Patent Description:
In general, polymers such as polycarbonate, polyester, and the like are prepared by using raw materials derived from petroleum resources. However, in recent years, as there is a concern about depletion of petroleum resources, polymer resins using raw materials obtained from biomass resources such as plants and the like are required. In addition, since there is also a concern about global warming due to an increase and accumulation of carbon dioxide emissions, which causes climate change, etc., development of polymers using plant-derived monomers that emit very little carbon during the manufacturing process as raw materials is required.

On the other hand, <NUM>,<NUM>-cyclopentanediol is synthesized from cyclopentadiene, and the cyclopentadiene may be obtained by cracking dicyclopentadiene and reacted as shown in Reaction Scheme <NUM>.

The cyclopentadiene is highly reactive in the Diels-Alder reaction and converted back to the dicyclopentadiene within just a few hours at room temperature. Accordingly, the cyclopentadiene has a disadvantage of needing to be stored at -<NUM> but used just for several days.

On the other hand, furfural is an organic compound derived from plants materials such as corn cobs, oats, bran, rice bran, bagasse, and sawdust. In other words, the furfural is a biomass-based chemical material, and the <NUM>,<NUM>-cyclopentanediol may be prepared from the furfural.

On the other hand, conventional linear polyester has inferior transparency due to a low free volume of the entire polymer and is flexible due to the linearity but has a problem of soft strength, and conventional polyurethane has a problem of soft strength.

Accordingly, it is necessary to develop polyester having excellent transparency and strength and polyurethane having excellent strength is required, and in addition, to make the polyester and the polyurethane environmentally-friendly by using a biomass-derived monomer.

In order to solve the above problems, the present inventors have conducted research and as a result, when biomass-derived <NUM>,<NUM>-cyclopentanediol is included as a monomer of a polymer, an environmentally friendly polyester with excellent transparency and strength may be provided and polyurethane having excellent strength may be provided.

Accordingly, an object of the present invention is to provide an environmentally friendly polyester polymer having excellent transparency and strength, or an environmentally friendly polyurethane polymer having excellent strength, by including biomass-derived monomers.

Another object of the present invention is to provide a method for preparing a polyester polymer and a polyurethane polymer including a biomass-derived monomer.

In addition, described herein is a polymer compound represented by Chemical Formula <NUM> including a <NUM>,<NUM>-cyclopentanediol monomer:
<CHM>
wherein m is an integer of <NUM> to <NUM> and n is an integer of <NUM> to <NUM>.

In addition, the present invention provides a method for preparing a polymer represented by Chemical Formula <NUM>, which includes (i) adding a catalyst to an aqueous solution of biomass-derived furfuryl alcohol to prepare <NUM>-hydroxy-<NUM>-cyclopentenone,.

In addition, described herein is a method of preparing a polymer represented by Chemical Formula <NUM> which includes (i) adding a catalyst to a furfuryl alcohol aqueous solution to prepare <NUM>-hydroxy-<NUM>-cyclopentenone;.

wherein m is an integer of <NUM> to <NUM> and n is an integer of <NUM> to <NUM>.

The polyester polymer of the present invention is environmentally friendly including biomass-derived monomers, and thus it has excellent transparency due to an increase in a free volume of the polymer, and has excellent strength by including cyclic monomers.

In addition, the polyurethane polymer of the present invention is environmentally friendly by including biomass-derived monomers, and has an excellent strength effect.

Conventionally, <NUM>,<NUM>-cyclopentanediol is prepared from cyclopentadiene derived from a non-renewable fossil fuel resource. However, materials produced from the fossil fuel resource, such as petroleum, have a limited reserve and need to be ungently replaced with environmentally-friendly materials due to high carbon dioxide emissions.

Accordingly, the present invention is to provide a polymer including a <NUM>,<NUM>-cyclopentanediol monomer, which is prepared from a raw material extracted from biomass, wherein the polymer is not only environmentally-friendly and economical but also has excellent transparency due to the <NUM>,<NUM>-cyclopentanediol monomer reducing crystallinity of the polymer and excellent strength due to a cyclic structure of the <NUM>,<NUM>-cyclopentanediol monomer.

In other words, the present invention relates to a polymer compound represented by Chemical Formula <NUM> including the biomass-derived <NUM>,<NUM>-cyclopentanediol monomer.

In addition, described herein is a polymer compound represented by Chemical Formula <NUM> including a <NUM>,<NUM>-cyclopentanediol monomer. <CHM>
wherein m is an integer of <NUM> to <NUM> and n is an integer of <NUM> to <NUM>.

The polymer compounds of Chemical Formula <NUM> and Chemical Formula <NUM> may include the <NUM>,<NUM>-cyclopentanediol monomer, and the <NUM>,<NUM>-cyclopentanediol is a biomass-derived compound prepared from biomass-derived furfuryl alcohol.

Specifically, the biomass-derived <NUM>,<NUM>-cyclopentanediol is prepared through a hydrogenation reaction of furfuryl alcohol, a derivative of furfural extracted from plant materials such as corn cobs, oats, bran, rice bran, and sawdust. Accordingly, a polymer of Chemical Formula <NUM> or Chemical Formula <NUM> including the biomass-derived <NUM>,<NUM>-cyclopentanediol monomer may be environmentally-friendly and exhibit economical effects.

As R of the polymer compound of Chemical Formula <NUM> may have the compound of Chemical Formula <NUM>, the polymer compound of Chemical Formula <NUM> may be a polymer compound of Chemical Formula <NUM>.

The compound of Chemical Formula <NUM>, succinic anhydride, may be bonded to the R position of Chemical Formula <NUM>.

Therefore, the polymer compound of Chemical Formula <NUM> may be a random block copolymer of a <NUM>,<NUM>-cyclopentanediol monomer, a terephthalic acid monomer, and a succinic anhydride monomer, which are biomass-derived compounds.

In addition, as R of the polymer compound of Chemical Formula <NUM> may have the compound of Chemical Formula <NUM>, the polymer compound of Chemical Formula <NUM> may be a polymer compound of Chemical Formula <NUM>.

<NUM>,<NUM>-furandicarboxylic acid as the compound of Chemical Formula <NUM> may be bonded to the R position of Chemical Formula <NUM>.

Therefore, the polymer compound of Chemical Formula <NUM> may be a random block copolymer of a <NUM>,<NUM>-cyclopentanediol monomer, a terephthalic acid monomer, and a <NUM>,<NUM>-furandicarboxylic acid monomer, which are biomass-derived compounds.

When b of the polymer compound of Chemical Formula <NUM> is less than <NUM>, transmittance and strength are low, but when the b is greater than <NUM>, the cyclic structure (aromatic ring) of cyclopentane may increase birefringence, so that when the polymer compound of Chemical Formula <NUM> is formed into a film, image distortion may occur due to light scattering and viewing angles.

When the molecular weight of the polymer compound of Chemical Formula <NUM> is less than <NUM>, the polymer compound becomes a polymer having a low molecular weight, deteriorating properties of the polymer such as tensile strength, flexural strength, and the like, but when the molecular weight is greater than <NUM>, as attraction between the polymers increases, the properties of the polymer such as tensile strength and flexural strength extremely increase, and when the polymer compound of Chemical Formula <NUM> is formed into a film, the film may be easily broken.

Conventional polyester not including the <NUM>,<NUM>-cyclopentanediol monomer has a linear structure and thus a low free volume. Accordingly, excellent transparency is not secured. In addition, since a monomer with a cyclic structure is not included, excellent strength is not obtained.

However, the polymer compound of Chemical Formula <NUM> of the present invention includes the biomass-derived <NUM>,<NUM>-cyclopentanediol monomer with a cyclic structure and thus has a three-dimensional structure, which increases a free volume and thereby increases fluidity of a polymer chain. Accordingly, excellent transparency may be obtained, and excellent strength also may be achieved due to the cyclic structure.

Specifically, the polymer compound of Chemical Formula <NUM> of the present invention has a transparency (haze) of <NUM> % to <NUM> %, desirably <NUM> % to <NUM> %, more desirably <NUM> % to <NUM> % of a <NUM>-thick specimen measured according to ASTM D1003. In addition, the flexural strength according to ASTM D-<NUM> may be <NUM> N to <NUM> N, and the tensile strength according to ASTM D-<NUM> may be <NUM> MPa to <NUM> MPa.

In addition, the polymer compound of Chemical Formula <NUM> may be a copolymer of a <NUM>,<NUM>-cyclopentanediol monomer and <NUM>,<NUM>-diphenylmethane diisocyanate, which are the biomass-derived compounds.

When n of the polymer compound of Chemical Formula <NUM> is less than <NUM>, the polymer compound of Chemical Formula <NUM> becomes less hard and thus may lose rigidity, but when n is greater than <NUM>, the polymer compound becomes extremely hard and thus may be easily broken.

The conventional polyurethane that does not include the <NUM>,<NUM>-cyclopentanediol monomer has a softness characteristic, but may have a rigid characteristic by including the <NUM>,<NUM>-cyclopentanediol monomer.

Specifically, the polymer compound of Chemical Formula <NUM> of the present invention may have a flexural strength of <NUM> N to <NUM> N according to ASTM D-<NUM> and a tensile strength of <NUM> MPa to <NUM> MPa according to ASTM D-<NUM>.

Therefore, the polymer compounds of Chemical Formula <NUM> and Chemical Formula <NUM>, including the biomass-derived <NUM>,<NUM>-cyclopentanediol monomer of the present invention, are environmentally friendly, and may have economical effects. In addition, the polymer compound of Chemical Formula <NUM> has excellent transparency and strength, and the polymer compound of Chemical Formula <NUM> has excellent strength.

In addition, the present invention relates to a method for preparing a polymer compound represented by Chemical Formula <NUM>, which includes.

The step (i) may be a process of adding a catalyst to an aqueous solution of biomass-derived furfuryl alcohol to prepare <NUM>-hydroxy-<NUM>-cyclopentenone.

The biomass-derived furfuryl alcohol may be a derivative of furfural extracted from plant materials such as corn cobs, oats, bran, rice bran, and sawdust. In other words, the furfuryl alcohol ois a biomass-derived compound.

The step (i) uses water as a solvent, which is economical and environmentally friendly.

The catalyst of the step (i) may include at least one selected from calcium oxide, lead oxide, aluminum oxide, iron oxide, calcium chloride, zinc acetate, paratoluene sulfonic acid, stannous chloride, stannous sulfate, stannous oxide, tin oxide, stannous octoate, tetraphenyl tin, a tin powder, and titanium tetrachloride, and desirably calcium oxide.

The catalyst of the step (i) may be included in an amount of <NUM> to <NUM> wt%, and desirably <NUM> wt% to <NUM> wt% based on the total weight of the furfuryl alcohol aqueous solution. When the catalyst is included in an amount of less than <NUM> wt%, the reaction does not occur and <NUM>-hydroxy-<NUM>-cyclopentenone may not be prepared, and when it exceeds <NUM> wt%, it is not economical because there are many unreacted catalysts.

In addition, in the step (i), <NUM>-hydroxy-<NUM>-cyclopentenone may be prepared by stirring after adding a catalyst to a furfuryl alcohol aqueous solution, wherein stirring may be performed at a temperature of <NUM> to <NUM> for <NUM> minutes to <NUM> hour.

The step (ii) is adding a catalyst to the <NUM>-hydroxy-<NUM>-cyclopentenone prepared in the step (i) to prepare <NUM>,<NUM>-cyclopentanediol.

The catalyst is added to a solution in which the <NUM>-hydroxy-<NUM>-cyclopentenone is dissolved in an organic solvent, wherein the organic solvent may include at least one selected from <NUM>-methyltetrahydrofuran, methanol, and acetone, and desirably, <NUM>-methyltetrahydrofuran.

In addition, the catalyst of the step (ii) may be a ruthenium-based catalyst. In the step (ii), <NUM>,<NUM>-cyclopentanediol may be prepared by a hydrogenation reaction.

The catalyst of the step (ii) may be included in an amount of <NUM> wt% to <NUM> wt%, and desirably, <NUM> wt% to <NUM> wt% based on the total weight of the solution in which <NUM>-hydroxy-<NUM>-cyclopentenone is dissolved in the organic solvent. When the catalyst is less than <NUM> wt%, the reaction does not occur, not obtaining <NUM>,<NUM>-cyclopentanediol, but when included in an amount of greater than <NUM> wt%, it is not economical.

In addition, in the step (ii), the catalyst is added to the furfuryl alcohol aqueous solution and then stirred, preparing the <NUM>-hydroxy-<NUM>-cyclopentenone, wherein the stirring may be performed under a hydrogen atmosphere at <NUM> to <NUM> for <NUM> hours to <NUM> hours.

The steps (i) and (ii) are shown in Reaction Scheme <NUM>.

The step (iii) is to mix and react the biomass-derived <NUM>,<NUM>-cyclopentanediol prepared in the step (ii); terephthalic acid; and succinic anhydride or <NUM>,<NUM>-furandicarboxylic acid; and in the step (iii), the polymer compound of Chemical Formula <NUM> is prepared.

Specifically, the step (iii) is to prepare the polymer compound of Chemical Formula <NUM> by adding the monomer to a tetrahydrofuran solvent under a nitrogen atmosphere and then stirring them at <NUM> to <NUM> for <NUM> hours to <NUM> hours.

In addition, described herein is a method of preparing a polymer represented by Chemical Formula <NUM> which includes:.

The steps (i) and (ii) are the same as the method for preparing the polymer compound of Chemical Formula <NUM>.

The step (iii) is to mix and react the biomass-derived <NUM>,<NUM>-cyclopentanediol prepared in the step (ii) and <NUM>,<NUM>-diphenylmethane diisocyanate, preparing the polymer compound of Chemical Formula <NUM>.

Specifically, the step (iii) is to add the monomer to a tetrahydrofuran solvent and then stirring them under a nitrogen atmosphere at <NUM> to <NUM> for <NUM> hours to <NUM> hours, preparing the polymer compound of Chemical Formula <NUM>.

Hereinafter, although described with reference to examples of the present invention, the following examples are for illustrating the present invention, and the scope of the present invention is not limited thereto.

An aqueous solution was prepared by dissolving <NUM> of furfuryl alcohol, a derivative of furfural extracted from biomass, in <NUM> of water. Subsequently, <NUM> of calcium oxide was added to the aqueous solution and then stirred at <NUM> for <NUM> hours, preparing <NUM>-hydroxy-<NUM>-cyclopentenone.

Then, <NUM> of the <NUM>-hydroxy-<NUM>-cyclopentenone was dissolved in <NUM> of <NUM>-methyltetrahydrofuran, preparing a solution. <NUM> of ruthenium was added to the solution to perform a hydrogenation reaction at <NUM> for <NUM> hours, preparing biomass-derived <NUM>,<NUM>-cyclopentanediol.

<NUM> of the <NUM>,<NUM>-cyclopentanediol (Cpdiol) and <NUM> of terephthalic acid (TPA) were added to tetrahydrofuran and then stirred under a nitrogen atmosphere at <NUM> for <NUM> hours, preparing a polymer compound represented by Chemical Formula <NUM> and having a molecular weight of <NUM>/mol.

<NUM> of ethylene glycol (EG) and <NUM> of terephthalic acid (TPA) were added to tetrahydrofuran and then stirred under a nitrogen atmosphere at <NUM> for <NUM> hours, preparing a polymer compound represented by Chemical Formula <NUM> and having a molecular weight of <NUM>/mol.

The polymer of Chemical Formula <NUM> according to Preparation Example <NUM> and the polymer of Chemical Formula <NUM> according to Comparative Preparation Example <NUM> were measured with respect to a bending degree by using the Gaussian <NUM> program.

As a result, the polymer of Chemical Formula <NUM> including a biomass-derived <NUM>,<NUM>-cyclopentanediol monomer had a bending degree of <NUM>° (<FIG>), and the polymer of Chemical Formula <NUM> including no <NUM>,<NUM>-cyclopentanediol monomer had a bending degree of <NUM>°, which showed a linear structure (<FIG>).

In other words, when the biomass-derived <NUM>,<NUM>-cyclopentanediol monomer was included, the polymer had a three-dimensional structure, and when polymerized thereby, the polymer was expected to have a higher free volume.

In addition, electron distribution diagrams of the polymer of Chemical Formula <NUM> according to Preparation Example <NUM> and the polymer of Chemical Formula <NUM> according to Comparative Preparation Example <NUM> are shown in <FIG>, and HOMO and LUMO energy levels of the polymers of Chemical Formulas <NUM> and <NUM> are shown in Table <NUM>.

Referring to the results of Table <NUM>, the polymer of Chemical Formula <NUM> including the biomass-derived <NUM>,<NUM>-cyclopentanediol monomer exhibited higher HOMO and LUMO energy levels than the polymer of Chemical Formula <NUM> including no <NUM>,<NUM>-cyclopentanediol monomer. This result exhibits that the polymer including the biomass-derived <NUM>,<NUM>-cyclopentanediol monomer had excellent thermal stability and high transmittance (transparency), compared with the polymer including no biomass-derived <NUM>,<NUM>-cyclopentanediol monomer.

<NUM>,<NUM>-cyclopentanediol was prepared in the same manner as in Preparation Example <NUM>.

<NUM> of the <NUM>,<NUM>-cyclopentanediol, <NUM> of terephthalic acid, and <NUM> of succinic anhydride were added to tetrahydrofuran and then stirred under a nitrogen atmosphere at <NUM> for <NUM> hours, preparing a polymer represented by Chemical Formula <NUM> and having a molecular weight of <NUM>/mol.

<NUM> of the <NUM>,<NUM>-cyclopentanediol, <NUM> of terephthalic acid, and <NUM> of <NUM>,<NUM>-furandicarboxylic acid (FDCA) were added to tetrahydrofuran and then stirred under a nitrogen atmosphere at <NUM> for <NUM> hours, preparing a polymer represented by Chemical Formula <NUM> and having a molecular weight of about <NUM>/mol.

<NUM> of the <NUM>,<NUM>-cyclopentanediol and <NUM> of <NUM>,<NUM>-diphenylmethane diisocyanate were added to tetrahydrofuran and then stirred under a nitrogen atmosphere at <NUM> for <NUM> hours, preparing a polymer represented by Chemical Formula <NUM> and having a molecular weight of about <NUM>/mol. <CHM>
<CHM>.

<NUM> of terephthalic acid, <NUM> of <NUM>,<NUM>-furandicarboxylic acid, and <NUM> of butylene glycol were added to tetrahydrofuran and then stirred under a nitrogen atmosphere at <NUM> for <NUM> hours, preparing a polymer represented by Chemical Formula <NUM> and having a molecular weight of about <NUM>/mol.

<NUM> of <NUM>,<NUM>-diphenylmethane diisocyanate and <NUM> of ethylene glycol were added to tetrahydrofuran and then stirred under a nitrogen atmosphere at <NUM> for <NUM> hours, preparing a polymer represented by Chemical Formula <NUM> and having a molecular weight of about <NUM>/mol.

The polymer compound represented by Chemical Formula <NUM> according to Example <NUM>, the polymer compound represented by Chemical Formula <NUM> according to Example <NUM>, the polymer compound represented by Chemical Formula <NUM> according to Reference Example <NUM>, the polymer compound represented by Chemical Formula <NUM> according to Comparative Example <NUM>, and the polymer compound represented by Chemical Formula <NUM> according to Comparative Example <NUM> were measured with respect to transparency, flexural strength, and tensile strength, and the results are shown in Table <NUM>.

The transparency, the flexural strength, and the tensile strength are measured as follows.

Transparency (transmittance): measured according to ASTM D1003. According to ASTM D1003, <NUM>-thick specimens were measured with respect to light transmittance (total light transmittance) by using a hazemeter (NDH 5000W, Nippon Denshoku Industries Co.

Flexural strength: measured according to ASTM D-<NUM>. According to ASTM D-<NUM>, flexural strength specimens were prepared and measured with respect to flexural strength at <NUM>±<NUM> under RH of <NUM>±<NUM> % after <NUM> hours by using a universal testing machine (UTM). Herein, a cross-head speed of the universal testing machine was set to <NUM>/min.

Tensile strength: measured according to ASTM D-<NUM>. According to ASTM D-<NUM>, a tensile strength specimen was prepared and measured with respect to tensile strength at room temperature by using the universal testing machine (UTM). Herein, the cross-head speed of the universal testing machine (UTM) was set to <NUM>/min.

As a result, the polymer compounds of Chemical Formulas <NUM> and <NUM> including a monomer of biomass-derived <NUM>,<NUM>-cyclopentanediol according to the present invention exhibited more excellent transparency than that of the polymer according to Chemical Formula <NUM>.

The transparency was related to a measurement result of a molecular structure, and the polymer compounds of Chemical Formulas <NUM> and <NUM> included <NUM>,<NUM>-cyclopentanediol and thus had a three-dimensional structure, which increased a free volume and thus fluidity of a polymer chain, and accordingly, exhibited excellent transparency.

On the other hand, the polymer compound of Chemical Formula <NUM> had a linear structure and exhibited no increase in a free volume and thus had insufficient transparency, compared with the polymer compounds of Chemical Formulas <NUM> and <NUM>.

In addition, the polymer compounds of Chemical Formulas <NUM>, and <NUM> including biomass-derived <NUM>,<NUM>-cyclopentanediol as a monomer according to the present invention exhibited excellent flexural strength and tensile strength, compared with the polymer compounds of Chemical Formulas <NUM> and <NUM>.

The reason is that since strength was obtained by <NUM>,<NUM>-cyclopentanediol with a cyclic structure included as a monomer, a polymer compound of the present invention including the biomass-derived <NUM>,<NUM>-cyclopentanediol as a monomer exhibited excellent flexural strength and tensile strength.

The present invention relates to a polymer compound including a biomass-derived <NUM>,<NUM>-cyclopentanediol monomer and a method of manufacturing the same, and the polyester polymer of the present invention includes the biomass-derived monomer and thus is environmentally-friendly, exhibits excellent transparency due to an increase in a free volume, and in addition, includes a cyclic monomer and thus exhibits excellent strength.

Claim 1:
A polymer compound represented by Chemical Formula <NUM> comprising a biomass-derived <NUM>,<NUM>-cyclopentanediol monomer:
<CHM>
wherein R is a compound of Chemical Formula <NUM> or Chemical Formula <NUM>,
<CHM>
<CHM>
wherein * is a linking position, and
a is an integer of <NUM> to <NUM>, b is an integer of <NUM> to <NUM>, and c is an integer of <NUM> to <NUM>.