the remaining portion to remove the portion dissolved in methanol. At this time, the molecular weight was about 15,000, the yield was 80% or more.

Comparative Example 2

In the case of using Aspergillus peroxidase, the relative activity of the peroxidase according to the reaction organic solvent type and the buffer capacity was measured and shown in Table 2 below. Unlike other solvents, when the ratio of t-butanol and the buffer solution is 5: 5, the peroxidase activity is very high compared to the volume ratio of the other organic solvent or the buffer solution. Considering the hydrophobicity of the substrate in the polymerization of the kadol containing two hydroxyl groups in the benzene ring, it is very important to select a solvent that can easily dissolve it and maintain the peroxidase activity. 4 shows the effect of buffer capacity on molecular weight and yield in the polymerization of kadol using aspergillus peroxidase. When the ratio of the buffer solution and the organic solvent became 5: 5, it was observed that insoluble precipitate was formed as the reaction time proceeded. At this time, the yield is about 80% as shown in Figure 4, when the buffer capacity is smaller than this, the enzyme activity is reduced and the yield is obtained low, while in the case of high enzyme activity is increased but the solubility of the resulting polycardol is also reduced, also yield This decreasing problem occurred. On the other hand, in the case of molecular weight, it did not change greatly depending on the buffer capacity in the range of 11,000 to 17,000. In the case of polycardol, which is a reaction product, it was confirmed by hydrogen nuclear magnetic resonance spectroscopy that the unsaturated group in the side chain did not react, which is similar to polycardanol.

Buffer capacity / organic solvent ratio 0 % 10% 20% 30% 40% 50% Isopropanol 0.3 1.0 0 0 0 0 Methanol 0.5 0.3 0 0 0 0 ethanol 0.3 0.3 0 0 0 0 t-butanol 0.5 12.8 37.5 23.7 0.53 75.0 1,4-dioxane 0.3 0.3 0 0 0 0 DMF 0.5 0 0 0 0 0 Acetone 0.3 0.5 0 0 0 0

Example 6

Under the same reaction conditions as in Example 5, the polymerization characteristics of the polycardol with the change of temperature were tested. In general, one of the reasons for synthesizing polymers using enzymes as catalysts is that unlike general inorganic catalysts, the reaction can proceed under mild reaction conditions. The remaining activity of Aspergillus peroxidase according to temperature is shown in FIG. 5. As shown in FIG. 5, the enzyme activity was measured to be good when the reaction temperature was 25 to 27 ° C., but when the reaction temperature was 30 ° C. or higher, the activity of the enzyme was rapidly decreased.

Changes in the yield and molecular weight of the polykadol according to the reaction temperature are shown in FIG. 6. The yield of enzyme polymer peaked at 27 ° C. and decreased significantly under other conditions. In particular, at a high temperature of more than 30 ℃ it is believed that this result is obtained because the activity of the enzyme is rapidly reduced as shown in FIG. In the case of molecular weight, it can be seen that the temperature decreases constantly.

Example 7

In the same experimental conditions as in Example 4, we examined the activity of aspergillus peroxidase and the yield and molecular weight change of polycardol according to the change of hydrogen peroxide concentration in the polymerization using polycardol as a monomer.

The change in peroxidase activity according to the concentration of hydrogen peroxide used is shown in FIG. 7, where the lower the concentration of hydrogen peroxide used, the more stable the peroxidase activity is. However, in order to synthesize polycardol, hydrogen peroxide, which is an oxidizing agent, is required. The molecular weight and yield of the polycardol polymerized using Aspergillus peroxidase are shown in FIG. 8. Yield is the highest value when the injection of 1.0 mmole, which is 1/2 to the substrate ie the kadol, yields more than 80%. On the other hand, the molecular weight decreased with increasing hydrogen peroxide concentration. This is because the decrease in the activity of the enzyme is greatly increased when the hydrogen peroxide concentration is high, it is determined that the polymerization of the polycardol is not made continuously. This can be seen in FIG. 9, but as the hydrogen peroxide concentration is increased, polycardol in a narrow molecular weight range (the longer the residence time means the lower molecular weight) can be seen to be mainly synthesized. On the other hand, the smaller the hydrogen peroxide concentration, it can be seen that the polycardol having a broad molecular weight distribution is synthesized. This is believed to be directly involved in the molecular weight distribution because hydrogen peroxide concentration acts as an important factor in the activity of the enzyme.

Example 8

Polycardanol and polycardol synthesized in Examples 1, 4, and 5 are linear polymers soluble in a solvent.

0.5% cobalt naphthenate and 0.5% methylethylketoneperoxide per polycardanol were added to allow crosslinking of polycardanol. This is to allow the unsaturated fatty acid groups present in the polycardanol to crosslink with each other, thereby forming a strong coating on the surface when coated on the surface. The hardness measurement results of the coating film formed by adding cobalt naphthenate and methyl ethyl ketone peroxide are shown in Table 3 below. Hardness was measured by standard pencil hardness method.

Remarks term Curing agent (% by weight) 1 hours 1 day 3 days 5 days 9th Do not administer - - - - - Cobalt Naphthenate (0.5) - 5B 2H 3H 3H Cobalt Naphthenate (1.0) - 6B 3H 3H 4H Cobalt naphthenate (0.5) / MEKP (0.5) Contact possible 2H 4H 5H 5H Commercial Marine Paints Contact possible 2H 2H 3H 4H Remarks: Antifouling paint for ships (International Paint, Netherlands) Remark: MEKP: Methyl ethyl ketone peroxide

As shown in Table 3 above, when cobalt naphthenate, which is a curing catalyst, is not added, the hardness does not increase at all over time. Increasing the content of cobalt naphthenate can be seen that the hardness increases within a short time. When methyl ethyl ketone peroxide was added to the same at the same time, the curing process proceeds very quickly, and it can be seen that the hardness is almost similar to or higher than that of commercial antifouling paints.

Example 9

In the same conditions as in Example 8, the polycardol was tested for curing and compared with that of polycardanol. After adding cobalt naphthenate to the cadol, polycardol, and polycardanol, the hardness measurement results using a pencil hardness meter are shown in Table 4 below.

sample Curing agent (cobalt naphthenate) time 2 hours 1 day 3 days 5 days 9th 14 days 20 days Cadol l 0.06% - - - - - - - 0.12% - - - - - - - 0.18% - - - - - - - Polycardoll 0.06% set 4B 1H 3H 4H 4H 5H 0.12% set 4B 3H 4H 5H 6H 7H 0.18% set 1H 2H 4H 5H 5H 7H Polarcardanol 0.06% set 1H 2H 4H 4H 4H 4H 0.12% set 1H 2H 4H 4H 4H 5H 0.18% set 1H 2H 4H 4H 4H 5H International Paint CompanyKRF 952 set 3H 3H 3H 3H 3H 3H set 3H 3H 3H 3H 3H 3H lacquer - - HB H 2H 3H 3H

As can be seen in Table 4, the cadol can be seen that the hardening does not proceed even if cobalt naphthenate is added, but the polycardol and the polycardanol are hardened compared to the polycardanol, and the hardening strength of the polycardol is greater. You can see that. This result shows that the polycardol shows excellent curing properties compared to the polycardanol having two hydroxyl groups. On the other hand, natural lacquer can be seen that the curing speed is quite slow.

Example 10

The antioxidant capacity of the cured coating film in Examples 8-9 was measured. First, 1 ml of 500 μM dippiech was added to 100 ml of distilled water, and then a coating film of 1 g-cured polycardanol and polycardol was deposited. The absorbance of DPI was measured at 517 nm with time, and the antioxidant capacity was measured using a decrease in DPI. The results are shown in Table 5 below.

The degree of contamination by marine adherents such as barnacles when the cured coating film of polycardanol, polycardol, or lacquer is deposited in seawater is shown in Table 6 below.

30 minutes 90 minutes 300 minutes Polycardanol 20% 30% 60% Polycardoll 35% 40% 70% Lacquer coating 20% 30% 40%

As shown in Table 5, it can be confirmed that the antioxidant power of the polycardol is considerably greater than that of the polycardanol and the lacquer coating film. This antioxidant power is known to be able to suppress the hardening of adhesive proteins secreted by marine attachment organisms such as barnacles. As a result, a coating film having an antioxidant power can retain the property of preventing contamination by marine adherents such as barnacles and mussels.

Early 1 month 3 months 6 months 12 months Polycardanol 0 pcs 0 pcs One Three 6 pcs Polycardoll 0 pcs 0 pcs 0 pcs 0 pcs One Lacquer coating 0 pcs 2 6 pcs All 13 All 25 Remarks) Specimen size: 15 centimeters wide, 30 centimeters long.

As shown in Table 6, it can be seen that the adhesion ability of the crackle to the polycardol cured coating film is greatly inhibited. This coincides with the trend of Table 5 above, and it is determined that the antioxidant power prevented the hardening of the adhesion protein of the bark, and as a result, only a small number of barnacles could be attached.

As described above, the curable polycardanol and polycardol polymerized using a oxidoreductase as a biocatalyst according to the present invention have properties similar to those of conventional lacquers, which can be used as a substitute for lacquer coatings. It can be used as an internal coating material for food storage containers and devices, and most importantly as an antifouling coating material to prevent contamination of marine adherents. In addition, the industrial applications of phenolic polymers, which have been commonly used, are expected to be applied to brake lining materials, brake pad materials, ink materials, adhesive materials, and epoxy resin materials. In particular, it can be said to have great significance by presenting a method of synthesizing functional materials capable of meeting social demands such as replacing existing marine antifouling paints containing heavy metals such as tin and copper.

In addition, the method for producing a phenolic polymer using the biocatalyst used in the present invention is possible without using harsh conditions (high temperature, high pressure) and toxic chemicals (formalin series) that are used in synthesizing a conventional phenolic polymer. Compared to the phenolic polymer of the phenolic polymer having a much larger molecular weight in terms of obtaining the technical effect and the future-oriented environmentally friendly process has the effect.

FIG. 1A is a nuclear magnetic resonance spectrum of cardanol, and FIG. 1B is a polycardanol nuclear magnetic resonance spectrum.

2 is a graph showing the change in peroxidase activity according to the type of solvent.

3 is a graph showing the change in activity of Aspergillus peroxidase according to the type of solvent.

4 is a graph showing the yield and molecular weight change of polykadol according to the buffer capacity.

5 is a graph showing the change of Aspergillus peroxidase activity according to the reaction temperature.

6 is a graph showing the change in yield and molecular weight of polycardol according to the reaction temperature.

7 is a graph showing the change in peroxidase activity according to the concentration of hydrogen peroxide added.

8 is a graph showing changes in yield and molecular weight of polycardol according to the concentration of hydrogen peroxide added.

9 is a graph showing the molecular weight distribution of polycardol according to the concentration of hydrogen peroxide added.

Claims (13)

delete 0.1 wt% to 1.0 wt% of a vegetable phenolic monomer selected from cadol, cardanol, anacardic acid, zinc high-ic acid, methylcardol, urushiol, thitsiol, langool and laccol with respect to the vegetable phenolic monomer. A method for producing a phenolic polymer, characterized in that the polymerization is carried out in an alcoholic organic solvent to which an oxidoreductase is added. The method of claim 2, wherein the oxidoreductase is selected from polyphenol oxidase, peroxidase, and laccase. delete The method according to claim 2, wherein the oxidizing agent is added with hydrogen peroxide or organic hydrogen peroxide at a ratio of 0.1 to 1.0 mole per mole of vegetable phenol monomer. The method of claim 2, wherein the alcohol-based organic solvent comprises a buffer solution 30 to 70% by volume. The method of claim 2, wherein the alcohol-based organic solvent is 30 to 70% by volume based on the total reactant volume. The capsaicin and noniamide according to claim 2, wherein the polymerization reaction is capsaicin. A method for producing a phenolic polymer, characterized in that additional addition of at least one compound selected from hydroquinone. Antioxidant material, characterized in that it contains a phenolic polymer prepared according to claim 2. A paint characterized in that it contains a phenolic polymer prepared according to the method of claim 2. A phenolic polymer prepared by curing the phenolic polymer prepared according to the method of claim 2 using 0.05 to 0.3% by weight based on the amount of the phenolic polymer used as a curing catalyst. Antioxidant material, characterized in that the cured phenolic polymer of claim 11. A paint characterized by containing the cured phenolic polymer of claim 11.