Polyol composition using glucose-containing saccharide composition and polyurethane foam containing the same

Abstract

The present invention relates to a polyol composition comprising a polysaccharide alcohol, an anhydrosugar alcohol derived from the polysaccharide alcohol, and an anhydrosugar alcohol polymer, and a polyurethane foam comprising the same. More specifically, the present invention relates to a polyol composition comprising: a) a monoanhydrosugar alcohol; b) a dianhydrosugar alcohol; c) a polysaccharide alcohol; d) an anhydrosugar alcohol derived from the polysaccharide alcohol; and e) a polymer of one or more of the above a) to d). The polyol composition satisfies specific physical property requirements, such as number average molecular weight (Mn), polydispersity index (PDI), and average number of OH groups per molecule, and when used as a raw material for polyurethane, the polyol composition has improved physical properties, such as strength, elongation, and thermal insulation. The polyol composition can be produced using a hydrogenated sugar composition obtained from a sugar mixture containing glucose and polysaccharides (disaccharides or higher), which improves productivity and allows for cost reduction compared to when conventional high-purity hydrogenated sugars are used. The present invention also relates to a polyol composition and polyurethane foam comprising the same.

Description

[Technical field]

[0001] The present invention relates to a polyol composition using a glucose-containing saccharide composition and a polyurethane foam containing the same, and more specifically, the polyol composition contains a monoanhydrosugar alcohol; b) a dianhydrosugar alcohol; c) a polysaccharide alcohol; d) an anhydrosugar alcohol derived from a polysaccharide alcohol; and e) one or more polymers of the above a) to d). The polyol composition satisfies specific physical property conditions such as number average molecular weight (Mn), polydispersity index (PDI) and average number of OH groups per molecule, and can produce a polyurethane foam exhibiting molded density, compressive strength and excellent heat insulation (low thermal conductivity) without reducing existing physical properties. The present invention relates to a polyol composition using a glucose-containing saccharide composition and a polyurethane foam containing the same, which can improve productivity and reduce costs by producing the polyol composition using a hydrogenated sugar composition obtained from a saccharide mixture containing glucose and polysaccharides (saccharides of disaccharides or more) rather than hydrogenated sugar obtained from high purity glucose. [Background technology]

[0002] Hydrogenated sugars (also called "sugar alcohols") are compounds obtained by adding hydrogen to the reducing end group of sugars. Generally, HOCH2 (CHOH) n They have the formula CH2OH (where n is an integer between 2 and 5) and are classified into tetritols, pentitols, hexitols and heptitols (having 4, 5, 6 and 7 carbon atoms, respectively) according to the number of carbon atoms. Among them, hexitols with 6 carbon atoms include sorbitol, mannitol, iditol, galactitol, etc., and sorbitol and mannitol are particularly useful substances.

[0003] Anhydrous sugar alcohols are substances formed by removing one or more water molecules from the inside of hydrogenated sugar. When one water molecule is removed, it becomes a tetraol with four hydroxyl groups in the molecule, and when two water molecules are removed, it becomes a diol with two hydroxyl groups in the molecule. They can be produced using hexitol derived from starch (e.g., Patent Documents 1 and 2). Anhydrous sugar alcohols are environmentally friendly substances derived from renewable natural resources, and have long been of interest, and production methods have been researched. Among such anhydrous sugar alcohols, isosorbide produced from sorbitol currently has the widest range of industrial applications.

[0004] Anhydrous sugar alcohols can be used in various fields, such as in the treatment of heart and vascular diseases, adhesives for patches, medicines such as oral cleansers, solvents for compositions in the cosmetic industry, and emulsifiers in the food industry. In addition, they have the effect of increasing the glass transition temperature of polymeric substances such as polyester, PET, polycarbonate, polyurethane, and epoxy resin, thereby improving the strength of such substances, and are environmentally friendly materials derived from natural products, so they are very useful in the plastics industry, such as bioplastics. In addition, it is also known that anhydrous sugar alcohols can be used as adhesives, environmentally friendly plasticizers, biodegradable polymers, and environmentally friendly solvents for water-soluble lacquers.

[0005] As described above, anhydrosugar alcohols have attracted great interest due to their wide range of applications, and the level of industrial practical application is increasing.

[0006] In the past, by-products produced in the process of dehydrating hydrogenated sugars to produce anhydrous sugar alcohols have not been used for any special purposes, such as simply as binders.

[0007] Patent Document 3 discloses a polyol composition containing anhydrous sugar alcohol and anhydrous sugar alcohol polymer, which are produced by dehydrating hydrogenated sugar and then distilling under reduced pressure. However, when a polyol composition is produced using sorbitol with a purity of 99% or more as disclosed in this patent document, the ratio of polysaccharide (sugars of disaccharides or more) alcohols and anhydrous sugar alcohols derived therefrom is low during purification through distillation after the dehydration reaction, resulting in a problem of a low distillation yield of dianhydrous sugar alcohols (e.g., isosorbide). In addition, when the polyol composition disclosed in this patent document is used as a polyol component of polyurethane foam, the produced polyurethane foam has low physical properties such as molding density, compressive strength, and heat insulation. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] Korean Patent No. 10-1079518 [Patent Document 2] Korean Patent Application Publication No. 10-2012-0066904 [Patent Document 3] Korean Patent Application Publication No. 10-2017-0015290 Summary of the Invention [Problem to be solved by the invention]

[0009] The object of the present invention is to provide a polyol composition using a glucose-containing saccharide composition, which comprises a) a monoanhydrosugar alcohol; b) a dianhydrosugar alcohol; c) a polysaccharide alcohol; d) an anhydrosugar alcohol derived from a polysaccharide alcohol; and e) a polymer of one or more of the above a) to d), and which satisfies specific levels of physical property conditions of the polyol composition, such as number average molecular weight (Mn), polydispersity index (PDI) and average number of OH groups per molecule, and which can produce a polyurethane foam exhibiting improved molded density and compressive strength and excellent heat insulation (low thermal conductivity) without deteriorating existing physical properties, and which is produced using a hydrogenated sugar composition obtained from a saccharide mixture containing glucose and polysaccharides (saccharides of disaccharides or more) rather than hydrogenated sugar obtained from high-purity glucose, thereby enabling improved productivity and cost reduction. [Means for solving the problem]

[0010] In order to solve the above-mentioned technical problems, the present invention provides a method for producing a polysaccharide alcohol comprising the steps of: a) a monoanhydrosugar alcohol; b) a dianhydrosugar alcohol; c) a polysaccharide alcohol represented by the following formula (1); d) an anhydrosugar alcohol derived from a polysaccharide alcohol represented by the following formula (1); and e) one or more polymers of the above a) to d); (i) the composition has a number average molecular weight (Mn) of 193 to 1,589 g / mol; (ii) the composition has a polydispersity index (PDI) of 1.13 to 3.41; and (iii) the average number of -OH groups per molecule in the composition is 2.54 to 21.36.

[0011] [ka] (In the formula, n is an integer of 0 to 4.)

[0012] In another aspect of the present invention, there is provided an alkylene oxide-added polyol composition produced by subjecting an alkylene oxide to an addition reaction with the polyol composition of the present invention.

[0013] In another aspect of the present invention, there is provided a polyol premix composition comprising a polyol component, a catalyst, a surfactant and a blowing agent, wherein the polyol component is the alkylene oxide-added polyol composition of the present invention or a mixture of the alkylene oxide-added polyol composition of the present invention and a polyol other than the alkylene oxide-added polyol composition.

[0014] In another aspect of the present invention, there is provided a composition for producing a two-component polyurethane foam, comprising: the polyol premix composition as a first component; and a polyisocyanate as a second component.

[0015] In another aspect of the present invention, there is provided a method for producing a polyurethane foam, which comprises mixing and reacting a polyol premix composition as a first component with a polyisocyanate as a second component.

[0016] In another aspect of the present invention, there is provided a polyurethane foam produced by mixing and reacting the polyol premix composition of the present invention as a first component with a polyisocyanate as a second component. Effect of the Invention

[0017] The polyol composition according to the present invention contains not only monoanhydrosugar alcohols and dianhydrosugar alcohols, but also polysaccharide alcohols, anhydrosugar alcohols derived from polysaccharide alcohols, and one or more polymers thereof, and therefore can produce polyurethane foams that exhibit improved molding density and compressive strength and excellent thermal insulation properties (low thermal conductivity) without deteriorating existing physical properties. In addition, since the polyol composition of the present invention is produced using a hydrogenated sugar composition obtained from a sugar mixture containing glucose and polysaccharides (sugars of disaccharides or more), the fluidity is increased by the polysaccharide (sugars of disaccharides or more) alcohol and the anhydrosugar alcohol derived therefrom, improving the fluidity during distillation, and improving the distillation yield of dianhydrosugar alcohol (e.g., isosorbide) in the distillate. Therefore, compared to the conventional technology, the cost of the raw materials used can be reduced, and the productivity can be improved by improving the distillation yield of anhydrosugar alcohol.

[0018] Furthermore, since the polyol composition of the present invention can be obtained by using by-products obtained during the process of producing the internal dehydration product of hydrogenated sugar, the problem of by-products can be solved, and economical and environmental friendliness can be improved. In particular, since the initial raw material is not a high-purity glucose product but a sugar composition containing impurities other than glucose (disaccharides, higher polysaccharides, etc.), economical efficiency can be further improved by reducing costs. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0019] The present invention will now be described in more detail. The polyol composition of the present invention comprises: a) a monoanhydrosugar alcohol; b) a dianhydrosugar alcohol; c) a polysaccharide alcohol represented by the following formula (1); d) an anhydrosugar alcohol derived from the polysaccharide alcohol represented by the following formula (1); and e) one or more polymers of the above a) to d).

[0020] [ka] (In the formula, n is an integer of 0 to 4.)

[0021] The anhydrous sugar alcohol can be produced by dehydrating hydrogenated sugars derived from natural products. Hydrogenated sugars (also called "sugar alcohols") refer to compounds obtained by adding hydrogen to the reducing end group of sugars, and are generally represented by the formula HOCH2 (CHOH). nThey have the formula CH2OH (where n is an integer between 2 and 5) and are classified into tetritols, pentitols, hexitols, and heptitols (with 4, 5, 6, and 7 carbon atoms, respectively) according to the number of carbon atoms. Among these, hexitols with 6 carbon atoms include sorbitol, mannitol, iditol, and galactitol, and sorbitol and mannitol are very useful substances.

[0022] The polyol composition of the present invention contains a) monoanhydrosugar alcohol; b) dianhydrosugar alcohol; c) polysaccharide alcohol represented by the following formula (1); d) anhydrosugar alcohol derived from the polysaccharide alcohol represented by the formula (1); and e) one or more polymers, preferably two or more, more preferably all of the a) to d) described above. These can be obtained in the process of producing a hydrogenated sugar composition by hydrogenating a glucose-containing sugar composition (e.g., a sugar composition containing disaccharides or more polysaccharides containing glucose, mannose, fructose, and maltose), heating the obtained hydrogenated sugar composition under an acid catalyst to cause a dehydration reaction, and subjecting the obtained dehydration reaction product to thin-film distillation. More specifically, a) to e) contained in the polyol composition of the present invention may all be by-products remaining after the obtained dehydration reaction product is subjected to thin-film distillation to obtain a thin-film distillation liquid.

[0023] A monoanhydrosugar alcohol is an anhydrosugar alcohol formed by removing one water molecule from the inside of a hydrogenated sugar, and has a tetraol form having four hydroxyl groups in the molecule.

[0024] In the present invention, the type of the a) monoanhydrosugar alcohol is not particularly limited, but may be preferably a monoanhydrosugar hexitol, more specifically, 1,4-anhydrohexitol, 3,6-anhydrohexitol, 2,5-anhydrohexitol, 1,5-anhydrohexitol, 2,6-anhydrohexitol, or a mixture of two or more thereof.

[0025] Dianhydrosugar alcohols are anhydrous sugar alcohols formed by removing two water molecules from inside a hydrogenated sugar, and have a diol form with two hydroxyl groups in the molecule, and can be produced using hexitol derived from starch. Dianhydrosugar alcohols are environmentally friendly substances derived from renewable natural resources, so they have long been attracting attention, and research on their production methods has been progressing. Among such dianhydrosugar alcohols, isosorbide produced from sorbitol is currently industrially applicable.

[0026] In the present invention, the type of the dianhydrosugar alcohol b) is not particularly limited, but may be preferably a dianhydrosugar hexitol, more specifically, 1,4-3,6-dianhydrohexitol. The 1,4-3,6-dianhydrohexitol may be isosorbide, isomannide, isoidide, or a mixture of two or more thereof.

[0027] In the present invention, c) a compound represented by the following formula (1): [ka] (In the formula, n is an integer of 0 to 4.) The polysaccharide alcohol represented by the formula (I) can be produced by hydrogenating a disaccharide or higher polysaccharide containing maltose.

[0028] In the present invention, d) anhydrous sugar alcohol derived from a polysaccharide alcohol represented by formula (1) is represented by the following formula (2): [ka] (In the formula, n is an integer of 0 to 4.) A compound represented by the following formula (3): [ka] (In the formula, n is an integer of 0 to 4.) The compound may be selected from the group consisting of compounds represented by the formula:

[0029] In the present invention, e) one or more polymers of a) to d) may include one or more selected from the group consisting of condensation polymers obtained by the following condensation reactions. In the following condensation reactions, the condensation positions and condensation order between monomers are not particularly limited and can be selected without limitation within the range that can be generally predicted by a person of ordinary skill in this field: Condensation reaction of monoanhydrosugar alcohols, Condensation reaction of dianhydrosugar alcohols, Condensation reaction of polysaccharide alcohol represented by the formula (1), A condensation reaction of anhydrosugar alcohol derived from a polysaccharide alcohol represented by the formula (1), - Condensation reaction of monoanhydrosugar alcohols and dianhydrosugar alcohols, - Condensation reaction of monoanhydrosugar alcohol with polysaccharide alcohol represented by formula (1), - Condensation reaction of a monoanhydrosugar alcohol with an anhydrosugar alcohol derived from a polysaccharide alcohol represented by formula (1), - Condensation reaction of dianhydrosugar alcohol with polysaccharide alcohol represented by formula (1), - Condensation reaction of dianhydrosugar alcohol with anhydrosugar alcohol derived from a polysaccharide alcohol represented by formula (1), A condensation reaction between a polysaccharide alcohol represented by formula (1) and an anhydrosugar alcohol derived from the polysaccharide alcohol represented by formula (1), Condensation reaction of monoanhydrosugar alcohol, dianhydrosugar alcohol and polysaccharide alcohol represented by formula (1), Condensation reaction of monoanhydrosugar alcohol, dianhydrosugar alcohol and anhydrosugar alcohol derived from a polysaccharide alcohol represented by formula (1), - a condensation reaction of a monoanhydrosugar alcohol, a polysaccharide alcohol represented by formula (1), and an anhydrosugar alcohol derived from a polysaccharide alcohol represented by formula (1), A condensation reaction of a dianhydrosugar alcohol, a polysaccharide alcohol represented by formula (1), and an anhydrosugar alcohol derived from a polysaccharide alcohol represented by formula (1), or Condensation reaction of monoanhydrosugar alcohol, dianhydrosugar alcohol, polysaccharide alcohol represented by formula (1), and anhydrosugar alcohol derived from the polysaccharide alcohol represented by formula (1).

[0030] In one embodiment, the polyol composition of the present invention may contain, for example, a) 0.1 to 20 wt%, specifically 0.6 to 20 wt%, more specifically 0.7 to 15 wt%, of the monoanhydrosugar alcohol, b) 0.1 to 28 wt%, specifically 1 to 25 wt%, more specifically 3 to 20 wt%, of the dianhydrosugar alcohol, c) the total content of the polysaccharide alcohol represented by formula (1) and d) the anhydrosugar alcohol derived from the polysaccharide alcohol represented by formula (1) may be 0.1 to 6.5 wt%, specifically 0.5 to 6.4 wt%, more specifically 1 to 6.3 wt%, and e) one or more polymers of a) to d) may be contained in an amount of 55 to 90 wt%, specifically 60 to 89.9 wt%, more specifically 70 to 89.9 wt%, relative to the total weight of the composition, but these are not particularly limited.

[0031] In the polyol composition of the present invention, the number average molecular weight (Mn) of the polyol composition may be 193 or more, 195 or more, 200 or more, 202 or more, 205 or more, or 208 or more. In addition, the number average molecular weight (Mn) of the polyol composition of the present invention may be 1,589 or less, 1,560 or less, 1,550 or less, 1,520 or less, 1,500 or less, 1,490 or less, or 1,480 or less.

[0032] In one embodiment, the number average molecular weight (Mn) of the polyol composition may be 193 to 1,589, specifically 195 to 1,550, more specifically 200 to 1,520, even more specifically 202 to 1,500, and even more specifically 205 to 1,490. If the number average molecular weight of the polyol composition is less than 193, it may be difficult to form a foam when the polyol composition is used as a polyol component to produce a polyurethane foam, and if the number average molecular weight exceeds 1,589, the molding density, compressive strength, and heat insulation of the foam may be reduced when the polyol composition is used as a polyol component to produce a polyurethane foam.

[0033] In the polyol composition of the present invention, the polyol composition may have a polydispersity index (PDI) of 1.13 or more, 1.15 or more, 1.20 or more, 1.23 or more, or 1.25 or more. Also, the polydispersity index (PDI) of the polyol composition of the present invention may be 3.41 or less, 3.40 or less, 3.35 or less, 3.30 or less, 3.25 or less, 3.22 or less, or 3.19 or less.

[0034] In one embodiment, the polydispersity index (PDI) of the polyol composition may be 1.13 to 3.41, specifically 1.13 to 3.40, more specifically 1.15 to 3.35, even more specifically 1.20 to 3.25, and even more specifically 1.23 to 3.22. If the polydispersity index of the polyol composition is less than 1.13, it may be difficult to form a foam when the polyol composition is used as a polyol component to produce a polyurethane foam, and if it exceeds 3.41, the molded density, compressive strength, and heat insulation of the foam may be reduced when the polyol composition is used as a polyol component to produce a polyurethane foam.

[0035] In the polyol composition of the present invention, the average number of -OH groups per molecule in the polyol composition may be 2.54 or more, 2.60 or more, 2.65 or more, 2.70 or more, 2.75 or more, or 2.78 or more. Also, the average number of -OH groups per molecule in the polyol composition of the present invention may be 21.36 or less, 21.30 or less, 21.0 or less, 20.5 or less, 20.0 or less, 19.95 or less, or 19.92 or less.

[0036] More specifically, the average number of -OH groups per molecule in the polyol composition may be 2.54 to 21.36, more specifically 2.60 to 21.30, and even more specifically 2.65 to 21.0. If the average number of -OH groups per molecule in the polyol composition is less than 2.54, it may be difficult to form a foam when the polyol composition is used as a polyol component to produce a polyurethane foam, and if it exceeds 21.36, the molding density, compressive strength, and heat insulation of the foam may decrease when the polyol composition is used as a polyol component to produce a polyurethane foam.

[0037] In one embodiment, the polyol composition of the present invention may be produced by hydrogenating a glucose-containing saccharide composition (e.g., a saccharide composition containing disaccharides or higher polysaccharides including glucose, mannose, fructose, and maltose) to produce a hydrogenated sugar composition, heating the obtained hydrogenated sugar composition in the presence of an acid catalyst to cause a dehydration reaction, and thin-film distilling the obtained dehydration reaction product. Specifically, the polyol composition of the present invention may be a by-product remaining after thin-film distillation of the obtained dehydration reaction product to obtain a thin-film distillation liquid.

[0038] More specifically, a glucose-containing saccharide composition is hydrogenated under hydrogen pressure conditions of 30 atmospheres to 80 atmospheres and heating conditions of 110°C to 135°C to produce a hydrogenated sugar composition, and the obtained hydrogenated sugar composition is dehydrated under reduced pressure conditions of 1 mmHg to 100 mmHg and heating conditions of 105°C to 200°C to obtain a dehydration reaction product. Thin-film distillation of the obtained dehydration reaction product can be performed under reduced pressure conditions of 2 mbar or less and heating conditions of 150°C to 175°C, but the reaction conditions are not limited thereto.

[0039] The glucose content of the glucose-containing saccharide composition may be 41 wt% or more, 42 wt% or more, 45 wt% or more, 47 wt% or more, or 50 wt% or more, relative to the total weight of the saccharide composition, and may be 99.5 wt% or less, 99 wt% or less, 98.5 wt% or less, 98 wt% or less, 97.5 wt% or less, or 97 wt% or less, for example, 41 to 99.5 wt%, 45 to 98.5 wt%, or 50 to 98 wt%.

[0040] If the glucose content in the saccharide composition is less than 41% by weight, the number average molecular weight, the average number of -OH groups per molecule, and the polydispersity index of the polyol composition will be too high, and when the polyol composition is used as a polyol component to produce a polyurethane foam, the molded density, compressive strength, and thermal insulation of the foam may decrease. If the glucose content in the saccharide composition is more than 99.5% by weight, the number average molecular weight and polydispersity index of the polyol composition will be too low, and it may be difficult to form a polyurethane foam.

[0041] The content of polysaccharide alcohols (sugar alcohols of disaccharides or higher) contained in the hydrogenated sugar composition may be 0.8% by weight or more, 1% by weight or more, 2% by weight or more, or 3% by weight or more, relative to the total dry weight of the hydrogenated sugar composition (here, dry weight means the weight of the solid content after removing water from the hydrogenated sugar composition), and may be 57% by weight or less, 55% by weight or less, 52% by weight or less, 50% by weight or less, or 48% by weight or less, for example, 0.8 to 57% by weight, 1 to 55% by weight, or 3 to 50% by weight.

[0042] If the content of polysaccharide alcohol in the hydrogenated sugar composition is less than 0.8% by weight, the effect of improving fluidity due to the polysaccharide alcohol and the anhydrosugar alcohol derived therefrom is small, and the distillation yield of the dianhydrosugar alcohol (e.g., isosorbide) may decrease.If the content of polysaccharide alcohol in the hydrogenated sugar composition exceeds 57% by weight, there may be a problem that the distillation yield of the dianhydrosugar alcohol is significantly reduced when the dehydration reaction product of the hydrogenated sugar composition is subjected to thin-film distillation.

[0043] Furthermore, if the polysaccharide alcohol content in the hydrogenated sugar composition is less than 0.8% by weight, when a polyol composition is produced using this hydrogenated sugar composition and a polyurethane foam is formed by applying this polyol composition, the polyurethane foam itself may not be formed, or even if a foam is formed, it may be difficult to maintain the shape of the foam. If the polysaccharide alcohol content in the hydrogenated sugar composition exceeds 57% by weight, the viscosity of the polyol composition produced using this hydrogenated sugar composition becomes very high, and the processability of the polyurethane foam and the heat insulating properties of the produced polyurethane foam may decrease due to an increase in thermal conductivity.

[0044] In another aspect of the present invention, there is provided an alkylene oxide-added polyol composition produced by subjecting the polyol composition of the present invention to an addition reaction with an alkylene oxide.

[0045] In the alkylene oxide-added polyol composition of the present invention, the amount of alkylene oxide added may be 10 parts by weight or more, 20 parts by weight or more, 30 parts by weight or more, 50 parts by weight or more, 80 parts by weight or more, or 90 parts by weight or more, or 200 parts by weight or less, 180 parts by weight or less, 150 parts by weight or less, 120 parts by weight or less, or 110 parts by weight or less, for example, 10 to 200 parts by weight, 20 to 180 parts by weight, 50 to 150 parts by weight, 80 to 120 parts by weight, or 90 to 110 parts by weight, relative to 100 parts by weight of the polyol composition. If the amount of alkylene oxide added is less than 10 parts by weight, the viscosity of the alkylene oxide-added polyol composition may become too high, making it difficult to compound or produce polyurethane. If the amount of alkylene oxide added exceeds 200 parts by weight, the effect of adding the alkylene oxide becomes large, and the properties of the core polyol composition are not expressed, so that the effect of improving the physical properties of the polyurethane may be small.

[0046] In another aspect of the present invention, there is provided a polyol premix composition comprising a polyol component, a catalyst, a surfactant and a blowing agent, or the polyol component is a mixture of the alkylene oxide-added polyol composition and a polyol other than the polyol composition.

[0047] In the present invention, the alkylene oxide-added polyol composition may be used alone as the polyol component, or the alkylene oxide-added polyol composition may be used in combination with other polyols. The polyol other than the alkylene oxide-added polyol composition may be any conventional polyol used for the production of polyurethane foams without any restrictions.

[0048] In one embodiment, examples of polyols that can be used other than the alkylene oxide-added polyol composition include, but are not limited to, trifunctional polyether polyols having an active hydrogen equivalent of 3,000 to 5,000 and a hydroxyl value of 50 to 70 mgKOH / g, sorbitol-based polyols having a hydroxyl value of 400 to 600 mgKOH / g, basic polyols having a hydroxyl value of 400 to 600 mgKOH / g, glycerin and pentaerythritol-based polyols having a hydroxyl value of 300 to 500 mgKOH / g, and polyols having a hydroxyl value of 300 to 350 mgKOH / g.

[0049] In one embodiment, when a mixture of the alkylene oxide-added polyol composition and a polyol other than the polyol composition is used as a polyol component, the content of the alkylene oxide-added polyol composition may be 1 wt% or more, preferably 5 wt% or more, more preferably 10 wt% or more, based on the total weight of the mixture. If the content of the alkylene oxide-added polyol composition is less than 1 wt%, the effect of improving the physical properties of the polyurethane foam (e.g., molding density, hardness, compressive strength, and heat insulation properties, etc.), the effect of improving the economy by reducing the burden on the environment, and the cost reduction may be small.

[0050] The catalyst used in the present invention is not particularly limited, but may be an amine catalyst, an organometallic catalyst, or a mixture thereof that promotes the reaction between the polyol and the isocyanate compound.

[0051] In the present invention, the type of amine catalyst is not particularly limited, but preferably one or a mixture of two or more tertiary amine catalysts can be used. More specifically, triethylenediamine, triethylamine, N-methylmorpholine, N-ethylmorpholine, or a combination thereof can be used.

[0052] As the organometallic catalyst, an organometallic catalyst commonly used in the production of polyurethane foams can be used, for example, an organotin catalyst, more specifically, tin octoate, dibutyltin dilaurate (DBTDL), tin bis[2-ethylhexanoate], or a combination thereof can be used.

[0053] In the polyol premix composition of the present invention, the catalyst may be contained in an amount of 0.01 to 5 parts by weight, more preferably 0.1 to 2.5 parts by weight, based on 100 parts by weight of the polyol component. If the amount of catalyst used is too small, the reaction may be slow, resulting in poor curing or foam collapse during foam formation, while if the amount of catalyst used is too large, the reaction may be too fast or shrinkage may occur.

[0054] The surfactant used in the present invention prevents the coalescence or destruction of cells formed when cells are formed inside the polyurethane foam, and serves to make the shape and size of the formed cells uniform.

[0055] In the present invention, the surfactant can be any surfactant that is generally used in the production of polyurethane foam, and for example, a silicone surfactant can be preferably used. The silicone surfactant can be at least one selected from silicone oil and its derivatives, and specifically, can be a polyalkylene oxide methylsiloxane copolymer.

[0056] In the polyol premix composition of the present invention, the surfactant may be contained in an amount of 0.01 to 10 parts by weight, preferably 0.1 to 8 parts by weight, more preferably 0.5 to 6 parts by weight, based on 100 parts by weight of the polyol component, but is not limited thereto. If the amount of the surfactant used is too small, the foam molding may become non-uniform, and conversely, if the amount is too large, the foam may shrink.

[0057] The blowing agent used in the present invention can be appropriately selected from known blowing agents conventionally used in the production of polyurethane foams, taking into consideration the desired physical properties of the foam.

[0058] In the present invention, as the blowing agent, typically water can be used, and other blowing agents selected from methylene chloride, n-butane, isobutane, n-pentane, isopentane, dimethyl ether, acetone, carbon dioxide, 1,1-dichloro-1-fluoroethane, or combinations thereof can also be used. These blowing agents can be used appropriately according to the required properties of the foam, such as density, in accordance with known methods of use.

[0059] In the polyol premix composition of the present invention, the amount of the foaming agent used is not particularly limited, and for example, 0.1 to 60 parts by weight, more specifically 0.5 to 55 parts by weight, may be used relative to 100 parts by weight of the polyol component, but is not limited thereto.

[0060] In one embodiment of the present invention, the blowing agent may be, but is not limited to, 0.5 to 10 parts by weight of water alone or a mixture of 1 to 6 parts by weight of water and 0.1 to 49 parts by weight of methylene chloride per 100 parts by weight of the polyol component.

[0061] The polyol premix composition of the present invention may further contain auxiliary additives selected from the group consisting of flame retardants, colorants, UV stabilizers, thickeners, foam stabilizers, fillers, or combinations thereof, within the range not impairing the desired physical properties.

[0062] The content of the auxiliary additive is not particularly limited and may be selected within a range that does not impair the desired physical properties of the polyol premix composition. In one embodiment, the auxiliary additive may be included in an amount of 0.01 to 5 parts by weight, more preferably 0.1 to 2 parts by weight, based on 100 parts by weight of the polyol component.

[0063] In another aspect of the present invention, there is provided a composition for producing a two-component polyurethane foam, comprising: a first component, the polyol premix composition of the present invention; and a second component, a polyisocyanate.

[0064] In the present invention, the polyisocyanate can be used without any particular limitation as long as it can be used for producing polyurethane foam. For example, polyisocyanates selected from the group consisting of aliphatic polyisocyanates, alicyclic polyisocyanates, araliphatic polyisocyanates, aromatic polyisocyanates, heterocyclic polyisocyanates, and combinations thereof can be used, and unmodified polyisocyanates or any modified polyisocyanates can be used.

[0065] Specifically, the polyisocyanate may be methylene diisocyanate, ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,12-dodecane diisocyanate, cyclobutane-1,3-diisocyanate, cyclohexanol-1,3-diisocyanate, cyclohexane-1,4-diisocyanate, isophorone diisocyanate, 2-4-hexahydrotoluene diisocyanate, 2,6-hexahydrotoluene diisocyanate, diisocyanate, cyclohexane-1,4-diisocyanate, cyclohexane-1,5-diisocyanate, cyclohexane-1,6-diisocyanate, cyclohexane-1,7-diisocyanate, cyclohexane-1,8-diisocyanate, cyclohexane-1,9-diisocyanate, cyclohexane-1,10-diisocyanate, cyclohexane-1,12 ... The isocyanate may be selected from the group consisting of cyclohexylmethane-4,4'-diisocyanate (HMDI), 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, diphenylmethane-2,4'-diisocyanate, methylene diphenyl diisocyanate (MDI), polymeric methylene diphenyl diisocyanate (PMDI), naphthalene-1,5-diisocyanate, or combinations thereof.

[0066] In one embodiment, the polyisocyanate may be a mixture of 2,4-toluene diisocyanate and 2,6-toluene diisocyanate (2,4- / 2,6-isomer ratio=80 / 20) or polymeric methylene diphenyl diisocyanate.

[0067] In the present invention, the amount of polyisocyanate used is preferably 70 to 130, particularly preferably 80 to 120, and further preferably 100 to 120, in terms of isocyanate index (NCO index). The isocyanate index is the ratio of the number of equivalents of isocyanate to the number of equivalents of hydroxyl groups present in the polyol in the urethane reactant, and means the amount of isocyanate used relative to the theoretical equivalent. An isocyanate index of less than 100 means that an excess of polyol is present, and an isocyanate index of more than 100 means that an excess of isocyanate is present. If the isocyanate index is less than 70, there is a problem that the reactivity is low, the gelling reaction is slow, and curing cannot be performed. If the isocyanate index is more than 130, there is a problem that the hard segment becomes too large and shrinks.

[0068] In the composition for producing a two-component polyurethane foam of the present invention, the first component and the second component may be present separately and not in contact with each other, or may be mixed immediately before use or in situ.

[0069] In another aspect of the present invention, there is provided a method for producing a polyurethane foam, which comprises mixing and reacting a first component, the polyol premix composition of the present invention, with a second component, a polyisocyanate, and a polyurethane foam, for example, a flexible or rigid polyurethane foam, produced thereby.

[0070] When the polyol premix composition of the present invention is used for producing the polyurethane foam, the polyurethane foam can be produced by adding a polyisocyanate to the polyol premix composition, stirring the mixture, and then pouring the mixture into a mold to allow curing and foaming to proceed.

[0071] When the two-component polyurethane foam producing composition of the present invention is used to produce the polyurethane foam, the polyurethane foam can be produced by mixing the first component and the second component contained in the composition, stirring, and then pouring the mixture into a mold to allow curing and foaming to proceed.

[0072] The apparatus and conditions (temperature, time, etc.) for producing the polyurethane foam are not particularly limited, and commonly used apparatus and conditions can be used as is or with appropriate modifications.

[0073] The present invention will be described in more detail with reference to the following examples and comparative examples, but the scope of the present invention is not limited thereto. EXAMPLES

[0074] <Production of polyol composition containing anhydrosugar alcohol and anhydrosugar alcohol polymer> Example A1: Preparation of a polyol composition using 97% by weight glucose and a thin film distillation apparatus A glucose product having a purity of 97% was hydrogenated in the presence of a nickel catalyst at 125°C under a hydrogen pressure of 60 atm to obtain 1,819 g of a liquid hydrogenated sugar composition having a concentration of 55% by weight (96% by weight of sorbitol, 0.9% by weight of mannitol, and 3.1% by weight of polysaccharide alcohols of disaccharides or higher, based on the total weight of the solid content). This composition was placed in a batch reactor equipped with a stirrer and concentrated by heating to 100°C to obtain 1,000 g of a concentrated hydrogenated sugar composition.

[0075] 1,000 g of the concentrated hydrogenated sugar composition and 9.6 g of sulfuric acid were added to the reactor. The temperature in the reactor was then raised to about 135°C, and a dehydration reaction was carried out under a reduced pressure of about 45 mmHg to convert the concentrated hydrogenated sugar composition into anhydrous sugar alcohol. After the dehydration reaction was completed, the temperature of the reaction product was cooled to below 110°C, and about 15.7 g of a 50% aqueous sodium hydroxide solution was added to neutralize the reaction product. The temperature was then cooled to below 100°C, and the reaction product was concentrated under a reduced pressure of 45 mmHg for more than 1 hour to remove residual moisture and low boiling point substances, thereby obtaining 831 g of a converted anhydrous sugar alcohol. The converted anhydrous sugar alcohol solution obtained was analyzed by gas chromatography to find that the amount of conversion to isosorbide was 71.9% by weight, and the molar conversion rate of sorbitol to isosorbide was calculated to be 77.6% using this.

[0076] The obtained converted anhydrous sugar alcohol solution (831 g) was put into a thin film distillation apparatus (SPD) and distilled. At this time, distillation was performed at a temperature of 160°C and a vacuum pressure of 1 mbar, and about 589 g of distillate was obtained (distillation yield: about 70.9%). At this time, the purity of isosorbide in the distillate was measured and found to be 96.8%, and the distillation yield of isosorbide calculated from this was 95.3%. After separating the distillate, about 242 g of a polyol composition was obtained, which contained 11.5 wt% isosorbide (dianhydrosugar alcohol), 0.4 wt% isomannide (dianhydrosugar alcohol), 7.4 wt% sorbitan (monoanhydrosugar alcohol), 2.5 wt% disaccharide or higher polysaccharide alcohols and anhydrosugar alcohols derived therefrom, and 78.2 wt% of their polymers, and had a number average molecular weight of 208 g / mol, a polydispersity index of 1.25, a hydroxyl value of 751 mgKOH / g, and an average number of -OH groups per molecule in the composition of 2.78.

[0077] Example A2: Preparation of a polyol composition using a sugar composition containing 85.2% by weight of glucose and a thin film distillation apparatus A hydrogenation reaction was carried out in the same manner as in Example 1, except that a 85.2% glucose-containing saccharide composition (85.2% glucose, 14.8% mannose, fructose and polysaccharides (disaccharides or higher such as maltose) in total) was used instead of the 97% pure glucose product, to obtain 1,852 g of a liquid hydrogenated sugar composition with a concentration of 54% by weight (solid content basis, 84.1% sorbitol, 2.8% mannitol and 13.1% polysaccharide alcohols of disaccharides or higher). This composition was placed in a batch reactor equipped with a stirrer, heated to 100°C and concentrated to obtain 1,000 g of a concentrated hydrogenated sugar composition.

[0078] Except for changing the content of sulfuric acid from 9.6 g to 8.4 g and the content of 50% sodium hydroxide aqueous solution from 15.7 g to 13.7 g, 1,000 g of the concentrated hydrogenated sugar composition was dehydrated in the same manner as in Example 1 to convert it into anhydrous sugar alcohol. As a result of the dehydration reaction, about 846 g of a converted anhydrous sugar alcohol solution was obtained. The converted anhydrous sugar alcohol solution obtained was analyzed by gas chromatography, and the amount of conversion to isosorbide was 61.7 wt %, and the molar conversion rate of sorbitol to isosorbide was calculated to be 77.4%.

[0079] The obtained converted anhydrosugar alcohol solution (846 g) was subjected to thin-film distillation in the same manner as in Example 1 to obtain about 528 g of a distillate (distillation yield: about 62.4%). At this time, the purity of isosorbide in the distillate was measured to be 96.5%, and the distillation yield of isosorbide calculated from this was 97.6%. After separating the distillate, about 318 g of a polyol composition was obtained, which contained 4.0 wt% isosorbide (dianhydrosugar alcohol), 1.6 wt% isomannide (dianhydrosugar alcohol), 2.1 wt% sorbitan (monohydrosugar alcohol), 5.1 wt% disaccharide or higher polysaccharide alcohols and anhydrosugar alcohols derived therefrom, and 87.2 wt% of their polymers, and the number average molecular weight of the composition was 720 g / mol, the polydispersity index of the composition was 2.54, the hydroxyl value of the composition was 754 mgKOH / g, and the average number of -OH groups per molecule in the composition was 9.68.

[0080] Example A3: Preparation of a polyol composition using a sugar composition containing 50.2% by weight of glucose and a thin film distillation apparatus A hydrogenation reaction was carried out in the same manner as in Example 1, except that a 50.2% glucose-containing saccharide composition (50.2% glucose and 49.8% total of mannose, fructose and polysaccharides (disaccharides or higher such as maltose)) was used instead of a 97% pure glucose product, to obtain 1,819 g of a liquid hydrogenated sugar composition with a concentration of 55% by weight (solid content basis, 48.5% sorbitol, 3.6% mannitol, 47.9% polysaccharide alcohols of disaccharides or higher). This composition was placed in a batch reactor equipped with a stirrer, heated to 100°C and concentrated to obtain 1,000 g of a concentrated hydrogenated sugar composition.

[0081] Except for changing the content of sulfuric acid from 9.6 g to 4.85 g, the content of 50% sodium hydroxide aqueous solution from 15.7 g to 7.9 g, and the reaction temperature to 120° C., 1,000 g of the concentrated hydrogenated sugar composition was subjected to a dehydration reaction and converted into anhydrous sugar alcohol in the same manner as in Example 1. As a result of the dehydration reaction, the converted anhydrous sugar alcohol solution obtained weighed about 890 g, and the converted anhydrous sugar alcohol solution was analyzed by gas chromatography, and the conversion amount of isosorbide was found to be 33.7% by weight, and the molar conversion rate of sorbitol to isosorbide was calculated to be 77.1%.

[0082] The obtained converted anhydrosugar alcohol solution (890 g) was subjected to thin-film distillation in the same manner as in Example 1 to obtain about 304 g of a distillate (distillation yield: about 34.2%). At this time, the purity of isosorbide in the distillate was measured to be 96.9%, and the distillation yield of isosorbide calculated from this was 98.3%. After separating the distillate, about 586 g of a polyol composition was obtained, which contained 0.9 wt% isosorbide (dianhydrosugar alcohol), 2.1 wt% isomannide (dianhydrosugar alcohol), 0.9 wt% sorbitan (monohydrosugar alcohol), 6.2 wt% of polysaccharide alcohols of disaccharides or higher and anhydrosugar alcohols derived therefrom, and 89.9 wt% of their polymers, and the number average molecular weight of the composition was 1,480 g / mol, the polydispersity index of the composition was 3.19, the hydroxyl value of the composition was 755 mgKOH / g, and the average number of -OH groups per molecule in the composition was 19.92.

[0083] Comparative Example A1: Preparation of a polyol composition by 99.9% by weight glucose crystallization and thin-film distillation A hydrogenation reaction was carried out in the same manner as in Example 1, except that 99.9% pure glucose crystals separated from a glucose production process were used instead of a 97% pure glucose product, to obtain 1,819 g of a liquid hydrogenated sugar composition with a concentration of 55% by weight (solid content basis, 99.1% by weight sorbitol, 0.2% by weight mannitol, and 0.7% by weight of disaccharide or higher polysaccharide alcohols). This composition was placed in a batch reactor equipped with a stirrer and concentrated by heating to 100°C, to obtain 1,000 g of a concentrated hydrogenated sugar composition.

[0084] Except for changing the content of sulfuric acid from 9.6 g to 9.9 g and the content of 50% sodium hydroxide aqueous solution from 15.7 g to 16.2 g, 1,000 g of the concentrated hydrogenated sugar composition was converted into anhydrous sugar alcohol by dehydration reaction in the same manner as in Example 1. As a result of the dehydration reaction, the converted anhydrous sugar alcohol solution obtained weighed about 827 g, and the converted anhydrous sugar alcohol solution was analyzed by gas chromatography to find that the amount of isosorbide converted was 74.2 wt %, and the molar conversion rate of sorbitol to isosorbide was calculated to be 77.2%.

[0085] The obtained converted anhydrosugar alcohol solution (827 g) was subjected to thin-film distillation in the same manner as in Example 1 to obtain about 555 g of distilled liquid (distillation yield: about 67.1%). At this time, the purity of isosorbide in the distilled liquid was measured and found to be 96.7%, and the distillation yield of isosorbide calculated from this was 87.5%. After separating the distilled liquid, about 272 g of a polyol composition was obtained, which contained 28.2 wt% isosorbide (dianhydrosugar alcohol), 17.4 wt% sorbitan (monohydrosugar alcohol) and 54.4 wt% of their polymer, had a number average molecular weight of 192 g / mol, a polydispersity index of 1.12, a hydroxyl value of 740 mgKOH / g, and an average number of -OH groups per molecule in the composition of 2.53.

[0086] Comparative Example A2: Preparation of a polyol composition using a sugar composition containing 40.1% by weight of glucose and a thin film distillation apparatus A hydrogenation reaction was carried out in the same manner as in Example 1, except that a 40.1% glucose-containing saccharide composition (40.1% glucose and 59.9% mannose, fructose and polysaccharides (disaccharides or higher such as maltose) in total) was used instead of the 97% pure glucose product, to obtain 1,819 g of a liquid hydrogenated sugar composition with a concentration of 55% by weight (solid content basis, 38.8% sorbitol, 4.1% mannitol, 57.1% polysaccharide alcohols of disaccharides or higher). This composition was placed in a batch reactor equipped with a stirrer, heated to 100°C and concentrated, to obtain 1,000 g of a concentrated hydrogenated sugar composition.

[0087] Except for changing the content of sulfuric acid from 9.6 g to 3.9 g and the content of 50% sodium hydroxide aqueous solution from 15.7 g to 6.3 g, 1,000 g of the concentrated hydrogenated sugar composition was subjected to a dehydration reaction and converted into anhydrous sugar alcohol in the same manner as in Example 1. As a result of the dehydration reaction, the converted anhydrous sugar alcohol solution obtained weighed about 902 g, and the converted anhydrous sugar alcohol solution was analyzed by gas chromatography, and the converted isosorbide content was found to be 26.8 wt %, and the molar conversion rate of sorbitol to isosorbide was calculated to be 77.4%.

[0088] The obtained converted anhydrosugar alcohol solution (902 g) was subjected to thin-film distillation in the same manner as in Example 1 to obtain about 246 g of a distillate (distillation yield: about 27.3%). At this time, the purity of isosorbide in the distillate was measured to be 96.1%, and the distillation yield of isosorbide calculated from this was 97.8%. After separating the distillate, about 663 g of a polyol composition was obtained, which contained 0.7 wt% isosorbide (dianhydrosugar alcohol), 2.3 wt% isomannide (dianhydrosugar alcohol), 0.5 wt% sorbitan (monohydrosugar alcohol), 6.5 wt% of polysaccharide alcohols of disaccharides or higher and anhydrosugar alcohols derived therefrom, and 90.0 wt% of their polymers, and the number average molecular weight of the composition was 1,590 g / mol, the polydispersity index of the composition was 3.42, the hydroxyl value of the composition was 754 mgKOH / g, and the average number of -OH groups per molecule in the composition was 21.37.

[0089] Comparative Example A3: Preparation of a sugar composition containing 96.8% by weight of glucose and a polyol composition using simple vacuum distillation The hydrogenation reaction was carried out in the same manner as in Example 1, except that a 96.8% glucose-containing saccharide composition (96.8% glucose and 3.2% total of mannose, fructose and polysaccharides (disaccharides or higher such as maltose)) was used instead of the 97% pure glucose product, to obtain 1,819 g of a liquid hydrogenated sugar composition with a concentration of 55% by weight (solid content basis, 95.7% sorbitol, 1.1% mannitol, 3.2% polysaccharide alcohols of disaccharides or higher). This composition was placed in a batch reactor equipped with a stirrer, heated to 100°C and concentrated to obtain 1,000 g of a concentrated hydrogenated sugar composition.

[0090] 1,000 g of the concentrated hydrogenated sugar composition was dehydrated in the same manner as in Example 1 to convert it into anhydrous sugar alcohol. As a result of the dehydration reaction, the converted anhydrous sugar alcohol solution obtained weighed about 832 g. The converted anhydrous sugar alcohol solution was analyzed by gas chromatography to find that the amount of isosorbide converted was 71.5% by weight, and the molar conversion rate of sorbitol to isosorbide was calculated to be 77.5%.

[0091] The obtained converted anhydrosugar alcohol solution (832 g) was subjected to simple reduced pressure distillation to obtain about 461 g of distillate (distillation yield: about 55.4%). At this time, the purity of isosorbide in the distillate was measured to be 96.6%, and the distillation yield of isosorbide calculated from this was 74.9%. After separating the distillate, about 371 g of a polyol composition was obtained, which contained 40.4 wt% isosorbide (dianhydrosugar alcohol), 0.4 wt% isomannide (dianhydrosugar alcohol), 3.2 wt% sorbitan (monohydrosugar alcohol), 2.0 wt% polysaccharide alcohols of disaccharides or higher and anhydrosugar alcohols derived therefrom, and 54.0 wt% of their polymers, the number average molecular weight of the composition was 210 g / mol, the polydispersity index of the composition was 3.94, the hydroxyl value of the composition was 710 mgKOH / g, and the average number of -OH groups per molecule in the composition was 2.66.

[0092] The yields of the polyol compositions of Examples A1 to A3 and Comparative Examples A1 to A3 are shown in Table 1 below, and the compositions and physical properties of each polyol composition are shown in Table 2 below.

[0093] [Table 1]

[0094] [Table 2]

[0095] [Yield measurement method] 1) Molar conversion rate to isosorbide (ISB) ISB molar conversion rate (%) = (moles of isosorbide produced / moles of sorbitol used) x 100 (%)

[0096] 2) Isosorbide (ISB) conversion amount The content (wt%) of isosorbide in the converted anhydrous sugar alcohol solution was measured by gas chromatography analysis, and the amount of converted isosorbide indicates the purity of isosorbide (ISB) in the converted anhydrous sugar alcohol solution.

[0097] 3) Distillation yield Distillation yield (%) = [mass of distillate (g) / mass of converted anhydrous sugar alcohol solution (g)] x 100 (%)

[0098] 4) Isosorbide (ISB) distillation yield ISB distillation yield (%) = [mass of isosorbide in the distillate (%) / mass of isosorbide in the converted anhydrous sugar alcohol solution (g)] × 100 (%)

[0099] [Method of measuring physical properties of polyol composition] 1) Number average molecular weight (Mn) and polydispersity index (PDI) 1 to 3 parts by weight of the polyol composition prepared in the examples and comparative examples were dissolved in N,N-dimethylformamide, and the number average molecular weight (Mn) and polydispersity index (PDI) were measured using a gel permeation chromatography (GPC) device (Agilent). The column used was PLgel 3μm MIXED-E 300×7.5mm (Agilent), the column temperature was 50°C, the developing solvent used was N,N-dimethylformamide containing 0.05M NaBr, flowed at 0.5mL / min, and polystyrene (Aldrich) was used as the standard substance.

[0100] 2) Hydroxyl value Each of the polyol compositions prepared in the examples and comparative examples was esterified using excess phthalic anhydride under imidazole catalysis in accordance with the hydroxyl value test standard ASTM D-4274D, and the hydroxyl value of the polyol composition was then measured by titrating the remaining phthalic anhydride with 0.5N sodium hydroxide (NaOH).

[0101] 3) Average number of -OH groups per molecule The average number of -OH groups per molecule in the polyol composition was calculated according to the following formula: [Average number of -OH groups per molecule] = (hydroxyl value × number average molecular weight) / 56,100

[0102] <Production of alkylene oxide-added polyol composition> Example B1: Preparation of an alkylene oxide-added polyol composition using the polyol composition of Example A1 100 g of the polyol composition obtained in Example A1 and 0.1 g of potassium hydroxide (KOH) were added to a high-pressure reactor equipped with a stirrer, and the temperature was raised to 120° C., after which 100 g of propylene oxide was added. Then, the mixture was reacted at 120° C. for 3 hours to obtain 191 g of an alkylene oxide-added polyol composition in which the amount of propylene oxide added was 100 parts by weight per 100 parts by weight of the polyol composition.

[0103] Example B2: Preparation of an alkylene oxide-added polyol composition using the polyol composition of Example A2 Except for using 100 g of the polyol composition obtained in Example A2 instead of the polyol composition obtained in Example A1, the same procedure as in Example B1 was repeated to obtain 190 g of an alkylene oxide-added polyol composition in which the amount of propylene oxide added was 100 parts by weight per 100 parts by weight of the polyol composition.

[0104] Example B3: Preparation of an alkylene oxide-added polyol composition using the polyol composition of Example A3 Except for using 100 g of the polyol composition obtained in Example A3 instead of the polyol composition obtained in Example A1, the same procedure as in Example B1 was repeated to obtain 192 g of an alkylene oxide-added polyol composition in which the amount of propylene oxide added was 100 parts by weight per 100 parts by weight of the polyol composition.

[0105] Comparative Example B1: Preparation of an alkylene oxide-added polyol composition using the polyol composition of Comparative Example A1 Except for using 100 g of the polyol composition obtained in Comparative Example A1 instead of the polyol composition obtained in Example A1, the same procedure as in Example B1 was repeated to obtain 187 g of an alkylene oxide-added polyol composition in which the amount of propylene oxide added was 100 parts by weight per 100 parts by weight of the polyol composition.

[0106] Comparative Example B2: Preparation of an alkylene oxide-added polyol composition using the polyol composition of Comparative Example A2 Except for using 100 g of the polyol composition obtained in Comparative Example A2 instead of the polyol composition obtained in Example A1, the same procedure as in Example B1 was repeated to obtain 192 g of an alkylene oxide-added polyol composition in which the amount of propylene oxide added was 100 parts by weight per 100 parts by weight of the polyol composition.

[0107] Comparative Example B3: Preparation of an alkylene oxide-added polyol composition using the polyol composition of Comparative Example A3 Except for using 100 g of the polyol composition obtained in Comparative Example A3 instead of the polyol composition obtained in Example A1, the same procedure as in Example B1 was repeated to obtain 190 g of an alkylene oxide-added polyol composition in which the amount of propylene oxide added was 100 parts by weight per 100 parts by weight of the polyol composition.

[0108] <Production of Rigid Polyurethane Foam> Examples C1 to C3 and Comparative Examples C1 to C4 The polyol component, catalyst, surfactant and blowing agent were mixed according to the components and content ratios shown in Table 3 below, and thoroughly mixed for 1 to 3 minutes at a stirring speed of 3,000 rpm to produce a polyol premix composition, which is the first component of the composition for producing two-component polyurethane foam of the present invention. The polyisocyanate component, which is the second component, was added to the produced polyol premix composition, and the mixture was stirred at a stirring speed of 3,000 rpm for 7 to 10 seconds to produce the composition for producing a two-component polyurethane foam of the present invention. Then, a polyethylene film was laid in a square box of 250 mm x 250 mm, and the composition for producing polyurethane foam prepared above was poured on top of it. The heat of the curing reaction of the polyurethane foam was confirmed to be 120°C using a rod-shaped thermometer. The physical properties of the prepared polyurethane foam specimen were then measured by the following evaluation methods, and the results are shown in Table 3 below.

[0109] [Method of measuring physical properties of polyurethane foam specimens] Molded Density: Measured according to ASTM D-1621 Compressive strength: Measured according to ASTM D-1621 Thermal Conductivity: Measured according to ASTM D-1621

[0110] [Ingredients used] 1) Polyol SL-494: Sorbitol-based polyol with a hydroxyl value of 460-500 mgKOH / g (SL-494; Mitsui Chemicals & SKC Polyurethanes) SR-500: Basic polyol with a hydroxyl value of 480-520 mgKOH / g (SR-500; Mitsui Chemicals & SKC Polyurethanes) PE-400: Glycerin and pentaerythritol-based polyol with a hydroxyl value of 400 mg KOH / g (PE-400; manufactured by SKC) AK-1001: Polyol with a hydroxyl value of 320-340 mg KOH / g (AK POL-1001; manufactured by Aekyung Chemical Co., Ltd.) Example B1: Alkylene oxide-added polyol composition prepared in Example B1 Example B2: Alkylene oxide-added polyol composition prepared in Example B2 Example B3: Alkylene oxide-added polyol composition prepared in Example B3 Comparative Example B1: Alkylene oxide-added polyol composition prepared in Comparative Example B1 Comparative Example B2: Alkylene oxide-added polyol composition prepared in Comparative Example B2 Comparative Example B3: Alkylene oxide-added polyol composition prepared in Comparative Example B3

[0111] 2) Polyisocyanate M20R: Polymeric methylene diphenyl diisocyanate (M20R; manufactured by Basp Co., Ltd., Korea) The NCO index was fixed at 110 based on the equivalent ratio of isocyanate, water and polyol having hydroxyl groups.

[0112] 3) Catalyst PC5: Amine catalyst (PC5; manufactured by Air Products) 33LV: Amine catalyst (DABCO 33LV; Air Products)

[0113] 4) Surfactants B8462: Surfactant (B8462; Evonik)

[0114] 5) Foaming agent ·water 141b: 1,1-dichloro-1-fluoroethane (HCFC-141b; Soo Kyung Chemical Co., Ltd.)

[0115] [Table 3]

[0116] As shown in Table 3, the specimens of Examples C1 to C3 prepared using the polyol compositions of Examples A1 to A3 according to the present invention as the polyol component had good foam conditions and showed excellent molding density, compressive strength, and insulation properties (low thermal conductivity) compared to the specimen of Comparative Example C3, which is a conventional polyurethane foam specimen, and showed improved economic efficiency through cost reduction.

[0117] Meanwhile, in the case of the specimen of Comparative Example C1 prepared using the polyol composition of Comparative Example A1 as the polyol component, it was difficult to form a polyurethane foam due to the low number average molecular weight and low polydispersity index of the polyol composition. In the case of the specimen of Comparative Example C2 prepared using the polyol composition of Comparative Example A2 as the polyol component, the molding density and compressive strength of the foam were low and the heat insulation was also poor (high thermal conductivity) due to the high number average molecular weight, high polydispersity index and high average number of -OH groups per molecule of the polyol composition, compared to the specimen of Comparative Example C3, which is a conventional polyurethane foam specimen.

[0118] In addition, in the case of the specimen of Comparative Example C4 prepared using the polyol composition of Comparative Example A3 as the polyol component, it was possible to form a polyurethane foam, but since the polydispersity index of the polyol composition was too high, the molded density and compressive strength of the foam were low and the insulation properties were poor (high thermal conductivity) compared to the conventional polyurethane foam specimen of Comparative Example C3.

Claims

1. An alkylene oxide-added polyol composition in which an alkylene oxide is added to a polyol composition, The polyol composition comprises: a) monoanhydrosugar alcohol; b) dianhydrosugar alcohol; c) a polysaccharide alcohol represented by the following formula (1): d) anhydrous sugar alcohol derived from a polysaccharide alcohol represented by the following formula (1); and e) one or more polymers of a) to d); Including, (i) the number average molecular weight (Mn) of the polyol composition is 193 to 1,589 g / mol; (ii) the polydispersity index (PDI) of the polyol composition is from 1.13 to 3.41; (iii) An alkylene oxide-added polyol composition, wherein the average number of --OH groups per molecule in the polyol composition is 2.54 to 21.

36. 【Chemistry 1】 (In the formula, n is an integer from 0 to 4.)

2. d) The anhydrosugar alcohol derived from the polysaccharide alcohol represented by the formula (1) is represented by the following formula (2): 【Chemistry 2】 (In the formula, n is an integer from 0 to 4.) a compound represented by the following formula (3): 【Chemistry 3】 (In the formula, n is an integer from 0 to 4.) 2. The alkylene oxide-added polyol composition according to claim 1, wherein the alkylene oxide-added polyol is selected from the group consisting of compounds represented by the formula:

3. 2. The alkylene oxide-added polyol composition according to claim 1, wherein the monoanhydrosugar alcohol is a monoanhydrosugar hexitol.

4. 2. The alkylene oxide-added polyol composition according to claim 1, wherein the dianhydrosugar alcohol is a dianhydrosugar hexitol.

5. e) The alkylene oxide-added polyol composition according to claim 1, wherein the one or more polymers of a) to d) include one or more selected from the group consisting of condensation polymers obtained by the following condensation reactions: - Condensation reaction of monoanhydrosugar alcohols, - Condensation reaction of dianhydrosugar alcohols, - Condensation reaction of polysaccharide alcohol represented by formula (1), - Condensation reaction of anhydrosugar alcohol derived from a polysaccharide alcohol represented by formula (1), - Condensation reaction of monoanhydrosugar alcohol with dianhydrosugar alcohol, - Condensation reaction of monoanhydrosugar alcohol with polysaccharide alcohol represented by formula (1), - a condensation reaction of a monoanhydrosugar alcohol with an anhydrosugar alcohol derived from a polysaccharide alcohol represented by formula (1), - Condensation reaction of dianhydrosugar alcohol with polysaccharide alcohol represented by formula (1), - A condensation reaction of a dianhydrosugar alcohol with an anhydrosugar alcohol derived from a polysaccharide alcohol represented by formula (1), - A condensation reaction between a polysaccharide alcohol represented by formula (1) and an anhydrosugar alcohol derived from the polysaccharide alcohol represented by formula (1), - Condensation reaction of monoanhydrosugar alcohol, dianhydrosugar alcohol and polysaccharide alcohol represented by formula (1), - Condensation reaction of monoanhydrosugar alcohol, dianhydrosugar alcohol and anhydrosugar alcohol derived from a polysaccharide alcohol represented by formula (1), - a condensation reaction of a monoanhydrosugar alcohol, a polysaccharide alcohol represented by formula (1), and an anhydrosugar alcohol derived from the polysaccharide alcohol represented by formula (1), - a condensation reaction of a dianhydrosugar alcohol, a polysaccharide alcohol represented by formula (1), and an anhydrosugar alcohol derived from the polysaccharide alcohol represented by formula (1), or Condensation reaction of monoanhydrosugar alcohol, dianhydrosugar alcohol, polysaccharide alcohol represented by formula (1), and anhydrosugar alcohol derived from the polysaccharide alcohol represented by formula (1).

6. The alkylene oxide-added polyol composition according to claim 1, which is produced by subjecting a glucose-containing saccharide composition to a hydrogenation reaction to produce a hydrogenated sugar composition, heating the resulting hydrogenated sugar composition in the presence of an acid catalyst to cause a dehydration reaction, and subjecting the resulting dehydration reaction product to thin-film distillation.

7. 7. The alkylene oxide-added polyol composition according to claim 6, wherein the glucose-containing saccharide composition contains 41% by weight to 99.5% by weight of glucose based on the total weight of the saccharide composition.

8. The alkylene oxide-added polyol composition according to claim 6, wherein the hydrogenated sugar composition contains 0.8 to 57% by weight of the polysaccharide alcohol represented by formula (1) based on the total dry weight of the hydrogenated sugar composition.

9. The hydrogenation reaction is carried out under a hydrogen pressure condition of 30 to 80 atmospheres and a heating condition of 110 to 135°C, The dehydration reaction is carried out under reduced pressure conditions of 1 mmHg to 100 mmHg and heating conditions of 105°C to 200°C, The alkylene oxide-added polyol composition according to claim 6, wherein the thin-film distillation is carried out under reduced pressure conditions of 2 mbar or less and heating conditions of 150°C to 175°C.

10. The composition includes a polyol component, a catalyst, a surfactant, and a blowing agent, A polyol premix composition, wherein the polyol component is the alkylene oxide-added polyol composition according to claim 1, or a mixture of the alkylene oxide-added polyol composition according to claim 1 and a polyol other than the alkylene oxide-added polyol composition.

11. The polyol premix composition of claim 10 which is a first component; and A second component, a polyisocyanate; A composition for producing a two-component polyurethane foam comprising:

12. A method for producing a polyurethane foam, comprising mixing and reacting the polyol premix composition according to claim 10 as a first component with a polyisocyanate as a second component.

13. 11. A polyurethane foam produced by mixing and reacting the polyol premix composition according to claim 10 as a first component and a polyisocyanate as a second component.

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