Novel high-purity glycerol derivative with protected oxygen at position 2, monomer for polycarbonate polymerization capable of controlling biodegradation rate including biodegradation off-on using same, and method for preparing polymer in which monomer is polymerized

Abstract

The present invention relates to a novel high-purity glycerol derivative with protected oxygen at position 2, a monomer for polycarbonate polymerization capable of controlling a biodegradation rate including biodegradation off-on using same, and a method for preparing a polymer in which the monomer is polymerized. The novel high-purity glycerol derivative with protected oxygen at position 2 provided by the present invention uses inexpensive glycerol, synthesizes high-purity 1,3-diacetin using a chemoenzymatic synthesis method, and then has a structure in which oxygen at position 2 is directly protected without delay time, thereby being usable as a stable novel monomer precursor for polycarbonate polymerization that can be stored at room temperature for a long period of time without deterioration. In addition, the precursor according to the present invention can be synthesized as a monomer for polycarbonate polymerization when deacetylated, and enables preparation of a polycarbonate-based polymer capable of variously controlling a biodegradation rate including biodegradation off-on is possible.

Description

A novel, high-purity, oxygen-protected glycerol derivative, a monomer for polycarbonate polymerization capable of controlling biodegradation rate, including biodegradation off-on, using the same, and a method for producing a polymer polymerized with the monomer

[0001] The present invention relates to a novel high-purity glycerol derivative with protected oxygen at 2nd position, a monomer for polycarbonate polymerization capable of controlling biodegradation rate including biodegradation off-on using the same, and a method for producing a polymer polymerized with the monomer.

[0002] Biodegradable materials are being applied not only in medicine and pharmaceuticals, but also in diverse fields such as packaging materials, automotive parts, electrical and electronic components, and building materials. Research on this topic is becoming increasingly active as environmental pollution issues arise. These biodegradable materials require extended biodegradation by blocking biodegradation until the required degradation point. Most biodegradable materials currently in use rely on hydrolysis, and methods are used to extend the life of the biodegradable material by blocking moisture infiltration. However, methods that utilize metal coatings to block moisture present a contradiction between biodegradability and the means of extending the lifespan, as the coated metal does not biodegrade. Altering the chemical structure or molecular weight of biodegradable materials to extend the lifespan of biodegradable materials can only control the rate of biodegradation, making it difficult to control the timing of biodegradation.

[0003] In addition, 2-O-THPE-propane-l,3-diol (CAS RN 150196-31-9) with a purity of 95-98%, which is currently used in the synthesis of precursors for polycarbonate polymerization with controllable biodegradation rates, is sold at a high price of USD 986.00 / 1g and USD 1700.00 / 5g (as of March 24, 2025) (SciFinder-n), and thus has a very low economic feasibility for use as a precursor for polymer synthesis.

[0004] Meanwhile, with the recent surge in biodiesel production, the price of purified pure glycerol is very low due to the excess production of glycerol as a byproduct.

[0005] The method of obtaining high purity 1,3-acetine or derivatives synthesized based on the 1,3-diacyl glyceride (DAG) structure, such as 2-O-THPE-propane-l,3-diol, by chemical methods requires several complex and harsh chemical reaction steps, as it is impossible to directly synthesize high purity 1,3-diacetin from glycerol by chemical methods, resulting in high synthesis costs and low yields, making it very uneconomical due to the high cost of synthesis and low yield.

[0006] In addition, using a known chemical enzymatic synthesis method, pure 1,3-DAG can be synthesized by selectively combining acyl groups, including acetyl groups, depending on the position of glycerol. However, as shown below, due to the acyl group migration phenomenon, some of the 1,3-DAG gradually changes to 1,2-DAG, causing 1,3-DAG and 1,2-DAG to coexist. Therefore, even if pure 1,3-MAG is synthesized, it cannot be stored in a state of non-deterioration after synthesis, making it an uncommercializable substance.

[0007] [Correction pursuant to Rule 91 08.07.2025][Deleted]

[0008] In addition, when synthesizing a glycerol precursor based on the 1,3-DAG structure, the problem of deterioration over time can be solved by quickly converting high-purity 1,3-DAG or high-purity 2-MAG into a structure in which acyl group transfer does not occur immediately after synthesis, and then converting it to the original pure 1,3-DAG only when necessary. However, no attempt has been made to solve this problem to date.

[0009] Accordingly, the inventors of the present invention have developed a technology to improve the above-mentioned problems, by using inexpensive glycerol as a starting material for the synthesis of a monomer for polycarbonate polymerization and synthesizing high-purity 1,3-diacetin using a chemical enzymatic synthesis method, and then immediately protecting the second oxygen without delay, thereby synthesizing a glycerol derivative (2-O-protected 1,3-diacetin), which is a precursor of a stable new monomer for polycarbonate polymerization that can be stored at room temperature for a long period of time without deterioration, and by deacetylating this, they synthesized a monomer for polycarbonate polymerization with high purity and low cost, which can control the biodegradation rate including biodegradation off-on, and further confirmed that polycarbonate can be synthesized economically and with high purity by polymerizing the monomer.

[0010] Accordingly, an object of the present invention is to provide a precursor compound of a monomer for polycarbonate polymerization having a chemically protective structure of a hydroxyl group at position 2.

[0011] Another object of the present invention is to provide a method for producing a precursor compound of the monomer for polycarbonate polymerization.

[0012] Another object of the present invention is to provide a carbonate monomer having a hexagonal ring structure using the monomer for polycarbonate polymerization of the present invention, a biodegradable polycarbonate polymer polymerized with the monomer, and a method for producing the biodegradable polycarbonate polymer.

[0013] Accordingly, the present invention provides a precursor compound of a monomer for polycarbonate polymerization having a chemical protection structure of a hydroxyl group at position 2 represented by the following chemical formula 1.

[0014] <Chemical Formula 1>

[0015]

[0016] In the above chemical formula 1,

[0017] R 1 A chain-like (C3-C40) alkyl group; a branched (C3-C40) alkyl group; a (C3-C40) cycloalkyl group; a (C3-C40) heterocycloalkyl group; a (C3-C40) alkenyl group; a (C3-C40) alkynyl group; a (C1-C30) heteroalkyl group; a (C6-C40) aryl group; a (C3-C40) heteroaryl group; a (C6-C40) aryl (C1-C40) alkyl group; a (C2-C40) alkyl (C6-C40) aryl group; -Si(R 2 )(R 3 )(R 4 ) silyl group; -C(=O)NHR 5 , -C(=O)NHR 6 2-person acyl group; or -S(=O)2R 7 In sulfonyl group; and,

[0018] R 2 Inland R 4 are each independently hydrogen, (C1-C40)alkyl group or (C6-C40)aryl group, and R 2 Inland R 4 At least one of them is a (C1-C40) alkyl group or a (C6-C40) aryl group,

[0019] R 5 Inland R 7are each independently a (C1-C40) alkyl group, a branched (C3-C40) alkyl group, a (C3-C40) alkenyl group, a (C3-C40) alkynyl group, a (C1-C30) heteroalkyl group, a (C3-C40) cycloalkyl group, a (C3-C40) heterocycloalkyl group, a (C6-C40) aryl group, a (C3-C40) heteroaryl group, a (C6-C40) aryl(C1-C40) alkyl group, a (C2-C40) alkyl(C6-C40) aryl group, or a substituent derived from a hydrophilic polymer.

[0020] In one embodiment of the present invention, the precursor compound of the monomer for polycarbonate polymerization may have acyl group migration suppressed.

[0021] In addition, the present invention provides a method for producing a precursor compound of a monomer for polycarbonate polymerization according to the present invention, comprising: (1) a step of synthesizing a 1,3-diacetin compound using glycerol as a starting material by a chemical enzymatic synthesis method; and (2) a continuous synthesis step of converting the oxygen of the second hydroxyl group of the 1,3-diacetin compound into a functional group capable of protecting it.

[0022] In one embodiment of the present invention, the chemical enzyme synthesis method of step (1) may be performed by an initial reaction step in which glycerol and vinyl acetate are used as reactants and a fixed enzyme catalyst is used as an acetylation reaction catalyst of glycerol is started at a temperature of 20°C to 30°C; a later reaction step in which the reaction temperature is rapidly lowered by at least 10°C from the initial reaction temperature at the point where glycerol is exhausted to increase the purity of the 1,3-diacetin compound; and a termination step in which the reaction is terminated just before triacetin is produced.

[0023] In one embodiment of the present invention, the immobilized enzyme catalyst may be selected from the group consisting of immobilized Candia antarctica lipase B (Calb), immobilized Thermomyces lanuginosus lipase (TLL), and immobilized Rhizomucor miehei lipase (RML).

[0024] In one embodiment of the present invention, after the termination step, the prepared 1,3-diacetin compound can be separated and purified by removing the immobilized enzyme catalyst by filtration or sedimentation; adding a solvent such as tetrahydrofuran, diethyl ether, or benzene to completely dissolve the 1,3-diacetin compound; distilling under reduced pressure at a temperature of 30°C to 40°C; and then separating and purifying the resulting product by medium-pressure column chromatography.

[0025] In one embodiment of the present invention, the functional group of step (2) may be selected from the group consisting of halide, methyl isomer, nitrile, aldehyde, isocyanate, thiocyanate, silyl isomer, azide, cyanide, and alkoxyalkyl isomer.

[0026] In one embodiment of the present invention, the functional group of step (2) may be tetrahydropyranyl ether.

[0027] In addition, the present invention provides a precursor compound of a monomer for polycarbonate polymerization having a structural formula of the following chemical formula 2, wherein one of the two acetyl groups in the compound of the above chemical formula 1 is removed.

[0028] <Chemical Formula 2>

[0029]

[0030] In the above chemical formula 2,

[0031] R 1A chain-like (C3-C40) alkyl group; a branched (C3-C40) alkyl group; a (C3-C40) cycloalkyl group; a (C3-C40) heterocycloalkyl group; a (C3-C40) alkenyl group; a (C3-C40) alkynyl group; a (C1-C30) heteroalkyl group; a (C6-C40) aryl group; a (C3-C40) heteroaryl group; a (C6-C40) aryl (C1-C40) alkyl group; a (C2-C40) alkyl (C6-C40) aryl group; -Si(R 2 )(R 3 )(R 4 ) silyl group; -C(=O)R 5 , -C(=O)NHR 6 , -C(=O)NHR 7 2 or -C(=O)OR 8 acyl group; or -S(=O)2R 9 In sulfonyl group; and,

[0032] R 2 Inland R 4 are each independently hydrogen, (C1-C40)alkyl group or (C6-C40)aryl group, and R 2 Inland R 4 At least one of them is a (C1-C40) alkyl group or a (C6-C40) aryl group,

[0033] R 5 Inland R 9 are each independently a (C1-C40) alkyl group, a branched (C3-C40) alkyl group, a (C3-C40) alkenyl group, a (C3-C40) alkynyl group, a (C1-C30) heteroalkyl group, a (C3-C40) cycloalkyl group, a (C3-C40) heterocycloalkyl group, a (C6-C40) aryl group, a (C3-C40) heteroaryl group, a (C6-C40) aryl(C1-C40) alkyl group, and a (C2-C40) alkyl(C6-C40) aryl group.

[0034] In addition, the present invention provides a method for producing a precursor compound of a monomer for polycarbonate polymerization having a structural formula of Chemical Formula 2, which comprises a step of reacting the compound of Chemical Formula 1 with magnesium ethoxide dissolved in ethanol for less than 6 hours to deacetylate only one of the two acetyl groups in the compound of Chemical Formula 1 and convert it into a hydroxy group.

[0035] In addition, the present invention provides a carbonate monomer having a hexagonal ring structure, synthesized by subjecting the compound of the above chemical formula 1 to a deacetylation reaction in a mixed solvent of potassium carbonate (K2CO3), ethanol, and water, and then reacting it with ethyl chloroformate.

[0036] In addition, the present invention provides a biodegradable polycarbonate polymer in which the carbonate monomer is polymerized.

[0037] Furthermore, the present invention provides a method for producing a biodegradable polycarbonate polymer, comprising the step of using a guanidine-based material as a catalyst, using a compound having a hydroxyl group (-OH), a thiol group (-SH), or an amine functional group as a nucleophile, and performing a ring-opening polymerization reaction of the carbonate monomer of the present invention in the presence of an organic solvent at a temperature of 20°C to 30°C.

[0038] In one embodiment of the present invention, the catalyst may be at least one catalyst selected from the group consisting of cyclic guanidines such as 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), 1,5-diazabicyclo[4.3.0]non-5-ene (DBN), N-methyl-DBU, N-ethyl-DBU or N-propyl-DBU; acyclic guanidines such as tetramethylguanidine (TMG) or N,N,N',N'-tetramethyl-N''-phenylguanidine; and chiral guanidines.

[0039] In one embodiment of the present invention, the amine functional group is -NH2, or -NHR 1 , or -NHR 1 2, or -NR 1 3; the above R 1 Silver, (C1-C40) alkyl group; branched (C3-C40) alkyl group; (C3-C40) cycloalkyl group; (C3-C40) heterocycloalkyl group; (C3-C40) alkenyl group; (C3-C40) alkynyl group; (C1-C30) heteroalkyl group; (C6-C40) aryl group; (C3-C40) heteroaryl group; (C6-C40) aryl (C1-C40) alkyl group; (C2-C40) alkyl (C6-C40) aryl group; or -Si(R 2 )(R 3 )(R 4 ) may be a cylinder.

[0040] The novel, high-purity glycerol derivative with protected 2-oxygen provided by the present invention can be synthesized by using inexpensive glycerol and a chemical enzymatic synthesis method to synthesize high-purity 1,3-diacetin, and has a structure in which the 2-oxygen is protected immediately without any delay, so that it can be used as a stable new monomer precursor for polycarbonate polymerization that can be stored without deterioration at room temperature for a long period of time. In addition, the precursor according to the present invention can be synthesized as a monomer for polycarbonate polymerization by deacetylation, and has the effect of enabling the production of a polycarbonate polymer whose biodegradation rate can be controlled in various ways, including biodegradation off-on. Furthermore, the improved method for producing a polycarbonate monomer of the present invention that allows controllable biodegradation time ensures a high yield at low cost and enables mass production, thereby increasing the productivity and utility value of polycarbonate polymers.

[0041] Figure 1 is a diagram for the compound (A)-1 of step 1 prepared in Example 1 of the present invention. 1 This is the H NMR result.

[0042] Figure 2 is a diagram for the compound (A)-2 of step 2 prepared in Example 1 of the present invention. 1This is the H NMR result.

[0043] Figure 3 is for the compound (A)-3 of step 3 prepared in Example 1 of the present invention. 1 This is the H NMR result.

[0044] Figure 4 is a diagram for the compound (A) of step 1 manufactured in Example 1 of the present invention. 1 This is the H NMR result.

[0045] Figure 5 is a diagram of a polycarbonate polymer synthesized in Example 2 of the present invention. 1 This is the H NMR result.

[0046] Figure 6 is a diagram of a polycarbonate polymer synthesized in Example 2 of the present invention. 13 This is the C NMR result.

[0047] Unless otherwise defined herein, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.

[0048] As used herein, the singular forms may be intended to include the plural forms as well, unless the context clearly indicates otherwise.

[0049] Throughout this specification, the terms "comprises," "includes," "contains," or "has" a component, unless specifically stated to the contrary, do not exclude other components, but rather may include other components, and do not exclude additional unrecited elements, materials, or processes.

[0050] The term "biodegradable off-on material" as used herein refers to a material that can block (off) biodegradation of a biodegradable material until a desired time and induce (on) biodegradation of a biodegradable material at a desired time.

[0051] The numerical ranges used herein include the lower and upper limits and all values ​​within that range, increments logically derived from the shape and width of the defined range, all doubly defined values, and all possible combinations of the upper and lower limits of numerical ranges defined in different shapes. Unless otherwise specified herein, values ​​outside the defined range that may arise due to experimental error or rounding of values ​​are also included in the defined numerical range.

[0052] Below, the present disclosure will be described in detail. However, this is merely exemplary and the present disclosure is not limited to the specific embodiments described as examples.

[0053] The present invention is characterized by providing a precursor compound of a novel polycarbonate polymerization monomer having a chemical protection structure of a hydroxyl group at position 2 represented by the following chemical formula 1.

[0054] <Chemical Formula 1>

[0055]

[0056] In the above chemical formula 1, R 1 A chain-like (C3-C40) alkyl group; a branched (C3-C40) alkyl group; a (C3-C40) cycloalkyl group; a (C3-C40) heterocycloalkyl group; a (C3-C40) alkenyl group; a (C3-C40) alkynyl group; a (C1-C30) heteroalkyl group; a (C6-C40) aryl group; a (C3-C40) heteroaryl group; a (C6-C40) aryl (C1-C40) alkyl group; a (C2-C40) alkyl (C6-C40) aryl group; -Si(R 2 )(R 3 )(R 4 ) silyl group; -C(=O)NHR 5 , -C(=O)NHR 6 2-person acyl group; or -S(=O)2R 7 sulfonic acid; and R 2 Inland R 4 are each independently hydrogen, (C1-C40)alkyl group or (C6-C40)aryl group, and R 2Inland R 4 At least one of R is a (C1-C40) alkyl group or a (C6-C40) aryl group, 5 Inland R 7 may each independently be a (C1-C40) alkyl group, a branched (C3-C40) alkyl group, a (C3-C40) alkenyl group, a (C3-C40) alkynyl group, a (C1-C30) heteroalkyl group, a (C3-C40) cycloalkyl group, a (C3-C40) heterocycloalkyl group, a (C6-C40) aryl group, a (C3-C40) heteroaryl group, a (C6-C40) aryl(C1-C40) alkyl group, a (C2-C40) alkyl(C6-C40) aryl group, or a substituent derived from a hydrophilic polymer.

[0057] The precursor compound of the monomer for polycarbonate polymerization designed in the present invention is synthesized based on a 1,3-diacetin or 1,3-diacyl glyceride (DAG) structure, and in particular has the characteristic of having a chemical protection structure of the hydroxyl group at position 2 represented by the chemical formula 1, so that the movement of the acyl group is suppressed and the oxygen at position 2 can be chemically protected.

[0058] When synthesizing a glycerol precursor based on the 1,3-DAG structure, it is necessary to quickly convert high-purity 1,3-DAG or high-purity 2-MAG into a structure in which acyl group transfer does not occur immediately after synthesis, and then, only when necessary, to the original pure 1,3-DAG. However, the existing chemical synthesis methods for glycerol precursors were not based on the 1,3-diacetin or 1,3-DAG structure, and even after the development of chemical enzymatic synthesis methods, the problem of acyl group transfer has continued to exist.

[0059] In this respect, the present invention has newly synthesized a precursor compound of a monomer for polycarbonate polymerization capable of chemically protecting the 2nd oxygen of 1,3-diacetin or 1,3-DAG in a high-purity state, and the precursor compound suppresses the movement of the acyl group of 1,3-DAG, can be stored at room temperature for a long period of time, and can be used as a starting material to replace high-purity 1,3-DAG to synthesize other glycerol derivatives very cheaply and easily in high yield, and can further be usefully used in the synthesis of polycarbonate polymers.

[0060] Therefore, the present invention can provide a method for producing a precursor compound of a monomer for polycarbonate polymerization, having a chemical protection structure of a hydroxyl group at position 2 represented by the chemical formula 1.

[0061] The method for producing a precursor compound of a monomer for polycarbonate polymerization provided in the present invention comprises: (1) a step of synthesizing a 1,3-diacetin compound using glycerol as a starting material by a chemical enzymatic synthesis method; and (2) a continuous synthesis step of converting the oxygen of the second hydroxyl group of the 1,3-diacetin compound into a functional group capable of protecting it.

[0062] Here, the chemical enzyme synthesis method of step (1) can be performed by an initial reaction step in which glycerol and vinyl acetate are used as reactants and a reaction is started at a temperature of 20°C to 30°C using an immobilized enzyme catalyst as an acetylation reaction catalyst of glycerol; a later reaction step in which the reaction temperature is rapidly lowered by at least 10°C from the initial reaction temperature at the point where glycerol is exhausted to increase the purity of the 1,3-diacetin compound; and a termination step in which the reaction is terminated just before triacetin is produced.

[0063] The method according to the present invention has the characteristic of starting the initial reaction at room temperature (26°C) rather than the typical reaction temperature of 60°C in a reaction using an immobilized lipolytic enzyme, thereby inducing the formation of mainly 1-monoacetin and a small amount of diacetin, and further, by reducing the temperature by 10°C or more depending on the degree of reaction progress (the point at which all glycerol is consumed), thereby increasing the 1,3-diacetin formation rate and suppressing the progress of the reaction converting 1,3-diacetin into triacetin, thereby improving the yield of high-purity 1,3-diacetin.

[0064] More specifically, in one embodiment of the present invention, the initial reaction step is to mix glycerol and vinyl acetate at a specific molar ratio (e.g., glycerol: vinyl acetate = 1:2.5), add immobilized CalB (e.g., 25 wt% based on the total amount of substrate), and initiate the reaction under stirring. The initial reaction temperature is maintained at a specific temperature (e.g., 26°C) to promote monoacetin production. In this step, glycerol is consumed, and mainly monoacetin (mainly 1-monoacetin and a small amount of 2-monoacetin) and 1,3-diacetin are produced.

[0065] Next, the later reaction stage, which proceeds by rapidly lowering the reaction temperature, proceeds by rapidly lowering the reaction temperature by at least 10°C (e.g., from 26°C to 16°C or lower) at a point when the initial glycerol of the reaction has been substantially consumed (e.g., confirmed by thin layer chromatography (TLC)). This rapid temperature decrease can induce the following effects.

[0066] The effects of a rapid temperature drop include, first, the suppression of triacetin production. This significantly reduces the rate of further esterification from diacetin to triacetin, thereby suppressing the formation of triacetin byproducts and improving the selectivity of 1,3-diacetin.

[0067] Second, the yield of 1,3-diacetin can be increased. Under relatively low temperatures, the CalB enzyme can catalyze the isomerization of 1,2-diacetin to 1,3-diacetin. Therefore, lowering the temperature can increase the content of thermodynamically stable 1,3-diacetin, maximizing the final yield.

[0068] Third, it can induce monoacetin conversion. By inducing a reaction in which residual monoacetin is converted to diacetin, the yield of 1,3-diacetin can be further improved.

[0069] The immobilized enzyme catalyst usable in the present invention may be selected from the group consisting of immobilized Candia antarctica lipase B (Calb), immobilized Thermomyces lanuginosus lipase (TLL), and immobilized Rhizomucor miehei lipase (RML), and preferably, it may be immobilized Candia antarctica lipase B (Calb) enzyme.

[0070] In one embodiment of the present invention, immobilized Calb (Lipozyme 435), which is an immobilized lipolytic enzyme that has relatively low selectivity for glycerol 1 and 3 positions but in which the acetylation reaction of primary alcohol progresses well, is used, and when the synthesis of monoacetin and diacetin progresses, the reaction temperature is lowered by at least 10°C at the point where all glycerol is consumed, thereby inhibiting the progress of the reaction from diacetin to triacetin, converting monoacetin to 1,3-diacetin, and at the same time converting the already produced 1,2-diacetin to 1,3-diacetin with better chemical stability through interaction with the lipolytic enzyme, thereby producing high-purity 1,3-diacetin in a high yield.

[0071] In addition, in the chemical enzyme synthesis method of step (1) above, after performing a termination step for terminating the reaction immediately before triacetin is produced, a process of separating and purifying the additionally produced 1,3-diacetin compound can be performed.

[0072] The separation and purification of the 1,3-diacetin compound manufactured above is carried out by removing the immobilized enzyme catalyst by filtration or sedimentation; adding a solvent such as tetrahydrofuran, diethyl ether or benzene to completely dissolve the 1,3-diacetin compound; distilling under reduced pressure at a temperature of 30°C to 40°C; and separating and purifying it by medium-pressure column chromatography. Through this process, the occurrence of acyl group migration can be suppressed as much as possible.

[0073] In addition, in the above separation and purification process, solvent removal is carried out through the following process: a solvent (e.g., tetrahydrofuran, THF) is added to the reaction mixture from which the enzyme has been removed to dissolve the product, and this solution is subjected to rotary vacuum concentration under reduced pressure and a water bath temperature of approximately 37.5°C. At this time, due to the low boiling point of THF (approximately 66°C), the solvent rapidly evaporates and absorbs the surrounding heat, resulting in a temperature drop. By utilizing this heat of solvent evaporation, the temperature of the reactant can be suppressed and the concentration process can be quickly carried out while maintaining a relatively low temperature, which can minimize the occurrence of acyl group migration at high temperatures and increase the efficiency of the subsequent purification step.

[0074] Thereafter, high-purity 1,3-diacetin is separated and purified from the concentrated reaction mixture within a short period of time using medium-pressure liquid chromatography (MPLC). The chromatography column uses silica gel or a similar packing material, and the separation solvent is hexane, ethyl acetate, or a mixed solvent thereof, etc., and polar concentration gradient conditions are applied to effectively separate 1,3-diacetin.

[0075] Next, a continuous synthesis step can be performed to convert the oxygen of the second hydroxyl group of the 1,3-diacetin compound into a functional group capable of protecting it, and the functional group can be selected from the group consisting of a halide, a methyl isomer, a nitrile, an aldehyde, an isocyanate, a thiocyanate, a silyl isomer, an azide, a cyanide, and an alkoxyalkyl isomer.

[0076] The above functional group is intended to protect the oxygen of the second hydroxyl group immediately after rapid purification of high-purity 1,3-diacetin by medium-pressure liquid column chromatography, and is converted or substituted with the above functional group by a continuous synthesis method.

[0077] In one embodiment of the present invention, the separated high-purity 1,3-diacetin was reacted with 3,4-dihydro-2H-pyran (DHP) and a pyridinium p-toluenesulfonate (PPTS) catalyst to convert it into THPE-1,3-diacetin in which the 2-oxygen is protected by a tetrahydropyranyl isomer, thereby obtaining a precursor compound of a new polycarbonate polymerization monomer that suppresses acyl group migration, has high chemical stability, eliminates concerns about deterioration due to long-term storage, and is advantageous for commercialization and distribution, i.e., 1,3-diacetin in which the 2-oxygen is protected by a tetrahydropyranyl isomer; THPE-1,3-diacetin) compound.

[0078] In one embodiment of the present invention, the tetrahydropyranyl isopropyl group used as a functional group is easily removed under acid conditions, but the acetyl group is easily removed under basic conditions, and each can be completely removed by more than 99% through a very economical chemical reaction, so when used as a starting material for various chemical reactions, it has great advantages in terms of economic efficiency and chemical usability.

[0079] In addition, the 2-hydroxyl group (-OH) protected by the tetrahydropyranyl isomer of THPE-1,3-diacetin can be restored by the tetrahydropyranyl isomer removal method, which can be performed very easily and inexpensively with a yield of over 99%, and in addition, there are various secondary alcohol protection methods (e.g., tosyl, alkyl silyl isomer, alkyl isomer, alkoxyalkyl isomer, etc.) or functional group conversion methods (e.g., alkyl isomer, aryl isomer, halide, aldehyde, ketone, organic acid, nitrile, thiol, azide, cyanide, etc.) that can be performed at low temperatures to minimize acyl group migration, so that various new glycerol derivatives can be synthesized based on the 1,3-diacetin structure.

[0080] In addition, the 2-hydroxyl group (-OH) protected by the tetrahydropyranyl isomer of THPE-1,3-diacetin can be directly converted into various functional groups including, but not limited to, halides, methyl isomers, nitriles, aldehydes, isocyanates, thiocyanates, trialkylsilyl isomers, azides, and cyanides without prior removal of the tetrahydropyranyl isomer.

[0081] Therefore, the method of the present invention can produce a precursor compound of a new polycarbonate polymerization monomer in which compound modification due to acyl group migration is suppressed.

[0082] In addition, the method provided by the present invention can increase economic feasibility by enabling recycling of the immobilized enzyme, and by using a chemical enzyme synthesis method, a precursor compound of a new material, a monomer for polycarbonate polymerization in which oxygen is protected by a functional group at position 2, can be obtained with high purity in an environmentally friendly manner.

[0083] The present invention can also provide a precursor compound of a polycarbonate polymerization monomer having the structural formula of the following chemical formula 2, which is a substance in which only one acetyl group is removed from the precursor compound of a polycarbonate polymerization monomer having the structure of the chemical formula 1 provided in the present invention.

[0084] <Chemical Formula 2>

[0085]

[0086] In the above chemical formula 2, R 1 A chain-like (C3-C40) alkyl group; a branched (C3-C40) alkyl group; a (C3-C40) cycloalkyl group; a (C3-C40) heterocycloalkyl group; a (C3-C40) alkenyl group; a (C3-C40) alkynyl group; a (C1-C30) heteroalkyl group; a (C6-C40) aryl group; a (C3-C40) heteroaryl group; a (C6-C40) aryl (C1-C40) alkyl group; a (C2-C40) alkyl (C6-C40) aryl group; -Si(R 2 )(R 3 )(R 4 ) silyl group; -C(=O)R 5 , -C(=O)NHR 6 , -C(=O)NHR 7 2 or -C(=O)OR 8 acyl group; or -S(=O)2R 9 sulfonic acid; and R 2 Inland R 4 are each independently hydrogen, (C1-C40)alkyl group or (C6-C40)aryl group, and R 2 Inland R 4 At least one of R is a (C1-C40) alkyl group or a (C6-C40) aryl group, 5 Inland R 9 may each independently be a (C1-C40) alkyl group, a branched (C3-C40) alkyl group, a (C3-C40) alkenyl group, a (C3-C40) alkynyl group, a (C1-C30) heteroalkyl group, a (C3-C40) cycloalkyl group, a (C3-C40) heterocycloalkyl group, a (C6-C40) aryl group, a (C3-C40) heteroaryl group, a (C6-C40) aryl(C1-C40) alkyl group, or a (C2-C40) alkyl(C6-C40) aryl group.

[0087] The compound having the structure of the above chemical formula 2 is also a novel compound provided by the present invention, and is a stable compound that does not deteriorate at room temperature as well as at high temperatures of 100°C or higher, and therefore is suitable for long-term storage after mass production, and has great strengths in terms of economy and chemical usefulness.

[0088] The precursor compound of the monomer for polycarbonate polymerization having the structural formula of the above chemical formula 2 of the present invention can be manufactured through the following method, that is, the step of reacting the compound having the structure of the above chemical formula 1 with magnesium ethoxide dissolved in ethanol within 6 hours to deacetylate only one of the two acetyl groups in the compound of the above chemical formula 1 and convert it into a hydroxy group.

[0089] In one embodiment of the present invention, a novel compound, 3-O-acetyl-2-O-THPE-propane-1-ol (3Ac-2THPE-glycerol), was synthesized by removing only one acetyl group of THPE-1,3-diacetin.

[0090] The 1-hydroxyl group (-OH) of the above 3Ac-2THPE-glycerol compound can be converted into a functional group such as alkyl ether, aryl ether, p-methoxybenzyl (PMB), alkoxyalkyl ether, halide, nitrile, aldehyde, organic acid, isocyanate, thiocyanate, alkyl silyl ether, azide or cyanide to synthesize a new glycerol derivative, and the functional group is not limited to the types described above. Representative examples are as follows.

[0091] For halide synthesis, the halogenation reaction is carried out using a halogenating reagent such as thionyl chloride (SOCl₂) or phosphorus tribromide (PBr₃). For methyl isotherm synthesis, the Williamson ether synthesis reaction is carried out using a methylating reagent (e.g., methyl iodide, dimethyl sulfate) and a base (e.g., sodium hydroxide, potassium carbonate). For nitrile synthesis, the nucleophilic substitution reaction with sodium cyanide (NaCN) or potassium cyanide (KCN) is carried out using an appropriate alkyl halide. For isocyanate synthesis, the isocyanate is prepared by reacting a 1-amino amine with phosgene or a phosgene analogue (a step of converting the 1-amino hydroxyl group to an amine may be required for this functional group conversion). For thiocyanate synthesis, the halogenated compound is reacted with potassium thiocyanate (KSCN) to produce the thiocyanate. In the case of trialkylsilyl isomer synthesis, the silylation reaction is carried out using a trialkylsilyl chloride (e.g., TMSCl, TBSCl) and a base catalyst (e.g., triethylamine, imidazole). In the case of azide synthesis, the 1-halide is reacted with sodium azide (NaN₃) to produce an azide. In the case of cyanide synthesis, the 1-halide is reacted with copper(I) cyanide (CuCN), etc. to introduce a cyan group. The hydroxyl (-OH) group at position 1 of 3-O-acetyl-2-O-THPE-propan-1-ol (3Ac-2THPE-glycerol) can be converted into various functional groups using various other chemical reactions and mechanisms.

[0092] Furthermore, the present invention can provide a carbonate monomer having a hexagonal ring structure using a precursor compound of the novel polycarbonate polymerization monomer provided in the present invention.

[0093] The carbonate monomer having a hexagonal ring structure of the present invention is synthesized by deacetylating a precursor compound of the novel polycarbonate polymerization monomer provided in the present invention in a mixed solvent of potassium carbonate (K2CO3), ethanol, and water, and then reacting it with ethyl chloroformate.

[0094] In one embodiment of the present invention, it was confirmed that the compound having the structural formula of the above chemical formula 1 can be synthesized at a very low cost and in a high yield by performing a deacetylation reaction under very mild conditions in a mixed solvent of potassium carbonate, ethanol, and water. At this time, it was shown that the optimized combination of potassium carbonate and the mixed solvent of ethanol and water can affect the high selectivity to effectively remove only the acetyl groups at the 1st and 3rd positions while minimizing the effect on the protecting group (THPE) at the 2nd position, and it was found that this can suppress the production of unnecessary by-products and simplify the subsequent purification step, making the synthesis of the THPE-HMTC monomer very easy. Furthermore, the present invention can provide a method for preparing a biodegradable polycarbonate-based polymer by ring-opening polymerizing the carbonate monomer of the present invention.

[0095] The method for producing a degradable polycarbonate polymer according to the present invention includes a step of using a guanidine-based material as a catalyst, using a compound having a hydroxyl group (-OH), a thiol group (-SH), or an amine functional group as a nucleophile, and performing a ring-opening polymerization reaction of a carbonate monomer in the presence of an organic solvent at a temperature of 20°C to 30°C.

[0096] In one embodiment of the present invention, a THPE-PHTMC polymer was synthesized by ring-opening polymerization of a THPE-HMTC monomer having a tetrahydropyranyl isomer (THPE) protecting group.

[0097] In the method for producing a biodegradable polycarbonate polymer of the present invention, the catalyst may be at least one catalyst selected from the group consisting of cyclic guanidines such as 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), 1,5-diazabicyclo[4.3.0]non-5-ene (DBN), N-methyl-DBU, N-ethyl-DBU or N-propyl-DBU; acyclic guanidines such as tetramethylguanidine (TMG) or N,N,N',N'-tetramethyl-N''-phenylguanidine; and chiral guanidines.

[0098] In addition, the above amine functional group is -NH2, or -NHR 1 , or -NHR 1 2, or -NR 1 3; the above R 1 Silver, (C1-C40) alkyl group; branched (C3-C40) alkyl group; (C3-C40) cycloalkyl group; (C3-C40) heterocycloalkyl group; (C3-C40) alkenyl group; (C3-C40) alkynyl group; (C1-C30) heteroalkyl group; (C6-C40) aryl group; (C3-C40) heteroaryl group; (C6-C40) aryl (C1-C40) alkyl group; (C2-C40) alkyl (C6-C40) aryl group; or -Si(R 2 )(R 3 )(R 4 ) may be a cylinder;

[0099] The method for producing a biodegradable polycarbonate polymer of the present invention utilizes a guanidine-based chemical substance as a catalyst and various compounds having a hydroxyl group (-OH) as a nucleophile to effectively and continuously polymerize a THPE-HMTC monomer in an organic solvent environment at room temperature, thereby synthesizing THPE-PHTMC having a desired high molecular weight and physical properties.

[0100] Guanidine-based catalysts exhibit strong basicity and effectively promote the ring-opening polymerization reaction of carbonate monomers, and in particular, they exhibit high activity under the room temperature conditions presented in the present invention, enabling efficient synthesis of THPE-PHTMC polymers of a desired molecular weight while maintaining the stability of THPE.

[0101] In addition, compounds having a hydroxyl group (-OH), which can be used as a nucleophile to induce effective and sustained ring-opening polymerization of THPE-HMTC monomers, play an important role in initiating polymerization of monomers and introducing terminal structures into polymer chains, and specifically include linear aliphatic alcohols such as methanol, ethanol, propanol, and butanol, as well as polyhydric alcohols such as glycerol, ethylene glycol, propylene glycol, and polyethylene glycol (PEG). Furthermore, naturally occurring hydroxyl-rich sugar-derived substances such as polyoligosaccharides (e.g., cyclodextrin, maltodextrin), sorbitol, and polymers containing multiple hydroxyl groups in their repeating units such as polyvinyl alcohol (PVA) can also be utilized as nucleophiles, and can be applied to prepare polymers in the form of THPE-PHTMC copolymers or blends having biocompatibility or specific physical properties.

[0102] Hereinafter, the present invention will be described in more detail through examples. These examples are intended to more specifically illustrate the present invention, and the scope of the present invention is not limited to these examples.

[0103]

[0104] <Example 1>

[0105] Precursor of monomer for polycarbonate polymerization and production of monomer using the same

[0106] The present inventors prepared a monomer for polycarbonate polymerization through a compounding reaction of the following reaction formula, and the specific synthesis process is as described below.

[0107]

[0108] <Precursor of monomer for polycarbonate polymerization and a material using the same

[0109] Synthesis of monomers for polycarbonate polymerization>

[0110]

[0111] <1-1> Step 1

[0112] In a round-bottom flask, 50 g (1 eq) of glycerol was dissolved in 500 ml of tetrahydrofuran (THF), and then 121.5 g (2.6 eq) of vinyl acetate and 12.5 g (substrate-enzyme ratio, 0.25 w / w) of Lipozyme435 were added and stirred at 25.5°C for 1 hour. Afterwards, the mixture was stirred for an additional 30 minutes at 15°C. Afterwards, the enzyme was removed by filtering twice with a glass filter, concentrated, and purified by flash column chromatography (Hexane:Acetone) to obtain a 1,3-diacetin compound as a high-purity compound (A)-1 (purity 84.5%).

[0113] The NMR analysis results for the above purified compound (A)-1 are as follows (see Figure 1).

[0114] 1 H NMR (500 MHz, CDCl3) δ (ppm): 4.13-4.00 (m, 5H), 3.01 (br s, 1H), 2.03 (S, 6H).

[0115]

[0116] <1-2> Step 2

[0117] In a round-bottom flask, 80 g (1 eq) of the (A)-1 compound obtained in the above <1-1> was dissolved in 400 ml of dichloromethane (DCM), and then 11.4 g (0.1 eq) of p-toluenesulfonic acid (Pyridinium p-toluenesulfonate, PPTS) and 76.4 g (2 eq) of 3,4-dihydro-2H-pyran (3,4-dihydro-2H-pyran, DHP) were added and stirred at 25.5°C for 2 hours. Thereafter, extraction was performed using DCM and distilled water, and the organic layer was dried over MgSO4, filtered, and concentrated. Thereafter, the residue was purified by flash column chromatography (Hexane: Ethyl acetate) to obtain 1,3-diacetin compound (A)-2 with oxygen protected at the 2-position (purity 86%). The NMR analysis results for the compound (A)-2 obtained above are as follows (see Figure 2).

[0118] 1 H NMR (500 MHz, CDCl3) δ (ppm): 4.78 (t. 3H), 4.27-4.18 (m, 3H), 4.11-4.06 (m, 2H), 3.92-3.88 (m, 1H), 3.53-3.49 (m, 1H), 2.08-2.07 (d, 6H), 1.84-1.77 (m, 1H), 1.74-1.68 (m, 1H), 1.62-1.51 (m, 4H).

[0119]

[0120] <1-3> Step 3

[0121] In a round-bottom flask, 102 g (1 eq) of compound (A)-2 obtained in the above <1-2> was dissolved in a 1136 ml ethanol / water (4 v / v) mixture solution, and then 113.74 g (2.1 eq) of K2CO3 was added and stirred at 25.5°C for 3 hours. Afterwards, the mixture was filtered twice with a glass filter to remove K2CO3 first, concentrated, and then the compound was extracted and purified with diethyl ether through solid phase extraction (SPE) to obtain compound (A)-3 (purity 73.2%). The results of NMR analysis of the obtained compound (A)-3 are as follows (see Fig. 3).

[0122] 1 H NMR (500 MHz, CDCl3) δ (ppm): 4.62-4.60 (m, 1H), 4.03-3.99 (m, 1H), 3.80-3.76 (m, 1H), 3.68-3.54 (m, 5H), 2.03 (m, 1H), 1.88-1.81(m, 2H), 1.70-1.65 (m, 1H), 1.61-1.53 ​​(m, 4H).

[0123]

[0124] <1-4> Step 4

[0125] 50.5 g (1 eq) of the compound (A)-3 obtained above and 124.40 g (4 eq) of ethyl chloroformate were dissolved in 404 ml of THF in a 2-neck round-bottom flask under nitrogen conditions, and then 116 g (4 eq) of triethylamine (TEA) was added over 0.5 h at 0°C. After warming to room temperature, the mixture was stirred overnight, extracted with DCM and water, and the organic layer was dried over MgSO4, filtered, and concentrated. The residue was purified by flash column chromatography (Hexane:Acetone) and recrystallized from diethyl ether to obtain compound (A), a polycarbonate monomer (purity 62.7%). The results of NMR analysis of the obtained compound (A) are as follows (see Fig. 4).

[0126] 1 H NMR (500 MHz, CDCl3) δ (ppm): 4.83 (m, 1H), 4.53 (m, 2H), 4.45-4.44 (m, 2H), 4.16 (m, 1H), 3.87-3.82 (m, 1H), 3.58-3.54 (m, 1H), 1.88-1.81(m, 1H), 1.78-1.72 (m, 1H), 1.68-1.54 (m, 4H).

[0127]

[0128] <Example 2>

[0129] Polycarbonate polymerization using the polycarbonate monomer of the present invention

[0130] A biodegradable polycarbonate was synthesized through the following polymerization reaction using the polycarbonate polymerization monomer of the present invention synthesized in the above <Example 1>.

[0131]

[0132] <Polycarbonate polymerization using the polycarbonate monomer of the present invention>

[0133]

[0134] Specifically, 5 g (1 eq) of the polycarbonate monomer compound (A) obtained in <1-4> of the above <Example 1> was dissolved in 400 mL of dichloromethane (DCM) in a round-bottom flask, and then 5.35 mg (0.002 eq) of benzyl alcohol as an initiator and 7 mg (0.002 eq) of 1,5,7-triazabicyclodec-5-ene (TBD) as a catalyst were added and stirred at 28°C overnight. Thereafter, the produced polymer was dissolved in DCM, precipitated in 200 mL of ether, and the precipitated polymer was washed again with ether. Through this process, a polycarbonate polymer having a number average molecular weight (Mn) of 26064 g / mol and a polydispersity index (PDI) of 1.5 was obtained (purity 98%). The results of NMR analysis of the polycarbonate polymer obtained through the above polymerization reaction are as follows.

[0135] 1 H NMR (500 MHz, CDCl3) δ (ppm): 4.78 (m, 1H), 4.34-4.24 (m, 3H), 4.19-4.11 (m, 2H), 3.90-3.86 (m, 1H), 3.53-3.49 (m, 1H) 1.81-1.68 (m, 2H), 1.59-1.50 (m, 4H). above 1 The H NMR analysis graph is shown in Fig. 5.

[0136] 13 C NMR (125 MHz, CDCl3) δ 154.83, 98.06, 71.56, 67.21, 66.33, 62.20, 30.42, 25.30, 19.04. Mn = 14.34 Kg / mol, Ð = 1.51. 13 The C NMR analysis graph is shown in Fig. 6.

[0137]

[0138] Through the above results, the inventors of the present invention were able to find out that a new glycerol derivative with protected 2-oxygen can be synthesized from glycerol at low cost with high purity using a chemical enzyme synthesis method, and that a monomer for polymerizing a hexagonal cyclic polycarbonate can be synthesized using the new glycerol derivative with protected 2-oxygen synthesized in the present invention, and further that when the monomer is used, a polycarbonate polymer with a controllable biodegradation rate, including biodegradation off-on, can be synthesized economically and efficiently.

[0139]

[0140] The present invention has been described above, focusing on preferred embodiments thereof. Those skilled in the art will appreciate that the present invention can be implemented in modified forms without departing from its essential characteristics. Therefore, the disclosed embodiments should be considered illustrative rather than limiting. The scope of the present invention is set forth in the claims, not the foregoing description, and all differences within the scope equivalent thereto should be construed as being encompassed by the present invention.

Claims

1. A precursor compound of a monomer for polycarbonate polymerization, having a chemical protective structure of a hydroxyl group at position 2 represented by the following chemical formula 1; <Chemical Formula 1> In the above chemical formula 1, R 1 A chain-like (C3-C40) alkyl group; a branched (C3-C40) alkyl group; a (C3-C40) cycloalkyl group; a (C3-C40) heterocycloalkyl group; a (C3-C40) alkenyl group; a (C3-C40) alkynyl group; a (C1-C30) heteroalkyl group; a (C6-C40) aryl group; a (C3-C40) heteroaryl group; a (C6-C40) aryl (C1-C40) alkyl group; a (C2-C40) alkyl (C6-C40) aryl group; -Si(R 2 )(R 3 )(R 4 ) silyl group; -C(=O)NHR 5 , -C(=O)NHR 6 2-person acyl group; or -S(=O)2R 7 In sulfonyl group; and, R 2 Inland R 4 are each independently hydrogen, (C1-C40)alkyl group or (C6-C40)aryl group, and R 2 Inland R 4 At least one of them is a (C1-C40) alkyl group or a (C6-C40) aryl group, R 5 Inland R 7 are each independently a (C1-C40) alkyl group, a branched (C3-C40) alkyl group, a (C3-C40) alkenyl group, a (C3-C40) alkynyl group, a (C1-C30) heteroalkyl group, a (C3-C40) cycloalkyl group, a (C3-C40) heterocycloalkyl group, a (C6-C40) aryl group, a (C3-C40) heteroaryl group, a (C6-C40) aryl(C1-C40) alkyl group, a (C2-C40) alkyl(C6-C40) aryl group, or a substituent derived from a hydrophilic polymer.

2. In paragraph 1, A precursor compound of a monomer for polycarbonate polymerization, characterized in that the precursor compound of the monomer for polycarbonate polymerization is characterized in that acyl group migration is suppressed. 3.(1) A step of synthesizing a 1,3-diacetin compound using a chemical enzymatic synthesis method using glycerol as a starting material; and (2) A continuous synthesis step for converting the oxygen of the second hydroxyl group of the above 1,3-diacetin compound into a functional group capable of protecting it; A method for producing a precursor compound of a monomer for polycarbonate polymerization of claim 1.

4. In paragraph 3, The chemical enzyme synthesis method of step (1) above is: An initial reaction step in which glycerol and vinyl acetate are used as reactants and a reaction is initiated at a temperature of 20°C to 30°C using an immobilized enzyme catalyst as an acetylation reaction catalyst of glycerol; A late reaction step in which the purity of the 1,3-diacetin compound is increased by rapidly lowering the reaction temperature by at least 10°C from the initial reaction temperature at the point where glycerol is exhausted; and A method for producing a precursor compound of a monomer for polycarbonate polymerization according to claim 1, characterized in that the method comprises performing a termination step for terminating the reaction immediately before triacetin is produced.

5. In paragraph 4, The above immobilized enzyme catalyst is, A method for producing a precursor compound of a monomer for polycarbonate polymerization of claim 1, characterized in that the precursor compound is selected from the group consisting of immobilized Candia antarctica lipase B (Calb), immobilized Thermomyces lanuginosus lipase (TLL), and immobilized Rhizomucor miehei lipase (RML).

6. In paragraph 4, After the above termination step, the separation and purification of the manufactured 1,3-diacetin compound is carried out. The immobilized enzyme catalyst is removed by filtration or sedimentation; After completely dissolving the 1,3-diacetin compound by adding tetrahydrofuran, diethyl ether or benzene solvent, distillation under reduced pressure at a temperature of 30°C to 40°C; A method for producing a precursor compound of a monomer for polycarbonate polymerization of claim 1, characterized by separation and purification by medium-pressure column chromatography.

7. In paragraph 3, A method for producing a precursor compound of a monomer for polycarbonate polymerization of claim 1, characterized in that the functional group of the above step (2) is selected from the group consisting of halide, methyl isomer, nitrile, aldehyde, isocyanate, thiocyanate, silyl isomer, azide, cyan, and alkoxyalkyl isomer.

8. In paragraph 7, A method for producing a precursor compound of a monomer for polycarbonate polymerization of claim 1, characterized in that the functional group of step (2) above is tetrahydropyranyl.

9. A precursor compound of a monomer for polycarbonate polymerization having the structural formula of the following chemical formula 2, wherein one of the two acetyl groups in the compound of paragraph 1 is removed; <Chemical Formula 2> In the above chemical formula 2, R 1 A chain-like (C3-C40) alkyl group; a branched (C3-C40) alkyl group; a (C3-C40) cycloalkyl group; a (C3-C40) heterocycloalkyl group; a (C3-C40) alkenyl group; a (C3-C40) alkynyl group; a (C1-C30) heteroalkyl group; a (C6-C40) aryl group; a (C3-C40) heteroaryl group; a (C6-C40) aryl (C1-C40) alkyl group; a (C2-C40) alkyl (C6-C40) aryl group; -Si(R 2 )(R 3 )(R 4 ) silyl group; -C(=O)R 5 , -C(=O)NHR 6 , -C(=O)NHR 7 2 or -C(=O)OR 8 acyl group; or -S(=O)2R 9 In sulfonyl group; and, R 2 Inland R 4 are each independently hydrogen, (C1-C40)alkyl group or (C6-C40)aryl group, and R 2 Inland R 4 At least one of them is a (C1-C40) alkyl group or a (C6-C40) aryl group, R 5 Inland R 9 are each independently a (C1-C40) alkyl group, a branched (C3-C40) alkyl group, a (C3-C40) alkenyl group, a (C3-C40) alkynyl group, a (C1-C30) heteroalkyl group, a (C3-C40) cycloalkyl group, a (C3-C40) heterocycloalkyl group, a (C6-C40) aryl group, a (C3-C40) heteroaryl group, a (C6-C40) aryl(C1-C40) alkyl group, and a (C2-C40) alkyl(C6-C40) aryl group.

10. A step of reacting the compound of paragraph 1 with magnesium ethoxide dissolved in ethanol within 6 hours to deacetylate only one of the two acetyl groups in the compound of paragraph 1 and convert it into a hydroxyl group. A method for producing a precursor compound of a monomer for polycarbonate polymerization having the structural formula of Chemical Formula 2 of Article 9.

11. A carbonate monomer having a hexagonal ring structure, synthesized by deacetylating the compound of paragraph 1 in a mixed solvent of potassium carbonate (K2CO3), ethanol, and water, and then reacting it with ethyl chloroformate.

12. A biodegradable polycarbonate polymer polymerized with the carbonate monomer of Article 11.

13. Using guanidine series substances as catalysts, Compounds containing a hydroxyl group (-OH), a thiol group (-SH), or an amine functional group are used as nucleophiles. Comprising a step of performing a ring-opening polymerization reaction of the carbonate monomer of claim 10 in the presence of an organic solvent at a temperature of 20°C to 30°C. A method for producing a biodegradable polycarbonate polymer.

14. In paragraph 13, A method for producing a biodegradable polycarbonate polymer, characterized in that the catalyst uses at least one catalyst selected from the group consisting of cyclic guanidines such as 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), 1,5-diazabicyclo[4.3.0]non-5-ene (DBN), N-methyl-DBU, N-ethyl-DBU or N-propyl-DBU; acyclic guanidines such as tetramethylguanidine (TMG) or N,N,N',N'-tetramethyl-N''-phenylguanidine; and chiral guanidines.

15. In paragraph 13, The above amine functional group is -NH2, or -NHR 1 , or -NHR 1 2, or -NR 1 3; The above R 1 silver, (C1-C40) alkyl group; branched (C3-C40) alkyl group; (C3-C40) cycloalkyl group; (C3-C40) heterocycloalkyl group; (C3-C40) alkenyl group; (C3-C40) alkynyl group; (C1-C30) heteroalkyl group; (C6-C40) aryl group; (C3-C40) heteroaryl group; (C6-C40) aryl (C1-C40) alkyl group; (C2-C40) alkyl (C6-C40) aryl group; or -Si(R 2 )(R 3 )(R 4 ) is a silyl group; a method for producing a biodegradable polycarbonate polymer characterized by the following.

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