Polyester polyol copolymer and preparation method thereof

Abstract

The present disclosure relates to: a polyester polyol copolymer having excellent mechanical properties as well as environmental friendliness and biodegradable properties; and a method for preparing the polyester polyol copolymer.

Description

Technical Field

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims the benefit of Korean Patent Application No. 10-2023-0043731 filed in the Korean Intellectual Property Office on April 3, 2023, and Korean Patent Application No. 10-2024-0044963 filed in the Korean Intellectual Property Office on April 2, 2024, the disclosures of which are incorporated herein by reference in their entirety.

[0003] The present disclosure relates to polyester polyol copolymers and methods for preparing polyester polyol copolymers. Background Art

[0004] Polyglycolic acid (PGA), which is a type of aliphatic polyester, has attracted attention as an environmentally friendly material having biodegradable properties and excellent tensile strength and elastic modulus.

[0005] Unlike previously used petroleum-based resins such as polystyrene resins, polyvinyl chloride resins, polyethylene, etc., polyglycolic acid has the effects of preventing the depletion of petroleum resources and inhibiting carbon dioxide emissions, etc., and therefore, it can reduce environmental pollution, which is a disadvantage of petroleum-based plastic products. Therefore, as environmental pollution problems caused by waste plastics, etc. have emerged as social problems, efforts are being made to expand the application range of polyglycolic acid to products using general plastics (petroleum-based resins), such as food packaging materials and containers, electronic product housings, etc.

[0006] However, compared with existing petroleum-based resins, polyglycolic acid has poor elongation (elongation at break) and thus exhibits a characteristic of being easily broken (brittleness). Therefore, polyglycolic acid has limitations in its processability and thus limits its applicability as a general-purpose resin.

[0007] Therefore, there is a need to study a copolymer having an effect of improving elongation characteristics and the like while maintaining the mechanical characteristics of polyglycolic acid. Summary of the invention

[0008] Technical issues

[0009] An object of the present disclosure is to provide a polyester polyol copolymer which is excellent in biodegradability and exhibits excellent physical properties such as tensile strength and elastic modulus and simultaneously has improved elongation, and a method for preparing the polyester polyol copolymer.

[0010] Technical Solution

[0011] According to one embodiment of the present disclosure, a polyester polyol copolymer is provided, the polyester polyol copolymer comprising: a repeating unit represented by the following Chemical Formula 1, a repeating unit represented by the following Chemical Formula 2, and a repeating unit represented by the following Chemical Formula 3, wherein the repeating unit represented by Chemical Formula 1 is included in an amount of 5 wt% or more and 95 wt% or less based on the entire repeating units, and wherein the repeating unit represented by Chemical Formula 3 is included in an amount of 95 parts by weight or less based on 100 parts by weight of the repeating unit represented by Chemical Formula 2:

[0012] [Chemical formula 1]

[0013]

[0014] wherein in Chemical Formula 1, L1 is an alkylene group having 3 or less carbon atoms, and n is an integer of 3 or more,

[0015] [Chemical formula 2]

[0016]

[0017] [Chemical formula 3]

[0018]

[0019] In Chemical Formula 3, L2 is an alkylene group having 2 or more carbon atoms.

[0020] According to another embodiment of the present disclosure, there is provided a method for preparing a polyester polyol copolymer, comprising: subjecting a glycolide monomer and a monomer represented by the following Chemical Formula 5 to ring-opening polymerization in the presence of a compound represented by the following Chemical Formula 4 to prepare the polyester polyol copolymer, wherein the monomer represented by Chemical Formula 5 is included in an amount of 95 parts by weight or less based on 100 parts by weight of the glycolide monomer:

[0021] [Chemical formula 4]

[0022]

[0023] Wherein in Chemical Formula 4, L1 is an alkylene group having 3 or less carbon atoms, and n is an integer of 5 or more,

[0024] [Chemical formula 5]

[0025]

[0026] In Chemical Formula 5, L2 is an alkylene group having 2 or more carbon atoms.

[0027] Now, a polyester polyol copolymer and a method for preparing the polyester polyol copolymer according to specific embodiments of the present disclosure will be described in more detail.

[0028] Unless particularly mentioned herein, the term “include” or “comprising” means including / containing some elements (or components) without any limitation, and should not be interpreted as excluding the addition of other elements (or components).

[0029] In the present disclosure, the terms “first”, “second”, etc. are used to describe a plurality of components, and these terms are only used to distinguish a certain component from other components.

[0030] In addition, if the steps constituting the preparation method described herein are specified as sequential or continuous, or unless otherwise specified, a step and other steps constituting a preparation method should not be interpreted as limited to the order described herein. Therefore, the order of the steps constituting the preparation method can be changed within the range that can be easily understood by those skilled in the art, and in this case, incidental changes that are obvious to those skilled in the art are not included in the scope of the present disclosure.

[0031] In addition, unless otherwise specified herein, weight average molecular weight can be measured using gel permeation chromatography (GPC). Specifically, the prepolymer or copolymer is dissolved in chloroform to a concentration of 2 mg / ml, and then 20 μl of the solution is injected into the GPC, and GPC analysis is performed at 40 ° C. At this time, chloroform is used as the mobile phase for GPC, with a flow rate of 1.0 mL / min, and the column used is two Agilent Mixed-B units in series. RI detector is used as a detector. The value of Mw can be obtained using a calibration curve formed using a polystyrene standard sample. Nine polystyrene standard samples with molecular weights of 2,000 g / mol, 10,000 g / mol, 30,000 g / mol, 70,000 g / mol, 200,000 g / mol, 700,000 g / mol, 2,000,000 g / mol, 4,000,000 g / mol and 10,000,000 g / mol are used.

[0032] In the present disclosure, copolymer is meant to include all random copolymers, block copolymers, graft copolymers, and the like.

[0033] In the present disclosure, the term "block" refers to a polymer comprising at least two repeating units connected to each other, wherein the repeating units are identical, and the term "block copolymer" refers to a copolymer comprising at least two types of different blocks connected to each other via a direct bond or via a linking group, wherein there are one or more blocks of each block type.

[0034] In the present disclosure, polyester polyol refers to a polymer including an ester group -(C=O)-O- as a repeating unit and having a hydroxyl group (-OH) at the terminal.

[0035] According to one embodiment of the present disclosure, a polyester polyol copolymer is provided, comprising: a repeating unit represented by Chemical Formula 1, a repeating unit represented by Chemical Formula 2, and a repeating unit represented by Chemical Formula 3, wherein the repeating unit represented by Chemical Formula 3 is included in an amount of 95 parts by weight or less based on 100 parts by weight of the repeating unit represented by Chemical Formula 2.

[0036] The present inventors have found that since the polyester polyol copolymer of the embodiment includes the repeating unit represented by Chemical Formula 1, the repeating unit represented by Chemical Formula 2, and the repeating unit represented by Chemical Formula 3 at the same time, excellent mechanical properties and elongation can be simultaneously achieved, and have completed the present disclosure.

[0037] Specifically, since the polyester polyol copolymer of the above embodiment includes the repeating unit represented by Chemical Formula 1, the repeating unit represented by Chemical Formula 2, and the repeating unit represented by Chemical Formula 3 at the same time, the excellent elongation exhibited by the repeating unit represented by Chemical Formula 1 and the excellent mechanical properties exhibited by the repeating unit represented by Chemical Formula 2 and the repeating unit represented by Chemical Formula 3 can be simultaneously achieved.

[0038] Specifically, the polyester polyol copolymer of one embodiment may include a repeating unit represented by the following Chemical Formula 1, a repeating unit represented by the following Chemical Formula 2, and a repeating unit represented by the following Chemical Formula 3.

[0039] [Chemical formula 1]

[0040]

[0041] [Chemical formula 2]

[0042]

[0043] [Chemical formula 3]

[0044]

[0045] wherein in Chemical Formula 1, L1 is an alkylene group having 3 or less carbon atoms, and n is an integer of 3 or more, and in Chemical Formula 3, L2 is an alkylene group having 2 or more carbon atoms.

[0046] Since the conventional polyester polyol copolymer does not include the repeating unit represented by Chemical Formula 1, it has a problem in that due to the high melting point and high crystallinity, conventional common polymer processing methods such as thermoforming and film processing methods are impossible, and thus processability is limited. Unlike the conventional polyester polyol copolymer, the polyester polyol copolymer of one embodiment of the present disclosure includes the repeating unit represented by Chemical Formula 1, which has excellent low-temperature physical properties and anti-hydrolysis stability, and at the same time can achieve excellent elongation due to the low glass transition temperature.

[0047] The copolymer may include all random copolymers, block copolymers, graft copolymers, etc. For example, the copolymer may be a block copolymer.

[0048] The polyester polyol copolymer according to one embodiment of the present disclosure comprises a first block comprising a repeating unit represented by Chemical Formula 1 and a second block comprising a repeating unit represented by Chemical Formula 2, wherein the first block and the second block are bonded by a direct bond, an ester bond, an amide bond, a urethane bond, or a carbonate bond, and therefore, it can compensate for the disadvantage of reduced elongation properties of a biodegradable resin comprising only polyglycolic acid. In addition, these polyester polyol copolymers have excellent biodegradability while supplementing the mechanical properties of each homopolymer.

[0049] That is, in the polyester polyol copolymer of one embodiment of the present disclosure, the repeating unit represented by Chemical Formula 1, the repeating unit represented by Chemical Formula 2, and the repeating unit represented by Chemical Formula 3 may be connected by a direct bond, an ester bond, an amide bond, a urethane bond, a urea bond, or a carbonate bond.

[0050] Furthermore, in the copolymer of one embodiment of the present disclosure, the repeating unit represented by Chemical Formula 2 and the repeating unit represented by Chemical Formula 3 may be connected by a direct bond, an ester bond, an amide bond, a urethane bond, a urea bond, or a carbonate bond.

[0051] In Chemical Formula 1, L1 may be an alkylene group having 3 or less carbon atoms, and the alkylene group may be substituted or unsubstituted.

[0052] In addition, in Chemical Formula 1, n may be an integer of 5 or more and 5000 or less.

[0053] Specifically, in Chemical Formula 1, n may be an integer of 5 or more, 10 or more, or 5000 or less, 4000 or less, 3000 or less, 2000 or less, 1500 or less, 1000 or less, 500 or less, 100 or less, 50 or less, or 30 or less, or may be an integer of 5 or more and 5000 or less, 5 or more and 4000 or less, 5 or more and 3000 or less, 5 or more and 2000 or less, 5 or more and 1500 or less, 5 or more and 1000 or more. or less, 10 or more and 500 or less, 10 or more and 100 or less, 10 or more and 50 or less, 10 or more and 30 or less, 10 or more and 5000 or less, 10 or more and 4000 or less, 10 or more and 3000 or less, 10 or more and 2000 or less, 10 or more and 1500 or less, 10 or more and 1000 or less, 10 or more and 500 or less, 10 or more and 100 or less, 10 or more and 50 or less, or an integer of 10 or more and 30 or less.

[0054] In Chemical Formula 1, n may mean a repetition number in a repeating unit represented by Chemical Formula 1. In Chemical Formula 1, when n is an integer of 5 or more, compared with a case where n is less than 5, sufficient elongation may be ensured.

[0055] In addition, n in Chemical Formula 1 being 5 or more may mean that the copolymer of the above embodiment includes a first block including a repeating unit represented by Chemical Formula 1.

[0056] The repeating unit represented by Chemical Formula 1 may be a repeating unit derived from a compound represented by Chemical Formula 4 below.

[0057] [Chemical formula 4]

[0058]

[0059] Wherein in Chemical Formula 4, L1 is an alkylene group having 3 or less carbon atoms, and n is an integer of 5 or more.

[0060] Specifically, in Chemical Formula 4, L1 may be an alkylene group having 3 or less carbon atoms, wherein the alkylene group may be substituted or unsubstituted.

[0061] In addition, in Chemical Formula 4, n may be an integer of 5 or more and 5000 or less.

[0062] Specifically, in Chemical Formula 4, n may be an integer of 5 or more, 10 or more, or 5000 or less, 4000 or less, 3000 or less, 2000 or less, 1500 or less, 1000 or less, 500 or less, 100 or less, 50 or less, or 30 or less, or may be an integer of 5 or more and 5000 or less, 5 or more and 4000 or less, 5 or more and 3000 or less, 5 or more and 2000 or less, 5 or more and 1500 or less, 5 or more and 1000 or less. or less, 10 or more and 500 or less, 10 or more and 100 or less, 10 or more and 50 or less, 10 or more and 30 or less, 10 or more and 5000 or less, 10 or more and 4000 or less, 10 or more and 3000 or less, 10 or more and 2000 or less, 10 or more and 1500 or less, 10 or more and 1000 or less, 10 or more and 500 or less, 10 or more and 100 or less, 10 or more and 50 or less, or an integer of 10 or more and 30 or less.

[0063] Specifically, the repeating unit represented by Chemical Formula 1 may include a repeating unit represented by the following Chemical Formula 1-1:

[0064] [Chemical formula 1-1]

[0065]

[0066] In Chemical Formula 1-1, R1 to R6 are each independently hydrogen or an alkyl group, and n is an integer of 5 or more.

[0067] Specifically, in Chemical Formula 1-1, n may be an integer of 5 or more, 10 or more, or 5000 or less, 4000 or less, 3000 or less, 2000 or less, 1500 or less, 1000 or less, 500 or less, 100 or less, 50 or less, or 30 or less, or may be an integer of 5 or more and 5000 or less, 5 or more and 4000 or less, 5 or more and 3000 or less, 5 or more and 2000 or less, 5 or more and 1500 or less, 5 or more and 1000 or less. or less, 5 or more and 500 or less, 5 or more and 100 or less, 5 or more and 50 or less, 5 or more and 30 or less, 10 or more and 5000 or less, 10 or more and 4000 or less, 10 or more and 3000 or less, 10 or more and 2000 or less, 10 or more and 1500 or less, 10 or more and 1000 or less, 10 or more and 500 or less, 10 or more and 100 or less, 10 or more and 50 or less, or an integer of 10 or more and 30 or less.

[0068] Since the polyester polyol copolymer of one embodiment of the present disclosure includes a repeating unit represented by Chemical Formula 1-1, it has excellent low-temperature physical properties and anti-hydrolysis stability, and at the same time allows high-temperature thermoforming, such as polymer processing methods, thermoforming and film processing methods, and thus can achieve excellent processability. In addition, due to the low glass transition temperature, the crystallinity is reduced, so that excellent elongation and excellent processability can be achieved.

[0069] Meanwhile, since the polyester polyol copolymer according to one embodiment of the present disclosure includes the repeating unit represented by Chemical Formula 2, excellent mechanical properties may be achieved.

[0070] The repeating unit represented by Chemical Formula 2 may be a repeating unit derived from a glycolide monomer.

[0071] When the compound represented by Chemical Formula 4 is introduced into the comonomer of glycolide monomer, various physical properties of glycolide can be improved, but the physical properties may differ according to the connection structure of each repeating unit and the degree of introduction of each repeating unit. Therefore, the polyester polyol copolymer of one embodiment of the present disclosure can adjust the mechanical properties while maintaining the physical properties inherent to glycolide by adjusting the connection structure of each repeating unit and the degree of introduction of the repeating unit represented by Chemical Formula 1.

[0072] The copolymer may include a repeating unit represented by the following Chemical Formula 7.

[0073] [Chemical formula 7]

[0074]

[0075] In Chemical Formula 7, m is an integer of 2 or more.

[0076] Including the repeating unit represented by Chemical Formula 7 in which m is an integer of 2 or more may mean that the copolymer of the above embodiment includes the second block including the repeating unit represented by Chemical Formula 2.

[0077] Alternatively, the polyester polyol copolymer may include a repeating unit represented by Chemical Formula 3 below.

[0078] [Chemical formula 3]

[0079]

[0080] In Chemical Formula 3, L2 is an alkylene group having 2 or more carbon atoms.

[0081] That is, the polyester polyol copolymer may include a repeating unit represented by Chemical Formula 1, a repeating unit represented by Chemical Formula 2, and a repeating unit represented by Chemical Formula 3.

[0082] Since the polyester polyol copolymer includes the repeating unit represented by Chemical Formula 3, processability may be improved, a biodegradable rate may be adjusted, and analysis of materials may be facilitated.

[0083] The repeating unit represented by Chemical Formula 3 may be a repeating unit derived from a compound represented by Chemical Formula 5 below.

[0084] [Chemical formula 5]

[0085]

[0086] In Chemical Formula 5, L2 is an alkylene group having 2 or more carbon atoms.

[0087] The polyester polyol copolymer including the repeating unit represented by Chemical Formula 3 may be prepared by subjecting the compound represented by Chemical Formula 4, glycolide, and the compound represented by Chemical Formula 5 to ring-opening polymerization.

[0088] Specifically, the repeating unit represented by Chemical Formula 3 may include a repeating unit represented by the following Chemical Formula 3-1.

[0089] [Chemical formula 3-1]

[0090]

[0091] The repeating unit represented by Chemical Formula 3-1 may be a repeating unit derived from a lactide monomer.

[0092] The copolymer may include a repeating unit represented by Chemical Formula 8 below.

[0093] [Chemical formula 8]

[0094]

[0095] In Chemical Formula 8, p is an integer of 2 or more.

[0096] Including the repeating unit represented by Chemical Formula 8 in which p is an integer of 2 or more may mean that the copolymer of the above embodiment includes the third block including the repeating unit represented by Chemical Formula 3.

[0097] The polyester polyol copolymer of the above embodiment may include the repeating unit represented by Chemical Formula 1 in an amount of 5 wt % or more and 95 wt % or less based on the entire repeating units.

[0098] Since the polyester polyol copolymer of the above embodiment includes the repeating unit represented by Chemical Formula 1 in an amount of 5 wt % or more and 95 wt % or less based on the total repeating units, it can improve elongation while maintaining excellent mechanical properties, and thus simultaneously achieve excellent mechanical properties and elongation.

[0099] Specifically, the polyester polyol copolymer of the above embodiment may include the repeating unit represented by Chemical Formula 1 in an amount of 5 wt % or more, 10 wt % or more, 15 wt % or more, 20 wt % or more, or 95 wt % or less, 90 wt % or less, 80 wt % or less, 75 wt % or less, 50 wt % or less, 5 wt % or more and 95 wt % or less, 5 wt % or more and 90 wt % or less, 5 wt % or more and 80 wt % or less, 5 wt % or more and 75 wt % or less, 5 wt % or more and 50 wt % or less, 10 wt % or more and 95 wt % or less, 10 wt % or more and % or more and 80% by weight or less, 10% or more and 75% by weight or less, 10% or more and 50% by weight or less, 15% or more and 95% by weight or less, 15% or more and 90% by weight or less, 15% or more and 80% by weight or less, 15% or more and 75% by weight or less, 15% or more and 50% by weight or less, 20% or more and 95% by weight or less, 20% or more and 90% by weight or less, 20% or more and 80% by weight or less, 20% or more and 75% by weight or less, or 20% or more and 50% by weight or less.

[0100] Since the polyester polyol copolymer of the above embodiment includes the repeating unit represented by Chemical Formula 1 in an amount of 5 wt % or more and 95 wt % or less based on the entire repeating units, it can simultaneously achieve excellent mechanical properties and elongation.

[0101] If the polyester polyol copolymer includes the repeating unit represented by Chemical Formula 1 in an amount of less than 5 wt % based on the total repeating units, elongation may be poor and thus processability may be limited. If it includes the repeating unit represented by Chemical Formula 1 in an amount of more than 95 wt % based on the total repeating units, mechanical properties may be deteriorated.

[0102] Meanwhile, the polyester polyol copolymer may include the repeating unit represented by Chemical Formula 3 in an amount of 0.01 mole or more and less than 0.25 mole based on 1 mole of the repeating unit represented by Chemical Formula 2.

[0103] Specifically, the polyester polyol copolymer may include the repeating unit represented by Chemical Formula 3 in an amount of 0.01 mol or more and less than 0.25 mol, 0.01 mol or more and 0.24 mol or less, 0.01 mol or more and 0.2 mol or less, 0.05 mol or more and less than 0.25 mol, 0.05 mol or more and 0.24 mol or less, 0.05 mol or more and 0.2 mol or less, 0.08 mol or more and less than 0.25 mol, 0.08 mol or more and 0.24 mol or less, or 0.08 mol or more and 0.2 mol or less, based on 1 mol of the repeating unit represented by Chemical Formula 2.

[0104] If the polyester polyol copolymer includes the repeating unit represented by Chemical Formula 3 in an amount of less than 0.01 mol based on 1 mol of the repeating unit represented by Chemical Formula 2, processability may be reduced or the rate of biodegradation may not be adjusted, and if the content is 0.25 mol or more, mechanical properties may be deteriorated due to reduced crystallinity.

[0105] Meanwhile, the polyester polyol copolymer may include the repeating unit represented by Chemical Formula 2 in an amount of 10 moles or more based on 1 mole of the repeating unit represented by Chemical Formula 1.

[0106] More specifically, the polyester polyol copolymer may include the repeating unit represented by Chemical Formula 2 in an amount of 10 moles or more, 20 moles or more, 30 moles or more, 40 moles or more, 45 moles or more, 200 moles or less, 150 moles or less, 100 moles or less, 10 moles or more and 200 moles or less, 20 moles or more and 200 moles or less, 30 moles or more and 200 moles or less, 40 moles or more and 200 moles or less, based on 1 mole of the repeating unit represented by Chemical Formula 1. 45 moles or more and 200 moles or less, 10 moles or more and 150 moles or less, 20 moles or more and 150 moles or less, 30 moles or more and 150 moles or less, 40 moles or more and 150 moles or less, 45 moles or more and 150 moles or less, 10 moles or more and 100 moles or less, 20 moles or more and 100 moles or less, 30 moles or more and 100 moles or less, 40 moles or more and 100 moles or less, or 45 moles or more and 100 moles or less.

[0107] Since the polyester polyol includes the repeating unit represented by Chemical Formula 2 in an amount of 10 moles or more based on 1 mole of the repeating unit represented by Chemical Formula 1, excellent mechanical properties may be achieved.

[0108] If the polyester polyol copolymer includes the repeating unit represented by Chemical Formula 2 in an amount less than 10 moles based on 1 mole of the repeating unit represented by Chemical Formula 1, mechanical properties of the prepared polyester polyol copolymer may be deteriorated.

[0109] In addition, the polyester polyol copolymer may include the repeating unit represented by Chemical Formula 3 in an amount of 1.1 moles or more based on 1 mole of the repeating unit represented by Chemical Formula 1.

[0110] More specifically, the polyester polyol copolymer may include the repeating unit represented by Chemical Formula 3 in an amount of 1.1 mol or more, 1.5 mol or more, 2.0 mol or more, 3 mol or more, 5 mol or more, 50 mol or less, 40 mol or less, 20 mol or less, 10 mol or less, 1.1 mol or more and 50 mol or less, 1.5 mol or more and 50 mol or less, 2.0 mol or more and 50 mol or less, 3 mol or more and 50 mol or less, 5 mol or more and 50 mol or less, 1.1 mol or more and 40 mol or less, 1.5 mol or more and 50 mol or less, 2.0 mol or more and 50 mol or less, 3 mol or more and 50 mol or less, 5 mol or more and 50 mol or less, 1.1 mol or more and 40 mol or less, 1.5 mol or more and 50 mol or less, 2.0 mol or more and 50 mol or less, 5 moles or more and 40 moles or less, 2.0 moles or more and 40 moles or less, 3 moles or more and 40 moles or less, 5 moles or more and 40 moles or less, 1.1 moles or more and 20 moles or less, 1.5 moles or more and 20 moles or less, 2.0 moles or more and 20 moles or less, 3 moles or more and 20 moles or less, 5 moles or more and 20 moles or less, 1.1 moles or more and 10 moles or less, 1.5 moles or more and 10 moles or less, 2.0 moles or more and 10 moles or less, 3 moles or more and 10 moles or less, or 5 moles or more and 10 moles or less.

[0111] Since the polyester polyol copolymer includes the repeating unit represented by Chemical Formula 3 in an amount of 1.1 moles or more based on 1 mole of the repeating unit represented by Chemical Formula 1, excellent mechanical properties may be achieved.

[0112] If the polyester polyol copolymer includes the repeating unit represented by Chemical Formula 3 in an amount less than 1.1 moles based on 1 mole of the repeating unit represented by Chemical Formula 1, mechanical properties of the prepared polyester polyol copolymer may be deteriorated.

[0113] In addition, the polyester polyol copolymer may include the repeating unit represented by Chemical Formula 3 in an amount of 95 parts by weight or less, based on 100 parts by weight of the repeating unit represented by Chemical Formula 2.

[0114] Specifically, the polyester polyol copolymer may include the repeating unit represented by Chemical Formula 3 in the following amounts, based on 100 parts by weight of the repeating unit represented by Chemical Formula 2: 1 part by weight or more, 5 parts by weight or more, 10 parts by weight or more, 95 parts by weight or less, 90 parts by weight or less, 75 parts by weight or less, 50 parts by weight or less, 30 parts by weight or less, 25 parts by weight or less, 1 part by weight or more and 95 parts by weight or less, 1 part by weight or more and 90 parts by weight or less, 1 part by weight or more and 75 parts by weight or less, 1 part by weight or more and 50 parts by weight or less, 1 part by weight or more and 30 parts by weight or less, 1 part by weight or more and 10 parts by weight or less. 5 parts by weight or more and 25 parts by weight or less, 5 parts by weight or more and 95 parts by weight or less, 5 parts by weight or more and 90 parts by weight or less, 5 parts by weight or more and 75 parts by weight or less, 5 parts by weight or more and 50 parts by weight or less, 5 parts by weight or more and 30 parts by weight or less, 5 parts by weight or more and 25 parts by weight or less, 10 parts by weight or more and 95 parts by weight or less, 10 parts by weight or more and 90 parts by weight or less, 10 parts by weight or more and 75 parts by weight or less, 10 parts by weight or more and 50 parts by weight or less, 10 parts by weight or more and 30 parts by weight or less, or 10 parts by weight or more and 25 parts by weight or less.

[0115] Since the polyester polyol copolymer includes the repeating unit represented by Chemical Formula 3 in an amount of 95 parts by weight or less based on 100 parts by weight of the repeating unit represented by Chemical Formula 2, effects of improving heat resistance and biodegradability and improving moisture and gas barrier properties may be achieved.

[0116] In addition, the copolymer may include a structure in which any one selected from the repeating unit represented by Chemical Formula 7 and the repeating unit represented by Chemical Formula 8 is bonded to both ends of a functional group represented by the following Chemical Formula 9.

[0117] [Chemical formula 9]

[0118]

[0119] Specifically, the copolymer may include a structure in which a repeating unit represented by Chemical Formula 7 is bonded to both ends of a functional group of Chemical Formula 9, or a structure in which a repeating unit represented by Chemical Formula 8 is bonded to both ends of a functional group of Chemical Formula 9, or a structure in which a repeating unit represented by Chemical Formula 7 and a repeating unit represented by Chemical Formula 8 are respectively bonded to both ends of a functional group of Chemical Formula 9.

[0120] More specifically, the copolymer may include any one selected from repeating units represented by the following Chemical Formulae 10-1 to 10-3.

[0121] [Chemical formula 10-1]

[0122]

[0123] [Chemical formula 10-2]

[0124]

[0125] [Chemical formula 10-3]

[0126]

[0127] For example, the copolymer may include copolymers represented by the following Chemical Formulas 11-1 to 11-3.

[0128] [Chemical formula 11-1]

[0129]

[0130] [Chemical formula 11-2]

[0131]

[0132] [Chemical formula 11-3]

[0133]

[0134] The polyester polyol copolymer may have a weight average molecular weight (Mw) measured using gel permeation chromatography (GPC) of 10,000 g / mol or more and 500,000 g / mol or less.

[0135] Specifically, the weight average molecular weight (Mw) of the polyester polyol copolymer measured using gel permeation chromatography (GPC) may be 10,000 g / mol or more, 15,000 g / mol or more, 20,000 g / mol or more, 30,000 g / mol or more, 35,000 g / mol or more, 500,000 g / mol or less, 400,000 g / mol or less, 300,000 g / mol or less, 200,000 g / mol or less, 100,000 g / mol or less, and 10,000 g / mol or more and 500,000 g / mol or less, 15,000 g / mol or more. 00 g / mol or more and 500,000 g / mol or less, 20,000 g / mol or more and 500,000 g / mol or less, 30,000 g / mol or more and 500,000 g / mol or less, 35,000 g / mol or more and 500,000 g / mol or less, 10,000 g / mol or more and 400,000 g / mol or less, 15,000 g / mol or more and 400,000 g / mol or less, 20,000 g / mol or more and 400,000 g / mol or less, 30,000 g / mol or more and 400,000 g / mol or less, 35,000 g / mol or more and 500,000 g / mol or less, 10,000 g / mol or more and 400,000 g / mol or less, 15,000 g / mol or more and 400,000 g / mol or less, 20,000 g / mol or more and 400,000 g / mol or less, 30,000 g / mol or more and 400,000 g / mol or less, 35,000 g / mol or more and 500,000 g / mol or less g / mol or more and 400,000 g / mol or less, 10,000 g / mol or more and 300,000 g / mol or less, 15,000 g / mol or more and 300,000 g / mol or less, 20,000 g / mol or more and 300,000 g / mol or less, 30,000 g / mol or more and 300,000 g / mol or less, 35,000 g / mol or more and 300,000 g / mol or less, 10,000 g / mol or more and 200,000 g / mol or less, 15,000 g / mol or more and 200,000 g / mol or less, 20,000 g / mol or more and 300,000 g / mol or less, 0 g / mol or more and 200,000 g / mol or less, 30,000 g / mol or more and 200,000 g / mol or less, 35,000 g / mol or more and 200,000 g / mol or less, 10,000 g / mol or more and 100,000 g / mol or less, 15,000 g / mol or more and 100,000 g / mol or less, 20,000 g / mol or more and 100,000 g / mol or less, 30,000 g / mol or more and 100,000 g / mol or less, or 35,000 g / mol or more and 100,000 g / mol or less.

[0136] Meanwhile, the polyester polyol copolymer according to one embodiment of the present disclosure may have a tensile elongation of 150% or more.

[0137] Specifically, the polyester polyol copolymer of one embodiment of the present disclosure has a tensile elongation of 150% or more, 200% or more, 250% or more, 10000% or less, 5000% or less, 1000% or less, 500% or less, 300% or less, 150% or more and 10000% or less, 150% or more and 5000% or less, 150% or more and 1000% or less, 150% or more and 500% or less, 150% or more and 300% or less. 00% or less, 200% or more and 10000% or less, 200% or more and 5000% or less, 200% or more and 1000% or less, 200% or more and 500% or less, 200% or more and 300% or less, 250% or more and 10000% or less, 250% or more and 5000% or less, 250% or more and 1000% or less, 250% or more and 500% or less, or 250% or more and 300% or less.

[0138] The method for measuring tensile elongation is not particularly limited, but can be measured, for example, according to ASTM D638. More specifically, an ASTM D536 V-type test specimen is manufactured at 190° C. to 200° C. using a hot press device, and then can be measured using a UTM device at 10 mm / sec, 60 kg / f load.

[0139] The polyester polyol copolymer of one embodiment of the present disclosure may be a biodegradable polyester polyol copolymer exhibiting biodegradability.

[0140] In the present disclosure, a biodegradable resin or a biodegradable (co)polymer means a resin or (co)polymer that causes natural degradation when exposed to the outside. Specifically, it may refer to a resin or (co)polymer that degrades by 20% by weight or more based on the weight of the initial resin or (co)polymer when exposed to an external environment at room temperature (10° C. to 30° C.) for 30 days or longer.

[0141] That is, the polyester polyol copolymer of the above embodiment may cause natural degradation when exposed to the outside, and specifically, may be degraded by more than 20 wt % when exposed to an external environment at room temperature (10° C. to 30° C.) for more than 30 days.

[0142] The method of measuring biodegradability is not particularly limited, but for example, at room temperature (10° C. to 30° C.), the moisture content in aerobic compost is set to a level of 40% or more and 70% or less, then the compost and the resin or (co)polymer are mixed at a weight ratio of 10:1, and the biodegradability can be measured by calculating the ratio of the mass degraded into water and CO2 based on the initial mass of the sample over time.

[0143] According to another embodiment of the present disclosure, a method for preparing a polyester polyol copolymer may be provided, the method comprising subjecting a glycolide monomer and a monomer represented by the following Chemical Formula 5 to ring-opening polymerization in the presence of a compound represented by the following Chemical Formula 4 to prepare a polyester polyol copolymer, wherein the monomer represented by Chemical Formula 5 is included in an amount of 95 parts by weight or less based on 100 parts by weight of the glycolide monomer.

[0144] [Chemical formula 4]

[0145]

[0146] Wherein in Chemical Formula 4, L1 is an alkylene group having 3 or less carbon atoms, and n is an integer of 5 or more,

[0147] [Chemical formula 5]

[0148]

[0149] In Chemical Formula 5, L2 is an alkylene group having 2 or more carbon atoms.

[0150] Specifically, in Chemical Formula 4, L1 may be an alkylene group having 3 or less carbon atoms, wherein the alkylene group may be substituted or unsubstituted.

[0151] In addition, in Chemical Formula 4, n may be an integer of 5 or more and 5000 or less.

[0152] Specifically, in Chemical Formula 4, n may be an integer of 5 or more, 10 or more, or 5000 or less, 4000 or less, 3000 or less, 2000 or less, 1500 or less, 1000 or less, 500 or less, 100 or less, 50 or less, or 30 or less, or may be an integer of 5 or more and 5000 or less, 5 or more and 4000 or less, 5 or more and 3000 or less, 5 or more and 2000 or less, 5 or more and 1500 or less, 5 or more and 1000 or more. or less, 10 or more and 500 or less, 10 or more and 100 or less, 10 or more and 50 or less, 10 or more and 30 or less, 10 or more and 5000 or less, 10 or more and 4000 or less, 10 or more and 3000 or less, 10 or more and 2000 or less, 10 or more and 1500 or less, 10 or more and 1000 or less, 10 or more and 500 or less, 10 or more and 100 or less, 10 or more and 50 or less, or an integer of 10 or more and 30 or less.

[0153] Specifically, the repeating unit represented by Chemical Formula 4 may include a compound represented by the following Chemical Formula 4-1.

[0154] [Chemical formula 4-1]

[0155]

[0156] In Chemical Formula 4-1, R1 to R6 are each independently hydrogen or an alkyl group, and n is an integer of 5 or more.

[0157] In the preparation method of the polyester polyol copolymer according to the above embodiment, the polyester polyol copolymer may include the repeating unit derived from the compound represented by Chemical Formula 4 in an amount of 5 wt % or more and 95 wt % or less based on the entire repeating units.

[0158] The repeating unit derived from the compound represented by Chemical Formula 4 may be the repeating unit represented by Chemical Formula 1.

[0159] Specifically, the polyester polyol copolymer according to the above embodiment may include the repeating unit derived from the compound represented by Chemical Formula 4 in an amount of 5 wt % or more, 10 wt % or more, 15 wt % or more, 20 wt % or more, or 95 wt % or less, 90 wt % or less, 80 wt % or less, 75 wt % or less, 50 wt % or less, 5 wt % or more and 95 wt % or less, 5 wt % or more and 90 wt % or less, 5 wt % or more and 80 wt % or less, 5 wt % or more and 75 wt % or less, 5 wt % or more and 50 wt % or less, 10 wt % or more and 95 wt % or less, 10 wt % or more and 15 ... less. % or more and 90 wt % or less, 10 wt % or more and 80 wt % or less, 10 wt % or more and 75 wt % or less, 10 wt % or more and 50 wt % or less, 15 wt % or more and 95 wt % or less, 15 wt % or more and 90 wt % or less, 15 wt % or more and 80 wt % or less, 15 wt % or more and 75 wt % or less, 15 wt % or more and 50 wt % or less, 20 wt % or more and 95 wt % or less, 20 wt % or more and 90 wt % or less, 20 wt % or more and 80 wt % or less, 20 wt % or more and 75 wt % or less, or 20 wt % or more and 50 wt % or less.

[0160] Since the polyester polyol copolymer prepared according to the method for preparing a polyester polyol copolymer according to the above embodiment includes the repeating unit derived from the compound represented by Chemical Formula 4 in an amount of 5 wt % or more and 95 wt % or less based on the total repeating units, excellent mechanical properties and elongation can be simultaneously achieved.

[0161] If the polyester polyol copolymer includes less than 5 wt % of the repeating unit represented by Chemical Formula 1 based on the total repeating units, elongation is poor and thus processability may be limited. If the repeating unit represented by Chemical Formula 1 is included in an amount of more than 95 wt % based on the total repeating units, mechanical properties may be deteriorated.

[0162] The molar content of the repeating unit derived from the compound represented by Chemical Formula 4 may be achieved by adjusting the ratio of each monomer used in the polyester polyol copolymer of the above embodiment.

[0163] If the weight ratio of the compound represented by Chemical Formula 4 to the glycolide monomer is less than 1:99, the elongation is poor and thus the processability may be limited. If the weight ratio of the compound represented by Chemical Formula 4 to the glycolide monomer is greater than 99:1, the mechanical properties of the prepared polyester polyol copolymer may be deteriorated.

[0164] The compound represented by Chemical Formula 4 may have a weight average molecular weight (Mw) of 500 g / mol to 10,000 g / mol as measured using gel permeation chromatography (GPC).

[0165] Specifically, the weight average molecular weight (Mw) of the compound represented by Chemical Formula 4 measured using gel permeation chromatography (GPC) may be 500 g / mol or more, 700 g / mol or more, 800 g / mol or more, 1000 g / mol or more, 10,000 g / mol or less, 5000 g / mol or less, 2000 g / mol or less, or 1500 g / mol or less, or may be 500 g / mol or more and 10,000 g / mol or less, 700 g / mol or more and 10,000 g / mol or less, 800 g / mol or more and 10,000 g / mol or less, 1000 g / mol or more and 10,000 g / mol or less, 500 g / mol or more and 5,000 g / mol or less. g / mol or less, 700 g / mol or more and 5,000 g / mol or less, 800 g / mol or more and 5,000 g / mol or less, 1000 g / mol or more and 5,000 g / mol or less, 500 g / mol or more and 2,000 g / mol or less, 700 g / mol or more and 2,000 g / mol or less, 800 g / mol or more and 2,000 g / mol or less, 1000 g / mol or more and 2,000 g / mol or less, 500 g / mol or more and 1500 g / mol or less, 700 g / mol or more and 1500 g / mol or less, 800 g / mol or more and 1500 g / mol or less, or 1000 g / mol or more and 1500 g / mol or less.

[0166] The step of subjecting the glycolide monomer to ring-opening polymerization in the presence of the compound represented by Chemical Formula 4 to prepare the polyester polyol copolymer can be performed by bulk polymerization substantially free of solvent. At this time, substantially free of solvent may include using a small amount of solvent to dissolve the catalyst, for example, using less than 1 ml of solvent per 1 kg of the monomer used. Since the step of subjecting the glycolide monomer to ring-opening polymerization in the presence of the compound represented by Chemical Formula 4 to prepare the copolymer is performed by bulk polymerization, the step of removing the solvent after polymerization can be omitted, and degradation or loss of the resin during such a solvent removal process can also be suppressed.

[0167] In addition, in the preparation method of the polyester polyol copolymer, the monomer represented by Chemical Formula 5 may be included in an amount of 95 parts by weight or less based on 100 parts by weight of the glycolide monomer.

[0168] Preferably, in the preparation method of the polyester polyol copolymer, the monomer represented by Chemical Formula 5 may be included in the following amounts, based on 100 parts by weight of the glycolide monomer: 1 part by weight or more, 5 parts by weight or more, 10 parts by weight or more, 95 parts by weight or less, 90 parts by weight or less, 75 parts by weight or less, 50 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 1 part by weight or more and 95 parts by weight or less, 1 part by weight or more and 90 parts by weight or less, 1 part by weight or more and 75 parts by weight or less, 1 part by weight or more and 50 parts by weight or less, 1 part by weight or more and 30 parts by weight or less, 1 part by weight or more and 10 parts by weight or less. 5 parts by weight or more and 20 parts by weight or less, 5 parts by weight or more and 95 parts by weight or less, 5 parts by weight or more and 90 parts by weight or less, 5 parts by weight or more and 75 parts by weight or less, 5 parts by weight or more and 50 parts by weight or less, 5 parts by weight or more and 30 parts by weight or less, 5 parts by weight or more and 20 parts by weight or less, 10 parts by weight or more and 95 parts by weight or less, 10 parts by weight or more and 90 parts by weight or less, 10 parts by weight or more and 75 parts by weight or less, 10 parts by weight or more and 50 parts by weight or less, 10 parts by weight or more and 30 parts by weight or less, or 10 parts by weight or more and 20 parts by weight or less.

[0169] Since the monomer represented by Chemical Formula 5 is included in an amount of 95 parts by weight or less based on 100 parts by weight of the glycolide monomer, the effects of improving heat resistance and biodegradability of the prepared polyester polyol copolymer and improving moisture and gas barrier properties may be achieved.

[0170] Meanwhile, the preparation method of the polyester polyol copolymer involves a ring-opening polymerization reaction of glycolide, and is therefore carried out in the presence of a glycolide ring-opening catalyst. Preferably, the step of subjecting the glycolide monomer and the monomer represented by Chemical Formula 5 to ring-opening polymerization in the presence of the compound represented by Chemical Formula 4 to prepare the polyester polyol copolymer may be carried out in the presence of a catalyst represented by the following Chemical Formula 6.

[0171] [Chemical formula 6]

[0172] MA 1 p A 2 2-p

[0173] Wherein in Chemical Formula 6, M is Al, Mg, Zn, Ca, Sn, Fe, Y, Sm, Lu, Ti or Zr, and

[0174] p is an integer from 0 to 2, and A 1 and A 2 Each is independently an alkoxy group or a carboxyl group. For example, the catalyst represented by Chemical Formula 4 may be tin(II)-2-ethylhexanoate (Sn(Oct)2).

[0175] In the step of subjecting the glycolide monomer and the monomer represented by Chemical Formula 5 to ring-opening polymerization in the presence of the compound represented by Chemical Formula 4 to prepare the polyester polyol copolymer, the catalyst represented by Chemical Formula 6 may be included in an amount of 0.001 parts by weight or less, based on 100 parts by weight of the compound represented by Chemical Formula 4, the glycolide monomer, and the monomer represented by Chemical Formula 5 in total.

[0176] Specifically, in the step of subjecting the glycolide monomer and the monomer represented by Chemical Formula 5 to ring-opening polymerization in the presence of the compound represented by Chemical Formula 4 to prepare the polyester polyol copolymer, the catalyst represented by Chemical Formula 6 may be included in an amount of 0.0001 parts by weight or more, 0.0002 parts by weight or more, 0.0003 parts by weight or more, 0.0004 parts by weight or more, 0.001 parts by weight or less, 0.0008 parts by weight or less, 0.0005 parts by weight or less, 0.0001 parts by weight or more and 0.001 parts by weight or less, 0.0002 parts by weight or more and 0.001 parts by weight or more, based on 100 parts by weight in total of the compound represented by Chemical Formula 4, the glycolide monomer, and the monomer represented by Chemical Formula 5. 0.0004 parts by weight or more and 0.001 parts by weight or less, 0.0001 parts by weight or more and 0.0008 parts by weight or less, 0.0002 parts by weight or more and 0.0008 parts by weight or less, 0.0003 parts by weight or more and 0.0008 parts by weight or less, 0.0004 parts by weight or more and 0.0008 parts by weight or less, 0.0001 parts by weight or more and 0.0005 parts by weight or less, 0.0002 parts by weight or more and 0.0005 parts by weight or less, 0.0003 parts by weight or more and 0.0005 parts by weight or less, or 0.0004 parts by weight or more and 0.0005 parts by weight or less.

[0177] In the step of subjecting the glycolide monomer and the monomer represented by Chemical Formula 5 to ring-opening polymerization in the presence of the compound represented by Chemical Formula 4 to prepare the polyester polyol copolymer, the catalyst represented by Chemical Formula 6 is included in an amount of 0.001 parts by weight or less based on 100 parts by weight in total of the compound represented by Chemical Formula 4, the glycolide monomer, and the monomer represented by Chemical Formula 5, the content of impurities in the prepared polyester polyol copolymer is minimized, and thus an excellent tensile elongation of 100% or more can be achieved.

[0178] In the preparation method of the polyester polyol copolymer, the additive including the catalyst represented by Chemical Formula 6 may be included in an amount of 0.0001 parts by weight or more, 0.0002 parts by weight or more, 0.0003 parts by weight or more, 0.0004 parts by weight or more, 0.001 parts by weight or less, 0.0008 parts by weight or less, 0.0005 parts by weight or less, 0.0001 parts by weight or more and 0.001 parts by weight or less, 0.0002 parts by weight or more and 0.001 parts by weight or less, 0.0003 parts by weight or more and 0.0004 parts by weight or more, 0.001 parts by weight or more and 0.0008 parts by weight or less, 0.0005 parts by weight or less, 0.0001 parts by weight or more and 0.001 parts by weight or less, 0.0002 parts by weight or more and 0.001 parts by weight or less, 0.0003 parts by weight or more and 0.0004 parts by weight or more, 0.0004 parts by weight or more and 0.001 parts by weight or less, 0.0001 parts by weight or more and 0.0008 parts by weight or less, 0.0002 parts by weight or more and 0.0008 parts by weight or less, 0.0003 parts by weight or more and 0.0008 parts by weight or less, 0.0004 parts by weight or more and 0.0008 parts by weight or less, 0.0001 parts by weight or more and 0.0005 parts by weight or less, 0.0002 parts by weight or more and 0.0005 parts by weight or less, 0.0003 parts by weight or more and 0.0005 parts by weight or less, 0.0004 parts by weight or more and 0.0005 parts by weight or less.

[0179] In the method for preparing a polyester polyol copolymer, since an additive such as a catalyst represented by Chemical Formula 6 may be included in an amount of 0.001 parts by weight or less based on a total of 100 parts by weight of the compound represented by Chemical Formula 4, the glycolide monomer, and the monomer represented by Chemical Formula 5, the content of impurities in the prepared polyester polyol copolymer is minimized, and thus an excellent tensile elongation of 100% or more may be achieved.

[0180] Preferably, in the method for preparing the polyester polyol copolymer, the step of subjecting the glycolide monomer and the monomer represented by Chemical Formula 5 to ring-opening polymerization in the presence of the compound represented by Chemical Formula 4 to prepare the polyester polyol copolymer is performed at a temperature of 150° C. to 200° C. Preferably, the step of subjecting the glycolide monomer and the monomer represented by Chemical Formula 5 to ring-opening polymerization in the presence of the compound represented by Chemical Formula 4 to prepare the polyester polyol copolymer is performed for 5 minutes to 10 hours, more preferably 10 minutes to 1 hour.

[0181] According to one embodiment of the present disclosure, a molded article molded from a resin composition including the above polyester polyol copolymer may be provided. In addition to the polyester polyol copolymer, the resin composition including the copolymer may further include other additives for improving physical properties.

[0182] The molded article may include one or more molded articles selected from the group consisting of an injection molded article, an extrusion molded article, a blow molded article, a fiber, a nonwoven fabric, a foam, a film, and a sheet.

[0183] The use of the molded product is not particularly limited, but for example, the molded product may be electronic materials, building materials, food packaging, food containers (disposable cups, trays, etc.), industrial products, agricultural products (eg, covering films), etc.

[0184] Beneficial Effects

[0185] According to the present disclosure, a polyester polyol copolymer and a method for preparing the polyester polyol copolymer can be provided, the polyester polyol copolymer being excellent in biodegradability and showing excellent physical properties such as tensile strength and elastic modulus and having improved elongation at the same time. DETAILED DESCRIPTION

[0186] Hereinafter, the present disclosure will be described in detail with reference to the following examples. However, these examples are for illustrative purposes only, and the scope of the present disclosure is not limited thereto.

[0187] <Examples and Comparative Examples>

[0188] Example 1

[0189] 90 g (0.03 mol) of poly(trimethylene ether) glycol (n=33, number average molecular weight: 3000 g / mol), 189 g (1.63 mol) of glycolide, and 21 g (0.15 mol) of lactide were added to a 500 mL Teflon-coated round flask, and the temperature was adjusted to room temperature.

[0190] After 135 mg of tin (II) 2-ethylhexanoate was added to the flask, the flask was placed in an oil bath, the temperature was raised to 220° C. under a nitrogen atmosphere, and the mixture was subjected to a ring-opening polymerization reaction while stirring at 200 rpm for 2 hours. After the reaction was completed, the remaining monomers were removed by a devolatilization step of the product to obtain a polyester polyol copolymer.

[0191] Example 2

[0192] A polyester polyol copolymer was prepared in the same manner as in Example 1, except that in Example 1, 90 g (0.03 mol) of poly(trimethylene ether) glycol (n=33, number average molecular weight: 3000 g / mol), 169.3 g (1.46 mol) of glycolide and 40.6 g (0.29 mol) of lactide were added.

[0193] Comparative Example 1

[0194] A polyester polyol copolymer was prepared in the same manner as in Example 1, except that in Example 1, 90 g (0.03 mol) of poly(trimethylene ether) glycol (n=33, number average molecular weight: 3000 g / mol) and 210 g (1.81 mol) of glycolide were added without lactide.

[0195] Comparative Example 2

[0196] A polyester polyol copolymer was prepared in the same manner as in Example 1, except that in Example 1, 90 g (0.03 mol) of poly(trimethylene ether) glycol (n=33, number average molecular weight: 3000 g / mol) and 210 g (1.46 mol) of lactide were added instead of glycolide, and the temperature was raised to 170°C under a nitrogen atmosphere.

[0197] Comparative Example 3

[0198] A polyester polyol copolymer was prepared in the same manner as in Example 1, except that in Example 1, 90 g (0.03 mol) of poly(trimethylene ether) glycol (n=33, number average molecular weight: 3000 g / mol), 105 g (0.91 mol) of glycolide and 105 g (0.73 mol) of lactide were added so that the weight ratio of glycolide to lactide was 1:1.

[0199] Comparative Example 4

[0200] A polyester polyol copolymer was prepared in the same manner as in Example 1, except that in Example 1, 90 g (1.18 mol) of 1,3-propylene glycol, 105 g (0.91 mol) of glycolide and 105 g (0.73 mol) of lactide were added instead of poly(trimethylene ether) glycol (n=33, number average molecular weight: 3000 g / mol).

[0201] When the temperature was increased to 220° C. under a nitrogen atmosphere as in Example 1, it was confirmed that 1,3-propylene glycol having a boiling point of 210° C. disappeared, and the content of the repeating unit derived from 1,3-propylene glycol in the finally prepared polyester polyol copolymer was extremely small.

[0202] Furthermore, unlike Example 1, when the temperature was increased to 190° C., it was confirmed that glycolide was not sufficiently melted, and thus the molecular weight of the finally prepared polyester polyol copolymer was small, thus making it impossible to measure its physical properties.

[0203] Evaluate

[0204] (1) GPC (gel permeation chromatography) analysis

[0205] The number average molecular weight (Mn) of the polyester polyol copolymers of Examples and Comparative Examples was measured using gel permeation chromatography (GPC, Waters E2640).

[0206] Specifically, the polyester polyol copolymer of the embodiment and the comparative example is dissolved in HFIP (hexafluoroisopropanol) to a concentration of 2mg / ml, respectively, and then 20μl of the dissolved solution is injected into GPC. HFIP is used as the mobile phase for GPC, with a flow rate of 1.0mL / min, and GPC analysis is performed at 40°C. The column is two Agilent Mixed-B units connected in series. RI detector is used as a detector. The value of Mw is obtained using a calibration curve formed using polymethyl methacrylate (PMMA). Nine polystyrene standard samples with a weight average molecular weight of 2,000g / mol, 10,000g / mol, 30,000g / mol, 70,000g / mol, 200,000g / mol, 700,000g / mol, 2,000,000g / mol, 4,000,000g / mol and 10,000,000g / mol are used.

[0207] (3) Evaluation of physical properties

[0208] The tensile strength, Young's modulus, and tensile elongation of the polyester polyol copolymers of Examples and Comparative Examples were measured.

[0209] Specifically, the evaluation was performed according to ASTM D638. An ASTM D536 V-type test specimen was produced at 190 to 200°C using a hot press device (Limotem QM900S), and then measured using a UTM device (Universal Testing Machine) at a load of 10 mm / sec and 60 kg / f.

[0210] [Table 1]

[0211] Number average molecular weight (g / mol) Tensile strength(MPa) Young's modulus (MPa) Tensile elongation (%) Example 1 39500 17 970 290 Example 2 38000 25 885 245 Comparative Example 1 34000 52 1060 85 Comparative Example 2 25200 24 186 90 Comparative Example 3 34800 40 640 120 Comparative Example 4 Unable to measure Unable to measure Unable to measure Unable to measure

[0212] According to Table 1, it can be determined that the polyester polyol copolymer of the embodiment exhibits a tensile elongation of 245% or more, so that the elongation is ensured, which makes it possible to measure physical properties through thermoforming and processing. On the other hand, it can be determined that the polyester polyol copolymers of Comparative Examples 1 to 3 exhibit a tensile elongation of 120% or less, showing poor tensile elongation compared with the embodiment.

[0213] Furthermore, it was confirmed that the physical properties of the polyester polyol copolymer of Comparative Example 4 could not be measured.

[0214] (4) Measurement of biodegradation degree

[0215] Under the home composting conditions of EN17427, the biodegradation degrees of cellulose as a standard material and the polyester polyol copolymers of Examples and Comparative Examples were measured.

[0216] Specifically, under home composting conditions (28°C, aerobic composting conditions), the moisture content in the compost was set to 50%, and then the compost and the polymer were mixed at a weight ratio of 10:1 to measure the generated CO2. Degradation (%) refers to the value obtained by calculating the mass of water and CO2 degraded based on the initial mass of the sample. In addition, for comparison, the results were compared with the biodegradation measurement results of cellulose (Sigma Aldrich, cellulose, catalog number 310697) as a standard substance.

[0217] As a result of the degradation measurement of the polyester polyol copolymer of Example 1, it was determined that the copolymer decomposed by about 29% or more based on its initial mass within 30 days. Thus, it was determined that the segmented polyester polyol copolymer of Example 1 had biodegradable characteristics even under relatively mild home composting conditions.

Claims

1. A polyester polyol copolymer comprising: A repeating unit represented by the following Chemical Formula 1, a repeating unit represented by the following Chemical Formula 2, and a repeating unit represented by the following Chemical Formula 3, wherein the repeating unit represented by Chemical Formula 3 is included in an amount of 95 parts by weight or less based on 100 parts by weight of the repeating unit represented by Chemical Formula 2: [Chemical formula 1] Wherein in Chemical Formula 1, L1 is an alkylene group having 3 or less carbon atoms, and n is an integer of 3 or greater, [Chemical formula 2] [Chemical formula 3] Wherein in chemical formula 3, L2 is an alkylene group having 2 or more carbon atoms.

2. The polyester polyol copolymer according to claim 1, wherein: The repeating unit represented by Chemical Formula 3 is included in an amount of 0.01 mol or more and less than 0.25 mol based on 1 mol of the repeating unit represented by Chemical Formula 2.

3. The polyester polyol copolymer according to claim 1, wherein: The repeating unit represented by Chemical Formula 1 includes a repeating unit represented by the following Chemical Formula 1-1: [Chemical formula 1-1] Wherein in Chemical Formula 1-1, R1 to R6 are each independently hydrogen or alkyl, and n is an integer of 5 or more.

4. The polyester polyol copolymer according to claim 1, wherein: In Chemical Formula 1, n is an integer of 5 or more and 5000 or less.

5. The polyester polyol copolymer according to claim 1, wherein: The polyester polyol copolymer includes the repeating unit represented by Chemical Formula 1 in an amount of 5 wt % or more and 95 wt % or less based on the entire repeating units.

6. The polyester polyol copolymer according to claim 1, wherein: The repeating unit represented by Chemical Formula 2 is included in an amount of 10 moles or more based on 1 mole of the repeating unit represented by Chemical Formula 1.

7. The polyester polyol copolymer according to claim 1, wherein: The repeating unit represented by Chemical Formula 3 is included in an amount of 1.1 moles or more based on 1 mole of the repeating unit represented by Chemical Formula 1.

8. The polyester polyol copolymer according to claim 1, wherein: The copolymer comprises a repeating unit represented by the following Chemical Formula 7: [Chemical formula 7] Wherein in Chemical Formula 7, m is an integer of 2 or more.

9. The polyester polyol copolymer according to claim 1, wherein: The copolymer comprises a repeating unit represented by the following Chemical Formula 8: [Chemical formula 8] Wherein in chemical formula 8, p is an integer of 2 or more.

10. The polyester polyol copolymer according to claim 1, wherein: The copolymer includes a structure in which any one selected from a repeating unit represented by the following Chemical Formula 7 and a repeating unit represented by the following Chemical Formula 8 is bonded to both ends of a functional group of the following Chemical Formula 9, [Chemical formula 7] Wherein in Chemical Formula 7, m is an integer of 2 or greater, [Chemical formula 8] In chemical formula 8, p is an integer of 2 or greater, [Chemical formula 9] 11. The polyester polyol copolymer according to claim 1, wherein: The polyester polyol copolymer has a weight average molecular weight of 10,000 g / mol or more and 500,000 g / mol or less.

12. The polyester polyol copolymer according to claim 1, wherein: The polyester polyol copolymer has a tensile elongation of 100% or more.

13. A method for preparing a polyester polyol copolymer, comprising: subjecting a glycolide monomer and a monomer represented by the following Chemical Formula 5 to ring-opening polymerization in the presence of a compound represented by the following Chemical Formula 4 to prepare a polyester polyol copolymer, Wherein the monomer represented by Chemical Formula 5 is included in an amount of 95 parts by weight or less based on 100 parts by weight of the glycolide monomer: [Chemical formula 4] Wherein in chemical formula 4, L1 is an alkylene group having 3 or less carbon atoms, and n is an integer of 5 or greater, [Chemical formula 5] Wherein in Chemical Formula 5, L2 is an alkylene group having 2 or more carbon atoms.

14. The method for preparing a polyester polyol copolymer according to claim 13, wherein: The polyester polyol copolymer includes the repeating unit derived from the compound represented by Chemical Formula 4 in an amount of 5 wt % or more and 95 wt % or less based on the entire repeating units.

15. The method for preparing a polyester polyol copolymer according to claim 13, wherein: The compound represented by Chemical Formula 4 has a weight average molecular weight of 500 g / mol to 10,000 g / mol.

16. The method for preparing a polyester polyol copolymer according to claim 13, wherein: Subjecting the glycolide monomer and the monomer represented by Chemical Formula 5 to ring-opening polymerization in the presence of the compound represented by Chemical Formula 4 to prepare a polyester polyol copolymer is carried out in the presence of a catalyst represented by the following Chemical Formula 6: [Chemical formula 6] MA 1 p A 2 2-p Wherein in Chemical Formula 6, M is Al, Mg, Zn, Ca, Sn, Fe, Y, Sm, Lu, Ti or Zr, p is an integer from 0 to 2, A 1 and A 2 Each is independently an alkoxy group or a carboxyl group.

17. The method for preparing a polyester polyol copolymer according to claim 16, wherein: In subjecting the glycolide monomer and the monomer represented by Chemical Formula 5 to ring-opening polymerization in the presence of the compound represented by Chemical Formula 4 to prepare the polyester polyol copolymer, The catalyst represented by Chemical Formula 6 is included in an amount of 0.001 parts by weight or less based on 100 parts by weight in total of the compound represented by Chemical Formula 4, the glycolide monomer, and the monomer represented by Chemical Formula 5.

18. The method for preparing a polyester polyol copolymer according to claim 16, wherein: The catalyst is tin(II) 2-ethylhexanoate.

19. A molded product molded from a resin composition comprising the polyester polyol copolymer according to claim 1.

20. The shaped article according to claim 19, wherein The molded article includes one or more molded articles selected from the group consisting of injection molded articles, extrusion molded articles, blow molded articles, fibers, nonwoven fabrics, foams, films, and sheets.

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