Polyol composition and method for preparing same, composition for polyurethane preparation including polyol composition, and battery module

Abstract

The polyol composition, the composition for polyurethane preparation including the polyol composition, and the battery module according to the present invention include a compound represented by Chemical Formula 1 (see the specification of the present invention). Furthermore, the polyol composition according to the present invention comprises a first unit derived from at least one 1, 4: 3, 6-dianhydrohexitol and a second unit derived from an alkylene oxide, and the polyol composition according to the present invention has an unsaturation degree of 0.02 meq / g or less according to the following determination method (see the specification of the present invention).

Description

Technical Field

[0001] The present invention relates to a polyol composition, a method for preparing the polyol composition, a composition for preparing a polyurethane comprising the polyol composition, and a battery module comprising the polyol composition. Background Art

[0002] Polyurethane foam has excellent heat insulation and flame retardancy. Such polyurethane foam is used in various fields such as packaging boxes, building boards, home appliances, packaging materials, building interior materials, and thermal insulation materials. Polyurethane foam can be manufactured by foaming polyurethane, and polyurethane can be manufactured by addition-polymerization of polyols and isocyanates.

[0003] Polyol is a liquid polymer substance having two or more hydroxyl groups (-OH) bonded to the ends of its hydrocarbon chain. Polyols are generally manufactured from petroleum-based raw materials. However, due to recent issues such as the depletion of petroleum resources and the reduction of greenhouse gas emissions related to environmental protection, there is an increasing demand for environmentally friendly and renewable materials. Anhydrous alcohols are an environmentally friendly substance derived from renewable natural resources, and much research has been conducted on their ability to improve the properties of polyurethanes. Among anhydrous alcohols, 1,4:3,6-dianhydrohexitol (derived from biomass such as corn, wheat, and sugar, and containing polysaccharides as its components) is widely used as a raw material for polyols. Summary of the invention

[0004] Technical issues

[0005] Therefore, the present invention is made in view of the above problems, and one of the objects of the present invention is to provide a polyol composition having excellent reactivity with isocyanate and allowing excellent hardness and appearance quality of polyurethane foam produced therefrom, a method for preparing the polyol composition, a composition for preparing a polyurethane including the polyol composition, and a battery module including the polyol composition.

[0006] Technical Solutions

[0007] According to aspects of the present invention, the above and other objects can be achieved by providing a polyol composition comprising a compound represented by the following Formula 1:

[0008] [Formula 1]

[0009]

[0010] Among them, R 1 and R 4 are each independently a substituted or unsubstituted straight chain alkylene group having 2 to 10 carbon atoms, R 2 and R 3Each is independently a substituted or unsubstituted branched alkylene group having 3 to 10 carbon atoms, x is an integer from 1 to 10, a and d are each independently an integer from 1 to 6, b and c are each independently an integer from 0 to 30, and b+c is an integer from 1 to 60.

[0011] In an embodiment of the present invention, the compound represented by Formula 1 may include a unit derived from at least one 1,4:3,6-dianhydrohexitol.

[0012] In an embodiment of the present invention, R 1 and R 4 Each independently may be a substituted or unsubstituted ethylene group.

[0013] In an embodiment of the present invention, R 2 and R 3 Each independently may be a substituted or unsubstituted propylene group.

[0014] In an embodiment of the present invention, the ratio of (a+d):(b+c) may be 1:1.5 to 1:6.

[0015] In an embodiment of the present invention, the compound represented by Formula 1 may be a compound represented by the following Formula 2:

[0016] [Formula 2]

[0017]

[0018] wherein x' is an integer from 1 to 5, a' and d' are each independently an integer from 1 to 3, and b' and c' are each independently an integer from 1 to 18.

[0019] In embodiments of the present invention, the polyol composition may have an acid value of about 0.0005 to about 0.0100 mgKOH / g.

[0020] In embodiments of the present invention, the polyol composition may have a number average molecular weight (Mn) of about 300 to about 12,000 g / mol.

[0021] In embodiments of the present invention, the polyol composition may have a polydispersity index (PDI) of about 1.0 to about 1.3.

[0022] According to another aspect of the present invention, there is provided a polyol composition, comprising: a first unit and a second unit, the first unit being derived from at least one 1,4:3,6-dianhydrohexitol, and the second unit being derived from an alkylene oxide, wherein the unsaturation is 0.02 meq / g or less according to the following measurement method:

[0023] <Measurement method>

[0024] 1) preparing a first flask and a second flask, the first flask containing 30 g of the polyol composition, the second flask not containing the polyol composition, and adding 50 ml of mercuric acetate to each of the first flask and the second flask, followed by stirring for 30 minutes;

[0025] 2) adding 9 g of sodium bromide (NaBr) to each of the first flask and the second flask, followed by stirring for 30 minutes;

[0026] 3) 0.5 ml of 1% phenolphthalein indicator was added to each of the first flask and the second flask, followed by titration with 0.1 normal potassium hydroxide (KOH).

[0027] 4) Calculate the degree of unsaturation according to the following formula 1:

[0028] [Formula 1]

[0029] Unsaturation (meq / g) = (V s ×V b ×0.1×F) / M

[0030] Among them, V s represents the amount (ml) of 0.1N potassium hydroxide (KOH) added to the first flask, V b represents the amount (ml) of 0.1 normal potassium hydroxide (KOH) added to the second flask, F represents the factor of the 0.1 normal potassium hydroxide (KOH), and M represents the weight (g) of the polyol composition added to the first flask.

[0031] In an embodiment of the present invention, the 1,4:3,6-dianhydrohexitol may include isosorbide.

[0032] In an embodiment of the present invention, the second unit derived from an alkylene oxide may include a substituted or unsubstituted linear alkylene group having 2 to 10 carbon atoms.

[0033] In an embodiment of the present invention, the polyol composition may include a compound represented by the following Formula 3:

[0034] [Formula 3]

[0035]

[0036] Among them, R 1 and R 2each independently represents a substituted or unsubstituted alkylene group having 2 to 10 carbon atoms, a and f are each independently an integer from 1 to 60, b and e are each independently an integer from 1 to 6, c and d are each independently an integer from 1 to 30, and x is an integer from 1 to 5.

[0037] In an embodiment of the present invention, R in Formula 3 1 and R 2 Each may independently be a substituted or unsubstituted branched alkylene group having 3 to 10 carbon atoms.

[0038] In an embodiment of the present invention, R in Formula 3 1 and R 2 Each may independently be a polymer in which 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 are randomly polymerized.

[0039]

Advantage Effect

[0040] Since the polyol composition according to the present invention includes compounds that can be prepared from renewable natural resources, it is environmentally friendly and has an energy-saving effect.

[0041] Since the polyol composition according to the present invention includes a compound containing a linear alkylene group and a branched alkylene group in the form of a block copolymer, the content of hydroxyl group (-OH) in the primary alcohol is high compared to existing polyols, and thus has excellent reactivity with isocyanate. Therefore, the polyurethane foam produced from the polyol composition can have mechanical properties and processing properties comparable to or better than those of the polyurethane foam manufactured from the existing petroleum-based polyol composition.

[0042] Since the polyol composition according to the present invention has a lower APHA color value, it can be applied to industries that require product transparency.

[0043] The polyol composition according to the present invention can minimize color change even when exposed to a high temperature environment, so that the reliability of the product with respect to color can be ensured when the polyol composition is stored or transported.

[0044] The polyol composition according to the present invention exhibits a low acid value, so that the activity of the catalyst used in the production of the polyurethane foam is not reduced, and the reactivity between the polyol composition and the isocyanate-based composition is improved.

[0045] According to the polyol composition of the present invention, since the content of monofunctional alcohol is greatly reduced, it has excellent reactivity with isocyanate. Therefore, when the polyurethane resin is manufactured from the polyol composition, the crosslinking reaction and the formation of a high molecular weight structure can be smoothly performed, thereby improving the physical properties of the polyurethane resin.

[0046] The polyol composition according to the present invention includes a compound in which the ratio of a linear alkylene group to a branched alkylene group is controlled, so that the surface appearance of a polyurethane foam produced from the polyol composition is excellent.

[0047] The method for preparing a polyether polyol according to the present invention has the effect of greatly reducing the content of a monofunctional alcohol as a product, thereby achieving excellent reactivity with isocyanate. Therefore, when manufacturing a polyurethane resin, a crosslinking reaction and the formation of a high molecular weight structure can be smoothly performed, which has the effect of improving the physical properties of the polyurethane resin.

[0048] The polyether polyol according to the present invention has a high primary alcohol content compared to existing polyols, thereby having excellent reactivity with isocyanate. Therefore, when polyurethane foam is produced from the polyether polyol, a crosslinking reaction and the formation of a high molecular weight structure can be smoothly performed, thereby improving the physical properties of the polyurethane foam. BRIEF DESCRIPTION OF THE DRAWINGS

[0049] Figure 1 is a flow chart briefly illustrating a process of preparing a polyol composition according to a first embodiment.

[0050] Figure 2 is a cross-sectional view briefly illustrating a battery module according to a first embodiment.

[0051] Figure 3 The compound prepared in Preparation Example 1-1 is shown. 13 C NMR spectrum.

[0052] Figure 4 The compounds prepared in Preparation Examples 1-6 are shown 13 C NMR spectrum.

[0053] Figure 5 is a flow chart briefly illustrating a process of preparing a polyol composition according to a third embodiment.

[0054] Figure 6 is a flow chart briefly illustrating a process of preparing a polyol composition according to a fourth embodiment.

[0055] Figure 7 is a flow chart briefly illustrating a process for preparing a polyether polyol according to a fifth embodiment.

[0056] Figure 8 is a flowchart illustrating in detail the steps for preparing the first polymer according to the fifth embodiment.

[0057] Fig. 9 is a flow chart briefly illustrating a process for preparing a polyether polyol according to the sixth embodiment.

[0058] Fig.10 The polyether polyol produced in Production Example 6-1 is shown. 13 C NMR spectrum.

[0059] Fig.11 The polyether polyol produced in Comparative Production Example 6-1 is shown. 13 C NMR. DETAILED DESCRIPTION

[0060] The structural or functional descriptions of the embodiments disclosed in this specification or this application are only for explaining the embodiments of the technical concepts according to the present invention. The embodiments of the technical concepts according to the present invention can be implemented in various forms other than the embodiments disclosed in this specification or this application, and it should not be understood that the technical concepts of the present invention are limited to the embodiments described in this specification or this application.

[0061] In this specification or application, when a component is "included", unless otherwise explicitly stated, this means that only the component is included, or the component may also include other components. In addition, it should be understood that, unless otherwise specified, all numerical ranges of physical property values, sizes, etc. of the components described in this specification or application are modified by the term "about" in all cases.

[0062] <Polyol Composition According to First Example>

[0063] The polyol composition according to the present invention may include a compound represented by the following Formula 1:

[0064] [Formula 1]

[0065]

[0066] In formula 1, R 1 and R 4 are each independently a substituted or unsubstituted straight chain alkylene group having 2 to 10 carbon atoms, R 2 and R 3 Each is independently a substituted or unsubstituted branched alkylene group having 3 to 10 carbon atoms, x is an integer from 1 to 10, a and d are each independently an integer from 1 to 6, b and c are each independently an integer from 0 to 30, and b+c is an integer from 1 to 60.

[0067] The compound represented by Formula 1 may include a parent structure that is a unit derived from at least one 1,4:3,6-dianhydrohexitol. The 1,4:3,6-dianhydrohexitol may include isosorbide.

[0068] Isosorbide can be obtained by dehydration reaction of D-sorbitol which is a renewable natural resource. Since the polyol composition of the present invention includes the compound, it has environmental friendliness and energy-saving effects.

[0069] R 1 and R 4 R may be independently substituted or unsubstituted ethylene. 1 and R 4 It may be derived from a substituted or unsubstituted linear alkylene oxide group having 2 to 10 carbon atoms. 1 and R 4 They may each independently be ethylene.

[0070] R 2 and R 3 Each independently may be a substituted or unsubstituted propylene group.

[0071] R 2 and R 3 It may be derived from a substituted or unsubstituted branched alkylene oxide group having 3 to 10 carbon atoms. 2 and R 3 They may each independently be a propylene group.

[0072] The compound represented by Formula 1 may have the form of a block copolymer in which a propylene group derived from a branched alkylene group is polymerized to a parent structure derived from at least one 1,4:3,6-dianhydrohexitol to form a block, and an ethylene group derived from a linear alkylene group is polymerized to a propylene group to form a block.

[0073] In this way, blocks polymerized with ethylene are formed at both ends of the compound represented by Formula 1, so that the content of hydroxyl groups (-OH) of primary alcohol is higher than that of existing polyol compounds, thereby having excellent reactivity with isocyanate. In addition, polyurethane foams containing the compound can achieve mechanical properties and processing properties comparable to or greater than those of polyurethane foams manufactured from existing petroleum-based polyol compositions.

[0074] 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. (a+b) and (c+d) are each independently 3 to 50. Preferably, (a+b) and (c+d) are each independently 3 to 30, 3 to 20, 5 to 20, 5 to 10, or 5 to 9.

[0075] When the range is satisfied, the polyurethane foam including the compound may have improved hardness, reduced permanent compression set, and excellent appearance due to a smooth surface.

[0076] In addition, when the appropriate level of compression force deformation (CFD) is reached and polyurethane foam is thus applied to the battery module, the volume change caused by the expansion of the battery cell can be buffered so that the volume can be kept constant, thereby improving product stability. CFD is a parameter that represents the repulsive force when the measurement target is compressed.

[0077] CFD can be evaluated by measuring the repulsive force when the polyurethane foam is cut into 5 cm×5 cm size at room temperature and compressed using a device such as a universal testing machine (UTM). For example, the repulsive force when the polyurethane foam is compressed by 25% can be evaluated by the CFD 25% value, and the ideal CFD 25% value range can be about greater than 0.06 kg / cm 2 To less than 0.15kg / cm 2 In addition, the repulsive force when the polyurethane foam is compressed by 50% can be evaluated by the CFD 50% value, and the ideal CFD 50% value range may be about greater than 0.10 kg / cm 2 and less than about 0.20kg / cm 2 .

[0078] The compound represented by Formula 1 may be a compound represented by the following Formula 2:

[0079] [Formula 2]

[0080]

[0081] In Formula 2, x' is an integer of 1 to 5, a' and d' are each independently an integer of 1 to 3, and b' and c' are each independently an integer of 1 to 18.

[0082] Specifically, the type of compound represented by the following Formula 2 can be represented by the compounds of the following Formulas A to I:

[0083] [Formula A]

[0084]

[0085] [Formula B]

[0086]

[0087] [Formula C]

[0088]

[0089] [Formula D]

[0090]

[0091] [Formula E]

[0092]

[0093] [Formula F]

[0094]

[0095] [Formula G]

[0096]

[0097] [Formula H]

[0098]

[0099] [Formula I]

[0100]

[0101] [Formula J]

[0102]

[0103] [Formula K]

[0104]

[0105] [Formula L]

[0106]

[0107] The content of the compound represented by Formula 1 can account for 50 weight % to 99 weight % of the total weight of the polyol composition. Preferably, the content of the compound represented by Formula 1 can account for 60 weight % to 99 weight %, 70 weight % to 99 weight %, 75 weight % to 99 weight %, 77 weight % to 99 weight % or 80 weight % to 99 weight % of the total weight of the polyol composition. When this scope is met, when polyurethane foam is manufactured by polyol composition, the viscosity of the composition increases, thereby not causing the problem of unsmooth foaming. In addition, the molding density and hardness of the manufactured polyurethane foam can be improved.

[0108] Polyol composition can include antioxidant.This antioxidant can improve the thermal stability of the polyurethane foam obtained by polyol composition.This antioxidant can be selected from one or more of the following: based on phenol antioxidant (for example, butylated hydroxytoluene), based on sulphur antioxidant (for example, mercaptopropionic acid derivatives etc.) and based on phosphorus antioxidant (for example, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide etc.).The content of this antioxidant can be with 0.01 weight % to 3 weight %, 0.01 weight % to 2 weight %, 0.02 weight % to 2 weight %, 0.02 weight % to 1 weight % or 0.03 weight % to 1 weight % of the gross weight accounting for polyol composition.

[0109] The controlled polymerization rate (CPR) 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. CRP is an indicator of the amount of alkaline substances in the polyol composition, and can be measured by quantifying the amount of hydrochloric acid (concentration: 0.001N) to be neutralized and titrated after mixing 30 g of the polyol composition with 50 ml of methanol according to the experimental method of ASTM D6437. When this range is satisfied, it is easy to control reactivity during the product manufacturing process, and the product can meet the specifications.

[0110] The degree of unsaturation (DOU) of the polyol composition can 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. DOU is an index of the degree of multiple bonds included in the chemical structure, and DOU can be measured by mixing 30g of the polyol composition with 50ml of mercuric acetate and titrating it. When this range is met, an open cell structure can be fully formed during polyurethane manufacturing to prevent shrinkage and improve physical properties.

[0111] The acid value of the polyol composition can be 0.0005mgKOH / g to 0.0100mgKOH / g, 0.0005mgKOH / g to 0.0050mgKOH / g, 0.0005mgKOH / g to 0.0030mgKOH / g or 0.0005mgKOH / g to 0.0020mgKOH / g. Acid value is an index of the amount of alkali (KOH) required for neutralizing the acidic components of 1g of sample. When this range is met, the acid resistance of the polyurethane foam manufactured by the polyol composition can be enhanced.

[0112] The number average molecular weight (Mn) of the polyol composition can be 100g / mol to 15,000g / mol, 100g / mol to 14,000g / mol, 100g / mol to 13,000g / mol, 300g / mol to 12,000g / mol, 300g / mol to 2,000g / mol, 300g / mol to 1,000g / mol or 400g / mol to 600g / mol. The polydispersity index (PDI) of the polyol composition can be 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 this range is met, the reactivity between the polyol composition and the isocyanate can be improved.

[0113] The American Public Health Association (APHA) color value of the polyol composition can be 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 (HUNTERLAB) according to the test method of ASTM D-1209, and the lower the color value, the clearer and more transparent it can be evaluated. When this range is met, by-products such as unreacted ethylene oxide and unreacted propylene oxide are hardly generated in the polyol composition, so the reliability of the product can be improved.

[0114] The active oxygen content in 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 measurement of active oxygen may be performed using a known method, for example, by a spectrophotometer using a calibration curve showing changes in absorbance according to the active oxygen content. When this range is met, side reactions may be reduced, storage stability may be improved, and color change may not occur.

[0115] The viscosity of polyol composition at room temperature can be 200cPs to 800cPs, 300cPs to 800cPs, 350cPs to 800cPs, 400cPs to 800cPs or 450cPs to 700cPs. Viscosity can be measured using known methods, such as non-contact viscometer. When meeting this scope, it is possible to prevent bubbles from being generated during the production of polyurethane foam, to prevent uneven solidification, and to improve processability.

[0116] The method for preparing a polyol composition according to the present invention comprises: step (a): performing a dehydration treatment by mixing at least one 1,4:3,6-dianhydrohexitol with a catalyst, step (b): generating a first polymer by reacting the dehydrated 1,4:3,6-dianhydrohexitol with a substituted or unsubstituted branched alkylene oxide having 3 to 10 carbon atoms, and step (c): generating a second polymer by reacting the first polymer with a substituted or unsubstituted linear alkylene oxide having 2 to 10 carbon atoms after completing the generation of the first polymer according to step (b), wherein the polyol composition comprises a compound represented by the following formula 1:

[0117] [Formula 1]

[0118]

[0119] In formula 1, R 1 and R 4 are each independently a substituted or unsubstituted straight chain alkylene group having 2 to 10 carbon atoms, R 2 and R 3 Each is independently a substituted or unsubstituted branched alkylene group having 3 to 10 carbon atoms, x is an integer from 1 to 10, a and d are each independently an integer from 1 to 6, b and c are each independently an integer from 0 to 30, and b+c is an integer from 1 to 60.

[0120] Figure 1 is a flow chart briefly illustrating the preparation process of the polyol composition according to the present invention. Figure 1 The preparation 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 1,4:3,6-dianhydrohexitol.

[0121] 1,4:3,6-dianhydrohexitol can exist in three isomers: isomannide, isoidide, and isosorbide. The difference between the three isomers can be that the relative configuration of the two hydroxyl groups (-OH) in each compound is different. Isomanitol can be obtained by the dehydration reaction of D-mannitol. Isoidide can be obtained by the dehydration reaction of L-iditol. Considering the manufacturing process and efficiency, in S10, among the three 1,4:3,6-dianhydrohexitol isomers, it is preferred to use isosorbide.

[0122] Isosorbide can be obtained by a dehydration reaction of D-sorbitol. Specifically, isosorbide can be obtained by a dehydration reaction of D-sorbitol under reduced pressure in the presence of an acidic catalyst.

[0123] The acid catalyst is used to promote the dehydration reaction of D-sorbitol. The acid catalyst can be a soluble acid catalyst, a homogeneous acid catalyst, or an acid-treated heterogeneous acid catalyst. Specifically, the acid catalyst can be sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, p-toluenesulfonic acid, methanesulfonic acid, sulfated metal oxide, or a heteropolyacid catalyst. Preferably, sulfuric acid is used as the acid catalyst.

[0124] The amount of the acid catalyst added may be 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 D-sorbitol. When this range is met, the dehydration reaction rate of D-sorbitol can be increased and the amount of residual catalyst can be minimized.

[0125] The D-sorbitol can be in powder form, or the D-sorbitol can also be in the form of an aqueous solution containing 50wt% to 90wt% of D-sorbitol. In addition, the D-sorbitol can be extracted from nature, or obtained by a synthetic process of reducing glucose.

[0126] Isosorbide can be obtained by removing one water molecule from D-sorbitol to form 1,4-sorbitan as an intermediate product, and then additionally removing one water molecule from 1,4-sorbitan.

[0127] 1,4-sorbitol anhydride can be formed by adding an acidic catalyst to a reactor containing D-sorbitol, and performing dehydration at 80° C. to 140° C. for 1 to 5 hours under normal pressure. When this temperature range is met, the generation of impurities other than 1,4-sorbitol anhydride is reduced, and the dehydration reaction efficiency of converting D-sorbitol into 1,4-sorbitol anhydride is improved.

[0128] Isosorbide can be obtained by the following steps: after 1,4-sorbitan is formed, dehydration is performed at 110° C. to 350° C. under normal pressure for 1 to 10 hours. When this temperature range is met, the generation of impurities other than isosorbide can be reduced, and the dehydration reaction efficiency of converting 1,4-sorbitan to isosorbide can be improved.

[0129] The dehydration treatment for forming 1,4-sorbitan can be performed at a lower temperature than the dehydration treatment for obtaining isosorbide. When the temperature of the dehydration treatment for forming 1,4-sorbitan is controlled to be lower than the temperature of the dehydration treatment for obtaining isosorbide, isosorbide can be obtained at a high yield even without using an acid catalyst.

[0130] Isosorbide can be obtained by the following reaction formula 1:

[0131] [Reaction 1]

[0132]

[0133] The 1,4:3,6-dianhydrohexitol can be mixed with a catalyst to produce active 1,4:3,6-dianhydrohexitol. The 1,4:3,6-dianhydrohexitol can be added to a batch reactor.

[0134] The 1,4:3,6-dianhydrohexitol may be added to the batch reactor in an amount of about 15 wt % to about 50 wt %, about 15 wt % to about 40 wt %, about 25 wt % to about 40 wt %, or about 25 wt % to about 35 wt % based on the total amount of raw materials added to the batch reactor.

[0135] 1,4:3,6-dianhydrohexitol can be introduced into the batch reactor in solid form. 1,4:3,6-dianhydrohexitol can be introduced into the batch reactor in powder form.

[0136] The particles of 1,4:3,6-dianhydrohexitol can be spherical, flake-shaped, or rod-shaped.

[0137] 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.

[0138] The average particle diameter of 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 diameter is measured using a laser diffraction method, and in a particle diameter distribution curve, the average particle diameter may be defined as a particle diameter corresponding to 50% of the volume cumulative amount.

[0139] The moisture content of 1,4:3,6-dianhydrohexitol may be less than about 5 wt%, less than about 4 wt%, less than about 3 wt%, less than about 2 wt%, or less than about 1 wt%. The moisture content may be calculated by subtracting the weight of 1,4:3,6-dianhydrohexitol after drying from the weight of 1,4:3,6-dianhydrohexitol before drying, dividing by the value of the weight of 1,4:3,6-dianhydrohexitol before drying, and then multiplying by 100%. Drying is performed by increasing the temperature from room temperature to about 150° C. and then maintaining it at 150° C., and the total drying time may be set to 20 minutes, including a 5-minute temperature increase step.

[0140] 1,4:3,6-dianhydrohexitol can be introduced into the batch reactor in an aqueous solution state.1,4:3,6-dianhydrohexitol can be introduced into the batch reactor in a concentration of about 70 wt % to about 90 wt %, about 75 wt % to about 90 wt %, or about 75 wt % to about 85 wt %.

[0141] 1,4:3,6-dianhydrohexitol can be introduced into the batch reactor in batches. 1,4:3,6-dianhydrohexitol can be introduced into the batch reactor in the following time periods: about 5 minutes to about 60 minutes, about 10 minutes to about 50 minutes, or about 20 minutes to about 40 minutes. 1,4:3,6-dianhydrohexitol can be added to the batch reactor in equal parts in the following time periods: about 5 minutes to about 60 minutes, about 10 minutes to about 50 minutes, or about 20 minutes to about 40 minutes.

[0142] The catalyst may be a basic catalyst. The basic catalyst may include one or more strong bases selected from the group consisting of potassium hydroxide, sodium hydroxide, potassium metal, and sodium metal.

[0143] The basic catalyst may include a double metal cyanide. The double metal cyanide 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.

[0144] The basic catalyst may include imidazole or an imidazole derivative. The imidazole derivative may be 1,2-dimethylimidazole or 1-isobutyl-2-methylimidazole.

[0145] The catalyst can be introduced into the batch reactor in an aqueous solution state. For example, an aqueous potassium hydroxide solution can be introduced into the batch reactor. The catalyst can be introduced into the batch reactor after the introduction of 1,4:3,6-dianhydrohexitol. The catalyst can be introduced into the batch reactor in batches. The catalyst can be introduced into the batch reactor within the following time period: about 1 minute to about 20 minutes, about 3 minutes to about 15 minutes, or about 8 minutes to about 12 minutes. 1,4:3,6-dianhydrohexitol can be introduced into the batch reactor separately in equal parts within the following time period: about 1 minute to about 20 minutes, about 3 minutes to about 15 minutes, or about 8 minutes to about 12 minutes.

[0146] In S10, the dehydration treatment of 1,4:3,6-dianhydrohexitol may be performed by mixing a catalyst having 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 1,4:3,6-dianhydrohexitol. When this range is satisfied, the dehydration reaction rate of 1,4:3,6-dianhydrohexitol may be increased, and the amount of residual catalyst may be minimized.

[0147] The dehydration treatment of 1,4:3,6-dianhydrohexitol may be performed at a temperature ranging from 80°C to about 120°C, from about 90°C to about 120°C, or from about 100°C to about 120°C.

[0148] The dehydration treatment of 1,4:3,6-dianhydrohexitol may be performed 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.

[0149] The dehydration treatment of 1,4:3,6-dianhydrohexitol may be performed for about 1 hour to about 6 hours, about 1 hour to about 5 hours, or about 2 hours to about 4 hours.

[0150] The dehydration treatment of 1,4:3,6-dianhydrohexitol may be performed at about 80° C. to about 120° C. for about 1 hour to about 5 hours. Preferably, the dehydration treatment of 1,4:3,6-dianhydrohexitol may be performed at about 80° C. to about 120° C. under a pressure condition of about 0.1 torr to about 20.0 torr for about 2 hours to about 4 hours.

[0151] After S10, the moisture content in 1,4:3,6-dianhydrohexitol may be less than about 2,000 ppm, less than about 1,000 ppm, less than about 500 ppm, or about 300 ppm or less. Due to the low moisture content of 1,4:3,6-dianhydrohexitol, the yield of the polyol composition may be increased.

[0152] The preparation method of the present invention may include a step of preparing a first polymer (S20). In S20, the first polymer is prepared by reacting dehydrated 1,4:3,6-dianhydrohexitol with a substituted or unsubstituted branched alkylene oxide having 3 to 10 carbon atoms.

[0153] The substituted or unsubstituted branched alkylene oxide having 3 to 10 carbon atoms may be propylene oxide.Propylene oxide may be introduced into a batch reactor.

[0154] The introduction process of propylene oxide may be performed under a temperature condition of about 80°C to about 130°C, about 90°C to about 130°C, or about 100°C to about 120°C.

[0155] The introduction of propylene oxide may be performed 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.

[0156] The introduction process of propylene oxide can be performed 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 introduction process of propylene oxide can be performed for about 6 hours to about 9 hours at about 80° C. to about 120° C. under a pressure condition of about 2 torr to about 8 torr.

[0157] The introduction rate of propylene oxide 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.

[0158] Propylene oxide may be introduced into the batch reactor in an amount of about 100 to about 500 parts by weight, about 150 to about 500 parts by weight, or about 150 to about 450 parts by weight based on 100 parts by weight of 1,4:3,6-dianhydrohexitol.

[0159] Propylene oxide may undergo an addition reaction with dehydrated 1,4:3,6-dianhydrohexitol in a batch reactor. A first polymer may be prepared by the addition reaction, in which a repeating unit derived from propylene oxide is included in the parent structure of 1,4:3,6-dianhydrohexitol. The repeating unit derived from propylene oxide may refer to a component or structure derived from propylene oxide, or propylene oxide itself.

[0160] The addition reaction between 1,4:3,6-dianhydrohexitol and propylene oxide may be performed at a temperature of about 80°C to about 150°C, about 90°C to about 150°C, or about 100°C to about 140°C.

[0161] The addition reaction between 1,4:3,6-dianhydrohexitol and propylene oxide 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. Preferably, the addition reaction between 1,4:3,6-dianhydrohexitol and propylene oxide can be performed at about 100° C. to about 140° C. for about 1 hour to about 2 hours.

[0162] The step (S20) may further include a process of removing branched alkylene oxide residues after preparing the first polymer. The branched alkylene oxide residues may be propylene oxide. By removing the branched alkylene oxide residues, the reactivity with isocyanate can be improved, the hardness and appearance of the polyurethane foam can be improved, and the economic efficiency of manufacturing can be improved.

[0163] The process of removing the propylene oxide residue may be performed at a temperature of about 80°C to about 150°C, about 90°C to about 150°C, or about 100°C to about 140°C.

[0164] The process of removing the propylene oxide residue may be performed 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.

[0165] The process of removing the propylene oxide residue can be performed for about 10 minutes to about 120 minutes, about 10 minutes to about 60 minutes, or about 20 minutes to about 40 minutes. Preferably, the process of removing the propylene oxide residue can be performed at about 100° C. to about 140° C. under a pressure condition of about 0.1 torr to about 20.0 torr for about 20 minutes to about 40 minutes.

[0166] The preparation method of the present invention may include a step of preparing a second polymer (S30). In S30, the second polymer may be prepared by reacting the first polymer with a substituted or unsubstituted linear alkylene oxide having 2 to 10 carbon atoms.

[0167] The weight ratio of the branched alkylene oxide in S20 to the linear alkylene oxide in 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 this range is satisfied, the reactivity with isocyanate may be increased, and the hardness and appearance quality of the polyurethane foam manufactured from the polyol composition may be improved.

[0168] The substituted or unsubstituted linear alkylene oxide having 2 to 10 carbon atoms may be ethylene oxide. The ethylene oxide may be introduced into a batch reactor in which the first polymer has been prepared.

[0169] The introduction process of ethylene oxide may be performed under a temperature condition of about 80°C to about 140°C, about 90°C to about 140°C, or about 120°C to about 130°C.

[0170] The introduction of ethylene oxide may be performed 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.

[0171] The introduction process of ethylene oxide can be performed 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 introduction process of ethylene oxide can be performed at about 120° C. to about 130° C. under a pressure condition of about 0.1 torr to about 30.0 torr for about 2 hours to about 3 hours.

[0172] The introduction rate of ethylene oxide 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.

[0173] The ethylene oxide may be introduced into the batch reactor in an amount of about 10 to about 100 parts by weight, about 20 to about 100 parts by weight, about 20 to about 80 parts by weight, or about 20 to about 60 parts by weight, based on 100 parts by weight of 1,4:3,6-dianhydrohexitol.

[0174] Ethylene oxide can undergo an addition reaction with the first polymer in a batch reactor. A second polymer can be prepared by the addition reaction, in which the first polymer includes repeating units derived from ethylene oxide. In addition, a second polymer can be prepared, in which repeating units derived from propylene oxide and repeating units derived from ethylene oxide as a block copolymer are included. The repeating units derived from ethylene oxide can refer to components or structures derived from ethylene oxide, or ethylene oxide itself.

[0175] The addition reaction between 1,4:3,6-dianhydrohexitol and ethylene oxide may be performed at a temperature of about 80°C to about 150°C, about 90°C to about 150°C, or about 100°C to about 140°C.

[0176] The addition reaction of 1,4:3,6-dianhydrohexitol with ethylene oxide 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. Preferably, the addition reaction between 1,4:3,6-dianhydrohexitol and ethylene oxide can be performed at about 100° C. to about 140° C. for about 1 hour to about 2 hours.

[0177] In S30, after preparing the second polymer, a process of removing linear alkylene oxide residues may be further included. The linear alkylene oxide residues may be ethylene oxide.

[0178] The process of removing the ethylene oxide residue may be performed at a temperature of about 80°C to about 150°C, about 90°C to about 150°C, or about 100°C to about 140°C.

[0179] The process of removing the propylene oxide residue may be performed 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.

[0180] The process of removing the ethylene oxide residue can be performed 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 process of removing the ethylene oxide residue can be performed for about 40 minutes to about 80 minutes under a temperature condition of about 100° C. to about 140° C. and a pressure condition of about 0.1 torr to about 20.0 torr.

[0181] The preparation method of the present invention may further include a step of removing metal ion residues (S40) and a filtering step (S50). In S40, the metal ion residues in the polyol composition may be removed, and in S50, the polyol composition from which the metal ion residues have been removed may be filtered.

[0182] In S40, an additive may be added to the polyol composition that has undergone the reaction to remove metal ion residues. The additive may be one or more selected from the following: diatomaceous earth, alumina, MAGNESOL, CELITE, AMBOSOL, and silica gel.

[0183] The additive can be introduced into the polyol composition that has been reacted in the form of an aqueous dispersion. The additive can be introduced into the polyol composition that has been reacted in the following weight parts: the weight of the additive is 1 to 10 parts by weight, 1 to 8 parts by weight, 2 to 8 parts by weight, 3 to 8 parts by weight, 3 to 6 parts by weight based on 100 parts by weight of 1,4:3,6-dianhydrohexitol.

[0184] Next, in S40, a process of neutralizing the polyol composition to which the additive is added may be performed. The neutralization process may 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. Next, a process of removing moisture from the polyol composition that has undergone the neutralization process may be performed. The moisture removal process may be performed at a temperature of about 90°C to about 130°C, about 95°C to about 130°C, or about 100°C to about 130°C. As required, in S40, a process of detecting metal ion residues may be performed, and when metal ion residues are not detected, the polyol composition may be performed 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 moisture has been removed may be filtered. Additives and by-products may be filtered out.

[0185] The polyol composition prepared according to the preparation method may include a compound represented by the following Formula 1: [Formula 1]

[0186]

[0187] In formula 1, R 1 and R 4 are each independently a substituted or unsubstituted straight chain alkylene group having 2 to 10 carbon atoms, R 2 and R 3 Each is independently a substituted or unsubstituted branched alkylene group having 3 to 10 carbon atoms, x is an integer from 1 to 10, a and d are each independently an integer from 1 to 6, b and c are each independently an integer from 0 to 30, and b+c is an integer from 1 to 60.

[0188] The compound represented by Formula 1 may be the same as the aforementioned compound.

[0189] The composition for preparing polyurethane according to the present invention may include a polyol composition and an isocyanate-based composition, and the polyol composition may include the compound represented by Formula 1 described above.

[0190] The isocyanate composition may include at least one selected from the group consisting of an aliphatic polyisocyanate, an alicyclic polyisocyanate, an araliphatic polyisocyanate, an aromatic polyisocyanate, and a heterocyclic polyisocyanate.

[0191] The isocyanate composition may include an unmodified polyisocyanate or a modified polyisocyanate.

[0192] The polyisocyanate may include at least one selected from the group consisting of 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, dicyclohexylmethane-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 diphenylmethane diisocyanate (PMDI), and naphthalene-1,5-diisocyanate.

[0193] As the polyisocyanate, toluene diisocyanate prepared by mixing 2,4-toluene diisocyanate and 2,6-toluene diisocyanate (2,4- / 2,6-isomer ratio=80 / 20) may be used, or polymeric diphenylmethane diisocyanate may be used.

[0194] The appropriate amount of the polyisocyanate used may be 70 to 130, 80 to 120 in terms of isocyanate index (NCO index). Preferably, the appropriate amount of the polyisocyanate used may be 100 to 120 in terms of isocyanate index (NCO index).

[0195] The isocyanate index refers to the ratio of the number of equivalents of hydroxyl groups (—OH) present in the polyol to the number of equivalents of isocyanate in the polyurethane reactant, and means the amount of isocyanate used relative to the theoretical equivalent.

[0196] If the isocyanate index is less than 100, this means that an excess of polyol is present, whereas if the isocyanate index is greater than 100, this means that an excess of isocyanate is present.

[0197] If the isocyanate index is less than 70, the reactivity is low, the gelation reaction is delayed, and curing may not occur, whereas if the isocyanate index is greater than 130, the amount of hard segments may excessively increase, and a shrinkage problem may occur.

[0198] The composition for preparing polyurethane may include a curing catalyst. The curing catalyst is not specifically limited, and the curing catalyst may be an amine catalyst, an organometallic catalyst or a mixture thereof. The curing catalyst may play a role in promoting the reaction between the polyol composition and the isocyanate composition.

[0199] The type of amine catalyst is not particularly limited, and preferably one or a mixture of two or more selected from tertiary amine catalysts is used as the amine catalyst. For example, at least one selected from the following groups can be used as the amine catalyst: triethylenediamine, triethylamine, N-methylmorpholine, N-ethylmorpholine.

[0200] As the organic metal catalyst, an organic metal catalyst commonly used in the production of polyurethane foam can be used. For example, at least one selected from the group consisting of tin octoate, dibutyltin dilaurate (DBTDL), and di[2-ethylhexanoate]tin can be used.

[0201] The curing catalyst may be included in an amount of 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 this range is met, poor curing, shrinkage, or sedimentation of the polyurethane foam during formation can be reduced.

[0202] The composition for preparing polyurethane may include a foam stabilizer, which may prevent cells formed inside the polyurethane foam from being merged or destroyed, and may play a role in regulating the formation of cells having uniform shapes and sizes.

[0203] The foam stabilizer is not particularly limited as long as it is a stabilizer commonly used in the production of polyurethane foam, and for example, a silicone-based foam stabilizer can be used. The silicone-based foam stabilizer can be selected from one or more of silicone oils and derivatives thereof, and specifically can be a polyalkylene oxide-methylsiloxane copolymer.

[0204] 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 this range is satisfied, shrinkage of the manufactured foam may be prevented, and uniform formability may be exhibited.

[0205] The composition for preparing polyurethane may include a blowing agent. A representative example of the blowing agent is water, and in addition to water, at least one selected from the following may be used: 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 general method of use, and may also be appropriately used according to the density of the desired foam or its other characteristics.

[0206] The blowing agent may be used in an amount of about 0.1 to about 60 parts by weight, about 0.2 to about 60 parts by weight, about 0.3 to about 60 parts by weight, about 0.3 to about 50 parts by weight, or about 1 to about 30 parts by weight, based on 100 parts by weight of the polyol composition.

[0207] The composition for preparing polyurethane may not contain a blowing agent. That is, in the process of preparing polyurethane foam using the composition for preparing polyurethane, a gaseous blowing agent such as nitrogen may be directly injected into the composition for preparing polyurethane to form fine cells.

[0208] The composition for preparing the polyurethane may further include auxiliary additives selected from the group consisting of flame retardants, colorants, UV stabilizers, thickeners, foam stabilizers, fillers, and combinations thereof.

[0209] The composition for preparing polyurethane may be a one-component type or a two-component type. When the composition for preparing polyurethane is a two-component type, it may be divided into two components and stored, and the two components may be mixed immediately before the production process of the polyurethane resin is performed.

[0210] When the composition for preparing polyurethane is of a two-component type, the composition for preparing polyurethane may include a first component mainly composed of a polyol composition and a second component mainly composed of an isocyanate composition.

[0211] The first component may include a polyol composition, a curing catalyst, a foam stabilizer, a blowing agent, and other additives.

[0212] The second component may include an isocyanate composition.

[0213] Polyurethane foam can be produced from a composition for preparing polyurethane. The method for producing polyurethane foam may include: step (a): supplying a second component through an isocyanate supply device, gas supply step (b): supplying a gas for foaming through a gas supply device, step (c): supplying a first component through a polyol supply device, step (d): mixing the first component, the second component, and the gas for foaming through a mixer to prepare a polyurethane foam composition, and step (e): curing the polyurethane foam composition.

[0214] The gas used for foaming in step (b) may include nitrogen or carbon dioxide.

[0215] The first component of step (c) may also include a curing catalyst, a foam stabilizer, a blowing agent, and other additives.

[0216] When the first component supplied in step (c) is included in the blowing agent, the gas supplying step of step (b) may be omitted.

[0217] The produced polyurethane foam may include micro-closed cells in its interior. For example, the polyurethane foam may include micro-closed pores.

[0218] The average diameter of the micro-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.

[0219] A battery module according to the present invention may include: a shell, a plurality of battery cells and polyurethane foam, wherein the plurality of battery cells are accommodated inside the shell, the polyurethane foam is arranged between the plurality of battery cells, the polyurethane foam includes a composition for preparing polyurethane, the composition includes a polyol composition and an isocyanate-based composition, and the polyol composition may include a compound represented by Formula 1 described above.

[0220] Figure 2 FIG. 2 is a cross-sectional view briefly illustrating a battery module according to the present invention. Figure 2 , the battery module 100 according to the present invention includes a housing 101. The housing 101 may be a structure designed to accommodate a plurality of battery cells 102 inside the housing 101 and protect them from external impacts, etc. The housing 101 may be made of a metal material having high mechanical strength. However, the material of the housing 101 is not limited to a metal material, and the housing 101 may also be made of a non-metal material to ensure insulation.

[0221] The battery module 100 may include a thermally conductive adhesive 104. The thermally conductive adhesive 104 may fix the plurality of battery cells 102 into the housing 101, and the thermally conductive adhesive may allow heat of the plurality of battery cells 102 to be well transferred to the housing 101. As the thermally conductive adhesive 104, various organic or inorganic resins such as a thermally conductive epoxy adhesive, a thermally conductive silicone adhesive, and a thermally conductive polyurethane adhesive may be used.

[0222] The plurality of battery cells 102 may be configured in a bag shape, wherein the number of stacked pieces per unit area may be maximized. The plurality of battery cells 102 configured in a bag shape may be manufactured by accommodating an electrode assembly including a positive electrode, a negative electrode, and a separator into a unit housing of a laminate sheet, and then heat-melting a sealing portion of the unit housing. However, the plurality of battery cells 102 may not necessarily be configured in a bag shape, and may be configured in a square, cylindrical, or other various shapes, as long as the storage capacity required for the equipment to be installed in the future can be achieved.

[0223] The battery module 100 includes a plurality of battery cells 102 and a polyurethane foam 103, wherein the plurality of battery cells 102 are contained in a housing 101, and the polyurethane foam 103 is arranged between the plurality of battery cells 102. The polyurethane foam 103 has excellent vibration absorbency and excellent compression repulsion, so that even if the plurality of battery cells 102 expand, dimensional stability can be maintained. In addition, damage to the battery module 100 due to the expansion of the plurality of battery cells 102 can be prevented. The plurality of battery cells 102 may have different degrees of expansion depending on the chemical properties and the use environment. In view of this, the maximum compressible thickness range of the polyurethane foam 103 can be selected within the range of the expanded thickness that can accommodate the plurality of battery cells 102, etc.

[0224] <Polyol Composition According to Second Example>

[0225] The polyol composition according to the present invention may include a first unit derived from at least one 1,4:3,6-dianhydrohexitol and a second unit derived from an alkylene oxide, and may have an American Public Health Association (APHA) color value of 20 or less according to ASTM-D1209.

[0226] The 1,4:3,6-dianhydrohexitol and isosorbide may be the same as the 1,4:3,6-dianhydrohexitol and isosorbide described above.

[0227] The polyol composition may include a first unit derived from 1,4:3,6-dianhydrohexitol, and the first unit accounts for a content of 5 to 50 weight %, 10 to 50 weight %, 10 to 45 weight %, 15 to 45 weight %, or 20 to 45 weight % of the gross weight of the polyol composition. When this range is met, when polyurethane foam is manufactured according to the polyol composition, the viscosity of the composition will increase, and the problem of unsmooth foaming will not be caused. In addition, the molding density and hardness of the manufactured polyurethane foam can be improved.

[0228] The alkylene oxide may be the same as the alkylene oxide described above.

[0229] Generally, polyol compositions prepared from petroleum-based raw materials exhibit high APHA color values, making it difficult to apply them to industries that require product transparency. In addition, there is also the problem that the color value of APHA rises rapidly under high temperature conditions, resulting in an increase in color of the polyol composition during storage or transportation.

[0230] Therefore, the polyol composition according to the present invention can be manufactured from renewable natural resources, and compared with the polyol composition manufactured from petroleum-based raw materials, the polyol composition according to the present invention exhibits a lower APHA color value, thereby being environmentally friendly and suitable for industries requiring product transparency. In addition, even when exposed to high temperature environments, color changes can be minimized, so the reliability of the product in terms of color can be ensured when the polyol composition is stored or transported.

[0231] The polyol composition according to the present invention has an American Public Health Association (APHA) 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.

[0232] Specifically, the color of the polyol composition may be measured using ColorQuest XE (HunterLab), and the American Public Health Association (APHA) color value (platinum-cobalt system) may be measured from the color number of the polyol composition according to ASTM-D1209.

[0233] When this range is met, the polyol composition can be colorless and transparent, and polyurethane foam with lower 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, so the reliability of the product can be improved.

[0234] The content of the metal remaining in the polyol composition accounting for the gross weight of the polyol composition can be 10ppm or less, 7ppm or less, 5ppm or less, 4ppm or less, 3ppm or less or 1ppm or less. The metal can include potassium. When this range is met, even if the polyol composition is exposed to a hot environment, the color change caused by the metal ion can be minimized.

[0235] The difference between the second APHA color value and the first APHA color value of the polyol composition may be 10 or less, 8 or less, or 5 or less, according to the following measurement method:

[0236] <Measurement method>

[0237] 1) The first APHA color value of the polyol composition is measured according to ASTM-D1209.

[0238] 2) The polyol composition was stored in an oven at 75°C for 10 minutes.

[0239] 3) The polyol composition was taken out of the oven, and then exposed to the atmosphere for 24 hours.

[0240] 4) According to ASTM-D1209, the second APHA color value of the polyol composition is measured.

[0241] When this range is satisfied, product reliability regarding color can be ensured when the polyol composition is stored or transported.

[0242] The viscosity of the polyol composition at 25°C can be 200cPs to 800cPs, 300cPs to 800cPs, 350cPs to 800cPs, 350cPs to 700cPs or 350cPs to 600cPs. Viscosity can be measured using known methods, for example, viscosity can be measured using a non-contact viscometer. When this range is met, the storage stability of the polyol composition can be improved, the production of bubbles can be prevented when producing polyurethane foam, and uneven solidification can be prevented, so processability can be improved.

[0243] The number average molecular weight (Mn) of the polyol composition can be 300g / mol to 20,000g / mol, 300g / mol to 18,000g / mol, 300g / mol to 15,000g / mol, 300g / mol to 12,000g / mol, 500g / mol to 12,000g / mol, 500g / mol to 10,000g / mol, or 500g / mol to 3,000g / mol. The polydispersity index (PDI) of the polyol composition can be 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 this range is met, the reactivity between the polyol composition and the isocyanate can be improved.

[0244] The polyol composition may also include an antioxidant as described above.

[0245] The polyol composition can have the controlled polymerization rate (CPR) values ​​described above.

[0246] The polyol composition may have an acid value as described above.

[0247] The polyol composition may have the active oxygen content values ​​described above.

[0248] The polyol composition may include the compound represented by Formula 1 described above.

[0249] The method for preparing a polyol composition according to the present invention may include: step (a): performing a dehydration treatment by mixing at least one 1,4:3,6-dianhydrohexitol with a catalyst; step (b): generating a first polymer by reacting the dehydrated 1,4:3,6-dianhydrohexitol with a substituted or unsubstituted branched alkylene oxide having 3 to 10 carbon atoms; and step (c): after completing the generation of the first polymer according to step (b), generating a second polymer by reacting the first polymer with a substituted or unsubstituted linear alkylene oxide having 2 to 10 carbon atoms, wherein the polyol composition may have an American Public Health Association (APHA) color value of 20 or less according to ASTM-D1209.

[0250] The method for preparing the polyol composition according to the present invention can be carried out in the same manner as described above. Figure 1 Execute in the same way as the content.

[0251] The polyol composition prepared according to the preparation method can have an American Public Health Association (APHA) color value 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 according to ASTM-D1209.

[0252] Specifically, the color of the polyol composition may be measured using ColorQuest XE (HunterLab), and the American Public Health Association (APHA) color value (platinum-cobalt system) may be determined from the color number of the polyol composition according to ASTM-D1209.

[0253] When this range is met, the prepared polyol composition can be colorless and transparent, and a 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, so the reliability of the product can be improved.

[0254] The composition for preparing polyurethane according to the present invention includes a first unit derived from at least one 1,4:3,6-dianhydrohexitol and a second unit derived from an alkylene oxide, and the composition for preparing polyurethane according to the present invention includes a polyol composition according to ASTM-D1209, and the polyol composition has an American Public Health Association (APHA) color value of 20 or less.

[0255] The polyol composition and the isocyanate-based composition may be the same as the polyol composition and the isocyanate-based composition described above.

[0256] The polyurethane foam can be produced from the composition for preparing polyurethane. The composition for preparing polyurethane can be the same as the composition for preparing polyurethane described above.

[0257] The battery module according to the present invention is a battery module including a shell, a plurality of battery cells and a polyurethane foam, wherein the plurality of battery cells are accommodated inside the shell, the polyurethane foam is arranged between the plurality of battery cells, the polyurethane foam includes a composition for preparing a polyurethane, the composition includes a polyol composition and an isocyanate-based composition, and the polyol composition includes a first unit and a second unit, the first unit is derived from at least one 1,4:3,6-dianhydrohexitol, the second unit is derived from an alkylene oxide, and the polyol composition has an American Public Health Association (APHA) color value of 20 or less according to ASTM-D1209.

[0258] The battery module according to the present invention can refer to the above-described Figure 3 Same content as the battery module.

[0259] <Polyol Composition According to Third Example>

[0260] The polyol composition according to the present invention may include a first unit derived from at least one 1,4:3,6-dianhydrohexitol and a second unit derived from an alkylene oxide, and may have an acid value of less than 0.02 mgKOH / g according to the following measurement method.

[0261] <Measurement method>

[0262] 1) A first flask and a second flask were prepared, the first flask contained the polyol composition, and the second flask contained no polyol composition, and 50 ml of methanol was added to each of the first flask and the second flask, followed by stirring for 30 minutes.

[0263] 2) 0.5 ml of 1% phenolphthalein indicator was added to each of the first flask and the second flask, and then titrated with 0.02 normal potassium hydroxide (KOH) until the composition in the first flask and the second flask turned pink for 30 seconds.

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

[0265] [Formula 1]

[0266] Acid value (mgKOH / g) = [(V s -V b )×56.1×N×F] / M.

[0267] In Formula 1, V sThe amount (ml) of 0.02 N potassium hydroxide (KOH) consumed for titrating the composition in the first flask, V b The amount (ml) of 0.02 N potassium hydroxide (KOH) consumed for titrating the composition in the second flask, N represents the normality of potassium hydroxide (KOH), F represents the factor of 0.02 N potassium hydroxide (KOH), and M represents the weight (g) of the polyol composition added to the first flask.

[0268] 1,4:3,6-Dianhydrohexitol and isosorbide may be the same as the 1,4:3,6-dianhydrohexitol and isosorbide described above.

[0269] The alkylene oxide may be the same as the alkylene oxide described above.

[0270] Generally, polyol compositions manufactured from petroleum-based raw materials exhibit a relatively high acid value, and in the production of polyurethane foams, the activity of the amine catalysts used is reduced through neutralization between the catalysts and the polyol compositions, resulting in a problem of reduced reactivity between the polyol compositions and the isocyanate-based compositions. This is because it reduces the production process efficiency and moldability of polyurethane foams.

[0271] Therefore, the polyol composition according to the present invention can be prepared from renewable natural resources. Compared with polyol compositions prepared from petroleum-based raw materials, the polyol composition according to the present invention exhibits a lower acid value, making it environmentally friendly. In addition, the activity of the catalysts used in the production of polyurethane foams is not reduced, and the reactivity between the polyol composition and the isocyanate-based composition can be increased. Therefore, the production process efficiency and moldability of polyurethane foams can be improved.

[0272] According to the following measurement method, the polyol composition according to the present invention has an acid value of less than 0.02 mg KOH / g:

[0273] <Measurement method>

[0274] 1) Prepare a first flask and a second flask. The first flask contains the polyol composition, and the second flask does not contain the polyol composition. Add 50 ml of methanol to each of the first flask and the second flask, and then stir for 30 minutes.

[0275] 2) Add 0.5 ml of 1% phenolphthalein indicator to each of the first flask and the second flask, and then titrate with 0.02 N potassium hydroxide (KOH) until the compositions in the first flask and the second flask turn pink and remain pink for 30 seconds.

[0276] 3) Use the following formula 1 to calculate the acid value:

[0277] [Formula 1]

[0278] Acid value (mgKOH / g) = [(V s -V b )×56.1×N×F] / M.

[0279] In Formula 1, V s V represents the amount (ml) of 0.02N potassium hydroxide (KOH) consumed to titrate the composition in the first flask, V b represents the amount (ml) of 0.02 normal potassium hydroxide (KOH) consumed for titrating the composition in the second flask, N represents the normality of potassium hydroxide (KOH), F represents the factor of 0.02 normal potassium hydroxide (KOH), and M represents the weight (g) of the polyol composition added to the first flask.

[0280] According to the measuring method, the polyol composition has an acid value of each of the following: 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. In addition, the lower limit of the acid value does not need to be limited, but can be greater than 0 mgKOH / g, 0.005 mgKOH / g or greater, or 0.010 mgKOH / g or greater. When this range is met, the acid resistance of the polyurethane foam manufactured by the polyol composition can be enhanced, and the reactivity between the polyol composition and the isocyanate-based composition can be improved.

[0281] The residual metal content in the polyol composition may be the same as the metal content described above.

[0282] The viscosity of the polyol composition may be the same as described above.

[0283] The polyol composition according to the present invention may have the American Public Health Association (APHA) color value described above.

[0284] The polyol composition can have the number average molecular weight (Mn) and polydispersity index (PDI) described above.

[0285] The polyol composition may also include an antioxidant as described above.

[0286] The polyol composition can have the controlled polymerization rate (CPR) values ​​described above.

[0287] The polyol composition may have the active oxygen content values ​​described above.

[0288] The polyol composition may include the compound represented by Formula 1 described above.

[0289] The method for preparing a polyol composition according to the present invention may include: step (a): performing a dehydration treatment by mixing at least one 1,4:3,6-dianhydrohexitol with a catalyst, step (b): generating a first polymer by reacting the dehydrated 1,4:3,6-dianhydrohexitol with a substituted or unsubstituted branched alkylene oxide having 3 to 10 carbon atoms, and step (c): generating a second polymer by reacting the first polymer with a substituted or unsubstituted linear alkylene oxide having 2 to 10 carbon atoms after completing the generation of the first polymer according to step (b), wherein the polyol composition may have an acid value of less than 0.02 mgKOH / g according to the following measurement method:

[0290] <Measurement method>

[0291] 1) A first flask and a second flask were prepared, the first flask contained the polyol composition, and the second flask contained no polyol composition, and 50 ml of methanol was added to each of the first flask and the second flask, followed by stirring for 30 minutes.

[0292] 2) 0.5 ml of 1% phenolphthalein indicator was added to each of the first flask and the second flask, and then titrated with 0.02 normal potassium hydroxide (KOH) until the composition in the first flask and the second flask turned pink for 30 seconds.

[0293] 3) Calculate the acid value using the following formula 1:

[0294] [Formula 1]

[0295] Acid value (mgKOH / g) = [(V s -V b )×56.1×N×F] / M.

[0296] In Formula 1, V s V represents the amount (ml) of 0.02N potassium hydroxide (KOH) consumed to titrate the composition in the first flask, V b represents the amount (ml) of 0.02 normal potassium hydroxide (KOH) consumed for titrating the composition in the second flask, N represents the normality of potassium hydroxide (KOH), F represents the factor of 0.02 normal potassium hydroxide (KOH), and M represents the weight (g) of the polyol composition added to the first flask.

[0297] Figure 5 is a flow chart briefly illustrating the process of preparing a polyol composition according to the present invention. Figure 5The preparation method of the present invention may include a dehydration step (S10-1). The step (S10-1) may be the same as the step (S10) described above.

[0298] The preparation method of the present invention may include a step (S20-1) of preparing a first polymer. The step (S20-1) may be the same as the step (S20) described above.

[0299] The preparation method of the present invention may include a step (S30-1) of preparing a second polymer. The step (S30-1) may be the same as the step (S30) described above.

[0300] The preparation method of the present invention may further include: step (S40-1): removing metal ion residues and filtering; and step (S0-1): adding an antioxidant. In step (S40-1), the metal ion residues in the polyol composition may be removed and filtered, and, in step (S50-1), a process of adding an antioxidant to the polyol composition may be performed.

[0301] In step (S40-1), an additive may be introduced into the polyol composition that has undergone the reaction to remove metal ion residues. The additive may be one or more selected from the group consisting of diatomaceous earth, alumina, MAGNESOL, CELITE, AMBOSOL, and silica gel.

[0302] The additive may be introduced into the polyol composition that has been reacted in the form of an aqueous dispersion. The additive may be introduced into the polyol composition that has been reacted 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 1,4:3,6-dianhydrohexitol.

[0303] Next, in S40-1, a process of neutralizing the polyol composition to which the additive is added may be performed. The neutralization process may 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. Next, a water removal process may be performed on the polyol composition that has undergone the neutralization process. The water removal process may be performed at a temperature of about 90°C to about 130°C, about 95°C to about 130°C, or about 100°C to about 130°C. As required, step (S40-1) may include a process of detecting metal ion residues, and when metal ion residues are not detected, the polyol composition may be performed 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 moisture has been removed may be filtered. Additives and by-products may be filtered out.

[0304] In S50-1, an antioxidant may be added to the polyol composition, the antioxidant comprising one or more selected from the following: a phenol-based antioxidant (e.g., butylated hydroxytoluene), a sulfur-based antioxidant (e.g., mercaptopropionic acid derivatives, etc.), and a phosphorus-based antioxidant (e.g., 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, etc.). The antioxidant may be introduced 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 may improve the thermal stability of the polyurethane foam obtained from the polyol composition and may reduce odor production.

[0305] The polyol composition prepared according to the preparation method has an acid value 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 according to the following measurement method, and there is no need to particularly limit the lower limit of the acid value, but the lower limit may be greater than 0 mgKOH / g, 0.005 mgKOH / g or more, or 0.010 mgKOH / g or more:

[0306] <Measurement method>

[0307] 1) A first flask and a second flask were prepared, the first flask contained the polyol composition, and the second flask contained no polyol composition, and 50 ml of methanol was added to each of the first flask and the second flask, followed by stirring for 30 minutes.

[0308] 2) 0.5 ml of 1% phenolphthalein indicator was added to each of the first flask and the second flask, and then titrated with 0.02 normal potassium hydroxide (KOH) until the composition in the first flask and the second flask turned pink for 30 seconds.

[0309] 3) Calculate the acid value using the following formula 1:

[0310] [Formula 1]

[0311] Acid value (mgKOH / g) = [(V s -V b )×56.1×N×F] / M.

[0312] In Formula 1, V s V represents the amount (ml) of 0.02N potassium hydroxide (KOH) consumed to titrate the composition in the first flask, V b represents the amount (ml) of 0.02 normal potassium hydroxide (KOH) consumed for titrating the composition in the second flask, N represents the normality of potassium hydroxide (KOH), F represents the factor of 0.02 normal potassium hydroxide (KOH), and M represents the weight (g) of the polyol composition added to the first flask.

[0313] When this range is satisfied, the acid resistance of a polyurethane foam produced from the polyol composition may be enhanced, and the reactivity between the polyol composition and the isocyanate-based composition may be improved.

[0314] The composition for preparing polyurethane according to the present invention may include a first unit and a second unit, the first unit being derived from at least one 1,4:3,6-dianhydrohexitol, the second unit being derived from an alkylene oxide, and according to the following measurement method, the composition for preparing polyurethane according to the present invention may include a polyol composition and an isocyanate-based composition, the polyol composition including an acid value of less than 0.02 mgKOH / g:

[0315] <Measurement method>

[0316] 1) A first flask and a second flask were prepared, the first flask contained the polyol composition, and the second flask contained no polyol composition, and 50 ml of methanol was added to each of the first flask and the second flask, followed by stirring for 30 minutes.

[0317] 2) 0.5 ml of 1% phenolphthalein indicator was added to each of the first flask and the second flask, and then titrated with 0.02 normal potassium hydroxide (KOH) until the composition in the first flask and the second flask turned pink for 30 seconds.

[0318] 3) Calculate the acid value using the following formula 1:

[0319] [Formula 1]

[0320] Acid value (mgKOH / g) = [(V s -V b )×56.1×N×F] / M.

[0321] In Formula 1, V s V represents the amount (ml) of 0.02N potassium hydroxide (KOH) consumed to titrate the composition in the first flask, V b represents the amount (ml) of 0.02 normal potassium hydroxide (KOH) consumed for titrating the composition in the second flask, N represents the normality of potassium hydroxide (KOH), F represents the factor of 0.02 normal potassium hydroxide (KOH), and M represents the weight (g) of the polyol composition added to the first flask.

[0322] The polyol composition and the isocyanate-based composition may be the same as the polyol composition and the isocyanate-based composition described above.

[0323] The polyurethane foam can be produced from the composition for preparing polyurethane. The composition for preparing polyurethane can be the same as the composition for preparing polyurethane described above.

[0324] The battery module according to the present invention is a battery module including a housing, a plurality of battery cells and a polyurethane foam, wherein the plurality of battery cells are accommodated inside the housing, the polyurethane foam is arranged between the plurality of battery cells, the polyurethane foam includes a composition for preparing a polyurethane, the composition includes a polyol composition and an isocyanate-based composition, and the polyol composition includes a first unit and a second unit, the first unit is derived from at least one 1,4:3,6-dianhydrohexitol, the second unit is derived from an alkylene oxide, and the polyol composition has an acid value of less than 0.02 mgKOH / g according to the following measurement method:

[0325] <Measurement method>

[0326] 1) A first flask and a second flask were prepared, the first flask contained the polyol composition, and the second flask contained no polyol composition, and 50 ml of methanol was added to each of the first flask and the second flask, followed by stirring for 30 minutes.

[0327] 2) 0.5 ml of 1% phenolphthalein indicator was added to each of the first flask and the second flask, and then titrated with 0.02 normal potassium hydroxide (KOH) until the composition in the first flask and the second flask turned pink for 30 seconds.

[0328] 3) Calculate the acid value using the following formula 1:

[0329] [Formula 1]

[0330] Acid value (mgKOH / g) = [(V s -V b )×56.1×N×F] / M.

[0331] In Formula 1, V s V represents the amount (ml) of 0.02N potassium hydroxide (KOH) consumed to titrate the composition in the first flask, V b represents the amount (ml) of 0.02 normal potassium hydroxide (KOH) consumed for titrating the composition in the second flask, N represents the normality of potassium hydroxide (KOH), F represents the factor of 0.02 normal potassium hydroxide (KOH), and M represents the weight (g) of the polyol composition added to the first flask.

[0332] The battery module according to the present invention can refer to the above-described Figure 3 The battery module has the same contents.

[0333] <Polyol Composition According to Fourth Example>

[0334] The polyol composition according to the present invention may include a first unit derived from at least one 1,4:3,6-dianhydrohexitol and a second unit derived from an alkylene oxide, and the polyol composition may have a degree of unsaturation (DOU) of 0.02 meq / g or less according to the following measurement method:

[0335] <Measurement method>

[0336] 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 mercuric acetate was added to each of the first flask and the second flask, followed by stirring for 30 minutes.

[0337] 2) 9 g of sodium bromide (NaBr) was added to each of the first flask and the second flask, followed by stirring for 30 minutes.

[0338] 3) 0.5 ml of 1% phenolphthalein indicator was added to each of the first flask and the second flask, followed by titration with 0.1 normal potassium hydroxide (KOH).

[0339] 4) Calculate DOU according to the following formula 1:

[0340] [Formula 1]

[0341] Degree of unsaturation (meq / g) = (V s × V b × 0.1 × F) / M.

[0342] In Formula 1, V s represents the amount (ml) of 0.1 N potassium hydroxide (KOH) added to the first flask, V b represents the amount (ml) of 0.1 N potassium hydroxide (KOH) added to the second flask, F represents the factor of 0.1 N potassium hydroxide (KOH), and M represents the weight (g) of the polyol composition added to the first flask.

[0343] 1,4:3,6-Dianhydrohexitol and isosorbide can be the same as the 1,4:3,6-dianhydrohexitol and isosorbide described above.

[0344] The alkylene oxide can be the same as the alkylene oxide described above.

[0345] According to the following measurement method, the DOU of the polyol composition can be 0.02 meq / g or less: <Measurement method>

[0346] 1) Prepare a first flask and a second flask. The first flask contains 30 g of the polyol composition, the second flask contains no polyol composition, and 50 ml of mercuric acetate is added to each of the first flask and the second flask, followed by stirring for 30 minutes.

[0347] 2) Add 9 g of sodium bromide (NaBr) to each of the first flask and the second flask, followed by stirring for 30 minutes.

[0348] 3) Add 0.5 ml of 1% phenolphthalein indicator to each of the first flask and the second flask, and then titrate with 0.1 N potassium hydroxide (KOH).

[0349] 4) Calculate the DOU according to the following Formula 1:

[0350] [Formula 1]

[0351] Degree of unsaturation (meq / g) = (V s × V b × 0.1 × F) / M.

[0352] In Formula 1, V s represents the amount (ml) of 0.1 N potassium hydroxide (KOH) added to the first flask, V brepresents the amount (ml) of 0.1 normal potassium hydroxide (KOH) added to the second flask, F represents the factor of 0.1 normal potassium hydroxide (KOH), and M represents the weight (g) of the polyol composition added to the first flask.

[0353] The unsaturation degree refers to the content of monofunctional alcohol in the polyol composition. Specifically, the unsaturation degree can be expressed as mg unsaturation equivalent per 1 g of the polyol composition (meq / g).

[0354] The monofunctional alcohol may be produced in a process of addition-polymerizing propylene oxide and 1,4:3,6-dianhydrohexitol using a catalyst. Specifically, the monofunctional alcohol may be produced in a process of rearrangement of propylene oxide to allyl alcohol.

[0355] The monofunctional alcohol may result in a reduction in the functional groups of the polyol composition, and during the production of polyurethane using the polyol composition, the monofunctional alcohol may hinder the formation of crosslinking and high molecular weight structure, which may result in a decrease in the physical properties of the polyurethane resin.

[0356] The unsaturation of the polyol composition may be 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 this range is met, the reactivity with isocyanate is excellent, and when the polyurethane resin is manufactured from the polyol composition, the crosslinking reaction and the formation of the high molecular weight structure may be smoothly performed, so that the physical properties of the polyurethane resin may be improved.

[0357] The polyol composition may include a compound represented by the following Formula 3:

[0358] [Formula 3]

[0359]

[0360] In formula 3, R 1 and R 2 each independently represents a substituted or unsubstituted alkylene group having 2 to 10 carbon atoms, a and f are each independently an integer from 1 to 60, b and e are each independently an integer from 1 to 6, c and d are each independently an integer from 1 to 30, and x is an integer from 1 to 5.

[0361] The compound represented by Formula 3 may include a parent structure derived from at least one 1,4:3,6-dianhydrohexitol. The 1,4:3,6-dianhydrohexitol may include isosorbide.

[0362] 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. (b+c) and (d+e) may each independently be 3 to 50. Preferably, (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 this range is satisfied, the polyurethane foam including the compound may have improved hardness, reduced permanent compression set, and excellent appearance due to its smooth surface.

[0363] In addition, when the appropriate level of compression force deformation (CFD) is reached and polyurethane foam is thus applied to the battery module, the volume change caused by the expansion of the battery cell can be buffered so that the volume can be kept constant, thereby improving product stability. CFD is a parameter that represents the repulsive force when the measurement target is compressed.

[0364] CFD can be evaluated by measuring the repulsive force when the polyurethane foam is cut into 5 cm×5 cm size at room temperature and compressed using a device such as a universal testing machine (UTM). For example, the repulsive force when the polyurethane foam is compressed by 25% can be evaluated by the CFD 25% value, and the expected CFD 25% value range can be about greater than 0.06 kg / cm 2 To less than about 0.15kg / cm 2 In addition, the repulsive force when the polyurethane foam is compressed by 50% can be evaluated by the CFD 50% value, and the expected CFD 50% value range may be about greater than 0.09 kg / cm 2 and less than about 0.20kg / cm 2 .

[0365] In formula 3, R 1 and R 2 Each independently may be a substituted or unsubstituted branched alkylene group having 3 to 10 carbon atoms. The branched alkylene group may be propylene oxide.

[0366] In formula 3, R 1 and R 2Each independently may be a polymer in which 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 are randomly polymerized. The linear alkylene group may be ethylene oxide.

[0367] In the compound represented by Formula 3, a first block and a second block may be formed, wherein a branched alkylene group is polymerized to a parent structure derived from at least one 1,4:3,6-dianhydrohexitol; wherein a straight chain alkylene group is coupled to the first block. In addition, a third block may be formed, wherein a branched alkylene group is coupled to the second block. In addition, a third block may be formed, in which a straight chain alkylene group and a branched chain alkylene group are randomly coupled to the second block.

[0368] The type of compound represented by Formula 3 can be represented by the following compounds of Formula A to Formula G: [Formula A]

[0369]

[0370] [Formula B]

[0371]

[0372] [Formula C]

[0373]

[0374] [Formula D]

[0375]

[0376] [Formula E]

[0377]

[0378] [Formula F]

[0379]

[0380] [Formula G]

[0381]

[0382] The polyol composition may also include an antioxidant as described above.

[0383] The polyol composition can have the controlled polymerization rate (CPR) values ​​described above.

[0384] The polyol composition may have an acid value as described above.

[0385] The polyol composition can have the number average molecular weight (Mn) and polydispersity index (PDI) described above.

[0386] The polyol composition can have the American Public Health Association (APHA) color value described above.

[0387] The polyol composition may have the active oxygen content values ​​described above.

[0388] The viscosity of the polyol composition may be the same as described above.

[0389] The method for preparing a polyol composition according to the present invention may include: step (a): initiating a polymerization reaction by mixing at least one 1,4:3,6-dianhydrohexitol with a basic catalyst; step (b): reacting the 1,4:3,6-dianhydrohexitol with an alkylene oxide to prepare a prepolymer; step (c): reacting the prepolymer prepared in step (b) with an alkylene oxide in the presence of a double metal cyanide catalyst to prepare a polyol composition, wherein the unsaturation of the polyol composition is 0.02 meq / g or less according to the following measurement method:

[0390] <Measurement method>

[0391] 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 mercuric acetate was added to each of the first flask and the second flask, followed by stirring for 30 minutes.

[0392] 2) 9 g of sodium bromide (NaBr) was added to each of the first flask and the second flask, followed by stirring for 30 minutes.

[0393] 3) 0.5 ml of 1% phenolphthalein indicator was added to each of the first flask and the second flask, followed by titration with 0.1 normal potassium hydroxide (KOH).

[0394] 4) Calculate DOU according to the following formula 1:

[0395] [Formula 1]

[0396] Unsaturation (meq / g) = (V s ×V b ×0.1×F) / M.

[0397] In Formula 1, V s represents the amount (ml) of 0.1N potassium hydroxide (KOH) added to the first flask, V b represents the amount (ml) of 0.1 normal potassium hydroxide (KOH) added to the second flask, F represents the factor of 0.1 normal potassium hydroxide (KOH), and M represents the weight (g) of the polyol composition added to the first flask.

[0398] Figure 6 is a flow chart briefly illustrating the preparation process of the polyol composition according to the present invention. Figure 6 The preparation method of the present invention may include a step of initiating a polymerization reaction (S10-2). In step (S10-2), at least one 1,4:3,6-dianhydrohexitol may be mixed with a basic catalyst. The 1,4:3,6-dianhydrohexitol and the basic catalyst may be the same as the 1,4:3,6-dianhydrohexitol and the basic catalyst described above.

[0399] The preparation method of the present invention may include a step (S20-2) of preparing a prepolymer. In step (S20-2), the prepolymer may be prepared by reacting 1,4:3,6-dianhydrohexitol with alkylene oxide. The method for preparing the prepolymer may be the same as the method for preparing the second polymer described above.

[0400] The preparation method of the present invention may include a step (S30-2) of preparing a polyol composition. In step (S30-2), the polyol composition may be prepared by reacting the prepolymer prepared in S20-2 with an alkylene oxide in the presence of a double metal cyanide catalyst.

[0401] The double metal cyanide catalyst can be represented by the following formula 4:

[0402] [Formula 4]

[0403] M a [M'(CN)6] b L c L' d .

[0404] In 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), M' is a metal element selected from the group consisting of 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 integers, and the sum of a, b, c, and d is equal to the sum of the charges of M and M'.

[0405] The double metal cyanide catalyst can be prepared by reacting a metal salt and a metal cyanide with a complexing agent. The metal salt can be a water-soluble metal salt. The metal cyanide can be a water-soluble metal cyanide. Specifically, the water-soluble metal cyanide can be potassium hexacyanocobaltate (III), potassium hexacyanoferrate (II), potassium hexacyanoferrate (III), calcium hexacyanocobaltate (II), or lithium hexacyanoferrate (II) (lithium hexacyanoferrate).

[0406] When a double metal cyanide catalyst is used in S30-2, the generation of monofunctional alcohols may be reduced when the first prepolymer is polymerized with propylene oxide. Therefore, the unsaturation of the polyol composition may be reduced, so that when the polyurethane resin is produced, the crosslinking reaction and the formation of a high molecular weight structure can be smoothly carried out, and the physical properties of the polyurethane resin can be improved.

[0407] In S30-2, it is preferred not to use a double metal cyanide catalyst and a basic catalyst simultaneously, because the amount of the basic catalyst may increase according to the selective activity of the double metal cyanide catalyst, so that a large amount of the basic catalyst may remain after the production of the polyol composition. Therefore, an additional process for removing the basic catalyst is basically required, which may reduce the efficiency of the production process. In addition, the basic catalyst may increase the generation of monofunctional alcohols, hindering the crosslinking reaction and the formation of high molecular weight structures when producing polyurethane resins, and the physical properties of the polyurethane resins may decrease.

[0408] The polyol composition prepared according to the preparation method may include a compound represented by the following Formula 3:

[0409]

[0410] In formula 3, R 1 and R 2 each independently represents a substituted or unsubstituted alkylene group having 2 to 10 carbon atoms, a and f are each independently an integer from 1 to 60, b and e are each independently an integer from 1 to 6, c and d are each independently an integer from 1 to 30, and x is an integer from 1 to 5.

[0411] The composition for preparing polyurethane according to the present invention may include a first unit and a second unit, the first unit being derived from at least one 1,4:3,6-dianhydrohexitol, the second unit being derived from an alkylene oxide, and the composition for preparing polyurethane according to the present invention may include a polyol composition having a DOU of 0.02 meq / g or less according to the following measurement method.

[0412] <Measurement method>

[0413] 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 mercuric acetate was added to each of the first flask and the second flask, followed by stirring for 30 minutes.

[0414] 2) 9 g of sodium bromide (NaBr) was added to each of the first flask and the second flask, followed by stirring for 30 minutes.

[0415] 3) 0.5 ml of 1% phenolphthalein indicator was added to each of the first flask and the second flask, followed by titration with 0.1 normal potassium hydroxide (KOH).

[0416] 4) Calculate DOU according to the following formula 1:

[0417] [Formula 1]

[0418] Unsaturation (meq / g) = (V s ×V b ×0.1×F) / M.

[0419] In Formula 1, V s represents the amount (ml) of 0.1N potassium hydroxide (KOH) added to the first flask, V b represents the amount (ml) of 0.1 normal potassium hydroxide (KOH) added to the second flask, F represents the factor of 0.1 normal potassium hydroxide (KOH), and M represents the weight (g) of the polyol composition added to the first flask.

[0420] The polyol composition and the isocyanate-based composition may be the same as the polyol composition and the isocyanate-based composition described above.

[0421] The polyurethane foam may be produced from a composition for preparing polyurethane, and the composition for preparing the polyurethane foam may be the same as the composition for preparing polyurethane described above.

[0422] The battery module according to the present invention is a battery module including a housing, a plurality of battery cells, and a polyurethane foam, the plurality of battery cells being accommodated inside the housing, the polyurethane foam being arranged between the plurality of battery cells, the polyurethane foam including a composition for preparing a polyurethane, the composition including a polyol composition and an isocyanate-based composition, and the polyol composition including a first unit and a second unit, the first unit being derived from at least one 1,4:3,6-dianhydrohexitol, the second unit being derived from an alkylene oxide, and the polyol composition having a DOU of 0.02 meq / g or less according to the following measurement method:

[0423] <Measurement method>

[0424] 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 mercuric acetate was added to each of the first flask and the second flask, followed by stirring for 30 minutes.

[0425] 2) 9 g of sodium bromide (NaBr) was added to each of the first flask and the second flask, followed by stirring for 30 minutes.

[0426] 3) 0.5 ml of 1% phenolphthalein indicator was added to each of the first flask and the second flask, followed by titration with 0.1 normal potassium hydroxide (KOH).

[0427] 4) Calculate DOU according to the following formula 1:

[0428] [Formula 1]

[0429] Unsaturation (meq / g) = (V s ×V b ×0.1×F) / M.

[0430] In Formula 1, V s represents the amount (ml) of 0.1N potassium hydroxide (KOH) added to the first flask, V b represents the amount (ml) of 0.1 normal potassium hydroxide (KOH) added to the second flask, F represents the factor of 0.1 normal potassium hydroxide (KOH), and M represents the weight (g) of the polyol composition added to the first flask.

[0431] The battery module according to the present invention can refer to the above-described Figure 3 The battery module has the same contents.

[0432] <Polyol Composition According to Fifth Example>

[0433] The polyether polyol according to the present invention may be included in the polyol composition.

[0434] The method for preparing a polyether polyol according to the present invention may include: step (a): reacting at least one 1,4:3,6-dianhydrohexitol with a first alkylene oxide in the presence of a basic catalyst to prepare a first polymer, and step (b): reacting the first polymer with a second alkylene oxide in the presence of a double metal cyanide catalyst to prepare a second polymer.

[0435] Figure 7 The process of preparing polyether polyol according to the present invention is briefly described. Figure 7, the preparation method of the present invention may include a step (S10-3) of preparing a first polymer. In step (S10-3), the first polymer may be prepared by reacting at least one 1,4:3,6-dianhydrohexitol with a first alkylene oxide in the presence of a basic catalyst. Step (S10-3) may be the same as the step of preparing a prepolymer described above.

[0436] The 1,4:3,6-dianhydrohexitol and isosorbide may be the same as the 1,4:3,6-dianhydrohexitol and isosorbide described above.

[0437] The alkylene oxide may be the same as the alkylene oxide described above.

[0438] Specifically, step (a) may include: step (a-1): mixing 1,4:3,6-dianhydrohexitol with an alkaline catalyst to perform a dehydration treatment, step (a-2): after the dehydration treatment, reacting 1,4:3,6-dianhydrohexitol with a substituted or unsubstituted branched alkylene oxide having 3 to 10 carbon atoms to prepare a 1-1 polymer, and step (a-3): after completing the production of the 1-1 polymer, reacting the 1-1 polymer with a substituted or unsubstituted straight-chain alkylene oxide having 2 to 10 carbon atoms to prepare a 1-2 polymer.

[0439] After step (a-3), step (a) may include: step (a-4): removing metal ion residues in the composition including the polymer 1-2; and step (a-5): filtering the composition.

[0440] Figure 8 A flow chart specifically illustrates the steps of preparing the first polymer. Figure 8 , step (S10-3) may include: performing a dehydration treatment step (S11). In step (S11), the dehydration treatment may be performed by mixing 1,4:3,6-dianhydrohexitol with an alkaline catalyst.

[0441] 1,4:3,6-dianhydrohexitol can be introduced into a batch reactor.

[0442] The 1,4:3,6-dianhydrohexitol may be introduced into the batch reactor in an amount of about 15 wt % to about 50 wt %, about 15 wt % to about 40 wt %, about 25 wt % to about 40 wt %, or about 25 wt % to about 35 wt % based on the total amount of the raw materials added to the batch reactor.

[0443] 1,4:3,6-dianhydrohexitol can be introduced into the batch reactor in solid form. 1,4:3,6-dianhydrohexitol can be introduced into the batch reactor in powder form.

[0444] The particles of 1,4:3,6-dianhydrohexitol can be spherical, flake-shaped, or rod-shaped.

[0445] 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.

[0446] The average particle diameter of 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 diameter is measured using a laser diffraction method, and in a particle diameter distribution curve, the average particle diameter may be defined as a particle diameter corresponding to 50% of the volume cumulative amount.

[0447] The moisture content of 1,4:3,6-dianhydrohexitol may be less than about 5 wt%, less than about 4 wt%, less than about 3 wt%, less than about 2 wt%, or less than about 1 wt%. The moisture content may be calculated by subtracting the weight of 1,4:3,6-dianhydrohexitol after drying from the weight of 1,4:3,6-dianhydrohexitol before drying, dividing by the value of the weight of 1,4:3,6-dianhydrohexitol before drying, and then multiplying by 100%. Drying is performed by increasing the temperature from room temperature to about 150° C. and then maintaining it at 150° C., and the total drying time may be set to 20 minutes, including a 5-minute temperature increase step.

[0448] 1,4:3,6-dianhydrohexitol can be introduced into the batch reactor in an aqueous solution state.1,4:3,6-dianhydrohexitol can be introduced into the batch reactor in a concentration of about 70 wt % to about 90 wt %, about 75 wt % to about 90 wt %, or about 75 wt % to about 85 wt %.

[0449] 1,4:3,6-dianhydrohexitol can be introduced into the batch reactor in batches. 1,4:3,6-dianhydrohexitol can be introduced into the batch reactor within the following time period: about 5 minutes to about 60 minutes, about 10 minutes to about 50 minutes, or about 20 minutes to about 40 minutes. 1,4:3,6-dianhydrohexitol can be added to the batch reactor in equal parts within the following time period: about 5 minutes to about 60 minutes, about 10 minutes to about 50 minutes, or about 20 minutes to about 40 minutes.

[0450] The basic catalyst may include one or more strong bases selected from the group consisting of potassium hydroxide, sodium hydroxide, potassium metal, and sodium metal.

[0451] In S11, preferably no double metal cyanide catalyst (DMC) is used. Generally, double metal cyanide catalysts may substantially require a catalyst activation induction time of 1 hour or more, and since polymerization reaction rarely or not occurs before the catalyst is activated, the efficiency of the production process may be significantly reduced.

[0452] The alkaline catalyst can be introduced into the batch reactor in an aqueous solution state. For example, an aqueous potassium hydroxide solution can be introduced into the batch reactor. The alkaline catalyst can be introduced into the batch reactor after the introduction of 1,4:3,6-dianhydrohexitol. The alkaline catalyst can be introduced into the batch reactor in batches. The alkaline catalyst can be introduced into the batch reactor within the following time period: about 1 minute to about 20 minutes, about 3 minutes to about 15 minutes, or about 8 minutes to about 12 minutes. 1,4:3,6-dianhydrohexitol can be introduced into the batch reactor separately in equal parts within the following time period: about 1 minute to about 20 minutes, about 3 minutes to about 15 minutes, or about 8 minutes to about 12 minutes.

[0453] In S11, the alkaline catalyst and 1,4:3,6-dianhydrohexitol may be mixed in a weight ratio of 1:10 to 1000, 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 (alkaline catalyst: 1,4:3,6-dianhydrohexitol) to perform a dehydration treatment of 1,4:3,6-dianhydrohexitol. When this range is met, the dehydration reaction rate of 1,4:3,6-dianhydrohexitol can be increased, and the amount of residual alkaline catalyst can be minimized.

[0454] The dehydration treatment of 1,4:3,6-dianhydrohexitol may be performed at about 80°C to about 120°C, about 90°C to about 120°C, or about 100°C to about 120°C.

[0455] The dehydration treatment of 1,4:3,6-dianhydrohexitol may be performed 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.

[0456] The dehydration treatment of 1,4:3,6-dianhydrohexitol may be performed for about 1 hour to about 6 hours, about 1 hour to about 5 hours, or about 2 hours to about 4 hours.

[0457] The dehydration treatment of 1,4:3,6-dianhydrohexitol may be performed at about 80° C. to about 120° C. for about 1 hour to about 5 hours. Preferably, the dehydration treatment of 1,4:3,6-dianhydrohexitol may be performed at about 80° C. to about 120° C. under a pressure condition of about 0.1 torr to about 20.0 torr for about 2 hours to about 4 hours.

[0458] After the dehydration treatment of S11, the content of the remaining moisture in the total weight of the composition may be less than 2000ppm, 1000ppm or less, 500ppm or less, or 300ppm or less. The composition may refer to 1,4:3,6-dianhydrohexitol after dehydration. When this range is met, the yield of the polyether polyol can be increased, and the mechanical properties of the polyurethane foam produced by the polyether polyol can be improved.

[0459] Step (S10-3) may include a step (S12) of preparing a 1-1 polymer. Step (S12) may include a step of reacting 1,4:3,6-dianhydrohexitol with a substituted or unsubstituted branched alkylene oxide having 3 to 10 carbon atoms after the dehydration treatment to prepare the 1-1 polymer.

[0460] In S12, 1,4:3,6-dianhydrohexitol and a substituted or unsubstituted branched alkylene oxide having 3 to 10 carbon atoms may be reacted in a batch reactor, and the obtained branched alkylene oxide may be introduced into the batch reactor at a rate of 3 to 6 g / min, 3.5 to 6 g / min, 3.5 to 5.5 g / min, or 4 to 5 g / min.

[0461] The branched alkylene oxide may be introduced into the batch reactor in an amount of about 100 to about 500 parts by weight, about 150 to about 500 parts by weight, or about 150 to about 450 parts by weight, based on 100 parts by weight of 1,4:3,6-dianhydrohexitol.

[0462] The substituted or unsubstituted branched alkylene oxide having 3 to 10 carbon atoms may be propylene oxide.

[0463] Propylene oxide may be introduced into a batch reactor.

[0464] The introduction process of propylene oxide may be performed under a temperature condition of about 80°C to about 130°C, about 90°C to about 130°C, or about 100°C to about 120°C.

[0465] The introduction of propylene oxide may be performed 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.

[0466] The introduction process of propylene oxide can be performed 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 introduction process of propylene oxide can be performed for about 6 hours to about 9 hours at about 80° C. to about 120° C. under a pressure condition of about 2 torr to about 8 torr.

[0467] Propylene oxide may undergo an addition reaction with 1,4:3,6-dianhydrohexitol in a batch reactor. A 1-1 polymer may be prepared through the addition reaction, in which a repeating unit derived from propylene oxide is included in the parent structure of 1,4:3,6-dianhydrohexitol. The repeating unit derived from propylene oxide may refer to a component or structure derived from propylene oxide, or propylene oxide itself.

[0468] The addition reaction between 1,4:3,6-dianhydrohexitol and propylene oxide may be performed at a temperature of about 80°C to about 150°C, about 90°C to about 150°C, or about 100°C to about 140°C.

[0469] The addition reaction of 1,4:3,6-dianhydrohexitol with propylene oxide 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. Preferably, the addition reaction between 1,4:3,6-dianhydrohexitol and propylene oxide can be performed at about 100° C. to about 140° C. for about 1 hour to about 2 hours.

[0470] S12 may further include a process of removing branched alkylene oxide residues after preparing the 1-1 polymer. The branched alkylene oxide residues may be propylene oxide. By removing the branched alkylene oxide residues, the reactivity with isocyanate can be improved, the hardness and appearance of the polyurethane foam can be improved, and the economic efficiency of manufacturing can be improved.

[0471] The process of removing the propylene oxide residue may be performed at a temperature of about 80°C to about 150°C, about 90°C to about 150°C, or about 100°C to about 140°C.

[0472] The process of removing the propylene oxide residue may be performed 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.

[0473] The process of removing the propylene oxide residue can be performed for about 10 minutes to about 120 minutes, about 10 minutes to about 60 minutes, or about 20 minutes to about 40 minutes. Preferably, the process of removing the propylene oxide residue can be performed at about 100° C. to about 140° C. under a pressure condition of about 0.1 torr to about 20.0 torr for about 20 minutes to about 40 minutes.

[0474] Step (S10-3) may include a step (S13) of preparing the 1-2 polymer. Step (S13) may include, after the production of the 1-1 polymer is completed, reacting the 1-1 polymer with a substituted or unsubstituted linear alkylene oxide having 2 to 10 carbon atoms to prepare the 1-2 polymer.

[0475] In S13, the 1-1 polymer and a substituted or unsubstituted linear alkylene oxide having 2 to 10 carbon atoms are reacted in a batch reactor, and the linear alkylene oxide may be introduced into the batch reactor at a rate of 1.5 to 3 g / min, 1.6 to 3 g / min, 1.7 to 3 g / min, 1.8 to 3 g / min, or 2.0 to 3 g / min.

[0476] The linear alkylene oxide may be introduced into the batch reactor in an amount of about 10 to about 100 parts by weight, about 10 to about 90 parts by weight, or about 20 to about 80 parts by weight, based on 100 parts by weight of 1,4:3,6-dianhydrohexitol.

[0477] The amount of the linear alkylene oxide in step (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 in step (S12). When this range is met, the reactivity with isocyanate may be increased, and the hardness and appearance quality of the polyurethane foam produced by the polyether polyol may be improved.

[0478] The substituted or unsubstituted linear alkylene oxide having 2 to 10 carbon atoms may be ethylene oxide.

[0479] The ethylene oxide may be introduced into the batch reactor in which the 1-1 polymer has been prepared.

[0480] The introduction process of ethylene oxide may be performed under a temperature condition of about 80°C to about 140°C, about 90°C to about 140°C, or about 120°C to about 130°C.

[0481] The introduction of ethylene oxide may be performed 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.

[0482] The introduction process of ethylene oxide can be performed 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 introduction process of ethylene oxide can be performed at about 120° C. to about 130° C. under a pressure condition of about 0.1 torr to about 30.0 torr for about 2 hours to about 3 hours.

[0483] Ethylene oxide can undergo an addition reaction with the 1-1 polymer in a batch reactor. A second polymer can be prepared by the addition reaction, in which the first polymer includes repeating units derived from ethylene oxide. In addition, a 1-2 polymer can be prepared, in which repeating units derived from propylene oxide and repeating units derived from ethylene oxide as a block copolymer are included. The repeating units derived from ethylene oxide can refer to a component or structure derived from ethylene oxide, or ethylene oxide itself.

[0484] The addition reaction between the 1-1 polymer and ethylene oxide may be performed at a temperature of about 80°C to about 150°C, about 90°C to about 150°C, or about 100°C to about 140°C.

[0485] The addition reaction of the 1-1 polymer with ethylene oxide 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. Preferably, the addition reaction between the 1-1 polymer and ethylene oxide can be performed at about 100° C. to about 140° C. for about 1 hour to about 2 hours.

[0486] In S13, after preparing the 1-2 polymer, a process of removing linear alkylene oxide residues may be included. The linear alkylene oxide residues may be ethylene oxide.

[0487] The process of removing the ethylene oxide residue may be performed at a temperature of about 80°C to about 150°C, about 90°C to about 150°C, or about 100°C to about 140°C.

[0488] The process of removing the propylene oxide residue may be performed 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.

[0489] The process of removing the ethylene oxide residue can be performed 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 process of removing the ethylene oxide residue can be performed for about 40 minutes to about 80 minutes under a temperature condition of about 100° C. to about 140° C. and a pressure condition of about 0.1 torr to about 20.0 torr.

[0490] Step (S10-3) may include a step (S14) of removing metal ion residues; and a filtering step (S15). Step (S14) may include a step of removing metal ion residues in the composition containing 1-2 polymer after step (S13). Step (S15) may include a step of filtering the composition.

[0491] In S14, metal adsorbents and filter aids may be used to remove metal ions.

[0492] The metal adsorbent can adsorb, for example, residual potassium ions. The filtration process of the polyether polyol can be smoothly performed by the filter aid. When only the metal adsorbent is used, the filtration process of the polyether polyol may not be smoothly performed, and when only the filter aid is used, the content of residual metal ions may increase, which may deteriorate the physical properties of the final product. Therefore, it is best to use the metal adsorbent and the filter aid at the same time.

[0493] As the metal adsorbent, AMBOSOL can be used.

[0494] As a filter aid, diatomaceous earth can be used.

[0495] The metal adsorbent and the filter aid can be introduced into the reacted polyether polyol in the form of an aqueous dispersion. The metal adsorbent and the filter aid can be introduced into the reacted polyether polyol in the following weight parts per 100 weight parts of 1,4:3,6-dianhydrohexitol: 1 to 10 weight parts, 1 to 8 weight parts, 2 to 8 weight parts, 3 to 8 weight parts, 3 to 6 weight parts.

[0496] After step (S14), a process of neutralizing the polyether polyol can be performed. The neutralization process 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. Next, a moisture removal process can be performed on the polyether polyol that has undergone the neutralization process. The moisture removal process can be performed at a temperature of about 90°C to about 130°C, about 95°C to about 130°C, or about 100°C to about 130°C. As needed, a process of detecting metal ion residues can be performed, and when no metal ion residues are detected, the polyether polyol can be performed 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.

[0497] In S15 , the polyether polyol from which the moisture has been removed may be filtered, and additives and by-products may be removed by filtering.

[0498] After step (S15), the content of the metal remaining in the polyether polyol can be 100ppm or less, 80ppm or less, 50ppm or less, 30ppm or less, 10ppm or less, 5ppm or less, 4ppm or less, 3ppm or less, 2ppm or less, or 1ppm or less. When this range is met, the mechanical properties of the polyurethane foam produced by the polyether polyol can be improved.

[0499] The preparation method of the present invention may include a step (S20-3) of preparing a second polymer. Step (S20) may include a step of reacting the first polymer with a second alkylene oxide in the presence of a double metal cyanide catalyst to prepare the second polymer.

[0500] The second polymer may be referred to as a polyether polyol.

[0501] The weight ratio of the double metal cyanide catalyst: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 this range is satisfied, an economical and efficient polymerization process may be performed.

[0502] Step (S20) may include a step of performing a dehydration treatment by heating a reactor containing the first polymer, and a step of reacting the first polymer with a second alkylene oxide in the presence of a double metal cyanide catalyst to prepare a second polymer after the dehydration treatment.

[0503] The second alkylene oxide may include a substituted or unsubstituted branched alkylene oxide having 3 to 10 carbon atoms; or a mixture of a 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.

[0504] The branched alkylene oxide may be propylene oxide.

[0505] The linear alkylene oxide may be ethylene oxide.

[0506] It is undesirable to react only the first polymer with ethylene oxide in the presence of a double metal cyanide catalyst. Since double metal cyanide catalysts have low reactivity with ethylene oxide, it is desirable to react the double metal cyanide catalyst with a mixture of propylene oxide and ethylene oxide to add ethylene to the first polymer.

[0507] The double metal cyanide catalyst may be the same as the double metal cyanide catalyst described above.

[0508] When a double metal cyanide catalyst is used in step (S20-3), the generation of monofunctional alcohol may be reduced when the first polymer is polymerized with the second alkylene oxide. Therefore, the unsaturation of the polyether polyol may be reduced, so that when the polyurethane resin is produced, the crosslinking reaction and the formation of a high molecular weight structure can be smoothly carried out, and the physical properties of the polyurethane resin can be improved.

[0509] In step (S20-3), it is desirable not to use an alkaline catalyst. In addition, in step (S20-3), it is desirable not to use a double metal cyanide catalyst and an alkaline catalyst simultaneously. According to the selective activity of the double metal cyanide catalyst, the amount of the alkaline catalyst used may increase, so that a large amount of alkaline catalyst may remain after the production of the polyether polyol. Therefore, an additional process for removing the alkaline catalyst must be required, which may reduce the efficiency of the production process. In addition, the alkaline catalyst may increase the generation of monofunctional alcohols, which may hinder the formation of cross-linking reactions and high molecular weight structures when manufacturing polyurethane resins, and may deteriorate the physical properties of polyurethane resins.

[0510] The polyether polyol composition prepared by the aforementioned method for preparing a polyether polyol according to the present invention may include a first unit derived from at least one 1,4:3,6-dianhydrohexitol and a second unit derived from an alkylene oxide.

[0511] The 1,4:3,6-dianhydrohexitol and isosorbide may be the same as the 1.4:3.6-dianhydrohexitol and isosorbide described above.

[0512] The alkylene oxide may be the same as the alkylene oxide described above.

[0513] The polyether polyol composition may have a DOU of 0.02 meq / g or less according to the following measurement method:

[0514] <Measurement method>

[0515] 1) A first flask containing 30 g of polyether polyol and a second flask containing no polyether polyol were prepared, and 50 ml of mercuric acetate was added to each of the first flask and the second flask, followed by stirring for 30 minutes.

[0516] 2) 9 g of sodium bromide (NaBr) was added to each of the first flask and the second flask, followed by stirring for 30 minutes.

[0517] 3) 0.5 ml of 1% phenolphthalein indicator was added to each of the first flask and the second flask, followed by titration with 0.1 normal potassium hydroxide (KOH).

[0518] 4) Calculate DOU according to the following formula 1:

[0519] [Formula 1]

[0520] Unsaturation (meq / g) = (V s ×V b ×0.1×F) / M.

[0521] In Formula 1, V s represents the amount (ml) of 0.1N potassium hydroxide (KOH) added to the first flask, V b represents the amount (ml) of 0.1 normal potassium hydroxide (KOH) added to the second flask, F represents the factor of 0.1 normal potassium hydroxide (KOH), and M represents the weight (g) of the polyol composition added to the first flask.

[0522] The unsaturation degree refers to the content of monofunctional alcohol in the polyether polyol. Specifically, the unsaturation degree can be expressed as mg unsaturation equivalent per 1 g of the polyether polyol (meq / g).

[0523] The monofunctional alcohol may be produced in a process of addition-polymerizing propylene oxide and 1,4:3,6-dianhydrohexitol using a catalyst. Specifically, the monofunctional alcohol may be produced in a process of rearrangement of propylene oxide to allyl alcohol.

[0524] The monofunctional alcohol may cause a reduction in the functional groups of the polyether polyol, and during the production of polyurethane when the polyether polyol is used, the monofunctional alcohol may hinder the formation of crosslinking and a high molecular weight structure, which may result in a decrease in the physical properties of the polyurethane resin.

[0525] The unsaturation degree of the polyether polyol composition may be 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 this range is satisfied, the reactivity with isocyanate is excellent, and when a polyurethane resin is manufactured from the polyether polyol composition, a crosslinking reaction and the formation of a high molecular weight structure may be smoothly performed, so that the physical properties of the polyurethane resin may be improved.

[0526] The polyether polyol composition may include the compound represented by Formula 3 described above.

[0527] The polyether polyol composition may include compounds of Formula A to Formula G described above.

[0528] The polyether polyol composition may also include an antioxidant as described above.

[0529] The polyether polyol composition can have the controlled polymerization rate (CPR) values ​​described above.

[0530] The polyether polyol composition may have an acid value as described above.

[0531] The polyether polyol composition may have the number average molecular weight (Mn) and polydispersity index (PDI) described above.

[0532] The polyether polyol composition may have the American Public Health Association (APHA) color value described above.

[0533] The polyether polyol composition may have the active oxygen content values ​​described above.

[0534] The viscosity of the polyether polyol composition may be the same as described above.

[0535] The composition for preparing polyurethane according to the present invention may include the polyether polyol composition and the isocyanate-based composition described above.

[0536] The polyurethane foam may be produced from a composition for preparing polyurethane. The composition for preparing polyurethane may be the same as the composition for preparing polyurethane described above.

[0537] The battery module according to the present invention may be a battery module including a housing, a plurality of battery cells and polyurethane foam, wherein the plurality of battery cells are accommodated inside the housing, and the polyurethane foam is arranged between the plurality of battery cells. The polyurethane foam may include a composition for preparing polyurethane, the composition including a polyether polyol composition according to the aforementioned method for preparing a polyether polyol and an isocyanate-based composition, and the polyether polyol composition may include a first unit and a second unit, the first unit being derived from at least one 1,4:3,6-dianhydrohexitol, and the second unit being derived from an alkylene oxide.

[0538] The battery module according to the present invention can refer to the above-described Figure 3 The battery module has the same contents.

[0539] <Polyol Composition According to Sixth Example>

[0540] The polyether polyol according to the present invention may include a first unit derived from at least one 1,4:3,6-dianhydrohexitol and a second unit derived from an alkylene oxide, and may include a primary alcohol content of 10 to 90 mol%.

[0541] The 1,4:3,6-dianhydrohexitol and isosorbide may be the same as the 1,4:3,6-dianhydrohexitol and isosorbide described above.

[0542] The alkylene oxide may be the same as the alkylene oxide described above.

[0543] The content of primary alcohol in the polyether polyol may be 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%. The content of primary alcohol can be determined by the amount of the polyether polyol. 13 The relative ratio of the peak at about 61 ppm appearing in the C NMR spectrum is measured. When this range is satisfied, the reactivity with isocyanate is excellent, and when a polyurethane foam is produced from the polyether polyol, a crosslinking reaction and the formation of a high molecular weight structure can be smoothly performed, so that the physical properties of the polyurethane foam can be improved.

[0544] The unsaturation degree of the polyether polyol may be 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 this range is satisfied, the reactivity with isocyanate is excellent, and when polyurethane foam is manufactured from the polyether polyol, crosslinking reaction and formation of a high molecular weight structure may be smoothly performed, so that the physical properties of the polyurethane foam may be improved.

[0545] The polyether polyol may include the compound represented by Formula 3 described above.

[0546] The polyether polyol composition may include compounds of Formula A to Formula G described above.

[0547] The polyether polyol composition may also include an antioxidant as described above.

[0548] The polyether polyol composition may have an acid value as described above.

[0549] The polyether polyol composition may have the number average molecular weight (Mn) and polydispersity index (PDI) described above.

[0550] The polyether polyol composition may have the American Public Health Association (APHA) color value described above.

[0551] The polyether polyol composition may have the active oxygen content values ​​described above.

[0552] The viscosity of the polyether polyol composition may be the same as described above.

[0553] The method for preparing a polyether polyol according to the present invention may include: step (a): preparing a first polymer, the first polymer including units derived from at least one 1,4:3,6-dianhydrohexitol; and step (b): reacting the first polymer with a mixture including ethylene oxide and propylene oxide in the presence of a double metal cyanide catalyst to prepare a second polymer, wherein the content of primary alcohol in the polyether polyol is 10 mol% to 90 mol%.

[0554] Fig. 9 is a flow chart briefly illustrating the process of preparing polyether polyol according to the present invention. Fig. 9The preparation method of the present invention may include a step (S10-4) of preparing a first polymer. Step (S10-4) may be performed in the same manner as step (S10-3) described above.

[0555] The preparation method of the present invention may include a step (S20-4) of preparing a second polymer. The step (S20-4) may be performed in the same manner as the step (S20-3) described above.

[0556] The composition for preparing polyurethane according to the present invention may include a first unit and a second unit, the first unit being derived from at least one 1,4:3,6-dianhydrohexitol, the second unit being derived from an alkylene oxide, and the composition for preparing polyurethane according to the present invention may include a polyol composition including a polyether polyol having a primary alcohol content of 10 mol % to 90 mol %, and an isocyanate-based composition.

[0557] The polyurethane foam may be produced from a composition for preparing polyurethane, and the composition for preparing the polyurethane foam may be the same as the composition for preparing polyurethane described above.

[0558] The battery module according to the present invention is a battery module including a shell, a plurality of battery cells and a polyurethane foam, wherein the plurality of battery cells are accommodated inside the shell, the polyurethane foam is arranged between the plurality of battery cells, the polyurethane foam includes a composition for preparing a polyurethane, the composition includes a polyol composition and an isocyanate-based composition, and the polyol composition includes a first unit and a second unit, the first unit is derived from at least one 1,4:3,6-dianhydrohexitol, the second unit is derived from an alkylene oxide, and the polyol composition may include a polyether polyol, wherein the content of the primary alcohol is 10 mol% to 90 mol%.

[0559] The battery module according to the present invention can refer to the above-described Figure 3 The battery module has the same contents.

[0560] Hereinafter, the present invention is described in more detail based on Examples and Comparative Examples. However, the following Examples and Comparative Examples are only examples for explaining the present invention in more detail, and the present invention is not limited to the following Examples and Comparative Examples.

[0561] <First Preparation Example, First Example, and First Experimental Example>

[0562] First Preparation Example

[0563] Preparation Example 1-1—Preparation of the compound represented by formula A

[0564] 803 g of isosorbide and 23 g of potassium hydroxide were added to a pressurizable and heatable reactor. Next, the inside of the reactor was replaced with nitrogen, heated to 112° C., and then moisture inside the reactor was removed under vacuum and reduced pressure.

[0565] The reaction was carried out at a temperature of about 115°C for 6 hours while 1900 g of propylene oxide was introduced into the reactor at a constant rate, where the temperature of the reactor was controlled not to exceed 117°C.

[0566] The reactor was stirred until all the propylene oxide residues in the reactor were reacted, and after the reaction was completed, the temperature of the reactor was heated to 123° C. Next, 310 g of ethylene oxide was added to the reactor at a constant rate, and the reaction was continued for 1 hour and 30 minutes at about 120° C. Here, the temperature of the reactor was controlled not to exceed 125° C.

[0567] After the reaction was completed, the temperature of the reactor was lowered to 90° C., and then stirred at about 100° C. for 3 hours while 50 g of AMBOSOL and 5 g of diatomaceous earth were introduced into the reactor to remove remaining metal ions in the product.

[0568] After confirming that no residual metal ions were detected in the product, the temperature of the reactor was lowered to 70° C., and then the residual by-products were removed by a filter, thereby obtaining 3,013 g of a compound represented by the following formula A. The structure of the compound is shown by Figure 3 As shown in 13 C NMR spectrum was used for confirmation.

[0569] [Formula A]

[0570]

[0571] 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.

[0572] Preparation Example 1-2 - Preparation of the compound represented by Formula B

[0573] 3,283 g of a compound represented by the following formula B was obtained in the same manner as in Preparation Example 1-1, except that 580 g of ethylene oxide was added instead of 310 g of ethylene oxide in Preparation Example 1-1, and 13C NMR spectroscopy confirmed the structure of the compound.

[0574] [Formula B]

[0575]

[0576] 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.

[0577] Preparation Example 1-3 - Preparation of the compound represented by Formula C

[0578] 2,603 ​​g of a compound represented by the following formula C was obtained in the same manner as in Preparation Example 1-1, except that 520 g of ethylene oxide was added instead of 310 g of ethylene oxide in Preparation Example 1-1 and 1,280 g of propylene oxide was added instead of 1,900 g of propylene oxide in Preparation Example 1-1, and 13 C NMR spectroscopy confirmed the structure of the compound.

[0579] [Formula C]

[0580]

[0581] 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.

[0582] Preparation Example 1-4 - Preparation of Compounds Represented by Formula D

[0583] 2,443 g of a compound represented by the following formula D was obtained in the same manner as in Preparation Example 1-1, except that 560 g of ethylene oxide was added instead of 310 g of ethylene oxide in Preparation Example 1-1 and 1,080 g of propylene oxide was added instead of 1,900 g of propylene oxide in Preparation Example 1-1, and 13 C NMR spectroscopy confirmed the structure of the compound.

[0584] [Formula D]

[0585]

[0586] 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.

[0587] Preparation Example 1-5 – Preparation of compounds represented by formula E

[0588] 2453 g of a compound represented by the following formula E was obtained in the same manner as in Preparation Example 1-1, except that 680 g of ethylene oxide was added instead of 310 g of ethylene oxide in Preparation Example 1-1 and 990 g of propylene oxide was added instead of 1900 g of propylene oxide in Preparation Example 1-1, and by 13 C NMR spectroscopy confirmed the structure of the compound.

[0589] [Formula E]

[0590]

[0591] 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.

[0592] Preparation Example 1-6 - Preparation of Compounds Represented by Formula M

[0593] 796 g of isosorbide and 22 g of potassium hydroxide were introduced into a pressurizable and heatable reactor, and then the inside of the reactor was replaced with nitrogen and heated to 112° C., and then moisture inside the reactor was removed under vacuum and reduced pressure conditions.

[0594] The reactor was heated to 122° C., while 1904 g of propylene oxide and 300 g of ethylene oxide were added to the reactor at a constant rate. Next, the reaction was carried out at about 120° C. for 7 hours. Here, the temperature of the reactor was controlled not to exceed 125° C.

[0595] After the reaction was completed, the temperature of the reactor was lowered to 90° C., and then stirred at about 100° C. for 3 hours while 50 g of AMBOSOL and 5 g of diatomaceous earth were introduced into the reactor to provide the remaining metal ions in the product.

[0596] After confirming that no residual metal ions were detected in the product, the temperature of the reactor was lowered to 70° C., and then the residual by-products were removed by a filter, thereby obtaining 3000 g of a compound represented by the following formula M, and the structure of the compound is shown by Figure 4 As shown in 13 C NMR spectrum was used for confirmation.

[0597] [Formula M]

[0598]

[0599] 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.

[0600] Preparation Example 1-7 - Preparation of the compound represented by Formula N

[0601] 2,086 g of a compound represented by the following formula N was obtained in the same manner as in Preparation Example 1-6, except that 980 g of ethylene oxide was added instead of 300 g of ethylene oxide in Preparation Example 1-6 and 310 g of propylene oxide was added instead of 1904 g of propylene oxide in Preparation Example 1-6, and by 13 C NMR spectroscopy confirmed the structure of the compound.

[0602] [Formula N]

[0603]

[0604] 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.

[0605] Preparation Example 1-8 - Preparation of Compounds Represented by Formula O

[0606] 810 g of isosorbide and 20 g of potassium hydroxide were introduced into a pressurizable and heatable reactor. Next, the inside of the reactor was replaced with nitrogen, heated to 112° C., and then moisture inside the reactor was removed under vacuum and reduced pressure.

[0607] The reaction was carried out at 115°C for 2 hours while adding 1,900 g of propylene oxide to the reactor at a constant rate. Next, the reactor was heated to 122°C while adding 300 g of ethylene oxide at a constant rate. Next, the reaction was carried out at about 120°C for 7 hours. Here, the temperature of the reactor was controlled not to exceed 125°C.

[0608] After the reaction was completed, the temperature of the reactor was lowered to 90° C., and then stirred at about 100° C. for 3 hours while 50 g of AMBOSOL and 5 g of diatomaceous earth were introduced into the reactor to provide the remaining metal ions in the product.

[0609] After confirming that no residual metal ions were detected in the product, the temperature of the reactor was lowered to 70° C., and then the residual by-products were removed by a filter, thereby obtaining 3,010 g of a compound represented by the following formula O, and 13 C NMR spectroscopy confirmed the structure of the compound.

[0610] [Formula O]

[0611]

[0612] 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.

[0613] First Example - Production of Polyurethane Foam

[0614] Example 1-1

[0615] 30 g of the compound prepared in Preparation Example 1-1 was introduced into a plastic beaker. Next, 3.5 g of distilled water, 0.2 g of B-8629 (Evonik Co.) and 0.9 g of L-1501 (Momentive Co.) as silicone foam stabilizers, 0.5 g of D-33LV (Air Products Co.) 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. Next, mixing was performed at 4000 rpm for 3 minutes with a high-speed stirrer to obtain a mixture.

[0616] Next, 58 g of methylene diphenyl isocyanate (CG-3701S, KUMHO Co.) was added to the mixture and foamed to produce a polyurethane foam.

[0617] Example 1-2

[0618] A polyurethane foam was produced by the same process as in Example 1-1, except that 30 g of the compound prepared in Preparation Example 1-2 was added to a plastic beaker instead of 30 g of the compound prepared in Preparation Example 1-1.

[0619] Examples 1-3

[0620] A polyurethane foam was produced by the same process as in Example 1-1, except that 30 g of the compound prepared in Preparation Example 1-3 was added to a plastic beaker instead of 30 g of the compound prepared in Preparation Example 1-1.

[0621] Examples 1-4

[0622] A polyurethane foam was produced by the same process as Example 1-1, except that 30 g of the compound prepared in Preparation Example 1-4 was added to a plastic beaker instead of 30 g of the compound prepared in Preparation Example 1-1.

[0623] Examples 1-5

[0624] A polyurethane foam was produced by the same process as Example 1-1, except that 30 g of the compound prepared in Preparation Example 1-5 was added to a plastic beaker instead of 30 g of the compound prepared in Preparation Example 1-1.

[0625] Comparative Example 1-1

[0626] A polyurethane foam was produced by the same process as in Example 1-1, except that 30 g of the compound prepared in Preparation Example 1-6 was added to a plastic beaker instead of 30 g of the compound prepared in Preparation Example 1-1.

[0627] Comparative Example 1-2

[0628] A polyurethane foam was produced by the same process as Example 1-1, except that 30 g of the compound prepared in Preparation Example 1-7 was added to a plastic beaker instead of 30 g of the compound prepared in Preparation Example 1-1.

[0629] Comparative Examples 1-3

[0630] A polyurethane foam was produced by the same process as in Example 1-1, except that 30 g of the compound prepared in Preparation Example 1-8 was added to a plastic beaker instead of 30 g of the compound prepared in Preparation Example 1-1.

[0631] First Experimental Example

[0632] Experimental Example 1-1 – Acid Value Measurement

[0633] Each container containing the phthalic anhydride solution was added with 2.75 g of the compound prepared in Preparation Example 1-1 to Preparation Example 1-8, and then the reaction was continued for 30 minutes at 115° C. Next, when titrated with a 0.5 normal concentration sodium hydroxide (NaOH) solution, the pH was observed and the volume (ml) of sodium hydroxide (NaOH) required to reach the inflection point was measured.

[0634] Additionally, a blank test was performed, and the volume (ml) of sodium hydroxide (NaOH) required to reach the pH inflection point was measured in the same manner as the procedure.

[0635] Next, the acid value of the compound was calculated based on the measured value, and the results are shown in Table 1 below.

[0636] Experimental Example 1-2 - Measurement of number average molecular weight

[0637] Using the acid values ​​measured in Experimental Example 1-1 and the following Relationship 1, the number average molecular weights of the compounds prepared in Preparation Example 1-1 to Preparation Example 1-8 were calculated, and the results are shown in Table 1 below.

[0638] [Equation 1]

[0639] Number average molecular weight (g / mol) = (56,100 × equivalent number) / measured acid value

[0640] Experimental Example 1-3 – Polydispersity Index Measurement

[0641] 0.1 g of each of the compounds prepared in Preparation Example 1-1 to Preparation Example 1-8 was dissolved in 10 g of THF, and then the polydispersity index of the solution obtained by filtering the insoluble components was measured using gel permeation chromatography (GPC). The results are shown in Table 1 below.

[0642] Experimental Example 1-4 – Measurement of the hydroxyl (-OH) content of primary alcohol

[0643] After confirming that the compounds prepared in each of Preparation Examples 1-1 to 1-8 are 13 After C NMR spectroscopy, 13 The peak at about 61 ppm appearing in the CNMR spectrum was analyzed to calculate the content. The results are shown in Table 1 below.

[0644] Experimental Example 1-5 – Evaluation of high temperature storage stability

[0645] The compounds prepared in each of Preparation Example 1-1 to Preparation Example 1-8 were added to a 450 ml sample bottle, and then, stored in an oven at 45° C. for 150 days, and then evaluated for high temperature storage stability according to the following criteria. The results are shown in Table 1 below.

[0646] -○: No layer separation occurred

[0647] -×: Layer separation occurs

[0648] [Table 1]

[0649]

[0650] Experimental Example 1-6 – Hardness Evaluation

[0651] Each polyurethane foam produced in Examples 1-1 to 1-5 and Comparative Examples 1-1 to Comparative Examples 1-3 was cut into a size of 5 cm×5 cm to make a sample. Next, a universal testing machine (UTM) was used to measure the repulsive force when the sample was compressed 25% and the repulsive force when the sample was compressed 50% at room temperature, and the results are shown in Table 2 below.

[0652] Experimental Example 1-7 – Elongation Evaluation

[0653] Each polyurethane foam produced in Example 1-1 to Example 1-5 and Comparative Example 1-1 to Comparative Example 1-3 was cut into a size of 5 cm×5 cm to prepare a sample. Next, the elongation was measured using a universal testing machine (UTM) according to ASTM D-3574-86, and the results are shown in Table 2 below.

[0654] Experimental Example 1-8 – Evaluation of Pinhole Generation

[0655] The generation of pinholes in the polyurethane foams produced in each of 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. - Satisfactory: No more than one pinhole with a diameter of 3 mm or less was observed on the surface area of ​​800 mm×800 mm of the polyurethane foam.

[0656] - Bad: There are 2 or more pinholes with a diameter of 3 mm or less on the surface area of ​​800 mm × 800 mm of the polyurethane foam.

[0657] Experimental Example 1-9 – Appearance Evaluation

[0658] The appearance of the polyurethane foam produced in each of 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 the following Table 2. - Satisfactory: The entire surface of the polyurethane foam is smooth when observed with the naked eye.

[0659] - Bad: When observed with the naked eye, roughness appears on at least part of the entire surface of the polyurethane foam.

[0660] Experimental Example 1-10 - Evaluation of Foaming Characteristics

[0661] The uniformity of the foaming cells of the surface and cross section of each 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 foam after formation was measured. The foaming properties were evaluated according to the following criteria, and the results are shown in Table 2 below.

[0662] -◎: The foamed cells are uniform and have a density of 0.020 g / cm 3 Up to 0.030g / cm 3 -○: Uniform foaming cells were observed, but the density was 0.020 g / cm 3 Up to 0.030g / cm 3 -×: The foamed cells are not uniform and the density is 0.020 g / cm 3 Up to 0.030g / cm 3 outside the scope of.

[0663] Experimental Example 1-11 – Color Evaluation

[0664] In order to evaluate the color of the polyurethane foam produced in each of Examples 1-1 to 1-5 and Comparative Examples 1-1 to 1-3, the yellowness was measured using MiniScan XE Plus (HUNTERLAB) according to ASTM E313-96, and the results are shown in the following Table 2. A larger measured value indicates closer to yellow, while a smaller measured value indicates clearer and more transparent.

[0665] [Table 2]

[0666]

[0667]

[0668] As shown in Table 1 and Table 2, it is confirmed that, since the polyol compositions of Examples 1-1 to 1-5 include compounds represented by Formula 1, they exhibit excellent mechanical properties and appearance characteristics compared to Comparative Examples 1-1 to 1-3. Specifically, since the polyol compositions of Examples 1-1 to 1-5 have a block copolymer form, wherein branched alkylene is bonded to a parent structure, the parent structure includes a unit derived from 1,4:3,6-dianhydrohexitol, and a linear alkylene is bonded to a branched alkylene, and the polyol compositions of Examples 1-1 to 1-5 include a high content of primary alcohol hydroxyl groups, which have excellent reactivity with isocyanates. Therefore, the polyurethane foam produced by the polyol composition has improved mechanical properties. In addition, by controlling the content ratio of branched alkylene to linear alkylene in the compounds contained in the polyol compositions of Examples 1-1 to 1-5, the appearance state of the polyurethane foam produced by the polyol composition can be improved.

[0669] <Second Manufacturing Example, Second Embodiment, and Second Experimental Example>

[0670] Second Manufacturing Example - Preparation of Polyol Composition

[0671] Preparation Example 2-1

[0672] 802 g of isosorbide and 23 g of potassium hydroxide were added to a pressurizable and heatable reactor. Next, the inside of the reactor was replaced with nitrogen, heated to 112° C., and then moisture inside the reactor was removed under vacuum and reduced pressure.

[0673] The reaction was carried out at a temperature of about 115°C for 6 hours while 1900 g of propylene oxide was introduced into the reactor at a constant rate. Here, the temperature of the reactor was controlled not to exceed 115°C.

[0674] The reactor was stirred until all the propylene oxide residues in the reactor were reacted, and after the reaction was completed, the temperature of the reactor was heated to 120° C. Next, 280 g of ethylene oxide was added to the reactor at a constant rate, and the reaction was continued for 1 hour and 30 minutes at about 120° C. Here, the temperature of the reactor was controlled not to exceed 125° C.

[0675] After the reaction was completed, the temperature of the reactor was cooled to 90° C., 50 g of AMBOSOL and 5 g of diatomaceous earth were introduced into the reactor, and the reactor was stirred at about 100° C. for 3 hours to remove the remaining metal ions in the product.

[0676] After confirming that residual metal ions were not detected in the product, the temperature of the reactor was lowered to 70° C., and then the residual by-products were removed through a filter, thereby obtaining 3,000 g of a polyol composition.

[0677] Preparation Example 2-2

[0678] The polyol composition was obtained by the same process as Preparation Example 2-1, except that 2,100 g of propylene oxide was added to the reactor instead of 1,900 g of propylene oxide in Preparation Example 2-1.

[0679] Preparation Example 2-3

[0680] The polyol composition was obtained by the same process as Preparation Example 2-1, except that 310 g of ethylene oxide was added to the reactor instead of 280 g of ethylene oxide in Preparation Example 2-1.

[0681] Preparation Example 2-4

[0682] The polyol composition was obtained by the same process as Preparation Example 2-1, except that 2,000 g of propylene oxide was added to the reactor instead of 1,900 g of propylene oxide in Preparation Example 2-1 and 300 g of ethylene oxide was added to the reactor instead of 280 g of ethylene oxide.

[0683] Preparation Example 2-5

[0684] The polyol composition was obtained by the same process as Preparation 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 Preparation Example 2-1.

[0685] Preparation Example 2-6

[0686] The polyol composition was obtained by the same process as 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.

[0687] Preparation Example 2-7

[0688] The polyol composition was obtained by the same process as Preparation Example 2-1, except that the residual metal ions in the reactant were removed by stirring for 1 hour instead of stirring for 3 hours as in Preparation Example 2-1.

[0689] Preparation Example 2-8

[0690] The polyol composition was obtained by the same process 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 remaining metal ions in the reactants were removed by stirring for 1 hour instead of stirring for 3 hours in Preparation Example 2-1.

[0691] Comparative Preparation Example 2-1

[0692] 386 g of monopropylene glycol (MPG) and 17.5 g of potassium hydroxide were added to a pressurizable and heatable reactor. Next, the inside of the reactor was replaced with nitrogen and heated to 112° C., and then moisture inside the reactor was removed under vacuum and reduced pressure.

[0693] The reaction was carried out at about 110°C for 6 hours and 30 minutes while 2,132 g of propylene oxide was introduced into the reactor at a constant rate. Here, the temperature of the reactor was controlled not to exceed 115°C.

[0694] The reactor was stirred until all the propylene oxide residues were reacted, and after the reaction was completed, the reactor was heated to about 122° C. Next, the reaction was continued at about 120° C. for 1 hour and 30 minutes while 280 g of ethylene oxide was added to the reactor at a constant rate. Here, the temperature of the reactor was controlled not to exceed 125° C.

[0695] After the reaction was completed, the temperature of the reactor was cooled to 90° C., 50 g of AMBOSOL and 5 g of diatomaceous earth were added to the reactor, and the reactor was stirred at about 115° C. for 3 hours to remove the remaining metal ions in the reactants.

[0696] After confirming that residual metal ions were not detected in the product, the temperature of the reactor was lowered to 70° C., and then the residual by-products were removed through a filter, thereby obtaining 2,800 g of a polyol composition.

[0697] Comparative Preparation Example 2-2

[0698] The polyol composition was obtained by the same process as 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.

[0699] Comparative Preparation Example 2-3

[0700] The polyol composition was obtained by the same process as Comparative Preparation Example 2-1, except that stirring was performed for 1 hour instead of stirring for 3 hours in Comparative Preparation Example 2-1 to remove the remaining metal ions in the reactant.

[0701] Comparative Preparation Example 2-4

[0702] The polyol composition was obtained by the same process as Comparative Preparation Example 2-2, except that stirring was performed for 1 hour instead of stirring for 3 hours in Comparative Preparation Example 2-2 to remove the remaining metal ions in the reactant.

[0703] Second Example - Preparation of Polyurethane Foam

[0704] Example 2-1

[0705] 30 g of the polyol composition prepared in Preparation Example 2-1 was introduced into a plastic beaker. Next, 4.0 g of distilled water, 0.3 g of B-8629 (Evonik Co.) and 1.2 g of L-1501 (Momentive Co.) as silicone foam stabilizers, 0.5 g of D-33LV (Air Products Co.) 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. Next, mixing was performed at 4000 rpm for 3 minutes with a high-speed stirrer to obtain a mixture.

[0706] Next, 58 g of methylene diphenyl isocyanate (CG-3701S, KUMHO Co.) was added to the mixture and foamed to produce a polyurethane foam.

[0707] Examples 2-2 to 2-8 and Comparative Examples 2-1 to 2-4

[0708] A polyurethane foam was produced by the same procedure as in Example 2-1, except that 30 g of the polyol composition shown in Table 3 below was added instead of 30 g of the polyol composition prepared in Preparation Example 2-1.

[0709] Second embodiment

[0710] Experimental Example 2-1 – Measurement of APHA Color Value

[0711] ColorQuest XE (HunterLab) was used to measure the color of each polyol composition of Manufacturing Examples 2-1 to 2-8 and Comparative Manufacturing Examples 2-1 to 2-4. According to ASTM-D1209, the American Public Health Association (APHA) color value (platinum-cobalt system) was measured by the color number of the polyol composition. The results are shown in Table 3 below.

[0712] Experimental Example 2-2 – Measurement of Residual Metal Content

[0713] The residual metal content in each of the polyol compositions of Production Examples 2-1 to 2-8 and Comparative Production Examples 2-1 to 2-4 was measured using atomic absorption spectrometry. The results are shown in Table 3 below.

[0714] Experimental Example 2-3 – APHA color value measurement after treatment at high temperature

[0715] The polyol compositions of each of Manufacturing Examples 2-1 to 2-8 and Comparative Manufacturing Examples 2-1 to 2-4 were stored in an oven at 75°C for 10 minutes. Next, the polyol compositions were exposed to air for 24 hours. Next, the American Public Health Association (APHA) color value was measured under the same conditions as those of Experimental Example 2-1. The results are shown in Table 3 below.

[0716] Experimental Example 2-4 - Measurement of number average molecular weight

[0717] 2.75g of polyol composition prepared in each of manufacturing examples 2-1 to 2-8 and comparative manufacturing examples 2-1 to 2-4 was introduced into each container containing phthalic anhydride solution, and then the reaction lasted for 30 minutes at 115°C. Next, pH was observed while titrating with a sodium hydroxide (NaOH) solution of 0.5 normal concentration, and the volume (ml) of sodium hydroxide (NaOH) required to reach the inflection point was measured. In addition, a blank test was performed, and the volume (ml) of sodium hydroxide (NaOH) required to reach the pH inflection point was measured in the same manner as the process. Next, the acid value (mgKOH / g) of the polyol composition was calculated based on the measured value. Next, the number average molecular weight of the polyol composition prepared in each of manufacturing examples 2-1 to 2-8 and comparative manufacturing examples 2-1 to 2-4 was calculated using the acid value and the following relational formula 1. The results are shown in Table 3 below.

[0718] [Equation 1]

[0719] Number average molecular weight (g / mol) = (56,100 × equivalent number) / measured acid value

[0720] Experimental Example 2-5 – Viscosity Measurement

[0721] The viscosity of each of the polyol compositions of Production Examples 2-1 to 2-8 and Comparative Production Examples 2-1 to 2-4 was measured using DV-III manufactured by Brookfield Corporation at 25° C. The results are shown in Table 3 below.

[0722] Experimental Example 2-6 - Storage Stability Evaluation

[0723] The polyol compositions of each of Preparation Examples 2-1 to 2-8 and Comparative Preparation Examples 2-1 to 2-4 were added to a 450 ml sample bottle and then 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. The results are shown in Table 3 below.

[0724] -○: No layer separation occurred

[0725] -×: Turbid or layer separation occurs

[0726] [Table 3]

[0727]

[0728]

[0729] Experimental Example 2-7 – Polyurethane Foam Color Evaluation

[0730] The color of the polyurethane foam produced in each of Examples 2-1 to 2-8 and Comparative Examples 2-1 to 2-4 was evaluated by naked eyes. The results are shown in Table 4 below:

[0731] Experimental Example 2-8 - Evaluation of Physical Properties of Polyurethane Foam

[0732] The polyurethane foam produced in each of Examples 2-1 to 2-8 and Comparative Examples 2-1 to 2-4 was cut into a size of 5 cm×5 cm to make a sample. Next, the compression hardness, elongation, compression set, and repeated compression set of the sample were measured using a universal testing machine (UTM) according to ASTM D3574-86. The results are shown in Table 4 below.

[0733] [Table 4]

[0734]

[0735]

[0736] As shown in Tables 3 and 4, it was confirmed that the polyol compositions according to Preparation Examples 2-1 to 2-8 and which can be prepared from renewable natural resources have a transparent color compared to the polyol compositions according to Comparative Preparation Examples 2-1 to 2-4. In particular, it was confirmed that since the content of metal residues in the polyol compositions according to Preparation Examples 2-1 to 2-6 was 1 ppm or less, when the polyol compositions according to Preparation Examples 2-1 to 2-6 were exposed to a high temperature environment, color changes depending on metal ions were minimized.

[0737] Furthermore, it was also 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 comparable to or superior to those of the polyurethane foams produced from petroleum-based raw materials in Comparative Examples 2-1 to 2-4.

[0738] Therefore, it was confirmed that the polyol composition according to the present invention and the polyurethane foam containing the same are environmentally friendly, exhibit high transparency and excellent storage stability, and because no petroleum-based raw materials are used, exhibit mechanical properties equivalent to or better than those using petroleum-based raw materials.

[0739] <Third Preparation Example, Third Example, and Third Experimental Example>

[0740] Third Preparation Example - Preparation of Polyol Composition

[0741] Production Example 3-1

[0742] 800 g of isosorbide and 22 g of potassium hydroxide were added to a pressurizable and heatable reactor. Next, the inside of the reactor was replaced with nitrogen, heated to 112° C., and then moisture inside the reactor was removed under vacuum and reduced pressure.

[0743] The reaction was carried out at a temperature of about 115°C for 6 hours while 1880 g of propylene oxide was introduced into the reactor at a constant rate. Here, the temperature of the reactor was controlled not to exceed 115°C.

[0744] The reactor was stirred until all the propylene oxide residues in the reactor were reacted, and after the reaction was completed, the temperature of the reactor was heated to 120° C. Next, 275 g of ethylene oxide was added to the reactor at a constant rate, and the reaction was continued for 1 hour and 30 minutes at about 120° C. Here, the temperature of the reactor was controlled not to exceed 125° C.

[0745] After the reaction was completed, the temperature of the reactor was cooled to 90° C., 50 g of AMBOSOL and 5 g of diatomaceous earth were introduced into the reactor, and the reactor was stirred at about 100° C. for 3 hours to remove the remaining metal ions in the product.

[0746] After confirming that no residual metal ions were detected in the product, the temperature of the reactor was lowered to 70° C., and then the residual by-products were removed by a filter. 300 ppm of an antioxidant (SN-1076, SONGWON Co.) was added based on the total weight of the reactants, and then reacted for 10 minutes, subsequently obtaining 3,000 g of a polyol composition.

[0747] Production Example 3-2

[0748] A polyol composition was obtained by the same procedure 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 in Production Example 3-1.

[0749] Production Example 3-3

[0750] The polyol composition was obtained by the same process 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.

[0751] Production Example 3-4

[0752] The polyol composition was obtained by the same process 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 in Production Example 3-1 and 300 g of ethylene oxide was added instead of 275 g of ethylene oxide in Production Example 3-1.

[0753] Production Example 3-5

[0754] The polyol composition was obtained by the same process 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.

[0755] Production Example 3-6

[0756] The polyol composition was obtained by the same process 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.

[0757] Comparative Production Example 3-1

[0758] 388 g of monopropylene glycol (MPG) and 18 g of potassium hydroxide were added to a pressure- and heat-retainable reactor. Next, the inside of the reactor was purged with nitrogen, and it was heated to 112°C, and then the moisture inside the reactor was removed under vacuum and reduced pressure.

[0759] The reaction was carried out at about 110°C for 7 hours while introducing 2,100 g of propylene oxide into the reactor at a constant rate. Here, the temperature of the reactor was controlled not to exceed 115°C.

[0760] The reactor was stirred until all the propylene oxide residues had reacted, and after the reaction was completed, the reactor was heated to about 122°C. Next, the reaction was carried out at about 120°C for 1 hour 30 minutes while adding 270 g of ethylene oxide to the reactor at a constant rate. Here, the temperature of the reactor was controlled not to exceed 125°C.

[0761] After the reaction was completed, the temperature of the reactor was cooled to 90°C, 50 g of AMBOSOL and 5 g of diatomaceous earth were added to the reactor, and the reactor was stirred at about 115°C for 3 hours to remove the remaining metal ions in the reaction product.

[0762] After confirming that no residual metal ions were detected in the product, the temperature of the reactor was lowered to 70°C, and then the residual by-products were removed through a filter to obtain 2,800 g of a polyol composition.

[0763] Comparative Manufacturing Example 3-2

[0764] The polyol composition was obtained by the same process as 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.

[0765] Comparative Manufacturing Example 3-3

[0766] The polyol composition was obtained by the same process as 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.

[0767] Comparative Manufacturing Example 3-4

[0768] The polyol composition was obtained by the same process as Comparative Preparation Example 3-2, except that 388 g of dipropylene glycol (DPG) was added to the reactor instead of 400 g of dipropylene glycol (DPG) in Comparative Preparation Example 3-2.

[0769] Example 3 - Preparation of polyurethane foam

[0770] Example 3-1

[0771] 30 g of the polyol composition prepared in Preparation Example 3-1 was introduced into a plastic beaker. Next, 4.0 g of distilled water, 0.3 g of B-8629 (Evonik Co.) and 1.2 g of L-1501 (Momentive Co.) as silicone foam stabilizers, 0.5 g of D-33LV (Air Products Co.) 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. Next, mixing was performed at 4000 rpm for 3 minutes with a high-speed stirrer to obtain a mixture.

[0772] Next, 58 g of methylene diphenyl isocyanate (CG-3701S, KUMHO Co.) was added to the mixture and foamed to produce a polyurethane foam.

[0773] Examples 3-2 to 3-6 and Comparative Examples 3-1 to 3-4

[0774] A polyurethane foam was produced by the same procedure as in Example 3-1, except that 30 g of the polyol composition shown in Table 6 below was added instead of 30 g of the polyol composition prepared in Preparation Example 3-1.

[0775] Third embodiment

[0776] Experimental Example 3-1 - Acid Value Measurement

[0777] 15g of the polyol composition prepared in each of Manufacturing Examples 3-1 to 3-6 and Comparative Manufacturing Examples 3-1 to 3-4 was added to a 100ml first flask. In addition, a 100ml second flask was prepared for a blank test. Next, 50ml of methanol and a magnetic bar for removing impurities were added to each of the first flask and the second flask, and the stoppers of the first flask and the second flask were sealed, followed by stirring for 30 minutes.

[0778] Next, 0.5 ml of 1% phenolphthalein indicator was added to each of the first flask and the second flask, and titrated with 0.02 N (normality) potassium hydroxide (KOH) until the pink color at the end point was maintained for 30 seconds when observed with the naked eye. The acid value was calculated according to the following formula 1, and the results are shown in the following Table 5.

[0779] [Formula 1]

[0780] Acid value (mgKOH / g) = [(V s -V b )×56.1×N×F] / M

[0781] In Formula 1, V s V represents the amount (ml) of 0.02N potassium hydroxide (KOH) consumed to titrate the composition in the first flask, V b represents the amount (ml) of 0.02 normal potassium hydroxide (KOH) consumed for titrating the composition in the second flask, N represents the normality of potassium hydroxide (KOH), F represents the factor of 0.02 normal potassium hydroxide (KOH), and M represents the weight (g) of the polyol composition added to the first flask.

[0782] Experimental Example 3-2 - Measurement of number average molecular weight

[0783] 2.75g of polyol composition prepared in each of manufacturing examples 3-1 to 3-6 and comparative manufacturing examples 3-1 to 3-4 was introduced into each container containing phthalic anhydride solution, and then the reaction lasted for 30 minutes at 115°C. Next, pH was observed while titrating with a sodium hydroxide (NaOH) solution of 0.5 normal concentration, and the volume (ml) of sodium hydroxide (NaOH) required to reach the inflection point was measured. In addition, a blank test was performed, and the volume (ml) of sodium hydroxide (NaOH) required to reach the pH inflection point was measured in the same manner as the process. Then, the acid value (mgKOH / g) of the polyol composition was calculated based on the measured value. Next, the number average molecular weight of the polyol composition prepared in each of manufacturing examples 3-1 to 3-6 and comparative manufacturing examples 3-1 to 3-4 was calculated using the acid value and the following relationship 1, and the results are shown in Table 5 below.

[0784] [Equation 1]

[0785] Number average molecular weight (g / mol) = (56,100 × equivalent number) / measured acid value

[0786] Experimental Example 3 - Measurement of Active Oxygen Content

[0787] After purging the first flask of 25 ml with nitrogen for 2 minutes, 3 g of the polyol composition prepared in each of Preparation Examples 1 to 6 and Comparative Preparation Examples 3-1 to 3-4 was added to the first flask, and then purged with nitrogen. In addition, a second flask of 25 ml was prepared for a blank test.

[0788] Next, add the ferrous thiocyanate of 20ml respectively to the first flask and the second flask, dilute with methanol, and the reaction lasts for 5 minutes.Use ultraviolet visible spectrophotometer (Cary50conc, Varian company) and quartz cuvette (10mm × 10mm), respectively to the absorbance of the distilled water under 500nm wavelength, the absorbance of the material added to the first flask and the absorbance of the material added to the second flask are measured.According to the absorbance of the material added to the first flask and the difference of the absorbance of the material added to the second flask calculate actual absorbance.Next, use calibration curve to calculate the amount of active oxygen, and result is shown in table 5 below.

[0789] Experimental Example 3-4 – Viscosity Measurement

[0790] The viscosity of each of the polyol compositions of Production Examples 3-1 to 3-6 and Comparative Production Examples 3-1 to 3-4 was measured using DV-III manufactured by Brookfield Corporation at 25° C. The results are shown in Table 3 below.

[0791] [Table 5]

[0792] Acid value Number average molecular weight Active oxygen content Viscosity unit mgKOH / g g / mol ppm cP Production Example 3-1 0.010 445 7.9 395 Production Example 3-2 0.010 477 10.3 415 Production Example 3-3 0.012 470 8.3 395 Production Example 3-4 0.010 515 9.1 410 Manufacturing Example 3-5 0.012 450 13.3 400 Manufacturing Example 3-6 0.012 450 12.3 400 Comparative Manufacturing Example 3-1 0.020 515 310.4 785 Comparative Manufacturing Example 3-2 0.040 535 380.5 660 Comparative Manufacturing Example 3-3 0.023 515 300.6 800 Comparative Manufacturing Example 3-4 0.045 535 399.5 755

[0793] Experimental Example 3-5 – Processing Time

[0794] The total process time taken to produce the polyurethane foam in each of Examples 3-1 to 3-6 and Comparative Examples 3-1 to 3-4 was measured. The results are shown in Table 6 below.

[0795] Experimental Example 3-6 – Formability Evaluation

[0796] When the polyurethane foams of each of Examples 3-1 to 3-6 and Comparative Examples 3-1 to 3-4 were produced, the time when the polyurethane foam started to expand (cream time; CT) and the time when the polyurethane foam expanded and swelled (rise time; RT) were measured. When the CT of the polyurethane foam was 7 to 10 seconds and the RT thereof was 90 to 100 seconds, the moldability was evaluated to be good. The results are shown in Table 6 below.

[0797] Experimental Example 3-7-Evaluation of the physical properties of polyurethane foam

[0798] The polyurethane foam produced in each of Examples 3-1 to 3-6 and Comparative Examples 3-1 to 3-4 was cut into a size of 5 cm × 5 cm to make a sample. Next, the compression hardness, elongation, compression set, and repeated compression set of the sample were measured using a universal testing machine (UTM) according to ASTM D3574-86. The results are shown in Table 6 below.

[0799] [Table 6]

[0800]

[0801] As shown in Table 5 and Table 6, it was confirmed that the polyol polymers according to Preparation Examples 3-1 to 3-6, which may be prepared from renewable natural resources, exhibited lower acid values ​​than the polyol compositions according to Comparative Preparation Examples 3-1 to 3-4.

[0802] Therefore, it was confirmed that the polyol compositions according to Manufacturing Examples 3-1 to 3-6 exhibited improved reactivity with the isocyanate-based composition, compared with the polyol compositions according to Comparative Manufacturing Examples 3-1 to 3-4, so that the process time for producing polyurethane foam was reduced and moldability was improved.

[0803] Furthermore, 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 comparable to or superior to those of the polyurethane foams of Comparative Examples 3-1 to 3-4 produced from petroleum-based raw materials.

[0804] Therefore, it is confirmed that the polyol composition according to the present invention and the polyurethane foam containing the same are environmentally friendly, and exhibit a low acid value, improved process time efficiency and moldability, and because no petroleum-based raw materials are used, the mechanical properties are equivalent to or better than the case of using petroleum-based raw materials.

[0805] <Fourth Preparation Example, Fourth Example, and Fourth Experimental Example>

[0806] Fourth Preparation Example - Preparation of Polyol Composition

[0807] Production Example 4-1

[0808] Step (1) – Preparation of prepolymer

[0809] 796 g of isosorbide and 22 g of potassium hydroxide were added to a pressurizable and heatable reactor. Next, the inside of the reactor was replaced with nitrogen, heated to 112° C., and then moisture inside the reactor was removed under vacuum and reduced pressure.

[0810] The reaction was carried out at a temperature of about 115°C for 6 hours while 1904 g of propylene oxide was introduced into the reactor at a constant rate. Here, the temperature of the reactor was controlled not to exceed 115°C.

[0811] The reactor was stirred until all the propylene oxide residues in the reactor were reacted, and after the reaction was completed, the temperature of the reactor was heated to 120° C. Next, 270 g of ethylene oxide was added to the reactor at a constant rate, and the reaction was continued for 1 hour and 30 minutes at about 120° C. Here, the temperature of the reactor was controlled not to exceed 125° C.

[0812] After the reaction was completed, the temperature of the reactor was cooled to 90° C., 50 g of AMBOSOL and 5 g of diatomaceous earth were introduced into the reactor, and the reactor was stirred at about 100° C. for 3 hours to remove the remaining metal ions in the product.

[0813] After confirming that no residual metal ions were detected in the product, the temperature of the reactor was lowered to 70° C., and then the residual by-products were removed by a filter, thereby obtaining 3,000 g of a prepolymer. Step (2)—Preparation of a polyol composition

[0814] 796 g of the prepolymer was added to a pressurizable and heatable reactor. Next, the inside of the reactor was replaced with nitrogen, and heated to 112° C., and then moisture inside the reactor was removed under vacuum and reduced pressure.

[0815] 0.14 g of double metal cyanide was added to the reactor, and then the reaction was carried out at about 110° C. for about 6 hours and 30 minutes while 2204 g of propylene oxide was added at a constant rate. Here, the temperature of the reactor was controlled not to exceed 115° C.

[0816] Stirring was maintained until all propylene oxide residues in the reactor were reacted. The temperature of the reactor was lowered to 90° C., and then 3000 g of a polyol composition was obtained.

[0817] Production Example 4-2

[0818] The polyol composition was obtained by the same process as in Production Example 4-1, except that 2,204 g of a mixture of propylene oxide and ethylene oxide at a weight ratio of 6:4 was added to the reactor instead of 2,204 g of propylene oxide in step (2) of Production Example 4-1.

[0819] Production Example 4-3

[0820] The polyol composition was obtained by the same process as in Production Example 4-1, except that 2,204 g of a mixture of propylene oxide and ethylene oxide at a weight ratio of 5:5 was added to the reactor instead of 2,204 g of propylene oxide in step (2) of Production Example 4-1.

[0821] Production Example 4-4

[0822] The polyol composition was obtained by the same process as in Production Example 4-1, except that 2,204 g of a mixture of propylene oxide and ethylene oxide at a weight ratio of 4:6 was added to the reactor instead of 2,204 g of propylene oxide in step (2) of Production Example 4-1.

[0823] Manufacturing Example 4-5

[0824] A polyol composition was obtained by the same process as in Production Example 4-1, except that 25 g of potassium hydroxide was added to the reactor instead of 22 g of potassium hydroxide in step (1) of Production Example 4-1.

[0825] Manufacturing Example 4-6

[0826] A polyol composition was obtained by the same procedure as in Production Example 4-1, except that 2,100 g of propylene oxide was added to the reactor instead of 1,904 g of propylene oxide in step (1) of Production Example 4-1.

[0827] Manufacturing Example 4-7

[0828] The polyol composition was obtained by the same process as in Production 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 Production Example 4-1.

[0829] Production Example 4-8

[0830] The polyol composition was obtained by the same process as in Production Example 4-1, except that 0.25 g of double metal cyanide was added to the reactor instead of 0.14 g of double metal cyanide in step (2) of Production Example 4-1.

[0831] Production Example 4-9

[0832] The polyol composition was obtained by the same process as in Production Example 4-1, except that 0.10 g of double metal cyanide was added to the reactor instead of 0.14 g of double metal cyanide in step (2) of Production Example 4-1.

[0833] Production Example 4-10

[0834] The polyol composition was obtained by the same process as in Production Example 4-1, except that 2,300 g of propylene oxide was added to the reactor instead of 2,204 g of propylene oxide in step (2) of Production Example 4-1.

[0835] Comparative Production Example 4-1

[0836] 796 g of the prepolymer obtained in step (1) of Production Example 4-1 and 9.8 g of potassium hydroxide were added to a pressure-resistant and heatable reactor. Next, the inside of the reactor was purged with nitrogen, and it was heated to 112 °C, and then the moisture inside the reactor was removed under vacuum and reduced pressure.

[0837] The reaction was carried out at about 110 °C for about 9 hours and 30 minutes while adding 2,204 g of propylene oxide to the reactor at a constant rate. Here, the temperature of the reactor was controlled not to exceed 115 °C.

[0838] The reactor was stirred until all the propylene oxide residues had reacted. After completion of the reaction, the temperature of the reactor was cooled to 90 °C, 50 g of AMBOSOL and 5 g of diatomaceous earth were added to the reactor, and the reactor was stirred at about 100 °C for 3 hours to remove the remaining metal ions in the reaction product.

[0839] After confirming that no residual metal ions were detected in the product, the temperature of the reactor was lowered to 70 °C, and then the residual by-products were removed through a filter to obtain 3000 g of the polyol composition.

[0840] Comparative Manufacturing Example 4-2

[0841] The polyol composition was obtained by the same process as Comparative Production Example 4-1, except that 2,204 g of a mixture including propylene oxide and ethylene oxide at a weight ratio of 6:4 was added to the reactor instead of 2,204 g of propylene oxide in Comparative Production Example 4-1.

[0842] Comparative Manufacturing Example 4-3

[0843] 796 g of isosorbide was added to the pressurizable and heatable reactor. Next, the inside of the reactor was replaced with nitrogen, and heated to 112° C., and then moisture inside the reactor was removed under vacuum and reduced pressure.

[0844] A polymerization reaction was attempted at about 110° C. for about 2 hours while adding 2204 g of propylene oxide at a constant rate after introducing 0.14 g of double metal cyanide into the reactor, but the polymerization reaction of isosorbide with propylene oxide did not proceed because the double metal cyanide catalyst was not activated.

[0845] Comparative Manufacturing Example 4-4

[0846] 796 g of the prepolymer obtained in step (1) of Production Example 4-1 was added to a pressurizable and heatable reactor. Next, the interior of the reactor was replaced with nitrogen, heated to 112° C., and then the moisture inside the reactor was removed under vacuum and reduced pressure.

[0847] 0.14 g of double metal cyanide and 22 g of potassium hydroxide were added to the reactor, and then the reaction was carried out at about 110° C. for about 9 hours and 30 minutes while adding 2,204 g of propylene oxide at a constant rate. Here, the temperature of the reactor was controlled not to exceed 115° C.

[0848] The reactor was stirred until all the propylene oxide residues were reacted. After the reaction was completed, the temperature of the reactor was cooled to 90° C., 50 g of AMBOSOL and 5 g of diatomaceous earth were added to the reactor, and the reactor was stirred at about 100° C. for 3 hours to remove the remaining metal ions in the reactants.

[0849] After confirming that residual metal ions were not detected in the product, the temperature of the reactor was lowered to 70° C., and then the residual by-products were removed through a filter, thereby obtaining 3,000 g of a polyol composition.

[0850] Fourth embodiment -right Preparation of polyurethane foam

[0851] Example 4-1

[0852] 30 g of the polyol composition prepared in Manufacturing Example 4-1 was added to a plastic beaker. Next, 3.5 g of distilled water, 0.2 g of B-8629 (Evonik Co.) and 0.9 g of L-1501 (Momentive Co.) as silicone foam stabilizers, 0.5 g of D-33LV (Air Products Co.) 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. Next, mixing was performed at 4000 rpm for 3 minutes using a high-speed stirrer to obtain a mixture.

[0853] Next, 58 g of methylene diphenyl isocyanate (CG-3701S, KUMHO Co.) was added to the mixture and foamed to produce a polyurethane foam.

[0854] Examples 4-2 to 4-10 and Comparative Examples 4-1 to 4-4

[0855] A polyurethane foam was produced by the same procedure as in Example 4-1, except that 30 g of the polyol composition shown in Table 8 below was added instead of 30 g of the polyol composition prepared in Preparation Example 4-1.

[0856] Fourth Experimental Example

[0857] Experimental Example 4-1 – DOU Measurement

[0858] 30 g of the polyol composition prepared in each of Manufacturing Examples 4-1 to 4-10 and Comparative Manufacturing Examples 4-1 to 4-4 was added to a 250 ml first flask. In addition, a 250 ml second flask was prepared for a blank test. Next, 50 ml of mercuric acetate and a magnetic bar for removing impurities were added to each of the first flask and the second flask, and the stoppers of the first flask and the second flask were sealed, followed by stirring for 30 minutes.

[0859] Next, 9 g of sodium bromide (NaBr) was added to each of the first flask and the second flask, followed by stirring for 30 minutes. Next, 0.5 ml of 1% phenolphthalein indicator was added to each of the first flask and the second flask, and titrated with 0.1 N (normality) potassium hydroxide (KOH) until the pink color at the end point was maintained for 15 seconds when observed with the naked eye. The degree of unsaturation was calculated by the following formula 1, and the results are shown in Table 7 below.

[0860] [Formula 1]

[0861] Unsaturation (meq / g) = (V s ×Vb ×0.1×F) / M.

[0862] In Formula 1, V s represents the amount (ml) of 0.1N potassium hydroxide (KOH) added to the first flask, V b represents the amount (ml) of 0.1 normal potassium hydroxide (KOH) added to the second flask, F represents the factor of 0.1 normal potassium hydroxide (KOH), and M represents the weight (g) of the polyol composition added to the first flask.

[0863] Experimental Example 4-2 - Measurement of number average molecular weight

[0864] 2.75g of polyol composition prepared in each of manufacturing examples 4-1 to 4-10 and comparative manufacturing examples 4-1 to 4-4 was introduced into each container containing phthalic anhydride solution, and then the reaction lasted for 30 minutes at 115°C. Next, pH was observed while titrating with a sodium hydroxide (NaOH) solution of 0.5 normal concentration, and the volume (ml) of sodium hydroxide (NaOH) required to reach the inflection point was measured. In addition, a blank test was performed, and the volume (ml) of sodium hydroxide (NaOH) required to reach the pH inflection point was measured in the same manner as the process. Next, the acid value (mgKOH / g) of the polyol composition was calculated based on the measured value. Next, the number average molecular weight of the polyol composition prepared in each of manufacturing examples 4-1 to 4-10 and comparative manufacturing examples 4-1 to 4-4 was calculated using the acid value and the following relational formula 1. The results are shown in Table 7 below.

[0865] [Equation 1]

[0866] Number average molecular weight (g / mol) = (56,100 × equivalent number) / measured acid value

[0867] Experimental Example 4-3 – Reactivity Evaluation

[0868] When the polyol composition of each of Production Examples 4-1 to 4-10 and Comparative Production Examples 4-1 to 4-4 was prepared using the catalyst, the reactivity thereof was evaluated according to the following criteria. The results are shown in Table 7 below.

[0869] -◎: The polymerization reaction proceeds smoothly.

[0870] -○: The polymerization reaction proceeds, but the polymerization reaction rate is slow.

[0871] -X: The catalyst was not activated, and thus the polymerization reaction did not proceed.

[0872] [Table 7]

[0873]

[0874]

[0875] Experimental Example 4-4 - Evaluation of Physical Properties of Polyurethane Foam

[0876] The polyurethane foams produced in Examples 4-1 to 4-10 and Comparative Examples 4-1 to 4-4 were each cut into a size of 5 cm × 5 cm to fabricate samples. Next, a universal testing machine (UTM) was used to measure the compression hardness, elongation at break, compression set, and repeated compression set of the samples according to ASTM D3574-86. The results are shown in Table 8 below.

[0877] [Table 8]

[0878]

[0879]

[0880] As shown in Tables 7 and 8, it was confirmed that, based on a number average molecular weight of about 2,000 g / mol to 2,400 g / mol, compared with the polyurethane foams of Comparative Examples 4-1 to 4-4, the polyurethane foams produced from the polyol compositions having an unsaturation of 0.02 meq / g or less in Examples 4-1 to 4-10 exhibited a significant improvement in mechanical properties such as hardness and elongation at break. In addition, it was also confirmed that the difference in unsaturation may vary depending on the type of catalyst or the timing of introduction of the catalyst during the production of the polyol composition. Specifically, in the case of Comparative Production Example 3, it was confirmed that since a double metal cyanide catalyst was used instead of a potassium hydroxide catalyst during the prepolymer preparation process in step (1), the catalyst was not activated, resulting in no polymerization reaction. In addition, it was also confirmed that during the polyol composition preparation process in step (2), when a potassium hydroxide catalyst was used instead of a double metal cyanide catalyst, or when a double metal cyanide catalyst and a potassium hydroxide catalyst were used in combination, the DOU of the prepared polyol composition exceeded 0.02 meq / g, and the physical properties such as hardness, elongation at break, compression set, and repeated compression set of the polyurethane foam deteriorated.

[0881] <Fifth Manufacturing Example, Fifth Embodiment, Fifth Experimental Example>

[0882] Fifth Manufacturing Example - Preparation of Polyether Polyol

[0883] Production Example 5-1

[0884] Step (1) - Preparation of the First Polymer

[0885] Isosorbide and potassium hydroxide were added to a pressurizable and heatable batch reactor at a weight ratio of 50:1 (isosorbide: potassium hydroxide). Next, the interior of the reactor was replaced with nitrogen, heated to 112° C., and then the moisture inside the reactor was removed under vacuum and reduced pressure for about 3 hours.

[0886] The reaction was carried out at about 115° C. for about 6 hours and 30 minutes, while 240 parts by weight of propylene oxide based on 100 parts by weight of isosorbide was introduced into the reactor at a rate of about 4 g / min. Here, the temperature of the reactor was controlled not to exceed 115° C. The reactor was stirred until all the propylene oxide residues were reacted, and after the reaction was completed, the reactor was heated to about 122° C.

[0887] Next, the reaction was carried out at about 120° C. for about 1 hour and 30 minutes, while 34 parts by weight of ethylene oxide based on 100 parts by weight of isosorbide was introduced into the reactor at a rate of about 2 g / min. Here, the temperature of the reactor was controlled not to exceed 125° C.

[0888] After the reaction was completed, the reactor was cooled to about 90° C., AMBOSOL as a metal adsorbent and diatomaceous earth as a filter aid were added to the reactor, and the reactor was stirred at about 100° C. for 3 hours to remove the remaining metal ions in the reactants.

[0889] Next, after confirming that the residual metal ions were not detected, the temperature of the reactor was lowered to 70° C., and then the residual by-products were filtered, thereby obtaining a first polymer.

[0890] Step (2) - Preparation of the Second Polymer

[0891] The first polymer was added to the reactor. Next, the inside of the reactor was replaced with nitrogen, and heated to 112° C., and then moisture inside the reactor was removed under vacuum and reduced pressure conditions.

[0892] Next, the first polymer and double metal cyanide were added to the reactor at a weight ratio of 5,680:1.

[0893] Next, the reaction was carried out at about 115° C. for about 6 hours and 30 minutes, while 270 parts by weight of propylene oxide based on 100 parts by weight of the first polymer was introduced into the reactor at a rate of about 4 g / min. Here, the temperature of the reactor was controlled not to exceed 115° C. Stirring was maintained until all propylene oxide residues in the reactor were reacted. The temperature of the reactor was reduced to 90° C., and then the second polymer, i.e., polyether polyol, was obtained.

[0894] Production Example 5-2

[0895] The second polymer is obtained by the same process as in Manufacturing Example 5-1, except that 270 parts by weight of a mixture comprising propylene oxide and ethylene oxide mixed in a weight ratio of 6:4 based on 100 parts by weight of the first polymer is introduced into the reactor, instead of introducing 270 parts by weight of propylene oxide based on 100 parts by weight of the first polymer as in step (2) of Manufacturing Example 5-1.

[0896] Production Example 5-3

[0897] The second polymer was obtained by the same process as in Manufacturing Example 5-1, except that isosorbide and potassium hydroxide were introduced into the reactor at a weight ratio of 70:1 (isosorbide:potassium hydroxide), instead of isosorbide and potassium hydroxide being introduced at a weight ratio of 50:1 (isosorbide:potassium hydroxide) as in step (1) of Manufacturing Example 5-1.

[0898] Production Example 5-4

[0899] The second polymer was obtained by the same process as in Production Example 5-1, except that 350 parts by weight of propylene oxide per 100 parts by weight of isosorbide were introduced into the reactor instead of 240 parts by weight of propylene oxide per 100 parts by weight of isosorbide as in step (1) of Production Example 5-1.

[0900] Production Example 5-5

[0901] The second polymer was obtained by the same process as in Production Example 5-1, except that 60 parts by weight of ethylene oxide per 100 parts by weight of isosorbide were introduced into the reactor instead of 34 parts by weight of ethylene oxide per 100 parts by weight of isosorbide as in step (1) of Production Example 5-1.

[0902] Production Example 5-6

[0903] The second polymer was obtained by the same process as in Production Example 5-1, except that the water in the reactor was removed for about 1 hour instead of about 3 hours as in step (1) of Production Example 5-1.

[0904] Production Example 5-7

[0905] The second polymer is obtained by the same process as in Manufacturing Example 5-1, except that the first polymer and the double metal cyanide are added to the reactor at a weight ratio of 20,500:1 (first polymer:double metal cyanide), instead of introducing the first polymer and the double metal cyanide into the reactor at a weight ratio of 5,680:1 (first polymer:double metal cyanide).

[0906] Comparative Manufacturing Example 5-1

[0907] Step (1) - Preparation of the first polymer

[0908] Isosorbide and potassium hydroxide were added to a pressurizable and heatable batch reactor at a weight ratio of 50:1 (isosorbide: potassium hydroxide). Next, the interior of the reactor was replaced with nitrogen, heated to 112° C., and then the moisture inside the reactor was removed under vacuum and reduced pressure for about 3 hours.

[0909] The reaction was carried out at about 115° C. for about 6 hours and 30 minutes, while 240 parts by weight of propylene oxide based on 100 parts by weight of isosorbide was introduced into the reactor at a rate of about 4 g / min. Here, the temperature of the reactor was controlled not to exceed 115° C. The reactor was stirred until all the propylene oxide residues were reacted, and after the reaction was completed, the reactor was heated to about 122° C.

[0910] Next, the reaction was carried out at about 120° C. for about 1 hour and 30 minutes, while 34 parts by weight of ethylene oxide based on 100 parts by weight of isosorbide was introduced into the reactor at a rate of about 2 g / min. Here, the temperature of the reactor was controlled not to exceed 125° C.

[0911] After the reaction was completed, the reactor was cooled to about 90° C., AMBOSOL as a metal adsorbent and diatomaceous earth as a filter aid were added to the reactor, and the reactor was stirred at about 100° C. for 3 hours to remove the remaining metal ions in the reactants.

[0912] Next, after confirming that the residual metal ions were not detected, the temperature of the reactor was lowered to 70° C., and then the residual by-products were filtered, thereby obtaining a first polymer.

[0913] Step (2) - Preparation of the Second Polymer

[0914] The first polymer and potassium hydroxide were added to the reactor at a weight ratio of 100:1 (first polymer:potassium hydroxide). Next, the inside of the reactor was replaced with nitrogen, heated to 112° C., and then the moisture inside the reactor was removed under vacuum and reduced pressure.

[0915] Next, the reaction was carried out at about 115° C. for about 6 hours and 30 minutes, while 270 parts by weight of propylene oxide based on 100 parts by weight of the first polymer was introduced into the reactor at a rate of about 4 g / min. Here, the temperature of the reactor was controlled not to exceed 115° C.

[0916] Stirring was maintained until all propylene oxide residues in the reactor were reacted. The temperature of the reactor was lowered to 90°C, and then AMBOSOL as a metal adsorbent and diatomaceous earth as a filter aid were added to the reactor, and then the reactor was stirred at about 100°C for 3 hours to remove the remaining metal ions in the reactants.

[0917] Next, after confirming that the residual metal ions were not detected, the temperature of the reactor was lowered to 70° C., and then the residual by-products were filtered, thereby obtaining a polyether polyol as a second polymer.

[0918] Comparative Manufacturing Example 5-2

[0919] The second polymer is obtained by the same process as Comparative Manufacturing Example 5-1, except that 270 parts by weight of a mixture of propylene oxide and ethylene oxide in a weight ratio of 6:4 are introduced into the reactor based on 100 parts by weight of the first polymer, instead of introducing 270 parts by weight of propylene oxide into the reactor based on 100 parts by weight of the first polymer as in Comparative Manufacturing Example 5-1.

[0920] Comparative Manufacturing Example 5-3

[0921] Isosorbide was added to a pressurizable and heatable batch reactor. Next, the inside of the reactor was replaced with nitrogen, and heated to 112° C., and then moisture inside the reactor was removed under vacuum and reduced pressure.

[0922] Next, 0.017 parts by weight of double metal cyanide based on 100 parts by weight of isosorbide was added to the reactor.

[0923] Next, the polymerization reaction was carried out at about 115° C. for about 2 hours, while 270 parts by weight of propylene oxide based on 100 parts by weight of isosorbide was introduced into the reactor at a rate of about 4 g / min, but the double metal cyanide catalyst was not activated, so that the polymerization reaction of isosorbide and propylene oxide did not proceed.

[0924] Comparative Manufacturing Example 5-4

[0925] The second polymer was obtained by the same process as Comparative Production Example 5-1, except that isosorbide and potassium hydroxide were introduced into the reactor at a weight ratio of 20:1 (isosorbide: potassium hydroxide), instead of introducing isosorbide and potassium hydroxide into the reactor at a weight ratio of 50:1 (isosorbide: potassium hydroxide) as in step (1) of Comparative Production Example 5-1.

[0926] Comparative Production Example 5-5

[0927] Step (1) - Preparation of the first polymer

[0928] Isosorbide and potassium hydroxide were added to a pressure- and heat-resistant batch reactor at a weight ratio of 50:1 (isosorbide: potassium hydroxide). Next, the inside of the reactor was purged with nitrogen, and it was heated to 112 °C, and then the moisture inside the reactor was removed under vacuum and reduced pressure for about 1 hour.

[0929] The reaction was carried out at about 115 °C for about 6 hours and 30 minutes while introducing a mixture of propylene oxide and ethylene oxide at a weight ratio of 6:4 and at 270 parts by weight based on 100 parts by weight of isosorbide into the reactor at a rate of about 4 g / min. Here, the temperature of the reactor was controlled not to exceed 115 °C.

[0930] After completion of the reaction, the reactor was cooled to about 90 °C, AMBOSOL as a metal adsorbent and diatomaceous earth as a filter aid were added to the reactor, and the reactor was stirred at about 100 °C for 3 hours to remove residual metal ions in the reaction product.

[0931] Next, after confirming that no residual metal ions were detected, the temperature of the reactor was lowered to 70 °C, and then the residual by-products were filtered to obtain the first polymer.

[0932] Step (2) - Preparation of the second polymer

[0933] The first polymer and potassium hydroxide were added to the reactor at a weight ratio of 100:1 (first polymer: potassium hydroxide). Next, the inside of the reactor was purged with nitrogen, and it was heated to 112 °C, and then the moisture inside the reactor was removed under vacuum and reduced pressure.

[0934] Next, the reaction was carried out at about 115 °C for about 6 hours and 30 minutes while introducing propylene oxide at 270 parts by weight based on 100 parts by weight of the first polymer into the reactor at a rate of about 4 g / min. Here, the temperature of the reactor was controlled not to exceed 115 °C.

[0935] Stirring was maintained until all propylene oxide residues in the reactor were reacted. The temperature of the reactor was lowered to 90°C, and then AMBOSOL as a metal adsorbent and diatomaceous earth as a filter aid were added to the reactor, and the reactor was stirred at about 100°C for 3 hours to remove the remaining metal ions in the reactants.

[0936] Next, after confirming that the residual metal ions were not detected, the temperature of the reactor was lowered to 70° C., and then the residual by-products were filtered, thereby obtaining a polyether polyol as a second polymer.

[0937] Comparative Manufacturing Example 5-6

[0938] The second polymer was obtained by the same process as in Comparative Production Example 5-1, except that 250 parts by weight of ethylene oxide per 100 parts by weight of isosorbide were introduced into the reactor instead of 34 parts by weight of ethylene oxide per 100 parts by weight of isosorbide as in step (1) of Comparative Production Example 5-1.

[0939] The catalysts, reactants, and reaction conditions used in Production Examples 5-1 to 5-7 and Comparative Production Examples 5-1 to 5-6 are shown in Table 9 below.

[0940] [Table 9]

[0941]

[0942]

[0943] Fifth embodiment -right Preparation of polyurethane foam

[0944] Example 5-1

[0945] 30 g of the polyether polyol prepared in Production Example 5-1 was added to a plastic beaker. Next, 3.5 g of distilled water, 0.2 g of B-8629 (Evonik Co.) and 0.9 g of L-1501 (Momentive Co.) as silicone foam stabilizers, 0.5 g of D-33LV (Air Products Co.) 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. Next, mixing was performed at 4000 rpm for 3 minutes using a high-speed stirrer to obtain a mixture.

[0946] Next, 58 g of methylene diphenyl isocyanate (CG-3701S, KUMHO Co.) was added to the mixture and foamed to produce a polyurethane foam.

[0947] Examples 5-2 to 5-7 and Comparative Examples 5-1 to 5-6

[0948] A polyurethane foam was produced by the same procedure as in Example 5-1, except that 30 g of a polyether polyol shown in Table 11 below was added instead of 30 g of the polyether polyol prepared in Preparation Example 5-1.

[0949] Fifth Experimental Example

[0950] Experimental Example 5-1 – Measurement of Residual Moisture Content

[0951] After the dehydration treatment of step (1) of each of Manufacturing Examples 5-1 to 5-7 and Comparative Manufacturing Examples 5-1 to 5-6 was completed, the residual moisture content relative to the total weight of the dehydrated composition was measured by Karl Fischer coulometric titration, and the results are shown in Table 10 below.

[0952] Experimental Example 5-2 – DOU Measurement

[0953] 30 g of each of the polyether polyols prepared in Manufacturing Examples 5-1 to 5-7 and Comparative Manufacturing Examples 5-1 to 5-6 was added to a 250 ml first flask. In addition, a 250 ml second flask was prepared for a blank test. Next, 50 ml of mercuric acetate and a magnetic bar for removing impurities were added to each of the first flask and the second flask, and the stoppers of the first flask and the second flask were sealed, followed by stirring for 30 minutes.

[0954] Next, 9 g of sodium bromide (NaBr) was added to each of the first flask and the second flask, followed by stirring for 30 minutes. Next, 0.5 ml of 1% phenolphthalein indicator was added to each of the first flask and the second flask, and titrated with 0.1 N (normality) potassium hydroxide (KOH) until the pink color at the end point was maintained for 15 seconds when observed with the naked eye, so as to calculate the degree of unsaturation. The results are shown in Table 10 below.

[0955] Experimental Example 5-3 – Reactivity Evaluation

[0956] When the polyether polyol of each of Production Examples 5-1 to 5-7 and Comparative Production Examples 5-1 to 5-6 was prepared using the catalyst, the reactivity thereof was evaluated according to the following criteria. The results are shown in Table 10 below.

[0957] -◎: The polymerization reaction proceeds smoothly.

[0958] -○: The polymerization reaction proceeds, but the polymerization reaction rate is slow.

[0959] -X: The catalyst was not activated, and thus the polymerization reaction did not proceed.

[0960] Experimental Example 5-4 - Measurement of number average molecular weight

[0961] 2.75g of polyether polyol prepared in each of manufacturing examples 5-1 to 5-7 and comparative manufacturing examples 5-1 to 5-6 was introduced into each container containing phthalic anhydride solution, and then the reaction lasted for 30 minutes at 115°C. Next, pH was observed while titrating with a sodium hydroxide (NaOH) solution of 0.5 normal concentration, and the volume (ml) of sodium hydroxide (NaOH) required to reach the inflection point was measured. In addition, a blank test was performed, and the volume (ml) of sodium hydroxide (NaOH) required to reach the pH inflection point was measured in the same manner as the process. Next, the acid value (mgKOH / g) of the polyol composition was calculated based on the measured value. Next, the number average molecular weight of the polyether polyol prepared in each of manufacturing examples 5-1 to 5-7 and comparative manufacturing examples 5-1 to 5-6 was calculated using the acid value and the following relational formula 1. The results are shown in Table 10 below.

[0962] [Equation 1]

[0963] Number average molecular weight (g / mol) = (56,100 × equivalent number) / measured acid value

[0964] [Table 10]

[0965]

[0966]

[0967] Experimental Example 5-5 - Evaluation of the physical properties of polyurethane foam

[0968] The polyurethane foams produced in each of Examples 5-1 to 5-7 and Comparative Examples 5-1 to 5-6 were cut into a size of 5 cm×5 cm to prepare samples. Next, 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 11 below.

[0969] Experimental Example 5-6 – Appearance Evaluation

[0970] The appearance of the polyurethane foam produced in each of 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.

[0971] - Satisfactory: When observed with the naked eye, the entire surface of the polyurethane foam is smooth.

[0972] - Bad: When observed with the naked eye, roughness appears on at least part of the entire surface of the polyurethane foam.

[0973] Experimental Example 5-7 – Color Evaluation

[0974] In order to evaluate the color of the polyurethane foam produced in each of Examples 5-1 to 5-7 and Comparative Examples 5-1 to 5-6, the yellowness was measured using MiniScan XE Plus (HUNTERLAB) according to ASTM E313-96. The results are shown in Table 11 below. The larger the measured value, the closer to yellow, and the smaller the measured value, the clearer and more transparent.

[0975] [Table 11]

[0976]

[0977]

[0978] As shown in Tables 9 to 11, it was confirmed that the polyurethane foams of Examples 5-1 to 5-7 comprising the polyether polyol prepared according to the preparation method of the present invention showed significant improvements 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, 5-4 to 5-6. In addition, it was also confirmed that the polyurethane foams of Examples 5-1 to 5-7 had excellent appearance compared to the polyurethane foams of Comparative Examples 5-5 and 5-6.

[0979] It is confirmed that the difference in the mechanical properties of the polyurethane foam may vary depending on the type of catalyst and the time of catalyst injection during the production of the polyether polyol. Specifically, in Comparative Manufacturing Example 3, since a double metal cyanide catalyst was used instead of an alkaline catalyst in the first polymer production process of step (1), the polymerization reaction did not proceed due to the deactivation of the catalyst. In addition, it is confirmed that when an alkaline catalyst is used instead of a double metal cyanide catalyst in the process of preparing the second polymer, i.e., the polyether polyol, in step (2), the polyether polyol exhibits a higher DOU, and physical properties such as hardness, elongation, compression set, and repeated compression set of the polyurethane foam deteriorate. Here, it is also confirmed that the appearance of the polyurethane foam may vary depending on the content ratio of propylene oxide and ethylene oxide during the production of the polyether polyol.

[0980] <Sixth Manufacturing Example, Sixth Embodiment, and Sixth Experimental Example>

[0981] Sixth Manufacturing Example - Preparation of Polyether Polyol

[0982] Production Example 6-1

[0983] Step (1) – Preparation of prepolymer

[0984] 798 g of isosorbide and 21 g of potassium hydroxide were added to a pressurizable and heatable reactor. Next, the inside of the reactor was replaced with nitrogen, heated to 112° C., and then moisture inside the reactor was removed under vacuum and reduced pressure.

[0985] The reaction was continued for 6 hours at a temperature of about 115°C while 1900 g of propylene oxide was introduced into the reactor at a constant rate. Here, the temperature of the reactor was controlled not to exceed 115°C.

[0986] The reactor was stirred until all the propylene oxide residues in the reactor were reacted, and after the reaction was completed, the temperature of the reactor was heated to 122° C. Next, 275 g of ethylene oxide was added to the reactor at a constant rate, and the reaction was continued for 1 hour and 30 minutes at about 120° C. Here, the temperature of the reactor was controlled not to exceed 125° C.

[0987] After the reaction was completed, the temperature of the reactor was cooled to 90° C., 50 g of AMBOSOL and 5 g of diatomaceous earth were introduced into the reactor, and the reactor was stirred at about 100° C. for 3 hours to remove the remaining metal ions in the product.

[0988] After confirming that no residual metal ions were detected in the product, the temperature of the reactor was lowered to 70° C., and then the residual by-products were removed by a filter, thereby obtaining 3,000 g of a prepolymer. Step (2)—Preparation of polyether polyol

[0989] 795 g of the prepolymer was added to a pressurizable and heatable reactor. Next, the inside of the reactor was replaced with nitrogen, and heated to 112° C., and then moisture inside the reactor was removed under vacuum and reduced pressure.

[0990] 0.14 g of double metal cyanide was added to the reactor, and the reaction was carried out at about 110° C. for about 7 hours, while 2,200 g of a mixture containing propylene oxide and ethylene oxide in a weight ratio of 6:4 was introduced into the reactor. Here, the temperature of the reactor was controlled not to exceed 115° C.

[0991] The reactor was continuously stirred until the remaining mixture in the reactor was completely reacted. The temperature of the reactor was lowered to 90° C., and then 3000 g of polyether polyol was obtained.

[0992] Production Example 6-2

[0993] The polyether polyol was obtained by the same process as in Production Example 6-1, except that a mixture of propylene oxide and ethylene oxide in a weight ratio of 5.5:4.5 was introduced into the reactor instead of introducing a mixture of propylene oxide and ethylene oxide in a weight ratio of 6:4 into the reactor as in step (2) of Production Example 6-1.

[0994] Production Example 6-3

[0995] The polyether polyol was obtained by the same process as in Production Example 6-1, except that a mixture comprising propylene oxide and ethylene oxide in a weight ratio of 5:5 was introduced into the reactor instead of introducing a mixture comprising propylene oxide and ethylene oxide in a weight ratio of 6:4 into the reactor as in step (2) of Production Example 6-1.

[0996] Production Example 6-4

[0997] The polyether polyol was obtained by the same process as in Production Example 6-1, except that a mixture of propylene oxide and ethylene oxide in a weight ratio of 4.5:5.5 was introduced into the reactor instead of introducing a mixture of propylene oxide and ethylene oxide in a weight ratio of 6:4 into the reactor as in step (2) of Production Example 6-1.

[0998] Production Example 6-5

[0999] The polyether polyol is obtained by the same process as in Production Example 6-1, except that a mixture comprising propylene oxide and ethylene oxide in a weight ratio of 4:6 is introduced into the reactor instead of introducing a mixture comprising propylene oxide and ethylene oxide in a weight ratio of 6:4 into the reactor as in step (2) of Production Example 6-1.

[1000] Production Example 6-6

[1001] The polyether polyol was obtained by the same process as in Production Example 6-1, except that 0.16 g of double metal cyanide was introduced into the reactor instead of 0.14 g of double metal cyanide as in step (2) of Production Example 6-1.

[1002] Production Example 6-7

[1003] The polyether polyol was obtained by the same process as in Production Example 6-1, except that 0.12 g of double metal cyanide was introduced into the reactor instead of 0.14 g of double metal cyanide as in step (2) of Production Example 6-1.

[1004] Comparative Manufacturing Example 6-1

[1005] 796 g of the prepolymer obtained in step (1) of Production Example 6-1 and 9.8 g of potassium hydroxide were added to a pressurizable and heatable reactor. Next, the interior of the reactor was replaced with nitrogen, heated to 112° C., and then the moisture inside the reactor was removed under vacuum and reduced pressure.

[1006] The reaction was conducted at about 110° C. for about 9 hours and 30 minutes while introducing 2,204 g of a mixture including propylene oxide and ethylene oxide in a weight ratio of 6:4 into the reactor. Here, the temperature of the reactor was controlled not to exceed 115° C.

[1007] The reactor was stirred until the remaining mixture in the reactor was completely reacted. After the reaction was completed, the temperature of the reactor was cooled to 90° C., 50 g of AMBOSOL and 5 g of diatomaceous earth were added to the reactor, and the reactor was stirred at about 100° C. for 3 hours to remove residual metal ions.

[1008] After confirming that the residual metal ions were not detected, the temperature of the reactor was lowered to 70° C., and then the residual by-products were removed through a filter, thereby obtaining 3000 g of a polyether polyol.

[1009] Comparative Manufacturing Example 6-2

[1010] The polyether polyol was obtained by the same process as Comparative Production Example 6-1, except that a mixture comprising propylene oxide and ethylene oxide in a weight ratio of 5:5 was introduced into the reactor instead of a mixture comprising propylene oxide and ethylene oxide in a weight ratio of 6:4 as in Comparative Production Example 6-1.

[1011] Comparative Manufacturing Example 6-3

[1012] The polyether polyol was obtained by the same process as Comparative Production Example 6-1, except that a mixture comprising propylene oxide and ethylene oxide in a weight ratio of 30:1 was introduced into the reactor instead of a mixture comprising propylene oxide and ethylene oxide in a weight ratio of 6:4 as in Production Example 6-1.

[1013] Comparative Manufacturing Example 6-4

[1014] 795 g of the prepolymer obtained in step (1) of Production Example 6-1 was added to a pressurizable and heatable reactor. Next, the interior of the reactor was replaced with nitrogen, heated to 112° C., and then the moisture inside the reactor was removed under vacuum and reduced pressure.

[1015] A polymerization reaction was attempted at about 110° C. for about 2 hours while adding 2200 g of propylene oxide at a constant rate after introducing 0.14 g of double metal cyanide into the reactor, but the polymerization reaction of isosorbide with propylene oxide did not proceed because the double metal cyanide catalyst was not activated.

[1016] Comparative Manufacturing Example 6-5

[1017] 796 g of the prepolymer obtained in step (1) of Production Example 6-1 was added to a pressurizable and heatable reactor. Next, the interior of the reactor was replaced with nitrogen, heated to 112° C., and then the moisture inside the reactor was removed under vacuum and reduced pressure.

[1018] The reaction was carried out at about 110° C. for about 9 hours and 30 minutes, while 2204 g of a mixture including propylene oxide and ethylene oxide in a weight ratio of 6:4 was introduced into the reactor. Here, the temperature of the reactor was controlled not to exceed 115° C.

[1019] The reactor was stirred until the remaining mixture in the reactor was completely reacted, the reactor was cooled to 90° C., and then the remaining by-products were removed through a filter, thereby obtaining 3000 g of polyether polyol.

[1020] Comparative Manufacturing Example 6-6

[1021] The polyether polyol was obtained in the same manner as in Comparative Production Example 6-5, except that a mixture comprising propylene oxide and ethylene oxide in a weight ratio of 1:30 was introduced into the reactor instead of a mixture comprising propylene oxide and ethylene oxide in a weight ratio of 6:4 as in Comparative Production Example 6-5.

[1022] Example 6 - Preparation of polyurethane foam

[1023] Example 6-1

[1024] 30 g of the polyether polyol prepared in Production Example 6-1 was added to a plastic beaker. Next, 3.5 g of distilled water, 0.2 g of B-8629 (Evonik Co.) and 0.9 g of L-1501 (Momentive Co.) as silicone foam stabilizers, 0.5 g of D-33LV (Air Products Co.) 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. Next, mixing was performed at 4000 rpm for 3 minutes using a high-speed stirrer to obtain a mixture.

[1025] Next, 58 g of methylene diphenyl isocyanate (CG-3701S, KUMHO Co.) was added to the mixture and foamed to produce a polyurethane foam.

[1026] Examples 6-2 to 6-7 and Comparative Examples 6-1 to 6-6

[1027] A polyurethane foam was produced by the same procedure as in Example 6-1, except that 30 g of a polyether polyol shown in Table 13 below was added instead of 30 g of the polyether polyol prepared in Preparation Example 6-1.

[1028] Experimental Example 6

[1029] Experimental Example 6-1 - Measurement of Primary Alcohol Content

[1030] It was confirmed that the polyether polyols prepared in each of the preparation examples 6-1 to 6-7 and the comparative preparation examples 6-1 to 6-6 were 13 After C NMR spectroscopy, 13 The peak at about 61 ppm appearing in the C NMR spectrum was analyzed to calculate the content, and the results are shown in Table 12 below. In addition, the polyether polyol prepared in Production Example 6-1 13 C NMR spectrum is shown at Fig.10 and compared the polyether polyol prepared in Preparation Example 6-1 13 C NMR spectrum is shown at Fig.11 middle.

[1031] Experimental Example 6-2 - Measurement of number average molecular weight

[1032] 2.75g of polyether polyol prepared in manufacturing examples 6-1 to 6-7 and comparative manufacturing examples 6-1 to 6-6 were introduced into each container containing phthalic anhydride solution, and then reacted at 115°C for 30 minutes. Next, the pH value was observed while titrating with a sodium hydroxide (NaOH) solution of 0.5 normal concentration, and the volume (ml) of sodium hydroxide (NaOH) required to reach the inflection point was measured. In addition, a blank test was performed, and the volume (ml) of sodium hydroxide (NaOH) required to reach the pH inflection point was measured in the same manner as the process. Next, the acid value (mgKOH / g) of the polyether polyol was calculated based on the measured value. Next, the number average molecular weight of the polyether polyol prepared in each of manufacturing examples 6-1 to 6-7 and comparative manufacturing examples 6-1 to 6-6 was calculated using the acid value and the following relationship 1. The results are shown in Table 12 below.

[1033] [Equation 1]

[1034] Average molecular weight (g / mol) = (56,100 × equivalent number) / measured acid value

[1035] Experimental Example 6-3 – Viscosity Measurement

[1036] The viscosity of the polyether polyols prepared in each of Production Examples 6-1 to 6-7 and Comparative Production Examples 6-1 to 6-6 was measured at 25° C. using DV-III manufactured by Brookfield Corporation, and the results are shown in Table 12 below.

[1037] Experimental Example 6-4 - Storage Stability Evaluation

[1038] The polyether polyols prepared in each of Production Examples 6-1 to 6-7 and Comparative Production Examples 6-1 to 6-6 were added to a 450 ml sample bottle and then stored at -3°C for 1 hour. 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.

[1039] -○: No gelling occurs

[1040] -×: Gel phenomenon occurs

[1041] Experimental Example 6-5 – Reactivity Evaluation

[1042] The polyether polyols of Production Examples 6-1 to 6-7 and Comparative Production Examples 6-1 to 6-6 prepared using the catalyst were evaluated according to the following criteria, and the results are shown in Table 12 below.

[1043] -◎: The polymerization reaction proceeds smoothly.

[1044] -○: The polymerization reaction proceeds, but the polymerization reaction rate is slow.

[1045] -X: The catalyst was not activated, and thus the polymerization reaction did not proceed.

[1046] Experimental Example 6-6 – Measurement of Residual Metal Content

[1047] The residual metal content in the polyether polyols prepared in each of Production Examples 6-1 to 6-7 and Comparative Production Examples 6-1 to 6-6 was measured using atomic absorption spectrometry, and the results are shown in Table 12 below.

[1048] [Table 12]

[1049]

[1050]

[1051] Experimental Example 6-7 - Evaluation of Physical Properties of Polyurethane Foam

[1052] The polyurethane foam produced in each of Examples 6-1 to 6-7 and Comparative Examples 6-1 to 6-6 was cut into a size of 5 cm × 5 cm to make a sample. Next, the compression hardness, elongation, compression set, and repeated compression set of the sample were measured using a universal testing machine (UTM) according to ASTM D3574-86. The results are shown in Table 13 below.

[1053] [Table 13]

[1054]

[1055]

[1056] As shown in Tables 12 and 13, it was confirmed that the polyurethane foams produced from the polyether polyols in which the primary alcohol content was 10 mol % to 90 mol % of Examples 6-1 to 6-7 showed significant improvements in mechanical properties such as hardness and elongation compared with Comparative Examples.

[1057] Specifically, it was confirmed that since the primary alcohol content in the polyether polyols of Comparative Examples 6-1 to 6-3 was less than 10 mol%, the reactivity with isocyanate was reduced, so that the physical properties of the produced polyurethane foams were reduced. In addition, it was also confirmed that in the case of Comparative Example 6-4, even if a double metal cyanide catalyst was used, the polymerization reaction did not proceed due to the low reactivity with ethylene oxide. In addition, it was also confirmed that in the case of Comparative Examples 6-5 and 6-6, even if a potassium hydroxide catalyst having high reactivity with ethylene oxide was used, the physical properties of the produced polyurethane foams were reduced due to the high content of the residual catalyst.

[1058]

Industrial Applicability

[1059] The embodiments may be applied to a polyol composition having excellent reactivity with isocyanate and a polyurethane foam manufactured from the polyol composition allowing excellent hardness and appearance quality; a method for preparing the polyol composition; a composition for preparing a polyurethane including the polyol composition; and a battery module including the polyol composition.

Claims

1. A polyol composition, comprising a compound represented by the following formula 1: [Formula 1] in, R 1 and R 4 are each independently a substituted or unsubstituted straight-chain alkylene group having 2 to 10 carbon atoms, R 2 and R 3 are each independently a substituted or unsubstituted branched alkylene group having 3 to 10 carbon atoms, x is an integer from 1 to 10, a and d are each independently an integer from 1 to 6, b and c are each independently an integer from 0 to 30, and b+c is an integer from 1 to 60.

2. The polyol composition according to claim 1, in, The compound represented by Formula 1 includes a unit derived from at least one 1,4:3,6-dianhydrohexitol.

3. The polyol composition according to claim 1, in, R 1 and R 4 Each is independently a substituted or unsubstituted ethylene group.

4. The polyol composition according to claim 1, in, R 2 and R 3 Each is independently a substituted or unsubstituted propylene group.

5. The polyol composition according to claim 1, in, The ratio of (a+d):(b+c) is 1:1.5 to 1:

6.

6. The polyol composition according to claim 1, in, The compound represented by Formula 1 is a compound represented by the following Formula 2: [Formula 2] Wherein, x' is an integer from 1 to 5, a' and d' are each independently an integer from 1 to 3, and b' and c' are each independently an integer from 1 to 18.

7. The polyol composition according to claim 1, in, The polyol composition has an acid value of about 0.0005 to about 0.0100 mgKOH / g.

8. The polyol composition according to claim 1, in, The polyol composition has a number average molecular weight (Mn) of about 300 to about 12,000 g / mol.

9. The polyol composition according to claim 1, in, The polyol composition has a polydispersity index (PDI) of 1.0 to 1.

3.

10. A polyol composition, comprising: a first unit derived from at least one 1,4:3,6-dianhydrohexitol; as well as a second unit, the second unit being derived from an alkylene oxide, Wherein, the unsaturation is 0.02 meq / g or less according to the following measurement method: <Measurement method> 1) preparing a first flask and a second flask, the first flask containing 30 g of the polyol composition, the second flask not containing the polyol composition, and adding 50 ml of mercuric acetate to each of the first flask and the second flask, followed by stirring for 30 minutes; 2) adding 9 g of sodium bromide (NaBr) to each of the first flask and the second flask, followed by stirring for 30 minutes; 3) adding 0.5 ml of 1% phenolphthalein indicator to each of the first flask and the second flask, followed by titration with 0.1 normal potassium hydroxide (KOH); 4) Calculate the degree of unsaturation according to the following formula 1: [Formula 1] Unsaturation (meq / g) = (V s ×V b ×0.1×F) / M Among them, V s represents the amount (ml) of 0.1N potassium hydroxide (KOH) added to the first flask, V b represents the amount (ml) of 0.1 normal potassium hydroxide (KOH) added to the second flask, F represents the factor of the 0.1 normal potassium hydroxide (KOH), and M represents the weight (g) of the polyol composition added to the first flask.

11. The polyol composition according to claim 10, in, The 1,4:3,6-dianhydrohexitol includes isosorbide.

12. The polyol composition according to claim 10, in, The second unit derived from an alkylene oxide includes a substituted or unsubstituted linear alkylene group having 2 to 10 carbon atoms.

13. The polyol composition according to claim 10, in, The polyol composition includes a compound represented by the following formula 3: [Formula 3] Among them, 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 an integer from 1 to 60, b and e are each independently an integer from 1 to 6, c and d are each independently an integer from 1 to 30, and x is an integer of 1-5.

14. The polyol composition according to claim 13, in, In formula 3, R 1 and R 2 Each is independently a substituted or unsubstituted branched alkylene group having 3 to 10 carbon atoms.

15. The polyol composition according to claim 13, in, In formula 3, R 1 and R 2 Each is independently a polymer in which a substituted or unsubstituted straight-chain alkylene group having 2 to 10 carbon atoms and a substituted or unsubstituted branched-chain alkylene group having 3 to 10 carbon atoms are randomly polymerized.

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