Polymer compound containing cyclic monomer derived from biomass and method for preparing the same

Abstract

The present invention relates to a polyester or polyurethane polymer containing a 1,3-cyclopentanediol monomer derived from biomass and a preparation method thereof.

Description

Technical Field

[0001] The invention relates to a polymer compound containing 1,3-cyclopentanediol monomers derived from biomass and a preparation method thereof. Background Art

[0002] Generally, polymers such as polycarbonate and polyester are prepared using raw materials derived from petroleum resources. However, in recent years, petroleum resources are in danger of being depleted, and there is a need to provide polymer resins prepared using raw materials obtained from biomass resources such as plants. In addition, global warming caused by the increase in carbon dioxide emissions and accumulation will cause climate change, and from this point of view, it is also necessary to develop polymers using plant-derived monomers with very little carbon emissions during the preparation process as raw materials.

[0003] 1,3-cyclopentanediol is synthesized from cyclopentadiene, which can be obtained by cracking dicyclopentadiene, and undergoes a reaction as shown in the following reaction formula 1.

[0004] [Reaction 1]

[0005]

[0006] The cyclopentadiene is very reactive in the Diels-Alder reaction and can be converted back into dicyclopentadiene in less than a few hours at room temperature. Therefore, it can only be used for a few days if stored at -20°C.

[0007] Furfural is an organic compound extracted from plant materials such as corn cobs, oats, bran, rice bran, bagasse, sawdust, etc. That is, the furfural is a biomass-based chemical substance, and 1,3-cyclopentanediol can be prepared from the furfural.

[0008] On the other hand, the existing linear polyester has a low free volume of the entire polymer and poor transparency. Because it is linear, it is more flexible, but has a problem of weak strength. The existing polyurethane has a problem of weak strength.

[0009] Therefore, there is a need to develop polyesters and polyurethanes that are excellent in transparency and strength, and at the same time, there is a need to develop environmentally friendly polyesters and polyurethanes that use biomass-derived monomers.

[0010] [Prior art literature]

[0011] [Patent Document] Korean Patent Publication No. 10-1558574 Summary of the invention

[0012] Technical issues

[0013] The present inventors have conducted extensive studies to solve the above problems and found that when 1,3-cyclopentanediol derived from biomass is included as a polymer monomer, an environmentally friendly polyester having excellent transparency and strength can be provided, and a polyurethane having excellent strength can be provided.

[0014] Therefore, the present invention aims to provide a polyester polymer containing biomass-derived monomers and having excellent transparency and strength and being environmentally friendly, or a polyurethane polymer having excellent strength and being environmentally friendly.

[0015] In addition, the present invention aims to provide a method for preparing polyester polymers and polyurethane polymers containing biomass-derived monomers.

[0016] Technical Solution

[0017] In order to achieve the above object, the present invention provides a polymer compound of the following chemical formula 1 containing 1,3-cyclopentanediol monomer.

[0018] [Chemical formula 1]

[0019]

[0020] The R represents a compound of the following Chemical Formula 2 or Chemical Formula 3,

[0021] [Chemical formula 2]

[0022]

[0023] [Chemical formula 3]

[0024]

[0025] The * indicates the bonding position,

[0026] a represents an integer of 1 to 30, b represents an integer of 1 to 30, and c represents an integer of 1 to 30.

[0027] In addition, the present invention provides a polymer compound of the following Chemical Formula 4 containing a 1,3-cyclopentanediol monomer.

[0028] [Chemical formula 4]

[0029]

[0030] The m represents an integer of 1 to 30, and the n represents an integer of 1 to 30.

[0031] In addition, the present invention provides a method for preparing a polymer of the following chemical formula 1, which comprises:

[0032] (i) a step of adding a catalyst to an aqueous solution of furfuryl alcohol to prepare 4-hydroxy-2-cyclopentenone;

[0033] (ii) a step of adding a catalyst to the 4-hydroxy-2-cyclopentenone to prepare 1,3-cyclopentanediol; and

[0034] (iii) a step of mixing the 1,3-cyclopentanediol, terephthalic acid and succinic anhydride or 2,5-furandicarboxylic acid and reacting the mixture,

[0035] [Chemical formula 1]

[0036]

[0037] The R represents a compound of the following Chemical Formula 2 or Chemical Formula 3,

[0038] [Chemical formula 2]

[0039]

[0040] [Chemical formula 3]

[0041]

[0042] The * indicates the bonding position,

[0043] a represents an integer of 1 to 30, b represents an integer of 1 to 30, and c represents an integer of 1 to 30.

[0044] In addition, the present invention provides a method for preparing a polymer of the following chemical formula 4, which comprises:

[0045] (i) a step of adding a catalyst to an aqueous solution of furfuryl alcohol to prepare 4-hydroxy-2-cyclopentenone;

[0046] (ii) a step of adding a catalyst to the 4-hydroxy-2-cyclopentenone to prepare 1,3-cyclopentanediol; and

[0047] (iii) a step of mixing the 1,3-cyclopentanediol and 4,4-diphenylmethane diisocyanate and reacting them,

[0048] [Chemical formula 4]

[0049]

[0050] The m represents an integer of 1 to 30, and the n represents an integer of 1 to 30.

[0051] Beneficial Effects

[0052] The polyester polymer of the present invention contains biomass-derived monomers, so it is more environmentally friendly, and the free volume of the polymer is increased, so it has excellent transparency. Since it contains cyclic monomers, it has excellent strength.

[0053] In addition, the polyurethane polymer of the present invention comprises biomass-derived monomers, and is therefore more environmentally friendly and has excellent strength. BRIEF DESCRIPTION OF THE DRAWINGS

[0054] Figure 1 7 is a three-dimensional structural diagram showing the degree of bending of Chemical Formula 7.

[0055] Figure 2 3D is a three-dimensional structural diagram showing the degree of bending of Chemical Formula 8.

[0056] Figure 3 This is the HOMO electron cloud distribution diagram of the three-dimensional structural formula of Chemical Formula 7.

[0057] Figure 4 This is a LUMO electron cloud distribution diagram of the three-dimensional structural formula of Chemical Formula 7.

[0058] Figure 5 This is the HOMO electron cloud distribution diagram of the three-dimensional structural formula of Chemical Formula 8.

[0059] Figure 6 This is a LUMO electron cloud distribution diagram of the three-dimensional structural formula of Chemical Formula 8. DETAILED DESCRIPTION

[0060] Hereinafter, the present invention will be described in further detail.

[0061] Traditionally, 1,3-cyclopentanediol is produced from cyclopentadiene, which is a non-renewable fossil resource. However, materials produced from fossil fuels such as petroleum are limited in reserves and have high carbon dioxide emissions, so they are urgently needed to be replaced with environmentally friendly materials.

[0062] Therefore, in the present invention, 1,3-cyclopentanediol is prepared from raw materials extracted from biomass, and a polymer containing the 1,3-cyclopentanediol as a monomer is provided, which not only achieves environmental protection and economic effects, but also reduces the crystallinity of the polymer due to the inclusion of the 1,3-cyclopentanediol monomer, has excellent transparency, and contains the 1,3-cyclopentanediol monomer with a cyclic structure to provide a polymer with excellent strength.

[0063] That is, the present invention relates to a polymer compound of the following chemical formula 1, which comprises a 1,3-cyclopentanediol monomer.

[0064] [Chemical formula 1]

[0065]

[0066] The R represents a compound of the following Chemical Formula 2 or Chemical Formula 3,

[0067] [Chemical formula 2]

[0068]

[0069] [Chemical formula 3]

[0070]

[0071] The * indicates the bonding position,

[0072] a represents an integer of 1 to 30, b represents an integer of 1 to 30, and c represents an integer of 1 to 30.

[0073] In addition, the present invention relates to a polymer compound of the following chemical formula 4, which comprises a 1,3-cyclopentanediol monomer,

[0074] [Chemical formula 4]

[0075]

[0076] The m represents an integer of 1 to 30, and the n represents an integer of 1 to 30.

[0077] The polymer compounds of Chemical Formula 1 and Chemical Formula 4 include 1,3-cyclopentanediol monomers, and the 1,3-cyclopentanediol may be a biomass-derived compound prepared from furfuryl alcohol derived from biomass.

[0078] More specifically, 1,3-cyclopentanediol derived from biomass can be prepared by hydrogenating furfuryl alcohol, a derivative of furfural, extracted from plant materials such as corn cobs, oats, bran, rice bran, and sawdust. Therefore, the polymer of the chemical formula 1 or the chemical formula 4 containing the 1,3-cyclopentanediol monomer derived from biomass can show environmental and economic effects.

[0079] As R of the polymer compound of Chemical Formula 1 has the compound of Chemical Formula 2, the polymer compound of Chemical Formula 1 may be a polymer compound of the following Chemical Formula 5.

[0080] [Chemical formula 5]

[0081]

[0082] The compound of Chemical Formula 2 may be in the form of succinic anhydride bonded to the R position of Chemical Formula 1.

[0083] Therefore, the polymer compound of Chemical Formula 5 may be a random block copolymer of a biomass-derived compound 1,3-cyclopentanediol monomer, a terephthalic acid monomer, and a succinic anhydride monomer.

[0084] In addition, as R of the polymer compound of Chemical Formula 1 has the compound of Chemical Formula 3, the polymer compound of Chemical Formula 1 may be a polymer compound of the following Chemical Formula 6.

[0085] [Chemical formula 6]

[0086]

[0087] The compound 2,5-furandicarboxylic acid of the chemical formula 3 may be bonded to the R position of the chemical formula 1.

[0088] Therefore, the polymer compound of Chemical Formula 6 may be a random block copolymer of 1,3-cyclopentanediol monomer, terephthalic acid monomer, and 2,5-furandicarboxylic acid monomer, which are compounds derived from biomass.

[0089] If b of the polymer compound of Chemical Formula 1 is less than 1, permeability and strength are low, and if b of the polymer compound of Chemical Formula 1 is greater than 30, the cyclic structure (Aromatic Ring) of cyclopentane may increase birefringence, and when the polymer compound of Chemical Formula 1 is made into a film, light scattering and image distortion caused by viewing angle may occur.

[0090] In addition, the molecular weight of the polymer compound of Chemical Formula 1 is 10,000 to 70,000, preferably 11,700 to 55,000.

[0091] If the molecular weight of the polymer compound of Chemical Formula 1 is less than 10,000, it will become a polymer with a low molecular weight, and as a polymer, there will be no entanglement, thereby reducing the properties of the polymer such as tensile strength and bending strength. If the molecular weight is greater than 70,000, the attraction between the polymers increases, and the properties of the polymer such as tensile strength and bending strength increase excessively. When the polymer compound of Chemical Formula 1 is made into a film, it may be fragile.

[0092] Since the existing polyester without the 1,3-cyclopentanediol monomer has a linear structure, its free volume is low, and thus the transparency is poor. In addition, since it does not contain a cyclic structure monomer, the strength is poor.

[0093] However, the polymer compound of Chemical Formula 1 of the present invention contains a cyclic 1,3-cyclopentanediol monomer, and thus has a three-dimensional structure, thereby increasing the free volume, thereby increasing the fluidity of the polymer chain. Therefore, it can provide excellent transparency and excellent strength due to the cyclic structure.

[0094] Specifically, for the polymer compound of Chemical Formula 1 of the present invention, the transparency (haze) of a sample with a thickness of 2 mm measured according to ASTM D1003 is 80 to 100%, preferably 85 to 100%, and more preferably 95 to 100%. In addition, the bending strength according to ASTM D-790 may be 120 to 200 N, and the tensile strength according to ASTM D-638 may be 100 to 200 MPa.

[0095] In addition, the polymer compound of Chemical Formula 4 may be a copolymer of the biomass-derived compound 1,3-cyclopentanediol monomer and 4,4-diphenylmethane diisocyanate monomer.

[0096] If n of the polymer compound of Chemical Formula 4 is less than 1, the hardness of the polymer compound of Chemical Formula 4 decreases and may lose its firmness, while if n of the polymer compound of Chemical Formula 4 is greater than 30, it becomes too hard and brittle.

[0097] In addition, the molecular weight of the polymer compound of Chemical Formula 4 is 11,000 to 60,000, preferably 11,000 to 45,000.

[0098] The conventional polyurethane not containing the 1,3-cyclopentanediol monomer has a soft property, but the present invention contains the 1,3-cyclopentanediol monomer and thus can have a rigid property.

[0099] Specifically, for the polymer compound of Chemical Formula 4 of the present invention, the bending strength according to ASTM D-790 may be 120 to 200 N, and the tensile strength according to ASTM D-638 may be 110 to 200 MPa.

[0100] Therefore, the polymer compounds of Formula 1 and Formula 4 containing 1,3-cyclopentanediol monomer derived from biomass of the present invention can have environmental and economic effects. In addition, the polymer compound of Formula 1 can have excellent transparency and strength, and the polymer compound of Formula 4 can show excellent strength effects.

[0101] In addition, the present invention relates to a method for preparing a polymer compound of the following chemical formula 1, which comprises:

[0102] (i) a step of adding a catalyst to an aqueous solution of furfuryl alcohol to prepare 4-hydroxy-2-cyclopentenone;

[0103] (ii) a step of adding a catalyst to the 4-hydroxy-2-cyclopentenone to prepare 1,3-cyclopentanediol; and

[0104] (iii) a step of mixing the 1,3-cyclopentanediol, terephthalic acid and succinic anhydride or 2,5-furandicarboxylic acid and reacting the mixture,

[0105] [Chemical formula 1]

[0106]

[0107] The R represents a compound of the following Chemical Formula 2 or Chemical Formula 3,

[0108] [Chemical formula 2]

[0109]

[0110] [Chemical formula 3]

[0111]

[0112] The * indicates the bonding position,

[0113] a represents an integer of 1 to 30, b represents an integer of 1 to 30, and c represents an integer of 1 to 30.

[0114] The step (i) is a step of adding a catalyst to an aqueous solution of furfuryl alcohol to prepare 4-hydroxy-2-cyclopentenone.

[0115] The furfuryl alcohol may be a derivative of furfural extracted from plant materials such as corn cobs, oats, bran, rice bran, sawdust, etc. That is, the furfuryl alcohol may be a compound derived from biomass.

[0116] In the step (i), water is used as a solvent, thus having the advantages of saving costs and being environmentally friendly.

[0117] The catalyst of step (i) may include at least one selected from the group consisting of calcium oxide, lead oxide, aluminum oxide, iron oxide, calcium chloride, zinc acetate, p-toluenesulfonic acid, stannous chloride, stannous sulfate, stannous oxide, tin oxide, stannous octoate, tetraphenyltin, tin powder and titanium tetrachloride, preferably calcium oxide.

[0118] The catalyst of step (i) may contain 0.1 to 10 wt %, preferably 0.1 to 5 wt %, relative to the total weight of the furfuryl alcohol aqueous solution. If the content of the catalyst is less than 0.1 wt %, no reaction occurs and 4-hydroxy-2-cyclopentenone cannot be prepared, while if the content of the catalyst is greater than 10 wt %, it is uneconomical because there is a lot of unreacted catalyst.

[0119] In addition, in the step (i), after the catalyst is added to the furfuryl alcohol aqueous solution, 4-hydroxy-2-cyclopentenone can be prepared by stirring, and the stirring is carried out at a temperature of 100 to 300° C. for 10 minutes to 1 hour.

[0120] The step (ii) is a step of adding a catalyst to the 4-hydroxy-2-cyclopentenone prepared in the step (i) to prepare 1,3-cyclopentanediol.

[0121] The catalyst is added to a solution of the 4-hydroxy-2-cyclopentenone dissolved in an organic solvent. The organic solvent may include at least one selected from the group consisting of 2-methyltetrahydrofuran, methanol and acetone, preferably 2-methyltetrahydrofuran.

[0122] In addition, the catalyst in step (ii) may be a ruthenium-based catalyst. In step (ii), a hydrogenation reaction occurs, thereby preparing 1,3-cyclopentanediol.

[0123] The catalyst in step (ii) may contain 0.1 to 5 wt %, preferably 0.1 to 3 wt %, relative to the total weight of the solution of 4-hydroxy-2-cyclopentenone dissolved in an organic solvent. If the content of the catalyst is less than 0.1 wt %, no reaction will occur and 1,3-cyclopentanediol cannot be prepared, while if the content of the catalyst is greater than 5 wt %, it is uneconomical.

[0124] In addition, in the step (ii), after the catalyst is added to the furfuryl alcohol aqueous solution, 4-hydroxy-2-cyclopentenone can be prepared by stirring, and the stirring can be carried out at a temperature of 70 to 200° C. in a hydrogen environment for 2 to 6 hours.

[0125] The steps (i) and (ii) are shown in the following reaction formula 2.

[0126] [Reaction 2]

[0127]

[0128] The step (iii) is a step of mixing the 1,3-cyclopentanediol derived from biomass prepared in the step (ii), terephthalic acid, and succinic anhydride or 2,5-furandicarboxylic acid and reacting them. The polymer compound of Chemical Formula 1 is prepared in the step (iii).

[0129] Specifically, the step (iii) is to add the monomer into tetrahydrofuran solvent under a nitrogen environment and stir at a temperature of 150 to 250° C. for 2 to 6 hours, thereby preparing the polymer compound of Chemical Formula 1.

[0130] In addition, the present invention relates to a method for preparing a polymer compound of the following chemical formula 4, which comprises:

[0131] (i) a step of adding a catalyst to an aqueous solution of furfuryl alcohol to prepare 4-hydroxy-2-cyclopentenone;

[0132] (ii) a step of adding a catalyst to the 4-hydroxy-2-cyclopentenone to prepare 1,3-cyclopentanediol; and

[0133] (iii) a step of mixing the 1,3-cyclopentanediol and 4,4-diphenylmethane diisocyanate and reacting them,

[0134] [Chemical formula 4]

[0135]

[0136] The m represents an integer of 1 to 30, and the n represents an integer of 1 to 30.

[0137] The steps (i) and (ii) are the same as the method for preparing the polymer compound of Chemical Formula 1.

[0138] The step (iii) is a step of mixing the 1,3-cyclopentanediol derived from biomass prepared in the step (ii) and 4,4-diphenylmethane diisocyanate and reacting them. In the step (iii), the polymer compound of Chemical Formula 4 is prepared.

[0139] Specifically, the step (iii) is to add the monomer into tetrahydrofuran solvent under a nitrogen environment and stir at a temperature of 150 to 250° C. for 2 to 6 hours, thereby preparing the polymer compound of Chemical Formula 4.

[0140] Modes for Carrying Out the Invention

[0141] Hereinafter, description will be made with reference to embodiments of the present invention, but the following embodiments are only for illustrating the present invention, and the scope of the present invention is not limited to the following embodiments.

[0142] Preparation Example 1. Preparation of Poly(CPdiol-co-TPA)

[0143] 14 g of furfuryl alcohol (ie, a furfural derivative extracted from biomass) was dissolved in 685.97 mL of water to prepare an aqueous solution, 0.028 g of calcium oxide was added to the aqueous solution, and the mixture was stirred at 200° C. for 0.5 hours to prepare 4-hydroxy-2-cyclopentenone.

[0144] 248 g of the 4-hydroxy-2-cyclopentenone was dissolved in 2000 mL of 2-methyltetrahydrofuran to prepare a solution, 4 g of ruthenium was added to the solution and hydrogenated at 120° C. for 4 hours to prepare biomass-derived 1,3-cyclopentanediol.

[0145] 50 g of the 1,3-cyclopentanediol (Cpdiol) and 20 g of terephthalic acid (TPA) were added to tetrahydrofuran and stirred at 200° C. for 4 hours in a nitrogen environment to prepare a polymer compound of the following Chemical Formula 7 having a molecular weight of 12000 g / mol.

[0146] [Chemical formula 7]

[0147]

[0148] Comparative Preparation Example 1. Preparation of Poly(EG-co-TPA)

[0149] 50 g of ethylene glycol (EG) and 50 g of terephthalic acid (TPA) were added to tetrahydrofuran and stirred at 200° C. for 4 hours in a nitrogen environment to prepare a polymer compound of the following Chemical Formula 8 having a molecular weight of 40,000 g / mol.

[0150] [Chemical formula 8]

[0151]

[0152] Experimental Example 1. Measurement of the molecular structure of polyester

[0153] The bending degrees of the polymer of Chemical Formula 7 prepared in Preparation Example 1 and the polymer of Chemical Formula 8 prepared in Comparative Preparation Example 1 were measured using Gaussian 09 program.

[0154] According to the measurement results, for the polymer of Chemical Formula 7 containing 1,3-cyclopentanediol monomer derived from biomass, the bending degree is 101.59° ( Figure 1 ), but for the polymer of Chemical Formula 8 without 1,3-cyclopentanediol monomer, the bending degree is 179.99°, showing a linear structure ( Figure 2 ).

[0155] That is, when 1,3-cyclopentanediol monomer derived from biomass is included, it has a three-dimensional structure, and thus it can be expected to have a higher free volume when polymerized.

[0156] In addition, the electron distribution diagram of the polymer of Chemical Formula 7 prepared in the Preparation Example 1 and the polymer of Chemical Formula 8 prepared in the Comparative Preparation Example 1 is shown in FIG. Figures 3 to 6 , and the energy levels of HOMO and LUMO of Chemical Formula 7 and Chemical Formula 8 are shown in the following Table 1.

[0157]

Table 1

[0158] Chemical formula 7 Chemical formula 8 HOMO(eV) -7.31 -7.44 LUMO(eV) -2.07 -2.13

[0159] From the results in Table 1 above, the HOMO and LUMO energy levels of Chemical Formula 7 containing a 1,3-cyclopentanediol monomer derived from biomass are higher than those of Chemical Formula 8 not containing a 1,3-cyclopentanediol monomer. From the above results, it can be expected that the polymer containing a 1,3-cyclopentanediol monomer derived from biomass has better thermal stability than the polymer not containing a 1,3-cyclopentanediol monomer and has higher permeability (transparency).

[0160] Example 1. Preparation of poly[3-methoxy-3-oxopropionyloxy]cyclopentyl terephthalate methoxy-3-oxopropanoyloxy]cyclopentylmethylterephthalate)

[0161] The preparation method of 1,3-cyclopentanediol is the same as that of Preparation Example 1.

[0162] 50 g of the 1,3-cyclopentanediol, 20 g of terephthalic acid and 30 g of succinic anhydride were added to tetrahydrofuran and stirred at 200° C. for 4 hours in a nitrogen environment to prepare a polymer of the following Chemical Formula 5 with a molecular weight of 30084.48 g / mol.

[0163] [Chemical formula 5]

[0164]

[0165] Example 2. Preparation of poly[5-(4-methoxybutoxy)carbonyl]furan-2-carboxylic acid 4-(methoxycarbonyl)benzoic acid Anhydride (Poly[5-(4-methoxybutoxy)carbonyl]furan-2-carboxylic4-(methyoxycarbonyl) benzoicanhydride)

[0166] The preparation method of 1,3-cyclopentanediol is the same as that of Preparation Example 1.

[0167] 50 g of the 1,3-cyclopentanediol, 20 g of terephthalic acid and 30 g of 2,5-furandicarboxylic acid (FDCA) were added to tetrahydrofuran and stirred at 200° C. for 4 hours in a nitrogen environment to prepare a polymer of the following chemical formula 6 with a molecular weight of about 50,000 g / mol.

[0168] [Chemical formula 6]

[0169]

[0170] Example 3. Preparation of poly[3-methoxycyclopentyl-4-(4-acetamidobenzyl)phenylcarbamate] methoxycyclopentyl-4-(4-acetamidobenzyl)phenylcarbamate])

[0171] The preparation method of 1,3-cyclopentanediol is the same as that of Preparation Example 1.

[0172] 50 g of the 1,3-cyclopentanediol and 50 g of 4,4-diphenylmethane diisocyanate were added to tetrahydrofuran and stirred at 200° C. for 4 hours in a nitrogen environment to prepare a polymer of the following Chemical Formula 4 with a molecular weight of about 40,000 g / mol.

[0173] [Chemical formula 4]

[0174]

[0175] Comparative Example 1. Preparation of polyester

[0176] 20 g of terephthalic acid, 30 g of 2,5-furandicarboxylic acid and 50 g of butanediol were added to tetrahydrofuran and stirred at 200° C. for 4 hours in a nitrogen environment to prepare a polymer of the following Chemical Formula 9 having a molecular weight of about 20,000 g / mol.

[0177] [Chemical formula 9]

[0178]

[0179] Comparative Example 2. Preparation of polyurethane

[0180] 20 g of 4,4-diphenylmethane diisocyanate and 20 g of ethylene glycol were added to tetrahydrofuran and stirred at 230° C. for 4 hours in a nitrogen environment to prepare a polymer of the following Chemical Formula 10 having a molecular weight of about 50,000 g / mol.

[0181] [Chemical formula 10]

[0182]

[0183] Experimental Example 2. Measurement of Physical Properties of Polymer Compounds

[0184] The transparency, bending strength and tensile strength of the polymer compound of Chemical Formula 5 prepared in Example 1, the polymer compound of Chemical Formula 6 prepared in Example 2, the polymer compound of Chemical Formula 4 prepared in Example 3, the polymer compound of Chemical Formula 9 prepared in Comparative Example 1 and the polymer compound of Chemical Formula 10 prepared in Comparative Example 2 were measured, and the results are shown in Table 2 below.

[0185] The transparency, flexural strength and tensile strength were measured as follows.

[0186] Transparency (permeability): Measured in accordance with ASTM D 1003. In accordance with ASTM D 1003, the light transmittance (total light transmittance) of a sample having a thickness of 2.0 mm was measured using a turbidity meter (manufacturer: Nippon Denshoku, product name: NDH 5000W).

[0187] Bending strength: measured according to ASTM D-790. A bending strength specimen was prepared according to ASTM D-790, and the specimen was placed under the conditions of 23±2°C and 50±5%RH for 24 hours, and then the bending strength was measured using a universal testing machine (UTM). At this time, the crosshead speed of the universal testing machine was set to 5 mm / min.

[0188] Tensile strength: measured according to ASTM D-638. A tensile strength specimen was prepared according to ASTM D-638, and the tensile strength of the prepared specimen was measured using a universal testing machine (UTM) at room temperature. At this time, the crosshead speed of the universal testing machine was set to 5 mm / min.

[0189]

Table 2

[0190] transparency(%) Bending strength(N) Tensile strength(MPa) Example 1 97.2 170 150 Example 2 98.2 150 120 Example 3 98.4 155 130 Comparative Example 1 80.3 100 98 Comparative Example 2 81.2 98 100

[0191] The results show that the polymer compounds of Chemical Formula 5 and Chemical Formula 6 of the present invention containing 1,3-cyclopentanediol derived from biomass as a monomer have better transparency than the polymer of Chemical Formula 9 without 1,3-cyclopentanediol.

[0192] Transparency is related to the measurement result of the molecular structure in Experimental Example 1. Since the polymer compounds of Chemical Formula 5 and Chemical Formula 6 contain 1,3-cyclopentanediol and have a three-dimensional structure, the free volume increases, and the fluidity of the polymer chain increases, so they have excellent transparency.

[0193] On the other hand, the polymer compound of Chemical Formula 9 has a linear structure, the free volume does not increase, and the transparency is poor compared with the polymer compounds of Chemical Formula 5 and Chemical Formula 6.

[0194] In addition, the polymer compounds of Formula 4, Formula 5 and Formula 6 of the present invention containing 1,3-cyclopentanediol derived from biomass as a monomer have better flexural strength and tensile strength than the polymer compounds of Formula 9 and Formula 10 not containing 1,3-cyclopentanediol.

[0195] This indicates that the polymer compound of the present invention including 1,3-cyclopentanediol derived from biomass as a monomer has excellent flexural strength and tensile strength because the 1,3-cyclopentanediol including a cyclic structure as a monomer has excellent strength.

[0196] Industrial Applicability

[0197] The present invention relates to a polymer compound containing 1,3-cyclopentanediol monomers derived from biomass and a preparation method thereof. The polyester polymer of the present invention contains biomass-derived monomers, so it is more environmentally friendly and has an increased free volume of the polymer and excellent transparency. Since it contains cyclic monomers, it has an excellent strength effect.

Claims

1. A polymer compound of the following chemical formula 1 containing 1,3-cyclopentanediol monomer derived from biomass: [Chemical formula 1] The R represents a compound of the following Chemical Formula 2 or Chemical Formula 3, [Chemical formula 2] [Chemical formula 3] The * indicates the bonding position, a represents an integer of 1 to 30, b represents an integer of 1 to 30, and c represents an integer of 1 to 30.

2. The polymer compound of Chemical Formula 1 according to claim 1, characterized in that: The 1,3-cyclopentanediol included in the Chemical Formula 1 is a compound prepared from furfuryl alcohol derived from biomass.

3. The polymer compound of Chemical Formula 1 according to claim 1, characterized in that: The polymer compound of Chemical Formula 1 is a random copolymer of 1,3-cyclopentanediol monomer, terephthalic acid monomer and succinic anhydride monomer, or a random copolymer of 1,3-cyclopentanediol monomer, terephthalic acid monomer and 2,5-furandicarboxylic acid monomer.

4. The polymer compound of Chemical Formula 1 according to claim 1, characterized in that The molecular weight of the polymer compound of Chemical Formula 1 is 10,000 to 70,000.

5. The polymer compound of Chemical Formula 1 according to claim 1, characterized in that: The polymer compound of Chemical Formula 1 has a transparency of 80 to 100% according to ASTM D1003, a flexural strength of 120 to 200 N according to ASTM D-790, and a tensile strength of 100 to 200 MPa according to ASTM D-638.

6. A method for preparing a polymer compound of the following chemical formula 1, comprising: (i) a step of adding a catalyst to an aqueous solution of furfuryl alcohol to prepare 4-hydroxy-2-cyclopentenone; (ii) a step of adding a catalyst to the 4-hydroxy-2-cyclopentenone to prepare 1,3-cyclopentanediol; and (iii) a step of mixing the 1,3-cyclopentanediol, terephthalic acid and succinic anhydride or 2,5-furandicarboxylic acid and reacting the mixture, [Chemical formula 1] The R represents a compound of the following Chemical Formula 2 or Chemical Formula 3, [Chemical formula 2] [Chemical formula 3] The * indicates the bonding position, a represents an integer of 1 to 30, b represents an integer of 1 to 30, and c represents an integer of 1 to 30.

7. The method for preparing the polymer compound of Chemical Formula 1 according to claim 6, characterized in that: The furfuryl alcohol of step (i) is a compound derived from biomass.

8. The method for preparing the polymer compound of Chemical Formula 1 according to claim 6, characterized in that: The catalyst of step (i) comprises at least one selected from the group consisting of calcium oxide, lead oxide, aluminum oxide, iron oxide, calcium chloride, zinc acetate, p-toluenesulfonic acid, stannous chloride, stannous sulfate, stannous oxide, tin oxide, stannous octoate, tetraphenyltin, tin powder and titanium tetrachloride.

9. The method for preparing the polymer compound of Chemical Formula 1 according to claim 6, characterized in that: The catalyst in step (i) comprises 0.1 to 10 wt % relative to the total weight of the furfuryl alcohol aqueous solution.

10. The method for preparing the polymer compound of Chemical Formula 1 according to claim 6, characterized in that: The step (ii) is to add a catalyst to a solution of 4-hydroxy-2-cyclopentenone dissolved in an organic solvent, The organic solvent includes at least one selected from the group consisting of 2-methyltetrahydrofuran, methanol and acetone.

11. The method for preparing the polymer compound of Chemical Formula 1 according to claim 6, characterized in that: The catalyst of step (ii) is a ruthenium-based catalyst.

12. The method for preparing the polymer compound of Chemical Formula 1 according to claim 10, characterized in that: The catalyst in step (ii) comprises 0.1 to 5 wt % relative to the total weight of the solution of 4-hydroxy-2-cyclopentenone dissolved in the organic solvent.

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