Novel compound, polymer composition, molded article, and method for producing polymer composition

Abstract

To provide a method for effectively utilizing by-product glycerol.SOLUTION: A novel compound represented by formula (1) is synthesized from by-product glycerol. The polymer composition is polymerized by using the new compound as a monomer. R1 is, for example, -CH3, -C2H5, - CH2CH2OCH3, or - CH2 - Ph.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a novel compound, a polymer composition containing the novel compound as a monomer, a method for producing a polymer composition containing the novel compound as a monomer, and a molded article using the polymer composition. [Background technology]

[0002] Resource depletion and environmental pollution caused by the mass production and disposal of plastics have become a growing concern in recent years. With the establishment of the Sustainable Development Goals (SDGs) by the United Nations in 2015, the creation of clean biofuels using biomass as a starting material has become an urgent issue. Biofuels are considered important from the perspective of energy security, as they can be procured even in regions with limited fossil fuel resources. Representative biofuels include ethanol, a gasoline alternative, and BDF (registered trademark), a diesel alternative. In a broad sense, BDF refers to diesel engine fuel derived from bioresources, but in a more narrow sense, it refers to fatty acid methyl ester (FAME) produced from cooking oil (waste oil). BDF is a type of biomass energy and an attractive energy source with the potential to achieve carbon neutrality, which means virtually zero carbon dioxide emissions.

[0003] The most widely used method for producing BDF is the alkaline catalyst method using sodium hydroxide (NaOH) or potassium hydroxide (KOH). The main component of vegetable oil is triglyceride, which is transesterified with methanol in the presence of a base catalyst. The reaction temperature is approximately 60°C, which is close to the boiling point of methanol, and the reaction time is approximately 40 to 60 minutes. The BDF obtained in this process is washed with acid or separated by distillation and used as diesel engine fuel.

[0004] Meanwhile, during the production of BDF, approximately 20% of the glycerol produced is generated. This is called by-product glycerol. Because by-product glycerol has low purity, it is difficult to utilize effectively and is therefore treated as industrial waste, resulting in an increase in the price of BDF. While there have been reports of effective utilization of this by-product glycerol, such as using it as fuel, the method of burning it while mixing it with a small amount of petroleum-based fuel requires special facilities, making it difficult to utilize effectively in practice (Non-Patent Documents 1 and 2). Another proposed method involves adding excess sewage sludge to the by-product glycerol and subjecting it to anaerobic fermentation to decompose the by-product glycerol, and then utilizing the decomposition product industrially (Patent Document 1). However, this method has a low decomposition rate of by-product glycerol, and therefore cannot be considered an effective utilization method. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2012-039912 [Non-patent literature]

[0006] [Non-Patent Document 1] Kazuo Nakamura, Yoshitake Kuruzumi, Jun Ikegami: Study on the application of glycerin wastewater discharged from biodiesel production facilities to methane fermentation, Journal of the Japan Society of Waste Management, Vol. 19, No. 1, pp. 9-16 (2008) [Non-patent document 2] Makoto Miura: Utilization of BDF by-product glycerin in the Hokuroku region - Examination of concrete formwork release agent, Bulletin of Akita Polytechnic College attached to Tohoku Polytechnic University, Vol. 14, pp. 33-38 (2009) Summary of the Invention [Problem to be solved by the invention]

[0007] The present invention has been made in consideration of these problems, and aims to provide a method for effectively utilizing by-product glycerol. Effective utilization of by-product glycerol will contribute to carbon neutrality and reduce the price of BDF. [Means for solving the problem]

[0008] The present inventors have discovered a new method for effectively utilizing by-product glycerol to synthesize plastic materials, and have completed the present invention based on this finding.

[0009] That is, the present inventors have discovered a method for synthesizing a novel compound represented by the following formula (1) from by-product glycerol, and have also discovered a method for polymerizing a polymer composition using this novel compound as a monomer.

[0010] [ka]

[0011] Here, R1 is selected from the group consisting of (I), (II), (III) and (IV) below. (I)-CH3,-C2H5,-C3H7,-CH(CH3)2,-C4H9,-CH2-CH(CH3)2,-C(CH3)3,-CH(CH3)-C2H5,-CH(CH3)-C3H7,-CH2-CH(CH3)-C2H5,-CH(CH3)-CH(CH3)2,-C5H 11 ,-C(CH3)2-C2H5,-CH2-C(CH3)3,-CH(C2H5)2,-C2H4-CH(CH3)2,-C6H 13 ,-C3H6-CH(CH3)2,-C2H4-CH(CH3)-C2H5,-CH(CH3)-C4H9,-CH2-CH(CH3)-C3H7,-CH(CH3)-CH2-CH(CH3)2,-CH(CH3)-CH(CH3)-C2H 5,-CH2-CH(CH3)-CH(CH3)2,-CH2-C(CH3)2-C2H5,-C(CH3)2-C3H7,-C(CH3)2-CH(CH3)2,-C2H4-C(CH3)3, or -CH(CH3)-C(CH3)3; (II)-CH2OCH3,-CH2OCH2CH3,-CH2CH2OCH3,-CH2CH2OCH2CH3,-C3H6-OCH3,-C3H6-OC2H5,-CH2CO2CH3,-CH2CO2CH2CH3,-CH2CH2NHCH3, or -CH2CH2N(CH3)2; (III)-CH2-Ph,-CH2-CH2-Ph,-C3H6-Ph,-C(CH3)2-Ph,-C4H8-Ph,-CH2-C(CH3)2-Ph,-CH( CH3)-C2H4-Ph,-CH(CH3)-C3H6-Ph,-CH2-CH(CH3)-C2H4-Ph,-CH(CH3)-C(CH3)2-Ph,-C5H 10 -Ph,-C(CH3)2-C2H4-Ph,-C(C2H5)2-Ph,-C2H4-C(CH3)2-Ph,-C6H 12 -Ph,-C3H6-C(CH3)2-Ph,-C2H4-CH(CH3)-C2H4-Ph,-CH(CH3)-C4H8-Ph,-CH2-CH(CH3)-C3H6-Ph,-CH(CH3)-CH2-C(CH3)2-Ph,-CH (CH3)-CH(CH3)-C2H4-Ph, -CH2-CH(CH3)-C(CH3)2-Ph, -CH2-C(CH3)2-C2H4-Ph, -C(CH3)2-C3H6-Ph, or -C(CH3)2-C(CH3)2-Ph; (IV)-CH2-CH=CH2,-C(CH3)=CH2,-C2H4-CH=C,-CH2-CH=CH-CH3,-CH2-C(CH3)=CH2, -CH(CH3)-CH=CH2,-C(CH3)=CH-CH3,-CH2-C≡CH,-C2H4-C≡CH3, or -CH2-C≡C-CH3;

[0012] The R1 is a substituted or unsubstituted functional group, and when the R1 is substituted, it is substituted with one or more groups independently selected from the group consisting of the following (a) to (c): (a) a halogen atom, a hydroxyl group, a carboxy group, a mercapto group, an oxo group, a haloalkyl group having 1 to 6 carbon atoms, and a haloalkoxy group having 1 to 6 carbon atoms; (b) an alkoxy group having 1 to 6 carbon atoms, an alkylcarbonyl group having 2 to 6 carbon atoms, an alkoxycarbonyl group having 2 to 6 carbon atoms, an alkylsulfonyl group having 1 to 6 carbon atoms, an alkylsulfinyl group having 1 to 6 carbon atoms, an alkylcarbonyloxy group having 2 to 6 carbon atoms, and an alkylthio group having 1 to 6 carbon atoms; (c) an amino group, a carbamoyl group, a sulfamoyl group, a 3- to 8-membered cycloalkyl group, a 3- to 8-membered cycloalkoxy group, a 4- to 8-membered saturated heterocyclic group, a 6- to 10-membered aryl group, a 5- to 10-membered heteroaryl group, a 6- to 10-membered aryloxy group, and a 5- to 10-membered heteroaryloxy group; [Effects of the Invention]

[0013] According to the present invention, by-product glycerol can be effectively utilized. This contributes to carbon neutrality and reduces the price of BDF. Numerous attempts have been made to convert by-product glycerol into useful substances such as high-performance surfactants and synthetic intermediates for various chemical products, but problems with the reaction yield and purity of the products have prevented practical production. However, according to the present invention, plastic materials can be synthesized from by-product glycerol. Moreover, as shown in the examples below, the plastic materials that can be synthesized are biodegradable polymer compositions, and are extremely useful. [Brief explanation of the drawings]

[0014] [Figure 1] FIG. 1 shows the 1H-NMR spectrum of a bio-based polymer having a methoxymethyl (MOM) group in the side chain. [Figure 2] FIG. 1 shows the 13C-NMR spectrum of a bio-based polymer having a methoxymethyl (MOM) group in the side chain. [Figure 3] FIG. 1 shows a 1H-NMR spectrum of a bio-based polymer having an ethoxymethyl (EOM) group in the side chain. [Figure 4] FIG. 1 shows a 13C-NMR spectrum of a bio-based polymer having an ethoxymethyl (EOM) group in the side chain. [Figure 5] FIG. 1 shows the 1H-NMR spectrum of a bio-based polymer having 2-methoxyethoxymethyl (MEM) groups in the side chains. [Figure 6] FIG. 1 shows the 13C-NMR spectrum of a bio-based polymer having 2-methoxyethoxymethyl (MEM) groups in the side chains. [Figure 7] FIG. 1 shows a 1H-NMR spectrum of a bio-based polymer having a benzyloxy group in the side chain. [Figure 8] FIG. 1 shows a 13C-NMR spectrum of a bio-based polymer having benzyloxy groups in the side chains. DETAILED DESCRIPTION OF THE INVENTION

[0015] Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, these embodiments are intended to facilitate understanding of the principles of the present invention, and the scope of the present invention is not limited to the following embodiments. Other embodiments in which a person skilled in the art appropriately replaces the configuration of the following embodiments are also included in the scope of the present invention.

[0016] The present inventors have discovered a method for synthesizing a novel compound represented by the following formula (1) from by-product glycerol, and have also discovered a method for polymerizing a polymer composition using this novel compound as a monomer.

[0017] [ka]

[0018] Here, R1 is selected from the group consisting of (I), (II), (III) and (IV) below. (I)-CH3,-C2H5,-C3H7,-CH(CH3)2,-C4H9,-CH2-CH(CH3)2,-C(CH3)3,-CH(CH3)-C2H5,-CH(CH3)-C3H7,-CH2-CH(CH3)-C2H5,-CH(CH3)-CH(CH3)2,-C5H 11, -C(CH3)2-C2H5, -CH2-C(CH3)3, -CH(C2H5)2, -C2H4-CH(CH3)2, -C6H 13 , -C3H6-CH(CH3)2, -C2H4-CH(CH3)-C2H5, -CH(CH3)-C4H9, -CH2-CH(CH3)-C3H7, -CH(CH3)-CH2-CH(CH3)2, -CH(CH3)-CH(CH3)-C2H5, -CH2-CH(CH3)-CH(CH3)2, -CH2-C(CH3)2-C2H5, -C(CH3)2-C3H7, -C(CH3)2-CH(CH3)2, -C2H4-C(CH3)3, or -CH(CH3)-C(CH3)3; (II) -CH2OCH3, -CH2OCH2CH3, -CH2CH2OCH3, -CH2CH2OCH2CH3, -C3H6-OCH3, -C3H6-OC2H5, -CH2CO2CH3, -CH2CO2CH2CH3, -CH2CH2NHCH3, or -CH2CH2N(CH3)2; (III) -CH2-Ph, -CH2-CH2-Ph, -C3H6-Ph, -C(CH3)2-Ph, -C4H8-Ph, -CH2-C(CH3)2-Ph, -CH(CH3)-C2H4-Ph, -CH(CH3)-C3H6-Ph, -CH2-CH(CH3)-C2H4-Ph, -CH(CH3)-C(CH3)2-Ph, -C5H 10 -Ph, -C(CH3)2-C2H4-Ph, -C(C2H5)2-Ph, -C2H4-C(CH3)2-Ph, -C6H 12 -Ph, -C3H6-C(CH3)2-Ph, -C2H4-CH(CH3)-C2H4-Ph, -CH(CH3)-C4H8-Ph, -CH2-CH(CH3)-C3H6-Ph, -CH(CH3)-CH2-C(CH3)2-Ph, -CH(CH3)-CH(CH3)-C2H4-Ph, -CH2-CH(CH3)-C(CH3)2-Ph, -CH2-C(CH3)2-C2H4-Ph, -C(CH3)2-C3H6-Ph, or -C(CH3)2-C(CH3)2-Ph; (IV)-CH2-CH=CH2,-C(CH3)=CH2,-C2H4-CH=C,-CH2-CH=CH-CH3,-CH2-C(CH3)=CH2, -CH(CH3)-CH=CH2,-C(CH3)=CH-CH3,-CH2-C≡CH,-C2H4-C≡CH3, or -CH2-C≡C-CH3;

[0019] The R1 is a substituted or unsubstituted functional group, and when the R1 is substituted, it is substituted with one or more groups independently selected from the group consisting of the following (a) to (c): (a) a halogen atom, a hydroxyl group, a carboxy group, a mercapto group, an oxo group, a haloalkyl group having 1 to 6 carbon atoms, and a haloalkoxy group having 1 to 6 carbon atoms; (b) an alkoxy group having 1 to 6 carbon atoms, an alkylcarbonyl group having 2 to 6 carbon atoms, an alkoxycarbonyl group having 2 to 6 carbon atoms, an alkylsulfonyl group having 1 to 6 carbon atoms, an alkylsulfinyl group having 1 to 6 carbon atoms, an alkylcarbonyloxy group having 2 to 6 carbon atoms, and an alkylthio group having 1 to 6 carbon atoms; (c) an amino group, a carbamoyl group, a sulfamoyl group, a 3- to 8-membered cycloalkyl group, a 3- to 8-membered cycloalkoxy group, a 4- to 8-membered saturated heterocyclic group, a 6- to 10-membered aryl group, a 5- to 10-membered heteroaryl group, a 6- to 10-membered aryloxy group, and a 5- to 10-membered heteroaryloxy group;

[0020] In the novel compound of the present invention, in the following formula (1), R1 is preferably -CH3, -C2H5, -CH2CH2OCH3, or -CH2-Ph.

[0021] [ka]

[0022] The polymer composition according to the present invention is characterized by containing a polymer having a monomer unit represented by the following chemical formula (2):

[0023] [ka]

[0024] Here, n means the number of repeating monomer units, and x is 0.01 to 0.7.

[0025] R1 is selected from the group consisting of (I), (II), (III) and (IV) below. (I)-CH3,-C2H5,-C3H7,-CH(CH3)2,-C4H9,-CH2-CH(CH3)2,-C(CH3)3,-CH(CH3)-C2H5,-CH(CH3)-C3H7,-CH2-CH(CH3)-C2H5,-CH(CH3)-CH(CH3)2,-C5H 11 ,-C(CH3)2-C2H5,-CH2-C(CH3)3,-CH(C2H5)2,-C2H4-CH(CH3)2,-C6H 13 ,-C3H6-CH(CH3)2,-C2H4-CH(CH3)-C2H5,-CH(CH3)-C4H9,-CH2-CH(CH3)-C3H7,-CH(CH3)-CH2-CH(CH3)2,-CH(CH3)-CH(CH3)-C2H 5,-CH2-CH(CH3)-CH(CH3)2,-CH2-C(CH3)2-C2H5,-C(CH3)2-C3H7,-C(CH3)2-CH(CH3)2,-C2H4-C(CH3)3, or -CH(CH3)-C(CH3)3; (II)-CH2OCH3,-CH2OCH2CH3,-CH2CH2OCH3,-CH2CH2OCH2CH3,-C3H6-OCH3,-C3H6-OC2H5,-CH2CO2CH3,-CH2CO2CH2CH3,-CH2CH2NHCH3, or -CH2CH2N(CH3)2; (III)-CH2-Ph,-CH2-CH2-Ph,-C3H6-Ph,-C(CH3)2-Ph,-C4H8-Ph,-CH2-C(CH3)2-Ph,-CH( CH3)-C2H4-Ph,-CH(CH3)-C3H6-Ph,-CH2-CH(CH3)-C2H4-Ph,-CH(CH3)-C(CH3)2-Ph,-C5H 10-Ph,-C(CH3)2-C2H4-Ph,-C(C2H5)2-Ph,-C2H4-C(CH3)2-Ph,-C6H 12 -Ph,-C3H6-C(CH3)2-Ph,-C2H4-CH(CH3)-C2H4-Ph,-CH(CH3)-C4H8-Ph,-CH2-CH(CH3)-C3H6-Ph,-CH(CH3)-CH2-C(CH3)2-Ph,-CH (CH3)-CH(CH3)-C2H4-Ph, -CH2-CH(CH3)-C(CH3)2-Ph, -CH2-C(CH3)2-C2H4-Ph, -C(CH3)2-C3H6-Ph, or -C(CH3)2-C(CH3)2-Ph; (IV)-CH2-CH=CH2,-C(CH3)=CH2,-C2H4-CH=C,-CH2-CH=CH-CH3,-CH2-C(CH3)=CH2, -CH(CH3)-CH=CH2,-C(CH3)=CH-CH3,-CH2-C≡CH,-C2H4-C≡CH3, or -CH2-C≡C-CH3;

[0026] The R1 is a substituted or unsubstituted functional group, and when the R1 is substituted, it is substituted with one or more groups independently selected from the group consisting of the following (a) to (c): (a) a halogen atom, a hydroxyl group, a carboxy group, a mercapto group, an oxo group, a haloalkyl group having 1 to 6 carbon atoms, and a haloalkoxy group having 1 to 6 carbon atoms; (b) an alkoxy group having 1 to 6 carbon atoms, an alkylcarbonyl group having 2 to 6 carbon atoms, an alkoxycarbonyl group having 2 to 6 carbon atoms, an alkylsulfonyl group having 1 to 6 carbon atoms, an alkylsulfinyl group having 1 to 6 carbon atoms, an alkylcarbonyloxy group having 2 to 6 carbon atoms, and an alkylthio group having 1 to 6 carbon atoms; (c) an amino group, a carbamoyl group, a sulfamoyl group, a 3- to 8-membered cycloalkyl group, a 3- to 8-membered cycloalkoxy group, a 4- to 8-membered saturated heterocyclic group, a 6- to 10-membered aryl group, a 5- to 10-membered heteroaryl group, a 6- to 10-membered aryloxy group, and a 5- to 10-membered heteroaryloxy group;

[0027] In the polymer composition according to the present invention, in the following formula (2), R1 is preferably -CH3, -C2H5, -CH2CH2OCH3, or -CH2-Ph, where n represents the number of repeating monomer units and x is 0.01 to 0.7.

[0028] [ka]

[0029] That is, the polymer composition according to the present invention is represented by the following formula: n represents the number of repeating monomer units, and x is 0.01 to 0.7.

[0030] [ka]

[0031] The polymer composition according to the present invention is represented by the following formula: n represents the number of repeating monomer units, and x is 0.01 to 0.7.

[0032] [ka]

[0033] The polymer composition according to the present invention is represented by the following formula: n represents the number of repeating monomer units, and x is 0.01 to 0.7.

[0034] [ka]

[0035] The polymer composition according to the present invention is represented by the following formula: n represents the number of repeating monomer units, and x is 0.01 to 0.7.

[0036] [ka]

[0037] A method for producing the novel compound of the present invention will now be described.

[0038] That is, for example, the novel compound according to the present invention is synthesized from glycerol, which is a by-product when biodiesel fuel is produced from waste oil, through the following steps (i) to (vi).

[0039] [ka]

[0040] [ka]

[0041] [ka]

[0042] [ka]

[0043] [ka]

[0044] [ka]

[0045] A method for producing the polymer composition of the present invention will now be described.

[0046] That is, the polymer composition of the present invention is synthesized by radical polymerization using the novel compound produced in the above step (vi) as a monomer through the following step (vii).

[0047] [ka]

[0048] Here, R1 is selected from the group consisting of (I), (II), (III) and (IV) below. (I)-CH3,-C2H5,-C3H7,-CH(CH3)2,-C4H9,-CH2-CH(CH3)2,-C(CH3)3,-CH(CH3)-C2H5,-CH(CH3)-C3H7,-CH2-CH(CH3)-C2H5,-CH(CH3)-CH(CH3)2,-C5H 11 ,-C(CH3)2-C2H5,-CH2-C(CH3)3,-CH(C2H5)2,-C2H4-CH(CH3)2,-C6H 13 ,-C3H6-CH(CH3)2,-C2H4-CH(CH3)-C2H5,-CH(CH3)-C4H9,-CH2-CH(CH3)-C3H7,-CH(CH3)-CH2-CH(CH3)2,-CH(CH3)-CH(CH3)-C2H 5,-CH2-CH(CH3)-CH(CH3)2,-CH2-C(CH3)2-C2H5,-C(CH3)2-C3H7,-C(CH3)2-CH(CH3)2,-C2H4-C(CH3)3, or -CH(CH3)-C(CH3)3; (II)-CH2OCH3,-CH2OCH2CH3,-CH2CH2OCH3,-CH2CH2OCH2CH3,-C3H6-OCH3,-C3H6-OC2H5,-CH2CO2CH3,-CH2CO2CH2CH3,-CH2CH2NHCH3, or -CH2CH2N(CH3)2; (III)-CH2-Ph,-CH2-CH2-Ph,-C3H6-Ph,-C(CH3)2-Ph,-C4H8-Ph,-CH2-C(CH3)2-Ph,-CH( CH3)-C2H4-Ph,-CH(CH3)-C3H6-Ph,-CH2-CH(CH3)-C2H4-Ph,-CH(CH3)-C(CH3)2-Ph,-C5H 10 -Ph,-C(CH3)2-C2H4-Ph,-C(C2H5)2-Ph,-C2H4-C(CH3)2-Ph,-C6H 12-Ph,-C3H6-C(CH3)2-Ph,-C2H4-CH(CH3)-C2H4-Ph,-CH(CH3)-C4H8-Ph,-CH2-CH(CH3)-C3H6-Ph,-CH(CH3)-CH2-C(CH3)2-Ph,-CH (CH3)-CH(CH3)-C2H4-Ph, -CH2-CH(CH3)-C(CH3)2-Ph, -CH2-C(CH3)2-C2H4-Ph, -C(CH3)2-C3H6-Ph, or -C(CH3)2-C(CH3)2-Ph; (IV)-CH2-CH=CH2,-C(CH3)=CH2,-C2H4-CH=C,-CH2-CH=CH-CH3,-CH2-C(CH3)=CH2, -CH(CH3)-CH=CH2,-C(CH3)=CH-CH3,-CH2-C≡CH,-C2H4-C≡CH3, or -CH2-C≡C-CH3;

[0049] The R1 is a substituted or unsubstituted functional group, and when the R1 is substituted, it is substituted with one or more groups independently selected from the group consisting of the following (a) to (c): (a) a halogen atom, a hydroxyl group, a carboxy group, a mercapto group, an oxo group, a haloalkyl group having 1 to 6 carbon atoms, and a haloalkoxy group having 1 to 6 carbon atoms; (b) an alkoxy group having 1 to 6 carbon atoms, an alkylcarbonyl group having 2 to 6 carbon atoms, an alkoxycarbonyl group having 2 to 6 carbon atoms, an alkylsulfonyl group having 1 to 6 carbon atoms, an alkylsulfinyl group having 1 to 6 carbon atoms, an alkylcarbonyloxy group having 2 to 6 carbon atoms, and an alkylthio group having 1 to 6 carbon atoms; (c) an amino group, a carbamoyl group, a sulfamoyl group, a 3- to 8-membered cycloalkyl group, a 3- to 8-membered cycloalkoxy group, a 4- to 8-membered saturated heterocyclic group, a 6- to 10-membered aryl group, a 5- to 10-membered heteroaryl group, a 6- to 10-membered aryloxy group, and a 5- to 10-membered heteroaryloxy group;

[0050] The polymerization initiator used in the radical polymerization of step (vii) is not particularly limited, and examples thereof include di-tert-butyl peroxide, VAm-110, 2,2'-azobisisobutyronitrile (AIBN), 1,1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis-(2,4'-dimethylvaleronitrile), benzoyl peroxide (BPO), lauroyl peroxide (LPO), etc. Two or more of these polymerization initiators may be used in combination.

[0051] The polymerization solvent in the radical polymerization of step (vii) is not particularly limited, but examples thereof include aromatic hydrocarbon solvents such as toluene, xylene, and 1,2-dichlorobenzene; ether solvents such as tetrahydrofuran and 1,4-dioxane; aprotic polar solvents such as dimethyl sulfoxide, N-methyl-2-pyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide; and halogenated hydrocarbon solvents such as dichloromethane, dichloroethane, and chloroform. The solvents may be used alone or in combination. Alternatively, no solvent may be used.

[0052] The polymerization temperature in the radical polymerization of step (vii) is not particularly limited, but is, for example, in the range of 60 to 180°C, preferably in the range of 120 to 150°C. If the polymerization temperature is 60°C or higher, the polymerization reaction can proceed at an economical rate. If the polymerization temperature is 180°C or lower, the rate of chain transfer to the monomer can be suppressed, allowing a copolymer having the desired molecular weight to be produced.

[0053] The monomer concentration in the radical polymerization of step (vii) above is not particularly limited, but is, for example, in the range of 1.2M to 3.6M, and preferably in the range of 2.2M to 2.6M.

[0054] Step (vi) above is radical ring-opening polymerization. In radical ring-opening polymerization, radical species attack the monomer, generating radicals that migrate and cause ring cleavage. For this to occur, the ring must have sufficient strain to allow cleavage. Monomers with large ring strain selectively undergo ring-opening polymerization without vinyl polymerization, whereas monomers with small ring strain preferentially undergo ring-opening polymerization but with vinyl polymerization. The novel compound of the present invention is a compound with a 2-methylene-1,3-dioxolane skeleton, and preferentially undergoes ring-opening polymerization but with vinyl polymerization. When ring-opening polymerization occurs, the polymer chain contains ester bonds, resulting in a biodegradable polymer composition. To increase the ring-opening rate, it is preferable to use a dilute monomer concentration and a high polymerization temperature, as shown in the examples below.

[0055] The method for producing the polymer composition according to the present invention is preferably shown by the following synthesis scheme.

[0056] [ka]

[0057] The molded article of the present invention is a molded article using the polymer composition of the present invention. When the polymer composition is processed into a molded article in the present invention, it may be mixed or composited with other resins, and additives such as a foaming agent such as water or an inert gas, a light stabilizer, a plasticizer, an antioxidant, an ultraviolet absorber, a heat stabilizer, a flame retardant, a mold release agent, an inorganic additive, a filler, a crystal nucleating agent, an antistatic agent, a color inhibitor, a pigment, or an antiblocking agent may be used to further improve the physical properties.

[0058] Because the polymer composition according to the present invention is a biodegradable polymer composition, molded articles can be suitably used, for example, as agricultural and horticultural materials. Examples of agricultural and horticultural materials include mulch films, seedling raising pots, agricultural and horticultural tapes, fruit growing bags, stakes, fumigation sheets, and greenhouse films. For example, when used as seedling raising pots, adjusting their biodegradability allows them to have sufficient strength at the time of sowing and / or during the seedling growing stage and / or during distribution, and they can be decomposed after being buried in soil or water, eliminating the need to remove the seedling raising pots after growing the seedlings and before burying them in soil.

[0059] Because the polymer composition of the present invention is a biodegradable polymer composition, the molded articles can be suitably used as civil engineering and construction materials, such as vegetation nets, vegetation bags, vegetation pots, three-dimensional netting, civil engineering fibers, stakes, and heat insulating materials. [Example]

[0060] (1) Synthesis of polymeric compositions using 2-methylene-4-(methoxymethyl)-1,3-dioxolane as a monomer The polymer composition containing 2-methylene-4-(methoxymethyl)-1,3-dioxolane as a monomer was synthesized according to the following formula: Each synthesis step is explained below.

[0061] [ka]

[0062] Synthesis of (1-1)1-chloro-3-methoxy-2-propanol First, epichlorohydrin was synthesized from glycerol, a by-product produced when producing biodiesel fuel from used cooking oil (waste oil).

[0063] Next, epichlorohydrin (20.11 g, 217 mmol) was added dropwise to a solution of methanol (10.477 g, 327 mmol) and the Lewis acid BF3-Et2O (3.874 g, 27.3 mmol) stirred at 0°C. After the addition, the mixture was allowed to react at room temperature for 2 hours. After the reaction, water was added and the aqueous layer was extracted with dichloromethane (10 mL x 3) using a separatory funnel. The dichloromethane layer was removed, anhydrous magnesium sulfate was added, and the mixture was stirred for 30 minutes to dehydrate. The anhydrous sodium sulfate was removed by filtration, and the mixture was concentrated under reduced pressure. The target product was then obtained by vacuum distillation at 3 mbar and 67°C. Yield: 12.967 g / Yield: 47.9%

[0064] (1-2) Synthesis of methyl glycidyl ether Next, 50 wt% aqueous NaOH solution (23 g) was added dropwise to the resulting 1-chloro-3-methoxy-2-propanol (12.967 g). After the addition, the mixture was allowed to react at 20°C for 2 hours. After the reaction, the aqueous layer was extracted with dichloromethane (50 mL x 3) using a separatory funnel. The dichloromethane layer was removed, anhydrous magnesium sulfate was added, and the mixture was stirred for 30 minutes to dehydrate. The anhydrous sodium sulfate was removed by filtration, and the mixture was concentrated under reduced pressure. The target product was then obtained by vacuum distillation at 190 mbar and 75°C. Yield: 5.967 g / Yield: 31.2%

[0065] Synthesis of (1-3)3-methoxy-1,2-propanediol Next, an aqueous trifluoroacetic acid solution (TFA: 7 mL, water: 30 mL) was added dropwise to the obtained methyl glycidyl ether (15.903 g), and the mixture was allowed to react overnight at room temperature. After the reaction, the aqueous trifluoroacetic acid solution was removed by concentration under reduced pressure, and the target product was obtained by vacuum distillation at 3 mbar and 98°C. Yield: 10.538 g / Yield: 55.0%

[0066] (1-4) Synthesis of 2-(bromomethyl)-4-(methoxymethyl)-1,3-dioxolane Next, the resulting 3-methoxy-1,2-propanediol (11.512 g, 108.5 mmol) was mixed with bromoacetaldehyde diethyl acetal (21.378 g, 108.5 mmol), and 3.0 g of solid Amberlyst® 15 hydrogen form, an acid catalyst, was added and stirred at 85 ° C for 20 hours. After the reaction, the acid catalyst was removed by filtration, and the by-product ethanol was removed by vacuum concentration. The target product was then obtained by vacuum distillation at 2 mbar and 91 ° C. Yield: 14.401 g / Yield: 62.9%

[0067] (1-5) Synthesis of 2-methylene-4-(methoxymethyl)-1,3-dioxolane Next, a solution of 3.878 g of potassium tert-butoxide in 40 mL of THF was slowly added dropwise to a solution of the resulting 2-(bromomethyl)-4-(methoxymethyl)-1,3-dioxolane (2.639 g) and 0.26 g of tetra-n-butylammonium bromide in 50 mL of THF, and the mixture was allowed to react at 60 °C for 2 hours. After the reaction, an excess of hexane was added to the THF to form a hexane solution, and the KBr was crystallized and filtered off. The THF and hexane were then removed by vacuum concentration, and the target product was obtained by vacuum distillation at 3 mbar and 55 °C. Yield: 0.671 g / Yield: 41.2%

[0068] (1-6) Synthesis of biobased polymers with methoxymethyl (MOM) groups in the side chains The polymerization was carried out under the following three conditions. *Condition 1: 140°C, 2.4 M, 20 hours (monomer conversion: >99%, ring opening rate: 96.6%) Monomer 0.312 g / polymerization initiator di-tert-butyl peroxide 4.1 mg (1 mol%) / solvent 1,2-dichlorobenzene Mn: 2,380 Mw: 3,610 D: 1.52 *Condition 2: 140°C, bulk, 20 hours (monomer conversion: 33%, ring-opening rate: 65.7%) Monomer 0.3134 g / polymerization initiator di-tert-butyl peroxide 7.3 mg (2 mol%) / no solvent Mn: 1,840 Mw: 2,590 D: 1.41 *Condition 3: 100°C, 2.4 M, 20 hours (monomer conversion: 13.5%, ring opening rate: 70.8%) Monomer 0.3157 g / polymerization initiator VAm-110 7.5 mg (1 mol%) / solvent toluene Mn: 3,900 Mw: 15,380 D: 3.94

[0069] A test tube containing 2-methylene-4-(methoxymethyl)-1,3-dioxolane monomer, a polymerization initiator, and a solvent was sealed with a silicon W cap, followed by nitrogen substitution and freeze-degassing using liquid nitrogen as a cryogen. Polymerization was carried out for 20 hours in an oil bath at 140°C or 100°C. After polymerization, the solvent was removed under reduced pressure, and the polymer was purified by reprecipitation using hexane as a poor solvent and THF as a good solvent, and then dried overnight in a vacuum. The structure of the resulting polymer was determined as follows: 1 H-NMR spectrum, 13 The results were confirmed by C-NMR spectrum, DEPT 135° spectrum, HH COSY spectrum, HMQC spectrum, HMBC spectrum, and ATR FT-IR spectrum. Figure 1 shows the structure of the bio-based polymer with methoxymethyl (MOM) groups in the side chains. 1 2 shows the H-NMR spectrum of the bio-based polymer having a methoxymethyl (MOM) group in the side chain. 13The molecular weight was determined by SEC measurement (THF, 40°C, PMMA standard), and the weight average molecular weight (M w ), number average molecular weight (M n ), and polydispersity index (PDI) were confirmed.

[0070] (2) Synthesis of polymeric compositions using 2-methylene-4-(ethoxymethyl)-1,3-dioxolane as a monomer The polymer composition containing 2-methylene-4-(ethoxymethyl)-1,3-dioxolane as a monomer was synthesized according to the following formula: Each synthesis step is explained below.

[0071] [ka]

[0072] (2-1) Synthesis of 1-chloro-3-ethoxy-2-propanol First, epichlorohydrin was synthesized from glycerol, a by-product produced when producing biodiesel fuel from used cooking oil (waste oil).

[0073] Next, epichlorohydrin (10.055 g, 108.5 mmol) was added dropwise to a solution of ethanol (7.532 g, 163.5 mmol) and the Lewis acid BF3-Et2O (1.937 g, 13.65 mmol) stirred at 0°C. After the addition, the mixture was allowed to react at room temperature for 2 hours. After the reaction, water was added and the aqueous layer was extracted with dichloromethane (10 mL x 3) using a separatory funnel. The dichloromethane layer was removed, anhydrous magnesium sulfate was added, and the mixture was stirred for 30 minutes to dehydrate. The anhydrous sodium sulfate was removed by filtration, and the mixture was concentrated under reduced pressure. The target product was then obtained by vacuum distillation at 2 mbar and 65°C. Yield: 8.281 g / Yield: 55.0%

[0074] Synthesis of (2-2) ethyl glycidyl ether Next, 50 wt% aqueous NaOH solution (20 g) was added dropwise to the resulting 1-chloro-3-ethoxy-2-propanol (8.281 g). After the addition, the mixture was allowed to react at 20°C for 2 hours. After the reaction, the aqueous layer was extracted with dichloromethane (50 mL x 3) using a separatory funnel. The dichloromethane layer was removed, anhydrous magnesium sulfate was added, and the mixture was stirred for 30 minutes to dehydrate. The anhydrous sodium sulfate was removed by filtration, and the mixture was concentrated under reduced pressure. The target product was then obtained by vacuum distillation at 21 mbar and 50°C. Yield: 3.437 g / Yield: 56.3%

[0075] (2-3) Synthesis of 3-ethoxy-1,2-propanediol Next, an aqueous trifluoroacetic acid solution (TFA: 1.5 mL, water: 50 mL) was added dropwise to the resulting ethyl glycidyl ether (3.437 g), and the mixture was allowed to react overnight at room temperature. After the reaction, the aqueous trifluoroacetic acid solution was removed by concentration under reduced pressure, and the target product was obtained by vacuum distillation at 3 mbar and 101°C. Yield: 4.199 g

[0076] (2-4) Synthesis of 2-(bromomethyl)-4-(ethoxymethyl)-1,3-dioxolane Next, the resulting 3-ethoxy-1,2-propanediol (4.199 g, 34.9 mmol) was mixed with bromoacetaldehyde diethyl acetal (6.887 g, 34.9 mmol), and 1.4 g of solid Amberlyst® 15 hydrogen form (an acid catalyst) was added. The mixture was stirred at 85°C for 20 hours. After the reaction, the acid catalyst was removed by filtration, and the by-product ethanol was removed by concentration under reduced pressure. The target product was then obtained by vacuum distillation at 2 mbar and 91°C. Yield: 5.591 g / Yield: 71.1%

[0077] (2-5) Synthesis of 2-methylene-4-(ethoxymethyl)-1,3-dioxolane Next, a solution of 5.51 g of potassium tert-butoxide in 70 mL of THF was slowly added dropwise to a solution of the resulting 2-(bromomethyl)-4-(ethoxymethyl)-1,3-dioxolane (3.673 g) and 0.37 g of tetra-n-butylammonium bromide in 60 mL of THF, and the mixture was allowed to react at 60 °C for 2 hours. After the reaction, an excess of hexane was added to the THF to form a hexane solution, and the KBr was crystallized and filtered off. The THF and hexane were then removed by vacuum concentration, and the target product was obtained by vacuum distillation at 2 mbar and 68 °C. Yield: 1.443 g / Yield: 61.3%

[0078] (2-6) Synthesis of biobased polymers with ethoxymethyl (EOM) groups in the side chains The synthesis was carried out under the following three conditions. *Condition 1: 140°C, 2.4 M, 20 hours (monomer conversion: 93%, ring opening rate: 90.6%) Monomer 0.3459 g / polymerization initiator di-tert-butyl peroxide 10.5 mg (3 mol%) / solvent 1,2-dichlorobenzene Mn: 3,520 Mw: 5,790 D: 1.64 *Condition 2: 140°C, bulk, 20 hours (monomer conversion: 94.5%, ring opening rate: 76.2%) Monomer 0.376 g / polymerization initiator di-tert-butyl peroxide 24.3 mg (3 mol%) / no solvent Mn: 3,930 Mw: 6,210 D: 1.58 *Condition 3: 100°C, 2.4 M, 20 hours (monomer conversion: 84.5%, ring opening rate: 73.1%) Monomer 0.3475 g / Polymerization initiator VAm-110 22.5 mg (3 mol%) / Solvent 1,2-dichlorobenzene Mn: 4,600 Mw: 7,770 D: 1.69

[0079] A test tube containing 2-methylene-4-(ethoxymethyl)-1,3-dioxolane monomer, a polymerization initiator, and a solvent was sealed with a silicon W cap, and then the tube was purged with nitrogen and frozen and degassed using liquid nitrogen as a cryogen. Polymerization was carried out for 20 hours in an oil bath at 140°C or 100°C. After polymerization, the solvent was removed under reduced pressure, and the polymer was purified by reprecipitation using hexane as a poor solvent and THF as a good solvent, and then dried overnight in a vacuum. The structure of the resulting polymer was determined as follows: 1 H-NMR spectrum, 13 The results were confirmed by C-NMR spectrum, DEPT 135° spectrum, HH COSY spectrum, HMQC spectrum, HMBC spectrum, and ATR FT-IR spectrum. Figure 3 shows the structure of the bio-based polymer with ethoxymethyl (EOM) groups in the side chains. 1 4 shows the H-NMR spectrum of the bio-based polymer having an ethoxymethyl (EOM) group in the side chain. 13 The figure shows the C-NMR spectrum. The molecular weight was determined by SEC measurement (THF, 40 o C, PMMA standard) and the weight average molecular weight (M w ), number average molecular weight (M n ), and polydispersity index (PDI) were confirmed.

[0080] (3) Synthesis of polymeric compositions using 2-methylene-4-[(methoxyethoxy)methyl]-1,3-dioxolane as a monomer The polymer composition containing 2-methylene-4-[(methoxyethoxy)methyl]-1,3-dioxolane as a monomer was synthesized according to the following formula: Each synthesis step is explained below.

[0081] [ka]

[0082] Synthesis of (3-1)1-chloro-3-[(methoxyethoxy)methyl]-2-propanol First, epichlorohydrin was synthesized from glycerol, a by-product produced when producing biodiesel fuel from used cooking oil (waste oil).

[0083] Next, epichlorohydrin (10.055 g, 108.5 mmol) was added dropwise to a solution of 2-methoxyethanol (12.482 g, 163.5 mmol) and the Lewis acid BF3-Et2O (1.937 g, 13.65 mmol) stirred at 0°C. After the dropwise addition, the mixture was allowed to react at room temperature for 2 hours. After the reaction, water was added and the aqueous layer was extracted with dichloromethane (10 mL x 3) using a separatory funnel. The dichloromethane layer was removed, anhydrous magnesium sulfate was added, and the mixture was stirred for 30 minutes to dehydrate. The anhydrous sodium sulfate was removed by filtration, and the mixture was concentrated under reduced pressure. The target product was then obtained by vacuum distillation at 6 mbar and 101°C. Yield: 8.764 g / Yield: 48.69%

[0084] (3-2) Synthesis of (methoxyethoxy)methyl glycidyl ether To the resulting 1-chloro-3-[(methoxyethoxy)methyl]-2-propanol (8.764 g), 50 wt% aqueous NaOH solution (20 g) was added dropwise. After the addition, the mixture was allowed to react at 20°C for 2 hours. After the reaction, the aqueous layer was extracted with dichloromethane (50 mL x 3) using a separatory funnel. The dichloromethane layer was removed, anhydrous magnesium sulfate was added, and the mixture was stirred for 30 minutes to dehydrate. The anhydrous sodium sulfate was removed by filtration, and the mixture was concentrated under reduced pressure. The target product was then obtained by vacuum distillation at 3 mbar and 68°C. Yield: 5.658 g

[0085] (3-3) Synthesis of 3-[(methoxyethoxy)methyl]-1,2-propanediol To the obtained (methoxyethoxy)methyl glycidyl ether (2.827 g), an aqueous trifluoroacetic acid solution (TFA: 1 mL, water: 50 mL) was added dropwise, and the mixture was allowed to react at room temperature overnight. After the reaction, the aqueous trifluoroacetic acid solution was removed by concentration under reduced pressure, and the target product was obtained by vacuum distillation at 2 mbar and 115°C. Yield: 3.173 g

[0086] Synthesis of (3-4)2-(bromomethyl)-4-[(methoxyethoxy)methyl]-1,3-dioxolane The resulting 3-[(methoxyethoxy)methyl]-1,2-propanediol (1.692 g, 11.3 mmol) was mixed with bromoacetaldehyde diethyl acetal (2.267 g, 11.3 mmol), and 0.3 g of solid Amberlyst® 15 hydrogen form, an acid catalyst, was added. o The mixture was stirred at 20°C for 20 hours. After the reaction, the acid catalyst was removed by filtration, and the by-product ethanol was removed by vacuum concentration. Then, the mixture was distilled under reduced pressure at 2 mbar, 136 o C obtained the target. Yield: 0.847 g / Yield: 29.5%

[0087] (3-5) Synthesis of 2-methylene-4-[(methoxyethoxy)methyl]-1,3-dioxolane To a solution of the resulting 2-(bromomethyl)-4-[(methoxyethoxy)methyl]-1,3-dioxolane (2.873 g) and 0.28 g of tetra-n-butylammonium bromide dissolved in 40 mL of THF, a solution of 4.310 g of potassium tert-butoxide dissolved in 60 mL of THF was slowly added dropwise and reacted at 60 °C for 2 hours. After the reaction, an excess of hexane was added from the THF to form a hexane solution, and the KBr was crystallized and filtered off. The THF and hexane were then removed by vacuum concentration, and the target product was obtained by vacuum distillation at 2 mbar and 68 °C. Yield: 0.444 g / Yield: 22.6%

[0088] (3-6) Synthesis of biobased polymers with 2-methoxyethoxymethyl (MEM) groups in the side chains The synthesis was carried out under the following three conditions. *Condition 1: 140°C, 2.4 M, 20 hours (monomer conversion: >99%, ring opening rate: 95.6%) Monomer 0.418 g / polymerization initiator di-tert-butyl peroxide 18.0 mg (3 mol%) / solvent 1,2-dichlorobenzene Mn: 3,120 Mw: 11,590 D: 3.71 *Condition 2: 140°C, bulk, 20 hours (monomer conversion: 91%, ring opening rate: 95.9%) Monomer 0.327 g / polymerization initiator di-tert-butyl peroxide 8.24 mg (3 mol%) / no solvent Mn: 700 Mw: 4,240 D: 6.06 *Condition 3: 100°C, 2.4 M, 20 hours (monomer conversion: 98.3%, ring opening rate: 96.1%) Monomer 0.418 g / polymerization initiator VAm-110 22.5 mg (3 mol%) / solvent 1,2-dichlorobenzene Mn: 800 Mw: 8,000 D: 9.94

[0089] A test tube containing 2-methylene-4-[(methoxyethoxy)methyl]-1,3-dioxolane monomer, a polymerization initiator, and a solvent was sealed with a silicon W cap, followed by nitrogen substitution and freeze-degassing using liquid nitrogen as a cryogen. Polymerization was carried out for 20 hours in an oil bath at 140°C or 100°C. After polymerization, the solvent was removed under reduced pressure, and the polymer was purified by reprecipitation using hexane as a poor solvent and THF as a good solvent, and then dried overnight in a vacuum. The structure of the resulting polymer was determined as follows: 1 H-NMR spectrum, 13 The results were confirmed by C-NMR spectrum, DEPT 135° spectrum, HH COSY spectrum, HMQC spectrum, HMBC spectrum, and ATR FT-IR spectrum. Figure 5 shows the structure of the bio-based polymer with 2-methoxyethoxymethyl (MEM) groups in the side chain. 1 6 shows the H-NMR spectrum of the bio-based polymer having a 2-methoxyethoxymethyl (MEM) group in the side chain. 13 The molecular weight was determined by SEC measurement (THF, 40°C, PMMA standard), and the weight average molecular weight (M w ), number average molecular weight (M n ), and polydispersity index (PDI) were confirmed.

[0090] (4) Synthesis of polymeric compositions using 2-methylene-4-[(benzyloxy)methyl]-1,3-dioxolane as a monomer The polymer composition containing 2-methylene-4-[(benzyloxy)methyl]-1,3-dioxolane as a monomer was synthesized according to the following formula: Each synthesis step is explained below.

[0091] [ka]

[0092] (4-1) Synthesis of benzyl glycidyl ether First, epichlorohydrin was synthesized from glycerol, a by-product produced when producing biodiesel fuel from used cooking oil (waste oil).

[0093] Next, 4.2 mL (54.0 mmol) of epichlorohydrin and 0.356 g (1.10 mmol) of tetra-n-butylammonium bromide (TBAB) were dissolved in 9.3 mL (50% w / w) of aqueous NaOH solution and stirred. 5.6 mL (54.0 mmol) of benzyl alcohol was slowly added dropwise to this solution over 30 minutes, and the mixture was allowed to react at room temperature for 20 hours. After the reaction, pre-chilled distilled water (70 mL) was added to the solution, and the aqueous layer was extracted with ethyl acetate (3 × 50 mL) using a separatory funnel. The ethyl acetate layer was removed, anhydrous magnesium sulfate was added, and the mixture was stirred for 30 minutes for dehydration. The anhydrous sodium sulfate was removed by filtration, and the mixture was concentrated under reduced pressure. The target product was then obtained by column chromatography using a hexane / ethyl acetate mixture (v / v = 3 / 1) as the developing solvent and Wakogel® FC-40 as the packing. Yield: 2.807 g / Yield: 31.4% / Rf value: 0.42

[0094] (4-2)3-(benzyloxy)-1,2-propanediol The resulting benzyl glycidyl ether (2.81 g, 17.1 mmol) was mixed with 35 mL of distilled water, and sulfuric acid (0.35 mL) was slowly added dropwise to the resulting solution at room temperature. The mixture was allowed to react overnight. After the reaction, potassium carbonate was added to the reaction solution to neutralize it from an acidic solution. The aqueous layer was extracted with ethyl acetate (3 × 75 mL) using a separatory funnel. The ethyl acetate layer was then removed, anhydrous magnesium sulfate was added, and the mixture was stirred for 30 minutes for dehydration. The anhydrous sodium sulfate was removed by filtration, and the target product was obtained by concentration under reduced pressure. Yield: 2.59 g / Yield: 83.1%

[0095] (4-3) Synthesis of 2-(bromomethyl)-4-[(benzyloxy)methyl]-1,3-dioxolane The resulting 3-(benzyloxy)-1,2-propanediol (17.87 g, 10.0 mol) and bromoacetaldehyde diethyl acetal (19.63 g, 10.0 mol) were mixed, and 1.11 g of solid Amberlyst® 15 hydrogen form (acid catalyst) was added. The mixture was stirred at 85°C for 20 hours. After the reaction, the acid catalyst was removed by filtration, and the by-product ethanol was removed by vacuum concentration. The product was then purified by column chromatography using a hexane / diethyl ether (v / v=4 / 1) mixture and Wakogel® FC-40 as the packing. Yield: 14.17 g / Yield: 50.6 % / Rf value: 0.15

[0096] (4-4) Synthesis of 2-methylene-4-[(benzyloxy)methyl]-1,3-dioxolane To a solution of the resulting 2-(bromomethyl)-4-[(benzyloxy)methyl]-1,3-dioxolane (1.915 g, 6.67 mmol) and tetra-n-butylammonium bromide (0.225 g) in 55 mL of THF, a solution of potassium tert-butoxide (2.873 g, 25.6 mmol) in 30 mL of THF was slowly added dropwise and reacted at 60 °C for 2 hours. After the reaction, an excess of hexane was added to the THF to form a hexane solution, and the KBr was crystallized and filtered off. The THF and hexane were then removed by vacuum concentration, and the product was obtained by vacuum distillation using a Kugelrohr at <1 hPa and an oil bath temperature of 131 °C. Yield: 0.947 g Yield: 68.8%

[0097] (4-5) Synthesis of biobased polymers with benzyloxy groups in the side chains The synthesis was carried out under the following three conditions. *Condition 1: 140°C, 3.2M, 20 hours (monomer conversion: 85.5%, ring opening rate: 0%) Monomer 0.660 g / Polymerization initiator di-tert-butyl peroxide 9.99 mg (1 mol%) / Solvent 1,2-dichlorobenzene *Condition 2: 140°C, 2.4 M, 20 hours (monomer conversion: >99%, ring opening rate: 88.5%) Monomer 0.327 g / Polymerization initiator di-tert-butyl peroxide 8.24 mg (3 mol%) / Solvent 1,2-dichlorobenzene *Condition 3: 120°C, 1.81 M, 20 hours (monomer conversion: 39.5%, ring opening rate: 0%) Monomer 0.374 g / polymerization initiator Vam-110 5.66 mg (1 mol%) / solvent Toluene

[0098] A test tube containing 2-methylene-4-[(benzyloxy)methyl]-1,3-dioxolane monomer, polymerization initiator, and solvent was sealed with a silicon W cap, followed by nitrogen substitution and freeze-degassing using liquid nitrogen as a cryogen. Polymerization was carried out for 20 hours in an oil bath at 140°C or 120°C. After polymerization, the solvent was removed under reduced pressure, and the polymer was purified by reprecipitation using hexane as a poor solvent and THF as a good solvent in conditions 1 and 2, and water as a poor solvent in condition 3, and then dried overnight in a vacuum. The structure of the obtained polymer was determined using 1 H-NMR spectrum, 13 The results were confirmed by C-NMR spectrum, DEPT 135° spectrum, HH COSY spectrum, HMQC spectrum, and ATR FT-IR spectrum. 1 8 shows the H-NMR spectrum of the bio-based polymer having a benzyloxy group in the side chain. 13The molecular weight was determined by SEC measurement (THF, 40°C, PMMA standard), and the weight average molecular weight (M w ), number average molecular weight (M n ), and polydispersity index (PDI) were confirmed. [Industrial Applicability]

[0099] It can be used to effectively utilize by-product glycerol.

Claims

1. A novel compound represented by the following formula (1): 【Chemistry 1】 (where, R １ is selected from the group consisting of (I), (II), (III) and (IV): (I)-CH ３ ,-C ２ H ５ ,-C ３ H ７ ,-CH(CH ３ ) ２ ,-C ４ H ９ ,-CH ２ -CH(CH ３ ) ２ ,-C(CH ３ ) ３ ,-CH(CH ３ )-C ２ H ５ ,-CH(CH ３ )-C ３ H ７ ,-CH ２ -CH(CH ３ )-C ２ H ５ ,-CH(CH ３ )-CH(CH ３ ) ２ ,-C ５ H １１ ,-C(CH ３ ) ２ -C ２ H ５ ,-CH ２ -C(CH ３ ) ３ ,-CH(C ２ H ５ ) ２ ,-C ２ H ４ -CH(CH ３ ) ２ ,-C ６ H １３ ,-C ３ H ６ -CH(CH ３ ) ２ ,-C ２ H ４ -CH(CH ３ )-C ２ H ５ ,-CH(CH ３ )-C ４ H ９ ,-CH ２ -CH(CH ３ )-C ３ H ７ ,-CH(CH ３ )-CH ２ -CH(CH ３ ) ２ , -CH(CH ３ )-CH(CH ３ )-C ２ H ５ , -CH ２ -CH(CH ３ )-CH(CH ３ ) ２ , -CH ２ -C(CH ３ ) ２ -C ２ H ５ , -C(CH ３ ) ２ -C ３ H ７ , -C(CH ３ ) ２ -CH(CH ３ ) ２ , -C ２ H ４ -C(CH ３ ) ３ , or -CH(CH ３ )-C(CH ３ ) ３ ; (II)-CH ２ OCH ３ ,-CH ２ OCH ２ CH ３ ,-CH ２ CH ２ OCH ３ ,-CH ２ CH ２ OCH ２ CH ３ ,-C ３ H ６ -OCH ３ ,-C ３ H ６ -OC ２ H ５ ,-CH ２ CO ２ CH ３ ,-CH ２ CO ２ CH ２ CH ３ ,-CH ２ CH ２ NHCH ３ , or -CH ２ CH ２ N(CH ３ ) 2 ; (III)-CH ２ -Ph, -CH ２ -CH ２ -Ph, -C ３ H ６ -Ph, -C(CH) ３ ) ２ -Ph, -C ４ H ８ -Ph, -CH ２ -C(CH) ３ ) ２ -Ph, -CH(CH ３ )-C ２ H ４ -Ph, -CH(CH ３ )-C ３ H ６ -Ph, -CH ２ -CH(CH ３ )-C ２ H ４ -Ph, -CH(CH ３ )-C(CH ３ ) ２ -Ph, -C ５ H １０ -Ph, -C(CH) ３ ) ２ -C ２ H ４ -Ph, -C(C) ２ H ５ ) ２ -Ph, -C ２ H ４ -C(CH) ３ ) ２ -Ph, -C ６ H １２ -Ph, -C ３ H ６ -C(CH) ３ ) ２ -Ph, -C ２ H ４ -CH(CH ３ )-C ２ H ４ -Ph, -CH(CH ３ )-C ４ H ８ -Ph, -CH ２ -CH(CH ３ )-C ３ H ６ -Ph, -CH(CH ３ )-CH ２ -C(CH ３ ) ２ -Ph, -CH(CH ３ )-CH(CH ３ )-C ２ H ４ -Ph, -CH ２ -CH(CH ３ )-C(CH ３ ) ２ -Ph, -CH ２ -C(CH ３ ) ２ -C ２ H ４ -Ph, -C(CH ３ ) ２ -C ３ H ６ -Ph, or -C(CH ３ ) ２ -C(CH ３ ) ２ -Ph; (IV)-CH ２ -CH=CH ２ ,-C(CH ３ )=CH ２ ,-C ２ H ４ -CH=C,-CH ２ -CH=CH-CH ３ ,-CH ２ -C(CH ３ )=CH ２ ,-CH(CH ３ )-CH=CH ２ ,-C(CH ３ )=CH-CH ３ ,-CH ２ -C≡CH,-C ２ H ４ -C≡CH ３ , or -CH ２ -C≡C-CH ３ ; The R １ is a substituted or unsubstituted functional group, The R １ When is substituted, it is substituted with one or more groups independently selected from the group consisting of (a) to (c) below: (a) a halogen atom, a hydroxyl group, a carboxy group, a mercapto group, an oxo group, a haloalkyl group having 1 to 6 carbon atoms, and a haloalkoxy group having 1 to 6 carbon atoms; (b) an alkoxy group having 1 to 6 carbon atoms, an alkylcarbonyl group having 2 to 6 carbon atoms, an alkoxycarbonyl group having 2 to 6 carbon atoms, an alkylsulfonyl group having 1 to 6 carbon atoms, an alkylsulfinyl group having 1 to 6 carbon atoms, an alkylcarbonyloxy group having 2 to 6 carbon atoms, and an alkylthio group having 1 to 6 carbon atoms; (c) an amino group, a carbamoyl group, a sulfamoyl group, a 3- to 8-membered cycloalkyl group, a 3- to 8-membered cycloalkoxy group, a 4- to 8-membered saturated heterocyclic group, a 6- to 10-membered aryl group, a 5- to 10-membered heteroaryl group, a 6- to 10-membered aryloxy group, and a 5- to 10-membered heteroaryloxy group;

2. A novel compound represented by the following formula (1): 【Chemistry 2】 (where, R １ is -CH ３ , -C ２ H ５ , -CH ２ CH ２ OCH ３ , or -CH ２ -Ph).

3. A polymer composition comprising a polymer having a monomer unit represented by chemical formula (2). 【Transformation 3】 (where, n means the number of repeating monomer units, x is 0.01 to 0.7; R １ is selected from the group consisting of (I), (II), (III) and (IV): (I)-CH ３ ,-C ２ H ５ ,-C ３ H ７ ,-CH(CH ３ ) ２ ,-C ４ H ９ ,-CH ２ -CH(CH ３ ) ２ ,-C(CH ３ ) ３ ,-CH(CH ３ )-C ２ H ５ ,-CH(CH ３ )-C ３ H ７ ,-CH ２ -CH(CH ３ )-C ２ H ５ ,-CH(CH ３ )-CH(CH ３ ) ２ ,-C ５ H １１ ,-C(CH ３ ) ２ -C ２ H ５ ,-CH ２ -C(CH ３ ) ３ ,-CH(C ２ H ５ ) ２ ,-C ２ H ４ -CH(CH ３ ) ２ ,-C ６ H １３ ,-C ３ H ６ -CH(CH ３ ) ２ ,-C ２ H ４ -CH(CH ３ )-C ２ H ５ ,-CH(CH ３ )-C ４ H ９ ,-CH ２ -CH(CH ３ )-C ３ H ７ ,-CH(CH ３ )-CH ２ -CH(CH ３ ) ２ , -CH(CH ３ )-CH(CH ３ )-C ２ H ５ , -CH ２ -CH(CH ３ )-CH(CH ３ ) ２ , -CH ２ -C(CH ３ ) ２ -C ２ H ５ , -C(CH ３ ) ２ -C ３ H ７ , -C(CH ３ ) ２ -CH(CH ３ ) ２ , -C ２ H ４ -C(CH ３ ) ３ , or -CH(CH ３ )-C(CH ３ ) ３ ; (II)-CH ２ OCH ３ ,-CH ２ OCH ２ CH ３ ,-CH ２ CH ２ OCH ３ ,-CH ２ CH ２ OCH ２ CH ３ ,-C ３ H ６ -OCH ３ ,-C ３ H ６ -OC ２ H ５ ,-CH ２ CO ２ CH ３ ,-CH ２ CO ２ CH ２ CH ３ ,-CH ２ CH ２ NHCH ３ , or -CH ２ CH ２ N(CH ３ ) 2 ; (III)-CH ２ -Ph, -CH ２ -CH ２ -Ph, -C ３ H ６ -Ph, -C(CH) ３ ) ２ -Ph, -C ４ H ８ -Ph, -CH ２ -C(CH) ３ ) ２ -Ph, -CH(CH ３ )-C ２ H ４ -Ph, -CH(CH ３ )-C ３ H ６ -Ph, -CH ２ -CH(CH ３ )-C ２ H ４ -Ph, -CH(CH ３ )-C(CH ３ ) ２ -Ph, -C ５ H １０ -Ph, -C(CH) ３ ) ２ -C ２ H ４ -Ph, -C(C) ２ H ５ ) ２ -Ph, -C ２ H ４ -C(CH) ３ ) ２ -Ph, -C ６ H １２ -Ph, -C ３ H ６ -C(CH) ３ ) ２ -Ph, -C ２ H ４ -CH(CH ３ )-C ２ H ４ -Ph, -CH(CH ３ )-C ４ H ８ -Ph, -CH ２ -CH(CH ３ )-C ３ H ６ -Ph, -CH(CH ３ )-CH ２ -C(CH ３ ) ２ -Ph, -CH(CH ３ )-CH(CH ３ )-C ２ H ４ -Ph, -CH ２ -CH(CH ３ )-C(CH ３ ) ２ -Ph, -CH ２ -C(CH ３ ) ２ -C ２ H ４ -Ph, -C(CH ３ ) ２ -C ３ H ６ -Ph, or -C(CH ３ ) ２ -C(CH ３ ) ２ -Ph; (IV)-CH ２ -CH=CH ２ ,-C(CH ３ )=CH ２ ,-C ２ H ４ -CH=C,-CH ２ -CH=CH-CH ３ ,-CH ２ -C(CH ３ )=CH ２ ,-CH(CH ３ )-CH=CH ２ ,-C(CH ３ )=CH-CH ３ ,-CH ２ -C≡CH,-C ２ H ４ -C≡CH ３ , or -CH ２ -C≡C-CH ３ ; The R １ is a substituted or unsubstituted functional group, The R １ When is substituted, it is substituted with one or more groups independently selected from the group consisting of (a) to (c) below: (a) a halogen atom, a hydroxyl group, a carboxy group, a mercapto group, an oxo group, a haloalkyl group having 1 to 6 carbon atoms, and a haloalkoxy group having 1 to 6 carbon atoms; (b) an alkoxy group having 1 to 6 carbon atoms, an alkylcarbonyl group having 2 to 6 carbon atoms, an alkoxycarbonyl group having 2 to 6 carbon atoms, an alkylsulfonyl group having 1 to 6 carbon atoms, an alkylsulfinyl group having 1 to 6 carbon atoms, an alkylcarbonyloxy group having 2 to 6 carbon atoms, and an alkylthio group having 1 to 6 carbon atoms; (c) an amino group, a carbamoyl group, a sulfamoyl group, a 3- to 8-membered cycloalkyl group, a 3- to 8-membered cycloalkoxy group, a 4- to 8-membered saturated heterocyclic group, a 6- to 10-membered aryl group, a 5- to 10-membered heteroaryl group, a 6- to 10-membered aryloxy group, and a 5- to 10-membered heteroaryloxy group;

4. A polymer composition comprising a polymer having a monomer unit represented by chemical formula (2). 【Chemistry 4】 (where, n means the number of repeating monomer units, x is 0.01 to 0.7; R １ is -CH ３ , -C ２ H ５ , -CH ２ CH ２ OCH ３ , or -CH ２ -Ph).

5. The polymer composition according to claim 4, characterized in that it comprises a polymer having a monomer unit represented by chemical formula (2): 【Transformation 5】 (where, n means the number of repeating monomer units, x is 0.01 to 0.7; R １ Ha-CH ３ (It is).

6. The polymer composition according to claim 4, characterized in that it comprises a polymer having a monomer unit represented by chemical formula (2): 【Transformation 6】 (where, n means the number of repeating monomer units, x is 0.01 to 0.7; R １ Ha-C ２ H ５ (It is).

7. The polymer composition according to claim 4, characterized in that it comprises a polymer having a monomer unit represented by chemical formula (2): 【Transformation 7】 (where, n means the number of repeating monomer units, x is 0.01 to 0.7; R １ Ha-CH ２ CH ２ OCH ３ (It is).

8. The polymer composition according to claim 4, characterized in that it comprises a polymer having a monomer unit represented by chemical formula (2): 【Transformation 8】 (where, n means the number of repeating monomer units, x is 0.01 to 0.7; R １ Ha-CH ２ -Ph).

9. A molded article made using the polymer composition according to any one of claims 4 to 8.

10. The molded product according to claim 9, which is an agricultural or horticultural material.

11. The molded article according to claim 9, which is a civil engineering and construction material.

12. A method for producing a polymer composition, comprising synthesizing the polymer composition from glycerol, which is a by-product of producing biodiesel fuel from waste oil, through the following steps: 【Chemistry 9】

13. 13. The method for producing a polymer composition according to claim 12, wherein the radical polymerization reaction in synthesizing the polymer composition has a polymerization temperature of 120°C to 150°C and a monomer concentration of 1.2M to 3.6M.

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