Method for preparing flame retardant polyol and flame retardant polyol preparerd therefrom

Abstract

A method for producing a polyol according to the present invention comprises: (a) a step of polymerizing 3-hydroxypropionic acid to produce poly 3-hydroxypropionic acid; and (b) a step of reacting the poly 3-hydroxypropionic acid with a halogenated alcohol. According to the present invention, a novel polyol formed by the reaction of poly 3-hydroxypropionic acid with a halogenated alcohol can be provided, and accordingly, a polyol having physical properties that are flame-retardant than polyester polyol can be provided.

Description

Technology Field

[0001] The present invention relates to a method for producing a flame-retardant polyol based on 3-hydroxypropionic acid and a flame-retardant polyol produced thereby. Background Technology

[0003] Polyurethane resins serve as raw materials for plastic products with a wide range of applications. These resins, which contain urethane bonds within their molecules, are primarily synthesized through the reaction between diisocyanates and polyols.

[0004] The polyol used here refers to an active hydrogen compound that reacts with isocyanate to be used in polyurethane (PU), and has two or more active hydrogen groups such as hydroxyl groups, carboxyl groups, and amine groups in its molecule, and these polyols are classified according to their molecular weight for use.

[0005] Polyurethane (PU) utilizing polyester polyols exhibits excellent abrasion resistance, tear strength, flexibility, oil resistance, heat resistance, and elasticity, but hydrolysis may occur. Accordingly, the resistance to hydrolysis can be improved by using carbonate-based additives in polyurethane (PU) utilizing polyester polyols. Polyester polyols can be primarily used in rigid polyurethanes, insulation materials, artificial wood, refrigerators, freezer containers, coatings, adhesives, sealants, elastomers, etc.

[0007] Polyester polyols can be designed as aromatic or aliphatic types to achieve the desired physical properties. Aliphatic polyester polyols are formed through condensation reactions using dicarboxylic acids and diols at the terminal groups; however, such condensation reactions can generate water and consequently produce byproducts. In contrast, when manufacturing aliphatic polyester polyols using ring-opening polymerization, the process can proceed without the aforementioned problems. Therefore, manufacturing aliphatic polyester polyols using ring-opening polymerization offers the advantages of reaching high molecular weight in a relatively short time and allowing for easy control of molecular weight at low pressures.

[0008] As mentioned above, polyols can be manufactured using various polymerization methods, and research and development have been conducted to suit the physical properties of polyurethane.

[0010] Generally, polyurethane resins have mainly used polyester polyols made by reacting adipic acid refined from petroleum with glycol. However, this can cause environmental pollution in various forms during the manufacturing process, and also presents problems in terms of environmental pollution, such as the emission of large amounts of carbon dioxide during the post-use treatment process.

[0012] Technology utilizing biomass-based resins derived from plants, such as polylactic acid (PLA), is known to address environmental pollution issues. However, compared to conventional petroleum-based resins, polylactic acid-based polyols have inferior mechanical properties, such as impact resistance and heat resistance, which limit their range of application. Among biomass-based materials, 3-hydroxypropionic acid (3-HP) is currently being researched by the industry for various applications, including acrylic acid conversion, industrial solvents, and polyurethanes, in an effort to overcome these problems. 3-hydroxypropionic acid is also primarily used as a monomer for polyols in the development research of polyurethanes and polythiourethanes.

[0013] However, there is a problem in that it is difficult to control the molecular weight of polymers using 3-hydroxypropionic acid because the polymerization process of 3-hydroxypropionic acid is relatively complex and the molecular weight distribution at each conditional step due to condensation polymerization is very different. The problem to be solved

[0015] The objective of the present invention is to provide a method for producing a 3-hydroxypropionic acid-based flame-retardant polyol using a halogenated alcohol in conjunction with the polymerization of 3-hydroxypropionic acid, and to provide the flame-retardant polyol produced thereby. means of solving the problem

[0017] A method for manufacturing a polyol according to the present invention for achieving the above-mentioned objectives is,

[0018] (a) a step of polymerizing 3-hydroxypropionic acid to produce poly 3-hydroxypropionic acid; and (b) a step of reacting the poly 3-hydroxypropionic acid with a halogenated alcohol; thereby producing a polyol comprising a compound represented by the following chemical formula 1.

[0020] [Chemical Formula 1]

[0021]

[0022] In the above chemical formula 1,

[0023] R is a linker derived from the above-mentioned halogenated alcohol, and

[0024] The above n is an integer greater than or equal to 1, and m is an integer greater than or equal to 0.

[0026] Herein, the method for producing a polyol according to the present invention may further include (c) a step of removing unreacted monomers by lowering the pressure relative to the pressure of step (b).

[0028] In addition, the method for manufacturing a polyol according to the present invention may further include, after step (b), a purification step (d) of adding the polyol to a solution containing a polar solvent and / or an anion exchange resin and stirring.

[0030] In addition, the polyol according to the present invention for achieving the above-described objective is manufactured by the above-described manufacturing method and includes a compound represented by the above chemical formula 1. Effects of the invention

[0031] The manufacturing method of the present invention can produce a novel 3-HP-based polyol in which the molecular weight of the polyol can be easily controlled by using a halogenated alcohol in conjunction with the polymerization of 3-hydroxypropionic acid.

[0032] In addition, the present invention can produce a polyol with excellent physical properties using a relatively simple method with 3-hydroxypropionic acid and a halogenated alcohol.

[0033] In addition, the present invention can improve color and miscibility with ester polyols when manufacturing an ester in which a flame-retardant element is bonded to the polyol itself.

[0034] Accordingly, the present invention can maintain / improve the physical properties of urethane through the effect of flame-retardant elements bonded within the polyol.

[0035] Furthermore, while conventional flame-retardant components volatilize over time, causing a decline in flame retardancy and potentially having harmful effects on the human body, the polyol of the present invention does not volatilize over time because flame-retardant elements are chemically bonded within the polyol. Accordingly, the polyol of the present invention is characterized by its flame-retardant performance not deteriorating and not having harmful effects on the human body.

[0036] In addition, the present invention can provide a novel polyurethane, particularly endowed with flame retardancy. Specific details for implementing the invention

[0038] Hereinafter, the method for manufacturing the polyol of the present invention and the polyol manufactured therefrom will be described in detail with reference to the attached chemical formula and table.

[0040] Method for manufacturing polyol

[0042] First, the method for manufacturing the polyol of the present invention will be described in detail.

[0044] The method for producing a polyol according to the present invention comprises: (a) a step of polymerizing 3-hydroxypropionic acid to produce poly 3-hydroxypropionic acid; and (b) a step of reacting the poly 3-hydroxypropionic acid with a halogenated alcohol; thereby producing a polyol comprising a compound represented by the following chemical formula 1.

[0046] [Chemical Formula 1]

[0047]

[0048] In the above chemical formula 1,

[0049] R is a linker derived from the above-mentioned halogenated alcohol, and

[0050] The above n is an integer greater than or equal to 1, and m is an integer greater than or equal to 0.

[0052] The polyol of the present invention may have various molecular weights depending on the application example. Accordingly, it is preferable to polymerize the 3-hydroxypropionic acid contained in the polyol to induce poly 3-hydroxypropionic acid.

[0053] To this end, the manufacturing method of the present invention comprises the step of (a) polymerizing 3-hydroxypropionic acid.

[0055] Here, a catalyst can be used to induce poly 3-hydroxypropionic acid by polymerizing 3-hydroxypropionic acid.

[0057] At this time, the catalyst may include a Brønsted acid catalyst, a Lewis acid catalyst, or a mixed catalyst comprising a mixture of the Brønsted acid catalyst and the Lewis acid catalyst.

[0058] Preferably, the Brønsted acid catalyst may include one or more of 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.

[0059] Here, the ion exchange resin containing the sulfonic acid group may include one or more of Amberlyst 15, Amberlyst 36, Amberlyst 39, and Amberlite IR 120.

[0060] In addition, the Lewis acid catalyst comprises 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 one or more of tris((3,5-trifluoromethyl)phenyl)borane and tris(tetrafluoro-o-tolyl)borane.

[0062] Here, the molecular weight of the polyol can be controlled depending on the type and content of the catalyst.

[0063] The above catalyst may be used in an amount of 1 to 100 parts by weight per 100 parts by weight of the above 3-hydroxypropionic acid.

[0065] Additionally, it is preferable that step (a) be performed at a temperature of 30 to 300 ℃ and a pressure of 0.1 to 700 torr. More preferably, step (a) may be performed at a temperature of 50 to 150 ℃ and a pressure of 0.1 to 300 torr, and even more preferably, step (a) may be performed at a temperature of 70 to 150 ℃ and a pressure of 0.1 to 150 torr.

[0067] Next, the manufacturing method of the present invention comprises the step of (b) reacting the poly 3-hydroxypropionic acid with a halogenated alcohol to produce a polyol. Here, the poly 3-hydroxypropionic acid refers to polymerized 3-hydroxypropionic acid.

[0069] Here, the halogenated alcohol refers to an alcohol in which one or more functional groups are substituted with a halogen element. Preferably, the halogenated alcohol may include a halogenated diol. Also preferably, the halogenated alcohol is 3-bromopentane-2,4-diol, (2s,3s,4r)-4-bromopentane-2,3-diol, 5-bromo-2-(bromomethyl)pentane-1,4-diol, 5-bromopentane-1,4-diol, trans-2,3-dibromo-2-butene-1,4-diol, 4-bromobutane-1,3-diol, 3-bromobutane-1,2-propanediol, 2,2-bis(bromomethyl)-1,3-propanediol, 2,3-dibromo-1,4-butanediol, 3-chloropentane-2,4-diol, (2s,3s,4r)-4-chloropentane-2,3-diol, 5-chloro-2-(chloromethyl)pentane-1,4-diol, It may include one or more of 5-chloropentane-1,4-diol, trans-2,3-dichloro-2-butene-1,4-diol, 4-chlorobutane-1,3-diol, 3-chlorobutane-1,2-propanediol, 2,2-bis(chloromethyl)-1,3-propanediol and 2,3-dichloro-1,4-butanediol, but is not limited thereto.

[0071] By preparing a polyol using the above-mentioned halogenated alcohol, the polyol according to the present invention can have its mechanical properties, particularly flame retardancy, improved.

[0073] Preferably, the compound represented by Chemical Formula 1 may include one or more compounds represented by any one of Chemical Formulas 2 to 7 below, depending on the type of halogenated alcohol used.

[0075] [Chemical Formula 2]

[0076]

[0078] [Chemical Formula 3]

[0079]

[0081] [Chemical Formula 4]

[0082]

[0084] [Chemical Formula 5]

[0085]

[0087] [Chemical Formula 6]

[0088]

[0090] [Chemical Formula 7]

[0091]

[0092] In the above chemical formulas 2 to 7, X is a halogen element, n is an integer greater than or equal to 1, and m is an integer greater than or equal to 0. Preferably, the halogen element may include Br and Cl.

[0094] In addition, in the present invention, a catalyst may be used when reacting the poly 3-hydroxypropionic acid with the halogenated alcohol.

[0095] At this time, the catalyst may include a Brønsted acid catalyst, a Lewis acid catalyst, or a mixed catalyst comprising a mixture of the Brønsted acid catalyst and the Lewis acid catalyst.

[0096] Preferably, the Brønsted acid catalyst may include one or more of 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.

[0097] Here, the ion exchange resin containing the sulfonic acid group may include one or more of Amberlyst 15, Amberlyst 36, Amberlyst 39, and Amberlite IR 120.

[0098] In addition, the Lewis acid catalyst comprises 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 one or more of tris((3,5-trifluoromethyl)phenyl)borane and tris(tetrafluoro-o-tolyl)borane.

[0100] Here, the molecular weight of the polyol can be controlled depending on the type and content of the catalyst.

[0101] The above catalyst may be used in an amount of 1 to 100 parts by weight per 100 parts by weight of the above halogenated alcohol.

[0103] Additionally, it is preferable that step (b) be performed at a temperature of 30 to 300 ℃ and a pressure of 0.1 to 700 torr. More preferably, step (a) may be performed at a temperature of 50 to 150 ℃ and a pressure of 0.1 to 300 torr, and even more preferably, step (a) may be performed at a temperature of 70 to 150 ℃ and a pressure of 0.1 to 150 torr.

[0105] In addition, the method for manufacturing a polyol according to the present invention may further include, after step (b), a step (c) of removing unreacted monomers by lowering the pressure relative to the pressure of step (b).

[0106] Here, step (c) may be performed at the same temperature as step (b), but under a pressure lower than the pressure controlled in step (b).

[0107] Step (c) above may be performed at a temperature of 30 to 300 ℃ and a pressure of 0.1 to 500 torr, wherein the pressure is lower than the pressure of step (b).

[0109] In addition, the method for manufacturing a polyol according to the present invention may further include, after step (b), a purification step of (d) adding the polyol to a solution containing a polar solvent and / or an anion exchange resin and stirring.

[0111] The polyol produced through the manufacturing method of the present invention described above may contain unreacted oligomers and monomers that have not been polymerized or oligomerized.

[0112] The above unreacted oligomers and unreacted monomers may refer to oligomers and monomers with a molecular weight of less than 400, preferably less than 300, more preferably less than 90.

[0114] The unreacted oligomers and unreacted monomers contained in the above polyol can lower the degree of polymerization of the polyurethane and degrade the mechanical properties of the polyurethane.

[0115] Accordingly, the method of the present invention can remove unreacted oligomers and unreacted monomers with low molecular weight contained in the polyol by using the above-described step (d).

[0117] According to step (d), the polyol is introduced into a solution containing a polar solvent and / or anion exchange resin. As the mixture of the polyol and the solution is stirred, polymers with a molecular weight of 400 or more contained in the polyol precipitate in a solid state, while unreacted oligomers and unreacted monomers are mostly dissolved in the solution due to the difference in polarity of the polar solvent. Therefore, this can be used to separate polyols with low molecular weight and high molecular weight, and extraction can be carried out smoothly.

[0118] The above polar solvent is not particularly limited as long as it is a solvent material having polarity. Preferably, the polar solvent may include water, alcohol, or a polar mixed solvent of water and alcohol.

[0119] In addition, the type of alcohol is not limited, and the alcohol may be a straight-chain alcohol (ROH) and may include one or more of methanol, ethanol, n-propanol, n-butanol, n-pentanol, n-hexanol, n-heptanol, n-octanol, n-nonanol, and n-decanol, preferably may include at least one of methanol, ethanol, n-propanol, n-butanol, n-pentanol, n-hexanol, n-heptanol, and n-octanol, and more preferably may include one or more of methanol, ethanol, n-propanol, n-butanol, n-pentanol, and n-hexanol.

[0121] In addition, the above solution may contain an anion exchange resin. Preferably, in the present invention, the removal of unreacted oligomers and unreacted monomers with small molecular weights contained in the polyol can be maximized by using the polar solvent and the anion exchange resin. Specifically, the basic atomic group and the terminal chloride ion contained in the anion exchange resin can ion exchange molecules having hydroxide ions. Through the ion exchange action described above, unreacted oligomers and unreacted monomers with small molecular weights contained in the polyol can be removed.

[0123] In the present invention, an anion exchange resin having the above-described functional effects may be used without limitation, but preferably, the anion exchange resin may include an ammonium group or an amine group as a functional group.

[0125] In addition, the anion exchange resin containing basic atomic groups 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 trimethylamine group, or an anion exchange resin having a polyamine group may be used.

[0126] As an anion exchange resin containing basic atomic groups such as the ammonium group or amine group mentioned above, trademarks such as TRILITE (SAR11), TRILITE (AW90), and LEWATIT (A365) may be used.

[0128] These anion exchange resins can be used in gel, porous, or seeded forms and can have a narrow or wide particle size distribution. Furthermore, they are classified into strong basic and weak basic anion exchange resins depending on the basic strength of the atomic group, and accordingly, they can have different ion exchange capacities and selectivity.

[0130] In addition, the above anion exchange resins can be used alone or in combination of two or more.

[0132] After step (d) described above, the solution containing the polar solvent and the anion exchange resin can be completely removed, and the purified polyol can be obtained.

[0134] The above step (d) can be performed for 10 hours or less at a temperature range of 10 to 50 ℃ and stirring conditions of 2000 rpm or less so as to efficiently remove the unreacted oligomers and unreacted monomers. More preferably, the above step (b) can be performed for 10 minutes to 6 hours at a temperature range of 25 to 35 ℃ and stirring conditions of 200 to 800 rpm.

[0136] As described above, the polyol of the present invention may have various characteristics depending on the type of one or more halogenated alcohols and the polymerization reaction conditions.

[0138] polyol

[0140] Next, the polyol of the present invention will be described.

[0142] The polyol of the present invention is prepared by the method described above and is formed by the reaction of the poly 3-hydroxypropionic acid and the halogenated alcohol.

[0143] More specifically, the polyol of the present invention comprises a compound represented by the following chemical formula 1.

[0145] [Chemical Formula 1]

[0146]

[0147] In the above chemical formula 1,

[0148] R is a linker derived from the above-mentioned halogenated alcohol, and

[0149] The above n is an integer greater than or equal to 1, and m is an integer greater than or equal to 0.

[0151] The present invention can obtain a polyol using poly 3-hydroxypropionic acid polymerized from 3-hydroxypropionic acid represented by the following chemical formula 8.

[0153] [Chemical Formula 8]

[0154]

[0156] The polyol of the present invention includes a compound of the formula 1 formed by reacting a polymerized poly 3-hydroxypropionic acid with a halogenated alcohol.

[0158] In the present invention, the halogenated alcohol refers to an alcohol in which one or more functional groups are substituted with a halogen element. Preferably, the halogenated alcohol may include a halogenated diol. Also preferably, the halogenated alcohol is 3-bromopentane-2,4-diol, (2s,3s,4r)-4-bromopentane-2,3-diol, 5-bromo-2-(bromomethyl)pentane-1,4-diol, 5-bromopentane-1,4-diol, trans-2,3-dibromo-2-butene-1,4-diol, 4-bromobutane-1,3-diol, 3-bromobutane-1,2-propanediol, 2,2-bis(bromomethyl)-1,3-propanediol, 2,3-dibromo-1,4-butanediol, 3-chloropentane-2,4-diol, (2s,3s,4r)-4-chloropentane-2,3-diol, 5-chloro-2-(chloromethyl)pentane-1,4-diol, It may include one or more of 5-chloropentane-1,4-diol, trans-2,3-dichloro-2-butene-1,4-diol, 4-chlorobutane-1,3-diol, 3-chlorobutane-1,2-propanediol, 2,2-bis(chloromethyl)-1,3-propanediol and 2,3-dichloro-1,4-butanediol, but is not limited thereto.

[0160] By preparing a polyol using the above-mentioned halogenated alcohol, the polyol according to the present invention can have its mechanical properties, particularly flame retardancy, improved.

[0162] Preferably, the compound represented by Chemical Formula 1 may include one or more compounds represented by any one of Chemical Formulas 2 to 7 below, depending on the type of halogenated alcohol used.

[0164] [Chemical Formula 2]

[0165]

[0167] [Chemical Formula 3]

[0168]

[0170] [Chemical Formula 4]

[0171]

[0173] [Chemical Formula 5]

[0174]

[0176] [Chemical Formula 6]

[0177]

[0179] [Chemical Formula 7]

[0180]

[0181] In the above chemical formulas 2 to 7, X is a halogen element, n is an integer greater than or equal to 1, and m is an integer greater than or equal to 0. Preferably, the halogen element may include Br and Cl.

[0183] Preferably, the polyol 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.

[0184] In addition, the hydroxyl group value (Hv) of the polyol may be 10 to 1000, and preferably, the hydroxyl group value (Hv) may be 50 to 200.

[0185] In addition, the acid value (Av) of the polyol may be 10 or less, and more preferably less than 2.5.

[0186] In addition, the molecular weight distribution value (PDI) of the polyol may be 1 to 10. Preferably, the molecular weight distribution value (PDI) of the polyol may be 1 to 3.

[0187] Within the aforementioned range, polyols that can be used in the manufacture of polyurethane, etc., can be obtained. If a polyurethane is made using a polyol having characteristics outside the above range, its properties may be degraded.

[0189] To polymerize polyurethane, isocyanate groups are bonded with polyols. Depending on the molecular weight of the polyol, the properties of the polymerized polyurethane, such as elasticity and mechanical strength, may vary. Additionally, the hydroxyl group value resulting from the substituted OH groups affects the polymerization characteristics. Accordingly, it is important to produce a polyol that meets the required range of properties.

[0191] The polyol of the present invention can satisfy all the required various physical properties of polyurethane and is environmentally friendly.

[0193] Hereinafter, the properties of the aforementioned polyols will be explained through various examples and comparative examples. However, the following examples are intended to aid in understanding the invention, and the scope of the invention is not limited to the following examples.

[0195] <Example>

[0196] Polyols according to the examples were prepared according to each polymerization condition using the reactants and catalysts in Table 1 below.

[0198] Examples Halogenated alcohol used Input content of halogenated alcohol catalyst 1 4-bromobutane-1,3-diol 25% BrΨnsted acid 2 2,3-dibromo-1,4-butanediol 25% BrΨnsted acid 3 3-bromo-1,2-propanediol 25% BrΨnsted acid 4 4-bromobutane-1,2-diol 25% BrΨnsted acid 5 Trans-2,3-dibromo-2-butene-1,4-diol 25% BrΨnsted acid 6 2,2-bis(bromomethyl)-1,3-propanediol 25% BrΨnsted acid 7 3-Bromopentane-2,4-diol 25% BrΨnsted acid 8 (2S,3S,4R)-4-bromopentane-2,3-diol 25% BrΨnsted acid 9 5-bromopentane-1,4-diol 25% BrΨnsted acid 10 5-bromo-2-(bromomethyl)pentane-1,4-diol 25% BrΨnsted acid 11 4-bromobutane-1,3-diol 25% BrΨnsted acid

[0200] Here, the input content (%) of the halogenated alcohol used refers to the content (%) of the halogenated alcohol relative to the moles of 3-HP. For example, if 20g of 3-HP is used, 9.32g of 4-bromobutane-1,3-diol (25%) is used.

[0202] Example 1

[0203] For the preparation of the polyol according to Example 1, a 250 ml glass flask reactor, a Dean Stark trap, and a reflux condenser were used. To ensure uniform stirring, the reaction mixture was stirred at a speed of 250 rpm using a magnetic drive. In addition, the temperature of the upper and lower parts of the reactor was maintained at 90°C using a heating mantle and a mantle cover. The preparation of the polyol was carried out under a nitrogen atmosphere.

[0204] First, 20 g of 3-hydroxypropionic acid (3-HP) and 0.18 g of BrΨnsted acid catalyst (para-toluenesulfonic acid) were added to a reactor, and a polymerization reaction was carried out at a temperature of 90°C, a reaction time of 8 hours, a stirring speed of 300 rpm, and a vacuum pressure of 50 torr to induce polymerization of 3-HP.

[0205] Next, 9.32 g of 4-bromobutane-1,3-diol (25%) was added, and a polymerization reaction was induced to polymerize the polyol. The polymerization conditions were a temperature range of 90–120°C, a reaction time of 8 hours, a stirring speed of 300 rpm, and a vacuum pressure of 50 torr. During polymerization, water generated inside the installed Dean Stark trap was collected. The first sampling was performed every 4 hours to check the progress of polymerization. After the total 8-hour reaction was completed, the magnetic drive was temporarily stopped, the vacuum pressure was changed to atmospheric pressure, and the second sampling was performed.

[0206] Additionally, the vacuum pressure was lowered to 10 torr for 1 hour, and the temperature was maintained at 100 to 120°C to remove unreacted materials, low molecular weight oligomers, and monomers. Subsequently, the final product, the polyol according to Example 1, was obtained. Afterward, the pressure was released, and the reactor, Dean Stark trap, and reflux condenser installed at atmospheric pressure were separated.

[0208] The polyol according to Example 1 was prepared through the process described above.

[0210] Example 2

[0211] The polyol according to Example 2 was prepared in the same manner as Example 1, except for the types of reactants listed in Table 1.

[0213] Example 3

[0214] The polyol according to Example 3 was prepared in the same manner as Example 1, except for the types of reactants listed in Table 1.

[0216] Example 4

[0217] The polyol according to Example 4 was prepared in the same manner as Example 1, except for the types of reactants listed in Table 1.

[0219] Example 5

[0220] The polyol according to Example 5 was prepared in the same manner as Example 1, except for the types of reactants listed in Table 1.

[0222] Example 6

[0223] The polyol according to Example 6 was prepared in the same manner as Example 1, except for the types of reactants listed in Table 1.

[0225] Example 7

[0226] The polyol according to Example 7 was prepared in the same manner as Example 1, except for the types of reactants listed in Table 1.

[0228] Example 8

[0229] The polyol according to Example 8 was prepared in the same manner as Example 1, except for the types of reactants listed in Table 1.

[0231] Example 9

[0232] The polyol according to Example 9 was prepared in the same manner as Example 1, except for the types of reactants listed in Table 1.

[0234] Example 10

[0235] The polyol according to Example 10 was prepared in the same manner as Example 1, except for the types of reactants listed in Table 1.

[0237] Example 11

[0238] A polyol was prepared in the same manner as in Example 1, and the polyol of Example 11 was prepared by additionally undergoing the purification process as described below.

[0239] The prepared polyol was melted at 60°C for 10 minutes. Subsequently, a 1L glass reactor was prepared and equipped with a magnetic driver to facilitate stirring. 300ml of ultrapure water (deionized water) and 10g of anion exchange resin TRILITE (AW90, Samyang Corporation) were added to the reactor using a membrane filter. 16g of the molten polyol was slowly added to the ultrapure water. During this process, the stirring speed was maintained at 450 rpm, and stirring was carried out at room temperature for approximately 1 hour. During stirring, the molten polyol remained in a flake form and solidified. After stirring was finished, the mixture was poured into a Büchner funnel connected to a vacuum flask to obtain the solid polyol. The ultrapure 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.

[0240] A purified polyol according to Example 11 was obtained through the process described above.

[0242] Physical Property Evaluation Methods

[0243] To evaluate the characteristics of the polyol specimens prepared according to Examples 1 to 11 above, the following items were measured and the results are listed in Table 1 below.

[0245] (1) Molecular weight measurement method (GPC):

[0246] The molecular weight distribution of polymers is measured using gel permeation chromatography (GPC). Typically, GPC refers to a special type of liquid chromatography in which samples are separated according to the hydration volume of each inclusion. When a polymer solution is passed through a porous column layer of the GPC, which has pores similar in size to the polymer molecules, the polymer molecules are dispersed into and out of the pores. That is, low molecular weight molecules, which are smaller than the pores, can pass through all the pores and are dispersed into all pores, thereby increasing the time they take to pass through the column layer. Consequently, the separation of high molecular weight and low molecular weight becomes possible. As a result, the number-average molecular weight (Mn) and weight-average molecular weight (Mw) can be determined according to the molecular weight calculation formula.

[0247] This experiment was performed using gel permeation chromatography (Waters 2690), and StryagelHR. 2, 1, 0.5 columns were used.

[0248] The polyol was completely dissolved in tetrahydrofuran (THF), purified using a syringe filter, and then fed into a gel permeation chromatograph to measure its molecular weight. Under test conditions, the temperature was maintained at 40 ℃, and the flow rate was set to 1 mL / min with a concentration of 3 g / L. The molecular weight was calibrated using a polystyrene standard.

[0250] (2) Molecular weight distribution (Polydispersity Index, PDI)

[0251] It is also called polydispersity, and can be confirmed through the following calculation formula based on the molecular weight detected by GPC.

[0252] Weight-average molecular weight (Mn) / Number-average molecular weight (Mn)

[0254] (3) Method for measuring hydroxyl value (Hv)

[0255] The number average molecular weight of a polyol can be calculated based on its hydroxyl value. The hydroxyl value was measured according to the methods described in ASTM (E1899-08) and ASTM (D4274-94). The hydroxyl value is calculated by reacting the reagent with the polyol and titrating with 1 N-NaOH using the following formula.

[0256]

[0257] A = Volume of titrant consumed in the blank test (ml)

[0258] B = Volume of titrant consumed in the main test (ml)

[0259] Normal concentration of N = 1 N-NaOH aqueous solution

[0260] W = Amount of sample (g)

[0262] (4) Method for measuring acid value (Av)

[0263] The acid value of the polyol is preferably in the range of less than 3 mg KOH / g, preferably less than 2 mg KOH / g, more specifically less than 1 mg KOH / g. The acid value is used to measure the level of free organic acids in the polyol. The acid value is measured, for example, by the amount of KOH in mg required to neutralize an amount of 1 g of sample.

[0265] Examples Mn (g / mol) PDI Hv(mg KOH / g) AV(mg KOH / g) 1 961 1.58 120 < 2.0 2 896 1.61 138 < 2.0 3 912 1.57 127 < 2.0 4 973 1.71 119 < 2.0 5 877 2.14 140 < 2.2 6 867 2.02 142 < 2.3 7 933 1.62 122 < 2.2 8 758 2.39 167 < 2.5 9 894 1.88 135 < 2.3 10 917 1.74 131 < 2.3 11 1044 1.47 105 < 2.0

[0267] Referring to the results of Table 2 above, it can be seen that the embodiments according to the present invention have various characteristics depending on the type of halogenated alcohol, the type of catalyst, and the polymerization conditions.

[0268] As described above, the disclosed embodiments have been explained with reference to the attached table. Those skilled in the art will understand that the present invention may be practiced in forms different from the disclosed embodiments without changing the technical spirit or essential characteristics of the invention. The disclosed embodiments are illustrative and should not be interpreted restrictively.

Claims

Claim 1 A method for preparing a polyol comprising a compound represented by the following chemical formula 1, comprising: (a) a step of polymerizing 3-hydroxypropionic acid to produce poly 3-hydroxypropionic acid; and (b) a step of reacting the poly 3-hydroxypropionic acid with a halogenated alcohol; [Chemical Formula 1] In the above chemical formula 1, R is a linker derived from the above halogenated alcohol, n is an integer greater than or equal to 1, and m is an integer greater than or equal to 0. Claim 2 In claim 1, the above step (a) is a method for producing a polyol by polymerizing the 3-hydroxypropionic acid using a catalyst. Claim 3 A method for producing a polyol according to claim 2, wherein the catalyst comprises a Brønsted acid catalyst, a Lewis acid catalyst, or a mixed catalyst comprising a mixture of the Brønsted acid catalyst and the Lewis acid catalyst. Claim 4 In claim 3, the Brønsted acid catalyst comprises p-Toluenesulfonic acid (p-TSA), an ion exchange resin containing a sulfonic acid group, A method for producing a polyol comprising one or more of H2SO4, HCl, H2CO3, HNO3, HBF4, HSbF6, ClSO3H, FSO3H, CF3SO3H, and CH3SO3H. Claim 5 In claim 3, 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, A method for producing a polyol comprising one or more of tris((3,5-trifluoromethyl)phenyl)borane and tris(tetrafluoro-o-tolyl)borane. Claim 6 A method for producing a polyol according to claim 1, wherein step (a) is performed at a temperature of 30 to 300 ℃ and a pressure of 0.1 to 700 torr. Claim 7 The method of claim 1, wherein the halogenated alcohol is 3-bromopentane-2,4-diol, (2s,3s,4r)-4-bromopentane-2,3-diol, 5-bromo-2-(bromomethyl)pentane-1,4-diol, 5-bromopentane-1,4-diol, trans-2,3-dibromo-2-butene-1,4-diol, 4-bromobutane-1,3-diol, 3-bromobutane-1,2-propanediol, 2,2-bis(bromomethyl)-1,3-propanediol, 2,3-dibromo-1,4-butanediol, 3-chloropentane-2,4-diol, (2s,3s,4r)-4-chloropentane-2,3-diol, 5-chloro-2-(chloromethyl)pentane-1,4-diol, A method for producing a polyol comprising one or more of 5-chloropentane-1,4-diol, trans-2,3-dichloro-2-butene-1,4-diol, 4-chlorobutane-1,3-diol, 3-chlorobutane-1,2-propanediol, 2,2-bis(chloromethyl)-1,3-propanediol, and 2,3-dichloro-1,4-butanediol. Claim 8 A method for preparing a polyol according to claim 1, wherein the compound represented by Chemical Formula 1 comprises one or more compounds represented by any one of Chemical Formulas 2 to 7. [Chemical Formula 2] [Chemical Formula 3] [Chemical Formula 4] [Chemical Formula 5] [Chemical Formula 6] [Chemical Formula 7] (In the above chemical formulas 2 to 7, X is a halogen element, n is an integer greater than or equal to 1, and m is an integer greater than or equal to 0.) Claim 9 A method for producing a polyol according to claim 1, further comprising, after step (b), (c) a step of removing unreacted monomers by lowering the pressure relative to the pressure of step (a). Claim 10 A method for manufacturing a polyol according to claim 1, further comprising, after step (b), a purification step of (d) adding the polyol to a solution containing a polar solvent and / or anion exchange resin and stirring. Claim 11 A method for preparing a polyol according to claim 10, wherein the polar solvent comprises water, alcohol, or a polar mixed solvent of water and alcohol. Claim 12 In claim 10, a method for producing a polyol in which the anion exchange resin comprises an ammonium group or an amine group as a functional group. Claim 13 A method for producing a polyol according to claim 10, wherein step (d) is performed for 10 hours or less under stirring conditions of 2000 rpm or less and a temperature range of 10 to 50 ℃. Claim 14 A polyol prepared by the method of claim 1 and comprising a compound represented by the following chemical formula 1. [Chemical Formula 1] In the above chemical formula 1, R is a linker derived from the above halogenated alcohol, n is an integer greater than or equal to 1, and m is an integer greater than or equal to 0. Claim 15 The method of claim 14, wherein the halogenated alcohol is 3-bromopentane-2,4-diol, (2s,3s,4r)-4-bromopentane-2,3-diol, 5-bromo-2-(bromomethyl)pentane-1,4-diol, 5-bromopentane-1,4-diol, trans-2,3-dibromo-2-butene-1,4-diol, 4-bromobutane-1,3-diol, 3-bromobutane-1,2-propanediol, 2,2-bis(bromomethyl)-1,3-propanediol, 2,3-dibromo-1,4-butanediol, 3-chloropentane-2,4-diol, (2s,3s,4r)-4-chloropentane-2,3-diol, 5-chloro-2-(chloromethyl)pentane-1,4-diol, Polyol comprising one or more of 5-chloropentane-1,4-diol, trans-2,3-dichloro-2-butene-1,4-diol, 4-chlorobutane-1,3-diol, 3-chlorobutane-1,2-propanediol, 2,2-bis(chloromethyl)-1,3-propanediol, and 2,3-dichloro-1,4-butanediol. Claim 16 In claim 14, the compound represented by Chemical Formula 1 is a polyol comprising one or more compounds represented by any one of Chemical Formulas 2 to 7. [Chemical Formula 2] [Chemical Formula 3] [Chemical Formula 4] [Chemical Formula 5] [Chemical Formula 6] [Chemical Formula 7] (In the above chemical formulas 2 to 7, X is a halogen element, n is an integer greater than or equal to 1, and m is an integer greater than or equal to 0.) Claim 17 In claim 14, a polyol having a hydroxyl value (Hv) of 10 to 1000. Claim 18 In claim 14, a polyol having an acid value (Av) of 10 or less. Claim 19 In claim 14, a polyol having a number average molecular weight (Mn) of 100 to 1500. Claim 20 In claim 14, a polyol having a molecular weight distribution value (PDI) of 1 to 10.

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