Biomass-based polyol, preparation method therefor, and purification method therefor

Abstract

A polyol according to the present invention comprises a novel compound formed by reacting biomass-based 3-hydroxypropionic acid with biomass-based polyhydric alcohol, and thus an eco-friendly biomass-based polyol having the same physical properties as polyester polyol can be provided. To this end, the polyol according to the present invention comprises at least one of compounds represented by chemical formulae 1 to 3.

Description

Biomass-based polyol, its production method and purification method

[0001] The present invention relates to a biomass-based polyol, a method for producing the same, and a method for purifying the same.

[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 are mainly prepolymers based on methylene diisocyanate (MDI) and toluene diisocyanate (TDI), as well as their derivatives. In addition to these, other isocyanate series are used in other specialized fields. The polyols used are mainly aromatic polyether polyols with aromatic groups in the main chain and aliphatic polyester polyols with aliphatic groups in the main chain.

[0004] These polyurethane resins are used in various fields such as adhesives, coatings, injection molding materials, paints, inks, coatings, foaming agents, shoe parts, clothing, and medical polymers due to their excellent wear resistance, oil resistance, solvent resistance, and elasticity.

[0005]

[0006] Polyester polyols, made by reacting refined petroleum adipic acid with glycol, are primarily used in the production of polyurethane resins. However, this process can cause environmental pollution in various ways, and large amounts of carbon dioxide are emitted during post-use disposal, posing environmental problems.

[0007] Therefore, there is a need for bio-polyols using more environmentally friendly and sustainable bio-based materials.

[0008]

[0009] Biopolyols can be manufactured using natural vegetable oils such as castor oil, soybean oil, and rapeseed oil, or wood-based biomaterials such as cellulose and lignin.

[0010] These bio-polyols have a similar chemical structure to conventional polyols, but they have the advantage of being made from renewable natural materials rather than chemical products. However, conventional polyurethanes made from bio-polyols have physical properties that are inferior to conventional polyurethanes in many ways, such as being easily discolored, having low durability (e.g., bending strength or compressive strength), and producing an unpleasant odor. This has limited their use. Furthermore, bio-polyols have significantly low reactivity, hindering the synthetic reaction for manufacturing polyurethane, resulting in low yields.

[0011]

[0012] Therefore, there is a need to develop an eco-friendly polyol that has excellent properties and can improve environmental problems by utilizing biomaterials.

[0013]

[0014] 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.

[0015] Therefore, a method for producing bio-polyols with easy molecular weight control that can be applied to various fields is required.

[0016]

[0017] Furthermore, polyols used in polyurethanes contain large amounts of unreacted oligomers and unreacted monomers with relatively small molecular weights. Polyurethanes manufactured from polyols containing large amounts of the aforementioned unreacted monomers exhibit reduced polymerization degrees and polymerization yields. Consequently, polyurethanes manufactured from polyols containing large amounts of unreacted monomers may not exhibit the desired mechanical properties.

[0018] Therefore, a method for purifying bio-polyol that can be applied to various fields without substantially containing small molecular weight unreacted oligomers and unreacted monomers is required.

[0019] The present invention provides a novel bio-based polyol having excellent physical properties while utilizing biomass-based materials.

[0020] The purpose of the present invention is to provide a novel method for producing a bio-based polyol having excellent physical properties while using biomass-based materials, and also to provide a novel polyol production method that allows easy control of molecular weight and can be applied to various fields.

[0021] The purpose of the present invention is to provide a method for producing a novel bio-based polyol having excellent physical properties while using biomass-based materials, and to purify the polyol so that it substantially does not contain unreacted oligomers and monomers having small molecular weights.

[0022] In addition, an object of the present invention is to provide a novel method for producing polyol capable of minimizing residual monomer by controlling side reactions.

[0023] The polyol according to the first embodiment of the present invention for achieving the above-described task comprises at least one of the compounds represented by the following chemical formulas 1 to 3.

[0024]

[0025] [Chemical Formula 1]

[0026]

[0027] In the above chemical formula 1,

[0028] R is a linker derived from alcohol,

[0029] The above m is an integer greater than or equal to 1, and n is an integer greater than or equal to 0.

[0030]

[0031] [Chemical Formula 2]

[0032]

[0033] In the above chemical formula 2,

[0034] R is a linker derived from alcohol,

[0035] The above m is an integer greater than or equal to 1, n is an integer greater than or equal to 0, and p is an integer greater than or equal to 0.

[0036]

[0037] [Chemical Formula 3]

[0038]

[0039]

[0040] In the above chemical formula 3,

[0041] R is a linker derived from alcohol,

[0042] The above m is an integer greater than or equal to 1, n is an integer greater than or equal to 0, p is an integer greater than or equal to 0, and r is an integer greater than or equal to 0.

[0043]

[0044] In addition, the method for producing a polyol according to the present invention for achieving the above-described task includes a step of reacting 3-hydroxypropionic acid and alcohol with a catalyst.

[0045]

[0046] A method for producing a polyol 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 an alcohol to produce a polyol.

[0047]

[0048] A method for purifying a polyol according to a third embodiment of the present invention comprises (a) a polyol preparation step of preparing a polyol containing 3-hydroxypropionic acid; and (b) a polyol purification step of introducing the polyol into a solution containing a polar solvent and an anion exchange resin and stirring the solution.

[0049]

[0050] A method for purifying a polyol according to a fourth embodiment of the present invention comprises (a) a polyol preparation step of preparing a polyol containing 3-hydroxypropionic acid; and (b) a polyol purification step of introducing the polyol into a solution containing a polar solvent and stirring the polyol.

[0051]

[0052] A method for producing a polyol according to a fifth 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 an alcohol to produce a polyol; wherein step (a) comprises: (a-1) a first polymerization step performed at a temperature of 30 to 300°C; and (a-2) a second polymerization step performed at a temperature of 30 to 300°C.

[0053] The polyol according to the present invention comprises a novel compound formed by the reaction of bio-based 3-hydroxypropionic acid and bio-based alcohol, thereby providing an eco-friendly biomass-based polyol having the same physical properties as polyester polyol.

[0054] In addition, the polyol purification method of the present invention can produce a novel bio-based polyol having excellent physical properties while using a biomass-based material, and can also effectively remove unreacted monomers that have not been polymerized or oligomerized within the polyol.

[0055] In addition, the manufacturing method of the present invention can manufacture a novel bio-based polyol that can minimize residual monomer by controlling side reactions.

[0056]

[0057] Hereinafter, the polyol of the present invention and its production method will be specifically described with reference to the attached chemical formula and table.

[0058]

[0059] 1. First implementation sun

[0060]

[0061] polyol

[0062]

[0063] The polyol according to the first embodiment of the present invention is formed by the reaction of bio-based 3-hydroxypropionic acid and bio-based alcohol.

[0064] More specifically, the polyol of the present invention comprises at least one of the compounds represented by the following chemical formulas 1 to 3.

[0065]

[0066] [Chemical Formula 1]

[0067]

[0068] In the above chemical formula 1,

[0069] R is a linker derived from alcohol,

[0070] The above m is an integer greater than or equal to 1, and n is an integer greater than or equal to 0.

[0071]

[0072] [Chemical Formula 2]

[0073]

[0074] In the above chemical formula 2,

[0075] R is a linker derived from alcohol,

[0076] The above m is an integer greater than or equal to 1, n is an integer greater than or equal to 0, and p is an integer greater than or equal to 0.

[0077]

[0078] [Chemical Formula 3]

[0079]

[0080]

[0081] In the above chemical formula 3,

[0082] R is a linker derived from alcohol,

[0083] The above m is an integer greater than or equal to 1, n is an integer greater than or equal to 0, p is an integer greater than or equal to 0, and r is an integer greater than or equal to 0.

[0084]

[0085] The polyol of the present invention uses bio-based 3-hydroxypropionic acid represented by the following chemical formula 4.

[0086]

[0087] [Chemical Formula 4]

[0088]

[0089]

[0090] 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.

[0091]

[0092] The polyol of the present invention includes compounds represented by the chemical formulas 1 to 3 formed by the reaction of 3-hydroxypropionic acid and alcohol.

[0093]

[0094] In the present invention, it is preferable to use a bio-based alcohol such as 3-hydroxypropionic acid.

[0095] The above alcohol may be a dihydric alcohol, and preferably a dihydric to tetrahydric alcohol may be used.

[0096] The alcohols are 2,3-butanediol, 1,3-propanediol, 1,4-butanediol, 1,6 hexanediol and ethylene glycol, glycerol, pentaerythritol, trimethylolpropane, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-butynediol, neopentyl glycol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, bis(hydroxymethyl)cyclohexane, triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, dibutylene glycol, polybutylene glycoltrimethylolpropane, glycerol, trishydroxyethyl isocyanurate, castor oil and It may contain one or more types of dipentaerythritol, but there are no specific restrictions on the type of alcohol.

[0097]

[0098] In the above chemical formulas 1 to 3, R means a linking group derived from the alcohol.

[0099] The above R is linked to 3-hydroxypropionic acid by removing the OH group. In addition, the form of the above R may vary depending on the type of the alcohol.

[0100]

[0101] For example, when the alcohol is 1,3-propanediol, the chemical formula 1 can be represented by the following chemical formula 5.

[0102]

[0103] [Chemical Formula 5]

[0104]

[0105]

[0106] Preferably, the polyol of the present invention may have a number average molecular weight (Mn) of 200 to 10,000 and a weight average molecular weight (Mw) of 600 to 6,000.

[0107] Additionally, the hydroxyl value (Hv) of the polyol may be 10 to 1000, and preferably, the hydroxyl value (Hv) may be 10 to 500.

[0108] In addition, the acid value (Av) of the polyol may be 10 or less, and the molecular weight distribution value (PDI) may be 1 to 10. Preferably, the molecular weight distribution value (PDI) of the polyol may be 1 to 3.

[0109] Within the above range, a polyol that can be used in the manufacture of polyurethane, etc. can be obtained. If a polyol having properties outside the above range is used, the properties of the polyurethane may be deteriorated.

[0110]

[0111] Polyurethane polymerization involves the bonding of isocyanate groups and polyols. Depending on the polyol molecular weight, the polymerized polyurethane's physical properties, 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 that meets the required range of properties.

[0112]

[0113] The polyol of the present invention is a bio-based material that can satisfy all of the various properties of polyurethane required and is environmentally friendly.

[0114]

[0115] Method for producing polyol

[0116]

[0117] Next, a method for producing a polyol according to the first embodiment of the present invention will be described in detail.

[0118]

[0119] The method for producing a polyol of the present invention comprises a step of reacting 3-hydroxypropionic acid with an alcohol together with a catalyst. Here, the alcohol may be one or more polyhydric alcohols.

[0120]

[0121] In the manufacturing method of the present invention, when reacting 3-hydroxypropionic acid and the alcohol with a catalyst, it is preferable to perform the reaction at a temperature of 70 to 150°C and a pressure of 30 to 150 torr.

[0122]

[0123] Here, the catalyst may be a Bronsted acid catalyst or a Lewis acid catalyst.

[0124] Preferably, the Bronsted acid catalyst may include at least one of p-Toluenesulfonic acid (p-TSA), H2SO4, HCL, H2CO3, HNO3, HBF4, HSbF6, ClSO3H, FSO3H, CF3SO3H, and CH3SO3H.

[0125] 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.

[0126]

[0127] In addition, as described above, the alcohol may be a divalent alcohol, and preferably a divalent to tetravalent alcohol may be used.

[0128] The alcohols are 2,3-butanediol, 1,3-propanediol, 1,4-butanediol, 1,6 hexanediol and ethylene glycol, glycerol, pentaerythritol, trimethylolpropane, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-butynediol, neopentyl glycol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, bis(hydroxymethyl)cyclohexane, triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, dibutylene glycol, polybutylene glycoltrimethylolpropane, glycerol, trishydroxyethyl isocyanurate, castor oil and It may contain one or more types of dipentaerythritol, but there are no specific restrictions on the type of alcohol.

[0129]

[0130] The polyol of the present invention can have various characteristics depending on the type of one or more polyhydric alcohols and polymerization reaction conditions.

[0131]

[0132] 2. Second implementation sun

[0133]

[0134] A method for producing a polyol 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 an alcohol to produce a polyol.

[0135]

[0136] Polyols can have various molecular weights depending on the application. Accordingly, it is desirable to polymerize 3-hydroxypropionic acid contained in the polyol to derive poly-3-hydroxypropionic acid.

[0137] To this end, the manufacturing method of the present invention includes a step of (a) polymerizing 3-hydroxypropionic acid.

[0138]

[0139] Here, a catalyst can be used when polymerizing 3-hydroxypropionic acid to induce poly-3-hydroxypropionic acid.

[0140]

[0141] 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.

[0142] Preferably, the Bronsted acid catalyst may include at least one 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.

[0143] Here, the ion exchange resin containing the sulfonic acid group may include at least one of Amberlyst 15, Amberlyst 36, and Amberlite IR 120.

[0144] 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.

[0145]

[0146] Here, the molecular weight of the polyol can be controlled depending on the type and content of the catalyst.

[0147] 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.

[0148]

[0149] 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.

[0150]

[0151] Next, the manufacturing method of the present invention includes the step of (b) producing a polyol by reacting polymerized 3-hydroxypropionic acid with alcohol.

[0152]

[0153] Here, the alcohol may be one or more polyhydric alcohols.

[0154]

[0155] In addition, as described above, the alcohol may be a divalent alcohol, preferably a divalent to hexavalent alcohol, and more preferably a divalent to tetravalent alcohol.

[0156] The above alcohols are 1,3-butanediol, 2,3-butanediol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol and ethylene glycol, glycerol, pentaerythritol, trimethylolpropane, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,4-butynediol, neopentyl glycol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, 2-methyl-1,3-propanediol, 2-methyl-1,4-butanediol, 2-methyl-1,8-octanediol, 2,7-dimethyl-1,8-octanediol, 1,9-nonanediol, It may include at least one of 2-methyl-1,9-nonanediol, 2,8-dimethyl-1,9-nonanediol, 1,10-decanediol, 2,2-diethyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,4-cyclohexanediol, cyclohexanedimethanol, 3(or 4), 8(or 9)-dihydroxytricyclodecane, bis(hydroxymethyl)cyclohexane, triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, dibutylene glycol, polybutylene glycoltrimethylolpropane, glycerol, trishydroxyethyl isocyanurate, castor oil, dipentaerythritol, and sorbitol, but the type of alcohol is not particularly limited.

[0157]

[0158] In the manufacturing method of the present invention, when reacting the polymerized poly-3-hydroxypropionic acid and the alcohol with a catalyst, 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, 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, step (b) may be performed at a temperature of 70 to 150°C and a pressure of 0.1 to 150 torr.

[0159]

[0160] In addition, the polyol manufacturing method 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).

[0161] 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).

[0162] 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).

[0163]

[0164] As described above, the polyol of the present invention can have various properties depending on the type of one or more polyhydric alcohols and polymerization reaction conditions.

[0165]

[0166] Next, a polyol according to the second embodiment of the present invention will be described.

[0167]

[0168] The polyol of the present invention is manufactured by the above-described method and is formed by the reaction of polymerized 3-hydroxypropionic acid and alcohol.

[0169] More specifically, the polyol of the present invention comprises at least one of the compounds represented by the following chemical formulas 1 to 3.

[0170]

[0171] [Chemical Formula 1]

[0172]

[0173] In the above chemical formula 1,

[0174] R is a linker derived from alcohol,

[0175] The above m is an integer greater than or equal to 1, and n is an integer greater than or equal to 0.

[0176]

[0177] [Chemical Formula 2]

[0178]

[0179] In the above chemical formula 2,

[0180] R is a linker derived from alcohol,

[0181] The above m is an integer greater than or equal to 1, n is an integer greater than or equal to 0, and p is an integer greater than or equal to 0.

[0182]

[0183] [Chemical Formula 3]

[0184]

[0185]

[0186] In the above chemical formula 3,

[0187] R is a linker derived from alcohol,

[0188] The above m is an integer greater than or equal to 1, n is an integer greater than or equal to 0, p is an integer greater than or equal to 0, and r is an integer greater than or equal to 0.

[0189]

[0190] The polyol of the present invention uses bio-based 3-hydroxypropionic acid represented by the following chemical formula 4.

[0191]

[0192] [Chemical Formula 4]

[0193]

[0194]

[0195] 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.

[0196]

[0197] The polyol of the present invention includes compounds represented by the chemical formulas 1 to 3 formed by reacting poly 3-hydroxypropionic acid polymerized with alcohol.

[0198]

[0199] In the present invention, it is preferable to use a bio-based alcohol such as 3-hydroxypropionic acid.

[0200] The above alcohol is as described above.

[0201]

[0202]

[0203] In the above chemical formulas 1 to 3, R means a linking group derived from the alcohol.

[0204] The above R is linked to 3-hydroxypropionic acid by removing the OH group. In addition, the form of the above R may vary depending on the type of the alcohol.

[0205]

[0206] For example, when the alcohol is 1,3-propanediol, the chemical formula 1 can be represented by the following chemical formula 5.

[0207]

[0208] [Chemical Formula 5]

[0209]

[0210]

[0211] Preferably, the polyol of the present invention may have a number average molecular weight (Mn) of 100 to 1000 and a weight average molecular weight (Mw) of 200 to 2000.

[0212] Additionally, the hydroxyl value (Hv) of the polyol may be 10 to 1000, and preferably, the hydroxyl value (Hv) may be 100 to 200.

[0213] In addition, the acid value (Av) of the polyol may be 10 or less, and more preferably less than 2.

[0214] Additionally, 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.

[0215] Within the above range, a polyol that can be used in the manufacture of polyurethane, etc. can be obtained. If a polyol having properties outside the above range is used, the properties of the polyurethane may be deteriorated.

[0216]

[0217] Polyurethane polymerization involves the bonding of isocyanate groups and polyols. Depending on the polyol molecular weight, the polymerized polyurethane's physical properties, 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 that meets the required range of properties.

[0218]

[0219] The polyol of the present invention is a bio-based material that can satisfy all of the various properties of polyurethane required and is environmentally friendly.

[0220]

[0221] 3. Third Implementation Sun

[0222]

[0223] A method for purifying polyol according to the third embodiment of the present invention will be described in detail.

[0224]

[0225] The polyol purification method of the present invention comprises (a) a polyol preparation step of preparing a polyol containing 3-hydroxypropionic acid; and (b) a polyol purification step of adding the polyol and an anion exchange resin to a solution containing a polar solvent and stirring the mixture.

[0226]

[0227] First, the method of the present invention includes a polyol preparation step of (a) preparing a polyol containing 3-hydroxypropionic acid.

[0228]

[0229] The polyol manufactured according to the above method (a) is a polymer polymerized including 3-hydroxypropionic acid, and other components are not particularly limited.

[0230] Preferably, the polyol may include at least one compound represented by the following chemical formulas 1 to 3.

[0231]

[0232] [Chemical Formula 1]

[0233]

[0234] In the above chemical formula 1,

[0235] R is a linker derived from alcohol,

[0236] The above m is an integer greater than or equal to 1, and n is an integer greater than or equal to 0.

[0237]

[0238] [Chemical Formula 2]

[0239]

[0240] In the above chemical formula 2,

[0241] R is a linker derived from alcohol,

[0242] The above m is an integer greater than or equal to 1, n is an integer greater than or equal to 0, and p is an integer greater than or equal to 0.

[0243]

[0244] [Chemical Formula 3]

[0245]

[0246]

[0247] In the above chemical formula 3,

[0248] R is a linker derived from alcohol,

[0249] The above m is an integer greater than or equal to 1, n is an integer greater than or equal to 0, p is an integer greater than or equal to 0, and r is an integer greater than or equal to 0.

[0250]

[0251] The polyol of the present invention described above uses bio-based 3-hydroxypropionic acid represented by the following chemical formula 4.

[0252]

[0253] [Chemical Formula 4]

[0254]

[0255]

[0256] 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.

[0257]

[0258] In the present invention, it is preferable to use a bio-based alcohol such as 3-hydroxypropionic acid.

[0259] The above alcohol may be a dihydric alcohol, and preferably a dihydric to tetrahydric alcohol may be used.

[0260] The above alcohols are 1,3-butanediol, 2,3-butanediol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol and ethylene glycol, glycerol, pentaerythritol, trimethylolpropane, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,4-butynediol, neopentyl glycol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, 2-methyl-1,3-propanediol, 2-methyl-1,4-butanediol, 2-methyl-1,8-octanediol, 2,7-dimethyl-1,8-octanediol, 1,9-nonanediol, It may include at least one of 2-methyl-1,9-nonanediol, 2,8-dimethyl-1,9-nonanediol, 1,10-decanediol, 2,2-diethyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,4-cyclohexanediol, cyclohexanedimethanol, 3(or 4), 8(or 9)-dihydroxytricyclodecane, bis(hydroxymethyl)cyclohexane, triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, dibutylene glycol, polybutylene glycoltrimethylolpropane, glycerol, trishydroxyethyl isocyanurate, castor oil, dipentaerythritol, and sorbitol, but the type of alcohol is not particularly limited.

[0261]

[0262] In the above chemical formulas 1 to 3, R means a linking group derived from the alcohol.

[0263] The above R is linked to 3-hydroxypropionic acid by removing the OH group. In addition, the form of the above R may vary depending on the type of the alcohol.

[0264]

[0265] For example, when the alcohol is 1,3-propanediol, the chemical formula 1 can be represented by the following chemical formula 5.

[0266]

[0267] [Chemical Formula 5]

[0268]

[0269]

[0270] The above step (a) can be performed as a process including a step of (a1) reacting 3-hydroxypropionic acid and alcohol with a catalyst.

[0271]

[0272] In the above step (a1), when reacting 3-hydroxypropionic acid and the alcohol with a catalyst, it is preferable to perform the reaction at a temperature of 30 to 300°C and a pressure of 0.1 to 700 torr. More preferably, the above step (a1) can be performed at a temperature of 50 to 150°C and a pressure of 0.1 to 300 torr, and even more preferably, it can be performed at a temperature of 70 to 150°C and a pressure of 0.1 to 150 torr.

[0273]

[0274] Here, the catalyst may be a Bronsted acid catalyst, a Lewis acid catalyst, or a mixed catalyst of a Bronsted acid catalyst and a Lewis acid catalyst.

[0275] Preferably, the Bronsted acid catalyst is p-Toluenesulfonic acid (p-TSA), an ion exchange resin containing a sulfonic acid group, It may contain one or more of H2SO4, HCL, H2CO3, HNO3, HBF4, HSbF6, ClSO3H, FSO3H, CF3SO3H, and CH3SO3H.

[0276] Here, the ion exchange resin containing the sulfonic acid group may include at least one of Amberlyst 15, Amberlyst 36, and Amberlite IR 120.

[0277] 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.

[0278]

[0279] In addition, as described above, the alcohol may be a divalent alcohol, and preferably a divalent to tetravalent alcohol may be used.

[0280]

[0281] In addition, the step (a) above can be performed as a process including (a2-1) a step of polymerizing 3-hydroxypropionic acid; and (a2-2) a step of reacting the polymerized 3-hydroxypropionic acid with an alcohol to produce a polyol.

[0282]

[0283] Polyols can have various molecular weights depending on the application. Accordingly, it is desirable to polymerize 3-hydroxypropionic acid contained in the polyol to derive poly-3-hydroxypropionic acid.

[0284] For this purpose, the step (a) may include a step of polymerizing (a2-1) 3-hydroxypropionic acid.

[0285]

[0286] Here, a catalyst can be used when polymerizing 3-hydroxypropionic acid to induce poly-3-hydroxypropionic acid.

[0287]

[0288] 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.

[0289] Preferably, the Bronsted acid catalyst may include at least one 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.

[0290] Here, the ion exchange resin containing the sulfonic acid group may include at least one of Amberlyst 15, Amberlyst 36, and Amberlite IR 120.

[0291] 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.

[0292]

[0293] Here, the molecular weight of the polyol can be controlled depending on the type and content of the catalyst.

[0294] 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.

[0295]

[0296] In addition, it is preferable that the step (a2-1) is performed at a temperature of 30 to 300°C and a pressure of 0.1 to 700 torr. More preferably, the step (a2-1) 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 (a2-1) can be performed at a temperature of 70 to 150°C and a pressure of 0.1 to 150 torr.

[0297]

[0298] Next, the step (a) includes a step of producing a polyol by reacting (a2-2) polymerized 3-hydroxypropionic acid with alcohol.

[0299]

[0300] Here, the alcohol may be one or more polyhydric alcohols. Furthermore, as described above, the alcohol may be a polyhydric dihydric alcohol, preferably a dihydric to hexahydric alcohol, and more preferably a dihydric to tetrahydric alcohol. Preferred types of alcohols are as described above.

[0301]

[0302] In the above step (a2-2), when reacting the polymerized poly-3-hydroxypropionic acid and the alcohol with a catalyst, 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.

[0303]

[0304] In addition, the step (a) may further include, after the step (a2-2), a step (a2-3) of removing unreacted monomers by lowering the pressure compared to the pressure of the step (a2-2).

[0305] Here, the step (a2-3) may be performed at the same temperature as the step (a2-2), but is performed under a pressure lower than the pressure controlled in the step (a2-2).

[0306] The above step (a2-3) 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 (a2-2).

[0307]

[0308] Next, the method of the present invention includes a polyol purification step of (b) adding the polyol to a solution containing a polar solvent and an anion exchange resin and stirring.

[0309]

[0310] The polyol manufactured through the above step (a) is polymerized with 3-hydroxypropionic acid and alcohol, but may contain a large amount of unreacted oligomers and monomers that have not been polymerized or oligomerized.

[0311] 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.

[0312]

[0313] Unreacted oligomers and unreacted monomers contained in the above polyol can lower the degree of polymerization of polyurethane and deteriorate the mechanical properties of polyurethane.

[0314] Accordingly, the method of the present invention removes unreacted oligomers and unreacted monomers having low molecular weight contained in the polyol using the step (b) described above.

[0315]

[0316] (b) According to step (b), the polyol is introduced into a solution containing a polar solvent and an anion exchange resin. As the mixture of the polyol and the solution is stirred, polymers having a molecular weight of 400 or more contained in the polyol are precipitated in a solid state, and most of the unreacted oligomers and unreacted monomers are dissolved in the solution due to the difference in polarity of the polar solvent. Therefore, by utilizing this, polyols having low molecular weight and high molecular weight can be separated, and extraction can be performed smoothly.

[0317] 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.

[0318] 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.

[0319]

[0320] In addition, the solution includes an anion exchange resin along with a polar solvent. In the present invention, the removal of small-molecular-weight unreacted oligomers and unreacted monomers contained in the polyol is maximized by using the anion exchange resin. Specifically, the basic atom group and terminal chloride ions contained in the anion exchange resin can ion-exchange molecules having hydroxide ions. The ion exchange action described above can remove small-molecular-weight unreacted oligomers and unreacted monomers contained in the polyol.

[0321]

[0322] 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.

[0323]

[0324] 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.

[0325] 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.

[0326]

[0327] 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.

[0328]

[0329] Additionally, the above anion exchange resins can be used alone or in combination of two or more.

[0330]

[0331] After the above-described step (b), the solution including the polar solvent and the anion exchange resin can be removed, and a purified polyol can be obtained.

[0332]

[0333] The step (b) 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) 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.

[0334]

[0335] Next, the polyol of the present invention manufactured and purified using the above-described purification method will be described.

[0336]

[0337] The polyol of the present invention comprises at least one compound represented by the following chemical formulas 1 to 3 and is purified by the above-described method, so that the number average molecular weight (Mn) after purification increases compared to the number average molecular weight (Mn) before purification.

[0338]

[0339] [Chemical Formula 1]

[0340]

[0341] In the above chemical formula 1,

[0342] R is a linker derived from alcohol,

[0343] The above m is an integer greater than or equal to 1, and n is an integer greater than or equal to 0.

[0344]

[0345] [Chemical Formula 2]

[0346]

[0347] In the above chemical formula 2,

[0348] R is a linker derived from alcohol,

[0349] The above m is an integer greater than or equal to 1, n is an integer greater than or equal to 0, and p is an integer greater than or equal to 0.

[0350]

[0351] [Chemical Formula 3]

[0352]

[0353]

[0354] In the above chemical formula 3,

[0355] R is a linker derived from alcohol,

[0356] The above m is an integer greater than or equal to 1, n is an integer greater than or equal to 0, p is an integer greater than or equal to 0, and r is an integer greater than or equal to 0.

[0357]

[0358] As described above, the polyol of the present invention uses bio-based 3-hydroxypropionic acid represented by the following chemical formula 4.

[0359]

[0360] [Chemical Formula 4]

[0361]

[0362]

[0363] 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.

[0364]

[0365] The polyol of the present invention includes compounds represented by the chemical formulas 1 to 3 formed by reacting poly 3-hydroxypropionic acid polymerized with alcohol.

[0366]

[0367] In the present invention, it is preferable to use a bio-based alcohol such as 3-hydroxypropionic acid.

[0368] The alcohol may be a dihydric alcohol, preferably a dihydric to tetrahydric alcohol, and the preferred types of alcohol are as described above.

[0369]

[0370] In the above chemical formulas 1 to 3, R means a linking group derived from the alcohol.

[0371] The above R is linked to 3-hydroxypropionic acid by removing the OH group. In addition, the form of the above R may vary depending on the type of the alcohol.

[0372]

[0373] For example, when the alcohol is 1,3-propanediol, the chemical formula 1 can be represented by the following chemical formula 5.

[0374]

[0375] [Chemical Formula 5]

[0376]

[0377]

[0378] As the polyol of the present invention is purified by the above-described method, the number average molecular weight (Mn) after purification increases by 10% or more compared to the number average molecular weight (Mn) before purification.

[0379] Polyol is a polymerization of 3-hydroxypropionic acid and alcohol, but may contain a large amount of unreacted monomers that have not been polymerized or oligomerized.

[0380] The polyol of the present invention is purified using the above-described purification method, thereby substantially removing all unreacted monomers. Accordingly, the polyol of the present invention has an increased number-average molecular weight (Mn) due to the removal of low-molecular-weight unreacted monomers. Preferably, the polyol of the present invention can have a number-average molecular weight (Mn) that increases by at least 10% after purification compared to the number-average molecular weight (Mn) before purification.

[0381] Similarly, the polyol of the present invention has a reduced PDI value, hydroxyl value (Hv), and acid value (Av) due to the removal of low molecular weight unreacted monomers.

[0382]

[0383] 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 5000.

[0384] Additionally, the hydroxyl value (Hv) of the polyol may be 10 to 1000, and preferably, the hydroxyl value (Hv) may be 80 to 200.

[0385] In addition, the acid value (Av) of the polyol may be 10 or less, and more preferably less than 3.

[0386] Additionally, 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.

[0387] Within the above range, a polyol that can be used in the manufacture of polyurethane, etc. can be obtained. If a polyol having properties outside the above range is used, the properties of the polyurethane may be deteriorated.

[0388]

[0389] 4. The fourth implementation sun

[0390]

[0391] A method for purifying polyol according to the fourth embodiment of the present invention will be described in detail.

[0392]

[0393] The polyol purification method of the present invention comprises (a) a polyol preparation step of preparing a polyol containing 3-hydroxypropionic acid; and (b) a polyol purification step of introducing the polyol into a solution containing a polar solvent and stirring the solution.

[0394]

[0395] First, the method of the present invention includes a polyol preparation step of (a) preparing a polyol containing 3-hydroxypropionic acid.

[0396]

[0397] The polyol manufactured according to the above method (a) is a polymer polymerized including 3-hydroxypropionic acid, and other components are not particularly limited.

[0398] Preferably, the polyol may include at least one compound represented by the following chemical formulas 1 to 3.

[0399]

[0400] [Chemical Formula 1]

[0401]

[0402] In the above chemical formula 1,

[0403] R is a linker derived from alcohol,

[0404] The above m is an integer greater than or equal to 1, and n is an integer greater than or equal to 0.

[0405]

[0406] [Chemical Formula 2]

[0407]

[0408] In the above chemical formula 2,

[0409] R is a linker derived from alcohol,

[0410] The above m is an integer greater than or equal to 1, n is an integer greater than or equal to 0, and p is an integer greater than or equal to 0.

[0411]

[0412] [Chemical Formula 3]

[0413]

[0414]

[0415] In the above chemical formula 3,

[0416] R is a linker derived from alcohol,

[0417] The above m is an integer greater than or equal to 1, n is an integer greater than or equal to 0, p is an integer greater than or equal to 0, and r is an integer greater than or equal to 0.

[0418]

[0419] The polyol of the present invention described above uses bio-based 3-hydroxypropionic acid represented by the following chemical formula 4.

[0420]

[0421] [Chemical Formula 4]

[0422]

[0423]

[0424] 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.

[0425]

[0426] In the present invention, it is preferable to use a bio-based alcohol such as 3-hydroxypropionic acid.

[0427] The above alcohol may be a dihydric alcohol, and preferably a dihydric to tetrahydric alcohol may be used.

[0428] The above alcohols are 1,3-butanediol, 2,3-butanediol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol and ethylene glycol, glycerol, pentaerythritol, trimethylolpropane, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,4-butynediol, neopentyl glycol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, 2-methyl-1,3-propanediol, 2-methyl-1,4-butanediol, 2-methyl-1,8-octanediol, 2,7-dimethyl-1,8-octanediol, 1,9-nonanediol, It may include at least one of 2-methyl-1,9-nonanediol, 2,8-dimethyl-1,9-nonanediol, 1,10-decanediol, 2,2-diethyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,4-cyclohexanediol, cyclohexanedimethanol, 3(or 4), 8(or 9)-dihydroxytricyclodecane, bis(hydroxymethyl)cyclohexane, triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, dibutylene glycol, polybutylene glycoltrimethylolpropane, glycerol, trishydroxyethyl isocyanurate, castor oil, dipentaerythritol, and sorbitol, but the type of alcohol is not particularly limited.

[0429]

[0430] In the above chemical formulas 1 to 3, R means a linking group derived from the alcohol.

[0431] The above R is linked to 3-hydroxypropionic acid by removing the OH group. In addition, the form of the above R may vary depending on the type of the alcohol.

[0432]

[0433] For example, when the alcohol is 1,3-propanediol, the chemical formula 1 can be represented by the following chemical formula 5.

[0434]

[0435] [Chemical Formula 5]

[0436]

[0437]

[0438] The above step (a) can be performed as a process including a step of (a1) reacting 3-hydroxypropionic acid and alcohol with a catalyst.

[0439]

[0440] In the above step (a1), when reacting 3-hydroxypropionic acid and the alcohol with a catalyst, it is preferable to perform the reaction at a temperature of 30 to 300°C and a pressure of 0.1 to 700 torr. More preferably, the above step (a1) can be performed at a temperature of 50 to 150°C and a pressure of 0.1 to 300 torr, and even more preferably, it can be performed at a temperature of 70 to 150°C and a pressure of 0.1 to 150 torr.

[0441]

[0442] Here, the catalyst may be a Bronsted acid catalyst, a Lewis acid catalyst, or a mixed catalyst of a Bronsted acid catalyst and a Lewis acid catalyst.

[0443] Preferably, the Bronsted acid catalyst is p-Toluenesulfonic acid (p-TSA), an ion exchange resin containing a sulfonic acid group, It may contain one or more of H2SO4, HCL, H2CO3, HNO3, HBF4, HSbF6, ClSO3H, FSO3H, CF3SO3H, and CH3SO3H.

[0444] Here, the ion exchange resin containing the sulfonic acid group may include at least one of Amberlyst 15, Amberlyst 36, and Amberlite IR 120.

[0445] 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.

[0446]

[0447] In addition, as described above, the alcohol may be a divalent alcohol, and preferably a divalent to tetravalent alcohol may be used.

[0448]

[0449] In addition, the step (a) above can be performed as a process including (a2-1) a step of polymerizing 3-hydroxypropionic acid; and (a2-2) a step of reacting the polymerized 3-hydroxypropionic acid with an alcohol to produce a polyol.

[0450]

[0451] Polyols can have various molecular weights depending on the application. Accordingly, it is desirable to polymerize 3-hydroxypropionic acid contained in the polyol to derive poly-3-hydroxypropionic acid.

[0452] For this purpose, the step (a) may include a step of polymerizing (a2-1) 3-hydroxypropionic acid.

[0453]

[0454] Here, a catalyst can be used when polymerizing 3-hydroxypropionic acid to induce poly-3-hydroxypropionic acid.

[0455]

[0456] 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.

[0457] Preferably, the Bronsted acid catalyst may include at least one 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.

[0458] Here, the ion exchange resin containing the sulfonic acid group may include at least one of Amberlyst 15, Amberlyst 36, and Amberlite IR 120.

[0459] 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.

[0460]

[0461] Here, the molecular weight of the polyol can be controlled depending on the type and content of the catalyst.

[0462] 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.

[0463]

[0464] In addition, it is preferable that the step (a2-1) is performed at a temperature of 30 to 300°C and a pressure of 0.1 to 700 torr. More preferably, the step (a2-1) 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 (a2-1) can be performed at a temperature of 70 to 150°C and a pressure of 0.1 to 150 torr.

[0465]

[0466] Next, the step (a) includes a step of producing a polyol by reacting (a2-2) polymerized 3-hydroxypropionic acid with alcohol.

[0467]

[0468] Here, the alcohol may be one or more polyhydric alcohols. Furthermore, as described above, the alcohol may be a polyhydric dihydric alcohol, preferably a dihydric to hexahydric alcohol, and more preferably a dihydric to tetrahydric alcohol. Preferred types of alcohols are as described above.

[0469]

[0470] In the above step (a2-2), when reacting the polymerized poly-3-hydroxypropionic acid and the alcohol with a catalyst, 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.

[0471]

[0472] In addition, the step (a) may further include, after the step (a2-2), a step (a2-3) of removing unreacted monomers by lowering the pressure compared to the pressure of the step (a2-2).

[0473] Here, the step (a2-3) may be performed at the same temperature as the step (a2-2), but is performed under a pressure lower than the pressure controlled in the step (a2-2).

[0474] The above step (a2-3) 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 (a2-2).

[0475]

[0476] Next, the method of the present invention includes a polyol purification step of (b) adding the polyol to a solution containing a polar solvent and stirring.

[0477]

[0478] The polyol manufactured through the above step (a) is polymerized with 3-hydroxypropionic acid and alcohol, but may contain a large amount of unreacted oligomers and monomers that have not been polymerized or oligomerized.

[0479] 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.

[0480]

[0481] Unreacted oligomers and unreacted monomers contained in the above polyol can lower the degree of polymerization of polyurethane and deteriorate the mechanical properties of polyurethane.

[0482] Accordingly, the method of the present invention removes unreacted oligomers and unreacted monomers having low molecular weight contained in the polyol using the step (b) described above.

[0483]

[0484] (b) According to step (b), the polyol is introduced into a solution containing a polar solvent. As the mixture of the polyol and the solution is stirred, polymers having a molecular weight of 400 or more contained in the polyol are precipitated in a solid state, and most of the unreacted oligomers and unreacted monomers are dissolved in the solution due to the difference in polarity of the polar solvent. Therefore, by utilizing this, polyols having low molecular weight and high molecular weight can be separated, and extraction can be performed smoothly.

[0485] 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.

[0486] 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.

[0487]

[0488] After the above-described step (b), the solution including the polar solvent is completely removed, and a purified polyol can be obtained.

[0489]

[0490] The step (b) 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) 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.

[0491]

[0492]

[0493] Next, the polyol of the present invention manufactured and purified using the above-described purification method will be described.

[0494]

[0495] The polyol of the present invention comprises at least one compound represented by the following chemical formulas 1 to 3 and is purified by the above-described method, so that the number average molecular weight (Mn) after purification increases compared to the number average molecular weight (Mn) before purification.

[0496]

[0497] [Chemical Formula 1]

[0498]

[0499] In the above chemical formula 1,

[0500] R is a linker derived from alcohol,

[0501] The above m is an integer greater than or equal to 1, and n is an integer greater than or equal to 0.

[0502]

[0503] [Chemical Formula 2]

[0504]

[0505] In the above chemical formula 2,

[0506] R is a linker derived from alcohol,

[0507] The above m is an integer greater than or equal to 1, n is an integer greater than or equal to 0, and p is an integer greater than or equal to 0.

[0508]

[0509] [Chemical Formula 3]

[0510]

[0511]

[0512] In the above chemical formula 3,

[0513] R is a linker derived from alcohol,

[0514] The above m is an integer greater than or equal to 1, n is an integer greater than or equal to 0, p is an integer greater than or equal to 0, and r is an integer greater than or equal to 0.

[0515]

[0516] As described above, the polyol of the present invention uses bio-based 3-hydroxypropionic acid represented by the following chemical formula 4.

[0517]

[0518] [Chemical Formula 4]

[0519]

[0520]

[0521] 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.

[0522]

[0523] The polyol of the present invention includes compounds represented by the chemical formulas 1 to 3 formed by reacting poly 3-hydroxypropionic acid polymerized with alcohol.

[0524]

[0525] In the present invention, it is preferable to use a bio-based alcohol such as 3-hydroxypropionic acid.

[0526] The alcohol may be a dihydric alcohol, preferably a dihydric to tetrahydric alcohol, and the preferred types of alcohol are as described above.

[0527]

[0528] In the above chemical formulas 1 to 3, R means a linking group derived from the alcohol.

[0529] The above R is linked to 3-hydroxypropionic acid by removing the OH group. In addition, the form of the above R may vary depending on the type of the alcohol.

[0530]

[0531] For example, when the alcohol is 1,3-propanediol, the chemical formula 1 can be represented by the following chemical formula 5.

[0532]

[0533] [Chemical Formula 5]

[0534]

[0535]

[0536] As the polyol of the present invention is purified by the above-described method, the number average molecular weight (Mn) after purification increases by 10% or more compared to the number average molecular weight (Mn) before purification.

[0537] Polyol is a polymerization of 3-hydroxypropionic acid and alcohol, but may contain a large amount of unreacted monomers that have not been polymerized or oligomerized.

[0538] The polyol of the present invention is purified using the above-described purification method, thereby substantially removing all unreacted monomers. Accordingly, the polyol of the present invention has an increased number-average molecular weight (Mn) due to the removal of low-molecular-weight unreacted monomers. Preferably, the polyol of the present invention can have a number-average molecular weight (Mn) that increases by at least 10% after purification compared to the number-average molecular weight (Mn) before purification.

[0539] Similarly, the polyol of the present invention has a reduced PDI value, hydroxyl value (Hv), and acid value (Av) due to the removal of low molecular weight unreacted monomers.

[0540]

[0541] 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 5000.

[0542] Additionally, the hydroxyl value (Hv) of the polyol may be 10 to 1000, and preferably, the hydroxyl value (Hv) may be 80 to 200.

[0543] In addition, the acid value (Av) of the polyol may be 10 or less, and more preferably less than 3.

[0544] Additionally, 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.

[0545] Within the above range, a polyol that can be used in the manufacture of polyurethane, etc. can be obtained. If a polyol having properties outside the above range is used, the properties of the polyurethane may be deteriorated.

[0546]

[0547] 5. Fifth Implementation Sun

[0548]

[0549] A method for producing a polyol according to the fifth embodiment of the present invention will be described in detail.

[0550]

[0551] A method for producing a polyol according to a fifth 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 an alcohol to produce a polyol, wherein step (a) comprises (a-1) a first polymerization step performed at a temperature of 30 to 300°C; and (a-2) a second polymerization step performed at a temperature of 30 to 300°C.

[0552]

[0553] Polyols can have various molecular weights depending on the application. Accordingly, it is desirable to polymerize 3-hydroxypropionic acid contained in the polyol to derive poly-3-hydroxypropionic acid.

[0554] To this end, the manufacturing method of the present invention includes a step of (a) polymerizing 3-hydroxypropionic acid.

[0555]

[0556] Here, a catalyst can be used when polymerizing 3-hydroxypropionic acid to induce poly-3-hydroxypropionic acid.

[0557]

[0558] 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.

[0559] Preferably, the Bronsted acid catalyst may include at least one 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.

[0560] Here, the ion exchange resin containing the sulfonic acid group may include at least one of Amberlyst 15, Amberlyst 36, and Amberlite IR 120.

[0561] 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.

[0562]

[0563] Here, the molecular weight of the polyol can be controlled depending on the type and content of the catalyst.

[0564] 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.

[0565]

[0566] Here, the step (a) includes (a-1) a first polymerization step performed at a temperature of 30 to 300°C; and (a-2) a second polymerization step performed at a temperature of 30 to 300°C.

[0567]

[0568] The present invention utilizes at least two polymerization steps when polymerizing 3-hydroxypropionic acid. Accordingly, when polymerizing 3-hydroxypropionic acid, unreacted monomers can be minimized, side reactions can be controlled, and the molecular weight of poly-3-hydroxypropionic acid can be controlled to 1,000 to 2,000.

[0569] Here, the side reaction refers to the acrylic acid conversion reaction caused by the rapid temperature increase within the reactor when 3-hydroxypropionic acid is converted to polyol. The above-mentioned side reaction inhibits the polymerization reaction of the polyol, such as by inducing the polymerization of polyacrylic acid and reducing the yield of the polyol. Therefore, the above-mentioned side reaction should be minimized and a uniform polymerization reaction of the polyol should be induced. As described above, the present invention can reduce the side reaction by utilizing at least two polymerization stages when polymerizing 3-hydroxypropionic acid.

[0570]

[0571] First, the above step (a-1) refers to the first polymerization step performed at a temperature of 30 to 300°C. Through the above step (a-1), the 3-hydroxypropionic acid can be oligomerized. Furthermore, through the above step (a-1), unreacted substances can be minimized.

[0572]

[0573] Preferably, the step (a-1) can be performed at a temperature of 30 to 300°C and a pressure of 0.1 to 700 torr. More preferably, the step (a-1) 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-1) can be performed at a temperature of 70 to 150°C and a pressure of 0.1 to 150 torr.

[0574]

[0575] Next, step (a-2) is performed to control side reactions. Through step (a-2), side reactions can be reduced. Furthermore, through step (a-2), the molecular weight of poly-3-hydroxypropionic acid can be increased.

[0576]

[0577] Preferably, the step (a-2) may be performed at a temperature of 30 to 300°C and a pressure of 0.1 to 700 torr. More preferably, the step (a-1) may be performed at a temperature of 80 to 200°C and a pressure of 0.1 to 300 torr, and even more preferably, the step (a-1) may be performed at a temperature of 100 to 180°C and a pressure of 0.1 to 150 torr.

[0578]

[0579] Preferably, the step (a-2) can be performed at a higher temperature than the step (a-1).

[0580] The above step (a-1) is a step for oligomerization of 3-HP, which minimizes unreacted monomers of 3-HP and reduces the number of cases in which 3-HP can be converted to acrylic acid. Accordingly, the acid value of the polyol is lowered by the above step (a-1). The above step (a-2) induces a direct reaction of the polyol by polymerizing the oligomerized 3-HP with alcohol. For this purpose, the above step (a-2) is preferably performed at a higher temperature than the above step (a-1). As the temperature of the above step (a-2) is higher than the temperature of the above step (a-1), the degree of polymerization of the polyol increases and the required molecular weight of the polyol is easily achieved.

[0581]

[0582] Next, the manufacturing method of the present invention includes the step of (b) producing a polyol by reacting polymerized 3-hydroxypropionic acid with an alcohol.

[0583]

[0584] Here, the alcohol may be one or more polyhydric alcohols.

[0585]

[0586] In addition, as described above, the alcohol may be a divalent alcohol, preferably a divalent to hexavalent alcohol, and more preferably a divalent to tetravalent alcohol.

[0587] The above alcohols are 1,3-butanediol, 2,3-butanediol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol and ethylene glycol, glycerol, pentaerythritol, trimethylolpropane, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,4-butynediol, neopentyl glycol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, 2-methyl-1,3-propanediol, 2-methyl-1,4-butanediol, 2-methyl-1,8-octanediol, 2,7-dimethyl-1,8-octanediol, 1,9-nonanediol, It may include at least one of 2-methyl-1,9-nonanediol, 2,8-dimethyl-1,9-nonanediol, 1,10-decanediol, 2,2-diethyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,4-cyclohexanediol, cyclohexanedimethanol, 3(or 4), 8(or 9)-dihydroxytricyclodecane, bis(hydroxymethyl)cyclohexane, triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, dibutylene glycol, polybutylene glycoltrimethylolpropane, glycerol, trishydroxyethyl isocyanurate, castor oil, dipentaerythritol, and sorbitol, but the type of alcohol is not particularly limited.

[0588]

[0589] In the manufacturing method of the present invention, when reacting the polymerized poly-3-hydroxypropionic acid and the alcohol with a catalyst, 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, 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, step (b) may be performed at a temperature of 70 to 150°C and a pressure of 0.1 to 150 torr.

[0590]

[0591] In addition, the polyol manufacturing method 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).

[0592] 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).

[0593] 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).

[0594]

[0595] As described above, the polyol of the present invention can have various properties depending on the type of one or more polyhydric alcohols and polymerization reaction conditions.

[0596]

[0597] Next, the polyol of the present invention will be described.

[0598]

[0599] The polyol of the present invention is manufactured by the above-described method and is formed by the reaction of polymerized 3-hydroxypropionic acid and alcohol.

[0600] More specifically, the polyol of the present invention comprises at least one of the compounds represented by the following chemical formulas 1 to 3.

[0601]

[0602] [Chemical Formula 1]

[0603]

[0604] In the above chemical formula 1,

[0605] R is a linker derived from alcohol,

[0606] The above m is an integer greater than or equal to 1, and n is an integer greater than or equal to 0.

[0607]

[0608] [Chemical Formula 2]

[0609]

[0610] In the above chemical formula 2,

[0611] R is a linker derived from alcohol,

[0612] The above m is an integer greater than or equal to 1, n is an integer greater than or equal to 0, and p is an integer greater than or equal to 0.

[0613]

[0614] [Chemical Formula 3]

[0615]

[0616]

[0617] In the above chemical formula 3,

[0618] R is a linker derived from alcohol,

[0619] The above m is an integer greater than or equal to 1, n is an integer greater than or equal to 0, p is an integer greater than or equal to 0, and r is an integer greater than or equal to 0.

[0620]

[0621] The polyol of the present invention uses bio-based 3-hydroxypropionic acid represented by the following chemical formula 4.

[0622]

[0623] [Chemical Formula 4]

[0624]

[0625]

[0626] 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.

[0627]

[0628] The polyol of the present invention includes compounds represented by the chemical formulas 1 to 3 formed by reacting poly 3-hydroxypropionic acid polymerized with alcohol.

[0629]

[0630] In the present invention, it is preferable to use a bio-based alcohol such as 3-hydroxypropionic acid.

[0631] The above alcohol is as described above.

[0632]

[0633] In the above chemical formulas 1 to 3, R means a linking group derived from the alcohol.

[0634] The above R is linked to 3-hydroxypropionic acid by removing the OH group. In addition, the form of the above R may vary depending on the type of the alcohol.

[0635]

[0636] For example, when the alcohol is 1,3-propanediol, the chemical formula 1 can be represented by the following chemical formula 5.

[0637]

[0638] [Chemical Formula 5]

[0639]

[0640]

[0641] Preferably, the polyol of the present invention may have a number average molecular weight (Mn) of 1000 to 2000 and a weight average molecular weight (Mw) of 1000 to 3000.

[0642] Additionally, the hydroxyl value (Hv) of the polyol may be 10 to 1000, and preferably, the hydroxyl value (Hv) may be 100 to 200.

[0643] In addition, the acid value (Av) of the polyol may be 10 or less, and more preferably less than 2.

[0644] Additionally, 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.

[0645] Within the above range, a polyol that can be used in the manufacture of polyurethane, etc. can be obtained. If a polyol having properties outside the above range is used, the properties of the polyurethane may be deteriorated.

[0646]

[0647] Polyurethane polymerization involves the bonding of isocyanate groups and polyols. Depending on the polyol molecular weight, the polymerized polyurethane's physical properties, 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 that meets the required range of properties.

[0648]

[0649] The polyol of the present invention is a bio-based material that can satisfy all of the various properties of polyurethane required and is environmentally friendly.

[0650]

[0651] Hereinafter, the properties of the polyol 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.

[0652]

[0653] <Example>

[0654]

[0655] 1. Example according to the first embodiment

[0656]

[0657] To prepare a polyol, (A) 3-hydroxypropionic acid, (B) one or more polyhydric alcohols, and (C) a Lewis acid or Bronsted acid catalyst were prepared.

[0658]

[0659] (A) 3-hydroxypropionic acid

[0660] (Bl) 1,3-propanediol

[0661] (B2) 2,3-butanediol

[0662] (B3) 1,4-butanediol

[0663] (B4) Ethylene glycol

[0664] (C1) p-Toluenesulfonic acid (p-TSA)

[0665] (C2) Tin(II) 2-ethylhexanoate(TEH)

[0666] (C3) titanium isopropoxide (TIP)

[0667] (C4) titanium tetrabutoxide (TBO)

[0668] (C5) SnCl2

[0669]

[0670] Example 1-1

[0671] 20 g of 3-hydroxypropionic acid, 1.3 g of 1,3-propanediol, and 0.05 g of p-TSA were heated at about 90°C to perform dehydration polycondensation, and the reaction was continued while reducing the pressure to about 50 torr. Thereafter, the mixture was stirred at 300 rpm for about 7 hours to produce a polyol according to Example 1.

[0672]

[0673] Example 1-2

[0674] 20 g of 3-hydroxypropionic acid, 1.3 g of 2,3-butanediol, and 0.05 g of p-TSA were heated at about 90°C to perform dehydration polycondensation, and the reaction was continued while reducing the pressure to about 50 torr. Thereafter, the mixture was stirred at 300 rpm for about 7 hours to produce a polyol according to Example 2.

[0675]

[0676] Example 1-3

[0677] 20 g of 3-hydroxypropionic acid, 1.3 g of 1,4-butanediol, and 0.05 g of p-TSA were heated at about 90°C to perform dehydration polycondensation, and the reaction was continued while reducing the pressure to about 50 torr. Thereafter, the mixture was stirred at 300 rpm for about 7 hours to produce a polyol according to Example 3.

[0678]

[0679] Example 1-4

[0680] 20 g of 3-hydroxypropionic acid, 1.2 g of ethylene glycol, and 0.05 g of p-TSA were heated at about 90°C to perform dehydration polycondensation, and the reaction was continued while the pressure was reduced to about 50 torr. Thereafter, the mixture was stirred at 300 rpm for about 7 hours to produce a polyol according to Example 4.

[0681]

[0682] Example 1-5

[0683] 20 g of 3-hydroxypropionic acid, 1.3 g of 1,3-propanediol, and 0.1 g of TEH were heated at approximately 90°C to perform dehydration polycondensation, and the reaction was continued while reducing the pressure to approximately 50 torr. Thereafter, the mixture was stirred at 300 rpm for approximately 7 hours to produce a polyol according to Example 5.

[0684]

[0685] Example 1-6

[0686] 3-hydroxypropionic acid (OO g), 1,3-propanediol (OO g), and TIP (0.1 g) were heated at about 90°C to perform dehydration and polycondensation, and the reaction was continued while the pressure was reduced to about 50 torr. Thereafter, the mixture was stirred at 300 rpm for about 7 hours to produce a polyol according to Example 6.

[0687]

[0688] Example 1-7

[0689] 20 g of 3-hydroxypropionic acid, 1.3 g of 1,3-propanediol, and 0.1 g of TBO were heated at about 90°C to perform dehydration polycondensation, and the reaction was continued while reducing the pressure to about 50 torr. Thereafter, the mixture was stirred at 300 rpm for about 7 hours to produce a polyol according to Example 7.

[0690]

[0691] Example 1-8

[0692] 20 g of 3-hydroxypropionic acid, 1.3 g of 1,3-propanediol, and 20.1 g of SnCl were heated at about 90°C to perform dehydration polycondensation, and the reaction was continued while reducing the pressure to about 50 torr. Thereafter, the mixture was stirred at 300 rpm for about 7 hours to produce a polyol according to Example 8.

[0693]

[0694] Example 1-9

[0695] 20 g of 3-hydroxypropionic acid, 1.3 g of 1,3-propanediol, and 0.05 g of p-TSA were heated at about 80°C to perform dehydration polycondensation, and the reaction was continued while reducing the pressure to about 50 torr. Thereafter, the mixture was stirred at 300 rpm for about 7 hours to produce a polyol according to Example 9.

[0696]

[0697] Example 1-10

[0698] 20 g of 3-hydroxypropionic acid, 1.3 g of 1,3-propanediol, and 0.1 g of TBO were heated at about 80°C to perform dehydration polycondensation, and the reaction was continued while reducing the pressure to about 50 torr. Thereafter, the mixture was stirred at 300 rpm for about 7 hours to produce a polyol according to Example 10.

[0699]

[0700] Example 1-11

[0701] 20 g of 3-hydroxypropionic acid, 1.3 g of 1,3-propanediol, and 20.1 g of SnCl were heated at about 80°C to perform dehydration polycondensation, and the reaction was continued while reducing the pressure to about 50 torr. Thereafter, the mixture was stirred at 300 rpm for about 7 hours to produce a polyol according to Example 11.

[0702]

[0703] Example 1-12

[0704] 20 g of 3-hydroxypropionic acid, 1.3 g of 1,3-propanediol, and 0.05 g of p-TSA were heated at about 120°C to perform dehydration polycondensation, and the reaction was continued while reducing the pressure to about 50 torr. Thereafter, the mixture was stirred at 300 rpm for about 7 hours to produce a polyol according to Example 12.

[0705]

[0706] Example 1-13

[0707] 20 g of 3-hydroxypropionic acid, 1.3 g of 1,3-propanediol, and 20.1 g of SnCl were heated at about 120°C to perform dehydration polycondensation, and the reaction was continued while reducing the pressure to about 50 torr. Thereafter, the mixture was stirred at 300 rpm for about 7 hours to produce a polyol according to Example 13.

[0708]

[0709] Example 1-14

[0710] 20 g of 3-hydroxypropionic acid, 1.3 g of 1,3-propanediol, and 0.05 g of p-TSA were heated at about 120°C to perform dehydration polycondensation, and the reaction was continued while reducing the pressure to about 100 torr. Thereafter, the mixture was stirred at 300 rpm for about 7 hours to produce a polyol according to Example 14.

[0711]

[0712] Example 15

[0713] 20 g of 3-hydroxypropionic acid, 1.3 g of 1,3-propanediol, and 0.05 g of p-TSA were heated at about 120°C to perform dehydration polycondensation, and the reaction was continued while reducing the pressure to about 100 torr. Thereafter, the mixture was stirred at 300 rpm for about 7 hours to produce a polyol according to Example 15.

[0714]

[0715] <Method of evaluating physical properties>

[0716] In order to evaluate the properties of the polyol oligomer samples manufactured according to Examples 1-1 to 1-15, the following items were measured and the results are shown in Table 1 below.

[0717]

[0718] (1) Molecular weight measurement method (GPC):

[0719] The molecular weight distribution of a polymer is measured using gel permeation chromatography (GPC). Typically, GPC is a special type of liquid chromatography that separates a sample 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.

[0720] This experiment used gel permeation chromatography (Waters 2690), and the column used was StryagelHR. 2, 1, 0.5.

[0721] Polyol was completely dissolved in tetrahydrofurane (THF), purified using a syringe filter, and then subjected to gel permeation chromatography to measure its molecular weight. The test conditions were maintained at 40°C, with a flow rate of 1 mL / min and a concentration of 3 g / L.

[0722]

[0723] (2) Molecular weight distribution (Polydispersity Index, PDI)

[0724] It is also called polydispersity, and can be confirmed using the calculation formula below based on the molecular weight detected by GPC.

[0725] Weight average molecular weight (Mn) / Number average molecular weight (Mn)

[0726]

[0727] (3) Hydroxyl value (Hv) measurement method

[0728] 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 measured by reacting the measuring reagent with the polyol, titrating with 1 N-NaOH, and calculating it using the following equation.

[0729]

[0730] Hydroxyl value = [(AB) × N × 56.1] / W

[0731]

[0732] A = Volume of titrant consumed in the blank test (ml)

[0733] B = Volume of titrant consumed in this test (ml)

[0734] N = Normal concentration of 1 N-NaOH aqueous solution

[0735] W = amount of sample (g)

[0736]

[0737] (4) Acid value (Av) measurement method

[0738] The acid value of the polyol 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. The acid value is measured, for example, by the amount of KOH in mg required to neutralize 1 g of a sample.

[0739]

[0740] Mn (g / mol)Mw (g / mol)PDIHv(mg KOH / g)AV(mg KOH / g)Example 1-14586911.51244< 2.0Example 1-293722862.44119< 2.0Example 1-378812991.65142< 2.0Example 1-490619672.17124< 2.0Example 1-55708941.6197< 2.0Example 1-65007571.7224< 2.0Example 1-75008471.7224< 2.0Example 1-893915831.68119< 2.0Example 1-96179681.57181< 2.0 Example 1-101812561.41619< 2.0 Example 1-115027541.50223< 2.0 Example 1-1270710441.48158< 2.0 Example 1-1367410051.49166< 2.0 Example 1-1470518522.63159< 2.0 Example 1-1586658796.79130< 2.0

[0741]

[0742] Referring to the results in Table 1 above, it can be confirmed that the examples according to the present invention have various characteristics depending on the type of alcohol, the type of catalyst, and the polymerization conditions.

[0743]

[0744] 2. Example according to the second embodiment

[0745]

[0746] Polyols according to the examples were prepared according to each polymerization condition using the reactants and catalysts in Table 2 below. In Table 2, the catalyst content refers to the content % of the catalyst applied to each example when the catalyst content of Examples 2-1 to 2-4 is considered to be 100%. For example, if the catalyst of Examples 2-1 to 2-4 is 0.18 g, a catalyst content of 50% refers to 0.09 g.

[0747]

[0748] Example 3-HP Alcohol Catalyst Catalyst Content (%) 2-13-HP 1,3-Propanediol (PDO) BrΨnsted acid 100 2-23-HP 2,3-Butanediol (BDO) BrΨnsted acid 100 2-33-HP 1,4-Butanediol (BDO) BrΨnsted acid 100 2-43-HPEthylene Glycol (EG) BrΨnsted acid 100 2-5-13-HP 1,3-Propanediol (PDO) BrΨnsted acid 100 2-5-23-HP 1,3-Propanediol (PDO) BrΨnsted acid 75 2-5-33-HP 1,3-Propanediol (PDO) BrΨnsted acid 50 2-5-43-HP 1,3-Propanediol (PDO) BrΨnsted acid252-6-13-HP1,3-Propanediol (PDO)BrΨnsted acid502-6-23-HP1,3-Propanediol (PDO)BrΨnsted acid252-6-33-HP1,3-Propanediol (PDO)BrΨnsted acid12.52-7-13-HP1,3-Propanediol (PDO)BrΨnsted acid252-7-23-HP1,3-Propanediol (PDO)Lewis acid252-8-13-HP1,3-Propanediol (PDO)BrΨnsted acid62-8-23-HP1,3-Propanediol (PDO)Lewis acid62-93-HP1,3-Propanediol (PDO)BrΨnsted acid and Lewis acid25

[0749]

[0750] Example 2-1

[0751] For the production of polyol 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 ensure uniform stirring at 250 rpm. Furthermore, a heating mantle and mantle cover were used to maintain the temperature at 90°C at the top and bottom of the reactor, and the polyol was produced under a nitrogen atmosphere.

[0752] Step 1 Reaction: First, 20 g of 3-hydroxypropionic acid (3-HP) and 0.18 g of BrΨnsted acid catalyst (para-toluenesulfonic acid) were added to the reactor, and the polymerization reaction was carried out at a temperature of 90℃, a reaction time of 4 hr, a stirring speed of 250 rpm, and a vacuum pressure of 50 torr to induce the polymerization of 3-HP. During the polymerization of 3-HP, the generated water was collected inside the installed Dean Stark trap. After the reaction was completed, the magnetic drive was briefly stopped, the vacuum pressure was changed to normal pressure, and the diol to be added for polyol production was prepared.

[0753] Step 2 Reaction: Next, to proceed with the esterification reaction, 1.3 g of 1,3-propanediol was introduced into the reactor, and the magnetic drive was activated to begin slow stirring with the reactants. After stirring for 10 minutes, the polyol polymerization was carried out at a temperature of 90°C, a reaction time of 4 hours, a stirring speed of 250 rpm, and a vacuum pressure of 50 torr.

[0754] Step 3 reaction: Next, the temperature was changed to 90℃, the reaction time was changed to 2 hr, and the vacuum pressure was changed from 50 torr to 10 torr, accelerating the reaction to remove unreacted monomers and improve the reaction rate.

[0755] Afterwards, the reaction was terminated, the vacuum pressure was adjusted to atmospheric pressure, and the installed reactor, Dean Stark trap, and reflux condenser were separated.

[0756] Through the above-described process, a polyol according to Example 2-1 was manufactured.

[0757]

[0758] Example 2-2

[0759] The polyol according to Example 2-2 was prepared in the same manner as Example 2-1, except for the following contents.

[0760]

[0761] 3-HP content: 20 g

[0762] 2,3-Butanediol content: 1.3 g

[0763] Paratoluene sulfonic acid content: 0.18 g

[0764] Polymerization conditions: Same as Example 1

[0765]

[0766] Example 2-3

[0767] The polyol according to Example 2-3 was prepared in the same manner as Example 2-1, except for the following contents.

[0768]

[0769] 3-HP content: 20 g

[0770] 1,4-Butanediol content: 1.3 g

[0771] Paratoluene sulfonic acid content: 0.18 g

[0772] Polymerization conditions: Same as Example 1

[0773]

[0774] Example 2-4

[0775] The polyol according to Example 2-4 was prepared in the same manner as Example 2-1, except for the following contents.

[0776]

[0777] 3-HP content: 20 g

[0778] Ethylene Glycol (EG) content: 1.1 g

[0779] Paratoluene sulfonic acid content: 0.18 g

[0780] Polymerization conditions: Same as Example 1

[0781]

[0782] Examples 2-5-1 to 2-5-4

[0783] Polyols according to Examples 5-1 to 5-4 were manufactured in the same manner as in Example 2-1, except for the following contents.

[0784]

[0785] 3-HP content: 20 g

[0786] 1,3-Propanediol (PDO) content: 1.3 g

[0787] Paratoluene sulfonic acid content: as shown in Table 1 (0.18g, 0.14g 0.09g, 0.045g)

[0788] Step 1 reaction conditions: temperature 90℃, reaction time 4 hr, stirring speed 250 rpm, vacuum pressure 50 torr

[0789] Step 2 reaction conditions: temperature 120℃, reaction time 4 hr, stirring speed 250 rpm, vacuum pressure 50 torr

[0790] Step 3 reaction conditions: temperature 120℃, reaction time 2 hr, stirring speed 250 rpm, vacuum pressure 10 torr

[0791]

[0792] Examples 2-6-1 to 2-6-3

[0793] Polyols according to Examples 6-1 to 6-3 were prepared in the same manner as in Example 2-1, except for the following contents.

[0794]

[0795] 3-HP content: 20 g

[0796] 1,3-Propanediol (PDO) content: 1.3 g

[0797] Paratoluene sulfonic acid content: as shown in Table 1 (0.09g, 0.045g, 0.022g)

[0798] Step 1 reaction conditions: temperature 90℃, reaction time 4 hr, stirring speed 250 rpm, vacuum pressure 50 torr

[0799] Step 2 reaction conditions: temperature 90℃, reaction time 4 hr, stirring speed 250 rpm, vacuum pressure 50 torr

[0800] Step 3 reaction conditions: temperature 90℃, reaction time 2hr, stirring speed 250rpm, vacuum pressure 10torr

[0801]

[0802] Examples 2-7-1 to 2-7-2

[0803] Polyols according to Examples 7-1 to 7-2 were manufactured in the same manner as Example 2-1, except for the following contents.

[0804]

[0805] 3-HP content: 20 g

[0806] 1,3-Propanediol (PDO) content: 1.3 g

[0807] Paratoluene sulfonic acid content: As shown in Table 1 (0.045 g)

[0808] Tin chloride content: As shown in Table 1 (0.054 g)

[0809] Step 1 reaction conditions: temperature 80℃, reaction time 4 hr, stirring speed 250 rpm, vacuum pressure 50 torr

[0810] Step 2 reaction conditions: temperature 80℃, reaction time 4 hr, stirring speed 250 rpm, vacuum pressure 50 torr

[0811] Step 3 reaction conditions: temperature 80℃, reaction time 2 hr, stirring speed 250 rpm, vacuum pressure 10 torr

[0812]

[0813] Examples 2-8-1 to 2-8-2

[0814] Polyols according to Examples 8-1 to 8-2 were manufactured in the same manner as in Example 2-1, except for the following contents.

[0815]

[0816] 3-HP content: 20 g

[0817] 1,3-Propanediol (PDO) content: 1.3 g

[0818] Paratoluene sulfonic acid content: As shown in Table 1 (0.011 g)

[0819] Tin chloride content: As shown in Table 1 (0.013 g)

[0820] Step 1 reaction conditions: temperature 70℃, reaction time 4 hr, stirring speed 250 rpm, vacuum pressure 50 torr

[0821] Step 2 reaction conditions: temperature 70℃, reaction time 4 hr, stirring speed 250 rpm, vacuum pressure 50 torr

[0822] Step 3 reaction conditions: temperature 70℃, reaction time 2 hr, stirring speed 250 rpm, vacuum pressure 10 torr

[0823]

[0824] Example 2-9

[0825] The polyol according to Example 2-9 was prepared in the same manner as Example 2-1, except for the following contents.

[0826]

[0827] 3-HP content: 20 g

[0828] 1,3-Propanediol (PDO) content: 1.3 g

[0829] Using a mixed catalyst of 0.022 g of paratoluene sulfonic acid and 0.027 g of tin chloride

[0830] Step 1 reaction conditions: temperature 80℃, reaction time 4 hr, stirring speed 250 rpm, vacuum pressure 50 torr

[0831] Step 2 reaction conditions: temperature 80℃, reaction time 4 hr, stirring speed 250 rpm, vacuum pressure 50 torr

[0832] Step 3 reaction conditions: temperature 80℃, reaction time 2 hr, stirring speed 250 rpm, vacuum pressure 10 torr

[0833]

[0834] <Method of evaluating physical properties>

[0835] The polyol properties of the above examples were evaluated. The evaluation items and measurement methods are as described above.

[0836]

[0837] Example Mn (g / mol) PDI Hv (mg KOH / g) AV (mg KOH / g) 2-1894 1.599 120 < 2.02-2684 1.588 142 < 2.02-3785 1.684 126 < 2.02-4812 1.72 124 < 2.02-5-1984 1.812 112 < 2.02-5-2793 1.856 127 < 2.02-5-3699 1.605 138 < 2.02-5-4724 1.616 134 < 2.02-6-1755 1.566 131 < 2.02-6-2685 1.540 142 < 2.02-6-34591.407165< 2.02-7-16841.424144< 2.02-7-26411.480140< 2.02-8-14521.497168< 2.02-8-23141.460174< 2.02-96641.414147< 2.0

[0838]

[0839] Referring to the results in Table 3 above, it can be confirmed that the examples according to the present invention have various characteristics depending on the type of alcohol, type of catalyst, and polymerization conditions.

[0840]

[0841] 3. Example according to the third embodiment

[0842]

[0843] (1) Production of polyol

[0844]

[0845] 1) Manufacturing Example 3-1

[0846] For the production of polyol according to Manufacturing Example 3-1, a 250 ml glass flask reactor, a Dean Stark trap, and a reflux condenser were used. A magnetic drive was used to ensure uniform stirring at 250 rpm. Furthermore, a heating mantle and mantle cover were used to maintain the temperature at the top and bottom of the reactor at 90°C, and the polyol was produced under a nitrogen atmosphere.

[0847] Step 1 Reaction: First, 20 g of 3-hydroxypropionic acid (3-HP) and 0.18 g of BrΨnsted acid catalyst (para-toluenesulfonic acid) were added to the reactor, and the polymerization reaction was carried out at a temperature of 90℃, a reaction time of 4 hr, a stirring speed of 250 rpm, and a vacuum pressure of 50 torr to induce the polymerization of 3-HP. During the polymerization of 3-HP, the generated water was collected inside the installed Dean Stark trap. After the reaction was completed, the magnetic drive was briefly stopped, the vacuum pressure was changed to normal pressure, and the diol to be added for polyol production was prepared.

[0848] Step 2 Reaction: Next, to proceed with the esterification reaction, 1.3 g of 1,3-propanediol was introduced into the reactor, and the magnetic drive was activated to begin slow stirring with the reactants. After stirring for 10 minutes, the polyol polymerization was carried out at a temperature of 90°C, a reaction time of 4 hours, a stirring speed of 250 rpm, and a vacuum pressure of 50 torr.

[0849] Step 3 reaction: Next, the temperature was changed to 90℃, the reaction time was changed to 2 hr, and the vacuum pressure was changed from 50 torr to 10 torr, accelerating the reaction to remove unreacted monomers and improve the reaction rate.

[0850] Afterwards, the reaction was terminated, the vacuum pressure was adjusted to atmospheric pressure, and the installed reactor, Dean Stark trap, and reflux condenser were separated.

[0851] Through the above-described process, a polyol according to Manufacturing Example 3-1 was manufactured.

[0852]

[0853] 2) Manufacturing Example 3-2

[0854] For the production of polyol according to Manufacturing Example 3-2, a 250 ml glass flask reactor, a Dean-Stark trap, and a reflux condenser were used. A magnetic drive was used to ensure uniform stirring at 250 rpm. Furthermore, a heating mantle and mantle cover were used to maintain the temperature at 90°C at the top and bottom of the reactor, and the polyol was produced under a nitrogen atmosphere.

[0855] Step 1 Reaction: First, 20 g of 3-hydroxypropionic acid (3-HP) and 0.18 g of BrΨnsted acid catalyst (para-toluenesulfonic acid) were added to the reactor, and the polymerization reaction was carried out at a temperature of 90℃, a reaction time of 4 hr, a stirring speed of 250 rpm, and a vacuum pressure of 50 torr to induce the polymerization of 3-HP. During the polymerization of 3-HP, the generated water was collected inside the installed Dean Stark trap. After the reaction was completed, the magnetic drive was briefly stopped, the vacuum pressure was changed to normal pressure, and the diol to be added for polyol production was prepared.

[0856] Step 2 Reaction: Next, to proceed with the esterification reaction, 1.3 g of 1,3-propanediol was introduced into the reactor, and the magnetic drive was activated to begin slow stirring with the reactants. After stirring for 10 minutes, the polyol polymerization was carried out at a temperature of 120°C, a reaction time of 4 hours, a stirring speed of 250 rpm, and a vacuum pressure of 50 torr.

[0857] Step 3 reaction: Next, the temperature was changed to 120℃, the reaction time was changed to 2 hr, and the vacuum pressure was changed from 50 torr to 10 torr, accelerating the reaction to remove unreacted monomers and improve the reaction rate.

[0858] Afterwards, the reaction was terminated, the vacuum pressure was adjusted to atmospheric pressure, and the installed reactor, Dean Stark trap, and reflux condenser were separated.

[0859] Through the above-described process, a polyol according to Manufacturing Example 3-2 was manufactured.

[0860]

[0861] 3) Manufacturing Example 3-3

[0862] For the production of polyol according to Manufacturing Example 3-3, a 250 ml glass flask reactor, a Dean Stark trap, and a reflux condenser were used. A magnetic drive was used to ensure uniform stirring at 250 rpm. Furthermore, a heating mantle and mantle cover were used to maintain the temperature at 90°C at the top and bottom of the reactor, and the polyol was produced under a nitrogen atmosphere.

[0863] Step 1 Reaction: First, 20 g of 3-hydroxypropionic acid (3-HP) and 0.18 g of BrΨnsted acid catalyst (para-toluenesulfonic acid) were added to the reactor, and the polymerization reaction was carried out at a temperature of 80℃, a reaction time of 4 hr, a stirring speed of 250 rpm, and a vacuum pressure of 50 torr to induce the polymerization of 3-HP. During the polymerization of 3-HP, the generated water was collected inside the installed Dean Stark trap. After the reaction was completed, the magnetic drive was briefly stopped, the vacuum pressure was changed to normal pressure, and the diol to be added for polyol production was prepared.

[0864] Step 2 Reaction: Next, to proceed with the esterification reaction, 1.3 g of 1,3-propanediol was introduced into the reactor, and the magnetic drive was activated to begin slow stirring with the reactants. After stirring for 10 minutes, the polyol polymerization was carried out at a temperature of 80°C, a reaction time of 4 hours, a stirring speed of 250 rpm, and a vacuum pressure of 50 torr.

[0865] Step 3 reaction: Next, the temperature was changed to 80℃, the reaction time was changed to 2 hr, and the vacuum pressure was changed from 50 torr to 10 torr, accelerating the reaction to remove unreacted monomers and improve the reaction rate.

[0866] Afterwards, the reaction was terminated, the vacuum pressure was adjusted to atmospheric pressure, and the installed reactor, Dean Stark trap, and reflux condenser were separated.

[0867] Through the above-described process, a polyol according to Manufacturing Example 3-3 was manufactured.

[0868]

[0869] 4) Manufacturing Example 3-4

[0870] For the production of polyol according to Manufacturing Examples 3-4, a 250 ml glass flask reactor, a Dean Stark trap, and a reflux condenser were used. A magnetic drive was used to ensure uniform stirring at 250 rpm. Furthermore, a heating mantle and mantle cover were used to maintain the temperature at the top and bottom of the reactor at 90°C, and the polyol was produced under a nitrogen atmosphere.

[0871] Step 1 Reaction: First, 20 g of 3-hydroxypropionic acid (3-HP) and 0.18 g of BrΨnsted acid catalyst (para-toluenesulfonic acid) were added to the reactor, and the polymerization reaction was carried out at a temperature of 80℃, a reaction time of 4 hr, a stirring speed of 250 rpm, and a vacuum pressure of 100 torr to induce polymerization of 3-HP. During the polymerization of 3-HP, the generated water was collected inside the installed Dean Stark trap. After the reaction was completed, the magnetic drive was briefly stopped, the vacuum pressure was changed to normal pressure, and the diol to be added for polyol production was prepared.

[0872] Step 2 Reaction: Next, to proceed with the esterification reaction, 1.3 g of 1,3-propanediol was introduced into the reactor, and the magnetic drive was activated to begin slow stirring with the reactants. After stirring for 10 minutes, the polyol polymerization was carried out at a temperature of 80°C, a reaction time of 4 hours, a stirring speed of 250 rpm, and a vacuum pressure of 50 torr.

[0873] Step 3 reaction: Next, the temperature was changed to 80℃, the reaction time was changed to 2 hr, and the vacuum pressure was changed from 50 torr to 10 torr, accelerating the reaction to remove unreacted monomers and improve the reaction rate.

[0874] Afterwards, the reaction was terminated, the vacuum pressure was adjusted to atmospheric pressure, and the installed reactor, Dean Stark trap, and reflux condenser were separated.

[0875] Through the above-described process, a polyol according to Manufacturing Example 3-4 was manufactured.

[0876]

[0877] (2) Purification of polyol

[0878]

[0879] Afterwards, the polyol was purified as in Examples 3-1 to 3-8 according to the contents described in Table 4 below.

[0880]

[0881] Example Polyol Polar Solvent Anion Exchange Resin 3-1 Manufacturing Example 3-1 Ultrapure TRILITE (AW90, Samyang Corporation) 3-2 Manufacturing Example 3-1 Ethanol TRILITE (AW90, Samyang Corporation) 3-3 Manufacturing Example 3-2 Ultrapure TRILITE (SAR11, Samyang Corporation) 3-4 Manufacturing Example 3-2 Ethanol TRILITE (SAR11, Samyang Corporation) 3-5 Manufacturing Example 3-3 Ultrapure LEWATIT (A365, LANXESS) 3-6 Manufacturing Example 3-3 Ethanol LEWATIT (A365, LANXESS) 3-7 Manufacturing Example 3-4 Ultrapure TRILITE (AW90, Samyang Corporation) 3-8 Manufacturing Example 3-4 Methanol TRILITE (AW90, Samyang Corporation)

[0882]

[0883] 1) Example 3-1

[0884] The polyol of Manufacturing Example 3-1 was melted at 60℃ for 10 minutes. Then, a 1L glass reactor was prepared, a magnetic driver was installed for easy stirring, and 300ml of deionized water and 10g of anion exchange resin TRILITE (AW90, Samyang Corporation) were placed in the reactor using a membrane filter. 16g of the molten polyol was slowly added to the deionized water. The stirring speed was maintained at 450rpm, and the mixture was stirred at room temperature for about 1 hour. During stirring, the molten polyol was maintained in the form of flakes and solidified. After stirring, the mixture was poured into a Buchner funnel connected to a reduced pressure flask to obtain the obtained polyol solid. The deionized water and ion exchange resin were completely removed under reduced pressure for about 5 minutes, and the mixture was dried in a vacuum oven at 40℃.

[0885] Through the above-described process, a purified polyol according to Example 3-1 was obtained.

[0886]

[0887] 2) Examples 3-2 to 3-8

[0888] The purified polyols according to Examples 3-2 to 3-8 were obtained by the same process as Example 3-1, except for the types of polyol, polar solvent, and anion exchange resin described in Table 4.

[0889]

[0890] (3) Property evaluation

[0891]

[0892] In order to evaluate the properties of the polyol samples purified according to Examples 3-1 to 3-8, the following items were measured and the results are shown in Table 5 below. The measurement items and evaluation methods are as described above.

[0893]

[0894] Pre-purification MnPDIHvAvMnPDIHvAv3-18101.76128.23.109751.51113.2< 2.03-28101.76128.23.109471.62121.7< 2.33-38641.65131.15.8410231.30110.1< 2.03-48641.65131.15.849761.52113.8< 2.33-55481.59166.012.439011.25119.4< 2.03-65481.59166.012.438201.40135.2< 2.33-76431.54155.38.579621.25115.1< 2.03-86431.54155.38.578781.47125.2< 2.3

[0895]

[0896] Referring to the results in Table 5 above, it can be confirmed that the examples according to the present invention showed an increase in number average molecular weight (Mn) by at least 10% after purification, and also a decrease in PDI, Hv, and Av.

[0897] Accordingly, it can be seen that the polyol purified according to the method of the present invention has substantially all unreacted monomers with low molecular weights removed.

[0898]

[0899] 4. Example according to the fourth embodiment

[0900]

[0901] (1) Production of polyol

[0902]

[0903] 1) Manufacturing Example 4-1

[0904] For the production of polyol according to Manufacturing Example 4-1, a 250 ml glass flask reactor, a Dean Stark trap, and a reflux condenser were used. A magnetic drive was used to ensure uniform stirring at 250 rpm. Furthermore, a heating mantle and mantle cover were used to maintain the temperature at the top and bottom of the reactor at 90°C, and the polyol was produced under a nitrogen atmosphere.

[0905] Step 1 Reaction: First, 20 g of 3-hydroxypropionic acid (3-HP) and 0.18 g of BrΨnsted acid catalyst (para-toluenesulfonic acid) were added to the reactor, and the polymerization reaction was carried out at a temperature of 90℃, a reaction time of 4 hr, a stirring speed of 250 rpm, and a vacuum pressure of 50 torr to induce the polymerization of 3-HP. During the polymerization of 3-HP, the generated water was collected inside the installed Dean Stark trap. After the reaction was completed, the magnetic drive was briefly stopped, the vacuum pressure was changed to normal pressure, and the diol to be added for polyol production was prepared.

[0906] Step 2 Reaction: Next, to proceed with the esterification reaction, 1.3 g of 1,3-propanediol was introduced into the reactor, and the magnetic drive was activated to begin slow stirring with the reactants. After stirring for 10 minutes, the polyol polymerization was carried out at a temperature of 90°C, a reaction time of 4 hours, a stirring speed of 250 rpm, and a vacuum pressure of 50 torr.

[0907] Step 3 reaction: Next, the temperature was changed to 90℃, the reaction time was changed to 2 hr, and the vacuum pressure was changed from 50 torr to 10 torr, accelerating the reaction to remove unreacted monomers and improve the reaction rate.

[0908] Afterwards, the reaction was terminated, the vacuum pressure was adjusted to atmospheric pressure, and the installed reactor, Dean Stark trap, and reflux condenser were separated.

[0909] Through the above-described process, a polyol according to Manufacturing Example 4-1 was manufactured.

[0910]

[0911] 2) Manufacturing Example 4-2

[0912] For the production of polyol according to Manufacturing Example 4-2, a 250 ml glass flask reactor, a Dean Stark trap, and a reflux condenser were used. A magnetic drive was used to ensure uniform stirring at 250 rpm. Furthermore, a heating mantle and mantle cover were used to maintain the temperature at the top and bottom of the reactor at 90°C, and the polyol was produced under a nitrogen atmosphere.

[0913] Step 1 Reaction: First, 20 g of 3-hydroxypropionic acid (3-HP) and 0.18 g of BrΨnsted acid catalyst (para-toluenesulfonic acid) were added to the reactor, and the polymerization reaction was carried out at a temperature of 90℃, a reaction time of 4 hr, a stirring speed of 250 rpm, and a vacuum pressure of 50 torr to induce the polymerization of 3-HP. During the polymerization of 3-HP, the generated water was collected inside the installed Dean Stark trap. After the reaction was completed, the magnetic drive was briefly stopped, the vacuum pressure was changed to normal pressure, and the diol to be added for polyol production was prepared.

[0914] Step 2 Reaction: Next, to proceed with the esterification reaction, 1.3 g of 1,3-propanediol was introduced into the reactor, and the magnetic drive was activated to begin slow stirring with the reactants. After stirring for 10 minutes, the polyol polymerization was carried out at a temperature of 120°C, a reaction time of 4 hours, a stirring speed of 250 rpm, and a vacuum pressure of 50 torr.

[0915] Step 3 reaction: Next, the temperature was changed to 120℃, the reaction time was changed to 2 hr, and the vacuum pressure was changed from 50 torr to 10 torr, accelerating the reaction to remove unreacted monomers and improve the reaction rate.

[0916] Afterwards, the reaction was terminated, the vacuum pressure was adjusted to atmospheric pressure, and the installed reactor, Dean Stark trap, and reflux condenser were separated.

[0917] Through the above-described process, a polyol according to Manufacturing Example 4-2 was manufactured.

[0918]

[0919] 3) Manufacturing Example 4-3

[0920] For the production of polyol according to Manufacturing Example 4-3, a 250 ml glass flask reactor, a Dean Stark trap, and a reflux condenser were used. A magnetic drive was used to ensure uniform stirring at 250 rpm. Furthermore, a heating mantle and mantle cover were used to maintain the temperature at the top and bottom of the reactor at 90°C, and the polyol was produced under a nitrogen atmosphere.

[0921] Step 1 Reaction: First, 20 g of 3-hydroxypropionic acid (3-HP) and 0.18 g of BrΨnsted acid catalyst (para-toluenesulfonic acid) were added to the reactor, and the polymerization reaction was carried out at a temperature of 80℃, a reaction time of 4 hr, a stirring speed of 250 rpm, and a vacuum pressure of 50 torr to induce the polymerization of 3-HP. During the polymerization of 3-HP, the generated water was collected inside the installed Dean Stark trap. After the reaction was completed, the magnetic drive was briefly stopped, the vacuum pressure was changed to normal pressure, and the diol to be added for polyol production was prepared.

[0922] Step 2 Reaction: Next, to proceed with the esterification reaction, 1.3 g of 1,3-propanediol was introduced into the reactor, and the magnetic drive was activated to begin slow stirring with the reactants. After stirring for 10 minutes, the polyol polymerization was carried out at a temperature of 80°C, a reaction time of 4 hours, a stirring speed of 250 rpm, and a vacuum pressure of 50 torr.

[0923] Step 3 reaction: Next, the temperature was changed to 80℃, the reaction time was changed to 2 hr, and the vacuum pressure was changed from 50 torr to 10 torr, accelerating the reaction to remove unreacted monomers and improve the reaction rate.

[0924] Afterwards, the reaction was terminated, the vacuum pressure was adjusted to atmospheric pressure, and the installed reactor, Dean Stark trap, and reflux condenser were separated.

[0925] Through the above-described process, a polyol according to Manufacturing Example 4-3 was manufactured.

[0926]

[0927] 4) Manufacturing Example 4-4

[0928] For the production of polyol according to Manufacturing Example 4-4, a 250 ml glass flask reactor, a Dean Stark trap, and a reflux condenser were used. A magnetic drive was used to ensure uniform stirring at 250 rpm. Furthermore, a heating mantle and mantle cover were used to maintain the temperature at 90°C at the top and bottom of the reactor, and the polyol was produced under a nitrogen atmosphere.

[0929] Step 1 Reaction: First, 20 g of 3-hydroxypropionic acid (3-HP) and 0.18 g of BrΨnsted acid catalyst (para-toluenesulfonic acid) were added to the reactor, and the polymerization reaction was carried out at a temperature of 80℃, a reaction time of 4 hr, a stirring speed of 250 rpm, and a vacuum pressure of 100 torr to induce polymerization of 3-HP. During the polymerization of 3-HP, the generated water was collected inside the installed Dean Stark trap. After the reaction was completed, the magnetic drive was briefly stopped, the vacuum pressure was changed to normal pressure, and the diol to be added for polyol production was prepared.

[0930] Step 2 Reaction: Next, to proceed with the esterification reaction, 1.3 g of 1,3-propanediol was introduced into the reactor, and the magnetic drive was activated to begin slow stirring with the reactants. After stirring for 10 minutes, the polyol polymerization was carried out at a temperature of 80°C, a reaction time of 4 hours, a stirring speed of 250 rpm, and a vacuum pressure of 50 torr.

[0931] Step 3 reaction: Next, the temperature was changed to 80℃, the reaction time was changed to 2 hr, and the vacuum pressure was changed from 50 torr to 10 torr, accelerating the reaction to remove unreacted monomers and improve the reaction rate.

[0932] Afterwards, the reaction was terminated, the vacuum pressure was adjusted to atmospheric pressure, and the installed reactor, Dean Stark trap, and reflux condenser were separated.

[0933] Through the above-described process, a polyol according to Manufacturing Example 4-4 was manufactured.

[0934]

[0935] 5) Manufacturing Example 4-5

[0936] For the production of polyol according to Manufacturing Examples 4-5, a 250 ml glass flask reactor, a Dean Stark trap, and a reflux condenser were used. A magnetic drive was used to ensure uniform stirring at 250 rpm. Furthermore, a heating mantle and mantle cover were used to maintain the temperature at the top and bottom of the reactor at 90°C, and the polyol was produced under a nitrogen atmosphere.

[0937] Step 1 Reaction: First, 20 g of 3-hydroxypropionic acid (3-HP) and 0.18 g of BrΨnsted acid catalyst (para-toluenesulfonic acid) were added to the reactor, and the polymerization reaction was carried out at a temperature of 90℃, a reaction time of 4 hr, a stirring speed of 250 rpm, and a vacuum pressure of 100 torr to induce the polymerization of 3-HP. During the polymerization of 3-HP, the generated water was collected inside the installed Dean Stark trap. After the reaction was completed, the magnetic drive was briefly stopped, the vacuum pressure was changed to normal pressure, and the diol to be added for polyol production was prepared.

[0938] Step 2 Reaction: Next, to proceed with the esterification reaction, 1.3 g of 1,3-propanediol was introduced into the reactor, and the magnetic drive was activated to begin slow stirring with the reactants. After stirring for 10 minutes, the polyol polymerization was carried out at a temperature of 150°C, a reaction time of 4 hours, a stirring speed of 250 rpm, and a vacuum pressure of 50 torr.

[0939] Step 3 reaction: Next, the temperature was changed to 150℃, the reaction time was changed to 2 hr, and the vacuum pressure was changed from 50 torr to 10 torr, accelerating the reaction to remove unreacted monomers and improve the reaction rate.

[0940] Afterwards, the reaction was terminated, the vacuum pressure was adjusted to atmospheric pressure, and the installed reactor, Dean Stark trap, and reflux condenser were separated.

[0941] Through the above-described process, a polyol according to Manufacturing Example 4-5 was manufactured.

[0942]

[0943] (2) Purification of polyol

[0944]

[0945] Afterwards, the polyol was purified as in Examples 4-1 to 4-13 according to the contents described in Table 6 below.

[0946]

[0947] Example Polyol Polar Solvent 4-1 Preparation Example 4-1 Ultrapure 4-2 Preparation Example 4-1 Ethanol 4-3 Preparation Example 4-2 Ultrapure 4-4 Preparation Example 4-2 Ethanol 4-5 Preparation Example 4-3 Ultrapure 4-6 Preparation Example 4-3 Ethanol 4-7 Preparation Example 4-3 Ultrapure + Ethanol 4-8 Preparation Example 4-4 Ultrapure 4-9 Preparation Example 4-4 Ethanol 4-10 Preparation Example 4-4 Ultrapure + Ethanol 4-11 Preparation Example 4-5 Ultrapure 4-12 Preparation Example 4-5 Ethanol 4-13 Preparation Example 4-5 Ultrapure + Ethanol

[0948]

[0949] 1) Example 4-1

[0950] The polyol of Manufacturing Example 1 was melted at 60°C for 10 minutes. Then, a 1L glass reactor was prepared, a magnetic driver was installed to facilitate stirring, and 300 ml of deionized water was added to the reactor. 16 g of the molten polyol was slowly added to the deionized water. The stirring speed was maintained at 450 rpm, and the mixture was stirred at room temperature for about 1 hour. During stirring, the molten polyol was maintained 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 solid. The deionized water was completely removed under reduced pressure for about 5 minutes, and the mixture was dried in a vacuum oven at 40°C.

[0951] Through the above-described process, a purified polyol according to Example 4-1 was obtained.

[0952]

[0953] 2) Examples 4-2 to 4-13

[0954] The purified polyols according to Examples 4-2 to 4-13 were obtained by the same process as Example 4-1, except for the types of polyol and polar solvent described in Table 1.

[0955]

[0956] (3) Property evaluation

[0957]

[0958] In order to evaluate the properties of the polyol samples purified according to Examples 4-1 to 4-13 above, the following items were measured and the results are shown in Table 2 below.

[0959] The method of measuring the properties is as described above.

[0960]

[0961] Pre-purification MnPDIHvAvMnPDIHvAv4-18101.76128.23.109641.59114.8< 2.04-28101.76128.23.109401.64120.1< 2.34-38641.65131.15.8410111.35112.3< 2.04-48641.65131.15.849781.54123.7< 3.04-55481.59166.012.438811.36124.5< 2.04-65481.59166.012.438141.47138.9< 3.04-75481.59166.012.438471.41134.6< 2.54-86431.54155.38.579471.27116.3< 2.04-96431.54155.38.578991.41121.7< 3.04-106431.54155.38.579231.34119.4< 2.54-119541.84107.224.1713431.4778.2< 2.04-129541.84107.224.1711791.5887.1< 3.04-139541.84107.224.1712841.5183.8< 2.5

[0962]

[0963] Referring to the results in Table 7 above, it can be confirmed that the examples according to the present invention showed an increase in number average molecular weight (Mn) by at least 10% after purification, and also a decrease in PDI, Hv, and Av.

[0964] Accordingly, it can be seen that the polyol purified according to the method of the present invention has substantially all unreacted monomers with low molecular weights removed.

[0965]

[0966] 5. Example according to the fifth embodiment

[0967]

[0968] Polyols according to examples and comparative examples were prepared according to each polymerization condition using the reactants and catalysts in Table 8 below.

[0969]

[0970] 3-HP Alcohol Catalyst Example 5-13-HP 1,3-Propanediol (PDO) BrΨnsted acid Example 5-23-HP 1,3-Propanediol (PDO) BrΨnsted acid Example 5-33-HP 1,3-Propanediol (PDO) BrΨnsted acid Example 5-43-HP 1,4-Butanediol (BDO) BrΨnsted acid Example 5-53-HP 1,3-Propanediol (PDO) Lewis acid Example 5-63-HP 1,3-Propanediol (PDO) BrΨnsted acid Comparative Example 5-13-HP 1,3-Propanediol (PDO) BrΨnsted acid Comparative Example 5-23-HP 1,3-Propanediol (PDO) BrΨnsted acid Comparative Example 5-33-HP1,3-Propanediol (PDO)BrΨnsted acidComparative example 5-43-HP1,3-Propanediol (PDO)Lewis acid

[0971]

[0972] Example 5-1

[0973] For the production of polyol according to Example 5-1, a 250 ml glass flask reactor, a Dean-Stark trap, and a reflux condenser were used. A magnetic drive was used to ensure uniform stirring at 250 rpm. Furthermore, a heating mantle and mantle cover were used to maintain the temperature at 90°C at the top and bottom of the reactor, and the polyol was produced under a nitrogen atmosphere.

[0974]

[0975] (polymerization)

[0976] Step 1: First, 20 g of 3-hydroxypropionic acid (3-HP) and 0.18 g of BrΨnsted acid catalyst (para-toluenesulfonic acid) were added to the reactor, and a polymerization reaction was performed at a temperature of 90°C, a reaction time of 8 hr, a stirring speed of 250 rpm, and a vacuum pressure of 50 torr to induce polymerization of 3-HP.

[0977] Step 2: Next, a secondary polymerization reaction was conducted at a temperature of 120°C, a reaction time of 8 hours, a stirring speed of 250 rpm, and a vacuum pressure of 50 torr to induce polymerization of 3-HP. During the polymerization of 3-HP, the generated water collected inside the installed Dean-Stark trap. After the reaction was completed, the magnetic drive was briefly stopped, the vacuum pressure was changed to atmospheric pressure, and the diol to be introduced for polyol production was prepared.

[0978]

[0979] (ester reaction)

[0980] Next, to proceed with the esterification reaction, 1.3 g of 1,3-propanediol was introduced into the reactor, and the magnetic drive was started to slowly stir the reactants. After stirring for 10 minutes, the polymerization of the polyol was carried out at a temperature of 90°C, a reaction time of 4 hours, a stirring speed of 250 rpm, and a vacuum pressure of 50 torr.

[0981]

[0982] (Unreacted monomer removal reaction)

[0983] Next, the temperature was changed to 90℃, the reaction time was changed to 2 hr, and the vacuum pressure was changed from 50 torr to 10 torr, and the reaction was accelerated to remove unreacted monomers and improve the reaction rate.

[0984] Afterwards, the reaction was terminated, the vacuum pressure was adjusted to atmospheric pressure, and the installed reactor, Dean Stark trap, and reflux condenser were separated.

[0985] Through the above-described process, a polyol according to Example 5-1 was manufactured.

[0986]

[0987] Examples 5-2 to 5-6 and Comparative Examples 5-1 to 5-4

[0988] Examples 5-2 to 5-5 and Comparative Examples 5-1 to 5-4 produced polyols in the same manner as Example 1, but the conditions of the polymerization reaction were changed as shown in Table 2 below.

[0989]

[0990] Example 5-6 produced a polyol without performing the unreacted monomer removal process in Example 5-1.

[0991]

[0992] Polymerization reaction step 1 step 2 Example 5 - 190°C, 8 hours, 50 torr 120°C, 8 hours, 50 torr Example 5 - 290°C, 8 hours, 50 torr 130°C, 8 hours, 50 torr Example 5 - 390°C, 8 hours, 50 torr 150°C, 8 hours, 50 torr Example 5 - 490°C, 8 hours, 50 torr 120°C, 8 hours, 50 torr Example 5 - 590°C, 8 hours, 50 torr 120°C, 8 hours, 50 torr Example 5 - 690°C, 8 hours, 50 torr 120°C, 8 hours, 50 torr Comparative Example 5 - 190°C, 8 hours, 50 torr - Comparative Example 5-2120℃, 8 hours, 50 torr-Comparative example 5-3150℃, 8 hours, 50 torr-Comparative example 5-4120℃, 8 hours, 50 torr-

[0993] <Method of evaluating physical properties>

[0994] To evaluate the characteristics of the polyol samples manufactured according to the above examples and comparative examples, the physical properties were evaluated. The method for measuring the physical properties was as described above.

[0995] In addition, the method for measuring residual monomer and the method for measuring acrylic acid byproduct are as follows.

[0996]

[0997] - Residual monomer measurement method

[0998] The residual monomers of the examples and comparative examples were measured through H-NMR analysis. Here, the residual monomers refer to the 3-HP monomer and 3-HP dimer that were not polymerized. The residual monomers can be identified as peaks of CH2 peak 2.42, 3.80 ppm, OH 6.34 ppm, and COOH 12.1 ppm, and the content of the residual monomers can be confirmed through peak integration.

[0999]

[1000] -Method for measuring acrylic acid byproducts

[1001] Acrylic acid in the examples and comparative examples was measured through H-NM analysis. The acrylic acid can be confirmed as CH peak 5.99, 6.29 6.64 ppm, COOH 12.05 ppm, and the content of acrylic acid can be confirmed through peak integration.

[1002]

[1003] Mn (g / mol)PDIResidual Monomer (wt%)Acrylic Acid Byproduct (wt%)Hv (mg KOH / g)AV (mg KOH / g)Example 5-11,0411.430.010.002112<2.0Example 5-21,1931.560.010.004108<2.0Example 5-31,4231.680.010.00679<2.0Example 5-41,1081.730.010.004110<2.0Example 5-51,4191.920.050.00981<2.2Example 5-61.4201.980.090.01079<2.0Comparative Example 5-17862.240.210.020144< 2.0 Comparison Example 5-28842.110.210.020130< 2.0 Comparison Example 5-39722.470.270.050118< 2.2 Comparison Example 5-41,3472.330.070.02291< 2.4

[1004]

[1005] Referring to the results in Table 10 above, it can be confirmed that the examples according to the present invention have various characteristics depending on the type of alcohol, type of catalyst, and polymerization conditions. In addition, according to the manufacturing method of the present invention, since at least two polymerization steps are performed, the amount of residual monomer and acrylic acid byproduct is very small. However, the polyol according to the comparative example has a large amount of residual monomer and acrylic acid byproduct compared to the examples.

[1006]

[1007] 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. Containing at least one of the compounds represented by the following chemical formulas 1 to 3 Polyol. [Chemical Formula 1] In the above chemical formula 1, R is a linker derived from alcohol, The above m is an integer greater than or equal to 1, and n is an integer greater than or equal to 0. [Chemical formula 2] In the above chemical formula 2, R is a linker derived from alcohol, The above m is an integer greater than or equal to 1, n is an integer greater than or equal to 0, and p is an integer greater than or equal to 0. [Chemical Formula 3] In the above chemical formula 3, R is a linker derived from alcohol, The above m is an integer greater than or equal to 1, n is an integer greater than or equal to 0, p is an integer greater than or equal to 0, and r is an integer greater than or equal to 0.

2. In paragraph 1, The above alcohol is 2,3-butanediol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol and ethylene glycol, glycerol, pentaerythritol, trimethylolpropane, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-butynediol, neopentyl glycol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, bis(hydroxymethyl)cyclohexane, triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, dibutylene glycol, polybutylene glycoltrimethylolpropane, glycerol, trishydroxyethyl isocyanurate, castor oil and Containing at least one type of dipentaerythritol Polyol.

3. In paragraph 1, The hydroxyl value (Hv) is 10 to 1000. The acid value (Av) is 10 or less The average molecular weight (Mn) is 200 to 10,000. Molecular weight distribution (PDI) of 1 to 10 Polyol. A step of reacting 4.3-hydroxypropionic acid and alcohol with a catalyst. Method for producing polyol.

5. In paragraph 4, The above steps are It is performed under a temperature of 70 to 150 ℃ and a pressure of 10 to 300 torr. Method for producing polyol. 6.(a) a step of polymerizing 3-hydroxypropionic acid; and (b) a step of producing a polyol by reacting polymerized 3-hydroxypropionic acid with alcohol; Method for producing polyol.

7. In paragraph 6, Step (a) above Polymerizing the above 3-hydroxypropionic acid using a catalyst Method for producing polyol.

8. In paragraph 7, The above catalyst 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 polyol.

9. In paragraph 8, The above Bronsted acid catalyst p-Toluenesulfonic acid (p-TSA), ion exchange resin containing sulfonic acid group, H 2 SO 4 , HCL, H 2 CO 3 , HNO 3 , HBF 4 , HSbF 6 , ClSO 3 H, FSO 3 H, CF 3 SO 3 H and CH 3 SO 3 Containing at least one type of H Method for producing polyol.

10. In paragraph 8, The above Lewis acid catalyst Tin(II) 2-ethylhexanoate(TEH), Tin(II) Chloride(SnCl 2 ), 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, tris((3,5-trifluoroomethyl)phenyl)borane, and tris(tetrafluoro-o-tolyl)borane. Method for producing polyol.

11. In paragraph 6, 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 polyol.

12. In paragraph 6, The above alcohol is 1,3-Butanediol, 2,3-Butanediol, 1,3-Propanediol, 1,4-Butanediol, 1,6-Hexanediol and ethylene glycol, glycerol, pentaerythritol, trimethylolpropane, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,4-Butynediol, neopentyl glycol, 1,5-Pentanediol, 3-Methyl-1,5-Pentanediol, 1,8-Octanediol, 1,10-Decanediol, 1,12-Dodecanediol, 2-Methyl-1,3-Propanediol, 2-Methyl-1,4-Butanediol, 2-Methyl-1,8-Octanediol, 2,7-Dimethyl-1,8-Octanediol, 1,9-Nonanediol, Containing at least one of 2-methyl-1,9-nonanediol, 2,8-dimethyl-1,9-nonanediol, 1,10-decanediol, 2,2-diethyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,4-cyclohexanediol, cyclohexanedimethanol, 3(or 4), 8(or 9)-dihydroxytricyclodecane, bis(hydroxymethyl)cyclohexane, triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, dibutylene glycol, polybutylene glycoltrimethylolpropane, glycerol, trishydroxyethyl isocyanurate, castor oil, dipentaerythritol, and sorbitol Method for producing polyol.

13. In paragraph 6, After step (b) above, (c) a step of removing unreacted monomer by lowering the pressure compared to the pressure of step (b); Method for producing polyol. 14.(a) a polyol production step for producing a polyol containing 3-hydroxypropionic acid; and (b) a polyol purification step comprising adding the polyol to a solution containing a polar solvent and an anion exchange resin and stirring the same; Method for purifying polyol.

15. In paragraph 14, The above polar solvent is Containing water, alcohol or a polar mixed solvent of water and alcohol Method for purifying polyol.

16. In paragraph 15, The above alcohol is Containing at least one of methanol, ethanol, n-propanol, n-butanol, n-pentanol, n-hexanol, n-heptanol, n-octanol, n-nonanol and n-decanol, The above anion exchange resin Containing an ammonium group or an amine group as a functional group Method for purifying polyol.

17. In paragraph 14, Step (b) 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 purifying polyol.

18. In paragraph 14, Step (a) above (a1) comprising a step of reacting 3-hydroxypropionic acid and alcohol with a catalyst, It is performed under a temperature of 30 to 300 ℃ and a pressure of 0.1 to 700 torr.

19. In paragraph 18, The above catalyst A catalyst comprising a Bronsted acid catalyst, a Lewis acid catalyst or a mixed catalyst of a Bronsted acid catalyst and a Lewis acid catalyst. Method for producing polyol.

20. In paragraph 18, The above alcohol is 1,3-Butanediol, 2,3-Butanediol, 1,3-Propanediol, 1,4-Butanediol, 1,6-Hexanediol and ethylene glycol, glycerol, pentaerythritol, trimethylolpropane, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,4-Butynediol, neopentyl glycol, 1,5-Pentanediol, 3-Methyl-1,5-Pentanediol, 1,8-Octanediol, 1,10-Decanediol, 1,12-Dodecanediol, 2-Methyl-1,3-Propanediol, 2-Methyl-1,4-Butanediol, 2-Methyl-1,8-Octanediol, 2,7-Dimethyl-1,8-Octanediol, 1,9-Nonanediol, Containing at least one of 2-methyl-1,9-nonanediol, 2,8-dimethyl-1,9-nonanediol, 1,10-decanediol, 2,2-diethyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,4-cyclohexanediol, cyclohexanedimethanol, 3(or 4), 8(or 9)-dihydroxytricyclodecane, bis(hydroxymethyl)cyclohexane, triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, dibutylene glycol, polybutylene glycoltrimethylolpropane, glycerol, trishydroxyethyl isocyanurate, castor oil, dipentaerythritol, and sorbitol Method for producing polyol.

21. In paragraph 14, Step (a) above (a2-1) a step of polymerizing 3-hydroxypropionic acid; and (a2-2) a step of producing a polyol by reacting polymerized 3-hydroxypropionic acid with alcohol; Method for purifying polyol.

22. In paragraph 21, The above step (a2-1) Polymerizing the above 3-hydroxypropionic acid using a catalyst Method for purifying polyol.

23. In paragraph 22, The above catalyst 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 purifying polyol.

24. In paragraph 21, The above step (a2-1) It is performed under a temperature of 30 to 300 ℃ and a pressure of 0.1 to 700 torr. The above step (a2-2) It is performed under a temperature of 30 to 300 ℃ and a pressure of 0.1 to 700 torr. Method for purifying polyol.

25. In paragraph 21, After the above step (a2-2), (a2-3) a step of removing unreacted monomers by lowering the pressure compared to the pressure of step (a2-2); Method for purifying polyol. 26.(a) A polyol production step for producing a polyol containing 3-hydroxypropionic acid; and (b) a polyol purification step comprising adding the polyol to a solution containing a polar solvent and stirring; Method for purifying polyol.

27. In paragraph 26, The above polar solvent is Containing water, alcohol or a polar mixed solvent of water and alcohol Method for purifying polyol.

28. In paragraph 27, The above alcohol is Containing at least one of methanol, ethanol, n-propanol, n-butanol, n-pentanol, n-hexanol, n-heptanol, n-octanol, n-nonanol and n-decanol Method for purifying polyol.

29. In paragraph 26, Step (b) 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 purifying polyol.

30. In paragraph 26, Step (a) above (a1) comprising a step of reacting 3-hydroxypropionic acid and alcohol with a catalyst, It is performed under a temperature of 30 to 300 ℃ and a pressure of 0.1 to 700 torr. Method for purifying polyol.

31. In paragraph 30, The above catalyst A catalyst comprising a Bronsted acid catalyst, a Lewis acid catalyst or a mixed catalyst of a Bronsted acid catalyst and a Lewis acid catalyst. Method for producing polyol.

32. In paragraph 30, The above alcohol is 1,3-Butanediol, 2,3-Butanediol, 1,3-Propanediol, 1,4-Butanediol, 1,6-Hexanediol and ethylene glycol, glycerol, pentaerythritol, trimethylolpropane, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,4-Butynediol, neopentyl glycol, 1,5-Pentanediol, 3-Methyl-1,5-Pentanediol, 1,8-Octanediol, 1,10-Decanediol, 1,12-Dodecanediol, 2-Methyl-1,3-Propanediol, 2-Methyl-1,4-Butanediol, 2-Methyl-1,8-Octanediol, 2,7-Dimethyl-1,8-Octanediol, 1,9-Nonanediol, Containing at least one of 2-methyl-1,9-nonanediol, 2,8-dimethyl-1,9-nonanediol, 1,10-decanediol, 2,2-diethyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,4-cyclohexanediol, cyclohexanedimethanol, 3(or 4), 8(or 9)-dihydroxytricyclodecane, bis(hydroxymethyl)cyclohexane, triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, dibutylene glycol, polybutylene glycoltrimethylolpropane, glycerol, trishydroxyethyl isocyanurate, castor oil, dipentaerythritol, and sorbitol Method for producing polyol.

33. In paragraph 26, Step (a) above (a2-1) a step of polymerizing 3-hydroxypropionic acid; and (a2-2) a step of producing a polyol by reacting polymerized 3-hydroxypropionic acid with alcohol; Method for purifying polyol.

34. In paragraph 33, The above step (a2-1) Polymerizing the above 3-hydroxypropionic acid using a catalyst Method for purifying polyol.

35. In paragraph 34, The above catalyst 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 purifying polyol.

36. In paragraph 33, The above step (a2-1) It is performed under a temperature of 30 to 300 ℃ and a pressure of 0.1 to 700 torr, The above step (a2-2) It is performed under a temperature of 30 to 300 ℃ and a pressure of 0.1 to 700 torr. Method for purifying polyol.

37. In paragraph 33, After the above step (a2-2), (a2-3) a step of removing unreacted monomers by lowering the pressure compared to the pressure of step (a2-2); Method for purifying polyol. 38.(a) a step of polymerizing 3-hydroxypropionic acid; and (b) a step of producing a polyol by reacting polymerized 3-hydroxypropionic acid with alcohol; including, Step (a) above (a-1) a first polymerization step performed at a temperature of 30 to 300 ℃; and (a-2) a second polymerization step performed at a temperature of 30 to 300 ℃; Method for producing polyol.

39. In paragraph 38, Step (a) above Polymerizing the above 3-hydroxypropionic acid using a catalyst Method for producing polyol.

40. In paragraph 39, The above catalyst 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 polyol.

41. In paragraph 38, The above step (a-2) is performed at a higher temperature than the above step (a-1). Method for producing polyol.

42. In paragraph 38, 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 polyol.

43. In paragraph 38, The above alcohol is 1,3-Butanediol, 2,3-Butanediol, 1,3-Propanediol, 1,4-Butanediol, 1,6-Hexanediol and ethylene glycol, glycerol, pentaerythritol, trimethylolpropane, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,4-Butynediol, neopentyl glycol, 1,5-Pentanediol, 3-Methyl-1,5-Pentanediol, 1,8-Octanediol, 1,10-Decanediol, 1,12-Dodecanediol, 2-Methyl-1,3-Propanediol, 2-Methyl-1,4-Butanediol, 2-Methyl-1,8-Octanediol, 2,7-Dimethyl-1,8-Octanediol, 1,9-Nonanediol, Containing at least one of 2-methyl-1,9-nonanediol, 2,8-dimethyl-1,9-nonanediol, 1,10-decanediol, 2,2-diethyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,4-cyclohexanediol, cyclohexanedimethanol, 3(or 4), 8(or 9)-dihydroxytricyclodecane, bis(hydroxymethyl)cyclohexane, triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, dibutylene glycol, polybutylene glycoltrimethylolpropane, glycerol, trishydroxyethyl isocyanurate, castor oil, dipentaerythritol, and sorbitol Method for producing polyol.

44. In paragraph 38, After step (b) above, (c) a step of removing unreacted monomer by lowering the pressure compared to the pressure of step (b); Method for producing polyol.

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