KR102945827B1 - Polyol composition, composition for preparing polyurethane and battery module comprising the same - Google Patents

Abstract

The polyol composition according to the present invention comprises at least one first unit derived from 1,4:3,6-dianhydrohexitol and a second unit derived from alkylene oxide, and has a degree of unsaturation of 0.02 meq/g or less according to the following measurement method.
<Measurement Method> (Refer to Description of Invention)

Description

Polyol composition, composition for preparing polyurethane and battery module comprising the same

The present invention relates to a polyol composition, a composition for manufacturing polyurethane, and a battery module comprising the same.

Polyurethane foam possesses excellent thermal insulation properties and flame retardancy. Such polyurethane foam is used in various fields, including packaging boxes, construction panels, home appliances, packaging materials, building interior materials, and insulation materials. Polyurethane foam can be manufactured by foaming polyurethane, and polyurethane can be produced through the polyaddition reaction of polyols and isocyanates.

Polyols are liquid polymeric materials in which two or more alcohol groups (-OH) are bonded to the ends of hydrocarbon chains. Polyols are typically manufactured from petroleum-based raw materials. However, recently, there has been a growing demand for eco-friendly and renewable materials due to issues such as the depletion of petroleum resources and the reduction of greenhouse gases related to environmental protection. Anhydrous sugar alcohols are eco-friendly materials derived from renewable natural resources, and much research has been conducted on them as they can improve the physical properties of polyurethanes. Among anhydrous sugar alcohols, 1,4:3,6-dianhydrohexitol, which is derived from biomass such as corn, wheat, and sugar and contains polysaccharides as constituents, is widely used as a raw material for polyols.

The above 1,4:3,6-dianhydrohexitol and alkylene oxide can be prepared into polyols in the presence of a catalyst. The catalyst may be an alkali catalyst or a bimetallic cyanide catalyst. When the alkali catalyst is used, a large amount of monool is generated as a byproduct, which may reduce the reactivity between the polyol and the isocyanate. This hinders crosslinking and high molecular weight polymerization when manufacturing polyurethane resins, resulting in a problem where the physical properties of the polyurethane resin are degraded. On the other hand, when using a bimetallic cyanide catalyst, it is not economical, and there was a problem in that the initiation of the polymerization reaction between the isosorbide and the alkylene oxide did not proceed smoothly.

Accordingly, there is a need for the development of technology that can improve reactivity with isocyanates and produce polyurethane foam with excellent physical properties.

The present invention provides a polyol composition having excellent reactivity with isocyanate and excellent physical properties of the manufactured polyurethane foam, a composition for manufacturing polyurethane, and a battery module comprising the same.

The polyol composition according to the present invention comprises at least one first unit derived from 1,4:3,6-dianhydrohexitol and a second unit derived from alkylene oxide, and has a degree of unsaturation of 0.02 meq/g or less according to the following measurement method.

<Measurement Method>

1) Prepare a first flask into which 30g of the above polyol composition is added and a second flask into which the above polyol composition is not added, and add 50ml of mercury acetate to each of the first flask and the second flask, and stir for 30 minutes.

2) Add 9g of sodium bromide (NaBr) to each of the first flask and the second flask, and stir for 30 minutes.

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

4) Calculate the degree of unsaturation using the following Equation 1.

[Equation 1]

Degree of unsaturation (meq/g) = (V _s × V _b × 0.1 × F) / M

(In the above Formula 1, V _s is the amount (ml) of 0.1N potassium hydroxide (KOH) added to the first flask, V _b is the amount (ml) of 0.1N potassium hydroxide (KOH) added to the second flask, F is the factor of 0.1N potassium hydroxide (KOH), and M is the weight (g) of the polyol composition introduced into the first flask.)

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

In one embodiment of the present invention, the polyol composition may contain 5% to 50% by weight of a first unit derived from 1,4:3,6-dianhydrohexitol based on the total weight of the polyol composition.

In one embodiment of the present invention, the second unit derived from the alkylene oxide may include a substituted or unsubstituted branched alkylene group having 3 to 10 carbon atoms.

In one embodiment of the present invention, the polyol composition may contain 40% to 85% by weight of the branched alkylene group based on the total weight of the polyol composition.

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

In one embodiment of the present invention, the polyol composition may contain more than 0 weight% to 20 weight% of the linear alkylene group based on the total weight of the polyol composition.

In one embodiment of the present invention, the number average molecular weight (Mn) of the polyol composition may be 500 g/mol to 12,000 g/mol.

In one embodiment of the present invention, the polyol composition may include a compound represented by the following chemical formula 1.

[Chemical Formula 1]

In the above chemical formula 1,

_R1 and _R2 are each independently substituted or unsubstituted alkylene groups having 2 to 10 carbon atoms, and

a and f are each independently integers from 1 to 60, and

b and e are each independently integers from 1 to 6, and

c and d are each independently integers from 1 to 30, and

x is an integer from 1 to 5.

In one embodiment of the present invention, in the formula 1, _R1 and _R2 may each independently be a substituted or unsubstituted branched alkylene group having 3 to 10 carbon atoms.

In one embodiment of the present invention, in Formula 1, _R1 and _R2 may each independently polymerize 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 in a random manner.

In one embodiment of the present invention, the polyol composition may further include an antioxidant.

In one embodiment of the present invention, the polyol composition may contain the antioxidant in an amount of 0.03% to 1.00% by weight based on the total weight of the polyol composition.

The composition for manufacturing polyurethane according to the present invention comprises a polyol composition having a degree of unsaturation of 0.02 meq/g or less according to the following measurement method, and an isocyanate-based composition, comprising at least one first unit derived from 1,4:3,6-dianhydrohexitol and a second unit derived from alkylene oxide.

<Measurement Method>

1) Prepare a first flask into which 30g of the above polyol composition is added and a second flask into which the above polyol composition is not added, and add 50ml of mercury acetate to each of the first flask and the second flask, and stir for 30 minutes.

2) Add 9g of sodium bromide (NaBr) to each of the first flask and the second flask, and stir for 30 minutes.

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

4) Calculate the degree of unsaturation using the following Equation 1.

[Equation 1]

Degree of unsaturation (meq/g) = (V _s × V _b × 0.1 × F) / M

(In the above Formula 1, V _s is the amount (ml) of 0.1N potassium hydroxide (KOH) added to the first flask, V _b is the amount (ml) of 0.1N potassium hydroxide (KOH) added to the second flask, F is the factor of 0.1N potassium hydroxide (KOH), and M is the weight (g) of the polyol composition introduced into the first flask.)

A battery module according to the present invention comprises a housing, a plurality of battery cells accommodated inside the housing, and a polyurethane foam disposed between the plurality of battery cells, wherein the polyurethane foam comprises a composition for manufacturing polyurethane comprising a polyol composition and an isocyanate-based composition, and the polyol composition comprises at least one first unit derived from 1,4:3,6-dianhydrohexitol and a second unit derived from an alkylene oxide, and the degree of unsaturation according to the following measurement method is 0.02 meq/g or less.

<Measurement Method>

1) Prepare a first flask into which 30g of the above polyol composition is added and a second flask into which the above polyol composition is not added, and add 50ml of mercury acetate to each of the first flask and the second flask, and stir for 30 minutes.

2) Add 9g of sodium bromide (NaBr) to each of the first flask and the second flask, and stir for 30 minutes.

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

4) Calculate the degree of unsaturation using the following Equation 1.

[Equation 1]

Degree of unsaturation (meq/g) = (V _s × V _b × 0.1 × F) / M

(In the above Formula 1, V _s is the amount (ml) of 0.1N potassium hydroxide (KOH) added to the first flask, V _b is the amount (ml) of 0.1N potassium hydroxide (KOH) added to the second flask, F is the factor of 0.1N potassium hydroxide (KOH), and M is the weight (g) of the polyol composition introduced into the first flask.)

The polyol composition according to the present invention comprises isosorbide, which can be produced from renewable natural resources, thereby having the effect of being eco-friendly and capable of saving energy.

The polyol composition according to the present invention has a significantly reduced monool content, which has the effect of excellent reactivity with isocyanates. As a result, when manufacturing a polyurethane resin from the polyol composition, crosslinking and high molecular weight conversion proceed smoothly, thereby improving the physical properties of the polyurethane resin.

FIG. 1 is a flowchart briefly illustrating the manufacturing process of a polyol composition according to the present invention.
FIG. 2 is a simplified cross-sectional view of a battery module according to the present invention.

The structural or functional descriptions of the embodiments disclosed in this specification or application are merely illustrative for the purpose of explaining embodiments according to the technical concept of the present invention. Embodiments according to the technical concept of the present invention may be implemented in various forms other than those disclosed in this specification or application, and the technical concept of the present invention is not to be interpreted as being limited to the embodiments described in this specification or application.

Furthermore, when a component is described as "comprising" in this specification or application, this means that, unless specifically stated otherwise, it does not exclude other components but may include additional components. Additionally, all numerical ranges representing physical properties, dimensions, etc., of components described in this specification or application should be understood to be modified by the term "approximately" in all cases, unless otherwise specifically stated.

Hereinafter, a polyol composition, a composition for manufacturing polyurethane, and a battery module including the same according to the present invention will be described.

Polyol Composition

The polyol composition according to the present invention comprises at least one first unit derived from 1,4:3,6-dianhydrohexitol and a second unit derived from alkylene oxide, and has a degree of unsaturation of 0.02 meq/g or less according to the following measurement method.

<Measurement Method>

1) Prepare a first flask into which 30g of the above polyol composition is added and a second flask into which the above polyol composition is not added, and add 50ml of mercury acetate to each of the first flask and the second flask, and stir for 30 minutes.

2) Add 9g of sodium bromide (NaBr) to each of the first flask and the second flask, and stir for 30 minutes.

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

4) Calculate the degree of unsaturation using the following Equation 1.

[Equation 1]

Degree of unsaturation (meq/g) = (V _s × V _b × 0.1 × F) / M

In the above Equation 1, V _s is the amount (ml) of 0.1N potassium hydroxide (KOH) added to the first flask, V _b is the amount (ml) of 0.1N potassium hydroxide (KOH) added to the second flask, F is the factor of 0.1N potassium hydroxide (KOH), and M is the weight (g) of the polyol composition added to the first flask.

The above 1,4:3,6-dianhydrohexitol may exist as three isomers: isomannide, isoidide, and isosobide. These three isomers can be distinguished by differences in the relative configuration of two hydroxyl groups (-OH) in each compound. The above isomannide may be obtained by the dehydration reaction of D-mannitol. The above isoidide may be obtained by the dehydration reaction of L-iditol. Considering the manufacturing process and efficiency, at least one of the above 1,4:3,6-dianhydrohexitols may include isosorbide.

The above isosorbide can be obtained by the dehydration reaction of D-sorbitol, a renewable natural resource. By including the above compound, the polyol composition of the present invention is environmentally friendly and has the effect of saving energy.

Based on the total weight of the polyol composition, the polyol composition may contain a first unit derived from the 1,4:3,6-dianhydrohexitol in an amount of 5% to 50% by weight, 10% to 50% by weight, 10% to 45% by weight, 15% to 45% by weight, or 20% to 45% by weight. When the above range is satisfied, the problem of foaming not proceeding smoothly due to an increase in the viscosity of the composition when manufacturing polyurethane foam from the polyol composition is not caused, and the molding density and hardness of the manufactured polyurethane foam may be improved.

The second unit derived from the above alkylene oxide may include a substituted or unsubstituted branched alkylene group having 3 to 10 carbon atoms. The branched alkylene group may be propylene oxide.

The above polyol composition may contain the branched alkylene group in an amount of 20% to 90% by weight, 25% to 90% by weight, 30% to 90% by weight, 35% to 90% by weight, 35% to 85% by weight, or 40% to 85% by weight, based on the total weight of the polyol composition.

The second unit derived from the above alkylene oxide may include a substituted or unsubstituted linear alkylene group having 2 to 10 carbon atoms. The linear alkylene group may be ethylene oxide.

The above polyol composition may contain the linear alkylene group in an amount greater than 0 wt% to 40 wt%, greater than 0 wt% to 35 wt%, greater than 0 wt% to 30 wt%, greater than 0 wt% to 25 wt%, or greater than 0 wt% to 20 wt%, based on the total weight of the polyol composition.

The above polyol composition has a degree of unsaturation of 0.02 meq/g or less according to the following measurement method.

<Measurement Method>

1) Prepare a first flask into which 30g of the above polyol composition is added and a second flask into which the above polyol composition is not added, and add 50ml of mercury acetate to each of the first flask and the second flask, and stir for 30 minutes.

2) Add 9g of sodium bromide (NaBr) to each of the first flask and the second flask, and stir for 30 minutes.

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

4) Calculate the degree of unsaturation using the following Equation 1.

[Equation 1]

Degree of unsaturation (meq/g) = (V _s × V _b × 0.1 × F) / M

In the above Equation 1, V _s is the amount (ml) of 0.1N potassium hydroxide (KOH) added to the first flask, V _b is the amount (ml) of 0.1N potassium hydroxide (KOH) added to the second flask, F is the factor of 0.1N potassium hydroxide (KOH), and M is the weight (g) of the polyol composition added to the first flask.

The degree of unsaturation above refers to the content of monool in the polyol composition. Specifically, the degree of unsaturation can be expressed as mg unsaturated equivalent (meq/g) per 1g of the polyol composition.

The above monool can be produced in a process of addition polymerization of propylene oxide to 1,4:3,6-dianhydrohexitol using a catalyst. Specifically, the above monool can be produced in a process in which the propylene oxide is converted to an allyl alcohol.

The above monool may cause a decrease in the number of functional groups of the polyol composition, and if the above polyol composition is used, it may hinder crosslinking and high molecular weight development during polyurethane manufacturing, thereby degrading the physical properties of the polyurethane resin.

The degree of unsaturation of the above 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 the above range is satisfied, the reactivity with isocyanate is excellent, and when manufacturing a polyurethane resin from the polyol composition, crosslinking and high molecular weight can proceed smoothly, thereby improving the physical properties of the polyurethane resin.

The above polyol composition may include a compound represented by the following chemical formula 1.

[Chemical Formula 1]

In the above chemical formula 1, _R1 and _R2 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 from 1 to 5.

The compound represented by the above chemical formula 1 may include at least one core structure derived from 1,4:3,6-dianhydrohexitol. The at least one 1,4:3,6-dianhydrohexitol may include isosorbide.

The ratio of (b+e):(c+d) above may be 1:1.5 to 1:6. Preferably, the ratio of (b+e):(c+d) above may be 1:2 to 1:6, 1:2.5 to 1:6, or 1:3 to 1:6. (b+c) and (d+e) above may each independently be 3 to 50. Preferably, (b+c) and (d+e) above may each independently be 3 to 30, 3 to 20, 5 to 20, 5 to 10, or 5 to 9. When satisfying the above ranges, the polyurethane foam containing the compound has improved hardness, reduced permanent compression strain, and a smooth surface, which can have an excellent appearance.

In addition, by achieving an appropriate level of Compression Force Deformation (CFD), product stability can be improved by buffering volume changes caused by the expansion of battery cells when polyurethane foam is applied to battery modules, thereby maintaining a constant volume. The aforementioned CFD is a parameter that refers to the repulsive force when a measurement target is compressed.

The above CFD can be evaluated by measuring the repulsion force when the polyurethane foam is cut to a size of 5 cm × 5 cm at room temperature and compressed using a device such as a Universal Testing Machine (UTM). For example, the repulsion force when the polyurethane foam is compressed by 25% can be evaluated as a CFD 25% value, and the preferred CFD 25% value may have a range of approximately greater than 0.06 kg/ ^cm² to less than 0.15 kg/ ^cm² . Additionally, the repulsion force when the polyurethane foam is compressed by 50% can be evaluated as a CFD 50% value, and the preferred CFD 50% value may have a range of approximately greater than 0.09 kg/ ^cm² to less than 0.20 kg/ ^cm² .

In the above chemical formula 1, _R1 and _R2 may each independently be a substituted or unsubstituted branched alkylene group having 3 to 10 carbon atoms. The branched alkylene group may be propylene oxide.

In the above chemical formula 1, _R1 and _R2 may each be independently polymerized in a random manner by a substituted or unsubstituted linear alkylene group having 2 to 10 carbon atoms and a substituted or unsubstituted branched alkylene group having 3 to 10 carbon atoms. The linear alkylene group may be ethylene oxide.

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

The types of compounds represented by the above chemical formula 1 can be represented by compounds of the following chemical formulas A to G.

[Chemical Formula A]

[Chemical Formula B]

[Chemical Formula C]

[Chemical Formula D]

[Chemical Formula E]

[Chemical Formula F]

[Chemical Formula G]

The above polyol composition may further include an antioxidant. The antioxidant can improve the heat resistance stability of the polyurethane foam obtained from the above polyol composition. The antioxidant may be one or more selected from the group consisting of phenolic antioxidants (dibutylhydroxytoluene, etc.), sulfur-based antioxidants (mercaptopropionic acid derivatives, etc.), and phosphorus-based antioxidants (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, etc.). The content of the antioxidant may be 0.01% to 3% by weight, 0.01% to 2% by weight, 0.02% to 2% by weight, 0.02% to 1% by weight, or 0.03% to 1% by weight based on the total weight of the polyol composition.

The Controlled Polymerization Rate (CPR) of the above polyol composition may be 0.1 to 5, 0.1 to 4, 0.1 to 3, 0.1 to 2, 0.1 to 1.5, 0.1 to 1, or 0.2 to 1. The above CRP is an indicator representing the amount of alkaline substance in the polyol composition and can be measured by quantifying the amount of hydrochloric acid (concentration: 0.001N) obtained by neutralizing 30g of the above polyol composition with 50ml of methanol according to the test method of ASTM D6437. If the above range is satisfied, reactivity control is easy during the product manufacturing process, and the product can meet specifications.

The acid value of the above polyol composition may be 0.0005 mgKOH/g to 0.0100 mgKOH/g, 0.0005 mgKOH/g to 0.0050 mgKOH/g, 0.0005 mgKOH/g to 0.0030 mgKOH/g, or 0.0005 mgKOH/g to 0.0020 mgKOH/g. The above acid value is an indicator representing the amount of base (KOH) required to neutralize the acidic component of 1 g of a sample. If the above range is satisfied, the acid resistance of the polyurethane foam produced from the above polyol composition may be enhanced.

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

The APHA (American Public Health Association) color value of the above polyol composition may 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 a ColorQuest XE (Hunter Labs) according to the test method of ASTM D-1209, and a lower color value may be evaluated as clearer and more transparent. When the above range is satisfied, by-products such as unreacted ethylene oxide and unreacted propylene oxide are hardly generated in the polyol composition, thereby improving product reliability.

The active oxygen content of the above polyol composition may be 100 pmm or less, 90 pmm or less, 80 pmm or less, 50 pmm or less, 40 pmm or less, or 10 pmm or less. The active oxygen may be measured using known methods, for example, by using a spectrophotometer to measure the change in absorbance according to the active oxygen content using a calibration curve. When the above range is satisfied, side reactions are reduced, storage stability is improved, and no change in color may occur.

The viscosity of the above polyol composition at room temperature may be 200 cPs to 800 cPs, 300 cPs to 800 cPs, 350 cPs to 800 cPs, 400 cPs to 800 cPs, or 450 cPs to 700 cPs. The viscosity may be measured using known methods, for example, by using a non-contact viscometer. When the above range is satisfied, bubble formation during the manufacture of polyurethane foam can be prevented, uneven curing can be prevented, and workability can be improved.

Method for preparing a polyol composition

A method for preparing a polyol composition according to the present invention may include: (a) a step of initiating a polymerization reaction by mixing at least one type of 1,4:3,6-dianhydrohexitol with an alkali catalyst; (b) a step of preparing a prepolymer by reacting the 1,4:3,6-dianhydrohexitol with an alkylene oxide; and (c) a step of preparing a polyol composition by reacting the prepolymer prepared in step (b) with an alkylene oxide in the presence of a bimetallic cyanide catalyst, and the polyol composition may have a degree of unsaturation of 0.02 meq/g or less according to the following measurement method.

<Measurement Method>

1) Prepare a first flask into which 30g of the above polyol composition is added and a second flask into which the above polyol composition is not added, and add 50ml of mercury acetate to each of the first flask and the second flask, and stir for 30 minutes.

2) Add 9g of sodium bromide (NaBr) to each of the first flask and the second flask, and stir for 30 minutes.

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

4) Calculate the degree of unsaturation using the following Equation 1.

[Equation 1]

Degree of unsaturation (meq/g) = (V _s × V _b × 0.1 × F) / M

In the above Equation 1, V _s is the amount (ml) of 0.1N potassium hydroxide (KOH) added to the first flask, V _b is the amount (ml) of 0.1N potassium hydroxide (KOH) added to the second flask, F is the factor of 0.1N potassium hydroxide (KOH), and M is the weight (g) of the polyol composition added to the first flask.

FIG. 1 is a flowchart briefly illustrating the manufacturing process of a polyol composition according to the present invention. Referring to FIG. 1, the manufacturing method of the present invention may include a step (S10) of initiating a polymerization reaction. In S10, at least one type of 1,4:3,6-dianhydrohexitol and an alkali catalyst may be mixed.

The above 1,4:3,6-dianhydrohexitol may include isosorbide.

The above isosorbide can be obtained by the dehydration reaction of D-sorbitol. Specifically, the above isosorbide can be obtained by the dehydration reaction of D-sorbitol under reduced pressure conditions with an acid catalyst.

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

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

The above D-sorbitol may be in powder form or in the form of an aqueous solution containing the above D-sorbitol at a concentration of 50% to 90% by weight. Additionally, the above D-sorbitol may be obtained through a synthesis process by extraction from nature or reduction from glucose.

The above isosorbide can be obtained by a process in which one water molecule is removed from the above D-sorbitol to form 1,4-sorbitan, an intermediate product, and then one additional water molecule is removed from the above 1,4-sorbitan.

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

The above isosorbide can be obtained by dehydrating for 1 to 10 hours at a temperature of 110°C to 350°C under atmospheric pressure after the formation of the above 1,4-sorbitan. When the above temperature range is satisfied, the generation of impurities other than isosorbide can be reduced, and the efficiency of the dehydration reaction in which 1,4-sorbitan is converted into isosorbide can be improved.

The dehydration process in which the 1,4-sorbitan is formed may be at a lower temperature than the dehydration process in which the isosorbide is obtained. If the temperature of the dehydration process in which the 1,4-sorbitan is formed is controlled to be lower than the temperature of the dehydration process in which the isosorbide is obtained, isosorbide can be obtained in a high yield even without the use of an acid catalyst.

The above isosorbide can be obtained by the following reaction scheme 1.

[Reaction Equation 1]

At least one of the above 1,4:3,6-dianhydrohexitols can be mixed with an alkali catalyst to initiate a polymerization reaction. The above 1,4:3,6-dianhydrohexitol can be introduced into a batch reactor.

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

The above 1,4:3,6-dianhydrohexitol can be introduced into the batch reactor in a solid state. The above 1,4:3,6-dianhydrohexitol can be introduced into the batch reactor in powder form.

The particle shape of the above 1,4:3,6-dianhydrohexitol may be spherical, flake-shaped, or rod-shaped.

The purity of the above 1,4:3,6-dianhydrohexitol may be about 80% or more, about 90% or more, about 95% or more, or about 97% or more.

The average particle size of the above 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 above average particle size is measured using the laser diffraction method and can be defined as the particle size corresponding to 50% of the cumulative volume in the particle size distribution curve.

The moisture content of the above 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 can 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 the result by the weight of 1,4:3,6-dianhydrohexitol before drying, and then multiplying by 100. The drying can be performed by raising the temperature from room temperature to about 150°C and maintaining it at 150°C, so the total drying time can be set to 20 minutes, including a 5-minute temperature raising step.

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

The above 1,4:3,6-dianhydrohexitol may be introduced into the batch reactor in a lump sum. The above 1,4:3,6-dianhydrohexitol may be introduced into the batch reactor for about 5 minutes to about 60 minutes, about 10 minutes to about 50 minutes, or about 20 minutes to about 40 minutes. The above 1,4:3,6-dianhydrohexitol may be introduced into the batch reactor in divided portions with equal amounts for about 5 minutes to about 60 minutes, about 10 minutes to about 50 minutes, or about 20 minutes to about 40 minutes.

The above alkali catalyst may include one or more strong bases selected from the group consisting of potassium hydroxide, sodium hydroxide, potassium metal, and sodium metal.

In the above S10, it is preferable not to use a bimetallic cyanide catalyst (DMC). Generally, the bimetallic cyanide catalyst may require a catalyst activation induction time of at least one hour, and since little or no polymerization occurs until the catalyst is activated, the efficiency of the production process may be significantly reduced.

The alkali catalyst may be introduced into the batch reactor in an aqueous solution state. For example, an aqueous potassium hydroxide solution may be introduced into the batch reactor. The alkali catalyst may be introduced into the batch reactor after at least one type of 1,4:3,6-dianhydrohexitol has been introduced. The alkali catalyst may be introduced into the batch reactor in a lump sum. The alkali catalyst may be introduced into the batch reactor for about 1 minute to about 20 minutes, about 3 minutes to about 15 minutes, or about 8 minutes to about 12 minutes. The at least one type of 1,4:3,6-dianhydrohexitol may be introduced into the batch reactor in divided portions with equal amounts for about 1 minute to about 20 minutes, about 3 minutes to about 15 minutes, or about 8 minutes to about 12 minutes.

In the above S10, the alkali catalyst is mixed in an amount of 0.1 to 5.0 parts by weight, 0.5 to 4.0 parts by weight, or 1.0 to 3.0 parts by weight based on 100 parts by weight of at least one type of 1,4:3,6-dianhydrohexitol, so that the dehydration process of the 1,4:3,6-dianhydrohexitol can be carried out. When the above range is satisfied, the dehydration reaction rate of the 1,4:3,6-dianhydrohexitol can be improved, and the amount of residual alkali catalyst can be minimized.

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

The dehydration process of the above 1,4:3,6-dianhydrohexitol can be carried out under pressure conditions 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.

The dehydration process of the above 1,4:3,6-dianhydrohexitol may be carried out for about 1 hour to about 6 hours, about 1 hour to about 5 hours, or about 2 hours to about 4 hours.

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

After step S10 above, the moisture content in the 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 less than about 300 ppm. Due to the low moisture content of the 1,4:3,6-dianhydrohexitol, the yield of the polyol composition may be improved.

The manufacturing method of the present invention may include a step (S20) of preparing a prepolymer. In S20, the 1,4:3,6-dianhydrohexitol may be reacted with an alkylene oxide to prepare a prepolymer.

The alkylene oxide may be a branched alkylene oxide or a linear alkylene oxide. The above S20 may include the step of preparing a first prepolymer by reacting the 1,4:3,6-dianhydrohexitol with the branched alkylene oxide (S20-1), the step of preparing a second prepolymer by reacting the first prepolymer with the linear alkylene oxide (S20-2), the step of removing residual metal ions (S20-3), and the step of filtering (S20-4).

In the above S20-1, a first prepolymer can be prepared by reacting with a substituted or unsubstituted branched alkylene oxide having 3 to 10 carbon atoms. The substituted or unsubstituted branched alkylene oxide having 3 to 10 carbon atoms may be propylene oxide.

The above propylene oxide can be introduced into the above batch reactor.

The above process of adding propylene oxide can be carried out under temperature conditions of about 80°C to about 130°C, about 90°C to about 130°C, or about 100°C to about 120°C.

The above process of adding propylene oxide can be carried out under pressure conditions 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.

The above process of adding propylene oxide may be carried out for about 3 hours to about 10 hours, about 5 hours to about 10 hours, or about 6 hours to about 9 hours. Preferably, the process of adding propylene oxide may be carried out for about 6 hours to about 9 hours under temperature conditions of about 80°C to about 120°C and pressure conditions of about 2 torr to about 8 torr.

The input rate of the above 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.

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

The above propylene oxide may undergo an addition reaction with the 1,4:3,6-dianhydrohexitol in the batch reactor. By the addition reaction, a first prepolymer comprising repeating units derived from the propylene oxide in the 1,4:3,6-dianhydrohexitol core structure may be prepared. The derived repeating units may refer to a component, structure derived from the propylene oxide, or the propylene oxide itself.

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

The addition reaction between the 1,4:3,6-dianhydrohexitol and the propylene oxide may proceed 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 1,4:3,6-dianhydrohexitol and the propylene oxide may proceed for about 1 hour to about 2 hours under temperature conditions of about 100°C to about 140°C.

In the above S20-1, a process for removing residual branched alkylene oxide after preparing the first prepolymer may be further included. The residual branched alkylene oxide may be propylene oxide. By removing the residual branched alkylene oxide, reactivity with isocyanate is improved, the hardness and appearance of the polyurethane foam are improved, and manufacturing economic efficiency can be improved.

The above residual propylene oxide removal process may be carried out under temperature conditions of about 80°C to about 150°C, about 90°C to about 150°C, or about 100°C to about 140°C.

The above residual propylene oxide removal process can be carried out under pressure conditions 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.

The above residual propylene oxide removal process may be carried out 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 above residual propylene oxide removal process may be carried out for about 20 minutes to about 40 minutes under temperature conditions of about 100°C to about 140°C and pressure conditions of about 0.1 torr to about 20.0 torr.

In the above S20-2, a second prepolymer can be prepared by reacting the first prepolymer with a substituted or unsubstituted branched alkylene oxide having 2 to 10 carbon atoms. The substituted or unsubstituted linear alkylene oxide having 2 to 10 carbon atoms may be ethylene oxide.

The weight ratio of the branched alkylene oxide of S20-1 and the linear alkylene oxide of S20-2 may be 2:1 to 8:1, 3:1 to 7.5:1, 3.5:1 to 7.5:1, 3:1 to 7.5:1, 4.5:1 to 7.5:1, 5:1 to 7.5:1, or 5:1 to 7:1. When the above range is satisfied, reactivity with isocyanate is increased, and the hardness and appearance quality of the polyurethane foam prepared from the polyol composition may be improved.

The above ethylene oxide can be introduced into the batch reactor in which the production of the first prepolymer is completed.

The above process of introducing ethylene oxide may be carried out under temperature conditions of about 80°C to about 140°C, about 90°C to about 140°C, or about 120°C to about 130°C.

The above process of introducing ethylene oxide can be carried out under pressure conditions 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.

The above process of introducing ethylene oxide may be carried out for about 1 hour to about 5 hours, about 1 hour to about 3 hours, or about 2 hours to about 3 hours. Preferably, the above process of introducing ethylene oxide may be carried out for about 2 hours to about 3 hours under temperature conditions of about 120°C to about 130°C and pressure conditions of about 0.1 torr to about 30.0 torr.

The input rate of the above 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.

Based on 100 parts by weight of the above 1,4:3,6-dianhydrohexitol, the above 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.

The above ethylene oxide may undergo an addition reaction with the first prepolymer in the batch reactor. By the addition reaction, a second prepolymer comprising repeating units derived from the ethylene oxide may be prepared in the first prepolymer. Additionally, a second prepolymer comprising repeating units derived from the propylene oxide and repeating units derived from the ethylene oxide may be prepared as a block copolymer. The derived repeating units may refer to components, structures, or ethylene oxide itself derived from ethylene oxide.

The addition reaction between the first prepolymer and the ethylene oxide can be carried out under temperature conditions of about 80°C to about 150°C, about 90°C to about 150°C, or about 100°C to about 140°C.

The addition reaction between the first prepolymer and the ethylene oxide may proceed 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 first prepolymer and the ethylene oxide may proceed for about 1 hour to about 2 hours under temperature conditions of about 100°C to about 140°C.

In the above S20-2, after preparing the second prepolymer, a process for removing residual linear alkylene oxide may be further included. The residual linear alkylene oxide may be ethylene oxide.

The above residual ethylene oxide removal process may be carried out under temperature conditions of about 80°C to about 150°C, about 90°C to about 150°C, or about 100°C to about 140°C.

The above residual propylene oxide removal process can be carried out under pressure conditions 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.

The above residual ethylene oxide removal process may be carried out for about 30 minutes to about 200 minutes, about 30 minutes to about 100 minutes, or about 40 minutes to about 80 minutes. Preferably, the above residual ethylene oxide removal process may be carried out for about 40 minutes to about 80 minutes under temperature conditions of about 100°C to about 140°C and pressure conditions of about 0.1 torr to about 20.0 torr.

In the above S20-3, residual metal ions in the polyol composition are removed, and in the above S20-4, a process of filtering the polyol composition from which the residual metal ions have been removed may be performed.

In the above S20-3, an additive may be added to the polyol composition after the reaction is completed in order to remove the residual metal ions. The additive may be one or more selected from the group consisting of diatomite, alumina, magnesiumol, celite, embosol, and silica gel.

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

Subsequently, in S20-3, a neutralization process of the polyol composition into which the additive has been introduced may be carried out. The neutralization process may be for about 1 hour to about 4 hours, about 1 hour to about 3 hours, or about 1 hour to about 2 hours. Subsequently, a moisture removal process may be carried out on the polyol composition after the neutralization process is completed. The moisture removal process may be carried out at about 90°C to about 130°C, about 95°C to about 130°C, or about 100°C to about 130°C. If necessary, in S20-3, a process for detecting residual metal ions may be performed, and if the residual metal ions are not detected, the polyol composition may be maintained under temperature conditions of about 50°C to about 90°C, about 50°C to about 80°C, or about 60°C to about 80°C. In S20-4, the polyol composition from which moisture has been removed may be filtered. The additives and by-products can be filtered out by the above filtering.

The manufacturing method of the present invention may include a step (S30) of preparing a polyol composition. In S30, the polyol composition may be prepared by reacting the prepolymer prepared in S20 with an alkylene oxide in the presence of a bimetallic cyanide catalyst.

The above-mentioned bimetallic cyanide catalyst can be represented by the following chemical formula 2.

[Chemical Formula 2]

M _a [M'(CN) ₆ ] _b L _c L' _d

In the above chemical formula 2, 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 with a number average molecular weight of less than 200 g/mol, and a, b, c and d are integers, the sum of which is equal to the sum of the charge numbers of M and M'.

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

When the above-mentioned bimetallic cyanide catalyst is used in the above S30, the formation of monools can be reduced during the polymerization of the first prepolymer with propylene oxide. As a result, the degree of unsaturation in the polyol composition can be reduced, allowing crosslinking and high molecular weight to proceed smoothly when manufacturing the polyurethane resin, and the physical properties of the polyurethane resin can be improved.

In the above S30, it is preferable not to use the above-mentioned bimetallic cyanide catalyst and the above-mentioned alkali catalyst together. Depending on the selective activity of the above-mentioned bimetallic cyanide catalyst, the amount of the above-mentioned alkali catalyst used may increase, and a large amount of alkali catalyst may remain after the preparation of the polyol composition. As a result, an additional process to remove the above-mentioned alkali catalyst is necessarily required, which may reduce the efficiency of the manufacturing process. Furthermore, as the formation of monools is increased by the above-mentioned alkali catalyst, crosslinking and high molecular weight may be hindered when manufacturing the polyurethane resin, and the physical properties of the polyurethane resin may be degraded.

The polyol composition prepared according to the above manufacturing method may include a compound represented by the following chemical formula 1.

[Chemical Formula 1]

In the above chemical formula 1,

_R1 and _R2 are each independently substituted or unsubstituted alkylene groups having 2 to 10 carbon atoms, and

a and f are each independently integers from 1 to 60, and

b and e are each independently integers from 1 to 6, and

c and d are each independently integers from 1 to 30, and

x is an integer from 1 to 5.

Composition for manufacturing polyurethane

The composition for manufacturing polyurethane according to the present invention comprises a polyol composition having a degree of unsaturation of 0.02 meq/g or less according to the following measurement method, and an isocyanate-based composition, comprising at least one first unit derived from 1,4:3,6-dianhydrohexitol and a second unit derived from alkylene oxide.

<Measurement Method>

1) Prepare a first flask into which 30g of the above polyol composition is added and a second flask into which the above polyol composition is not added, and add 50ml of mercury acetate to each of the first flask and the second flask, and stir for 30 minutes.

2) Add 9g of sodium bromide (NaBr) to each of the first flask and the second flask, and stir for 30 minutes.

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

4) Calculate the degree of unsaturation using the following Equation 1.

[Equation 1]

Degree of unsaturation (meq/g) = (V _s × V _b × 0.1 × F) / M

In the above Equation 1, V _s is the amount (ml) of 0.1N potassium hydroxide (KOH) added to the first flask, V _b is the amount (ml) of 0.1N potassium hydroxide (KOH) added to the second flask, F is the factor of 0.1N potassium hydroxide (KOH), and M is the weight (g) of the polyol composition added to the first flask.

The above polyol composition may be the same as the polyol composition described above.

The above isocyanate-based composition may include at least one selected from the group consisting of aliphatic polyisocyanates, cycloaliphatic polyisocyanates, ar aliphatic polyisocyanates, aromatic polyisocyanates, and heterocyclic polyisocyanates.

The above isocyanate-based composition may include an unmodified polyisocyanate or a modified polyisocyanate.

The above polyisocyanates are 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, It may include at least one selected from the group consisting of diphenylmethane-2,4'-diisocyanate, diphenylmethane-4,4'-diisocyanate, polymeric methylene diphenyl diisocyanate (PMDI), and naphthalene-1,5-diisocyanate.

The above polyisocyanate may be a toluene diisocyanate mixed with 2,4-toluene diisocyanate and 2,6-toluene diisocyanate (2,4-/2,6-isomer ratio = 80/20) or a polymerizable (Polymeric) methylene diphenyl diisocyanate.

The amount of the above polyisocyanate used may be suitable as an isocyanate index (NCO index) of 70 to 130, 80 to 120, preferably 100 to 120.

The above isocyanate index is the ratio of the number of equivalents of hydroxyl groups (-OH) present in the polyol in the polyurethane reactant to the number of equivalents of isocyanate, representing the amount of isocyanate used relative to the theoretical equivalent.

If the above isocyanate index is less than 100, it means that an excess amount of polyol is present, and if the above isocyanate index exceeds 100, it means that an excess amount of isocyanate is present.

If the above isocyanate index is less than 70, the reactivity is reduced and the gelling reaction is delayed, which may result in a problem where the curing does not occur. If the above isocyanate index is greater than 130, the hard segment increases excessively, which may result in a shrinkage phenomenon.

The above composition for manufacturing polyurethane may include a curing catalyst. The curing catalyst is not particularly limited and may be an amine catalyst, an organometallic catalyst, or a mixture thereof. The curing catalyst may play a role in promoting the reaction between the polyol composition and the isocyanate composition.

The type of amine catalyst is not particularly limited, and preferably, one or a mixture of two or more selected from tertiary amine catalysts may be used. For example, at least one selected from the group consisting of triethylenediamine, triethylamine, N-methylmorpholine, and N-ethylmorpholine may be used.

The above organometallic catalyst may be an organometallic catalyst commonly used in the manufacture of polyurethane foam. For example, at least one selected from the group consisting of tin octylate, dibutyltin dilaurate (DBTDL), and tin bis[2-ethylhexanoate] may be used.

The content of 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 the above range is satisfied, curing failure, shrinkage, or the phenomenon of the polyurethane foam collapsing during formation may be reduced.

The above composition for manufacturing polyurethane may include a foam stabilizer. The foam stabilizer may serve to prevent cells from coalescing or breaking down when cells are formed inside the polyurethane foam, and to regulate the formation of cells having a uniform shape and size.

The above-mentioned foam stabilizer is not particularly limited as long as it is commonly used in the manufacture of polyurethane foam, for example, a silicone-based foam stabilizer may be used. The above-mentioned silicone-based foam stabilizer may be one or more selected from silicone oil and derivatives thereof, and specifically, it may be a polyalkylene oxide methylsiloxane copolymer.

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

The above composition for manufacturing polyurethane may include a blowing agent. Water may be used as a representative blowing agent, and in addition to water, at least one selected from the group consisting of methylene chloride, n-butane, isobutane, n-pentane, isopentane, dimethyl ether, acetone, carbon dioxide, and 1,1-dichloro1-fluoroethane may be used. The blowing agent may be used according to a conventional method of use and may be appropriately used depending on the required density of the foam or other characteristics.

The content of the foaming agent may be 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.

The above-described composition for manufacturing polyurethane may not include the foaming agent. That is, in the process of manufacturing polyurethane foam using the above-described composition for manufacturing polyurethane, a gaseous foaming agent, such as nitrogen gas, may be directly injected into the above-described composition for manufacturing polyurethane, thereby forming microcells.

The above-mentioned composition for manufacturing polyurethane may further include an auxiliary additive selected from the group consisting of flame retardants, colorants, UV stabilizers, thickeners, foam stabilizers, fillers, or combinations thereof.

The above polyurethane manufacturing composition may be a one-component or two-component type. If the above polyurethane manufacturing composition is a two-component type, it may be stored separately as two components and then mixed immediately before the manufacturing process of the polyurethane resin.

In the case where the above polyurethane manufacturing composition is a two-component type, the above polyurethane manufacturing composition may include a first component having the above polyol composition as the main component and a second component having the above isocyanate composition as the main component.

The first component above may include the polyol composition, the curing catalyst, the foaming agent, the foaming agent, and the other additives.

The second component above may include the isocyanate composition.

Method for manufacturing polyurethane foam

A polyurethane foam can be manufactured from the above polyurethane manufacturing composition. A method for manufacturing the polyurethane foam may include: (a) a step in which an isocyanate supplyer supplies the second component; (b) a gas supply step in which a gas supplyer supplies a foaming gas; (c) a step in which a polyol supplyer supplies the first component; (d) a step in which a mixer mixes the first component, the second component, and the foaming gas to manufacture a polyurethane foam composition; and (e) a step of curing the polyurethane foam composition.

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

The first component of step (c) above may further include a curing catalyst, a foaming agent, a foaming agent, and other additives.

If the first component supplied in step (c) above includes a foaming agent, the gas supply step of step (b) above may be omitted.

The manufactured polyurethane foam may contain fine closed cells inside. For example, the polyurethane foam may contain fine closed pores.

The average diameter of the micro-closed cell 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.

<Battery Module>

A battery module according to the present invention comprises a housing, a plurality of battery cells accommodated inside the housing, and a polyurethane foam disposed between the plurality of battery cells, wherein the polyurethane foam comprises a composition for manufacturing polyurethane comprising a polyol composition and an isocyanate-based composition, and the polyol composition comprises at least one first unit derived from 1,4:3,6-dianhydrohexitol and a second unit derived from an alkylene oxide, and the degree of unsaturation according to the following measurement method is 0.02 meq/g or less.

<Measurement Method>

1) Prepare a first flask into which 30g of the above polyol composition is added and a second flask into which the above polyol composition is not added, and add 50ml of mercury acetate to each of the first flask and the second flask, and stir for 30 minutes.

2) Add 9g of sodium bromide (NaBr) to each of the first flask and the second flask, and stir for 30 minutes.

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

4) Calculate the degree of unsaturation using the following Equation 1.

[Equation 1]

Degree of unsaturation (meq/g) = (V _s × V _b × 0.1 × F) / M

In the above Equation 1, V _s is the amount (ml) of 0.1N potassium hydroxide (KOH) added to the first flask, V _b is the amount (ml) of 0.1N potassium hydroxide (KOH) added to the second flask, F is the factor of 0.1N potassium hydroxide (KOH), and M is the weight (g) of the polyol composition added to the first flask.

FIG. 2 is a simplified cross-sectional view of a battery module according to the present invention. Referring to FIG. 2, the battery module (100) according to the present invention includes a housing (101). The housing (101) may be a structure configured to accommodate a plurality of battery cells (102) internally and protect them from external impacts. The housing (101) may be made of a metal material with high mechanical strength. However, the housing (101) is not limited to a metal material and may be made of a non-metal material to ensure insulation.

The battery module (100) may include a thermally conductive adhesive (104). The thermally conductive adhesive (104) can fix a plurality of battery cells (102) inside the housing (101) and allows the heat of the plurality of battery cells (102) to be effectively transferred to the housing (101). Various organic or inorganic resins, such as thermally conductive epoxy adhesive, thermally conductive silicone adhesive, and thermally conductive urethane adhesive, may be used as the thermally conductive adhesive (104).

The plurality of battery cells (102) may be provided in a pouch type such that the number of stacked cells per unit area can be maximized. The plurality of battery cells (102) provided in the pouch type may be manufactured by housing an electrode assembly including a positive electrode, a negative electrode, and a separator in a cell case made of a laminate sheet, and then heat-sealing the sealing portion of the cell case. However, the plurality of battery cells (102) are not necessarily provided in a pouch type, and may be provided in a prismatic, cylindrical, or various other shapes as long as the storage capacity required by the device to be mounted in the future is achieved.

The battery module (100) comprises a plurality of battery cells (102) housed inside a housing (101) and a polyurethane foam (103) disposed between the plurality of battery cells (102). The polyurethane foam (103) has excellent vibration absorption and repulsion force due to compression, so dimensional stability can be maintained even if swelling occurs in the plurality of battery cells (102). In addition, damage to the battery module (100) due to the expansion of the plurality of battery cells (102) can be prevented. Since the degree of expansion of the plurality of battery cells (102) may vary depending on their chemical properties and usage environment, the maximum compressible thickness range of the polyurethane foam (103) can be selected in a range capable of accommodating the expansion thickness of the plurality of battery cells (102), taking this into consideration.

The present invention will be described in more detail below based on examples and comparative examples. However, the following examples and comparative examples are merely illustrative for further explaining the present invention, and the present invention is not limited by the following examples and comparative examples.

Preparation Example - Preparation of Polyol Composition

Preparation Example 1

Step (1) - Preparation of prepolymer

796 g of isosorbide and 22 g of potassium hydroxide were introduced into a reactor capable of pressurization and heating. Subsequently, the inside of the reactor was purged using nitrogen and heated to 112°C, after which moisture inside the reactor was removed under vacuum reduced pressure conditions.

1,904 g of propylene oxide was introduced into the reactor at a constant rate, and the reaction was carried out for 6 hours at a temperature of approximately 115°C. At this time, the reactor temperature was controlled so as not to exceed 115°C.

The mixture was stirred until all the propylene oxide remaining in the reactor was reacted, and after the reaction was completed, the reactor temperature was heated to 122°C. Subsequently, 270g of ethylene oxide was introduced into the reactor at a constant rate, and the reaction was carried out for 1 hour and 30 minutes at a temperature of approximately 120°C. During this time, the reactor temperature was controlled so as not to exceed 125°C.

After the reaction was completed, the reactor temperature was cooled to 90°C, 50g of AMBOSOL and 5g of diatomite were added to the reactor, and the mixture was stirred for 3 hours at a temperature of about 100°C to remove residual metal ions in the reaction mixture.

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

Step (2) - Preparation of polyol composition

796 g of the above prepolymer was introduced into a reactor capable of pressurization and heating. Afterward, the inside of the reactor was purged using nitrogen and heated to 112°C, and then moisture inside the reactor was removed under vacuum reduced pressure conditions.

After adding 0.14g of double metal cyanide to the above reactor, 2,204g of propylene oxide was added at a constant rate, and the reaction was carried out for about 6 hours and 30 minutes at a temperature of about 110℃. At this time, the reactor temperature was controlled so as not to exceed 115℃.

Stirring was maintained until all the propylene oxide remaining in the reactor was reacted. After lowering the reactor temperature to 90°C, 3,000g of polyol composition was obtained.

Preparation Example 2

A polyol composition was obtained by the same process as in Preparation Example 1, except that instead of introducing 2,204 g of propylene oxide into the reactor in step (2) of Preparation Example 1, 2,204 g of a mixture of propylene oxide and ethylene oxide mixed in a weight ratio of 6:4 was introduced into the reactor.

Preparation Example 3

A polyol composition was obtained by the same process as in Preparation Example 1, except that instead of introducing 2,204 g of propylene oxide into the reactor in step (2) of Preparation Example 1, 2,204 g of a mixture of propylene oxide and ethylene oxide mixed in a weight ratio of 5:5 was introduced into the reactor.

Preparation Example 4

A polyol composition was obtained by the same process as in Preparation Example 1, except that instead of introducing 2,204 g of propylene oxide into the reactor in step (2) of Preparation Example 1, 2,204 g of a mixture of propylene oxide and ethylene oxide mixed in a weight ratio of 4:6 was introduced into the reactor.

Preparation Example 5

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

Preparation Example 6

A polyol composition was obtained by the same process as in Preparation Example 1, except that 2,100 g of propylene oxide was introduced into the reactor instead of 1,904 g of propylene oxide in step (1) of Preparation Example 1.

Preparation Example 7

A polyol composition was obtained by the same process as in Preparation Example 1, except that 300g of ethylene oxide was introduced into the reactor instead of 270g of ethylene oxide in step (1) of Preparation Example 1.

Preparation Example 8

A polyol composition was obtained by the same process as in Preparation Example 1, except that 0.25 g of bimetallic cyanide was added to the reactor instead of 0.14 g of bimetallic cyanide in step (2) of Preparation Example 1.

Preparation Example 9

A polyol composition was obtained by the same process as in Preparation Example 1, except that 0.10 g of bimetallic cyanide was introduced into the reactor instead of 0.14 g of bimetallic cyanide in step (2) of Preparation Example 1.

Preparation Example 10

A polyol composition was obtained by the same process as in Preparation Example 1, except that 2,300 g of propylene oxide was introduced into the reactor instead of 2,204 g of propylene oxide in step (2) of Preparation Example 1.

Comparative Manufacturing Example 1

796 g of the prepolymer obtained in step (1) of Preparation Example 1 and 9.8 g of potassium hydroxide were introduced into a reactor capable of pressurization and heating. Afterward, the inside of the reactor was purged using nitrogen and heated to 112°C, and then moisture inside the reactor was removed under vacuum reduced pressure conditions.

2,204 g of propylene oxide was introduced into the above reactor at a constant rate, and the reaction was carried out for about 9 hours and 30 minutes at a temperature of about 110°C. At this time, the reactor temperature was controlled so as not to exceed 115°C.

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

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

Comparative Manufacturing Example 2

A polyol composition was obtained by the same process as in Comparative Preparation Example 1, except that instead of introducing 2,204 g of propylene oxide into the reactor in Comparative Preparation Example 1, 2,204 g of a mixture of propylene oxide and ethylene oxide mixed in a weight ratio of 6:4 was introduced into the reactor.

Comparative Manufacturing Example 3

796 g of isosorbide was introduced into a reactor capable of pressurization and heating. Subsequently, the inside of the reactor was purged using nitrogen and heated to 112°C, after which moisture inside the reactor was removed under vacuum reduced pressure conditions.

After introducing 0.14g of double metal cyanide into the reactor, 2,204g of propylene oxide was introduced at a constant rate, and a polymerization reaction was attempted for about 2 hours at a temperature of about 110℃, but the catalyst of the double metal cyanide was not activated, so the polymerization reaction with the isosorbide and propylene oxide did not proceed.

Comparative Manufacturing Example 4

796 g of the prepolymer obtained in step (1) of Preparation Example 1 was introduced into a reactor capable of pressurization and heating. Afterward, the inside of the reactor was purged using nitrogen and heated to 112°C, and then moisture inside the reactor was removed under vacuum reduced pressure conditions.

After adding 0.14g of double metal cyanide and 22g of potassium hydroxide to the above reactor, 2,204g of propylene oxide was added at a constant rate, and the reaction was carried out for about 9 hours and 30 minutes at a temperature of about 110℃. At this time, the reactor temperature was controlled so as not to exceed 115℃.

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

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

Example - Polyurethane Foam Manufacturing

Example 1

30g of the polyol composition prepared in Preparation Example 1 was added to a plastic beaker. Subsequently, 3.5g of distilled water, 0.2g of B-8629 (Evonik) and 0.9g of L-1501 (Momentive) were added to the beaker as silicone foaming agents, 0.5g of D-33LV (Air Products) and 0.1g of M-50 (Tosoh) were added as amine catalysts, and 0.6g of diethanolamine was added as a crosslinking agent. Subsequently, the mixture was mixed with a high-speed stirrer at 4,000 rpm for 3 minutes to obtain a mixture.

Subsequently, 58 g of methylene diphenyl isocyanate (CG-3701S, Kumho Co.) was added to the above mixture and foamed to produce a polyurethane foam.

Examples 2 to 10 and Comparative Examples 1 to 4

Polyurethane foam was prepared by the same process as in Example 1, except that instead of adding 30g of the polyol composition prepared in Preparation Example 1 to a plastic beaker in Example 1, 30g of the polyol composition listed in Table 2 below was added.

Experimental Example

Experimental Example 1 - Measurement of Degree of Unsaturation

30 g of the polyol compositions prepared in Preparation Examples 1 to 10 and Comparative Preparation Examples 1 to 4 were each added to a 250 ml first flask. Separately, a 250 ml second flask was prepared for a blank test. Subsequently, 50 ml of mercuric acetate and a magnetic bar for removing impurities were added to each of the first and second flasks, and after sealing the stoppers of the first and second flasks, the mixture was stirred for 30 minutes.

Subsequently, 9g of sodium bromide (NaBr) was added to each of the first and second flasks and stirred for 30 minutes. Then, 0.5ml of 1% phenolphthalein indicator was added to each of the first and second flasks, and the mixture was titrated with 0.1N (normal concentration) potassium hydroxide (KOH) until the pink color was maintained for about 15 seconds at the endpoint when observed visually. The degree of unsaturation was calculated using Equation 1 below, and the results are shown in Table 1 below.

[Equation 1]

Degree of unsaturation (meq/g) = (V _s × V _b × 0.1 × F) / M

In the above Equation 1, V _s is the amount (ml) of 0.1N potassium hydroxide (KOH) added to the first flask, V _b is the amount (ml) of 0.1N potassium hydroxide (KOH) added to the second flask, F is the factor of 0.1N potassium hydroxide (KOH), and M is the weight (g) of the polyol composition added to the first flask.

Experimental Example 2 - Measurement of Number Average Molecular Weight

2.75 g of the polyol compositions prepared in Preparation Examples 1 to 10 and Comparative Preparation Examples 1 to 4 were each added to a container holding a phthalic anhydride solution, and the mixture was reacted at 115°C for 30 minutes. Subsequently, the pH was observed while titrating with a 0.5 N aqueous sodium hydroxide (NaOH) solution, and the volume (ml) of sodium hydroxide (NaOH) required to reach the pH inflection point was measured. Separately, 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 above. Subsequently, the acid value (mgKOH/g) of the polyol compositions was calculated based on the measured values. Then, using the above acid value and the following Equation 1, the number average molecular weight of the polyol compositions prepared in Preparation Examples 1 to 10 and Comparative Preparation Examples 1 to 4 was calculated, and the results are shown in Table 1 below.

[Relationship 1]

Number average molecular weight (g/mol) = (56,100 × number of equivalents) / measured acid value

Experimental Example 3 - Reactivity Evaluation

In preparing the polyol compositions of Preparation Examples 1 to 10 and Comparative Preparation Examples 1 to 4 using a catalyst, the reactivity was evaluated according to the following criteria, and the results are shown in Table 1 below.

- ◎: Polymerization reaction proceeds smoothly

- ○: Polymerization proceeds, but the rate of the polymerization reaction is slow

- ×: The catalyst is not activated, so the polymerization reaction does not proceed.

Step (1) Catalyst Step (1)
alkylene
oxide Step (2)
catalyst Step (2)
alkylene oxide Reactivity Degree of unsaturation
(meq/g) numerical average
molecular weight
(g/mol) Preparation Example 1 KOH PO ¹⁾ + EO ²⁾ DMC ³⁾ PO ◎ 0.004 2,000 Preparation Example 2 KOH PO+EO DMC PO+EO ◎ 0.003 2,100 Preparation Example 3 KOH PO+EO DMC PO+EO ◎ 0.003 2,100 Preparation Example 4 KOH PO+EO DMC PO+EO ◎ 0.003 2,000 Preparation Example 5 KOH PO+EO DMC PO ◎ 0.004 2,200 Preparation Example 6 KOH PO+EO DMC PO ◎ 0.004 2,400 Preparation Example 7 KOH PO+EO DMC PO ◎ 0.004 2,300 Preparation Example 8 KOH PO+EO DMC PO ◎ 0.003 2,000 Preparation Example 9 KOH PO+EO DMC PO ◎ 0.004 2,000 Preparation Example 10 KOH PO+EO DMC PO ◎ 0.004 2,100 Comparative Manufacturing Example 1 KOH PO+EO KOH PO ○ 0.040 2,000 comparison
Preparation Example 2 KOH PO+EO KOH PO+EO ○ 0.035 2,100 comparison
Preparation Example 3 DMC N/A ⁴⁾ × N/A ⁴⁾ comparison
Preparation Example 4 KOH PO+EO DMC+KOH PO ○ 0.025 2,000 1) PO: Propylene Oxide
2) EO: Ethylene Oxide
3) DMC: Double Metal Cyanide
4) N/A: The catalyst is not activated, so the polymerization reaction does not proceed.

Experimental Example 4 - Evaluation of Polyurethane Foam Properties

Polyurethane foams prepared in Examples 1 to 10 and Comparative Examples 1 to 4 were each cut into 5 cm × 5 cm dimensions to prepare samples. Subsequently, according to ASTM D3574-86, the compressive hardness, elongation, permanent compression set, and repeated compression set of the samples were measured using a Universal Testing Machine (UTM), and the results are shown in Table 2 below.

polyol
composition Degree of unsaturation
(meq/g) 25% compressive hardness ¹⁾
(kgf/ ^cm² ) 50% compression hardness ²⁾
(kgf/ ^cm² ) Growth Rate (%) Compression set (%) Iteration compression reduction (%) Example 1 Preparation Example 1 0.004 0.09 0.16 69 7 8 Example 2 Preparation Example 2 0.003 0.08 0.15 68 8 10 Example 3 Preparation Example 3 0.003 0.10 0.15 65 8 7 Example 4 Preparation Example 4 0.003 0.08 0.16 67 8 8 Example 5 Preparation Example 5 0.004 0.09 0.15 66 8 9 Example 6 Preparation Example 6 0.004 0.09 0.15 68 8 10 Example 7 Preparation Example 7 0.004 0.08 0.14 65 7 10 Example 8 Preparation Example 8 0.003 0.10 0.15 62 9 8 Example 9 Preparation Example 9 0.004 0.10 0.16 65 8 7 Example 10 Preparation Example 10 0.004 0.09 0.16 64 8 7 Comparative Example 1 Comparative Manufacturing Example 1 0.040 0.05 0.09 48 20 21 Comparative Example 2 Comparative Manufacturing Example 2 0.035 0.05 0.08 47 18 19 Comparative Example 3 Comparative Manufacturing Example 3 N/A ³⁾ Comparative Example 4 Comparative Manufacturing Example 4 0.025 0.06 0.09 50 17 20 1) 25% Compression Hardness: Repulsive force when the sample is compressed by 25%
2) 50% Compression Hardness: Rebound force when the sample is compressed by 25%
3) N/A: No sample was prepared as the polymerization reaction did not proceed.

As can be seen in Tables 1 and 2 above, it was confirmed that the polyurethane foams of Examples 1 to 10, prepared from polyol compositions with a degree of unsaturation of 0.02 meq/g or less based on a number average molecular weight of about 2,000 g/mol to 2,400 g/mol, showed significantly improved mechanical properties such as hardness and elongation compared to Comparative Examples 1 to 4. In addition, it was confirmed that the difference in the degree of unsaturation may vary depending on the type of catalyst or the timing of catalyst addition when preparing the polyol composition. Specifically, in the case of Comparative Example 3, it was confirmed that the problem of the polymerization reaction not proceeding was that the catalyst was not activated because a bimetallic cyanide catalyst was used instead of a potassium hydroxide catalyst in the prepolymer preparation process of step (1). In addition, when a potassium hydroxide catalyst is used instead of a bimetallic cyanide catalyst in the polyol composition manufacturing process of step (2), or when a bimetallic cyanide catalyst and a potassium hydroxide catalyst are used in combination, it was confirmed that the degree of unsaturation of the manufactured polyol composition exceeds 0.02 meq/g, and the physical properties of the polyurethane foam, such as hardness, elongation, compression set, and repeated compression set, were reduced.

100: Battery module
101: Housing
102: Battery cell
103: Polyurethane foam
104: Thermally conductive adhesive

Claims (15)

A first unit derived from at least one type of 1,4:3,6-dianhydrohexitol; and
It comprises a second unit derived from alkylene oxide, and
It comprises a block copolymer compound in which the second unit is bonded to the first unit core structure, and
The block copolymer compound comprises a first block having a substituted or unsubstituted branched alkylene group having 3 to 10 carbon atoms bonded to the first unit, a second block having a substituted or unsubstituted linear alkylene group having 2 to 10 carbon atoms bonded to the first block, and a third block having at least one of the branched alkylene group and the linear alkylene group bonded randomly to the second block.
Polyol composition having a degree of unsaturation of 0.02 meq/g or less according to the following measurement method:
<Measurement Method>
1) Prepare a first flask into which 30g of the above polyol composition is added and a second flask into which the above polyol composition is not added, and add 50ml of mercury acetate to each of the first flask and the second flask, and stir for 30 minutes.
2) Add 9g of sodium bromide (NaBr) to each of the first flask and the second flask, and stir for 30 minutes.
3) Add 0.5 ml of 1% phenolphthalein indicator to each of the first flask and the second flask, and titrate with 0.1 N potassium hydroxide (KOH).
4) Calculate the degree of unsaturation using the following Equation 1.
[Equation 1]
Degree of unsaturation (meq/g) = (V _s × V _b × 0.1 × F) / M
(In the above Formula 1, V _s is the amount (ml) of 0.1N potassium hydroxide (KOH) added to the first flask, V _b is the amount (ml) of 0.1N potassium hydroxide (KOH) added to the second flask, F is the factor of 0.1N potassium hydroxide (KOH), and M is the weight (g) of the polyol composition introduced into the first flask.) In paragraph 1,
A polyol composition in which at least one of the above 1,4:3,6-dianhydrohexitols comprises isosorbide. In paragraph 1,
The polyol composition comprises, based on the total weight of the polyol composition, a first unit derived from 1,4:3,6-dianhydrohexitol in an amount of 5% to 50% by weight. delete In paragraph 1,
The polyol composition comprises 40% to 85% by weight of the branched alkylene group based on the total weight of the polyol composition. delete In paragraph 1,
The polyol composition comprises the linear alkylene group in an amount greater than 0% by weight and up to 20% by weight, based on the total weight of the polyol composition. In paragraph 1,
A polyol composition having a number average molecular weight (Mn) of 500 g/mol to 12,000 g/mol. In paragraph 1,
The above polyol composition is a polyol composition comprising a compound represented by the following chemical formula 1:
[Chemical Formula 1]

In the above chemical formula 1,
_R1 and _R2 are each independently substituted or unsubstituted alkylene groups having 2 to 10 carbon atoms, and
a and f are each independently integers from 1 to 60, and
b and e are each independently integers from 1 to 6, and
c and d are each independently integers from 1 to 30, and
x is an integer from 1 to 5. In Paragraph 9,
A polyol composition in which, in the above chemical formula 1, _R1 and _R2 are each independently a substituted or unsubstituted branched alkylene group having 3 to 10 carbon atoms. In Paragraph 9,
A polyol composition in which, in the above chemical formula 1, _R1 and _R2 are each independently polymerized in a random manner from 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. In paragraph 1,
The above polyol composition is a polyol composition that further comprises an antioxidant. In Paragraph 12,
The polyol composition comprises the antioxidant in an amount of 0.03% to 1.00% by weight based on the total weight of the polyol composition. A polyol composition comprising a block copolymer compound comprising at least one first unit derived from 1,4:3,6-dianhydrohexitol and a second unit derived from an alkylene oxide, wherein the second unit is bonded to the first unit core structure, and wherein the block copolymer compound comprises a first block having a substituted or unsubstituted branched alkylene group having 3 to 10 carbon atoms bonded to the first unit, a second block having a substituted or unsubstituted linear alkylene group having 2 to 10 carbon atoms bonded to the first block, and a third block having at least one of the branched alkylene group and the linear alkylene group bonded randomly to the second block, and having a degree of unsaturation of 0.02 meq/g or less according to the following measurement method; and
Composition for manufacturing polyurethane comprising an isocyanate-based composition:
<Measurement Method>
1) Prepare a first flask into which 30g of the above polyol composition is added and a second flask into which the above polyol composition is not added, and add 50ml of mercury acetate to each of the first flask and the second flask, and stir for 30 minutes.
2) Add 9g of sodium bromide (NaBr) to each of the first flask and the second flask, and stir for 30 minutes.
3) Add 0.5 ml of 1% phenolphthalein indicator to each of the first flask and the second flask, and titrate with 0.1 N potassium hydroxide (KOH).
4) Calculate the degree of unsaturation using the following Equation 1.
[Equation 1]
Degree of unsaturation (meq/g) = (V _s × V _b × 0.1 × F) / M
(In the above Formula 1, V _s is the amount (ml) of 0.1N potassium hydroxide (KOH) added to the first flask, V _b is the amount (ml) of 0.1N potassium hydroxide (KOH) added to the second flask, F is the factor of 0.1N potassium hydroxide (KOH), and M is the weight (g) of the polyol composition introduced into the first flask.) Housing;
A plurality of battery cells housed inside the above housing; and
A battery module comprising polyurethane foam disposed between the plurality of battery cells,
The above polyurethane foam comprises a composition for manufacturing polyurethane that includes a polyol composition and an isocyanate-based composition, and
The above polyol composition comprises a first unit derived from at least one type of 1,4:3,6-dianhydrohexitol and a second unit derived from an alkylene oxide, and comprises a block copolymer compound in which the second unit is bonded to the first unit core structure, wherein the block copolymer compound comprises a first block in which a substituted or unsubstituted branched alkylene group having 3 to 10 carbon atoms is bonded to the first unit, a second block in which a substituted or unsubstituted linear alkylene group having 2 to 10 carbon atoms is bonded to the first block, and a third block in which at least one of the branched alkylene group and the linear alkylene group is randomly bonded to the second block, and the degree of unsaturation according to the following measurement method is 0.02 meq/g or less:
<Measurement Method>
1) Prepare a first flask into which 30g of the above polyol composition is added and a second flask into which the above polyol composition is not added, and add 50ml of mercury acetate to each of the first flask and the second flask, and stir for 30 minutes.
2) Add 9g of sodium bromide (NaBr) to each of the first flask and the second flask, and stir for 30 minutes.
3) Add 0.5 ml of 1% phenolphthalein indicator to each of the first flask and the second flask, and titrate with 0.1 N potassium hydroxide (KOH).
4) Calculate the degree of unsaturation using the following Equation 1.
[Equation 1]
Degree of unsaturation (meq/g) = (V _s × V _b × 0.1 × F) / M
(In the above Formula 1, V _s is the amount (ml) of 0.1N potassium hydroxide (KOH) added to the first flask, V _b is the amount (ml) of 0.1N potassium hydroxide (KOH) added to the second flask, F is the factor of 0.1N potassium hydroxide (KOH), and M is the weight (g) of the polyol composition introduced into the first flask.)