Polyol composition and method for producing the same, composition for producing polyurethane containing the polyol composition, and battery module

Abstract

The polyol composition, polyurethane-producing composition and battery module containing the polyol composition according to the present invention contain a compound represented by Chemical Formula 1 (see the description of the invention).

Description

[Technical Field]

[0001] The present invention relates to a polyol composition, a method for producing the same, a composition for producing polyurethane containing the polyol composition, and a battery module. [Background technology]

[0002] Polyurethane foams have excellent thermal insulation and flame retardancy. They are used in a variety of applications, including packaging boxes, building panels, home appliances, packaging materials, building interior materials, and thermal insulation. Polyurethane foams can be produced by foaming polyurethane, which can be produced by the polyaddition reaction of polyol and isocyanate.

[0003] Polyols are liquid polymers with two or more alcohol groups (-OH) attached to the end of a hydrocarbon chain. Polyols are typically produced from petroleum-based raw materials. However, in recent years, the depletion of petroleum resources and the need to reduce greenhouse gas emissions have led to a growing demand for environmentally friendly and renewable materials. Anhydrosugar alcohols are environmentally friendly substances derived from renewable natural resources, and various studies have been conducted on them because they can improve the physical properties of polyurethanes. Among anhydrosugar alcohols, 1,4:3,6-dianhydrohexitol, which is derived from biomass such as corn, wheat, and sugar and contains polysaccharides as a structural component, is widely used as a raw material for polyols. Summary of the Invention [Problem to be solved by the invention]

[0004] The present invention provides a polyol composition that has excellent reactivity with isocyanate and produces polyurethane foam with excellent hardness and appearance quality, a method for producing the same, a composition for producing polyurethane containing the polyol composition, and a battery module. [Means for solving the problem]

[0005] The polyol composition according to the present invention may contain a compound represented by Chemical Formula 1 below.

[0006] [ka]

[0007] In the above formula 1, R1 and R4 are each independently a substituted or unsubstituted linear alkylene group having 2 to 10 carbon atoms, R2 and R3 are each independently a substituted or unsubstituted branched alkylene group having 3 to 10 carbon atoms, x is a constant of 1 to 10, a and d are each independently a constant of 1 to 6, b and c are each independently a constant of 0 to 30, and b+c is a constant of 1 to 60.

[0008] In one embodiment of the present invention, the compound represented by Chemical Formula 1 above may contain at least one unit derived from 1,4:3,6-dianhydrohexitol.

[0009] In one embodiment of the present invention, R1 and R4 may each independently be a substituted or unsubstituted ethylene group.

[0010] In one embodiment of the present invention, R2 and R3 may each independently be a substituted or unsubstituted propylene group.

[0011] In one embodiment of the present invention, the ratio of (a+d):(b+c) may be 1:1.5 to 1:6.

[0012] In one embodiment of the present invention, the compound represented by Chemical Formula 1 above may be a compound represented by Chemical Formula 2 below.

[0013] [ka]

[0014] In the above formula 2, x' is a constant of 1 to 5, a' and d' are each independently a constant of 1 to 3, and b' and c' are each independently a constant of 1 to 18.

[0015] In one embodiment of the present invention, the acid value of the polyol composition may be 0.0005 mg KOH / g to 0.0100 mg KOH / g.

[0016] In one embodiment of the present invention, the number average molecular weight (Mn) of the polyol composition may be 300 g / mol to 12,000 g / mol.

[0017] In one embodiment of the present invention, the polyol composition may have a polydispersity index (PDI) of 1.0 to 1.3.

[0018] The polyol composition according to the present invention may contain first units derived from at least one kind of 1,4:3,6-dianhydrohexitol and second units derived from an alkylene oxide, and may have a degree of unsaturation of 0.02 meq / g or less, as measured by the following measurement method.

[0019] <Measurement method> 1) A first flask containing 30 g of the polyol composition and a second flask containing no polyol composition were prepared, and 50 ml of mercury acetate was added to each of the first flask and the second flask, followed by stirring for 30 minutes.

[0020] 2) 9 g of sodium bromide (NaBr) is added to each of the first flask and the second flask, and then the mixture is stirred for 30 minutes.

[0021] 3) Add 0.5 ml of 1% phenolphthalein indicator to each of the first and second flasks, and titrate with 0.1 N potassium hydroxide (KOH).

[0022] 4) Calculate the degree of unsaturation using the following formula 1.

[0023] [Formula 1] Unsaturation degree (meq / g)=(V s ×V b ×0.1×F) / M

[0024] (In the above formula 1, the V s is the amount (ml) of 0.1 N potassium hydroxide (KOH) added to the first flask, and V b is the amount (ml) of the 0.1 N potassium hydroxide (KOH) added to the second flask, F is a factor of the 0.1 N potassium hydroxide (KOH), and M is the weight (g) of the polyol composition added to the first flask.

[0025] In one embodiment of the present invention, the at least one 1,4:3,6-dianhydrohexitol may include isosorbide.

[0026] In one embodiment of the present invention, the second unit derived from the alkylene oxide may include a substituted or unsubstituted linear alkylene group having 2 to 10 carbon atoms.

[0027] In one embodiment of the present invention, the polyol composition may include a compound represented by the following Chemical Formula 3:

[0028] [ka]

[0029] In the above formula 3, R1 and R2 are each independently a substituted or unsubstituted alkylene group having 2 to 10 carbon atoms, a and f are each independently a constant of 1 to 60, b and e are each independently a constant of 1 to 6, c and d are each independently a constant of 1 to 30, and x is a constant of 1 to 5.

[0030] In one embodiment of the present invention, in the above formula 3, R1 and R2 may each independently be a substituted or unsubstituted branched alkylene group having 3 to 10 carbon atoms.

[0031] In one embodiment of the present invention, in the above Chemical Formula 3, R1 and R2 may each independently be a randomly polymerized substituted or unsubstituted linear alkylene group having 2 to 10 carbon atoms and a substituted or unsubstituted branched alkylene group having 3 to 10 carbon atoms. [Effects of the Invention]

[0032] The polyol composition according to the present invention is environmentally friendly and has energy-saving effects by containing compounds that can be produced from renewable natural resources.

[0033] The polyol composition according to the present invention contains a compound containing a linear alkylene group and a branched alkylene group in the form of a block copolymer, and thus has a higher content of primary alcohol hydroxyl groups (-OH) than conventional polyols and excellent reactivity with isocyanates. As a result, polyurethane foams produced from the polyol composition may have mechanical properties and processability that are equivalent to or superior to polyurethane foams produced from conventional petroleum-based polyol compositions.

[0034] The polyol compositions according to the present invention exhibit low APHA color values ​​and are applicable to industries requiring product clarity.

[0035] The polyol composition according to the present invention minimizes color change even when exposed to a high-temperature environment, thereby ensuring product reliability in terms of color when storing or transporting the polyol composition.

[0036] The polyol composition according to the present invention exhibits a low acid value, which prevents a decrease in the activity of a catalyst used in the production of polyurethane foam and improves the reactivity of the polyol composition with an isocyanate-based composition.

[0037] The polyol composition according to the present invention has a significantly reduced monool content and exhibits excellent reactivity with isocyanates, which facilitates crosslinking and polymerization when producing a polyurethane resin from the polyol composition, thereby improving the physical properties of the polyurethane resin.

[0038] The polyol composition according to the present invention includes a compound having a controlled ratio of linear alkylene group and branched alkylene group content, and thus the polyurethane foam produced from the polyol composition has excellent surface appearance.

[0039] The method for producing polyether polyol according to the present invention has the effect of significantly reducing the content of monools produced and having excellent reactivity with isocyanates, which facilitates crosslinking and high molecular weight during the production of polyurethane resin, thereby improving the physical properties of the polyurethane resin.

[0040] The polyether polyol according to the present invention has a higher primary alcohol content than conventional polyols and has excellent reactivity with isocyanates, which facilitates crosslinking and high molecular weight when producing polyurethane foam from the polyether polyol, thereby improving the physical properties of the polyurethane foam. [Brief explanation of the drawings]

[0041] [Figure 1]1 is a flow chart showing a simplified process for producing a polyol composition according to a first embodiment. [Figure 2] 1 is a cross-sectional view showing a simplified view of a battery module according to a first embodiment. [Figure 3] FIG. 1 shows the 13C NMR spectrum of the compound prepared in Preparation Example 1-1. [Figure 4] FIG. 1 shows the 13C NMR spectrum of the compound prepared in Preparation Example 1-6. [Figure 5] 1 is a flow chart showing a simplified process for producing a polyol composition according to a third embodiment. [Figure 6] 10 is a flow chart showing a simplified process for producing a polyol composition according to a fourth embodiment. [Figure 7] 10 is a flow chart showing a simplified process for producing a polyether polyol according to a fifth embodiment. [Figure 8] 10 is a flow chart specifically illustrating steps for producing a first polymer in a fifth embodiment. [Figure 9] 10 is a flow chart showing a simplified process for producing a polyether polyol according to a sixth embodiment. [Figure 10] FIG. 1 is a diagram showing the 13C NMR spectrum of the polyether polyol produced in Production Example 6-1. [Figure 11] FIG. 1 is a diagram showing the 13C NMR spectrum of the polyether polyol produced in Comparative Production Example 6-1. DETAILED DESCRIPTION OF THE INVENTION

[0042] Structural or functional descriptions of the embodiments disclosed in this specification or application are merely illustrative for the purpose of describing embodiments according to the technical concept of the present invention, and embodiments according to the technical concept of the present invention may be implemented in various forms other than the embodiments disclosed in this specification or application, and the technical concept of the present invention should not be construed as being limited to the embodiments described in this specification or application.

[0043] Furthermore, when a component in this specification or application is described as "comprising" another component, this does not mean that other components are excluded, but that other components may also be included, unless otherwise specified. Furthermore, any numerical range indicating the physical properties, dimensions, etc. of the components described in this specification or application should be understood to be modified by the term "about" in all cases, unless otherwise specified.

[0044] <Polyol composition according to the first embodiment> The polyol composition according to the present invention may contain a compound represented by Chemical Formula 1 below.

[0045] [ka]

[0046] In the above formula 1, R1 and R4 are each independently a substituted or unsubstituted linear alkylene group having 2 to 10 carbon atoms, R2 and R3 are each independently a substituted or unsubstituted branched alkylene group having 3 to 10 carbon atoms, x is a constant of 1 to 10, a and d are each independently a constant of 1 to 6, b and c are each independently a constant of 0 to 30, and b+c is a constant of 1 to 60.

[0047] The compound represented by Chemical Formula 1 may contain a core structure that is a unit derived from at least one kind of 1,4:3,6-dianhydrohexitol. The at least one kind of 1,4:3,6-dianhydrohexitol may contain isosorbide.

[0048] The isosorbide is obtained by dehydration of D-sorbitol, a renewable natural resource. The polyol composition of the present invention is environmentally friendly and has an energy-saving effect by containing the compound.

[0049] R1 and R4 may each independently be a substituted or unsubstituted ethylene group. R1 and R4 may each independently be derived from a substituted or unsubstituted linear alkylene oxide group having 2 to 10 carbon atoms. Preferably, R1 and R4 may each independently be an ethylene group.

[0050] The R2 and R3 may each independently be a substituted or unsubstituted propylene group.

[0051] The R2 and R3 may be derived from a substituted or unsubstituted branched alkylene group oxide having a carbon number of 3 to 10. Preferably, the R2 and R3 may each independently be a propylene group.

[0052] The compound represented by Chemical Formula 1 above may be in the form of a block copolymer in which a propylene group derived from the branched alkylene group is polymerized onto a core structure derived from at least one kind of 1,4:3,6-dianhydrohexitol to form a block, and an ethylene group derived from the linear alkylene group is polymerized onto the propylene group to form a block.

[0053] As such, the compound represented by Chemical Formula 1 has blocks formed by polymerizing ethylene groups at both ends, and may have a higher content of primary alcohol hydroxyl groups (-OH) than conventional polyol compounds, resulting in excellent reactivity with isocyanates. Furthermore, polyurethane foams containing the compound may exhibit mechanical properties and processability that are equal to or superior to polyurethane foams produced from conventional petroleum-based polyol compositions.

[0054] The ratio of (a+d):(b+c) may be 1:1.5 to 1:6. Preferably, the ratio of (a+d):(b+c) may be 1:2 to 1:6, 1:2.5 to 1:6, or 1:3 to 1:6. The ratios of (a+b) and (c+d) may each independently be 3 to 50. Preferably, the ratios of (a+b) and (c+d) may each independently be 3 to 30, 3 to 20, 5 to 20, 5 to 10, or 5 to 9.

[0055] When the above range is satisfied, the polyurethane foam containing the compound may have improved hardness, a reduced compression set, a smooth surface, and an excellent appearance.

[0056] In addition, by achieving an appropriate level of Compression Force Deformation (CFD), when polyurethane foam is applied to a battery module, it can buffer volume changes caused by the expansion of the battery cell and maintain a constant volume, thereby improving product stability. CFD is a parameter that indicates the repulsive force when a measurement object is compressed.

[0057] The CFD can be evaluated by measuring the resilience when the polyurethane foam is cut into 5 cm x 5 cm pieces at room temperature and compressed using a device such as a Universal Testing Machine (UTM). For example, the resilience when the polyurethane foam is compressed by 25% can be evaluated as the CFD 25% value, and a preferred CFD 25% value is greater than about 0.06 kg / cm. 2 Less than 0.15 kg / cm 2 The resilience when the polyurethane foam is compressed by 50% can be evaluated as a CFD 50% value, and the preferred CFD 50% value is greater than about 0.10 kg / cm. 2 Less than 0.20 kg / cm 2 It may have a range of

[0058] The compound represented by Chemical Formula 1 above may be a compound represented by Chemical Formula 2 below.

[0059] [ka]

[0060] In the above formula 2, x' is a constant of 1 to 5, a' and d' are each independently a constant of 1 to 3, and b' and c' are each independently a constant of 1 to 18.

[0061] Specifically, the types of compounds represented by Chemical Formula 2 above can be represented by the following compounds of Chemical Formulas A to I.

[0062] [ka]

[0063] [ka]

[0064] [ka]

[0065] [ka]

[0066] [ka]

[0067] [ka]

[0068] [ka]

[0069] [ka]

[0070] [ka]

[0071] [ka]

[0072] [ka]

[0073] [ka]

[0074] The content of the compound represented by Chemical Formula 1 may be 50 wt% to 99 wt% based on the total weight of the polyol composition. Preferably, the content of the compound represented by Chemical Formula 1 may be 60 wt% to 99 wt%, 70 wt% to 99 wt%, 75 wt% to 99 wt%, 77 wt% to 99 wt%, or 80 wt% to 99 wt% based on the total weight of the polyol composition. When the content satisfies the above ranges, when a polyurethane foam is produced from the polyol composition, the viscosity of the composition does not increase, which prevents smooth foaming, and the molded density and hardness of the produced polyurethane foam can be improved.

[0075] The polyol composition may contain an antioxidant. The antioxidant can improve the heat resistance stability of a polyurethane foam obtained from the polyol composition. The antioxidant may be at least one selected from the group consisting of phenol-based antioxidants (e.g., dibutylhydroxytoluene), sulfur-based antioxidants (e.g., mercaptopropionic acid derivatives), and phosphorus-based antioxidants (e.g., 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide). The content of the antioxidant may be 0.01 wt % to 3 wt %, 0.01 wt % to 2 wt %, 0.02 wt % to 2 wt %, 0.02 wt % to 1 wt %, or 0.03 wt % to 1 wt %, based on the total weight of the polyol composition.

[0076] The CPR (Controlled Polymerization Rate) of the polyol composition may be 0.1 to 5, 0.1 to 4, 0.1 to 3, 0.1 to 2, 0.1 to 1.5, 0.1 to 1, or 0.2 to 1. The CPR is an index indicating the amount of basic substances in the polyol composition, and can be measured by mixing 30 g of the polyol composition with 50 ml of methanol and then quantifying the amount of hydrochloric acid (concentration: 0.001 N) obtained by neutralization titration according to the experimental method of ASTM D6437. When the CPR satisfies the above range, reactivity can be easily controlled during the product manufacturing process, and product specifications can be met.

[0077] The degree of unsaturation of the polyol composition may be 0.001 meq / g to 0.015 meq / g, 0.001 meq / g to 0.010 meq / g, 0.001 meq / g to 0.009 meq / g, 0.001 meq / g to 0.008 meq / g, or 0.001 meq / g to 0.005 meq / g. The degree of unsaturation is an index indicating the degree of multiple bonds in the chemical structure and can be measured by mixing 30 g of the polyol composition with 50 ml of mercury acetate and then titrating it. When the degree of unsaturation satisfies the above range, sufficient open cells are formed during polyurethane production, preventing shrinkage and improving physical properties.

[0078] The acid value of the polyol composition may be 0.0005 mg KOH / g to 0.0100 mg KOH / g, 0.0005 mg KOH / g to 0.0050 mg KOH / g, 0.0005 mg KOH / g to 0.0030 mg KOH / g, or 0.0005 mg KOH / g to 0.0020 mg KOH / g. The acid value is an index indicating the amount of base (KOH) required to neutralize the acidic components of 1 g of a sample. When the above range is satisfied, the acid resistance of a polyurethane foam produced from the polyol composition can be enhanced.

[0079] The number average molecular weight (Mn) of the polyol composition may be 100 g / mol to 15,000 g / mol, 100 g / mol to 14,000 g / mol, 100 g / mol to 13,000 g / mol, 300 g / mol to 12,000 g / mol, 300 g / mol to 2,000 g / mol, 300 g / mol to 1,000 g / mol, or 400 g / mol to 600 g / mol. The polyol composition may have a polydispersity index (PDI) of 0.8 to 2.0, 0.8 to 1.9, 0.8 to 1.8, 0.8 to 1.6, 0.8 to 1.5, or 1.0 to 1.3. When the above ranges are satisfied, the reactivity of the polyol composition with isocyanate can be improved.

[0080] The polyol composition may have an APHA (American Public Health Association) color value of 0.1 to 40, 0.1 to 30, 0.1 to 25, 0.1 to 20, or 0.1 to 18. The APHA color value can be measured using ColorQuest XE (Hunter Labs) according to the ASTM D-1209 experimental method, and a lower color value indicates a cleaner and more transparent product. When the color value satisfies the above range, by-products such as unreacted ethylene oxide and unreacted propylene oxide are hardly generated in the polyol composition, thereby improving product reliability.

[0081] The active oxygen content of the polyol composition may be 100 ppm or less, 90 ppm or less, 80 ppm or less, 50 ppm or less, 40 ppm or less, or 10 ppm or less. The active oxygen content can be measured using a known method, for example, using a spectrophotometer to obtain a calibration curve of absorbance change depending on the active oxygen content. When the content satisfies the above range, side reactions are reduced, storage stability is improved, and color change may not occur.

[0082] The viscosity of the polyol composition at room temperature may be 200 cPs to 800 cPs, 300 cPs to 800 cPs, 350 cPs to 800 cPs, 400 cPs to 800 cPs, or 450 cPs to 700 cPs. The viscosity can be measured using a known method, for example, a non-contact viscometer. When the viscosity satisfies the above range, the generation of bubbles and uneven curing can be prevented during the production of polyurethane foam, and workability can be improved.

[0083] The method for producing a polyol composition according to the present invention includes: (a) a step of mixing at least one 1,4:3,6-dianhydrohexitol with a catalyst and performing a dehydration step; (b) a step of reacting the dehydrated at least one 1,4:3,6-dianhydrohexitol with a substituted or unsubstituted branched alkylene oxide having 3 to 10 carbon atoms to produce a first polymer; and (c) after the production of the first polymer in step (b) is completed, a step of reacting the first polymer with a substituted or unsubstituted linear alkylene oxide having 2 to 10 carbon atoms to produce a second polymer, and the polyol composition may contain a compound represented by Chemical Formula 1 below.

[0084] [ka]

[0085] In the above formula 1, R1 and R4 are each independently a substituted or unsubstituted linear alkylene group having 2 to 10 carbon atoms, R2 and R3 are each independently a substituted or unsubstituted branched alkylene group having 3 to 10 carbon atoms, x is a constant of 1 to 10, a and d are each independently a constant of 1 to 6, b and c are each independently a constant of 0 to 30, and b+c is a constant of 1 to 60.

[0086] Figure 1 is a flow chart showing a simplified process for producing a polyol composition according to the present invention. Referring to Figure 1, the production method of the present invention includes a dehydration step (S10). In S10, at least one 1,4:3,6-dianhydrohexitol is mixed with a catalyst to dehydrate the at least one 1,4:3,6-dianhydrohexitol.

[0087] The 1,4:3,6-dianhydrohexitol can exist as three isomers: isomannide, isoidide, and isosorbide. The three isomers can be distinguished by the relative configuration of the two hydroxyl groups (-OH) in each compound. Isomannide is obtained by dehydration of D-mannitol. Isoidide is obtained by dehydration of L-iditol. In consideration of the manufacturing process and efficiency, it is preferable to use isosorbide among the three 1,4:3,6-dianhydrohexitol isomers in S10.

[0088] The isosorbide is obtained by dehydration of D-sorbitol. Specifically, the isosorbide is obtained by dehydration of D-sorbitol under reduced pressure in the presence of an acid catalyst.

[0089] The acid catalyst functions to promote the dehydration reaction of the D-sorbitol. The acid catalyst may be a soluble acid catalyst, a homogeneous acid catalyst, or an acid-treated heterogeneous acid catalyst. Specifically, the acid catalyst may be sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, p-toluenesulfonic acid, methanesulfonic acid, sulfated metal oxide, or a heteropoly acid catalyst. Preferably, sulfuric acid can be used as the acid catalyst.

[0090] The acid catalyst may be added in an amount of 0.01 to 15.00 parts by weight, 0.01 to 10.00 parts by weight, or 0.01 to 5.00 parts by weight relative to 100 parts by weight of the D-sorbitol. When the amount is within the above range, the dehydration reaction rate of D-sorbitol can be improved and the amount of residual catalyst can be minimized.

[0091] The D-sorbitol may be in the form of a powder or an aqueous solution containing the D-sorbitol at a concentration of 50% to 90% by weight, or may be extracted from nature or obtained synthetically by reducing glucose.

[0092] The isosorbide is obtained by forming 1,4-sorbitan, an intermediate product, by removing one water molecule from the D-sorbitol, and then removing another water molecule from the 1,4-sorbitan.

[0093] The 1,4-sorbitan can be produced by adding the acid catalyst to a reactor containing the D-sorbitol and dehydrating the mixture under atmospheric pressure at a temperature of 80° C. to 140° C. for 1 hour to 5 hours. When the temperature range is satisfied, the production of impurities other than 1,4-sorbitan can be reduced, and the efficiency of the dehydration reaction in which D-sorbitol is converted into 1,4-sorbitan can be improved.

[0094] The isosorbide can be obtained by forming the 1,4-sorbitan and then dehydrating it at normal pressure for 1 to 10 hours at a temperature of 110 to 350° C. When the temperature range is satisfied, the production of impurities other than isosorbide can be reduced, and the efficiency of the dehydration reaction in which 1,4-sorbitan is converted to isosorbide can be improved.

[0095] The temperature of the dehydration step in which 1,4-sorbitan is formed may be lower than that of the dehydration step in which isosorbide is obtained. When the temperature of the dehydration step in which 1,4-sorbitan is formed is adjusted to be lower than that of the dehydration step in which isosorbide is obtained, isosorbide can be obtained in high yield even without using an acid catalyst.

[0096] The isosorbide can be obtained by the following reaction scheme 1:

[0097] [Reaction Scheme 1] JPEG2025527701000020.jpg37153

[0098] The at least one 1,4:3,6-dianhydrohexitol can be mixed with a catalyst to produce an active 1,4:3,6-dianhydrohexitol, which can be introduced into a batch reactor.

[0099] The 1,4:3,6-dianhydrohexitol may be added to the batch reactor in an amount of about 15% by weight to about 50% by weight, about 15% by weight to about 40% by weight, about 25% by weight to about 40% by weight, or about 25% by weight to about 35% by weight based on the total weight of the raw materials added to the batch reactor.

[0100] The 1,4:3,6-dianhydrohexitol may be added to the batch reactor in a solid state or in a powder form.

[0101] The shape of the 1,4:3,6-dianhydrohexitol particles may be spherical, flake-like or rod-like.

[0102] The purity of the 1,4:3,6-dianhydrohexitol may be about 80% or greater, about 90% or greater, about 95% or greater, or about 97% or greater.

[0103] The average particle size of the 1,4:3,6-dianhydrohexitol may be about 10 μm to about 200 μm, about 10 μm to about 150 μm, about 10 μm to about 100 μm, or about 30 μm to about 100 μm. The average particle size is measured using a laser diffraction method and can be defined as the particle size corresponding to 50% of the cumulative volume in the particle size distribution curve of the particles.

[0104] The functional percentage of the 1,4:3,6-dianhydrohexitol may be less than about 5% by weight, less than about 4% by weight, less than about 3% by weight, less than about 2% by weight, or less than about 1% by weight. The functional percentage can be calculated by subtracting the weight of the 1,4:3,6-dianhydrohexitol after drying from the weight of the 1,4:3,6-dianhydrohexitol before drying, dividing the result by the weight of the 1,4:3,6-dianhydrohexitol before drying, and multiplying by 100. The drying can be performed by increasing the temperature from room temperature to about 150°C and then maintaining it at 150°C, and the total drying time can be set to 20 minutes, including a 5-minute temperature increase step.

[0105] The 1,4:3,6-dianhydrohexitol may be introduced into the batch reactor in the form of an aqueous solution, or may be introduced into the batch reactor at a concentration of about 70% by weight to about 90% by weight, about 75% by weight to about 90% by weight, or about 75% by weight to about 85% by weight.

[0106] The 1,4:3,6-dianhydrohexitol may be added to the batch reactor all at once. The 1,4:3,6-dianhydrohexitol may be added to the batch reactor over about 5 to about 60 minutes, about 10 to about 50 minutes, or about 20 to about 40 minutes. The 1,4:3,6-dianhydrohexitol may be added to the batch reactor in equal amounts over about 5 to about 60 minutes, about 10 to about 50 minutes, or about 20 to about 40 minutes.

[0107] The catalyst may be a basic catalyst, which may include one or more strong bases selected from the group consisting of potassium hydroxide, sodium hydroxide, potassium metal, and sodium metal.

[0108] The basic catalyst may comprise a double metal cyanide, which may be prepared by reacting an aqueous solution of a metal salt with an aqueous solution of a metal cyanide salt in the presence of an organic complexing ligand.

[0109] The basic catalyst may include imidazole or an imidazole derivative, which may be 1,2-dimethylimidazole or 1-isobutyl-2-methylimidazole.

[0110] The catalyst may be added to the batch reactor in the form of an aqueous solution. For example, an aqueous potassium hydroxide solution may be added to the batch reactor. The catalyst may be added to the batch reactor after the at least one 1,4:3,6-dianhydrohexitol is added to the batch reactor. The catalyst may be added to the batch reactor all at once. The catalyst may be added to the batch reactor over about 1 minute to about 20 minutes, about 3 minutes to about 15 minutes, or about 8 minutes to about 12 minutes. The at least one 1,4:3,6-dianhydrohexitol may be added to the batch reactor in equal amounts over about 1 minute to about 20 minutes, about 3 minutes to about 15 minutes, or about 8 minutes to about 12 minutes.

[0111] In step S10, the catalyst may be mixed in an amount of 0.1 to 5.0 parts by weight, 0.5 to 4.0 parts by weight, or 1.0 to 3.0 parts by weight, based on 100 parts by weight of the at least one 1,4:3,6-dianhydrohexitol, to dehydrate the 1,4:3,6-dianhydrohexitol. When the amount is within the above range, the dehydration reaction rate of the 1,4:3,6-dianhydrohexitol can be improved and the amount of residual catalyst can be minimized.

[0112] The dehydration step of the 1,4:3,6-dianhydrohexitol can be carried out under temperature conditions of about 80°C to about 120°C, about 90°C to about 120°C, or about 100°C to about 120°C.

[0113] The dehydration step of the 1,4:3,6-dianhydrohexitol can be carried out under a pressure condition of about 0.1 torr to about 100.0 torr, about 0.1 torr to about 80.0 torr, or about 0.1 torr to about 20.0 torr.

[0114] The dehydration step of the 1,4:3,6-dianhydrohexitol can be carried out for about 1 hour to about 6 hours, about 1 hour to about 5 hours, or about 2 hours to about 4 hours.

[0115] The dehydration step of 1,4:3,6-dianhydrohexitol can be carried out for about 1 hour to about 5 hours at a temperature of about 80° C. to about 120° C. Preferably, the dehydration step of 1,4:3,6-dianhydrohexitol can be carried out for about 2 hours to about 4 hours at a temperature of about 80° C. to about 120° C. and a pressure of about 0.1 torr to about 20.0 torr.

[0116] After step S10, the 1,4:3,6-dianhydrohexitol may have a moisture content of less than about 2,000 ppm, less than about 1,000 ppm, less than about 500 ppm, or less than about 300 ppm. The low moisture content of the 1,4:3,6-dianhydrohexitol may improve the yield of the polyol composition.

[0117] The production method of the present invention may include a step (S20) of producing a first polymer, in which the dehydrated at least one kind of 1,4:3,6-dianhydrohexitol is reacted with a substituted or unsubstituted branched alkylene oxide having 3 to 10 carbon atoms to produce the first polymer.

[0118] The substituted or unsubstituted branched alkylene oxide having 3 to 10 carbon atoms may be propylene oxide. The propylene oxide may be charged into the batch reactor.

[0119] The propylene oxide introduction step can be carried out under temperature conditions of about 80°C to about 130°C, about 90°C to about 130°C, or about 100°C to about 120°C.

[0120] The propylene oxide introduction step can be carried out under a pressure condition of about 0.1 torr to about 100.0 torr, about 0.1 torr to about 50.0 torr, or about 0.1 torr to about 30.0 torr.

[0121] The propylene oxide introduction step can be carried out for about 3 hours to about 10 hours, about 5 hours to about 10 hours, or about 6 hours to about 9 hours. Preferably, the propylene oxide introduction step can be carried out under the temperature conditions of about 80°C to about 120°C and the pressure conditions of about 2 torr to about 8 torr for about 6 hours to about 9 hours.

[0122] The propylene oxide feeding rate may be about 100 kg / hr to about 1,000 kg / hr, about 300 kg / hr to about 1,000 kg / hr, or about 500 kg / hr to about 900 kg / hr.

[0123] The propylene oxide may be added to the batch reactor in an amount of about 100 parts by weight to about 500 parts by weight, about 150 parts by weight to about 500 parts by weight, or about 150 parts by weight to about 450 parts by weight based on 100 parts by weight of the 1,4:3,6-dianhydrohexitol.

[0124] The propylene oxide can undergo an addition reaction with the dehydrated 1,4:3,6-dianhydrohexitol in the batch reactor. The addition reaction can produce a first polymer containing a repeating unit derived from the propylene oxide in the 1,4:3,6-dianhydrohexitol core structure. The repeating unit derived from the propylene oxide may refer to a component or structure derived from propylene oxide, or propylene oxide itself.

[0125] The addition reaction of the 1,4:3,6-dianhydrohexitol and the propylene oxide can be carried out under temperature conditions of about 80°C to about 150°C, about 90°C to about 150°C, or about 100°C to about 140°C.

[0126] The addition reaction of the 1,4:3,6-dianhydrohexitol and the propylene oxide can be carried out for about 1 hour to about 4 hours, about 1 hour to about 3 hours, or about 1 hour to about 2 hours. Preferably, the addition reaction of the 1,4:3,6-dianhydrohexitol and the propylene oxide can be carried out at a temperature of about 100°C to about 140°C for about 1 hour to about 2 hours.

[0127] The above-mentioned step S20 may further include a step of removing residual branched alkylene oxide after producing the first polymer. The residual branched alkylene oxide may be propylene oxide. By removing the residual branched alkylene oxide, reactivity with isocyanate is improved, and the hardness of the polyurethane foam is increased, improving the appearance and improving production economy.

[0128] The step of removing the residual propylene oxide can be carried out under temperature conditions of about 80°C to about 150°C, about 90°C to about 150°C, or about 100°C to about 140°C.

[0129] The step of removing the residual propylene oxide can be carried out under a pressure condition of about 0.1 torr to about 100.0 torr, about 0.1 torr to about 80.0 torr, or about 0.1 torr to about 20.0 torr.

[0130] The step of removing the residual propylene oxide can be carried out for about 10 to about 120 minutes, about 10 to about 60 minutes, or about 20 to about 40 minutes. Preferably, the step of removing the residual propylene oxide can be carried out at a temperature of about 100°C to about 140°C and a pressure of about 0.1 torr to about 20.0 torr for about 20 to about 40 minutes.

[0131] The production method of the present invention may include a step (S30) of producing a second polymer. In S30, the first polymer may be reacted with a substituted or unsubstituted linear alkylene oxide having 2 to 10 carbon atoms to produce the second polymer.

[0132] The weight ratio of the branched alkylene oxide S20 to the linear alkylene oxide S30 may be 2:1 to 8:1, 3:1 to 7.5:1, 3.5:1 to 7.5:1, 3:1 to 7.5:1, 4.5:1 to 7.5:1, 5:1 to 7.5:1, or 5:1 to 7:1. When the ratio is within the above range, the reactivity with isocyanate increases, and the hardness and appearance quality of a polyurethane foam produced from the polyol composition can be improved.

[0133] The substituted or unsubstituted linear alkylene oxide having 2 to 10 carbon atoms may be ethylene oxide. The ethylene oxide may be introduced into the batch reactor after the production of the first polymer has been completed.

[0134] The ethylene oxide introduction step can be carried out under temperature conditions of about 80°C to about 140°C, about 90°C to about 140°C, or about 120°C to about 130°C.

[0135] The ethylene oxide introduction step can be carried out under a pressure condition of about 0.1 torr to about 100.0 torr, about 0.1 torr to about 50.0 torr, or about 0.1 torr to about 30.0 torr.

[0136] The step of introducing ethylene oxide can be carried out for about 1 hour to about 5 hours, about 1 hour to about 3 hours, or about 2 hours to about 3 hours. Preferably, the step of introducing ethylene oxide can be carried out at a temperature of about 120°C to about 130°C and a pressure of about 0.1 torr to about 30.0 torr for about 2 hours to about 3 hours.

[0137] The ethylene oxide feeding rate may be about 100 kg / hr to about 1,000 kg / hr, about 200 kg / hr to about 700 kg / hr, or about 300 kg / hr to about 600 kg / hr.

[0138] The ethylene oxide may be added to the batch reactor in an amount of about 10 parts by weight to about 100 parts by weight, about 20 parts by weight to about 100 parts by weight, about 20 parts by weight to about 80 parts by weight, or about 20 parts by weight to about 60 parts by weight, based on 100 parts by weight of the 1,4:3,6-dianhydrohexitol.

[0139] The ethylene oxide can undergo an addition reaction with the first polymer in the batch reactor. The addition reaction can produce a second polymer containing the ethylene oxide-derived repeating unit in the first polymer. Alternatively, a second polymer containing the propylene oxide-derived repeating unit and the ethylene oxide-derived repeating unit as a block copolymer can be produced. The ethylene oxide-derived repeating unit may refer to a component or structure derived from ethylene oxide, or ethylene oxide itself.

[0140] The addition reaction of the 1,4:3,6-dianhydrohexitol and the ethylene oxide can be carried out under temperature conditions of about 80°C to about 150°C, about 90°C to about 150°C, or about 100°C to about 140°C.

[0141] The addition reaction of the 1,4:3,6-dianhydrohexitol and the ethylene oxide can be carried out for about 1 hour to about 4 hours, about 1 hour to about 3 hours, or about 1 hour to about 2 hours. Preferably, the addition reaction of the 1,4:3,6-dianhydrohexitol and the ethylene oxide can be carried out at a temperature of about 100°C to about 140°C for about 1 hour to about 2 hours.

[0142] The above-mentioned step S30 may further include a step of removing the remaining linear alkylene oxide after producing the second polymer. The remaining linear alkylene oxide may be ethylene oxide.

[0143] The step of removing the residual ethylene oxide can be carried out under temperature conditions of about 80°C to about 150°C, about 90°C to about 150°C, or about 100°C to about 140°C.

[0144] The step of removing the residual propylene oxide can be carried out under a pressure condition of about 0.1 torr to about 100.0 torr, about 0.1 torr to about 80.0 torr, or about 0.1 torr to about 20.0 torr.

[0145] The step of removing the residual ethylene oxide can be carried out for about 30 minutes to about 200 minutes, about 30 minutes to about 100 minutes, or about 40 minutes to about 80 minutes. Preferably, the step of removing the residual ethylene oxide can be carried out at a temperature of about 100°C to about 140°C and a pressure of about 0.1 torr to about 20.0 torr for about 40 minutes to about 80 minutes.

[0146] The manufacturing method of the present invention may further include a step of removing residual metal ions (S40) and a filtering step (S50). In S40, residual metal ions in the polyol composition may be removed, and in S50, the polyol composition from which the residual metal ions have been removed may be filtered.

[0147] In step S40, an additive may be added to the polyol composition after the reaction to remove the residual metal ions. The additive may be at least one selected from the group consisting of diatomaceous earth, alumina, magnesol, celite, ambosol, and silica gel.

[0148] The additive may be added to the polyol composition after the reaction in the form of an aqueous dispersion, and the content of the additive may be 1 to 10 parts by weight, 1 to 8 parts by weight, 2 to 8 parts by weight, 3 to 8 parts by weight, or 3 to 6 parts by weight, based on 100 parts by weight of the 1,4:3,6-dianhydrohexitol.

[0149] Thereafter, in S40, the polyol composition containing the additives can be neutralized. The neutralization step can be performed for about 1 hour to about 4 hours, about 1 hour to about 3 hours, or about 1 hour to about 2 hours. After the neutralization step, the polyol composition can be subjected to a water removal step. The water removal step can be performed at about 90°C to about 130°C, about 95°C to about 130°C, or about 100°C to about 130°C. If necessary, in S40, a step of detecting the residual metal ions can be performed. If the residual metal ions are not detected, the polyol composition can be maintained at a temperature of about 50°C to about 90°C, about 50°C to about 80°C, or about 60°C to about 80°C. In S50, the polyol composition from which the water has been removed can be filtered. The additives and by-products can be removed by filtering.

[0150] The polyol composition produced according to the above production method may contain a compound represented by Chemical Formula 1 below.

[0151] [ka]

[0152] In the above formula 1, R1 and R4 are each independently a substituted or unsubstituted linear alkylene group having 2 to 10 carbon atoms, R2 and R3 are each independently a substituted or unsubstituted branched alkylene group having 3 to 10 carbon atoms, x is a constant of 1 to 10, a and d are each independently a constant of 1 to 6, b and c are each independently a constant of 0 to 30, and b+c is a constant of 1 to 60.

[0153] The compound represented by Chemical Formula 1 above may be the same as the compound described above.

[0154] The composition for producing polyurethane according to the present invention comprises a polyol composition and an isocyanate-based composition, and the polyol composition may comprise the compound represented by Chemical Formula 1 above.

[0155] The isocyanate composition may include at least one selected from the group consisting of an aliphatic polyisocyanate, a cycloaliphatic polyisocyanate, an araliphatic polyisocyanate, an aromatic polyisocyanate, and a heterocyclic polyisocyanate.

[0156] The isocyanate composition may comprise an unmodified polyisocyanate or a modified polyisocyanate.

[0157] The polyisocyanate may be methylene diisocyanate, ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,12-dodecane diisocyanate, cyclobutane-1,3-diisocyanate, cyclohexane-1,3-diisocyanate, cyclohexane-1,4-diisocyanate, isophorone diisocyanate, 2,4-hexahydrotoluene diisocyanate, 2,6-hexahydrotoluene diisocyanate, dicyclohexylmethyl The isocyanate may include at least one selected from the group consisting of toluene-4,4'-diisocyanate (HMDI), 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, diphenylmethane-2,4'-diisocyanate, diphenylmethane-4,4'-diisocyanate, polymeric methylene diphenyl diisocyanate (PMDI), and naphthalene-1,5-diisocyanate.

[0158] 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.

[0159] The amount of the polyisocyanate used may be 70 to 130, 80 to 120, and preferably 100 to 120 in terms of isocyanate index (NCO index).

[0160] The isocyanate index is the ratio of the equivalent number of hydroxyl groups (-OH) present in the polyol among the polyurethane reactants to the equivalent number of isocyanate, and means the amount of isocyanate used relative to the theoretical equivalent.

[0161] If the isocyanate index is less than 100, it means that an excess amount of polyol is present, and if the isocyanate index is greater than 100, it means that an excess amount of isocyanate is present.

[0162] If the isocyanate index is less than 70, the reactivity may decrease, the gelation reaction may be delayed, and the curing may not be successful. If the isocyanate index is more than 130, the hard segment may be increased too much, and the shrinkage phenomenon may occur.

[0163] The polyurethane-producing composition may contain a curing catalyst. The curing catalyst is not particularly limited and may be an amine catalyst, an organometallic catalyst, or a mixture thereof. The curing catalyst can function to promote the reaction between the polyol composition and the isocyanate composition.

[0164] The type of the amine catalyst is not particularly limited, and preferably, one or a mixture of two or more tertiary amine catalysts can be used, such as at least one selected from the group consisting of triethylene diamine, triethylamine, N-methyl morpholine, and N-ethyl morpholine.

[0165] The organometallic catalyst may be any organometallic catalyst commonly used in the production of polyurethane foams, such as at least one selected from the group consisting of stannous octoate, dibutyltin dilaurate (DBTDL), and tin bis[2-ethylhexanoate].

[0166] The content of the curing catalyst may be about 0.01 to about 5 parts by weight, 0.01 to about 4 parts by weight, 0.01 to about 3 parts by weight, 0.1 to about 3 parts by weight, or 0.1 to about 2.5 parts by weight, based on 100 parts by weight of the polyol composition. When the content is within the above range, poor curing or shrinkage or collapse during polyurethane foam formation can be reduced.

[0167] The composition for producing a polyurethane may contain a foam stabilizer, which prevents cells from coalescing or breaking when cells are formed inside the polyurethane foam, and regulates the formation of cells with a uniform pattern and size.

[0168] The foam stabilizer is not particularly limited as long as it is one that is commonly used in the production of polyurethane foam, and for example, a silicone-based foam stabilizer can be used. The silicone-based foam stabilizer may be one or more selected from silicone oils and their derivatives, and specifically may be a polyalkylene oxide methyl siloxane copolymer.

[0169] The content of the foam stabilizer may be about 0.01 to 10 parts by weight, about 0.1 to 10 parts by weight, about 0.2 to 10 parts by weight, about 0.3 to 10 parts by weight, about 0.4 to 10 parts by weight, or about 0.5 to 8 parts by weight, based on 100 parts by weight of the polyol composition. When the content is within the above range, shrinkage of the produced foam can be prevented and uniform moldability can be achieved.

[0170] The composition for producing polyurethane may contain a blowing agent. Water is a typical example of the blowing agent, but other blowing agents may also be used, such as at least one selected from the group consisting of methylene chloride, n-butane, isobutane, n-pentane, isopentane, dimethyl ether, acetone, carbon dioxide, and 1,1-dichloro-1-fluoroethane. The blowing agent may be used according to a conventional method, and may be selected appropriately depending on the density and other properties of the foam required.

[0171] The content of the blowing agent may be about 0.1 parts by weight to about 60 parts by weight, about 0.2 parts by weight to about 60 parts by weight, about 0.3 parts by weight to about 60 parts by weight, about 0.3 parts by weight to about 50 parts by weight, or about 1 part by weight to about 30 parts by weight, based on 100 parts by weight of the polyol composition.

[0172] The composition for producing a polyurethane may not contain a blowing agent, that is, a gas-phase blowing agent such as nitrogen gas may be directly injected into the composition for producing a polyurethane to form fine cells during the process of producing a polyurethane foam using the composition for producing a polyurethane.

[0173] The polyurethane-making composition may further comprise an auxiliary additive selected from the group consisting of a flame retardant, a colorant, a UV stabilizer, a thickener, a foam stabilizer, a filler, or a combination thereof.

[0174] The composition for producing a polyurethane may be a one-component type or a two-component type. When the composition for producing a polyurethane is a two-component type, it may be stored separately as two components, and the two components may be mixed immediately before the polyurethane resin production process.

[0175] When the composition for producing a polyurethane is a two-component type, the composition for producing a polyurethane may include a first component having the polyol composition as a main component and a second component having the isocyanate composition as a main component.

[0176] The first component may contain the polyol composition, the curing catalyst, the foam stabilizer, the foaming agent, and the other additives.

[0177] The second component may include the isocyanate composition.

[0178] A polyurethane foam can be produced from the polyurethane-producing composition. The method for producing a polyurethane foam may include: (a) a step of supplying the second component using an isocyanate supplier; (b) a gas supply step of supplying a blowing gas using a gas supplier; (c) a step of supplying the first component using a polyol supplier; (d) a step of mixing the first component, the second component, and the blowing gas using a mixer to produce a polyurethane foam composition; and (e) a step of curing the polyurethane foam composition.

[0179] The foaming gas in step (b) above may include nitrogen or carbon dioxide.

[0180] The first component in step (c) may further contain a curing catalyst, a foam stabilizer, a foaming agent, and other additives.

[0181] When the first component supplied in step (c) contains a foaming agent, the gas supply step in step (b) can be omitted.

[0182] The polyurethane foam thus produced may contain fine closed cells therein, for example, the polyurethane foam may contain fine closed pores.

[0183] The average diameter of the fine closed cells may be about 1 μm to about 200 μm, about 5 μm to about 200 μm, about 10 μm to about 200 μm, about 20 μm to about 200 μm, about 50 μm to about 200 μm, or about 50 μm to about 100 μm.

[0184] The battery module according to the present invention includes a housing, a plurality of battery cells accommodated inside the housing, and polyurethane foam disposed between the plurality of battery cells, wherein the polyurethane foam includes a composition for producing polyurethane including a polyol composition and an isocyanate-based composition, and the polyol composition may include the compound represented by Chemical Formula 1 described above.

[0185] FIG. 2 is a cross-sectional view illustrating a battery module according to the present invention. Referring to FIG. 2, a battery module 100 according to the present invention includes a housing 101. The housing 101 may be a structure that accommodates a plurality of battery cells 102 therein and protects them from external impacts. The housing 101 may be made of a metal material having high mechanical rigidity. However, the housing 101 is not limited to a metal material and may be made of a non-metal material to ensure insulation.

[0186] The battery module 100 may include a thermally conductive adhesive 104. The thermally conductive adhesive 104 can fix the plurality of battery cells 102 in the housing 101 and can effectively transfer heat from the plurality of battery cells 102 to the housing 101. The thermally conductive adhesive 104 can be made of various organic or inorganic resins such as a thermally conductive epoxy adhesive, a thermally conductive silicone adhesive, or a thermally conductive urethane adhesive.

[0187] The plurality of battery cells 102 may be provided in a pouch shape that can maximize the number of cells stacked per unit area. The plurality of battery cells 102 provided in the pouch shape may be manufactured by placing an electrode assembly including a positive electrode, a negative electrode, and a separator in a cell case made of a laminate sheet and then heat-sealing the seal of the cell case. However, the plurality of battery cells 102 do not necessarily have to be provided in a pouch shape, and may be provided in a rectangular, cylindrical, or other shape as long as the storage capacity required by the device to be installed is achieved.

[0188] The battery module 100 includes a plurality of battery cells 102 accommodated inside a housing 101 and polyurethane foam 103 disposed between the plurality of battery cells 102. The polyurethane foam 103 has excellent vibration absorption and resilience against compression, and can maintain dimensional stability even if the plurality of battery cells 102 swell. In addition, the battery module 100 can be prevented from being damaged by the expansion of the plurality of battery cells 102. The plurality of battery cells 102 may expand to different degrees depending on their chemical properties and usage environment. Taking this into consideration, the maximum compressible thickness range of the polyurethane foam 103 can be selected within a range that can withstand the expansion thickness of the plurality of battery cells 102.

[0189] <Polyol composition according to the second embodiment> The polyol composition according to the present invention may comprise first units derived from at least one 1,4:3,6-dianhydrohexitol and second units derived from an alkylene oxide, and may have an APHA (American Public Health Association) color value of 20 or less according to ASTM-D1209.

[0190] The 1,4:3,6-dianhydrohexitol and isosorbide may be the same as the 1,4:3,6-dianhydrohexitol and isosorbide described above.

[0191] The polyol composition may contain the first unit derived from 1,4:3,6-dianhydrohexitol in an amount of 5 wt% to 50 wt%, 10 wt% to 50 wt%, 10 wt% to 45 wt%, 15 wt% to 45 wt%, or 20 wt% to 45 wt%, based on the total weight of the polyol composition. When the amount satisfies the above range, when a polyurethane foam is produced from the polyol composition, the viscosity of the composition does not increase, which can cause problems with smooth foaming, and the molded density and hardness of the produced polyurethane foam can be improved.

[0192] The alkylene oxide may be the same as the alkylene oxide described above.

[0193] Polyol compositions typically made from petroleum-based raw materials have a high APHA color value, making them difficult to apply to industries that require transparent products.Furthermore, the APHA color value increases rapidly under high temperature conditions, causing the hue of the polyol composition to increase during storage or transportation.

[0194] Therefore, the polyol composition according to the present invention can be produced from renewable natural resources and exhibits a lower APHA color value than polyol compositions produced from petroleum-based raw materials, making it environmentally friendly and applicable to industries that require product transparency. Furthermore, even when exposed to high-temperature environments, color change is minimized, ensuring product reliability in terms of color when the polyol composition is stored or transported.

[0195] The polyol composition according to the present invention has an APHA (American Public Health Association) color value based on ASTM-D1209 of 25 or less, 24 or less, 23 or less, 22 or less, 21 or less, 20 or less, 19 or less, 18 or less, or 17 or less.

[0196] Specifically, the hue of the polyol composition is measured using ColorQuest XE (HunterLab), and the APHA (American Public Health Association) color value (platinum-cobalt system) based on ASTM-D1209 can be measured from the color number of the polyol composition.

[0197] When the above range is satisfied, the polyol composition is colorless and transparent, and polyurethane foam with low yellowness can be produced using the polyol. In addition, by-products such as unreacted ethylene oxide and unreacted propylene oxide are hardly generated in the polyol composition, which can improve product reliability.

[0198] The content of metals remaining in the polyol composition may be 10 ppm or less, 7 ppm or less, 5 ppm or less, 4 ppm or less, 3 ppm or less, or 1 ppm or less, based on the total weight of the polyol composition. The metal may include potassium. When the content is within the above range, color change due to metal ions can be minimized even when the polyol composition is exposed to a high-temperature environment.

[0199] The polyol composition may have a difference between the second APHA color value and the first APHA color value of 10 or less, 8 or less, or 5 or less, measured by the following method.

[0200] <Measurement method> 1) The first APHA color value of the polyol composition is measured based on ASTM-D1209.

[0201] 2) The polyol composition is stored in an oven at 75°C for 10 minutes.

[0202] 3) After removing the polyol composition from the oven, it is exposed to the atmosphere for 24 hours.

[0203] 4) The second APHA color value of the polyol composition is measured according to ASTM-D1209.

[0204] When the above range is satisfied, product reliability in terms of color can be ensured when the polyol composition is stored or transported.

[0205] The polyol composition may have a viscosity at 25°C of 200 cPs to 800 cPs, 300 cPs to 800 cPs, 350 cPs to 800 cPs, 350 cPs to 700 cPs, or 350 cPs to 600 cPs. The viscosity can be measured using a known method, for example, using a non-contact viscometer. When the viscosity satisfies the above range, the storage stability of the polyol composition can be improved, and when producing a polyurethane foam, the generation of bubbles can be prevented, curing imbalance can be prevented, and workability can be improved.

[0206] The number average molecular weight (Mn) of the polyol composition may be 300 g / mol to 20,000 g / mol, 300 g / mol to 18,000 g / mol, 300 g / mol to 15,000 g / mol, 300 g / mol to 12,000 g / mol, 500 g / mol to 12,000 g / mol, 500 g / mol to 10,000 g / mol, or 500 g / mol to 3,000 g / mol. The polyol composition may have a polydispersity index (PDI) of 0.8 to 2.0, 0.8 to 1.9, 0.8 to 1.8, 0.8 to 1.6, 0.8 to 1.5, or 1.0 to 1.3. When the above ranges are satisfied, the reactivity of the polyol composition with isocyanate can be improved.

[0207] The polyol composition may further contain the above-mentioned antioxidant.

[0208] The polyol composition may have the above-mentioned CPR (Controlled Polymerization Rate) value.

[0209] The polyol composition may have an acid value as described above.

[0210] The polyol composition may have the active oxygen content value described above.

[0211] The polyol composition may contain the compound represented by Chemical Formula 1 above.

[0212] The method for producing a polyol composition according to the present invention may include: (a) a step of mixing at least one 1,4:3,6-dianhydrohexitol with a catalyst and performing a dehydration step; (b) a step of reacting the dehydrated at least one 1,4:3,6-dianhydrohexitol with a substituted or unsubstituted branched alkylene oxide having 3 to 10 carbon atoms to produce a first polymer; and (c) after the production of the first polymer in step (b) is completed, a step of reacting the first polymer with a substituted or unsubstituted linear alkylene oxide having 2 to 10 carbon atoms to produce a second polymer. The polyol composition may have an APHA (American Public Health Association) color value according to ASTM-D1209 of 20 or less.

[0213] The method for producing a polyol composition according to the present invention can be carried out in the same manner as that shown in FIG.

[0214] The polyol composition produced according to the above production method may have an APHA (American Public Health Association) color value according to ASTM-D1209 of 25 or less, 24 or less, 23 or less, 22 or less, 21 or less, 20 or less, 19 or less, 18 or less, or 17 or less.

[0215] Specifically, the hue of the polyol composition is measured using ColorQuest XE (HunterLab), and the APHA (American Public Health Association) color value (platinum-cobalt system) based on ASTM-D1209 can be measured from the color number of the polyol composition.

[0216] When the above range is satisfied, the produced polyol composition is colorless and transparent, and polyurethane foam with low yellowness can be produced using the polyol. In addition, by-products such as unreacted ethylene oxide and unreacted propylene oxide are hardly generated in the polyol composition, thereby improving product reliability.

[0217] The composition for producing polyurethane according to the present invention includes a polyol composition that contains first units derived from at least one type of 1,4:3,6-dianhydrohexitol and second units derived from an alkylene oxide, and that has an APHA (American Public Health Association) color value based on ASTM-D1209 of 20 or less, and an isocyanate-based composition.

[0218] The polyol composition and the isocyanate-based composition may be the same as the polyol composition and the isocyanate-based composition described above.

[0219] A polyurethane foam can be produced from the composition for producing a polyurethane, which may be the same as the composition for producing a polyurethane described above.

[0220] The battery module according to the present invention includes a housing, a plurality of battery cells housed inside the housing, and polyurethane foam disposed between the plurality of battery cells. The polyurethane foam includes a composition for producing polyurethane, the composition including a polyol composition and an isocyanate-based composition. The polyol composition includes a first unit derived from at least one kind of 1,4:3,6-dianhydrohexitol and a second unit derived from an alkylene oxide. The battery module has an APHA (American Public Health Association) color value of 20 or less according to ASTM-D1209.

[0221] For the battery module according to the present invention, the same contents as those of FIG. 3 can be referred to.

[0222] <Polyol composition according to the third embodiment> The polyol composition according to the present invention may contain first units derived from at least one kind of 1,4:3,6-dianhydrohexitol and second units derived from an alkylene oxide, and may have an acid value of less than 0.02 mg KOH / g measured by the following method.

[0223] <Measurement method> 1) A first flask containing the polyol composition and a second flask not containing the polyol composition are prepared, and 50 ml of methanol is added to each of the first flask and the second flask, followed by stirring for 30 minutes.

[0224] 2) Add 0.5 ml of 1% phenolphthalein indicator to each of the first and second flasks, and titrate with 0.02 N potassium hydroxide (KOH) until the compositions in the first and second flasks are pink and last for 30 seconds.

[0225] 3) Calculate the acid value using the following formula 1.

[0226] [Formula 1] Acid value (mgKOH / g)=[(V s -V b )×56.1×N×F] / M

[0227] In the above formula 1, the V s is the amount (ml) of 0.02N potassium hydroxide (KOH) consumed to titrate the composition in the first flask, and V b is the amount (ml) of the 0.02N potassium hydroxide (KOH) consumed to titrate the composition in the second flask, N is the normality of the potassium hydroxide (KOH), F is a factor of the 0.02N potassium hydroxide (KOH), and M is the weight (g) of the polyol composition added to the first flask.

[0228] The 1,4:3,6-dianhydrohexitol and isosorbide may be the same as the 1,4:3,6-dianhydrohexitol and isosorbide described above.

[0229] The alkylene oxide may be the same as the alkylene oxide described above.

[0230] Generally, polyol compositions produced from petroleum-based raw materials have a high acid value, and the neutralization between the amine catalyst used in producing polyurethane foam and the polyol composition reduces the activity of the catalyst, resulting in a decrease in the reactivity of the polyol composition with the isocyanate-based composition, which reduces the efficiency of the polyurethane foam production process and decreases moldability.

[0231] Therefore, the polyol composition according to the present invention can be produced from renewable natural resources, exhibits a lower acid value than polyol compositions produced from petroleum-based raw materials, and is environmentally friendly. Furthermore, the activity of the catalyst used in the production of polyurethane foam is not reduced, and the reactivity between the polyol composition and the isocyanate-based composition can be improved, thereby improving the efficiency and moldability of the polyurethane foam production process.

[0232] The polyol composition according to the present invention has an acid value of less than 0.02 mgKOH / g, as measured by the following method.

[0233] <Measurement method> 1) A first flask containing the polyol composition and a second flask not containing the polyol composition are prepared, and 50 ml of methanol is added to each of the first flask and the second flask, followed by stirring for 30 minutes.

[0234] 2) Add 0.5 ml of 1% phenolphthalein indicator to each of the first and second flasks, and titrate with 0.02 N potassium hydroxide (KOH) until the compositions in the first and second flasks are pink and last for 30 seconds.

[0235] 3) Calculate the acid value using the following formula 1.

[0236] [Formula 1] Acid value (mgKOH / g)=[(V s -V b )×56.1×N×F] / M

[0237] In the above formula 1, the V s is the amount (ml) of 0.02N potassium hydroxide (KOH) consumed to titrate the composition in the first flask, and V bis the amount (ml) of the 0.02N potassium hydroxide (KOH) consumed to titrate the composition in the second flask, N is the normality of the potassium hydroxide (KOH), F is a factor of the 0.02N potassium hydroxide (KOH), and M is the weight (g) of the polyol composition added to the first flask.

[0238] The polyol composition may have an acid value measured by the above method of less than 0.02 mgKOH / g, 0.019 mgKOH / g or less, 0.018 mgKOH / g or less, 0.015 mgKOH / g or less, or 0.012 mgKOH / g or less, and the lower limit of the acid value is not particularly limited, but may be greater than 0 mgKOH / g, 0.005 mgKOH / g or more, or 0.010 mgKOH / g or more. When the above range is satisfied, the acid resistance of a polyurethane foam produced from the polyol composition may be enhanced, and the reactivity of the polyol composition with an isocyanate-based composition may be improved.

[0239] The content of metal remaining in the polyol composition may be the same as the content of metal described above.

[0240] The viscosity of the polyol composition may be similar to the viscosity described above.

[0241] The polyol compositions according to the present invention may have the aforementioned APHA (American Public Health Association) color values.

[0242] The polyol composition may have the number average molecular weight (Mn) and polydispersity index (PDI) described above.

[0243] The polyol composition may further contain the above-mentioned antioxidant.

[0244] The polyol composition may have the above-mentioned CPR (Controlled Polymerization Rate) value.

[0245] The polyol composition may have the active oxygen content value described above.

[0246] The polyol composition may contain the compound represented by Chemical Formula 1 above.

[0247] The method for producing a polyol composition according to the present invention may include: (a) a step of mixing at least one 1,4:3,6-dianhydrohexitol with a catalyst and performing a dehydration step; (b) a step of reacting the dehydrated at least one 1,4:3,6-dianhydrohexitol with a substituted or unsubstituted branched alkylene oxide having 3 to 10 carbon atoms to produce a first polymer; and (c) after the production of the first polymer in step (b) is completed, a step of reacting the first polymer with a substituted or unsubstituted linear alkylene oxide having 2 to 10 carbon atoms to produce a second polymer. The polyol composition may have an acid value of less than 0.02 mgKOH / g, as measured by the following method.

[0248] <Measurement method> 1) A first flask containing the polyol composition and a second flask not containing the polyol composition are prepared, and 50 ml of methanol is added to each of the first flask and the second flask, followed by stirring for 30 minutes.

[0249] 2) Add 0.5 ml of 1% phenolphthalein indicator to each of the first and second flasks, and titrate with 0.02 N potassium hydroxide (KOH) until the compositions in the first and second flasks are pink and last for 30 seconds.

[0250] 3) Calculate the acid value using the following formula 1.

[0251] [Formula 1] Acid value (mgKOH / g)=[(V s -V b )×56.1×N×F] / M

[0252] In the above formula 1, the V s is the amount (ml) of 0.02N potassium hydroxide (KOH) consumed to titrate the composition in the first flask, and V b is the amount (ml) of the 0.02N potassium hydroxide (KOH) consumed to titrate the composition in the second flask, N is the normality of the potassium hydroxide (KOH), F is a factor of the 0.02N potassium hydroxide (KOH), and M is the weight (g) of the polyol composition added to the first flask.

[0253] 5 is a flow chart showing a simplified process for preparing a polyol composition according to the present invention. Referring to FIG. 5, the method of the present invention may include a dehydration step (S10-1). Step S10-1 may be the same as step S10 described above.

[0254] The production method of the present invention may include a step (S20-1) of producing a first polymer. Step S20-1 may be the same as step S20 described above.

[0255] The production method of the present invention may include a step (S30-1) of producing a second polymer. Step S30-1 may be the same as step S30 described above.

[0256] The manufacturing method of the present invention may further include a step (S40-1) of removing and filtering residual metal ions and a step (S50-1) of adding an antioxidant. In S40-1, residual metal ions in the polyol composition are removed and filtered, and in S50-1, an antioxidant may be added to the polyol composition.

[0257] In the above S40-1, an additive may be added to the polyol composition after the reaction is completed to remove the residual metal ions. The additive may be at least one selected from the group consisting of diatomaceous earth, alumina, magnesol, celite, ambosol, and silica gel.

[0258] The additive may be added to the polyol composition after the reaction in the form of an aqueous dispersion, and the content of the additive may be 1 to 10 parts by weight, 1 to 8 parts by weight, 2 to 8 parts by weight, 3 to 8 parts by weight, or 3 to 6 parts by weight, based on 100 parts by weight of the 1,4:3,6-dianhydrohexitol.

[0259] Then, in S40-1, the polyol composition containing the additives can be neutralized. The neutralization can be carried out for about 1 hour to about 4 hours, about 1 hour to about 3 hours, or about 1 hour to about 2 hours. After the neutralization, the polyol composition can be subjected to a water removal process. The water removal process can be carried out at about 90°C to about 130°C, about 95°C to about 130°C, or about 100°C to about 130°C. If necessary, in S40-1, a process for detecting the residual metal ions can be carried out. If the residual metal ions are not detected, the polyol composition can be maintained at a temperature of about 50°C to about 90°C, about 50°C to about 80°C, or about 60°C to about 80°C. In S40, the polyol composition from which the water has been removed can be filtered. The filtering process can remove the additives and by-products.

[0260] In the above S50-1, the polyol composition may contain one or more antioxidants selected from the group consisting of phenolic antioxidants (e.g., dibutylhydroxytoluene), sulfur-based antioxidants (e.g., mercaptopropionic acid derivatives), and phosphorus-based antioxidants (e.g., 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide). The antioxidant may be added in an amount of 0.01 wt % to 3 wt %, 0.01 wt % to 2 wt %, 0.02 wt % to 2 wt %, 0.02 wt % to 1 wt %, or 0.03 wt % to 1 wt %, based on the total weight of the polyol composition. The antioxidant can improve the heat resistance stability of the polyurethane foam obtained from the polyol composition and reduce odor generation.

[0261] The polyol composition produced according to the above production method may have an acid value, measured by the following method, of less than 0.02 mgKOH / g, 0.019 mgKOH / g or less, 0.018 mgKOH / g or less, 0.015 mgKOH / g or less, or 0.012 mgKOH / g or less. The lower limit of the acid value is not particularly limited, but may be more than 0 mgKOH / g, 0.005 mgKOH / g or more, or 0.010 mgKOH / g or more.

[0262] <Measurement method> 1) A first flask containing the polyol composition and a second flask not containing the polyol composition are prepared, and 50 ml of methanol is added to each of the first flask and the second flask, followed by stirring for 30 minutes.

[0263] 2) Add 0.5 ml of 1% phenolphthalein indicator to each of the first and second flasks, and titrate with 0.02 N potassium hydroxide (KOH) until the compositions in the first and second flasks are pink and last for 30 seconds.

[0264] 3) Calculate the acid value using the following formula 1.

[0265] [Formula 1] Acid value (mgKOH / g)=[(V s -V b )×56.1×N×F] / M

[0266] In the above formula 1, the V s is the amount (ml) of 0.02N potassium hydroxide (KOH) consumed to titrate the composition in the first flask, and V b is the amount (ml) of the 0.02N potassium hydroxide (KOH) consumed to titrate the composition in the second flask, N is the normality of the potassium hydroxide (KOH), F is a factor of the 0.02N potassium hydroxide (KOH), and M is the weight (g) of the polyol composition added to the first flask.

[0267] When the above range is satisfied, the acid resistance of the polyurethane foam produced from the polyol composition may be enhanced, and the reactivity of the polyol composition with the isocyanate-based composition may be improved.

[0268] The composition for producing a polyurethane according to the present invention may include a polyol composition that contains first units derived from at least one kind of 1,4:3,6-dianhydrohexitol and second units derived from an alkylene oxide, and that has an acid value of less than 0.02 mg KOH / g as measured by the following method, and an isocyanate composition.

[0269] <Measurement method> 1) A first flask containing the polyol composition and a second flask not containing the polyol composition are prepared, and 50 ml of methanol is added to each of the first flask and the second flask, followed by stirring for 30 minutes.

[0270] 2) Add 0.5 ml of 1% phenolphthalein indicator to each of the first and second flasks, and titrate with 0.02 N potassium hydroxide (KOH) until the compositions in the first and second flasks are pink and last for 30 seconds.

[0271] 3) Calculate the acid value using the following formula 1.

[0272] [Formula 1] Acid value (mgKOH / g)=[(V s -V b )×56.1×N×F] / M

[0273] In the above formula 1, the V s is the amount (ml) of 0.02N potassium hydroxide (KOH) consumed to titrate the composition in the first flask, and V b is the amount (ml) of the 0.02N potassium hydroxide (KOH) consumed to titrate the composition in the second flask, N is the normality of the potassium hydroxide (KOH), F is a factor of the 0.02N potassium hydroxide (KOH), and M is the weight (g) of the polyol composition added to the first flask.

[0274] The polyol composition and the isocyanate-based composition may be the same as the polyol composition and the isocyanate-based composition described above.

[0275] A polyurethane foam can be produced from the composition for producing a polyurethane, which may be the same as the composition for producing a polyurethane described above.

[0276] The battery module according to the present invention includes a housing, a plurality of battery cells accommodated inside the housing, and polyurethane foam disposed between the plurality of battery cells, wherein the polyurethane foam includes a composition for producing polyurethane, the composition including a polyol composition and an isocyanate-based composition, and the polyol composition includes at least one first unit derived from 1,4:3,6-dianhydrohexitol and a second unit derived from an alkylene oxide, and has an acid value of less than 0.02 mgKOH / g as measured by the following method.

[0277] <Measurement method> 1) A first flask containing the polyol composition and a second flask not containing the polyol composition are prepared, and 50 ml of methanol is added to each of the first flask and the second flask, followed by stirring for 30 minutes.

[0278] 2) Add 0.5 ml of 1% phenolphthalein indicator to each of the first and second flasks, and titrate with 0.02 N potassium hydroxide (KOH) until the compositions in the first and second flasks are pink and last for 30 seconds.

[0279] 3) Calculate the acid value using the following formula 1.

[0280] [Formula 1] Acid value (mgKOH / g)=[(V s -V b )×56.1×N×F] / M

[0281] In the above formula 1, the V s is the amount (ml) of 0.02N potassium hydroxide (KOH) consumed to titrate the composition in the first flask, and V bis the amount (ml) of the 0.02N potassium hydroxide (KOH) consumed to titrate the composition in the second flask, N is the normality of the potassium hydroxide (KOH), F is a factor of the 0.02N potassium hydroxide (KOH), and M is the weight (g) of the polyol composition added to the first flask.

[0282] For the battery module according to the present invention, the same contents as those of FIG. 3 can be referred to.

[0283] <Polyol composition according to the fourth embodiment> The polyol composition according to the present invention may contain first units derived from at least one kind of 1,4:3,6-dianhydrohexitol and second units derived from an alkylene oxide, and may have a degree of unsaturation of 0.02 meq / g or less, as measured by the following measurement method.

[0284] <Measurement method> 1) A first flask containing 30 g of the polyol composition and a second flask containing no polyol composition were prepared, and 50 ml of mercury acetate was added to each of the first flask and the second flask, followed by stirring for 30 minutes.

[0285] 2) 9 g of sodium bromide (NaBr) is added to each of the first flask and the second flask, and then the mixture is stirred for 30 minutes.

[0286] 3) Add 0.5 ml of 1% phenolphthalein indicator to each of the first and second flasks, and titrate with 0.1 N potassium hydroxide (KOH).

[0287] 4) Calculate the degree of unsaturation using the following formula 1.

[0288] [Formula 1] Unsaturation degree (meq / g)=(V s ×V b ×0.1×F) / M

[0289] In the above formula 1, the V s is the amount (ml) of 0.1 N potassium hydroxide (KOH) added to the first flask, and V b is the amount (ml) of the 0.1 N potassium hydroxide (KOH) added to the second flask, F is a factor of the 0.1 N potassium hydroxide (KOH), and M is the weight (g) of the polyol composition added to the first flask.

[0290] The 1,4:3,6-dianhydrohexitol and isosorbide may be the same as the 1,4:3,6-dianhydrohexitol and isosorbide described above.

[0291] The alkylene oxide may be the same as the alkylene oxide described above.

[0292] The polyol composition may have a degree of unsaturation of 0.02 meq / g or less, as measured by the following method.

[0293] <Measurement method> 1) A first flask containing 30 g of the polyol composition and a second flask containing no polyol composition were prepared, and 50 ml of mercury acetate was added to each of the first flask and the second flask, followed by stirring for 30 minutes.

[0294] 2) 9 g of sodium bromide (NaBr) is added to each of the first flask and the second flask, and then the mixture is stirred for 30 minutes.

[0295] 3) Add 0.5 ml of 1% phenolphthalein indicator to each of the first and second flasks, and titrate with 0.1 N potassium hydroxide (KOH).

[0296] 4) Calculate the degree of unsaturation using the following formula 1.

[0297] [Formula 1] Unsaturation degree (meq / g)=(V s ×V b ×0.1×F) / M

[0298] In the above formula 1, the V s is the amount (ml) of 0.1 N potassium hydroxide (KOH) added to the first flask, and V b is the amount (ml) of the 0.1 N potassium hydroxide (KOH) added to the second flask, F is a factor of the 0.1 N potassium hydroxide (KOH), and M is the weight (g) of the polyol composition added to the first flask.

[0299] The degree of unsaturation means the content of monool in the polyol composition. Specifically, the degree of unsaturation may be expressed in mg unsaturated equivalents per 1 g of the polyol composition (meq / g).

[0300] The mono-ol can be produced by addition polymerization of propylene oxide with 1,4:3,6-dianhydrohexitol using a catalyst, specifically, by rearrangement of propylene oxide to allyl alcohol.

[0301] The monool may cause a decrease in the number of functional groups of the polyol composition, and when the polyol composition is used to produce polyurethane, crosslinking and high molecular weight may be hindered, resulting in deterioration of the physical properties of the polyurethane resin.

[0302] The polyol composition may have an unsaturation degree of 0.020 meq / g or less, 0.015 meq / g or less, 0.013 meq / g or less, 0.010 meq / g or less, 0.005 meq / g or less, 0.0045 meq / g or less, 0.0040 meq / g or less, 0.0038 meq / g or less, 0.0036 meq / g or less, 0.0034 meq / g or less, 0.0033 meq / g or less, 0.0032 meq / g or less, 0.0031 meq / g or less, or 0.0030 meq / g or less. When the degree of unsaturation is within the above range, the polyol composition has excellent reactivity with isocyanate, and when a polyurethane resin is produced from the polyol composition, crosslinking and polymerization can be smoothly carried out, resulting in improved physical properties of the polyurethane resin.

[0303] The polyol composition may contain a compound represented by the following Chemical Formula 3.

[0304] [ka]

[0305] In the above formula 3, R1 and R2 are each independently a substituted or unsubstituted alkylene group having 2 to 10 carbon atoms, a and f are each independently a constant of 1 to 60, b and e are each independently a constant of 1 to 6, c and d are each independently a constant of 1 to 30, and x is a constant of 1 to 5.

[0306] The compound represented by Chemical Formula 3 may contain a core structure derived from at least one kind of 1,4:3,6-dianhydrohexitol. The at least one kind of 1,4:3,6-dianhydrohexitol may contain isosorbide.

[0307] The ratio of (b+e):(c+d) may be 1:1.5 to 1:6. Preferably, the ratio of (b+e):(c+d) may be 1:2 to 1:6, 1:2.5 to 1:6, or 1:3 to 1:6. The ratios of (b+c) and (d+e) may each independently be 3 to 50. Preferably, the ratios of (b+c) and (d+e) may each independently be 3 to 30, 3 to 20, 5 to 20, 5 to 10, or 5 to 9. When the above ranges are satisfied, a polyurethane foam containing the compound may have improved hardness, a reduced compression set, a smooth surface, and excellent appearance.

[0308] In addition, by achieving an appropriate level of Compression Force Deformation (CFD), when polyurethane foam is applied to a battery module, it can buffer volume changes caused by the expansion of the battery cell and maintain a constant volume, thereby improving product stability. CFD is a parameter that indicates the repulsive force when a measurement object is compressed.

[0309] The CFD can be evaluated by measuring the resilience when the polyurethane foam is cut into 5 cm x 5 cm pieces at room temperature and compressed using a device such as a Universal Testing Machine (UTM). For example, the resilience when the polyurethane foam is compressed by 25% can be evaluated as the CFD 25% value, and a preferred CFD 25% value is greater than about 0.06 kg / cm. 2 Less than 0.15 kg / cm 2 The resilience when the polyurethane foam is compressed 50% can be evaluated as a CFD 50% value, and the preferred CFD 50% value is greater than about 0.09 kg / cm. 2 Less than 0.20 kg / cm 2 It may have a range of

[0310] In the above formula 3, R1 and R2 may each independently be a substituted or unsubstituted branched alkylene group having 3 to 10 carbon atoms. The branched alkylene group may be propylene oxide.

[0311] In the above formula 3, R1 and R2 may each independently be a random polymer of a substituted or unsubstituted linear alkylene group having 2 to 10 carbon atoms and a substituted or unsubstituted branched alkylene group having 3 to 10 carbon atoms. The linear alkylene group may be ethylene oxide.

[0312] The compound represented by Chemical Formula 3 may have a first block in which the branched alkylene group is polymerized on a core structure derived from at least one type of 1,4:3,6-dianhydrohexitol, and a second block in which the linear alkylene group is bonded to the first block. Alternatively, a third block in which the branched alkylene group is bonded to the second block may be formed. Alternatively, a third block in which the linear alkylene group and the branched alkylene group are bonded randomly to the second block may be formed.

[0313] The types of compounds represented by Chemical Formula 3 above can be represented by the following compounds A to G.

[0314] [ka]

[0315] [ka]

[0316] [ka]

[0317] [ka]

[0318] [ka]

[0319] [ka]

[0320] [ka]

[0321] The polyol composition may further contain the above-mentioned antioxidant.

[0322] The polyol composition may have the above-mentioned CPR (Controlled Polymerization Rate) value.

[0323] The polyol composition may have an acid value as described above.

[0324] The polyol composition may have the number average molecular weight (Mn) and polydispersity index (PDI) described above.

[0325] The polyol composition may have the aforementioned APHA (American Public Health Association) color values.

[0326] The polyol composition may have the active oxygen content value described above.

[0327] The viscosity of the polyol composition may be similar to the viscosity described above.

[0328] The method for producing a polyol composition according to the present invention may include the steps of: (a) mixing at least one 1,4:3,6-dianhydrohexitol with an alkali catalyst to initiate a polymerization reaction; (b) reacting the 1,4:3,6-dianhydrohexitol with an alkylene oxide to produce a prepolymer; and (c) reacting the prepolymer produced in step (b) with an alkylene oxide in the presence of a double metal cyanide catalyst to produce a polyol composition. The polyol composition may have an unsaturation level of 0.02 meq / g or less, as measured by the following method.

[0329] <Measurement method> 1) A first flask containing 30 g of the polyol composition and a second flask containing no polyol composition were prepared, and 50 ml of mercury acetate was added to each of the first flask and the second flask, followed by stirring for 30 minutes.

[0330] 2) 9 g of sodium bromide (NaBr) is added to each of the first flask and the second flask, and then the mixture is stirred for 30 minutes.

[0331] 3) Add 0.5 ml of 1% phenolphthalein indicator to each of the first and second flasks, and titrate with 0.1 N potassium hydroxide (KOH).

[0332] 4) Calculate the degree of unsaturation using the following formula 1.

[0333] [Formula 1] Unsaturation degree (meq / g)=(V s ×V b ×0.1×F) / M

[0334] In the above formula 1, the V s is the amount (ml) of 0.1 N potassium hydroxide (KOH) added to the first flask, and V bis the amount (ml) of the 0.1 N potassium hydroxide (KOH) added to the second flask, F is a factor of the 0.1 N potassium hydroxide (KOH), and M is the weight (g) of the polyol composition added to the first flask.

[0335] Figure 6 is a flow chart showing a simplified process for preparing a polyol composition according to the present invention. Referring to Figure 6, the method of the present invention may include a step (S10-2) of initiating a polymerization reaction. In S10-2, at least one 1,4:3,6-dianhydrohexitol and an alkali catalyst may be mixed. The 1,4:3,6-dianhydrohexitol and alkali catalyst may be the same as those described above.

[0336] The production method of the present invention may include a step (S20-2) of producing a prepolymer. In S20-2, the 1,4:3,6-dianhydrohexitol may be reacted with an alkylene oxide to produce a prepolymer. The method for producing the prepolymer may be the same as the method for producing the second polymer described above.

[0337] The production method of the present invention may include a step (S30-2) of producing a polyol composition, in which the prepolymer produced in S20-2 is reacted with an alkylene oxide in the presence of a double metal cyanide catalyst to produce the polyol composition.

[0338] The double metal cyanide catalyst may be represented by the following formula 4:

[0339] [ka]

[0340] In the above formula 4, M is a metal element selected from the group consisting of Zn(II), Fe(II), Ni(II), Mn(II), Co(II), Sn(II), Pb(II), Fe(III), Mo(IV), Mo(VI), Al(II), V(V), V(IV), Sr(II), W(IV), W(VI), Cu(II), and Cr(III), and M' is Fe(II), Fe(III), Co(II), Co(III). ), Cr(II), Cr(III), Mn(II), Mn(III), Ir(III), Ni(II), Rh(III), Ru(II), V(V), and V(IV), L is an alcohol ligand having 1 to 7 carbon atoms, L' is an ether having a number average molecular weight of less than 200 g / mol, and a, b, c, and d are constants whose sum is the same as the sum of the number of charges of M and M'.

[0341] The double metal cyanide catalyst can be prepared by reacting a metal salt and a metal cyanide with a complexing agent. The metal salt may be a water-soluble metal salt. The metal cyanide may be a water-soluble metal cyanide. Specifically, the water-soluble metal cyanide may be potassium(III) hexacyanocobaltate, potassium(II) hexacyanoferrate, potassium(III) hexacyanoferrate, calcium(II) hexacyanocobaltate, or lithium(II) hexacyanoferrate.

[0342] When the double metal cyanide catalyst is used in S30-2, the production of mono-ol can be reduced during the polymerization of the first prepolymer with propylene oxide, thereby reducing the degree of unsaturation in the polyol composition, facilitating crosslinking and increasing the molecular weight during the production of polyurethane resin, and improving the physical properties of the polyurethane resin.

[0343] In S30-2, it is preferable not to use the double metal cyanide catalyst and the alkali catalyst together. The selective activity of the double metal cyanide catalyst can increase the amount of alkali catalyst used, and a large amount of alkali catalyst can remain after producing the polyol composition. This inevitably requires an additional process to remove the alkali catalyst, reducing the efficiency of the production process. Furthermore, the alkali catalyst can increase the production of monools, which can hinder crosslinking and high molecular weight formation during the production of polyurethane resin, thereby reducing the physical properties of the polyurethane resin.

[0344] The polyol composition produced according to the above production method may contain a compound represented by Chemical Formula 3 below.

[0345] [ka]

[0346] In the above formula 3, R1 and R2 are each independently a substituted or unsubstituted alkylene group having 2 to 10 carbon atoms, a and f are each independently a constant of 1 to 60, b and e are each independently a constant of 1 to 6, c and d are each independently a constant of 1 to 30, and x is a constant of 1 to 5.

[0347] The composition for producing a polyurethane according to the present invention may include a polyol composition that contains first units derived from at least one type of 1,4:3,6-dianhydrohexitol and second units derived from an alkylene oxide, and that has an unsaturation degree of 0.02 meq / g or less, as measured by the following method, and an isocyanate composition.

[0348] <Measurement method> 1) A first flask containing 30 g of the polyol composition and a second flask containing no polyol composition were prepared, and 50 ml of mercury acetate was added to each of the first flask and the second flask, followed by stirring for 30 minutes.

[0349] 2) 9 g of sodium bromide (NaBr) is added to each of the first flask and the second flask, and then the mixture is stirred for 30 minutes.

[0350] 3) Add 0.5 ml of 1% phenolphthalein indicator to each of the first and second flasks, and titrate with 0.1 N potassium hydroxide (KOH).

[0351] 4) Calculate the degree of unsaturation using the following formula 1.

[0352] [Formula 1] Unsaturation degree (meq / g)=(V s ×V b ×0.1×F) / M

[0353] In the above formula 1, the V s is the amount (ml) of 0.1 N potassium hydroxide (KOH) added to the first flask, and V b is the amount (ml) of the 0.1 N potassium hydroxide (KOH) added to the second flask, F is a factor of the 0.1 N potassium hydroxide (KOH), and M is the weight (g) of the polyol composition added to the first flask.

[0354] The polyol composition and the isocyanate-based composition may be the same as the polyol composition and the isocyanate-based composition described above.

[0355] A polyurethane foam can be produced from the composition for producing a polyurethane, which may be the same as the composition for producing a polyurethane described above.

[0356] The battery module according to the present invention includes a housing, a plurality of battery cells accommodated inside the housing, and polyurethane foam disposed between the plurality of battery cells, wherein the polyurethane foam includes a composition for producing polyurethane, the composition including a polyol composition and an isocyanate-based composition, and the polyol composition includes at least one first unit derived from 1,4:3,6-dianhydrohexitol and a second unit derived from an alkylene oxide, and has a degree of unsaturation of 0.02 meq / g or less, as measured by the following method:

[0357] <Measurement method> 1) A first flask containing 30 g of the polyol composition and a second flask containing no polyol composition were prepared, and 50 ml of mercury acetate was added to each of the first flask and the second flask, followed by stirring for 30 minutes.

[0358] 2) 9 g of sodium bromide (NaBr) is added to each of the first flask and the second flask, and then the mixture is stirred for 30 minutes.

[0359] 3) Add 0.5 ml of 1% phenolphthalein indicator to each of the first and second flasks, and titrate with 0.1 N potassium hydroxide (KOH).

[0360] 4) Calculate the degree of unsaturation using the following formula 1.

[0361] [Formula 1] Unsaturation degree (meq / g)=(V s ×V b ×0.1×F) / M

[0362] In the above formula 1, the V s is the amount (ml) of 0.1 N potassium hydroxide (KOH) added to the first flask, and V bis the amount (ml) of the 0.1 N potassium hydroxide (KOH) added to the second flask, F is a factor of the 0.1 N potassium hydroxide (KOH), and M is the weight (g) of the polyol composition added to the first flask.

[0363] For the battery module according to the present invention, the same contents as those of FIG. 3 can be referred to.

[0364] <Polyol composition according to the fifth embodiment> The polyether polyol according to the present invention may be included in a polyol composition.

[0365] The method for producing a polyether polyol according to the present invention may include the steps of: (a) reacting at least one 1,4:3,6-dianhydrohexitol and a first alkylene oxide in the presence of an alkali catalyst to produce a first polymer; and (b) reacting the first polymer with a second alkylene oxide in the presence of a double metal cyanide catalyst to produce a second polymer.

[0366] 7 is a simplified flow chart illustrating a process for producing a polyether polyol according to the present invention. Referring to FIG. 7, the production method of the present invention may include a step (S10-3) of producing a first polymer. In S10-3, the first polymer may be produced by reacting at least one 1,4:3,6-dianhydrohexitol with a first alkylene oxide in the presence of an alkali catalyst. Step S10-3 may be the same as the step of producing a prepolymer described above.

[0367] The 1,4:3,6-dianhydrohexitol and isosorbide may be the same as the 1,4:3,6-dianhydrohexitol and isosorbide described above.

[0368] The alkylene oxide may be the same as the alkylene oxide described above.

[0369] Specifically, the step (a) may include: (a-1) mixing the 1,4:3,6-dianhydrohexitol with the alkali catalyst and performing a dehydration step; (a-2) after the dehydration step, reacting the 1,4:3,6-dianhydrohexitol with the substituted or unsubstituted branched alkylene oxide having 3 to 10 carbon atoms to produce a 1-1 polymer; and (a-3) after the production of the 1-1 polymer is completed, reacting the 1-1 polymer with the substituted or unsubstituted linear alkylene oxide having 2 to 10 carbon atoms to produce a 1-2 polymer.

[0370] The step (a) may include (a-4) removing residual metal ions in the composition containing the 1-2 polymer after the step (a-3), and (a-5) filtering the composition.

[0371] 8 is a flow chart specifically illustrating the steps of preparing a first polymer. Referring to FIG. 8, step (S10-3) may include step (S11) of performing a dehydration process. In step S11, the 1,4:3,6-dianhydrohexitol and the alkali catalyst may be mixed and then dehydrated.

[0372] The 1,4:3,6-dianhydrohexitol may be charged into a batch reactor.

[0373] The 1,4:3,6-dianhydrohexitol may be added to the batch reactor in an amount of about 15% by weight to about 50% by weight, about 15% by weight to about 40% by weight, about 25% by weight to about 40% by weight, or about 25% by weight to about 35% by weight based on the total weight of the raw materials added to the batch reactor.

[0374] The 1,4:3,6-dianhydrohexitol may be added to the batch reactor in a solid state or in a powder form.

[0375] The shape of the 1,4:3,6-dianhydrohexitol particles may be spherical, flake-like or rod-like.

[0376] The purity of the 1,4:3,6-dianhydrohexitol may be about 80% or greater, about 90% or greater, about 95% or greater, or about 97% or greater.

[0377] The average particle size of the 1,4:3,6-dianhydrohexitol may be about 10 μm to about 200 μm, about 10 μm to about 150 μm, about 10 μm to about 100 μm, or about 30 μm to about 100 μm. The average particle size is measured using a laser diffraction method and can be defined as the particle size corresponding to 50% of the cumulative volume in the particle size distribution curve of the particles.

[0378] The functional percentage of the 1,4:3,6-dianhydrohexitol may be less than about 5% by weight, less than about 4% by weight, less than about 3% by weight, less than about 2% by weight, or less than about 1% by weight. The functional percentage can be calculated by subtracting the weight of the 1,4:3,6-dianhydrohexitol after drying from the weight of the 1,4:3,6-dianhydrohexitol before drying, dividing the result by the weight of the 1,4:3,6-dianhydrohexitol before drying, and multiplying by 100. The drying is performed by increasing the temperature from room temperature to about 150°C and then maintaining the temperature at 150°C. The total drying time can be set to 20 minutes, including a 5-minute temperature increase step.

[0379] The 1,4:3,6-dianhydrohexitol may be introduced into the batch reactor in the form of an aqueous solution, or may be introduced into the batch reactor at a concentration of about 70% by weight to about 90% by weight, about 75% by weight to about 90% by weight, or about 75% by weight to about 85% by weight.

[0380] The 1,4:3,6-dianhydrohexitol may be added to the batch reactor all at once. The 1,4:3,6-dianhydrohexitol may be added to the batch reactor over about 5 to about 60 minutes, about 10 to about 50 minutes, or about 20 to about 40 minutes. The 1,4:3,6-dianhydrohexitol may be added to the batch reactor in equal amounts over about 5 to about 60 minutes, about 10 to about 50 minutes, or about 20 to about 40 minutes.

[0381] The alkaline catalyst may comprise one or more strong bases selected from the group consisting of potassium hydroxide, sodium hydroxide, potassium metal, and sodium metal.

[0382] In the above step S11, it is preferable not to use a double metal cyanide catalyst (DMC), which generally requires an induction period of one hour or more for catalyst activation, and little or no polymerization reaction occurs until the catalyst is activated, which can significantly reduce the efficiency of the production process.

[0383] The alkali catalyst may be added to the batch reactor in the form of an aqueous solution. For example, an aqueous potassium hydroxide solution may be added to the batch reactor. The alkali catalyst may be added to the batch reactor after the at least one 1,4:3,6-dianhydrohexitol is added to the batch reactor. The alkali catalyst may be added to the batch reactor all at once. The alkali catalyst may be added to the batch reactor over a period of about 1 minute to about 20 minutes, about 3 minutes to about 15 minutes, or about 8 minutes to about 12 minutes. The at least one 1,4:3,6-dianhydrohexitol may be added to the batch reactor in equal portions over a period of about 1 minute to about 20 minutes, about 3 minutes to about 15 minutes, or about 8 minutes to about 12 minutes.

[0384] In the above step S11, the dehydration step of the 1,4:3,6-dianhydrohexitol can be carried out by mixing the alkali catalyst and the 1,4:3,6-dianhydrohexitol at a weight ratio of 1:10 to 1,000, 1:10 to 500, 1:10 to 300, 1:10 to 200, 1:10 to 100, 1:20 to 100, or 1:30 to 100. When the ratio satisfies the above ranges, the dehydration reaction rate of the 1,4:3,6-dianhydrohexitol can be improved and the amount of residual alkali catalyst can be minimized.

[0385] The dehydration step of the 1,4:3,6-dianhydrohexitol can be carried out under temperature conditions of about 80°C to about 120°C, about 90°C to about 120°C, or about 100°C to about 120°C.

[0386] The dehydration step of the 1,4:3,6-dianhydrohexitol can be carried out under a pressure condition of about 0.1 torr to about 100.0 torr, about 0.1 torr to about 80.0 torr, or about 0.1 torr to about 20.0 torr.

[0387] The dehydration step of the 1,4:3,6-dianhydrohexitol can be carried out for about 1 hour to about 6 hours, about 1 hour to about 5 hours, or about 2 hours to about 4 hours.

[0388] The dehydration step of 1,4:3,6-dianhydrohexitol can be carried out for about 1 hour to about 5 hours at a temperature of about 80° C. to about 120° C. Preferably, the dehydration step of 1,4:3,6-dianhydrohexitol can be carried out for about 2 hours to about 4 hours at a temperature of about 80° C. to about 120° C. and a pressure of about 0.1 torr to about 20.0 torr.

[0389] After the dehydration step S11, the residual water content, based on the total weight of the composition, may be less than 2,000 ppm, 1,000 ppm or less, 500 ppm or less, or 300 ppm or less. The composition may refer to the dehydrated 1,4:3,6-dianhydrohexitol. When the above range is satisfied, the yield of polyether polyol may be improved, and the mechanical properties of polyurethane foams produced from the polyether polyol may be improved.

[0390] The step (S10-3) may include a step (S12) of preparing a 1-1 polymer. In the step S12, after the dehydration step, the 1,4:3,6-dianhydrohexitol and the substituted or unsubstituted branched alkylene oxide having 3 to 10 carbon atoms may be reacted to prepare a 1-1 polymer.

[0391] In the above S12, the 1,4:3,6-dianhydrohexitol and the substituted or unsubstituted branched alkylene oxide having 3 to 10 carbon atoms may be reacted in a batch reactor, and the branched alkylene oxide may be fed into the batch reactor at a rate of 3 g / min to 6 g / min, 3.5 g / min to 6 g / min, 3.5 g / min to 5.5 g / min, or 4 g / min to 5 g / min.

[0392] The branched alkylene oxide may be charged into the batch reactor in an amount of about 100 parts by weight to about 500 parts by weight, about 150 parts by weight to about 500 parts by weight, or about 150 parts by weight to about 450 parts by weight, relative to 100 parts by weight of the 1,4:3,6-dianhydrohexitol.

[0393] The substituted or unsubstituted branched alkylene oxide having 3 to 10 carbon atoms may be propylene oxide.

[0394] The propylene oxide may be charged into the batch reactor.

[0395] The propylene oxide introduction step can be carried out under temperature conditions of about 80°C to about 130°C, about 90°C to about 130°C, or about 100°C to about 120°C.

[0396] The propylene oxide introduction step can be carried out under a pressure condition of about 0.1 torr to about 100.0 torr, about 0.1 torr to about 50.0 torr, or about 0.1 torr to about 30.0 torr.

[0397] The propylene oxide introduction step can be carried out for about 3 hours to about 10 hours, about 5 hours to about 10 hours, or about 6 hours to about 9 hours. Preferably, the propylene oxide introduction step can be carried out under the temperature conditions of about 80°C to about 120°C and the pressure conditions of about 2 torr to about 8 torr for about 6 hours to about 9 hours.

[0398] The propylene oxide can undergo an addition reaction with the 1,4:3,6-dianhydrohexitol in the batch reactor. The addition reaction produces a 1-1 polymer containing a repeating unit derived from the propylene oxide in the core structure of the 1,4:3,6-dianhydrohexitol. The repeating unit derived from the propylene oxide may refer to a component or structure derived from the propylene oxide, or propylene oxide itself.

[0399] The addition reaction of the 1,4:3,6-dianhydrohexitol and the propylene oxide can be carried out under temperature conditions of about 80°C to about 150°C, about 90°C to about 150°C, or about 100°C to about 140°C.

[0400] The addition reaction of the 1,4:3,6-dianhydrohexitol and the propylene oxide can be carried out for about 1 hour to about 4 hours, about 1 hour to about 3 hours, or about 1 hour to about 2 hours. Preferably, the addition reaction of the 1,4:3,6-dianhydrohexitol and the propylene oxide can be carried out at a temperature of about 100°C to about 140°C for about 1 hour to about 2 hours.

[0401] The above-mentioned step S12 may further include a step of removing the remaining branched alkylene oxide after producing the 1-1 polymer. The remaining branched alkylene oxide may be propylene oxide. By removing the remaining branched alkylene oxide, the reactivity with isocyanate is improved, the hardness of the polyurethane foam is increased, the appearance is improved, and production economy can be improved.

[0402] The step of removing the residual propylene oxide can be carried out under temperature conditions of about 80°C to about 150°C, about 90°C to about 150°C, or about 100°C to about 140°C.

[0403] The step of removing the residual propylene oxide can be carried out under a pressure condition of about 0.1 torr to about 100.0 torr, about 0.1 torr to about 80.0 torr, or about 0.1 torr to about 20.0 torr.

[0404] The step of removing the residual propylene oxide can be carried out for about 10 to about 120 minutes, about 10 to about 60 minutes, or about 20 to about 40 minutes. Preferably, the step of removing the residual propylene oxide can be carried out at a temperature of about 100°C to about 140°C and a pressure of about 0.1 torr to about 20.0 torr for about 20 to about 40 minutes.

[0405] The step (S10-3) may include a step (S13) of preparing a 1-2 polymer. In the step S13, after the preparation of the 1-1 polymer is completed, the 1-1 polymer and the substituted or unsubstituted linear alkylene oxide having 2 to 10 carbon atoms may be reacted to prepare a 1-2 polymer.

[0406] In the above S13, the 1-1 polymer and the substituted or unsubstituted linear alkylene oxide having 2 to 10 carbon atoms can be reacted in the batch reactor, and the linear alkylene oxide may be introduced into the batch reactor at a rate of 1.5 g / min to 3 g / min, 1.6 g / min to 3 g / min, 1.7 g / min to 3 g / min, 1.8 g / min to 3 g / min, or 2.0 g / min to 3 g / min.

[0407] The linear alkylene oxide may be charged into the batch reactor in an amount of about 10 parts by weight to about 100 parts by weight, about 10 parts by weight to about 90 parts by weight, or about 20 parts by weight to about 80 parts by weight, relative to 100 parts by weight of the 1,4:3,6-dianhydrohexitol.

[0408] The linear alkylene oxide of S13 may be about 10 parts by weight to about 100 parts by weight, about 10 parts by weight to about 90 parts by weight, about 10 parts by weight to about 80 parts by weight, about 10 parts by weight to about 70 parts by weight, or about 10 parts by weight to about 60 parts by weight, relative to 100 parts by weight of the branched alkylene oxide of S12. When the amount is within the above range, the reactivity with isocyanate increases, and the hardness and appearance quality of a polyurethane foam produced from the polyether polyol may be improved.

[0409] The substituted or unsubstituted linear alkylene oxide having 2 to 10 carbon atoms may be ethylene oxide.

[0410] The ethylene oxide may be introduced into the batch reactor after the production of the 1-1 polymer has been completed.

[0411] The ethylene oxide introduction step can be carried out under temperature conditions of about 80°C to about 140°C, about 90°C to about 140°C, or about 120°C to about 130°C.

[0412] The ethylene oxide introduction step can be carried out under a pressure condition of about 0.1 torr to about 100.0 torr, about 0.1 torr to about 50.0 torr, or about 0.1 torr to about 30.0 torr.

[0413] The step of introducing ethylene oxide can be carried out for about 1 hour to about 5 hours, about 1 hour to about 3 hours, or about 2 hours to about 3 hours. Preferably, the step of introducing ethylene oxide can be carried out at a temperature of about 120°C to about 130°C and a pressure of about 0.1 torr to about 30.0 torr for about 2 hours to about 3 hours.

[0414] The ethylene oxide can undergo an addition reaction with the 1-1 polymer in the batch reactor. The addition reaction can produce a 1-2 polymer, which contains the ethylene oxide-derived repeating unit in the 1-1 polymer. Alternatively, a 1-2 polymer can be produced, which contains the propylene oxide-derived repeating unit and the ethylene oxide-derived repeating unit as a block copolymer. The ethylene oxide-derived repeating unit may refer to a component or structure derived from ethylene oxide, or ethylene oxide itself.

[0415] The addition reaction of the 1-1 polymer and the ethylene oxide can be carried out under temperature conditions of about 80°C to about 150°C, about 90°C to about 150°C, or about 100°C to about 140°C.

[0416] The addition reaction of the 1-1 polymer and the ethylene oxide can be carried out for about 1 hour to about 4 hours, about 1 hour to about 3 hours, or about 1 hour to about 2 hours. Preferably, the addition reaction of the 1-1 polymer and the ethylene oxide can be carried out at a temperature of about 100° C. to about 140° C. for about 1 hour to about 2 hours.

[0417] The above-mentioned step S13 may further include a step of removing the remaining linear alkylene oxide after producing the 1-2 polymer. The remaining linear alkylene oxide may be ethylene oxide.

[0418] The step of removing the residual ethylene oxide can be carried out under temperature conditions of about 80°C to about 150°C, about 90°C to about 150°C, or about 100°C to about 140°C.

[0419] The step of removing the residual propylene oxide can be carried out under a pressure condition of about 0.1 torr to about 100.0 torr, about 0.1 torr to about 80.0 torr, or about 0.1 torr to about 20.0 torr.

[0420] The step of removing the residual ethylene oxide can be carried out for about 30 minutes to about 200 minutes, about 30 minutes to about 100 minutes, or about 40 minutes to about 80 minutes. Preferably, the step of removing the residual ethylene oxide can be carried out at a temperature of about 100°C to about 140°C and a pressure of about 0.1 torr to about 20.0 torr for about 40 minutes to about 80 minutes.

[0421] The step (S10-3) may include a step (S14) of removing residual metal ions and a step (S15) of filtering. In step S14, a step of removing residual metal ions in the composition containing the 1-2 polymer may be performed after step S13. In step S15, a step of filtering the composition may be performed.

[0422] In S14, the metal ions can be removed using a metal adsorbent and filter aid.

[0423] The metal adsorbent can adsorb, for example, residual potassium ions. The filter aid facilitates the filtering process of the polyether polyol. If only the metal adsorbent is used, the filtering process of the polyether polyol may not be performed smoothly. If only the filter aid is used, the content of residual metal ions may increase, which may result in deterioration of the physical properties of the final product. Therefore, it is preferable to use both the metal adsorbent and the filter aid.

[0424] The metal adsorbent may be AMBOSOL.

[0425] The filter aid may be diatomaceous earth.

[0426] The metal adsorbent and filter aid may be added to the polyether polyol after the reaction in the form of an aqueous dispersion. The metal adsorbent and filter aid may be added to the polyether polyol after the reaction in an amount of 1 to 10 parts by weight, 1 to 8 parts by weight, 2 to 8 parts by weight, 3 to 8 parts by weight, or 3 to 6 parts by weight, based on 100 parts by weight of the 1,4:3,6-dianhydrohexitol.

[0427] After step S14, a neutralization step of the polyether polyol can be carried out. The neutralization step may be carried out for about 1 hour to about 4 hours, about 1 hour to about 3 hours, or about 1 hour to about 2 hours. Thereafter, the polyether polyol after the neutralization step can be subjected to a water removal step. The water removal step can be carried out at about 90°C to about 130°C, about 95°C to about 130°C, or about 100°C to about 130°C. If necessary, a step of detecting the residual metal ions can be carried out. If the residual metal ions are not detected, the polyether polyol can be maintained under a temperature condition of about 50°C to about 90°C, about 50°C to about 80°C, or about 60°C to about 80°C.

[0428] In S15, the polyether polyol from which the water has been removed may be filtered to remove the additives and by-products.

[0429] After step S15, the polyether polyol may have a residual metal content of 100 ppm or less, 80 ppm or less, 50 ppm or less, 30 ppm or less, 10 ppm or less, 5 ppm or less, 4 ppm or less, 3 ppm or less, 2 ppm or less, or 1 ppm or less. When the metal content is within the above range, the mechanical properties of a polyurethane foam produced from the polyether polyol may be improved.

[0430] The production method of the present invention may include a step (S20-3) of producing a second polymer, in which the first polymer and a second alkylene oxide are reacted in the presence of a double metal cyanide catalyst to produce the second polymer.

[0431] The second polymer has the same meaning as the polyether polyol.

[0432] The weight ratio of the double metal cyanide catalyst to the first polymer may be 1:100 to 1:20,000, 1:500 to 1:10,000, 1:1,000 to 1:10,000, or 1:2,000 to 1:10,000. When the ratio is within the above range, it is economical and the polymerization process can be carried out efficiently.

[0433] The step S20 may include a step of heating a reactor into which the first polymer is introduced to perform a dehydration process, and a step of reacting the first polymer with the second alkylene oxide in the presence of the double metal cyanide catalyst after the dehydration process to produce a second polymer.

[0434] The second alkylene oxide may be a substituted or unsubstituted branched alkylene oxide having 3 to 10 carbon atoms, or a mixture of the substituted or unsubstituted branched alkylene oxide having 3 to 10 carbon atoms and a substituted or unsubstituted linear alkylene oxide having 2 to 10 carbon atoms.

[0435] The branched alkylene oxide may be propylene oxide.

[0436] The linear alkylene oxide may be ethylene oxide.

[0437] It is not preferable to react only the first polymer with ethylene oxide in the presence of the double metal cyanide catalyst, but since the double metal cyanide catalyst has low reactivity with ethylene oxide, it is preferable to react a mixture of propylene oxide and ethylene oxide in order to add ethylene groups to the first polymer.

[0438] The double metal cyanide catalyst may be similar to the double metal cyanide catalysts described above.

[0439] In the above S20-3, when the double metal cyanide catalyst is used, the production of mono-ol can be reduced during the polymerization of the first polymer and the second alkylene oxide, which can reduce the degree of unsaturation in the polyether polyol, facilitate crosslinking and high molecular weight production during the production of polyurethane resin, and improve the physical properties of the polyurethane resin.

[0440] In S20-3, it is preferable not to use the alkali catalyst. Furthermore, it is also preferable not to use the double metal cyanide catalyst and the alkali catalyst together in S20-3. Depending on the selective activity of the double metal cyanide catalyst, the amount of alkali catalyst used may increase, and a large amount of alkali catalyst may remain after producing polyether polyol. This necessarily requires an additional process to remove the alkali catalyst, which can reduce the efficiency of the production process. Furthermore, the alkali catalyst increases the production of monools, which can hinder crosslinking and high molecular weight formation during polyurethane resin production, thereby reducing the physical properties of the polyurethane resin.

[0441] The polyether polyol composition produced according to the above-described method for producing a polyether polyol according to the present invention may contain at least one first unit derived from one or more 1,4:3,6-dianhydrohexitols and a second unit derived from an alkylene oxide.

[0442] The 1,4:3,6-dianhydrohexitol and isosorbide may be the same as the 1,4:3,6-dianhydrohexitol and isosorbide described above.

[0443] The alkylene oxide may be the same as the alkylene oxide described above.

[0444] The polyether polyol composition may have a degree of unsaturation of 0.02 meq / g or less, as measured by the following method.

[0445] <Measurement method> 1) A first flask containing 30 g of the polyether polyol and a second flask containing no polyether polyol are prepared, and 50 ml of mercury acetate is added to each of the first flask and the second flask, followed by stirring for 30 minutes.

[0446] 2) 9 g of sodium bromide (NaBr) is added to each of the first flask and the second flask, and then the mixture is stirred for 30 minutes.

[0447] 3) Add 0.5 ml of 1% phenolphthalein indicator to each of the first and second flasks, and titrate with 0.1 N potassium hydroxide (KOH).

[0448] 4) Calculate the degree of unsaturation using the following formula 1.

[0449] [Formula 1] Unsaturation degree (meq / g)=(V s ×V b ×0.1×F) / M

[0450] In the above formula 1, the V s is the amount (ml) of 0.1 N potassium hydroxide (KOH) added to the first flask, and V b is the amount (ml) of the 0.1 N potassium hydroxide (KOH) added to the second flask, F is a factor of the 0.1 N potassium hydroxide (KOH), and M is the weight (g) of the polyether polyol added to the first flask.

[0451] The degree of unsaturation means the content of monool in the polyether polyol. Specifically, the degree of unsaturation may be expressed as mg unsaturation equivalent (meq / g) per 1 g of the polyether polyol.

[0452] The mono-ol can be produced by addition polymerization of propylene oxide with 1,4:3,6-dianhydrohexitol using a catalyst, specifically, by rearrangement of propylene oxide to allyl alcohol.

[0453] The monool may cause a decrease in the number of functional groups of the polyether polyol, and when the polyether polyol is used to produce polyurethane, crosslinking and high molecular weight may be hindered, resulting in a decrease in the physical properties of the polyurethane resin.

[0454] The polyether polyol composition may have an unsaturation degree of 0.020 meq / g or less, 0.015 meq / g or less, 0.013 meq / g or less, 0.010 meq / g or less, 0.005 meq / g or less, 0.0045 meq / g or less, 0.0040 meq / g or less, 0.0038 meq / g or less, 0.0036 meq / g or less, 0.0034 meq / g or less, 0.0033 meq / g or less, 0.0032 meq / g or less, 0.0031 meq / g or less, or 0.0030 meq / g or less. When the unsaturation degree is within the above range, the polyether polyol composition has excellent reactivity with isocyanate, and when a polyurethane resin is produced from the polyether polyol composition, crosslinking and high molecular weight can be smoothly carried out, resulting in improved physical properties of the polyurethane resin.

[0455] The polyether polyol composition may contain the compound represented by Chemical Formula 3 above.

[0456] The polyether polyol composition may contain the compounds of Chemicals A to G described above.

[0457] The polyether polyol composition may further contain the above-mentioned antioxidant.

[0458] The polyether polyol composition may have the above-mentioned CPR (Controlled Polymerization Rate) value.

[0459] The polyether polyol composition may have the acid value described above.

[0460] The polyether polyol composition may have the number average molecular weight (Mn) and polydispersity index (PDI) described above.

[0461] The polyether polyol composition may have the aforementioned APHA (American Public Health Association) color values.

[0462] The polyether polyol composition may have the above-mentioned active oxygen content.

[0463] The viscosity of the polyether polyol composition may be similar to the viscosity described above.

[0464] The composition for producing polyurethane according to the present invention may contain the above-mentioned polyether polyol composition and isocyanate-based composition.

[0465] A polyurethane foam can be produced from the composition for producing a polyurethane, which may be the same as the composition for producing a polyurethane described above.

[0466] The battery module according to the present invention may include a housing, a plurality of battery cells accommodated inside the housing, and a polyurethane foam disposed between the plurality of battery cells. The polyurethane foam may include a composition for producing a polyurethane, the composition including a polyether polyol composition produced by the above-described method for producing a polyether polyol and an isocyanate-based composition, and the polyether polyol composition may include at least one first unit derived from 1,4:3,6-dianhydrohexitol and a second unit derived from an alkylene oxide.

[0467] For the battery module according to the present invention, the same contents as those of FIG. 3 can be referred to.

[0468] <Polyol composition according to the sixth embodiment> The polyether polyol according to the present invention contains first units derived from at least one kind of 1,4:3,6-dianhydrohexitol and second units derived from an alkylene oxide, and the content of the primary alcohol may be 10 mol % to 90 mol %.

[0469] The 1,4:3,6-dianhydrohexitol and isosorbide may be the same as the 1,4:3,6-dianhydrohexitol and isosorbide described above.

[0470] The alkylene oxide may be the same as the alkylene oxide described above.

[0471] The polyether polyol may have a primary alcohol content of 10 mol% to 90 mol%, 15 mol% to 90 mol%, 20 mol% to 90 mol%, 25 mol% to 90 mol%, or 30 mol% to 90 mol%. 13 This can be measured as the relative proportion of a peak at about 61 ppm in a C NMR spectrum. When the above range is satisfied, the reactivity with isocyanate is excellent, and when a polyurethane foam is produced from the polyether polyol, crosslinking and high molecular weight can be smoothly carried out, resulting in improved physical properties of the polyurethane foam.

[0472] The polyether polyol may have an unsaturation degree of 0.020 meq / g or less, 0.015 meq / g or less, 0.013 meq / g or less, 0.010 meq / g or less, 0.005 meq / g or less, 0.0045 meq / g or less, 0.0040 meq / g or less, 0.0038 meq / g or less, 0.0036 meq / g or less, 0.0034 meq / g or less, 0.0033 meq / g or less, 0.0032 meq / g or less, 0.0031 meq / g or less, or 0.0030 meq / g or less. When the degree of unsaturation is within the above range, the polyether polyol has excellent reactivity with isocyanate, and crosslinking and polymerization can be smoothly carried out when a polyurethane foam is produced from the polyether polyol, thereby improving the physical properties of the polyurethane foam.

[0473] The polyether polyol may contain the compound represented by Chemical Formula 3 above.

[0474] The polyether polyol composition may contain the compounds of Chemicals A to G described above.

[0475] The polyether polyol composition may further contain the above-mentioned antioxidant.

[0476] The polyether polyol composition may have the acid value described above.

[0477] The polyether polyol composition may have the number average molecular weight (Mn) and polydispersity index (PDI) described above.

[0478] The polyether polyol composition may have the aforementioned APHA (American Public Health Association) color values.

[0479] The polyether polyol composition may have the above-mentioned active oxygen content.

[0480] The viscosity of the polyether polyol composition may be similar to the viscosity described above.

[0481] The method for producing a polyether polyol according to the present invention includes: (a) preparing a first polymer containing at least one unit derived from 1,4:3,6-dianhydrohexitol; and (b) preparing a second polymer by reacting the first polymer with a mixture containing ethylene oxide and propylene oxide in the presence of a double metal cyanide catalyst. The polyether polyol may have a primary alcohol content of 10 mol% to 90 mol%.

[0482] 9 is a simplified flow chart illustrating a process for preparing a polyether polyol according to the present invention. Referring to FIG. 9, the method of the present invention may include a step (S10-4) of preparing a first polymer. Step S10-4 may be carried out in the same manner as step S10-3 described above.

[0483] The production method of the present invention may include a step (S20-4) of producing a second polymer. Step S20-4 can be carried out in the same manner as step S20-3 described above.

[0484] The composition for producing polyurethane according to the present invention may comprise a polyol composition containing a polyether polyol that contains at least one first unit derived from 1,4:3,6-dianhydrohexitol and a second unit derived from an alkylene oxide and has a primary alcohol content of 10 mol % to 90 mol %, and an isocyanate composition.

[0485] A polyurethane foam can be produced from the composition for producing a polyurethane, which may be the same as the composition for producing a polyurethane described above.

[0486] The battery module according to the present invention includes a housing, a plurality of battery cells accommodated inside the housing, and polyurethane foam disposed between the plurality of battery cells. The polyurethane foam includes a composition for producing polyurethane, the composition including a polyol composition and an isocyanate-based composition. The polyol composition may include a polyether polyol having a primary alcohol content of 10 mol% to 90 mol% and including at least one first unit derived from 1,4:3,6-dianhydrohexitol and a second unit derived from an alkylene oxide.

[0487] For the battery module according to the present invention, the same contents as those of FIG. 3 can be referred to.

[0488] The present invention will be described in more detail below with reference to examples and comparative examples. However, the following examples and comparative examples are merely illustrative examples for explaining the present invention in more detail, and the present invention is not limited by the following examples and comparative examples.

[0489] <First Production Example, First Example, First Experimental Example> 1st manufacturing example Preparation Example 1-1-Preparation of Compound Represented by Chemical A 803 g of isosorbide and 23 g of potassium hydroxide were placed in a pressurizable and heatable reactor. The inside of the reactor was then purged with nitrogen, heated to 112°C, and water in the reactor was removed under vacuum and reduced pressure conditions.

[0490] 1,900 g of propylene oxide was added to the reactor at a constant rate, and the reaction was carried out for 6 hours at a temperature of about 115°C, while the temperature of the reactor was controlled so as not to exceed 117°C.

[0491] The mixture was stirred until all of the propylene oxide remaining in the reactor had reacted, and after the reaction was completed, the temperature of the reactor was heated to 123°C. Then, 310g of ethylene oxide was added to the reactor at a constant rate, and the reaction was carried out for 1 hour and 30 minutes at a temperature of about 120°C. At this time, the temperature of the reactor was controlled so as not to exceed 125°C.

[0492] After the reaction was completed, the temperature of the reactor was lowered to 90°C, and then 50 g of AMBOSOL and 5 g of diatomaceous earth were added to the reactor, and the mixture was stirred at a temperature of about 100°C for 3 hours to provide metal ions remaining in the reactants.

[0493] After confirming that no metal ions remained in the reaction mixture, the temperature of the reactor was lowered to 70°C, and the remaining by-products were removed using a filter to obtain 3,013 g of a compound represented by the following formula A, the structure of which is shown in Figure 3. 13 This was confirmed by C NMR spectroscopy.

[0494] [ka]

[0495] 13 C NMR: δ61.31, 61.62, 65.95, 66.45, 66.58, 68.76, 70.38, 70.52, 70.70, 70.82 , 70.94, 73.00, 73.23, 73.34, 73.96, 74.31, 75.05, 75.36, 75.82, 76.50ppm.

[0496] Preparation Example 1-2-Preparation of Compound Represented by Chemical Formula B The same process as in Production Example 1-1 was carried out, except that 580 g of ethylene oxide was added instead of 310 g of ethylene oxide in Production Example 1-1, to obtain 3,283 g of a compound represented by the following chemical formula B, the structure of which is: 13 This was confirmed by C NMR spectroscopy.

[0497] [ka]

[0498] 13 C NMR: δ61.21, 61.63, 65.96, 66.43, 66.57, 68.72, 70.11, 70.23, 70.70, 70.90 , 70.96, 73.12, 73.43, 73.64, 73.96, 74.32, 75.15, 75.38, 75.92, 76.52ppm.

[0499] Preparation Example 1-3 - Preparation of Compound Represented by Chemical Formula C 2,603 ​​g of a compound represented by the following chemical formula C was obtained by the same process as in Production Example 1-1, except that 520 g of ethylene oxide was added instead of 310 g of ethylene oxide and 1,280 g of propylene oxide was added instead of 1,900 g of propylene oxide. The structure of the compound is: 13 This was confirmed by C NMR spectroscopy.

[0500] [ka]

[0501] 13 C NMR: δ61.22, 61.65, 64.86, 66.53, 66.58, 68.22, 69.12, 70.33, 70.81, 70.92 , 70.96, 73.02, 73.13, 73.54, 73.96, 74.22, 75.25, 75.39, 75.92, 76.50ppm.

[0502] Preparation Example 1-4-Preparation of Compound Represented by Chemical Formula D 2,443 g of a compound represented by the following chemical formula D was obtained by the same process as in Production Example 1-1, except that 560 g of ethylene oxide was added instead of 310 g of ethylene oxide and 1,080 g of propylene oxide was added instead of 1,900 g of propylene oxide. The structure of the compound is: 13This was confirmed by C NMR spectroscopy.

[0503] [ka]

[0504] 13 C NMR: δ61.23, 61.35, 64.67, 66.26, 66.37, 68.12, 69.32, 70.15, 70.71, 70.82 , 70.96, 73.03, 73.12, 73.54, 73.97, 74.22, 75.15, 75.39, 75.93, 76.50ppm.

[0505] Preparation Example 1-5-Preparation of Compound Represented by Chemical Formula E 2,453 g of a compound represented by the following chemical formula E was obtained by the same process as in Production Example 1-1, except that 680 g of ethylene oxide was added instead of 310 g of ethylene oxide and 990 g of propylene oxide was added instead of 1,900 g of propylene oxide. The structure of the compound is: 13 This was confirmed by C NMR spectroscopy.

[0506] [ka]

[0507] 13 C NMR: δ61.22, 61.65, 63.75, 66.24, 66.49, 68.12, 69.15, 70.23, 70.83, 70.91 , 70.93, 73.12, 73.15, 73.55, 73.97, 74.21, 75.30, 75.40, 75.82, 76.54ppm.

[0508] Preparation Example 1-6 - Preparation of Compound Represented by Chemical Formula M 796 g of isosorbide and 22 g of potassium hydroxide were placed in a pressurizable and heatable reactor. The inside of the reactor was then purged with nitrogen and heated to 112°C, after which moisture in the reactor was removed under vacuum and reduced pressure conditions.

[0509] 1,904 g of propylene oxide and 300 g of ethylene oxide were simultaneously added to the reactor at a constant rate, and the temperature of the reactor was heated to 122°C. Then, the reaction was carried out for 7 hours at a temperature of about 120°C. At this time, the temperature of the reactor was controlled so as not to exceed 125°C.

[0510] After the reaction was completed, the temperature of the reactor was lowered to 90°C, and then 50 g of AMBOSOL and 5 g of diatomaceous earth were added to the reactor, and the mixture was stirred at a temperature of about 100°C for 3 hours to provide metal ions remaining in the reactants.

[0511] After confirming that no metal ions remained in the reaction mixture, the temperature of the reactor was lowered to 70°C, and the remaining by-products were removed using a filter to obtain 3,000 g of a compound represented by the following formula M, the structure of which is shown in Figure 4. 13 This was confirmed by C NMR spectroscopy.

[0512] [ka]

[0513] 13 C NMR: δ65.91, 65.99, 66.74, 71.04, 72.27, 72.92, 73.17, 74.13, 74.46, 75.27, 75.39, 75.51, 75.61, 75.70, 76.11, 76.20, 76.42ppm.

[0514] Preparation Example 1-7-Preparation of Compound Represented by N 2,086 g of a compound represented by the following chemical formula N was obtained by the same process as in Production Example 1-6, except that 980 g of ethylene oxide was added instead of 300 g of ethylene oxide and 310 g of propylene oxide was added instead of 1,904 g of propylene oxide. The structure of the compound is: 13 This was confirmed by C NMR spectroscopy.

[0515] [ka]

[0516] 13 C NMR: δ65.82, 65.98, 66.75, 71.14, 72.37, 73.42, 73.57, 74.12, 74.56, 75.57, 75.69, 75.71, 75.91, 76.10, 76.13, 76.80, 76.88ppm.

[0517] Preparation Example 1-8-Preparation of Compound Represented by O 810 g of isosorbide and 20 g of potassium hydroxide were placed in a pressurizable and heatable reactor. The inside of the reactor was then purged with nitrogen and heated to 112°C, after which moisture in the reactor was removed under vacuum and reduced pressure conditions.

[0518] 1,900 g of propylene oxide was added to the reactor at a constant rate and the reaction was carried out at a temperature of 115°C for 2 hours. Then, 300 g of ethylene oxide was added at the same time at a constant rate and the temperature of the reactor was heated to 122°C. Then, the reaction was carried out at a temperature of about 120°C for 7 hours. At this time, the temperature of the reactor was controlled so as not to exceed 125°C.

[0519] After the reaction was completed, the temperature of the reactor was lowered to 90°C, and 50g of AMBOSOL and 5g of diatomaceous earth were added to the reactor, and the mixture was stirred at a temperature of about 100°C for 3 hours to provide metal ions remaining in the reactants.

[0520] After confirming that no metal ions remained in the reaction mixture, the temperature of the reactor was lowered to 70°C, and the remaining by-products were removed using a filter to obtain 3,010 g of a compound represented by the following formula O, the structure of which is: 13 This was confirmed by C NMR spectroscopy.

[0521] [ka]

[0522] 13 C NMR: δ65.90, 65.98, 66.75, 71.14, 72.28, 72.93, 73.15, 74.12, 74.46, 74.50 , 74.55, 74.57, 75.37, 75.49, 75.58, 75.63, 75.78, 76.13, 76.21, 76.45ppm.

[0523] Example 1 - Production of polyurethane foam Example 1-1 30 g of the compound prepared in Preparation Example 1-1 was placed in a plastic beaker. Then, 3.5 g of distilled water, 0.2 g of B-8629 (Evonik) and 0.9 g of L-1501 (Momentive) as silicone foam stabilizers, 0.5 g of D-33LV (Air Products) and 0.1 g of M-50 (Tosoh) as amine catalysts, and 0.6 g of diethanolamine as a crosslinking agent were added to the beaker. The mixture was then mixed at 4,000 rpm for 3 minutes using a high-speed stirrer to obtain a mixture.

[0524] Thereafter, 58 g of methylene diphenyl isocyanate (CG-3701S, Kumho Co., Ltd.) was added to the mixture, which was then foamed to produce a polyurethane foam.

[0525] Example 1-2 A polyurethane foam was prepared in the same manner as in Example 1-1, except that 30 g of the compound prepared in Preparation Example 1-2 was added to the plastic beaker instead of 30 g of the compound prepared in Preparation Example 1-1.

[0526] Examples 1-3 A polyurethane foam was prepared in the same manner as in Example 1-1, except that 30 g of the compound prepared in Preparation Example 1-3 was added to the plastic beaker instead of 30 g of the compound prepared in Preparation Example 1-1.

[0527] Examples 1-4 A polyurethane foam was prepared in the same manner as in Example 1-1, except that 30 g of the compound prepared in Preparation Example 1-4 was added to the plastic beaker instead of 30 g of the compound prepared in Preparation Example 1-1.

[0528] Examples 1-5 A polyurethane foam was prepared in the same manner as in Example 1-1, except that 30 g of the compound prepared in Preparation Example 1-5 was added to the plastic beaker instead of 30 g of the compound prepared in Preparation Example 1-1.

[0529] Comparative Example 1-1 A polyurethane foam was prepared in the same manner as in Example 1-1, except that 30 g of the compound prepared in Preparation Example 1-6 was added to the plastic beaker instead of 30 g of the compound prepared in Preparation Example 1-1.

[0530] Comparative Example 1-2 A polyurethane foam was prepared in the same manner as in Example 1-1, except that 30 g of the compound prepared in Preparation Example 1-7 was added to the plastic beaker instead of 30 g of the compound prepared in Preparation Example 1-1.

[0531] Comparative Examples 1-3 A polyurethane foam was prepared in the same manner as in Example 1-1, except that 30 g of the compound prepared in Preparation Example 1-8 was added to the plastic beaker instead of 30 g of the compound prepared in Preparation Example 1-1.

[0532] First experimental example Experimental Example 1-1 - Measurement of acid value 2.75 g of each of the compounds prepared in Preparation Examples 1-1 to 1-8 was added to each vessel containing the phthalic anhydride solution, and the mixture was reacted for 30 minutes at 115° C. Thereafter, the pH was monitored while titrating with 0.5 N aqueous sodium hydroxide (NaOH), and the volume (ml) of sodium hydroxide (NaOH) required to reach the inflection point was measured.

[0533] Separately, a blank test was conducted, in which the volume (ml) of sodium hydroxide (NaOH) required to reach the pH inflection point was measured in the same manner as above.

[0534] The acid value of the compound was then calculated based on the measured values, and the results are shown in Table 1 below.

[0535] Experimental Example 1-2: Measurement of number average molecular weight The number average molecular weights of the compounds prepared in Preparation Examples 1-1 to 1-8 were calculated using the acid value measured in Experimental Example 1-1 and the following Relational Formula 1, and the results are shown in Table 1 below.

[0536] [Equation 1] Number average molecular weight (g / mol) = (56,100 x equivalent weight) / measured acid number

[0537] Experimental Example 1-3 - Measurement of polydispersity index 0.1 g of each compound prepared in Preparation Examples 1-1 to 1-8 was dissolved in 10 g of THF, and the insoluble matter was removed using a filter. The resulting solution was subjected to gel permeation chromatography (GPC) to measure the polydispersity index. The results are shown in Table 1 below.

[0538] Experimental Example 1-4-Measurement of the content of primary alcohol hydroxyl groups (-OH) The compounds produced in Production Examples 1-1 to 1-8 were 13 After confirming with C NMR spectrum, 13 The peak at about 61 ppm shown in the C NMR spectrum was analyzed to calculate the content, and the results are shown in Table 1 below.

[0539] Experimental Example 1-5 - Evaluation of high temperature storage stability The compounds prepared in Preparation Examples 1-1 to 1-8 were each placed in a 450 ml sample bottle and stored in an oven at 45°C for 150 days. The high-temperature storage stability was evaluated according to the following criteria, and the results are shown in Table 1 below.

[0540] -○: No layer separation occurred -×: Layer separation has occurred

[0541] [Table 1]

[0542] Experimental Example 1-6 - Hardness evaluation The polyurethane foams produced in Examples 1-1 to 1-5 and Comparative Examples 1-1 to 1-3 were each cut into 5 cm x 5 cm samples. The resilience of each sample was measured at room temperature using a Universal Testing Machine (UTM) when it was compressed by 25% and when it was compressed by 50%. The results are shown in Table 2 below.

[0543] Experimental Example 1-7 - Evaluation of elongation rate The polyurethane foams produced in Examples 1-1 to 1-5 and Comparative Examples 1-1 to 1-3 were each cut into 5 cm x 5 cm samples, and the elongation was measured using a Universal Testing Machine (UTM) according to ASTM D-3574-86. The results are shown in Table 2 below.

[0544] Experimental Example 1-8 - Evaluation of pinhole occurrence The occurrence of pinholes in the polyurethane foams produced in Examples 1-1 to 1-5 and Comparative Examples 1-1 to 1-3 was evaluated according to the following criteria, and the results are shown in Table 2 below.

[0545] -Good: Not more than one pinhole with a diameter of 3 mm or less in a surface area of ​​800 mm x 800 mm of polyurethane foam - Poor: Two or more pinholes with a diameter of 3 mm or less in a surface area of ​​800 mm x 800 mm of polyurethane foam

[0546] Experimental Example 1-9 - Appearance evaluation The appearance of the polyurethane foams produced in Examples 1-1 to 1-5 and Comparative Examples 1-1 to 1-3 was evaluated according to the following criteria, and the results are shown in Table 2 below.

[0547] -Good: When visually observed, the entire surface of the polyurethane foam is smooth. - Poor: When visually observed, roughness is observed on at least a part of the entire surface of the polyurethane foam.

[0548] Experimental Example 1-10 - Evaluation of foaming properties The uniformity of the foam cells on the surface and cross section of the polyurethane foams produced in Examples 1-1 to 1-5 and Comparative Examples 1-1 to 1-3 was visually observed, and the density of the polyurethane foams after foaming was measured. The foaming characteristics were evaluated according to the following criteria, and the results are shown in Table 2 below.

[0549] ◎: The foam cells are uniform and the density is 0.020 g / cm 3 ~0.030g / cm 3 has a density range of -○: Foam cells are uniformly observed, but the density is less than 0.020 g / cm 3 ~0.030g / cm 3 Density range of - ×: The foam cells are not uniform and the density is 0.020 g / cm 3 ~0.030g / cm 3 Density range of

[0550] Experimental Example 1-11 - Hue Evaluation To evaluate the color of the polyurethane foams produced in Examples 1-1 to 1-5 and Comparative Examples 1-1 to 1-3, the yellowness index was measured using a Miniscan XE Plus (Hunter Labs) in accordance with ASTM E313-96, and the results are shown in Table 2. The higher the measured value, the closer to yellow the foam is, and the lower the measured value, the clearer and more transparent the foam is.

[0551] [Table 2]

[0552] As can be seen from Tables 1 and 2 above, the polyol compositions of Examples 1-1 to 1-5, which contain a compound represented by Chemical Formula 1, exhibited superior mechanical and appearance properties compared to Comparative Examples 1-1 to 1-3. Specifically, the compounds contained in the polyol compositions of Examples 1-1 to 1-5 have a structure in which a branched alkylene group is bonded to a core structure containing units derived from 1,4:3,6-dianhydrohexitol, and have the form of a block copolymer in which a linear alkylene group is bonded to the branched alkylene group. The compounds may also exhibit a high content of primary alcohol hydroxyl groups, resulting in excellent reactivity with isocyanates. As a result, polyurethane foams produced from these polyol compositions may have improved mechanical properties. Furthermore, the compounds contained in the polyol compositions of Examples 1-1 to 1-5 may exhibit improved appearances of polyurethane foams produced from these polyol compositions by adjusting the ratio of the branched alkylene group and linear alkylene group content.

[0553] <Second Production Example, Second Example, Second Experimental Example> Second Production Example - Production of Polyol Composition Manufacturing Example 2-1 802 g of isosorbide and 23 g of potassium hydroxide were placed in a pressurizable and heatable reactor. The inside of the reactor was then purged with nitrogen and heated to 112°C, after which moisture in the reactor was removed under vacuum and reduced pressure conditions.

[0554] While 1,900 g of propylene oxide was added to the reactor at a constant rate, the reaction was carried out for 6 hours at a temperature of about 115°C, while the temperature of the reactor was controlled so as not to exceed 115°C.

[0555] The mixture was stirred until all of the propylene oxide remaining in the reactor had reacted, and after the reaction was completed, the temperature of the reactor was heated to about 120°C. Then, 280g of ethylene oxide was added to the reactor at a constant rate, and the reaction was carried out for 1 hour and 30 minutes at a temperature of about 120°C. At this time, the temperature of the reactor was controlled so as not to exceed 125°C.

[0556] After the reaction was completed, the reactor was cooled to 90°C, and 50g of AMBOSOL and 5g of diatomaceous earth were added to the reactor. The mixture was stirred at a temperature of about 100°C for 3 hours to remove any metal ions remaining in the reaction mixture.

[0557] After confirming that no residual metal ions were detected in the reaction mixture, the temperature of the reactor was lowered to 70°C, and the remaining by-products were removed using a filter to obtain 3,000 g of a polyol composition.

[0558] Manufacturing Example 2-2 A polyol composition was obtained in the same manner as in Production Example 2-1, except that 2,100 g of propylene oxide was added to the reactor instead of 1,900 g of propylene oxide.

[0559] Manufacturing Example 2-3 A polyol composition was obtained in the same manner as in Production Example 2-1, except that 310 g of ethylene oxide was added to the reactor instead of 280 g of ethylene oxide in Production Example 2-1.

[0560] Manufacturing Example 2-4 A polyol composition was obtained by the same steps as in Production Example 2-1, except that 2,000 g of propylene oxide was added to the reactor instead of 1,900 g of propylene oxide, and 300 g of ethylene oxide was added instead of 280 g of ethylene oxide.

[0561] Manufacturing Example 2-5 A polyol composition was obtained by the same steps as in Production Example 2-1, except that 810 g of isosorbide and 25 g of potassium hydroxide were added to the reactor instead of 802 g of isosorbide and 23 g of potassium hydroxide in Production Example 2-1.

[0562] Manufacturing Example 2-6 A polyol composition was obtained in the same manner as in Preparation Example 2-1, except that 45 g of AMBOSOL and 6 g of diatomaceous earth were added to the reactor instead of 50 g of AMBOSOL and 5 g of diatomaceous earth in Preparation Example 2-1.

[0563] Manufacturing Example 2-7 A polyol composition was obtained by the same process as in Preparation Example 2-1, except that instead of stirring for 3 hours to remove metal ions remaining in the reaction mixture in Preparation Example 2-1, the reaction mixture was stirred for 1 hour to remove metal ions remaining in the reaction mixture.

[0564] Manufacturing Example 2-8 A polyol composition was obtained in the same manner as in Preparation Example 2-1, except that 40 g of AMBOSOL and 5 g of diatomaceous earth were added to the reactor instead of 50 g of AMBOSOL and 5 g of diatomaceous earth in Preparation Example 2-1, and the mixture was stirred for 1 hour to remove metal ions remaining in the reaction mixture instead of stirring for 3 hours to remove metal ions remaining in the reaction mixture.

[0565] Comparative Manufacturing Example 2-1 386 g of monopropylene glycol (MPG) and 17.5 g of potassium hydroxide were placed in a pressurizable and heatable reactor. The inside of the reactor was then purged with nitrogen and heated to 112°C, after which the water in the reactor was removed under vacuum and reduced pressure conditions.

[0566] 2,132 g of propylene oxide was added to the reactor at a constant rate, and the reaction was carried out for 6 hours and 30 minutes at a temperature of about 110°C, while the temperature of the reactor was controlled so as not to exceed 115°C.

[0567] The mixture was stirred until all of the propylene oxide remaining in the reactor had reacted, and after the reaction was completed, the temperature of the reactor was heated to about 122°C. Then, 280g of ethylene oxide was added to the reactor at a constant rate, and the reaction was carried out for 1 hour and 30 minutes at a temperature of about 120°C. At this time, the temperature of the reactor was controlled so as not to exceed 125°C.

[0568] After the reaction was completed, the reactor was cooled to 90°C, and 50g of AMBOSOL and 5g of diatomaceous earth were added to the reactor. The mixture was stirred at a temperature of about 115°C for 3 hours to remove any metal ions remaining in the reaction mixture.

[0569] After confirming that no residual metal ions were detected in the reaction mixture, the temperature of the reactor was lowered to 70°C, and the remaining by-products were removed using a filter to obtain 2,800 g of a polyol composition.

[0570] Comparative Manufacturing Example 2-2 A polyol composition was obtained in the same manner as in Comparative Preparation Example 2-1, except that 386 g of dipropylene glycol (DPG) was added to the reactor instead of 386 g of monopropylene glycol (MPG) in Comparative Preparation Example 2-1.

[0571] Comparative Manufacturing Example 2-3 A polyol composition was obtained by the same process as in Comparative Preparation Example 2-1, except that instead of stirring for 3 hours to remove metal ions remaining in the reactant in Comparative Preparation Example 2-1, the reactant was stirred for 1 hour to remove metal ions remaining in the reactant.

[0572] Comparative Manufacturing Example 2-4 A polyol composition was obtained by the same process as in Comparative Preparation Example 2-2, except that instead of stirring for 3 hours to remove metal ions remaining in the reactant in Comparative Preparation Example 2-2, the reactant was stirred for 1 hour to remove metal ions remaining in the reactant.

[0573] Example 2 - Polyurethane Foam Production Example 2-1 30 g of the polyol composition prepared in Preparation Example 2-1 was placed in a plastic beaker. Then, 4.0 g of distilled water, 0.3 g of B-8629 (Evonik) and 1.2 g of L-1501 (Momentive) as silicone foam stabilizers, 0.5 g of D-33LV (Air Products) and 0.2 g of M-50 (Tosoh) as amine catalysts, and 0.6 g of diethanolamine as a crosslinking agent were added to the beaker. The mixture was then mixed at 4,000 rpm for 3 minutes using a high-speed mixer to obtain a mixture.

[0574] Thereafter, 58 g of methylene diphenyl isocyanate (CG-3701S, Kumho Co., Ltd.) was added to the mixture, which was then foamed to produce a polyurethane foam.

[0575] Examples 2-2 to 2-8 and Comparative Examples 2-1 to 2-4 A polyurethane foam was prepared in the same manner as in Example 2-1, except that 30 g of a polyol composition shown in Table 3 below was added to the plastic beaker instead of 30 g of the polyol composition prepared in Preparation Example 2-1.

[0576] Second Experimental Example Experimental Example 2-1 - Measurement of APHA color value The color of each polyol composition prepared in Preparation Examples 2-1 to 2-8 and Comparative Preparation Examples 2-1 to 2-4 was measured using ColorQuest XE (HunterLab). From the color number of each polyol composition, the APHA (American Public Health Association) color value (platinum-cobalt system) based on ASTM-D1209 was measured, and the results are shown in Table 3 below.

[0577] Experimental Example 2-2 - Measurement of residual metal content The residual metal content in each of the polyol compositions prepared in Preparation Examples 2-1 to 2-8 and Comparative Preparation Examples 2-1 to 2-4 was measured using atomic absorption spectrometry, and the results are shown in Table 3 below.

[0578] Experimental Example 2-3: Measurement of APHA color value after high-temperature treatment Each of the polyol compositions prepared in Preparation Examples 2-1 to 2-8 and Comparative Preparation Examples 2-1 to 2-4 was stored in an oven at 75°C for 10 minutes. The polyol compositions were then exposed to the atmosphere for 24 hours. The APHA (American Public Health Association) color values ​​were then measured under the same conditions as in Experimental Example 2-1. The results are shown in Table 3 below.

[0579] Experimental Example 2-4: Measurement of number average molecular weight To each vessel containing the phthalic anhydride solution, 2.75 g of each of the polyol compositions prepared in Preparation Examples 2-1 to 2-8 and Comparative Preparation Examples 2-1 to 2-4 was added and reacted at 115°C for 30 minutes. The pH was then monitored by titration with 0.5N aqueous sodium hydroxide (NaOH), and the volume (ml) of sodium hydroxide (NaOH) required to reach the inflection point was measured. A separate blank test was also conducted, in which the volume (ml) of sodium hydroxide (NaOH) required to reach the pH inflection point was measured in the same manner as above. The acid value (mg KOH / g) of the polyol composition was then calculated based on the measured value. The number average molecular weight of the polyol compositions prepared in Preparation Examples 2-1 to 2-8 and Comparative Preparation Examples 2-1 to 2-4 was then calculated using the acid value and the following relational expression 1. The results are shown in Table 3.

[0580] [Equation 1] Number average molecular weight (g / mol) = (56,100 x equivalent weight) / measured acid number

[0581] Experimental Example 2-5 - Viscosity measurement The viscosity of each of the polyol compositions produced in Production Examples 2-1 to 2-8 and Comparative Production Examples 2-1 to 2-4 was measured at 25° C. using a Brookfield DV-III, and the results are shown in Table 3 below.

[0582] Experimental Example 2-6 - Evaluation of storage stability Each of the polyol compositions prepared in Preparation Examples 2-1 to 2-8 and Comparative Preparation Examples 2-1 to 2-4 was placed in a 450 ml sample bottle and stored in an oven at 30° C. for 100 days. After 100 days, the storage stability of the polyol compositions was evaluated according to the following criteria, and the results are shown in Table 3 below.

[0583] -○: No layer separation occurred -×: Turbidity or layer separation occurs

[0584] [Table 3]

[0585] Experimental Example 2-7 - Evaluation of color of polyurethane foam The polyurethane foams produced in Examples 2-1 to 2-8 and Comparative Examples 2-1 to 2-4 were visually evaluated for color, and the results are shown in Table 4 below.

[0586] Experimental Example 2-8 - Evaluation of the physical properties of polyurethane foam The polyurethane foams produced in Examples 2-1 to 2-8 and Comparative Examples 2-1 to 2-4 were each cut into 5cm x 5cm samples. The compression hardness, elongation, compression set, and repeated compression set of the samples were measured using a Universal Testing Machine (UTM) according to ASTM D3574-86, and the results are shown in Table 4 below.

[0587] [Table 4]

[0588] As can be seen from Tables 3 and 4, the polyol compositions of Preparation Examples 2-1 to 2-8, which can be produced from renewable natural resources, were found to have a clearer hue than the polyol compositions of Comparative Preparation Examples 2-1 to 2-4. In particular, the polyol compositions of Preparation Examples 2-1 to 2-6 had a residual metal content of 1 ppm or less, minimizing the phenomenon of color change due to metal ions when exposed to a high-temperature environment.

[0589] In addition, it was confirmed that the polyurethane foams of Examples 2-1 to 2-8 produced from the polyol compositions of Production Examples 2-1 to 2-8 exhibited mechanical properties equivalent to or better than those of Comparative Examples 2-1 to 2-4 produced from petroleum-based raw materials.

[0590] Therefore, it has been confirmed that the polyol composition according to the present invention and the polyurethane foam containing the same do not use petroleum-based raw materials, are environmentally friendly, exhibit high transparency, have excellent storage stability, and exhibit mechanical properties equal to or better than those of petroleum-based raw materials.

[0591] <Third Production Example, Third Example, Third Experimental Example> Third Production Example - Production of Polyol Composition Manufacturing Example 3-1 800 g of isosorbide and 22 g of potassium hydroxide were placed in a pressurizable and heatable reactor. The inside of the reactor was then purged with nitrogen and heated to 112°C, after which moisture in the reactor was removed under vacuum and reduced pressure conditions.

[0592] While 1,880 g of propylene oxide was added to the reactor at a constant rate, the reaction was carried out for 6 hours at a temperature of about 115°C, while the temperature of the reactor was controlled so as not to exceed 115°C.

[0593] The mixture was stirred until all of the propylene oxide remaining in the reactor had reacted, and after the reaction was completed, the temperature of the reactor was heated to about 120°C. Then, 275g of ethylene oxide was added to the reactor at a constant rate, and the reaction was carried out for 1 hour and 30 minutes at a temperature of about 120°C. At this time, the temperature of the reactor was controlled so as not to exceed 125°C.

[0594] After the reaction was completed, the reactor was cooled to 90°C, and 50g of AMBOSOL and 5g of diatomaceous earth were added to the reactor. The mixture was stirred at a temperature of about 100°C for 3 hours to remove any metal ions remaining in the reaction mixture.

[0595] After confirming that no residual metal ions were detected in the reactant, the temperature of the reactor was lowered to 70°C, and residual by-products were removed using a filter. 300 ppm of an antioxidant (SN-1076, Songwon Industrial Co., Ltd.) was added based on the total weight of the reactant, and the reaction was carried out for 10 minutes, yielding 3,000 g of a polyol composition.

[0596] Manufacturing Example 3-2 A polyol composition was obtained in the same manner as in Production Example 3-1, except that 2,0500 g of propylene oxide was added to the reactor instead of 1,880 g of propylene oxide.

[0597] Manufacturing Example 3-3 A polyol composition was obtained in the same manner as in Production Example 3-1, except that 290 g of ethylene oxide was added to the reactor instead of 275 g of ethylene oxide in Production Example 3-1.

[0598] Manufacturing Example 3-4 A polyol composition was obtained by the same steps as in Production Example 3-1, except that 2,000 g of propylene oxide was added to the reactor instead of 1,880 g of propylene oxide, and 300 g of ethylene oxide was added to the reactor instead of 275 g of ethylene oxide.

[0599] Manufacturing Example 3-5 A polyol composition was obtained in the same manner as in Production Example 3-1, except that 820 g of isosorbide and 27 g of potassium hydroxide were added to the reactor instead of 800 g of isosorbide and 22 g of potassium hydroxide in Production Example 3-1.

[0600] Manufacturing Example 3-6 A polyol composition was obtained by the same steps as in Production Example 3-1, except that 810 g of isosorbide and 24 g of potassium hydroxide were added to the reactor instead of 800 g of isosorbide and 22 g of potassium hydroxide in Production Example 3-1.

[0601] Comparative Manufacturing Example 3-1 388 g of monopropylene glycol (MPG) and 18 g of potassium hydroxide were charged into a pressurizable and heatable reactor. The inside of the reactor was then purged with nitrogen and heated to 112°C, after which the water in the reactor was removed under vacuum and reduced pressure conditions.

[0602] 2,100 g of propylene oxide was added to the reactor at a constant rate, and the reaction was carried out for 7 hours at a temperature of about 110°C, while the temperature of the reactor was controlled so as not to exceed 115°C.

[0603] The mixture was stirred until all of the propylene oxide remaining in the reactor had reacted, and after the reaction was completed, the temperature of the reactor was heated to about 122°C. Then, 270g of ethylene oxide was added to the reactor at a constant rate, and the reaction was carried out for 1 hour and 30 minutes at a temperature of about 120°C. At this time, the temperature of the reactor was controlled so as not to exceed 125°C.

[0604] After the reaction was completed, the reactor was cooled to 90°C, and 50g of AMBOSOL and 5g of diatomaceous earth were added to the reactor. The mixture was stirred at a temperature of about 115°C for 3 hours to remove any metal ions remaining in the reaction mixture.

[0605] After confirming that no residual metal ions were detected in the reaction mixture, the temperature of the reactor was lowered to 70°C, and the remaining by-products were removed using a filter to obtain 2,800 g of a polyol composition.

[0606] Comparative Manufacturing Example 3-2 A polyol composition was obtained in the same manner as in Comparative Preparation Example 3-1, except that 388 g of dipropylene glycol (DPG) was added to the reactor instead of 386 g of monopropylene glycol (MPG) in Comparative Preparation Example 3-1.

[0607] Comparative Manufacturing Example 3-3 A polyol composition was obtained in the same manner as in Comparative Preparation Example 3-1, except that 400 g of monopropylene glycol (MPG) was added to the reactor instead of 388 g of monopropylene glycol (MPG) in Comparative Preparation Example 3-1.

[0608] Comparative Manufacturing Example 3-4 A polyol composition was obtained in the same manner as in Comparative Preparation Example 3-2, except that 400 g of dipropylene glycol (DPG) was added to the reactor instead of 388 g of DPG in Comparative Preparation Example 3-2.

[0609] Example 3 - Polyurethane Foam Production Example 3-1 30 g of the polyol composition prepared in Preparation Example 3-1 was placed in a plastic beaker. Then, 4.0 g of distilled water, 0.3 g of B-8629 (Evonik) and 1.2 g of L-1501 (Momentive) as silicone foam stabilizers, 0.5 g of D-33LV (Air Products) and 0.2 g of M-50 (Tosoh) as amine catalysts, and 0.6 g of diethanolamine as a crosslinking agent were added to the beaker. The mixture was then mixed at 4,000 rpm for 3 minutes using a high-speed mixer to obtain a mixture.

[0610] Thereafter, 58 g of methylene diphenyl isocyanate (CG-3701S, Kumho Co., Ltd.) was added to the mixture, which was then foamed to produce a polyurethane foam.

[0611] Examples 3-2 to 3-6 and Comparative Examples 3-1 to 3-4 A polyurethane foam was prepared in the same manner as in Example 3-1, except that 30 g of a polyol composition shown in Table 6 below was added to the plastic beaker instead of 30 g of the polyol composition prepared in Preparation Example 3-1.

[0612] Third Experimental Example Experimental Example 3-1 - Measurement of acid value 15 g of each of the polyol compositions prepared in Preparation Examples 3-1 to 3-6 and Comparative Preparation Examples 3-1 to 3-4 was placed in a 100 ml first flask. Separately, a 100 ml second flask was prepared for a blank test. Then, 50 ml of methanol and a magnetic bar were placed in each of the first and second flasks to remove impurities. The stoppers of the first and second flasks were sealed and the mixture was stirred for 30 minutes.

[0613] Then, 0.5 ml of 1% phenolphthalein indicator was added to each of the first and second flasks, and titration was performed with 0.02 N (normality) potassium hydroxide (KOH) until a pink color was observed visually and maintained for 30 seconds at the end point. The acid value was calculated using the following formula 1, and the results are shown in Table 5 below.

[0614] [Formula 1] Acid value (mgKOH / g)=[(V s -V b )×56.1×N×F] / M

[0615] In the above formula 1, the V s is the amount (ml) of 0.02N potassium hydroxide (KOH) consumed to titrate the composition in the first flask, and V b is the amount (ml) of the 0.02N potassium hydroxide (KOH) consumed to titrate the composition in the second flask, N is the normality of the potassium hydroxide (KOH), F is a factor of the 0.02N potassium hydroxide (KOH), and M is the weight (g) of the polyol composition added to the first flask.

[0616] Experimental Example 3-2: Measurement of number average molecular weight To each vessel containing the phthalic anhydride solution, 2.75 g of each of the polyol compositions prepared in Preparation Examples 3-1 to 3-6 and Comparative Preparation Examples 3-1 to 3-4 was added and reacted at 115°C for 30 minutes. The pH was then monitored by titration with 0.5N aqueous sodium hydroxide (NaOH), and the volume (ml) of sodium hydroxide (NaOH) required to reach the inflection point was measured. Separately, a blank test was conducted, in which the volume (ml) of sodium hydroxide (NaOH) required to reach the pH inflection point was measured in the same manner as above. The acid value (mg KOH / g) of the polyol composition was then calculated based on the measured value. The number average molecular weight of the polyol compositions prepared in Preparation Examples 3-1 to 3-6 and Comparative Preparation Examples 3-1 to 3-4 was then calculated using the acid value and the following relational expression 1. The results are shown in Table 5.

[0617] [Equation 1] Number average molecular weight (g / mol) = (56,100 x equivalent weight) / measured acid number

[0618] Experimental Example 3 - Measurement of active oxygen content After purging the first 25 ml flask with nitrogen for 2 minutes, 3 g of the polyol compositions prepared in Preparation Examples 1 to 6 and Comparative Preparation Examples 3-1 to 3-4 were added to the first flask, followed by further purging with nitrogen. Separately, a second 25 ml flask was prepared for a blank test.

[0619] Then, 20 ml of ferrous thiocyanate was added to each of the first and second flasks, diluted with methanol, and reacted for 5 minutes. Using a UV-Vis spectrophotometer (Cary 50 conc., Varian) and a quartz cell (10 mm x 10 mm), the absorbance of distilled water, the absorbance of the material added to the first flask, and the absorbance of the material added to the second flask were measured at a wavelength of 500 nm. The actual absorbance was calculated from the difference between the absorbance of the material added to the first flask and the absorbance of the material added to the second flask. The amount of active oxygen was then calculated using a calibration curve, and the results are shown in Table 5 below.

[0620] Experimental Example 3-4 - Viscosity measurement The viscosity of each of the polyol compositions produced in Production Examples 3-1 to 3-6 and Comparative Production Examples 3-1 to 3-4 was measured at 25°C using a Brookfield DV-III, and the results are shown in Table 5 below.

[0621] [Table 5]

[0622] Experimental Example 3-5 - Process time The total process time for producing the polyurethane foams of Examples 3-1 to 3-6 and Comparative Examples 3-1 to 3-4 was measured, and the results are shown in Table 6 below.

[0623] Experimental Example 3-6 - Evaluation of formability When producing the polyurethane foams of Examples 3-1 to 3-6 and Comparative Examples 3-1 to 3-4, the time when the polyurethane foam started to rise (Cream Time; CT) and the time when the polyurethane foam rose (Rise Time; RT) were measured. If the CT of the polyurethane foam was 7 to 10 seconds and the RT was 90 to 100 seconds, the foam was evaluated to have good moldability, and the results are shown in Table 6 below.

[0624] Experimental Example 3-7 - Evaluation of the physical properties of polyurethane foam The polyurethane foams produced in Examples 3-1 to 3-6 and Comparative Examples 3-1 to 3-4 were each cut into 5cm x 5cm samples. Then, the compression hardness, elongation, compression set, and repeated compression set of the samples were measured using a UTM (Universal Testing Machine) in accordance with ASTM D3574-86, and the results are shown in Table 6 below.

[0625] [Table 6] JPEG2025527701000046.jpg44164

[0626] As can be seen from Tables 5 and 6 above, the polyol compositions of Preparation Examples 3-1 to 3-6, which can be produced from renewable natural resources, exhibited lower acid values ​​than the polyol compositions of Comparative Preparation Examples 3-1 to 3-4.

[0627] Therefore, it was confirmed that the polyol compositions of Production Examples 3-1 to 3-6 have improved reactivity with isocyanate-based compositions compared to the polyol compositions of Comparative Production Examples 3-1 to 3-4, reducing the process time for producing polyurethane foam and improving moldability.

[0628] It was also confirmed that the polyurethane foams of Examples 3-1 to 3-6 produced from Production Examples 3-1 to 3-6 exhibited mechanical properties equal to or better than those of the polyurethane foams of Comparative Examples 3-1 to 3-4 produced from petroleum-based raw materials.

[0629] Therefore, it has been confirmed that the polyol composition according to the present invention and the polyurethane foam containing the same do not use petroleum-based raw materials, are environmentally friendly, exhibit a low acid value, improve process time efficiency and moldability, and exhibit mechanical properties equal to or better than those of petroleum-based raw materials.

[0630] <Fourth Production Example, Fourth Example, Fourth Experimental Example> Fourth Production Example - Production of Polyol Composition Manufacturing Example 4-1 Step (1) - Preparation of Prepolymer 796 g of isosorbide and 22 g of potassium hydroxide were placed in a pressurizable and heatable reactor. The inside of the reactor was then purged with nitrogen and heated to 112°C, after which moisture in the reactor was removed under vacuum and reduced pressure conditions.

[0631] While 1,904 g of propylene oxide was added to the reactor at a constant rate, the reaction was carried out for 6 hours at a temperature of about 115°C, while the temperature of the reactor was controlled so as not to exceed 115°C.

[0632] The mixture was stirred until all of the propylene oxide remaining in the reactor had reacted, and after the reaction was completed, the temperature of the reactor was heated to 122°C. Then, 270g of ethylene oxide was added to the reactor at a constant rate, and the reaction was carried out for 1 hour and 30 minutes at a temperature of about 120°C. At this time, the temperature of the reactor was controlled so as not to exceed 125°C.

[0633] After the reaction was completed, the reactor was cooled to 90°C, and 50 g of AMBOSOL and 5 g of diatomaceous earth were added to the reactor. The mixture was stirred at a temperature of about 100°C for 3 hours to remove any metal ions remaining in the reaction mixture.

[0634] After confirming that no residual metal ions were detected in the reactant, the temperature of the reactor was lowered to 70°C, and the remaining by-products were removed using a filter to obtain 3,000 g of a prepolymer.

[0635] Step (2)—Preparation of the Polyol Composition 796 g of the prepolymer was charged into a pressurizable and heatable reactor, and then the inside of the reactor was purged with nitrogen and heated to 112°C, and then moisture in the reactor was removed under vacuum reduced pressure conditions.

[0636] 0.14 g of double metal cyanide was added to the reactor, and then 2,204 g of propylene oxide was added at a constant rate while the reaction was carried out for about 6 hours and 30 minutes at a temperature of about 110°C. At this time, the temperature of the reactor was controlled so as not to exceed 115°C.

[0637] The stirring was continued until all the propylene oxide remaining in the reactor had reacted. After the temperature of the reactor was lowered to 90° C., 3,000 g of a polyol composition was obtained.

[0638] Manufacturing Example 4-2 A polyol composition was obtained in the same manner as in Preparation Example 4-1, except that instead of adding 2,204 g of propylene oxide to the reactor in step (2) of Preparation Example 4-1, 2,204 g of a mixture of propylene oxide and ethylene oxide in a weight ratio of 6:4 was added to the reactor.

[0639] Manufacturing Example 4-3 A polyol composition was obtained in the same manner as in Preparation Example 4-1, except that instead of adding 2,204 g of propylene oxide to the reactor in step (2) of Preparation Example 4-1, 2,204 g of a mixture of propylene oxide and ethylene oxide in a weight ratio of 5:5 was added to the reactor.

[0640] Manufacturing Example 4-4 A polyol composition was obtained in the same manner as in Preparation Example 4-1, except that instead of adding 2,204 g of propylene oxide to the reactor in step (2) of Preparation Example 4-1, 2,204 g of a mixture of propylene oxide and ethylene oxide in a weight ratio of 4:6 was added to the reactor.

[0641] Manufacturing Example 4-5 A polyol composition was obtained in the same manner as in Preparation Example 4-1, except that 25 g of potassium hydroxide was added to the reactor in step (1) of Preparation Example 4-1 instead of 22 g of potassium hydroxide.

[0642] Manufacturing Example 4-6 A polyol composition was obtained in the same manner as in Preparation Example 4-1, except that 2,100 g of propylene oxide was added to the reactor in step (1) of Preparation Example 4-1 instead of 1,904 g of propylene oxide.

[0643] Manufacturing Example 4-7 A polyol composition was obtained in the same manner as in Preparation Example 4-1, except that 300 g of ethylene oxide was added to the reactor instead of 270 g of ethylene oxide in step (1) of Preparation Example 4-1.

[0644] Manufacturing Example 4-8 A polyol composition was obtained by the same process as in Preparation Example 4-1, except that 0.25 g of double metal cyanide was added to the reactor in step (2) of Preparation Example 4-1 instead of 0.14 g of double metal cyanide.

[0645] Manufacturing Example 4-9 A polyol composition was obtained by the same process as in Preparation Example 4-1, except that 0.10 g of double metal cyanide was added to the reactor in step (2) of Preparation Example 4-1 instead of 0.14 g of double metal cyanide.

[0646] Manufacturing Example 4-10 A polyol composition was obtained in the same manner as in Preparation Example 4-1, except that 2,300 g of propylene oxide was added to the reactor in step (2) of Preparation Example 4-1 instead of 2,204 g of propylene oxide.

[0647] Comparative Manufacturing Example 4-1 796 g of the prepolymer obtained in step (1) of Preparation Example 4-1 and 9.8 g of potassium hydroxide were placed in a pressurizable and heatable reactor. The inside of the reactor was then purged with nitrogen and heated to 112°C, after which moisture in the reactor was removed under vacuum and reduced pressure.

[0648] While 2,204 g of propylene oxide was added to the reactor at a constant rate, the reaction was carried out for about 9 hours and 30 minutes at a temperature of about 110°C, while the temperature of the reactor was controlled so as not to exceed 115°C.

[0649] The mixture was stirred until all of the propylene oxide remaining in the reactor was reacted. After the reaction was completed, the reactor was cooled to 90°C, and 50 g of AMBOSOL and 5 g of diatomaceous earth were added to the reactor. The mixture was stirred at a temperature of about 100°C for 3 hours to remove metal ions remaining in the reactants.

[0650] After confirming that no residual metal ions were detected in the reaction mixture, the temperature of the reactor was lowered to 70°C, and the remaining by-products were removed using a filter to obtain 3,000 g of a polyol composition.

[0651] Comparative Manufacturing Example 4-2 A polyol composition was obtained by the same process as in Comparative Preparation Example 4-1, except that instead of adding 2,204 g of propylene oxide to the reactor in Comparative Preparation Example 4-1, 2,204 g of a mixture of propylene oxide and ethylene oxide in a weight ratio of 6:4 was added to the reactor.

[0652] Comparative Manufacturing Example 4-3 796 g of isosorbide was placed in a pressurizable and heatable reactor, after which the inside of the reactor was purged with nitrogen and heated to 112°C, and then moisture in the reactor was removed under vacuum reduced pressure conditions.

[0653] After adding 0.14 g of double metal cyanide to the reactor, 2,204 g of propylene oxide was added at a constant rate and a polymerization reaction was attempted for about 2 hours at a temperature of about 110°C. However, the double metal cyanide catalyst was not activated, and the polymerization reaction between the isosorbide and propylene oxide did not occur.

[0654] Comparative Manufacturing Example 4-4 796 g of the prepolymer obtained in step (1) of Preparation Example 4-1 was placed in a pressurizable and heatable reactor, and the inside of the reactor was then purged with nitrogen and heated to 112°C, after which moisture in the reactor was removed under vacuum and reduced pressure conditions.

[0655] 0.14 g of double metal cyanide and 22 g of potassium hydroxide were added to the reactor, and then 2,204 g of propylene oxide was added at a constant rate while the reaction was carried out for about 9 hours and 30 minutes at a temperature of about 110°C. At this time, the temperature of the reactor was controlled so as not to exceed 115°C.

[0656] The mixture was stirred until all of the propylene oxide remaining in the reactor was reacted. After the reaction was completed, the reactor was cooled to 90°C, and 50 g of AMBOSOL and 5 g of diatomaceous earth were added to the reactor. The mixture was stirred at a temperature of about 100°C for 3 hours to remove metal ions remaining in the reactants.

[0657] After confirming that no residual metal ions were detected in the reaction mixture, the temperature of the reactor was lowered to 70°C, and the remaining by-products were removed using a filter to obtain 3,000 g of a polyol composition.

[0658] Example 4 - Polyurethane Foam Production Example 4-1 30 g of the polyol composition prepared in Preparation Example 4-1 was placed in a plastic beaker. Then, 3.5 g of distilled water, 0.2 g of B-8629 (Evonik) and 0.9 g of L-1501 (Momentive) as silicone foam stabilizers, 0.5 g of D-33LV (Air Products) and 0.1 g of M-50 (Tosoh) as amine catalysts, and 0.6 g of diethanolamine as a crosslinking agent were added to the beaker. The mixture was then mixed at 4,000 rpm for 3 minutes using a high-speed mixer to obtain a mixture.

[0659] Thereafter, 58 g of methylene diphenyl isocyanate (CG-3701S, Kumho Co., Ltd.) was added to the mixture, which was then foamed to produce a polyurethane foam.

[0660] Examples 4-2 to 4-10 and Comparative Examples 4-1 to 4-4 A polyurethane foam was prepared in the same manner as in Example 4-1, except that 30 g of a polyol composition shown in Table 8 below was added to the plastic beaker in place of 30 g of the polyol composition prepared in Preparation Example 4-1.

[0661] Fourth Experimental Example Experimental Example 4-1 - Measurement of unsaturation 30 g of each of the polyol compositions prepared in Preparation Examples 4-1 to 4-10 and Comparative Preparation Examples 4-1 to 4-4 was placed in a 250 ml first flask. Separately, a 250 ml second flask was prepared for a blank test. Then, 50 ml of mercuric acetate and a magnetic bar were placed in each of the first and second flasks to remove impurities. The stoppers of the first and second flasks were sealed and the mixture was stirred for 30 minutes.

[0662] Then, 9 g of sodium bromide (NaBr) was added to each of the first and second flasks, followed by stirring for 30 minutes. Then, 0.5 ml of 1% phenolphthalein indicator was added to each of the first and second flasks, and titration was performed with 0.1 N (normality) potassium hydroxide (KOH) until a pink color was observed visually and maintained for approximately 15 seconds at the end point. The degree of unsaturation was calculated using the following equation 1, and the results are shown in Table 7 below.

[0663] [Formula 1] Unsaturation degree (meq / g)=(V s ×V b ×0.1×F) / M

[0664] In the above formula 1, the V sis the amount (ml) of 0.1 N potassium hydroxide (KOH) added to the first flask, and V b is the amount (ml) of the 0.1 N potassium hydroxide (KOH) added to the second flask, F is a factor of the 0.1 N potassium hydroxide (KOH), and M is the weight (g) of the polyol composition added to the first flask.

[0665] Experimental Example 4-2: Measurement of number average molecular weight To each vessel containing the phthalic anhydride solution, 2.75 g of each of the polyol compositions prepared in Preparation Examples 4-1 to 4-10 and Comparative Preparation Examples 4-1 to 4-4 was added and reacted at 115°C for 30 minutes. The pH was then monitored by titration with 0.5N aqueous sodium hydroxide (NaOH), and the volume (ml) of sodium hydroxide (NaOH) required to reach the inflection point was measured. Separately, a blank test was conducted, in which the volume (ml) of sodium hydroxide (NaOH) required to reach the pH inflection point was measured in the same manner as above. The acid value (mg KOH / g) of the polyol composition was then calculated based on the measured value. The number average molecular weight of the polyol compositions prepared in Preparation Examples 4-1 to 4-10 and Comparative Preparation Examples 4-1 to 4-4 was then calculated using the acid value and the following relational expression 1. The results are shown in Table 7.

[0666] [Equation 1] Number average molecular weight (g / mol) = (56,100 x equivalent weight) / measured acid number

[0667] Experimental Example 4-3 - Evaluation of reactivity When the polyol compositions of Production Examples 4-1 to 4-10 and Comparative Production Examples 4-1 to 4-4 were produced using the catalysts, the reactivity was evaluated according to the following criteria, and the results are shown in Table 7 below.

[0668] -◎: Polymerization reaction proceeds smoothly -○: Polymerization reaction occurs, but the polymerization reaction rate is slow -×: The catalyst is not activated and the polymerization reaction does not occur.

[0669] [Table 7]

[0670] Experimental Example 4-4 - Evaluation of the physical properties of polyurethane foam The polyurethane foams produced in Examples 4-1 to 4-10 and Comparative Examples 4-1 to 4-4 were each cut into 5cm x 5cm samples. Then, the compression hardness, elongation, compression set, and repeated compression set of the samples were measured using a UTM (Universal Testing Machine) in accordance with ASTM D3574-86, and the results are shown in Table 8 below.

[0671] [Table 8]

[0672] As can be seen from Tables 7 and 8, the polyurethane foams of Examples 4-1 to 4-10, which were prepared from polyol compositions with an unsaturation level of 0.02 meq / g or less based on a number-average molecular weight of about 2,000 g / mol to 2,400 g / mol, exhibited significantly improved mechanical properties, such as hardness and elongation, compared to Comparative Examples 4-1 to 4-4. Furthermore, it was confirmed that the difference in unsaturation level may vary depending on the type of catalyst or the timing of catalyst addition during the preparation of the polyol composition. Specifically, in Comparative Preparation Example 3, the use of a double metal cyanide catalyst instead of a potassium hydroxide catalyst in the prepolymer preparation process (step (1)) resulted in inactivation of the catalyst and inability to undergo polymerization. In addition, when a potassium hydroxide catalyst, rather than a double metal cyanide catalyst, or a combination of a double metal cyanide catalyst and a potassium hydroxide catalyst is used in the polyol composition preparation process in step (2), the degree of unsaturation of the prepared polyol composition exceeds 0.02 meq / g, and the physical properties of the polyurethane foam, such as hardness, elongation, compression set, and repeated compression set, are found to be reduced.

[0673] <Fifth Production Example, Fifth Example, Fifth Experimental Example> Fifth Production Example - Production of Polyether Polyol Manufacturing Example 5-1 Step (1) - Preparation of the First Polymer Isosorbide and potassium hydroxide were charged into a pressurizable and heatable batch reactor at a weight ratio of 50:1. The reactor was then purged with nitrogen and heated to 112°C, after which moisture was removed from the reactor under vacuum for approximately 3 hours.

[0674] 240 parts by weight of propylene oxide per 100 parts by weight of isosorbide was added to the reactor at a rate of about 4 g / min, and the reaction was carried out for about 6 hours and 30 minutes at a temperature of about 115°C. The temperature of the reactor was controlled so that it did not exceed 115°C. The mixture was stirred until all the propylene oxide remaining in the reactor was reacted, and after the reaction was completed, the temperature of the reactor was heated to about 122°C.

[0675] Thereafter, 34 parts by weight of ethylene oxide was added to the reactor at a rate of about 2 g / min per 100 parts by weight of isosorbide, and the reaction was carried out for about 1 hour and 30 minutes at a temperature of about 120°C, while the temperature of the reactor was controlled so as not to exceed 125°C.

[0676] After the reaction was completed, the temperature of the reactor was cooled to about 90°C, and AMBOSOL as a metal adsorbent and diatomaceous earth as a filter aid were added to the reactor, followed by stirring at a temperature of about 100°C for 3 hours to remove metal ions remaining in the reactants.

[0677] Thereafter, after it was confirmed that no residual metal ions were detected, the temperature of the reactor was lowered to 70° C., and the residual by-products were filtered to obtain a first polymer.

[0678] Step (2)—Preparation of the Second Polymer The first polymer was introduced into the reactor, and then the inside of the reactor was purged with nitrogen, heated to about 112°C, and then moisture in the reactor was removed under vacuum reduced pressure conditions.

[0679] The reactor was then charged with the first polymer and double metal cyanide in a weight ratio of 5,680:1.

[0680] Then, 270 parts by weight of propylene oxide per 100 parts by weight of the first polymer was added to the reactor at a rate of about 4 g / min, and the reaction was carried out for about 6 hours and 30 minutes at a temperature of about 115°C. The temperature of the reactor was controlled so that it did not exceed 115°C. Stirring was maintained until all of the propylene oxide remaining in the reactor had reacted. The temperature of the reactor was then lowered to 90°C, and a second polymer, which was a polyether polyol, was obtained.

[0681] Manufacturing Example 5-2 A second polymer was obtained in the same manner as in Preparation Example 5-1, except that instead of adding 270 parts by weight of propylene oxide to 100 parts by weight of the first polymer to the reactor in step (2) of Preparation Example 5-1, 270 parts by weight of a mixture of propylene oxide and ethylene oxide in a weight ratio of 6:4 to 100 parts by weight of the first polymer was added to the reactor.

[0682] Manufacturing Example 5-3 A second polymer was obtained by the same process as in Preparation Example 5-1, except that in step (1) of Preparation Example 5-1, instead of charging isosorbide:potassium hydroxide into the reactor at a weight ratio of 50:1, isosorbide:potassium hydroxide was charged into the reactor at a weight ratio of 70:1.

[0683] Manufacturing Example 5-4 A second polymer was obtained in the same manner as in Preparation Example 5-1, except that 350 parts by weight of propylene oxide was added to the reactor per 100 parts by weight of isosorbide instead of 240 parts by weight of propylene oxide per 100 parts by weight of isosorbide in step (1) of Preparation Example 5-1.

[0684] Manufacturing Example 5-5 A second polymer was obtained in the same manner as in Preparation Example 5-1, except that 60 parts by weight of ethylene oxide was added to the reactor per 100 parts by weight of isosorbide instead of 34 parts by weight of ethylene oxide per 100 parts by weight of isosorbide in step (1) of Preparation Example 5-1.

[0685] Manufacturing Example 5-6 A second polymer was obtained by the same process as in Preparation Example 5-1, except that instead of removing the water from the reactor for about 3 hours in step (1) of Preparation Example 5-1, the water from the reactor was removed for about 1 hour.

[0686] Manufacturing Example 5-7 A second polymer was obtained by the same process as in Preparation Example 5-1, except that in step (2) of Preparation Example 5-1, instead of charging the first polymer:double metal cyanide into the reactor at a weight ratio of 5,680:1, the first polymer:double metal cyanide was charged into the reactor at a weight ratio of 20,500:1.

[0687] Comparative Manufacturing Example 5-1 Step (1) - Preparation of the First Polymer Isosorbide and potassium hydroxide were charged into a pressurizable and heatable batch reactor at a weight ratio of 50:1. The reactor was then purged with nitrogen and heated to 112°C, after which moisture was removed from the reactor under vacuum for approximately 3 hours.

[0688] 240 parts by weight of propylene oxide per 100 parts by weight of isosorbide was added to the reactor at a rate of about 4 g / min, and the reaction was carried out for about 6 hours and 30 minutes at a temperature of about 115°C. The temperature of the reactor was controlled so that it did not exceed 115°C. The mixture was stirred until all the propylene oxide remaining in the reactor was reacted, and after the reaction was completed, the temperature of the reactor was heated to about 122°C.

[0689] Thereafter, 34 parts by weight of ethylene oxide was added to the reactor at a rate of about 2 g / min per 100 parts by weight of isosorbide, and the reaction was carried out for about 1 hour and 30 minutes at a temperature of about 120°C, while the temperature of the reactor was controlled so as not to exceed 125°C.

[0690] After the reaction was completed, the temperature of the reactor was cooled to about 90°C, and AMBOSOL as a metal adsorbent and diatomaceous earth as a filter aid were added to the reactor, followed by stirring at a temperature of about 100°C for 3 hours to remove metal ions remaining in the reactants.

[0691] Thereafter, after it was confirmed that no residual metal ions were detected, the temperature of the reactor was lowered to 70° C., and the residual by-products were filtered to obtain a first polymer.

[0692] Step (2)—Preparation of the Second Polymer The first polymer and potassium hydroxide were charged into the reactor at a weight ratio of 100:1, and then the inside of the reactor was purged with nitrogen, heated to 112°C, and then moisture in the reactor was removed under vacuum reduced pressure conditions.

[0693] Thereafter, 270 parts by weight of propylene oxide was added to the reactor at a rate of about 4 g / min relative to 100 parts by weight of the first polymer, and the reaction was carried out for about 6 hours and 30 minutes at a temperature of about 115°C, while the temperature of the reactor was controlled so as not to exceed 115°C.

[0694] Stirring was continued until all of the propylene oxide remaining in the reactor had reacted. After the temperature of the reactor was lowered to 90°C, AMBOSOL as a metal adsorbent and diatomaceous earth as a filter aid were added to the reactor, and the mixture was stirred at a temperature of about 100°C for 3 hours to remove metal ions remaining in the reactant.

[0695] After confirming that no residual metal ions were detected, the temperature of the reactor was lowered to 70°C, and the residual by-products were filtered to obtain a second polymer, which was a polyether polyol.

[0696] Comparative Manufacturing Example 5-2 A second polymer was obtained by the same process as in Comparative Preparation Example 5-1, except that instead of adding 270 parts by weight of propylene oxide to 100 parts by weight of the first polymer to the reactor in Comparative Preparation Example 5-1, 270 parts by weight of a mixture of propylene oxide and ethylene oxide in a weight ratio of 6:4 was added to 100 parts by weight of the first polymer to the reactor.

[0697] Comparative Manufacturing Example 5-3 Isosorbide was charged into a pressurizable and heatable batch reactor, and then the inside of the reactor was purged with nitrogen and heated to 112°C, and then moisture in the reactor was removed under vacuum and reduced pressure conditions.

[0698] Then, 0.017 parts by weight of double metal cyanide was added to the reactor based on 100 parts by weight of the isosorbide.

[0699] Thereafter, 270 parts by weight of propylene oxide per 100 parts by weight of isosorbide was added to the reactor at a rate of about 4 g / min, and a polymerization reaction was attempted at a temperature of about 115°C for about 2 hours. However, the double metal cyanide catalyst was not activated, and the polymerization reaction between the isosorbide and propylene oxide did not occur.

[0700] Comparative Manufacturing Example 5-4 A second polymer was obtained by the same process as in Comparative Preparation Example 5-1, except that in step (1) of Comparative Preparation Example 5-1, instead of charging isosorbide:potassium hydroxide into the reactor at a weight ratio of 50:1, isosorbide:potassium hydroxide was charged into the reactor at a weight ratio of 20:1.

[0701] Comparative Manufacturing Example 5-5 Step (1) - Preparation of the First Polymer Isosorbide and potassium hydroxide were charged into a pressurizable and heatable batch reactor at a weight ratio of 50:1. The reactor was then purged with nitrogen and heated to 112°C, after which moisture was removed from the reactor under vacuum for about 1 hour.

[0702] 100 parts by weight of the isosorbide and 270 parts by weight of a mixture of propylene oxide and ethylene oxide in a weight ratio of 6:4 were added to the reactor at a rate of about 4 g / min, and the reaction was carried out for about 6 hours and 30 minutes at a temperature of about 115°C. At this time, the temperature of the reactor was controlled so as not to exceed 115°C.

[0703] After the reaction was completed, the temperature of the reactor was cooled to about 90°C, and AMBOSOL as a metal adsorbent and diatomaceous earth as a filter aid were added to the reactor, followed by stirring at a temperature of about 100°C for 3 hours to remove metal ions remaining in the reactants.

[0704] Thereafter, after it was confirmed that no residual metal ions were detected, the temperature of the reactor was lowered to 70° C., and the residual by-products were filtered to obtain a first polymer.

[0705] Step (2)—Preparation of the Second Polymer The first polymer and potassium hydroxide were charged into the reactor at a weight ratio of 100:1, and then the inside of the reactor was purged with nitrogen, heated to 112°C, and then moisture in the reactor was removed under vacuum reduced pressure conditions.

[0706] Thereafter, 270 parts by weight of propylene oxide was added to the reactor at a rate of about 4 g / min relative to 100 parts by weight of the first polymer, and the reaction was carried out for about 6 hours and 30 minutes at a temperature of about 115°C, while the temperature of the reactor was controlled so as not to exceed 115°C.

[0707] Stirring was continued until all of the propylene oxide remaining in the reactor had reacted. After the temperature of the reactor was lowered to 90°C, AMBOSOL as a metal adsorbent and diatomaceous earth as a filter aid were added to the reactor, and the mixture was stirred at a temperature of about 100°C for 3 hours to remove metal ions remaining in the reactant.

[0708] After confirming that no residual metal ions were detected, the temperature of the reactor was lowered to 70°C, and the residual by-products were filtered to obtain a second polymer, which was a polyether polyol.

[0709] Comparative Manufacturing Example 5-6 A second polymer was obtained in the same manner as in Comparative Preparation Example 5-1, except that in step (1) of Comparative Preparation Example 5-1, instead of adding 34 parts by weight of ethylene oxide to 100 parts by weight of isosorbide to the reactor, 250 parts by weight of ethylene oxide to 100 parts by weight of isosorbide was added to the reactor.

[0710] The catalysts, reactants, and reaction conditions used in the preparation steps of Preparation Examples 5-1 to 5-7 and Comparative Preparation Examples 5-1 to 5-6 are shown in Table 9 below.

[0711] [Table 9]

[0712] Example 5 - Production of Polyurethane Foam Example 5-1 30 g of the polyether polyol prepared in Preparation Example 5-1 was placed in a plastic beaker. Then, 3.5 g of distilled water, 0.2 g of B-8629 (Evonik) and 0.9 g of L-1501 (Momentive) as silicone foam stabilizers, 0.5 g of D-33LV (Air Products) and 0.1 g of M-50 (Tosoh) as amine catalysts, and 0.6 g of diethanolamine as a crosslinking agent were added to the beaker. The mixture was then mixed at 4,000 rpm for 3 minutes using a high-speed mixer to obtain a mixture.

[0713] Thereafter, 58 g of methylene diphenyl isocyanate (CG-3701S, Kumho Co., Ltd.) was added to the mixture, which was then foamed to produce a polyurethane foam.

[0714] Examples 5-2 to 5-7 and Comparative Examples 5-1 to 5-6 A polyurethane foam was produced in the same manner as in Example 5-1, except that 30 g of a polyether polyol shown in Table 11 below was added to the plastic beaker instead of 30 g of the polyether polyol produced in Preparation Example 5-1.

[0715] Fifth Experimental Example Experimental Example 5-1 - Measurement of residual moisture content After the dehydration step (1) of Preparation Examples 5-1 to 5-7 and Comparative Preparation Examples 5-1 to 5-6, the residual water content of each dehydrated composition relative to the total weight of the composition was measured by Karl Fischer coulometric titration, and the results are shown in Table 10 below.

[0716] Experimental Example 5-2 - Measurement of unsaturation 30 g of the polyether polyols prepared in Preparation Examples 5-1 to 5-7 and Comparative Preparation Examples 5-1 to 5-6 were each placed in a 250 ml first flask. Separately, a 250 ml second flask was prepared for a blank test. Then, 50 ml of mercuric acetate and a magnetic bar to remove impurities were placed in each of the first and second flasks. The stoppers of the first and second flasks were sealed and the mixture was stirred for 30 minutes.

[0717] Then, 9 g of sodium bromide (NaBr) was added to each of the first and second flasks, followed by stirring for 30 minutes. 0.5 ml of 1% phenolphthalein indicator was added to each of the first and second flasks, and the unsaturation degree was measured by titrating with 0.1 N (normality) potassium hydroxide (KOH) until a pink color was observed visually and maintained for about 15 seconds at the end point. The results are shown in Table 10 below.

[0718] Experimental Example 5-3 - Evaluation of reactivity When producing the polyether polyols of Production Examples 5-1 to 5-7 and Comparative Production Examples 5-1 to 5-6 using a catalyst, the reactivity was evaluated according to the following criteria, and the results are shown in Table 10 below.

[0719] -◎: Polymerization reaction proceeds smoothly -○: Polymerization reaction occurs, but the polymerization reaction rate is slow -×: The catalyst is not activated and the polymerization reaction does not occur.

[0720] Experimental Example 5-4: Measurement of number average molecular weight To each vessel containing the phthalic anhydride solution, 2.75 g of each of the polyether polyols prepared in Preparation Examples 5-1 to 5-7 and Comparative Preparation Examples 5-1 to 5-6 was added and reacted at 115°C for 30 minutes. The pH was then monitored by titration with 0.5N aqueous sodium hydroxide (NaOH), and the volume (ml) of sodium hydroxide (NaOH) required to reach the inflection point was measured. A separate blank test was also conducted, in which the volume (ml) of sodium hydroxide (NaOH) required to reach the pH inflection point was measured in the same manner as above. The acid value (mg KOH / g) of the polyol composition was then calculated based on the measured value. The number-average molecular weights of the polyether polyols prepared in Preparation Examples 5-1 to 5-7 and Comparative Preparation Examples 5-1 to 5-6 were then calculated using the acid value and the following relational expression 1. The results are shown in Table 10.

[0721] [Equation 1] Number average molecular weight (g / mol) = (56,100 x equivalent weight) / measured acid number

[0722] [Table 10]

[0723] Experimental Example 5-5 - Evaluation of the physical properties of polyurethane foam The polyurethane foams produced in Examples 5-1 to 5-7 and Comparative Examples 5-1 to 5-6 were each cut into 5cm x 5cm samples. Then, the compression hardness, elongation, compression set, and repeated compression set of the samples were measured using a UTM (Universal Testing Machine) in accordance with ASTM D3574-86, and the results are shown in Table 11 below.

[0724] Experimental Example 5-6 - Appearance evaluation The appearance of the polyurethane foams produced in Examples 5-1 to 5-7 and Comparative Examples 5-1 to 5-6 was evaluated according to the following criteria, and the results are shown in Table 11 below.

[0725] -Good: When visually observed, the entire surface of the polyurethane foam is smooth. - Poor: When visually observed, roughness is observed on at least a part of the entire surface of the polyurethane foam.

[0726] Experimental Example 5-7 - Hue Evaluation To evaluate the color of the polyurethane foams produced in Examples 5-1 to 5-7 and Comparative Examples 5-1 to 5-6, the yellowness index was measured using a Miniscan XE Plus (Hunter Labs) in accordance with ASTM E313-96, and the results are shown in Table 11. The larger the measured value, the closer to yellow the foam is, and the smaller the measured value, the clearer and more transparent the foam is.

[0727] [Table 11]

[0728] As can be seen from Tables 9 to 11, the polyurethane foams of Examples 5-1 to 5-7 containing the polyether polyols produced according to the production method of the present invention were significantly improved in mechanical properties such as hardness, elongation, compression set, and repeated compression set compared to the polyurethane foams of Comparative Examples 5-1, 5-2, and 5-4 to 5-6. Furthermore, the polyurethane foams of Examples 5-1 to 5-7 were also superior in appearance compared to Comparative Examples 5-5 and 5-6.

[0729] It was confirmed that the mechanical properties of the polyurethane foam may vary depending on the type of catalyst and the timing of catalyst addition during polyether polyol production. Specifically, in Comparative Preparation Example 3, a double metal cyanide catalyst was used instead of an alkali catalyst in the first polymer production process (step (1)), preventing the polymerization reaction from occurring due to catalyst deactivation. Furthermore, when an alkali catalyst was used instead of a double metal cyanide catalyst in the second polymer production process (step (2)), the polyether polyol exhibited a high degree of unsaturation, resulting in decreased physical properties such as hardness, elongation, compression set, and repeated compression set of the polyurethane foam. It was also confirmed that the appearance of the polyurethane foam may vary depending on the ratio of propylene oxide and ethylene oxide used during polyether polyol production.

[0730] <Sixth Production Example, Sixth Example, Sixth Experimental Example> 6th Production Example - Production of Polyether Polyol Manufacturing Example 6-1 Step (1) - Preparation of Prepolymer 798 g of isosorbide and 21 g of potassium hydroxide were placed in a pressurizable and heatable reactor. The inside of the reactor was then purged with nitrogen and heated to 112°C, after which moisture in the reactor was removed under vacuum and reduced pressure conditions.

[0731] While 1,900 g of propylene oxide was added to the reactor at a constant rate, the reaction was carried out for 6 hours at a temperature of about 115°C, while the temperature of the reactor was controlled so as not to exceed 115°C.

[0732] The mixture was stirred until all of the propylene oxide remaining in the reactor had reacted, and after the reaction was completed, the temperature of the reactor was heated to 122°C. Then, 275g of ethylene oxide was added to the reactor at a constant rate, and the reaction was carried out for 1 hour and 30 minutes at a temperature of about 120°C. At this time, the temperature of the reactor was controlled so as not to exceed 125°C.

[0733] After the reaction was completed, the reactor was cooled to 90°C, and 50g of AMBOSOL and 5g of diatomaceous earth were added to the reactor. The mixture was stirred at a temperature of about 100°C for 3 hours to remove any metal ions remaining in the reaction mixture.

[0734] After confirming that no residual metal ions were detected in the reactant, the temperature of the reactor was lowered to 70°C, and the remaining by-products were removed using a filter to obtain 3,000 g of a prepolymer.

[0735] Step (2)—Preparation of Polyether Polyols 795 g of the prepolymer was charged into a pressurizable and heatable reactor, and then the inside of the reactor was purged with nitrogen and heated to 112°C, and then moisture in the reactor was removed under vacuum reduced pressure conditions.

[0736] 0.14 g of double metal cyanide was added to the reactor, followed by 2,200 g of a mixture of propylene oxide and ethylene oxide in a weight ratio of 6:4, and the reaction was carried out at a temperature of about 110°C for about 7 hours, while the temperature of the reactor was controlled so as not to exceed 115°C.

[0737] The stirring was continued until the mixture remaining in the reactor was completely reacted. After the temperature of the reactor was lowered to 90° C., 3,000 g of polyether polyol was obtained.

[0738] Manufacturing Example 6-2 A polyether polyol was obtained by the same process as in Preparation Example 6-1, except that in step (2) of Preparation Example 6-1, instead of charging a mixture of propylene oxide and ethylene oxide in a weight ratio of 6:4 into the reactor, a mixture of propylene oxide and ethylene oxide in a weight ratio of 5.5:4.5 was charged into the reactor.

[0739] Manufacturing Example 6-3 A polyether polyol was obtained by the same process as in Preparation Example 6-1, except that in step (2) of Preparation Example 6-1, instead of charging a mixture of propylene oxide and ethylene oxide in a weight ratio of 6:4 into the reactor, a mixture of propylene oxide and ethylene oxide in a weight ratio of 5:5 was charged into the reactor.

[0740] Manufacturing Example 6-4 A polyether polyol was obtained by the same process as in Preparation Example 6-1, except that in step (2) of Preparation Example 6-1, instead of charging a mixture of propylene oxide and ethylene oxide in a weight ratio of 6:4 into the reactor, a mixture of propylene oxide and ethylene oxide in a weight ratio of 4.5:5.5 was charged into the reactor.

[0741] Manufacturing Example 6-5 A polyether polyol was obtained by the same process as in Preparation Example 6-1, except that instead of charging a mixture of propylene oxide and ethylene oxide in a weight ratio of 6:4 into the reactor in step (2) of Preparation Example 6-1, a mixture of propylene oxide and ethylene oxide in a weight ratio of 4:6 was charged into the reactor.

[0742] Manufacturing Example 6-6 A polyether polyol was obtained by the same process as in Preparation Example 6-1, except that 0.16 g of double metal cyanide was added to the reactor in step (2) of Preparation Example 6-1 instead of 0.14 g of double metal cyanide.

[0743] Manufacturing Example 6-7 A polyether polyol was obtained by the same process as in Preparation Example 6-1, except that 0.12 g of double metal cyanide was added to the reactor in step (2) of Preparation Example 6-1 instead of 0.14 g of double metal cyanide.

[0744] Comparative Manufacturing Example 6-1 6 g of the prepolymer 79 obtained in step (1) of Preparation Example 6-1 and 9.8 g of potassium hydroxide were placed in a pressurizable and heatable reactor. The inside of the reactor was then purged with nitrogen, heated to 112°C, and then the water in the reactor was removed under vacuum and reduced pressure conditions.

[0745] 2,204 g of a mixture of propylene oxide and ethylene oxide in a weight ratio of 6:4 was added to the reactor, and the reaction was carried out for about 9 hours and 30 minutes at a temperature of about 110°C. At this time, the temperature of the reactor was controlled so as not to exceed 115°C.

[0746] The mixture remaining in the reactor was stirred until it was completely reacted. After the reaction was completed, the reactor was cooled to 90°C, and 50 g of AMBOSOL and 5 g of diatomaceous earth were added to the reactor. The mixture was stirred at a temperature of about 100°C for 3 hours to remove residual metal ions.

[0747] After it was confirmed that the residual metal ions were not detected, the temperature of the reactor was lowered to 70° C., and the residual by-products were removed by a filter to obtain 3,000 g of polyether polyol.

[0748] Comparative Manufacturing Example 6-2 A polyether polyol was obtained by the same process as in Comparative Preparation Example 6-1, except that instead of charging a mixture of propylene oxide and ethylene oxide in a weight ratio of 6:4 into the reactor in Comparative Preparation Example 6-1, a mixture of propylene oxide and ethylene oxide in a weight ratio of 5:5 was charged into the reactor.

[0749] Comparative Manufacturing Example 6-3 A polyether polyol was obtained by the same process as in Comparative Preparation Example 6-1, except that instead of charging a mixture of propylene oxide and ethylene oxide in a weight ratio of 6:4 into the reactor in Preparation Example 6-1, a mixture of propylene oxide and ethylene oxide in a weight ratio of 30:1 was charged into the reactor.

[0750] Comparative Manufacturing Example 6-4 795 g of the prepolymer obtained in step (1) of Preparation Example 6-1 was placed in a pressurizable and heatable reactor, and the inside of the reactor was then purged with nitrogen and heated to 112°C, after which moisture in the reactor was removed under vacuum and reduced pressure conditions.

[0751] After adding 0.14 g of double metal cyanide to the reactor, 2,200 g of ethylene oxide was added at a constant rate and a polymerization reaction was attempted for about 2 hours at a temperature of about 110°C. However, the double metal cyanide catalyst was not activated, and the polymerization reaction between the prepolymer and ethylene oxide did not occur.

[0752] Comparative Manufacturing Example 6-5 796 g of the prepolymer obtained in step (1) of Preparation Example 6-1 and 9.8 g of potassium hydroxide were placed in a pressurizable and heatable reactor. The inside of the reactor was then purged with nitrogen and heated to 112°C, after which moisture in the reactor was removed under vacuum and reduced pressure.

[0753] 2,204 g of a mixture of propylene oxide and ethylene oxide in a weight ratio of 6:4 was added to the reactor, and the reaction was carried out for about 9 hours and 30 minutes at a temperature of about 110°C. At this time, the temperature of the reactor was controlled so as not to exceed 115°C.

[0754] The mixture remaining in the reactor was stirred until it was completely reacted. After the temperature of the reactor was cooled to 90° C., the remaining by-products were removed with a filter to obtain 3,000 g of polyether polyol.

[0755] Comparative Manufacturing Example 6-6 A polyether polyol was obtained by the same process as in Comparative Preparation Example 6-5, except that instead of charging a mixture of propylene oxide and ethylene oxide in a weight ratio of 6:4 into the reactor in Comparative Preparation Example 6-5, a mixture of propylene oxide and ethylene oxide in a weight ratio of 1:30 was charged into the reactor.

[0756] Example 6 - Production of polyurethane foam Example 6-1 30 g of the polyether polyol prepared in Preparation Example 6-1 was placed in a plastic beaker. Then, 3.5 g of distilled water, 0.2 g of B-8629 (Evonik) and 0.9 g of L-1501 (Momentive) as silicone foam stabilizers, 0.5 g of D-33LV (Air Products) and 0.1 g of M-50 (Tosoh) as amine catalysts, and 0.6 g of diethanolamine as a crosslinking agent were added to the beaker. The mixture was then mixed at 4,000 rpm for 3 minutes using a high-speed mixer to obtain a mixture.

[0757] Thereafter, 58 g of methylene diphenyl isocyanate (CG-3701S, Kumho Co., Ltd.) was added to the mixture, which was then foamed to produce a polyurethane foam.

[0758] Examples 6-2 to 6-7 and Comparative Examples 6-1 to 6-6 A polyurethane foam was produced in the same manner as in Example 6-1, except that 30 g of a polyether polyol listed in Table 13 below was added to the plastic beaker instead of 30 g of the polyether polyol produced in Preparation Example 6-1.

[0759] 6th Experimental Example Experimental Example 6-1-Measurement of primary alcohol content The polyether polyols produced in Production Examples 6-1 to 6-7 and Comparative Production Examples 6-1 to 6-6 were 13 After confirming with C NMR spectrum, 13 The peak at about 61 ppm shown in the C NMR spectrum was analyzed to calculate the content, and the results are shown in Table 12 below. 13 The C NMR spectrum is shown in FIG. 10. 13 The C NMR spectrum is shown in FIG.

[0760] Experimental Example 6-2: Measurement of number average molecular weight To each vessel containing the phthalic anhydride solution, 2.75 g of each of the polyether polyols prepared in Preparation Examples 6-1 to 6-7 and Comparative Preparation Examples 6-1 to 6-6 was added and reacted at 115°C for 30 minutes. The pH was then monitored by titration with 0.5N aqueous sodium hydroxide (NaOH), and the volume (ml) of sodium hydroxide (NaOH) required to reach the inflection point was measured. A separate blank test was also conducted, in which the volume (ml) of sodium hydroxide (NaOH) required to reach the pH inflection point was measured in the same manner as above. The acid value (mg KOH / g) of the polyether polyol was then calculated based on the measured value. The number-average molecular weights of the polyether polyols prepared in Preparation Examples 6-1 to 6-7 and Comparative Preparation Examples 6-1 to 6-6 were then calculated using the acid value and the following relational expression 1. The results are shown in Table 12.

[0761] [Equation 1] Number average molecular weight (g / mol) = (56,100 x equivalent weight) / measured acid number

[0762] Experimental Example 6-3 - Viscosity measurement The viscosity of each of the polyether polyols produced in Production Examples 6-1 to 6-7 and Comparative Production Examples 6-1 to 6-6 was measured at 25°C using a Brookfield DV-III, and the results are shown in Table 12 below.

[0763] Experimental Example 6-4 - Evaluation of storage stability Each of the polyether polyols produced in Production Examples 6-1 to 6-7 and Comparative Production Examples 6-1 to 6-6 was placed in a 450 ml sample bottle and stored for 1 hour at −3° C. After 1 hour, the storage stability of the polyether polyols was evaluated according to the following criteria, and the results are shown in Table 12 below.

[0764] -○: No gel phenomenon occurs -×: Gel phenomenon occurs

[0765] Experimental Example 6-5 - Evaluation of reactivity When producing the polyether polyols of Production Examples 6-1 to 6-7 and Comparative Production Examples 6-1 to 6-6 using a catalyst, the reactivity was evaluated according to the following criteria, and the results are shown in Table 12 below.

[0766] -◎: Polymerization reaction proceeds smoothly -○: Polymerization reaction occurs, but the polymerization reaction rate is slow -×: The catalyst is not activated and the polymerization reaction does not occur.

[0767] Experimental Example 6-6 - Measurement of residual metal content The residual metal content in each of the polyether polyols produced in Preparation Examples 6-1 to 6-7 and Comparative Preparation Examples 6-1 to 6-6 was measured using atomic absorption spectrometry, and the results are shown in Table 12 below.

[0768] [Table 12]

[0769] Experimental Example 6-7 - Evaluation of the physical properties of polyurethane foam The polyurethane foams produced in Examples 6-1 to 6-7 and Comparative Examples 6-1 to 6-6 were each cut into 5cm x 5cm samples. Then, the compression hardness, elongation, compression set, and repeated compression set of the samples were measured using a UTM (Universal Testing Machine) in accordance with ASTM D3574-86, and the results are shown in Table 13 below.

[0770] [Table 13]

[0771] As can be seen from Tables 12 and 13 above, the polyurethane foams of Examples 6-1 to 6-7, which were produced from polyether polyols with a primary alcohol content of 10 mol% to 90 mol%, were found to have significantly improved mechanical properties such as hardness and elongation compared to the comparative examples.

[0772] Specifically, in Comparative Examples 6-1 to 6-3, the primary alcohol content of the polyether polyol was less than 10 mol%, which reduced the reactivity with isocyanate and resulted in poor physical properties of the produced polyurethane foam. In Comparative Example 6-4, a double metal cyanide catalyst was used, but the polymerization reaction did not occur due to its low reactivity with ethylene oxide. In Comparative Examples 6-5 and 6-6, a potassium hydroxide catalyst, which has high reactivity with ethylene oxide, was used, but the residual catalyst content was high, resulting in poor physical properties of the produced polyurethane foam. [Industrial Applicability]

[0773] The examples are applicable to a polyol composition having excellent reactivity with isocyanate and producing polyurethane foam with excellent hardness and appearance quality, a method for producing the same, a composition for producing polyurethane containing the polyol composition, and a battery module.

Claims

1. A polyol composition comprising a compound represented by the following Chemical Formula 1: 【Chemical 1】 In the above formula 1, R １ and R ４ are each independently a substituted or unsubstituted linear alkylene group having 2 to 10 carbon atoms, R ２ and R ３ each independently represents a substituted or unsubstituted branched alkylene group having 3 to 10 carbon atoms, x is a constant between 1 and 10, a and d are each independently a constant from 1 to 6; b and c are each independently a constant of 0 to 30; b+c is a constant between 1 and 60.

2. The compound represented by Chemical Formula 1 above contains at least one unit derived from 1,4:3,6-dianhydrohexitol. The polyol composition of claim 1 .

3. The R １ and R ４ are each independently a substituted or unsubstituted ethylene group; The polyol composition of claim 1 .

4. The R ２ and R ３ are each independently a substituted or unsubstituted propylene group; The polyol composition of claim 1 .

5. the ratio of (a+d):(b+c) is 1:1.5 to 1:6; The polyol composition of claim 1 .

6. The compound represented by Chemical Formula 1 above is a compound represented by Chemical Formula 2 below: The polyol composition of claim 1: 【Chemistry 2】 In the above formula 2, x' is a constant between 1 and 5, a' and d' are each independently a constant of 1 to 3, b' and c' are each independently a constant of 1 to 18.

7. The acid value of the polyol composition is 0.0005 mg KOH / g to 0.0100 mg KOH / g. The polyol composition of claim 1 .

8. The number average molecular weight (Mn) of the polyol composition is 300 g / mol to 12,000 g / mol. The polyol composition of claim 1 .

9. The polydispersity index (PDI) of the polyol composition is 1.0 to 1.

3. The polyol composition of claim 1 .

10. a first unit derived from at least one 1,4:3,6-dianhydrohexitol; and a second unit derived from an alkylene oxide, The degree of unsaturation measured by the following method is 0.02 meq / g or less. Polyol Composition: <Measurement method> 1) A first flask containing 30 g of the polyol composition and a second flask containing no polyol composition were prepared, and 50 ml of mercury acetate was added to each of the first flask and the second flask, followed by stirring for 30 minutes. 2) 9 g of sodium bromide (NaBr) is added to each of the first flask and the second flask, and then the mixture is stirred for 30 minutes. 3) 0.5 ml of 1% phenolphthalein indicator is added to each of the first and second flasks, and titration is carried out with 0.1 N potassium hydroxide (KOH). 4) Calculate the degree of unsaturation using the following formula 1. [Formula 1] Unsaturation (meq / g) = (V ｓ ×V ｂ ×0.1×F) / M (In the above formula 1, the V ｓ is the amount (ml) of 0.1 N potassium hydroxide (KOH) added to the first flask, and V ｂ is the amount (ml) of the 0.1 N potassium hydroxide (KOH) added to the second flask, F is a factor of the 0.1 N potassium hydroxide (KOH), and M is the weight (g) of the polyol composition added to the first flask.

11. The at least one or more 1,4:3,6-dianhydrohexitols include isosorbide. The polyol composition of claim 10.

12. The second unit derived from the alkylene oxide contains a substituted or unsubstituted linear alkylene group having 2 to 10 carbon atoms. The polyol composition of claim 10.

13. The polyol composition contains a compound represented by the following Chemical Formula 3: The polyol composition of claim 10: 【Chemistry 3】 In the above formula 3, R １ and R ２ are each independently a substituted or unsubstituted alkylene group having 2 to 10 carbon atoms, a and f are each independently a constant from 1 to 60; b and e are each independently a constant from 1 to 6; c and d are each independently a constant of 1 to 30; x is a constant between 1 and 5.

14. In the above formula 3, the R １ and R ２ are each independently a substituted or unsubstituted branched alkylene group having 3 to 10 carbon atoms; The polyol composition of claim 13.

15. In the above formula 3, the R １ and R ２ are each independently a random polymer of a substituted or unsubstituted linear alkylene group having 2 to 10 carbon atoms and a substituted or unsubstituted branched alkylene group having 3 to 10 carbon atoms, The polyol composition of claim 13.

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