Method for preparing polyol copolymer and polyol copolymer prepared therefrom

Abstract

According to the present invention, a novel compound formed by a reaction of a polymerized biomass-based 3-hydroxypropionic acid with a polyester-based polyol and a polyether-carbonate-based polyol may be provided. Accordingly, a biomass-based eco-friendly polyol copolymer capable of achieving both physical properties similar to those of polyester polyol and polyether-carbonate-based properties may be provided.

Description

Method for producing a polyol copolymer and a polyol copolymer produced therefrom

[0001] The present invention relates to a method for producing a polyol copolymer and a polyol copolymer produced thereby.

[0002] Polyurethane resins are raw materials for a wide range of plastic products. These polyurethane resins contain urethane bonds within their molecules and are primarily synthesized through the reaction between diisocyanate and polyol.

[0003] The types of diisocyanates used in polyurethane polymerization are mainly prepolymers based on methylene diisocyanate (MDI) and toluene diisocyanate (TDI) and their derivatives, and other isocyanate series are used in other special fields.

[0004] The polyol used here refers to an active hydrogen compound used in polyurethane (PU) by reacting with isocyanate, and having two or more active hydrogen groups such as hydroxyl groups, carboxyl groups, and amine groups in the molecule. These polyols are classified for use according to their molecular weight. The polyols mainly used are polyether polyols with aromatic groups in the main chain and aliphatic polyester polyols with aliphatic groups in the main chain. Polyether polyols have excellent hydrolysis resistance and low-temperature properties, so they are widely used in PU Form and soft foam, and representative polyether polyols include PPG (propylene glycol), PTMEG (tetramethylene glycol), and PEG (ethylene glycol).

[0005] Polyester polyols offer excellent PU abrasion resistance, tear strength, flexibility, oil resistance, heat resistance, and elasticity, but they are susceptible to hydrolysis by water. To improve hydrolysis resistance, polycaprolactone (PCL) polyol, polycarbonate-based polyols, or polyether-based polyols can be used. These are primarily used in rigid polyurethane, insulation, artificial wood, refrigerators, freezer containers, and adhesives.

[0006]

[0007] Typically, polyurethane resins are made primarily from polyester polyols, which are made by reacting adipic acid and glycol, both refined from petroleum. However, this method poses environmental problems, as the manufacturing process can cause various types of environmental pollution, and large amounts of carbon dioxide are emitted during post-use disposal.

[0008] From an environmental perspective, resource recycling is a critical issue, and considering ESG considerations, the development of sustainable, eco-friendly bio-polyols is essential. Therefore, the bio-polyols required for development can be manufactured using natural plant-based oils such as castor oil, soybean oil, and rapeseed oil, or wood-based biomaterials such as cellulose and lignin.

[0009] These bio-polyols share a similar chemical structure to conventional polyols, yet offer the advantage of being derived from renewable natural resources rather than chemical products. However, conventional polyurethanes made from bio-polyols exhibit physical properties that are inferior to conventional polyurethanes in many ways. These include easy discoloration, poor durability (e.g., flexural and compressive strength), and unpleasant odors. This has limited their use.

[0010]

[0011] Therefore, it has become necessary to develop an eco-friendly polyol copolymer based on biomaterials that overcomes the above shortcomings and has excellent mechanical properties.

[0012]

[0013] Moreover, polyurethane possesses excellent abrasion resistance, oil resistance, solvent resistance, and elasticity, making it applicable to numerous fields such as adhesives, coatings, injection molded products, paints, inks, coatings, foaming agents, shoe parts, clothing, and medical polymers. Accordingly, polyurethanes require diverse structures and molecular weights depending on the application, necessitating the development of polyols tailored to the specific application. In particular, molecular weight is a crucial factor that can affect the mechanical strength and overall physical properties of polymerized urethanes, leading to a demand for polyols graded by molecular weight in related development industries and across industries.

[0014] Therefore, a method for producing an eco-friendly polyol copolymer with easy molecular weight control that can be applied to various fields is required.

[0015] The purpose of the present invention is to provide a method for producing a novel polyol copolymer having excellent physical properties while using biomass-based materials, and also being applicable to various fields and having easy control of molecular weight.

[0016] Another object of the present invention is to provide a novel polyol copolymer having excellent physical properties while using biomass-based materials.

[0017] A method for producing a polyol copolymer according to a first embodiment of the present invention for achieving the above-described task comprises: (a) a step of polymerizing 3-hydroxypropionic acid; and (b) a step of reacting the polymerized 3-hydroxypropionic acid with a compound represented by Chemical Formula 1 to produce a polyol copolymer.

[0018]

[0019] [Chemical Formula 1-1]

[0020]

[0021] (In Chemical Formula 1-1, R1 and R2 are the same or different, R1 and R2 are alkyl groups having 2 to 10 carbon atoms, and p is an integer greater than or equal to 1.)

[0022]

[0023] In addition, the polyol according to the first embodiment of the present invention for achieving the above-described task is manufactured by the above-described manufacturing method and includes a compound represented by the following chemical formula 2.

[0024]

[0025] [Chemical Formula 1-2]

[0026]

[0027] (In Chemical Formula 1-2, R1 and R2 are the same or different, R1 and R2 are alkyl groups having 2 to 10 carbon atoms, n and p are integers greater than or equal to 1, and m is an integer greater than or equal to 0.)

[0028]

[0029] A method for producing a polyol copolymer according to a second embodiment of the present invention comprises: (a) a step of polymerizing 3-hydroxypropionic acid; and (b) a step of reacting the polymerized 3-hydroxypropionic acid with a compound represented by Chemical Formula 2-1 to produce a polyol copolymer.

[0030]

[0031] [Chemical Formula 2-1]

[0032]

[0033] (In Chemical Formula 2-1, R1 and R2 are the same or different, R1 and R2 are hydrogen or an alkyl group having 1 to 10 carbon atoms, and n and m are integers greater than or equal to 1.)

[0034]

[0035] In addition, a polyol copolymer according to the second embodiment of the present invention for achieving the above-described task is manufactured by the above-described manufacturing method and includes a compound represented by the following chemical formula 2-2.

[0036]

[0037] [Chemical Formula 2-2]

[0038]

[0039] (In Chemical Formula 2-2, R1 and R2 are the same or different, R1 and R2 are hydrogen or an alkyl group having 1 to 10 carbon atoms, n, m and p are integers greater than or equal to 1, and q is an integer greater than or equal to 0.)

[0040] The manufacturing method of the present invention can manufacture a novel polyol copolymer having excellent physical properties while using a biomass-based material.

[0041] In addition, the manufacturing method of the present invention can manufacture a novel polyol copolymer that can contribute to the expression of excellent mechanical properties of a polyol copolymer while easily controlling the molecular weight of the polyol by introducing a step polymerization method.

[0042]

[0043] Hereinafter, the method for producing a polyol copolymer of the present invention and the polyol copolymer produced therefrom will be specifically described with reference to the attached chemical formula and table.

[0044]

[0045] (First implementation)

[0046]

[0047] Method for producing polyol copolymer

[0048]

[0049] First, the method for producing the polyol copolymer of the present invention will be described in detail.

[0050]

[0051] The method for producing a polyol of the present invention comprises: (a) a step of polymerizing 3-hydroxypropionic acid; and (b) a step of reacting the polymerized 3-hydroxypropionic acid with a compound represented by chemical formula 1-1 to produce a polyol copolymer.

[0052]

[0053] [Chemical Formula 1-1]

[0054]

[0055] In chemical formula 1-1, R1 and R2 are the same or different, R1 and R2 are alkyl groups having 2 to 10 carbon atoms, and p is an integer greater than or equal to 1.

[0056]

[0057] Polyol copolymers can have various molecular weights depending on the application. Accordingly, it is desirable to polymerize 3-hydroxypropionic acid contained in the polyol copolymer to produce poly-3-hydroxypropionic acid.

[0058] To this end, the manufacturing method of the present invention includes a step of (a) polymerizing 3-hydroxypropionic acid.

[0059]

[0060] Here, a catalyst can be used when polymerizing 3-hydroxypropionic acid to induce poly-3-hydroxypropionic acid.

[0061]

[0062] At this time, the catalyst may include a Bronsted acid catalyst, a Lewis acid catalyst, or a mixed catalyst in which the Bronsted acid catalyst and the Lewis acid catalyst are mixed.

[0063] Preferably, the Bronsted acid catalyst may include at least one of methanesulfonic acid (MSA), p-toluenesulfonic acid (p-TSA), an ion exchange resin containing a sulfonic acid group, H2SO4, HCL, H2CO3, HNO3, HBF4, HSbF6, ClSO3H, FSO3H, CF3SO3H, and CH3SO3H.

[0064] Here, the ion exchange resin containing the sulfonic acid group may include at least one of Amberlyst 15, Amberlyst 36, Amberlyst 39, and Amberlite IR 120.

[0065] In addition, the Lewis acid catalyst is Tin(II) 2-ethylhexanoate(TEH), Tin(II) Chloride(SnCl2), titanium isopropoxide(TIP), titanium tetrabutoxide(TBO), Dibutyltin diacetate, Dibutyltin dibromide, Dibutyltin dichloride, Dibutyltin dilaurate, Dibutyltin dimethoxide, Dibutyltin oxide, Dimethyltin diacetate, Dimethyltin dibromide, Diphenyltin dichloride, Diphenyltin oxide, Methyltin trichloride, Phenyltin trichloride, Tin(IV) acetate, Tin(IV) bromide, Tin(IV) chloride, Tin(IV) iodide, Tin(II) oxide, Tin(II) acetate, Tin(II) bromide, Tin(II) iodide, BCl3, BBr3, BF3, tris(pentafluorophenyl)borane, tris(trifluoromethylphenyl)borane, It may include at least one of tris((3,5-trifluoromethyl)phenyl)borane and tris(tetrafluoro-o-tolyl)borane.

[0066]

[0067] Here, the molecular weight of the polyol can be controlled depending on the type and content of the catalyst.

[0068] The above catalyst can be used in an amount of 1 to 100 parts by weight relative to 100 parts by weight of the above 3-hydroxypropionic acid.

[0069]

[0070] In addition, it is preferable that the step (a) is performed at a temperature of 30 to 300°C and a pressure of 0.1 to 700 torr. More preferably, the step (a) can be performed at a temperature of 50 to 150°C and a pressure of 0.1 to 300 torr, and even more preferably, the step (a) can be performed at a temperature of 70 to 150°C and a pressure of 0.1 to 150 torr.

[0071]

[0072] Next, the manufacturing method of the present invention includes a step of (b) producing a polyol copolymer by reacting polymerized 3-hydroxypropionic acid with a compound represented by chemical formula 1-1.

[0073]

[0074] [Chemical Formula 1-1]

[0075]

[0076] In chemical formula 1-1, R1 and R2 are the same or different, R1 and R2 are alkyl groups having 2 to 10 carbon atoms, and p is an integer greater than or equal to 1.

[0077]

[0078] The present invention can increase the number of alkyl chains by copolymerizing poly-3-hydroxypropionic acid with the compound represented by the above chemical formula 1. Accordingly, the polyol copolymer of the present invention can control mechanical strength, flexibility, elongation, etc. In addition, the physical properties of polyurethane can be improved by using the polyol copolymer of the present invention.

[0079]

[0080] In the above chemical formula 1-1, the number of alkyl chains can be changed by changing the types of R1 and R2. In the present invention, R1 and R2 may be alkyl groups having 2 to 10 carbon atoms, and preferably, R1 and R2 may be aliphatic hydrocarbons having 2 to 10 carbon atoms.

[0081]

[0082] In the manufacturing method of the present invention, when reacting the polymerized poly-3-hydroxypropionic acid with the compound represented by the above chemical formula 1-1, it is preferable that the reaction be performed at a temperature of 30 to 300°C and a pressure of 0.1 to 700 torr. More preferably, the step (b) may be performed at a temperature of 50 to 150°C and a pressure of 0.1 to 300 torr, and even more preferably, the step (b) may be performed at a temperature of 70 to 150°C and a pressure of 0.1 to 150 torr.

[0083]

[0084] In addition, the method for producing a polyol copolymer of the present invention may further include, after step (b), a step (c) of removing unreacted monomers by lowering the pressure compared to the pressure of step (b).

[0085] Here, step (c) may be performed at the same temperature as step (b), but is performed under a pressure lower than the pressure controlled in step (b).

[0086] The above step (c) can be performed at a temperature of 30 to 300°C and a pressure of 0.1 to 500 torr, but the pressure is lower than the pressure of step (b).

[0087]

[0088] In addition, the method for producing a polyol copolymer of the present invention may further include, after step (b), a purification step (d) of adding the polyol copolymer to a solution containing a polar solvent and / or an anion exchange resin and stirring.

[0089]

[0090] The polyol copolymer manufactured through the manufacturing method of the present invention described above may contain unreacted oligomers and monomers that have not been polymerized or oligomerized.

[0091] The above unreacted oligomer and unreacted monomer may mean an oligomer and monomer having a molecular weight of less than 400, preferably less than 300, and more preferably less than 90.

[0092]

[0093] Unreacted oligomers and unreacted monomers contained in the above polyol copolymer can lower the degree of polymerization of polyurethane and deteriorate the mechanical properties of polyurethane.

[0094] Accordingly, the method of the present invention can remove unreacted oligomers and unreacted monomers having low molecular weight contained in the polyol copolymer by using the step (d) described above.

[0095]

[0096] (d) According to step (d), the polyol copolymer is introduced into a solution containing a polar solvent and / or an anion exchange resin. As the mixture of the polyol copolymer and the solution is stirred, polymers having a molecular weight of 400 or more contained in the polyol copolymer are precipitated in a solid state, and unreacted oligomers and unreacted monomers are mostly dissolved in the solution due to the difference in polarity of the polar solvent. Therefore, by utilizing this, polyol copolymers having low molecular weight and high molecular weight can be separated, and extraction can be performed smoothly.

[0097] The polar solvent is not particularly limited as long as it is a solvent substance having polarity. Preferably, the polar solvent may include water, alcohol, or a polar mixed solvent of water and alcohol.

[0098] In addition, the type of the alcohol is not limited, and the alcohol may include at least one of methanol, ethanol, n-propanol, n-butanol, n-pentanol, n-hexanol, n-heptanol, n-octanol, n-nonanol, and n-decanol as a straight chain alkanol (ROH), preferably at least one of methanol, ethanol, n-propanol, n-butanol, n-pentanol, n-hexanol, n-heptanol, and n-octanol, and more preferably at least one of methanol, ethanol, n-propanol, n-butanol, n-pentanol, and n-hexanol.

[0099]

[0100] In addition, the solution may include an anion exchange resin. Preferably, in the present invention, the polar solvent and the anion exchange resin can be used to maximize the removal of unreacted oligomers and unreacted monomers having small molecular weights contained in the polyol copolymer. Specifically, the basic atom group and terminal chloride ions contained in the anion exchange resin can ion-exchange molecules having hydroxide ions. By the ion exchange action described above, unreacted oligomers and unreacted monomers having small molecular weights contained in the polyol copolymer can be removed.

[0101]

[0102] In the present invention, an anion exchange resin having the above-described functional effect can be used without limitation, but preferably, the anion exchange resin may include an ammonium group or an amine group as a functional group.

[0103]

[0104] In addition, the anion exchange resin containing a basic atomic group such as the ammonium group or amine group may be, for example, an anion exchange resin having a primary amine group, a secondary amine group, a tertiary amine group, or a polyamine group. Preferably, an anion exchange resin having a tertiary amine group, for example, a trimethyl amine group, or an anion exchange resin having a polyamine group may be used.

[0105] As an anion exchange resin containing a basic atomic group such as the above ammonium group or amine group, brands such as TRILITE (SAR11), TRILITE (AW90), and LEWATIT (A365) can be used.

[0106]

[0107] These anion exchange resins can be used in gel, porous, or seeded forms and can have narrow or broad particle size distributions. Furthermore, they are classified as strongly basic or weakly basic anion exchange resins based on the basicity of their atomic groups, which allows them to have different ion exchange capacities and selectivities.

[0108]

[0109] Additionally, the above anion exchange resins can be used alone or in combination of two or more.

[0110]

[0111] After the above-described step (d), the solution including the polar solvent and the anion exchange resin can be removed, and a purified polyol copolymer can be obtained.

[0112]

[0113] The step (d) above may be performed for 10 hours or less under stirring conditions of 2000 rpm or less and a temperature range of 10 to 50°C so as to efficiently remove the unreacted oligomers and unreacted monomers. More preferably, the step (b) above may be performed for 10 minutes to 6 hours under stirring conditions of 25 to 35°C and a temperature range of 200 to 800 rpm.

[0114]

[0115] As described above, the polyol copolymer of the present invention can have various characteristics depending on the type of compound represented by chemical formula 1-1 and the polymerization reaction conditions.

[0116]

[0117] polyol copolymer

[0118]

[0119] Next, the polyol copolymer of the present invention will be described.

[0120]

[0121] The polyol copolymer of the present invention is manufactured by the above-described method and is formed by reacting polymerized 3-hydroxypropionic acid with a compound represented by chemical formula 1-1.

[0122] More specifically, the polyol copolymer of the present invention comprises a compound represented by the following chemical formula 1-3.

[0123]

[0124] [Chemical Formula 1-2]

[0125]

[0126] In chemical formula 1-2, R1 and R2 are the same or different, R1 and R2 are alkyl groups having 2 to 10 carbon atoms, n and p are integers greater than or equal to 1, and m is an integer greater than or equal to 0.

[0127]

[0128] The polyol copolymer of the present invention uses bio-based 3-hydroxypropionic acid represented by the following chemical formula 1-2.

[0129]

[0130] [Chemical Formula 1-3]

[0131]

[0132]

[0133] The above 3-hydroxypropionic acid can be produced through a pure chemical process, but it can also be produced through a separation and purification process from a low-concentration 3-HP culture solution produced through a microbial-based fermentation process. In the present invention, it is preferred to use a bio-based 3-hydroxypropionic acid.

[0134]

[0135] The polyol copolymer of the present invention includes a compound such as the chemical formula 1-2 formed by reacting a poly 3-hydroxypropionic acid polymerized with the 3-hydroxypropionic acid and a compound represented by the chemical formula 1.

[0136]

[0137] [Chemical Formula 1-1]

[0138]

[0139] In chemical formula 1-1, R1 and R2 are the same or different, R1 and R2 are alkyl groups having 2 to 10 carbon atoms, and p is an integer greater than or equal to 1.

[0140]

[0141] The present invention can increase the number of alkyl chains by copolymerizing poly-3-hydroxypropionic acid with the compound represented by the above chemical formula 1-1. Accordingly, the polyol copolymer of the present invention can control mechanical strength, flexibility, elongation, etc. In addition, the polyol copolymer of the present invention can be used to improve the physical properties of polyurethane.

[0142]

[0143] In the above chemical formula 1-1, the number of alkyl chains can be changed by changing the types of R1 and R2. In the present invention, R1 and R2 may be alkyl groups having 2 to 10 carbon atoms, and preferably, R1 and R2 may be aliphatic hydrocarbons having 2 to 10 carbon atoms.

[0144]

[0145] The compound represented by the above chemical formula 1-1 has the OH group removed and is combined with 3-hydroxypropionic acid. In addition, the form and physical properties of chemical formula 2 may vary depending on the types of R1 and R2 in chemical formula 1.

[0146]

[0147] Preferably, the polyol copolymer of the present invention may have a number average molecular weight (Mn) of 100 to 1500 and a weight average molecular weight (Mw) of 200 to 2500.

[0148] Additionally, the hydroxyl value (Hv) of the polyol copolymer may be 10 to 1000, and preferably, the hydroxyl value (Hv) may be 100 to 200.

[0149] In addition, the acid value (Av) of the polyol copolymer may be 10 or less, and more preferably less than 2.

[0150] Additionally, the molecular weight distribution value (PDI) of the polyol copolymer may be 1 to 10. Preferably, the molecular weight distribution value (PDI) of the polyol copolymer may be 1 to 3.

[0151] Within the above-described range, a polyol copolymer that can be used for the production of polyurethane, etc. can be obtained. If a polyol copolymer having properties outside the above range is used, the properties of the polyurethane may be deteriorated.

[0152]

[0153] Polyurethane polymerization involves the bonding of isocyanate groups and polyols. Depending on the molecular weight of the polyol copolymer, the physical properties of the polymerized polyurethane, such as elasticity and mechanical strength, can vary. Furthermore, the hydroxyl value of the substituted OH groups influences polymerization characteristics. Therefore, it is crucial to develop a polyol copolymer that meets the required range of properties.

[0154]

[0155] The polyol copolymer of the present invention is a bio-based material that can satisfy all of the various properties of polyurethane required and is environmentally friendly.

[0156]

[0157] (Second implementation)

[0158]

[0159] Method for producing polyol copolymer

[0160]

[0161] First, the method for producing the polyol copolymer of the present invention will be described in detail.

[0162]

[0163] The method for producing a polyol of the present invention comprises: (a) a step of polymerizing 3-hydroxypropionic acid; and (b) a step of reacting the polymerized 3-hydroxypropionic acid with a compound represented by Chemical Formula 2-1 to produce a polyol copolymer.

[0164]

[0165] [Chemical Formula 2-1]

[0166]

[0167] In chemical formula 2-1, R1 and R2 are the same or different, R1 and R2 are hydrogen or an alkyl group having 1 to 10 carbon atoms, and n and m are integers greater than or equal to 1.

[0168]

[0169] Polyol copolymers can have various molecular weights depending on the application. Accordingly, it is desirable to polymerize 3-hydroxypropionic acid contained in the polyol copolymer to produce poly-3-hydroxypropionic acid.

[0170] To this end, the manufacturing method of the present invention includes a step of (a) polymerizing 3-hydroxypropionic acid.

[0171]

[0172] Here, a catalyst can be used when polymerizing 3-hydroxypropionic acid to induce poly-3-hydroxypropionic acid.

[0173]

[0174] At this time, the catalyst may include a Bronsted acid catalyst, a Lewis acid catalyst, or a mixed catalyst in which the Bronsted acid catalyst and the Lewis acid catalyst are mixed.

[0175] Preferably, the Bronsted acid catalyst may include at least one of methanesulfonic acid (MSA), p-toluenesulfonic acid (p-TSA), an ion exchange resin containing a sulfonic acid group, H2SO4, HCL, H2CO3, HNO3, HBF4, HSbF6, ClSO3H, FSO3H, CF3SO3H, and CH3SO3H.

[0176] Here, the ion exchange resin containing the sulfonic acid group may include at least one of Amberlyst 15, Amberlyst 36, Amberlyst 39, and Amberlite IR 120.

[0177] In addition, the Lewis acid catalyst is Tin(II) 2-ethylhexanoate(TEH), Tin(II) Chloride(SnCl2), titanium isopropoxide(TIP), titanium tetrabutoxide(TBO), Dibutyltin diacetate, Dibutyltin dibromide, Dibutyltin dichloride, Dibutyltin dilaurate, Dibutyltin dimethoxide, Dibutyltin oxide, Dimethyltin diacetate, Dimethyltin dibromide, Diphenyltin dichloride, Diphenyltin oxide, Methyltin trichloride, Phenyltin trichloride, Tin(IV) acetate, Tin(IV) bromide, Tin(IV) chloride, Tin(IV) iodide, Tin(II) oxide, Tin(II) acetate, Tin(II) bromide, Tin(II) iodide, BCl3, BBr3, BF3, tris(pentafluorophenyl)borane, tris(trifluoromethylphenyl)borane, It may include at least one of tris((3,5-trifluoromethyl)phenyl)borane and tris(tetrafluoro-o-tolyl)borane.

[0178]

[0179] Here, the molecular weight of the polyol can be controlled depending on the type and content of the catalyst.

[0180] The above catalyst can be used in an amount of 1 to 100 parts by weight relative to 100 parts by weight of the above 3-hydroxypropionic acid.

[0181]

[0182] In addition, it is preferable that the step (a) is performed at a temperature of 30 to 300°C and a pressure of 0.1 to 700 torr. More preferably, the step (a) can be performed at a temperature of 50 to 150°C and a pressure of 0.1 to 300 torr, and even more preferably, the step (a) can be performed at a temperature of 70 to 150°C and a pressure of 0.1 to 150 torr.

[0183]

[0184] Next, the manufacturing method of the present invention includes a step of (b) reacting polymerized 3-hydroxypropionic acid with a compound represented by chemical formula 1 to manufacture a polyol copolymer.

[0185]

[0186] [Chemical Formula 2-1]

[0187]

[0188] In chemical formula 2-1, R1 and R2 are the same or different, R1 and R2 are hydrogen or an alkyl group having 1 to 10 carbon atoms, and n and m are integers greater than or equal to 1.

[0189]

[0190] The present invention can provide a copolymer combining the characteristics of polyester polyol and polyether-carbonate polyol by copolymerizing poly-3-hydroxypropionic acid with a compound represented by the above chemical formula 2-1. More specifically, the present invention can improve hydrolysis resistance and heat resistance through the combination of polyester polyol and polyether-carbonate polyol. Accordingly, when the polyol copolymer of the present invention is used for coating purposes, a coating with enhanced durability and waterproofing can be provided. In addition, polyurethane with improved mechanical properties such as strength can be produced using the polyol copolymer of the present invention.

[0191]

[0192] Preferably, the compound represented by the above chemical formula 2-1 may be a CO2-based polyether-carbonate polyol. Preferably, the compound represented by the above chemical formula 1 may have a number average molecular weight (Mn) of 100 to 2000, and more preferably, a number average molecular weight (Mn) of 800 to 1200.

[0193]

[0194] In the manufacturing method of the present invention, when reacting the polymerized poly-3-hydroxypropionic acid with the compound represented by the above chemical formula 1, it is preferable that the reaction be performed at a temperature of 30 to 300°C and a pressure of 0.1 to 700 torr. More preferably, the step (b) may be performed at a temperature of 50 to 150°C and a pressure of 0.1 to 300 torr, and even more preferably, the step (b) may be performed at a temperature of 70 to 150°C and a pressure of 0.1 to 150 torr.

[0195]

[0196] In addition, the method for producing a polyol copolymer of the present invention may further include, after step (b), a step (c) of removing unreacted monomers by lowering the pressure compared to the pressure of step (b).

[0197] Here, step (c) may be performed at the same temperature as step (b), but is performed under a pressure lower than the pressure controlled in step (b).

[0198] The above step (c) can be performed at a temperature of 30 to 300°C and a pressure of 0.1 to 500 torr, but the pressure is lower than the pressure of step (b).

[0199]

[0200] In addition, the method for producing a polyol copolymer of the present invention may further include, after step (b), a purification step (d) of adding the polyol copolymer to a solution containing a polar solvent and / or an anion exchange resin and stirring.

[0201]

[0202] The polyol copolymer manufactured through the manufacturing method of the present invention described above may contain unreacted oligomers and monomers that have not been polymerized or oligomerized.

[0203] The above unreacted oligomer and unreacted monomer may mean an oligomer and monomer having a molecular weight of less than 400, preferably less than 300, and more preferably less than 90.

[0204]

[0205] Unreacted oligomers and unreacted monomers contained in the above polyol copolymer can lower the degree of polymerization of polyurethane and deteriorate the mechanical properties of polyurethane.

[0206] Accordingly, the method of the present invention can remove unreacted oligomers and unreacted monomers having low molecular weight contained in the polyol copolymer by using the step (d) described above.

[0207]

[0208] (d) According to step (d), the polyol copolymer is introduced into a solution containing a polar solvent and / or an anion exchange resin. As the mixture of the polyol copolymer and the solution is stirred, polymers having a molecular weight of 400 or more contained in the polyol copolymer are precipitated in a solid state, and unreacted oligomers and unreacted monomers are mostly dissolved in the solution due to the difference in polarity of the polar solvent. Therefore, by utilizing this, polyol copolymers having low molecular weight and high molecular weight can be separated, and extraction can be performed smoothly.

[0209] The polar solvent is not particularly limited as long as it is a solvent substance having polarity. Preferably, the polar solvent may include water, alcohol, or a polar mixed solvent of water and alcohol.

[0210] In addition, the type of the alcohol is not limited, and the alcohol may include at least one of methanol, ethanol, n-propanol, n-butanol, n-pentanol, n-hexanol, n-heptanol, n-octanol, n-nonanol, and n-decanol as a straight chain alkanol (ROH), preferably at least one of methanol, ethanol, n-propanol, n-butanol, n-pentanol, n-hexanol, n-heptanol, and n-octanol, and more preferably at least one of methanol, ethanol, n-propanol, n-butanol, n-pentanol, and n-hexanol.

[0211]

[0212] In addition, the solution may include an anion exchange resin. Preferably, in the present invention, the polar solvent and the anion exchange resin can be used to maximize the removal of unreacted oligomers and unreacted monomers having small molecular weights contained in the polyol copolymer. Specifically, the basic atom group and terminal chloride ions contained in the anion exchange resin can ion-exchange molecules having hydroxide ions. By the ion exchange action described above, unreacted oligomers and unreacted monomers having small molecular weights contained in the polyol copolymer can be removed.

[0213]

[0214] In the present invention, an anion exchange resin having the above-described functional effect can be used without limitation, but preferably, the anion exchange resin may include an ammonium group or an amine group as a functional group.

[0215]

[0216] In addition, the anion exchange resin containing a basic atomic group such as the ammonium group or amine group may be, for example, an anion exchange resin having a primary amine group, a secondary amine group, a tertiary amine group, or a polyamine group. Preferably, an anion exchange resin having a tertiary amine group, for example, a trimethyl amine group, or an anion exchange resin having a polyamine group may be used.

[0217] As an anion exchange resin containing a basic atomic group such as the above ammonium group or amine group, brands such as TRILITE (SAR11), TRILITE (AW90), and LEWATIT (A365) can be used.

[0218]

[0219] These anion exchange resins can be used in gel, porous, or seeded forms and can have narrow or broad particle size distributions. Furthermore, they are classified as strongly basic or weakly basic anion exchange resins based on the basicity of their atomic groups, which allows them to have different ion exchange capacities and selectivities.

[0220]

[0221] Additionally, the above anion exchange resins can be used alone or in combination of two or more.

[0222]

[0223] After the above-described step (d), the solution including the polar solvent and the anion exchange resin can be removed, and a purified polyol copolymer can be obtained.

[0224]

[0225] The step (d) above may be performed for 10 hours or less under stirring conditions of 2000 rpm or less and a temperature range of 10 to 50°C so as to efficiently remove the unreacted oligomers and unreacted monomers. More preferably, the step (b) above may be performed for 10 minutes to 6 hours under stirring conditions of 25 to 35°C and a temperature range of 200 to 800 rpm.

[0226]

[0227] As described above, the polyol copolymer of the present invention can have various characteristics depending on the type of compound represented by chemical formula 2-1 and the polymerization reaction conditions.

[0228]

[0229] polyol copolymer

[0230]

[0231] Next, the polyol copolymer of the present invention will be described.

[0232]

[0233] The polyol copolymer of the present invention is manufactured by the above-described method and is formed by reacting polymerized 3-hydroxypropionic acid with a compound represented by chemical formula 2-1.

[0234] More specifically, the polyol copolymer of the present invention comprises a compound represented by the following chemical formula 2-3.

[0235]

[0236] [Chemical Formula 2-2]

[0237]

[0238] In chemical formula 2-2, R1 and R2 are the same or different, R1 and R2 are hydrogen or an alkyl group having 1 to 10 carbon atoms, n, m and p are integers greater than or equal to 1, and q is an integer greater than or equal to 0.

[0239]

[0240] The polyol copolymer of the present invention uses bio-based 3-hydroxypropionic acid represented by the following chemical formula 2-2.

[0241]

[0242] [Chemical Formula 2-3]

[0243]

[0244]

[0245] The above 3-hydroxypropionic acid can be produced through a pure chemical process, but it can also be produced through a separation and purification process from a low-concentration 3-HP culture solution produced through a microbial-based fermentation process. In the present invention, it is preferred to use a bio-based 3-hydroxypropionic acid.

[0246]

[0247] The polyol copolymer of the present invention includes a compound such as the chemical formula 2-2 formed by reacting a poly 3-hydroxypropionic acid polymerized with the 3-hydroxypropionic acid and a compound represented by the chemical formula 2-1.

[0248]

[0249] [Chemical Formula 2-1]

[0250]

[0251] In chemical formula 2-1, R1 and R2 are the same or different, R1 and R2 are hydrogen or an alkyl group having 1 to 10 carbon atoms, and n and m are integers greater than or equal to 1.

[0252]

[0253] The present invention can provide a copolymer combining the characteristics of polyester polyol and polyether-carbonate polyol by copolymerizing poly-3-hydroxypropionic acid with a compound represented by the above chemical formula 2-1. More specifically, the present invention can improve hydrolysis resistance and heat resistance through the combination of polyester polyol and polyether-carbonate polyol. Accordingly, when the polyol copolymer of the present invention is used for coating purposes, a coating with enhanced durability and waterproofing can be provided. In addition, polyurethane with improved mechanical properties such as strength can be produced using the polyol copolymer of the present invention.

[0254]

[0255] Preferably, the compound represented by the above chemical formula 2-1 may be a CO2-based polyether-carbonate polyol. Preferably, the compound represented by the above chemical formula 2-1 may have a number average molecular weight (Mn) of 100 to 2000, and more preferably, a number average molecular weight (Mn) of 800 to 1200.

[0256]

[0257] The compound represented by the above chemical formula 2-1 has the OH and H groups at both ends removed and is combined with 3-hydroxypropionic acid. In addition, the shape and properties of chemical formula 2 may vary depending on the types of R1 and R2 in chemical formula 1.

[0258]

[0259] Preferably, the polyol copolymer of the present invention may have a number average molecular weight (Mn) of 100 to 2000 and a weight average molecular weight (Mw) of 500 to 8000.

[0260] Additionally, the hydroxyl value (Hv) of the polyol copolymer may be 10 to 1000, and preferably, the hydroxyl value (Hv) may be 100 to 200.

[0261] In addition, the acid value (Av) of the polyol copolymer may be 10 or less, and more preferably less than 3.

[0262] Additionally, the molecular weight distribution value (PDI) of the polyol copolymer may be 1 to 10. Preferably, the molecular weight distribution value (PDI) of the polyol copolymer may be 1 to 5.

[0263] Within the above-described range, a polyol copolymer that can be used for the production of polyurethane, etc. can be obtained. If a polyol copolymer having properties outside the above range is used, the properties of the polyurethane may be deteriorated.

[0264]

[0265] Polyurethane polymerization involves the bonding of isocyanate groups and polyols. Depending on the molecular weight of the polyol copolymer, the physical properties of the polymerized polyurethane, such as elasticity and mechanical strength, can vary. Furthermore, the hydroxyl value of the substituted OH groups influences polymerization characteristics. Therefore, it is crucial to develop a polyol copolymer that meets the required range of properties.

[0266]

[0267] The polyol copolymer of the present invention is a bio-based material that can satisfy all of the various properties of polyurethane required and is environmentally friendly.

[0268]

[0269] Hereinafter, the properties of the polyol copolymer described above will be described through various examples and comparative examples. However, the following examples are intended to aid understanding of the present invention, and the scope of the present invention is not limited to the following examples.

[0270]

[0271] <Example of the first implementation>

[0272]

[0273] Polyol copolymers according to the examples were prepared according to each polymerization condition using the reactants and catalysts in Table 1-1 below.

[0274] In Table 1-1, the content of the input compound refers to the weight part of the input compound when the content of 3-HP is considered to be 100 parts by weight.

[0275]

[0276] [Table 1-1]

[0277]

[0278]

[0279] Aliphatic polyester polyol U-1410 from Union Chemical Co. was used as the input compound. U-1410 is an aliphatic polyester polyol in which R1 is 4 and R2 is 6 in chemical formula 1.

[0280]

[0281] Example 1-1

[0282] For the production of polyol copolymers according to Example 1-1, a 250-ml glass flask reactor, a Dean-Stark trap, and a reflux condenser were used. A magnetic drive was used to stir the reactants at 250 rpm to ensure uniform stirring. Furthermore, a heating mantle and mantle cover were used to maintain the temperature at the top and bottom of the reactor at 90°C. The production of polyol copolymers was conducted under a nitrogen atmosphere.

[0283] First, 100 g of 3-hydroxypropionic acid (3-HP) and 0.22 g of BrΨnsted acid catalyst (para-toluenesulfonic acid) were added to a reactor, and a polymerization reaction was performed while changing the temperature at 110°C, the reaction time at 16 hr, the stirring speed at 250 rpm, and the vacuum pressure from 50 to 10 torr, thereby inducing polymerization of 3-HP.

[0284] Next, 5.0 g of aliphatic polyester polyol (5 parts by weight) was added to polymerize the polyol. The polymerization conditions were a temperature of 110°C, a reaction time of 8 hours, a stirring speed of 250 rpm, and a vacuum pressure of 10 torr. During polymerization, water generated inside the installed Dean Stark trap was collected. The first sampling was performed every 4 hours to monitor the progress of polymerization. After the reaction was completed, the magnetic drive was briefly stopped, the vacuum pressure was changed to atmospheric pressure, and a second sampling was performed.

[0285] Additionally, the vacuum pressure was lowered to 0.1 torr for 1 hour to remove unreacted substances and low-molecular-weight oligomers and monomers. Thereafter, the final product, a polyol copolymer according to Example 1, was obtained. Afterwards, the pressure was released, the reactor was set to atmospheric pressure, and the Dean-Stark trap and reflux condenser were separated.

[0286]

[0287] Through the above-described process, a polyol copolymer according to Example 1-1 was manufactured.

[0288]

[0289] Examples 1-2 to 1-10

[0290] Polyol copolymers according to Examples 1-2 to 1-10 were prepared in the same manner as Example 1-1 based on the reactants described in Table 1-1.

[0291]

[0292] Example 1-11

[0293] A polyol copolymer was prepared in the same manner as in Example 1-5, and the polyol of Example 1-11 was prepared by additionally undergoing the purification process as follows.

[0294] The prepared polyol copolymer was melted at 60°C for 10 minutes. Afterwards, a 1L glass reactor was prepared, a magnetic driver was installed for easy stirring, and 300 ml of deionized water and 10 g of anion exchange resin TRILITE (AW90, Samyang Corporation) were placed in the reactor using a membrane filter. 16 g of the molten polyol copolymer was slowly added to the deionized water. The stirring speed was maintained at 450 rpm, and the mixture was stirred at room temperature for approximately 1 hour. During stirring, the molten polyol copolymer remained in the form of flakes and solidified. After stirring, the mixture was poured into a Buchner funnel connected to a depressurized flask to obtain the obtained polyol copolymer solid. The deionized water and ion exchange resin were completely removed under reduced pressure for approximately 5 minutes, and the mixture was dried in a vacuum oven at 40°C.

[0295] Through the above-described process, a purified polyol copolymer according to Example 1-11 was obtained.

[0296]

[0297] <Method of evaluating physical properties>

[0298] In order to evaluate the properties of the polyol copolymer specimens manufactured according to Examples 1-1 to 1-11, the following items were measured and the results are shown in Table 1-1 below.

[0299]

[0300] (1) Molecular weight measurement method (GPC):

[0301] The molecular weight distribution of a polymer is measured using gel permeation chromatography (GPC). Typically, GPC is a special form of liquid chromatography in which a sample is separated according to the hydration volume of each component. When a polymer solution is passed through a porous column of the GPC, which has pores similar in size to the molecular size of the polymer, the polymer molecules are dispersed inside and outside the pores through the pores. In other words, molecules with low molecular weights that are smaller than the pores can pass through all the pores, and as they are dispersed into all the pores, the time it takes to pass through the column layer increases. This enables separation of high and low molecular weight molecules. Accordingly, the number-average molecular weight (Mn) and weight-average molecular weight (Mw) according to the molecular weight calculation formula can be confirmed.

[0302] This experiment used gel permeation chromatography (Waters 2690), and the column used was StryagelHR. 2, 1, 0.5.

[0303] Polyol copolymers were completely dissolved in tetrahydrofurane (THF) or chloroform, purified using a syringe filter, and then subjected to gel permeation chromatography to measure their molecular weights. The test conditions were maintained at 40°C, with a flow rate of 1 mL / min and a concentration of 3 g / L. Molecular weight standards were calibrated using polystyrene standards.

[0304]

[0305] (2) Molecular weight distribution (Polydispersity Index, PDI)

[0306] It is also called polydispersity, and can be confirmed using the calculation formula below based on the molecular weight detected by GPC.

[0307] Weight average molecular weight (Mn) / Number average molecular weight (Mn)

[0308]

[0309] (3) Hydroxyl value (Hv) measurement method

[0310] The number-average molecular weight of a polyol copolymer can be calculated based on the hydroxyl value. The hydroxyl value was measured according to the methods described in ASTM (E1899-08) and ASTM (D4274-94). The hydroxyl value is measured by reacting the measuring reagent with the polyol, titrating with 1 N-NaOH, and calculating it using the following equation.

[0311]

[0312] Hydroxyl value = ((AB) x N x 56.1) / W

[0313]

[0314] A = Volume of titrant consumed in the blank test (ml)

[0315] B = Volume of titrant consumed in this test (ml)

[0316] N = Normal concentration of 1 N-NaOH aqueous solution

[0317] W = amount of sample (g)

[0318]

[0319] (4) Acid value (Av) measurement method

[0320] The acid value of the polyol copolymer is preferably less than 3 mg KOH / g, preferably less than 2 mg KOH / g, and more specifically less than 1 mg KOH / g. The acid value is used to measure the level of free organic acids in the polyol copolymer. The acid value is measured, for example, by the amount of KOH in mg required to neutralize 1 g of a sample.

[0321]

[0322] [Table 1-2]

[0323]

[0324]

[0325] Referring to the results in Table 1-2 above, it can be confirmed that the examples according to the present invention have various characteristics depending on the content and type of aliphatic polyester polyol, the type of catalyst, and the polymerization conditions.

[0326]

[0327] <Example of the second implementation>

[0328]

[0329] Polyol copolymers according to the examples were prepared according to each polymerization condition using the reactants and catalysts in Table 2-1 below.

[0330] In Table 2-1, the content of the input compound refers to the weight part of the input compound when the content of 3-HP is considered to be 100 parts by weight.

[0331]

[0332] [Table 2-1]

[0333]

[0334]

[0335] The above input compound is a CO2-based polyether polyol represented by Chemical Formula 2-1, which means a compound formed by the reaction of a double metal cyanide (DMC) catalyst, propylene oxide, and polypropylene glycol. The number average molecular weight (Mn) of the input compound used in the example is 1000.

[0336]

[0337] Example 2-1

[0338] For the production of polyol copolymers according to Example 2-1, a 250-ml glass flask reactor, a Dean-Stark trap, and a reflux condenser were used. A magnetic drive was used to stir the reactants at 250 rpm to ensure uniform stirring. Furthermore, a heating mantle and mantle cover were used to maintain the temperature at the top and bottom of the reactor at 90°C. The production of polyol copolymers was conducted under a nitrogen atmosphere.

[0339] First, 100 g of 3-hydroxypropionic acid (3-HP) and 0.22 g of BrΨnsted acid catalyst (para-toluenesulfonic acid) were added to a reactor, and a polymerization reaction was performed while changing the temperature at 110°C, the reaction time at 16 hr, the stirring speed at 250 rpm, and the vacuum pressure from 50 to 10 torr, thereby inducing polymerization of 3-HP.

[0340] Next, 5.0 g of CO2-based polyether polyol (5 parts by weight) was added and the polyol was polymerized. The polymerization conditions were a temperature of 110°C, a reaction time of 8 hours, a stirring speed of 250 rpm, and a vacuum pressure of 10 torr. During polymerization, the water generated inside the installed Dean Stark trap was collected. The first sampling was performed every 4 hours to monitor the progress of polymerization. After the reaction was completed, the magnetic drive was briefly stopped, the vacuum pressure was changed to atmospheric pressure, and a second sampling was performed.

[0341] Additionally, the vacuum pressure was lowered to 0.1 torr for 1 hour to remove unreacted substances and low-molecular-weight oligomers and monomers. Thereafter, the final product, a polyol copolymer according to Example 2-1, was obtained. Afterwards, the pressure was released, the reactor was adjusted to atmospheric pressure, and the Dean-Stark trap and reflux condenser were separated.

[0342]

[0343] Through the above-described process, a polyol copolymer according to Example 2-1 was manufactured.

[0344]

[0345] Examples 2-2 to 2-7

[0346] Polyol copolymers according to Examples 2-2 to 2-7 were prepared in the same manner as Example 1 based on the reactants described in Table 2-1.

[0347]

[0348] Example 2-8

[0349] A polyol copolymer was prepared in the same manner as in Example 2-1, and the polyol of Example 2-8 was prepared by additionally undergoing the purification process as follows.

[0350] The prepared polyol copolymer was melted at 60°C for 10 minutes. Afterwards, a 1L glass reactor was prepared, a magnetic driver was installed for easy stirring, and 300 ml of deionized water and 10 g of anion exchange resin TRILITE (AW90, Samyang Corporation) were placed in the reactor using a membrane filter. 16 g of the molten polyol copolymer was slowly added to the deionized water. The stirring speed was maintained at 450 rpm, and the mixture was stirred at room temperature for approximately 1 hour. During stirring, the molten polyol copolymer remained in the form of flakes and solidified. After stirring, the mixture was poured into a Buchner funnel connected to a depressurized flask to obtain the obtained polyol copolymer solid. The deionized water and ion exchange resin were completely removed under reduced pressure for approximately 5 minutes, and the mixture was dried in a vacuum oven at 40°C.

[0351] Through the above-described process, a purified polyol copolymer according to Example 2-8 was obtained.

[0352]

[0353] <Method of evaluating physical properties>

[0354] The method for evaluating physical properties is as described above.

[0355]

[0356] [Table 2-2]

[0357]

[0358]

[0359] Referring to the results in Table 2-2 above, it can be confirmed that the examples according to the present invention have various characteristics depending on the content and type of CO2-based polyether polyol, the type of catalyst, and the polymerization conditions.

[0360]

[0361] The disclosed embodiments have been described with reference to the attached table as described above. Those skilled in the art will understand that the present invention can be implemented in forms other than the disclosed embodiments without altering the technical spirit or essential characteristics of the present invention. The disclosed embodiments are illustrative and should not be construed as limiting.

Claims

1. (a) a step of polymerizing 3-hydroxypropionic acid; and (b) a step of preparing a polyol copolymer by reacting polymerized 3-hydroxypropionic acid with a compound represented by chemical formula 1; Method for producing a polyol copolymer. [Chemical Formula 1] (In chemical formula 1, R1 and R2 are the same or different, R1 and R2 are alkyl groups having 2 to 10 carbon atoms, and p is an integer greater than or equal to 1.) 2. In paragraph 1, Step (a) above Polymerizing the above 3-hydroxypropionic acid using a catalyst Method for producing a polyol copolymer.

3. In paragraph 2, The above catalyst is A catalyst comprising a Bronsted acid catalyst, a Lewis acid catalyst, or a mixed catalyst comprising the Bronsted acid catalyst and the Lewis acid catalyst. Method for producing a polyol copolymer.

4. In paragraph 3, The above Bronsted acid catalyst Methanesulfonic acid (MSA), p-Toluenesulfonic acid (p-TSA), ion exchange resin containing sulfonic acid groups, Containing at least one of H2SO4, HCL, H2CO3, HNO3, HBF4, HSbF6, ClSO3H, FSO3H, CF3SO3H and CH3SO3H Method for producing a polyol copolymer.

5. In paragraph 3, The above Lewis acid catalyst is Tin(II) 2-ethylhexanoate(TEH), Tin(II) Chloride(SnCl2), titanium isopropoxide(TIP), titanium tetrabutoxide(TBO), Dibutyltin diacetate, Dibutyltin dibromide, Dibutyltin dichloride, Dibutyltin dilaurate, Dibutyltin dimethoxide, Dibutyltin oxide, Dimethyltin diacetate, Dimethyltin dibromide, Diphenyltin dichloride, Diphenyltin oxide, Methyltin trichloride, Phenyltin trichloride, Tin(IV) acetate, Tin(IV) bromide, Tin(IV) chloride, Tin(IV) iodide, Tin(II) oxide, Tin(II) acetate, Tin(II) bromide, Tin(II) iodide, BCl3, BBr3, BF3, Tris(pentafluorophenyl)borane, Tris(trifluoromethylphenyl)borane, Containing at least one of tris((3,5-trifluoroomethyl)phenyl)borane and tris(tetrafluoro-o-tolyl)borane Method for producing a polyol copolymer.

6. In paragraph 1, Step (a) above It is performed under a temperature of 30 to 300 ℃ and a pressure of 0.1 to 700 torr, Step (b) above It is performed under a temperature of 30 to 300 ℃ and a pressure of 0.1 to 700 torr. Method for producing a polyol copolymer.

7. In paragraph 1, After step (b) above, (c) a step of removing unreacted monomers by lowering the pressure compared to the pressure in step (b); Method for producing a polyol copolymer.

8. In paragraph 1, After step (b) above, (d) a purification step of adding the polyol copolymer to a solution containing a polar solvent and / or an anion exchange resin and stirring; Method for producing a polyol copolymer.

9. In paragraph 8, The above polar solvent is Containing water, alcohol or a polar mixed solvent of water and alcohol Method for producing a polyol copolymer.

10. In paragraph 8, The above anion exchange resin Containing an ammonium group or an amine group as a functional group Method for producing a polyol copolymer.

11. In paragraph 8, Step (d) above It is performed for less than 10 hours under the temperature range of 10 to 50 ℃ and stirring conditions of less than 2000 rpm. Method for producing a polyol copolymer.

12. Manufactured by the method of paragraph 1, Containing a compound represented by the following chemical formula 1-2 Polyol copolymer. [Chemical Formula 1-2] (In Chemical Formula 1-2, R1 and R2 are the same or different, R1 and R2 are alkyl groups having 2 to 10 carbon atoms, n and p are integers greater than or equal to 1, and m is an integer greater than or equal to 0.) 13. In paragraph 12, The hydroxyl value (Hv) is 10 to 1000, The acid value (Av) is 10 or less, The number average molecular weight (Mn) is 100 to 1500, Molecular weight distribution (PDI) of 1 to 10 Polyol copolymer. 14.(a) a step of polymerizing 3-hydroxypropionic acid; and (b) a step of preparing a polyol copolymer by reacting polymerized 3-hydroxypropionic acid with a compound represented by chemical formula 2-1; Method for producing a polyol copolymer. [Chemical Formula 2-1] (In Chemical Formula 2-1, R1 and R2 are the same or different, R1 and R2 are hydrogen or an alkyl group having 1 to 10 carbon atoms, and n and m are integers greater than or equal to 1.) 15. In paragraph 14, Step (a) above Polymerizing the above 3-hydroxypropionic acid using a catalyst Method for producing a polyol copolymer.

16. In paragraph 15, The above catalyst is A catalyst comprising a Bronsted acid catalyst, a Lewis acid catalyst, or a mixed catalyst comprising the Bronsted acid catalyst and the Lewis acid catalyst. Method for producing a polyol copolymer.

17. In paragraph 16, The above Bronsted acid catalyst Methanesulfonic acid (MSA), p-Toluenesulfonic acid (p-TSA), ion exchange resin containing sulfonic acid groups, Containing at least one of H2SO4, HCL, H2CO3, HNO3, HBF4, HSbF6, ClSO3H, FSO3H, CF3SO3H and CH3SO3H Method for producing a polyol copolymer.

18. In paragraph 16, The above Lewis acid catalyst is Tin(II) 2-ethylhexanoate(TEH), Tin(II) Chloride(SnCl2), titanium isopropoxide(TIP), titanium tetrabutoxide(TBO), Dibutyltin diacetate, Dibutyltin dibromide, Dibutyltin dichloride, Dibutyltin dilaurate, Dibutyltin dimethoxide, Dibutyltin oxide, Dimethyltin diacetate, Dimethyltin dibromide, Diphenyltin dichloride, Diphenyltin oxide, Methyltin trichloride, Phenyltin trichloride, Tin(IV) acetate, Tin(IV) bromide, Tin(IV) chloride, Tin(IV) iodide, Tin(II) oxide, Tin(II) acetate, Tin(II) bromide, Tin(II) iodide, BCl3, BBr3, BF3, Tris(pentafluorophenyl)borane, Tris(trifluoromethylphenyl)borane, Containing at least one of tris((3,5-trifluoroomethyl)phenyl)borane and tris(tetrafluoro-o-tolyl)borane Method for producing a polyol copolymer.

19. In paragraph 14, Step (a) above It is performed under a temperature of 30 to 300 ℃ and a pressure of 0.1 to 700 torr, Step (b) above It is performed under a temperature of 30 to 300 ℃ and a pressure of 0.1 to 700 torr. Method for producing a polyol copolymer.

20. In paragraph 14, After step (b) above, (c) a step of removing unreacted monomers by lowering the pressure compared to the pressure in step (b); Method for producing a polyol copolymer.

21. In paragraph 14, After step (b) above, (d) a purification step of adding the polyol copolymer to a solution containing a polar solvent and / or an anion exchange resin and stirring; Method for producing a polyol copolymer.

22. In paragraph 21, The above polar solvent is Containing water, alcohol or a polar mixed solvent of water and alcohol Method for producing a polyol copolymer.

23. In paragraph 21, The above anion exchange resin Containing an ammonium group or an amine group as a functional group Method for producing a polyol copolymer.

24. In paragraph 21, Step (d) above It is performed for less than 10 hours under the temperature range of 10 to 50 ℃ and stirring conditions of less than 2000 rpm. Method for producing a polyol copolymer.

25. Manufactured by the method of Article 14, Containing a compound represented by the following chemical formula 2-2 Polyol copolymer. [Chemical Formula 2-2] (In Chemical Formula 2-2, R1 and R2 are the same or different, R1 and R2 are hydrogen or an alkyl group having 1 to 10 carbon atoms, n, m and p are integers greater than or equal to 1, and q is an integer greater than or equal to 0.) 26. In paragraph 25, The hydroxyl value (Hv) is 10 to 1000, The acid value (Av) is 10 or less, The number average molecular weight (Mn) is 100 to 2000, Molecular weight distribution (PDI) of 1 to 10 Polyol copolymer.

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