KR20240026842A - Polyol composition, composition for preparing polyurethane and battery module comprising the same - Google Patents

Abstract

The polyol composition according to the present invention includes at least one first unit derived from 1,4:3,6-dianhydrohexitol, and a second unit derived from alkylene oxide, and the polyol composition according to the following measurement method The acid value is less than 0.02 mgKOH/g.
<Measurement method> (see description of invention)

Description

Polyol composition, composition for producing polyurethane, and battery module containing the same {POLYOL COMPOSITION, COMPOSITION FOR PREPARING POLYURETHANE AND BATTERY MODULE COMPRISING THE SAME}

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

Polyurethane foam has excellent thermal insulation properties and flame retardancy. These polyurethane foams are used in various fields such as packaging boxes, building panels, home appliances, packaging materials, building interior materials, and insulation materials. Polyurethane foam can be manufactured by foaming polyurethane, and polyurethane can be manufactured by a polyaddition reaction of polyol and isocyanate.

Polyol is a liquid polymer substance in which two or more alcohol groups (-OH) are bonded to the ends of a hydrocarbon chain. Types of polyol include polyether-based polyol, polyester-based polyol, and polycarbonate-based polyol.

Polyether polyol can generally be produced by adding alkylene oxide to monopropylene glycol (MPG) or dipropylene glycol (DPG). However, monopropylene glycol and dipropylene glycol are usually manufactured from petroleum-based raw materials, and recently, the demand for eco-friendly and renewable materials has increased due to the problem of depletion of petroleum resources and greenhouse gas reduction problems related to environmental protection.

In addition, polyether polyol produced by adding alkylene oxide to monopropylene glycol (MPG) or dipropylene glycol (DPG) exhibits a high acid value. This was a problem in that the activity of the catalyst was reduced due to the neutralization effect between the amine catalyst used in the production of polyurethane foam and the polyol composition, and the reactivity between the polyol composition and the isocyanate-based composition was reduced.

The present invention provides a polyol composition that is environmentally friendly and has a low acid value without deteriorating mechanical properties, thereby increasing the efficiency of the polyurethane foam manufacturing process, a composition for manufacturing polyurethane, and a battery module containing the same.

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

<Measurement method>

1) Prepare a first flask containing the polyol composition and a second flask without the polyol composition, add 50 ml of methanol to each of the first flask and the second flask, and then stir for 30 minutes.

2) Add 0.5 ml of 1% phenolphthalein indicator to each of the first flask and the second flask, and mix with 0.02N potassium hydroxide (KOH) until the composition of the first flask and the second flask turns pink for 30 seconds. Titrate.

3) Calculate the acid value according to Equation 1 below.

[Equation 1]

Acid value (mgKOH/g) = [(V _s - V _b ) × 56.1 × N × F]/M

(In Equation 1, V _s is the amount (ml) of the 0.02N potassium hydroxide (KOH) consumed to titrate the composition of the first flask, and V _b is the amount (ml) consumed to titrate the composition of the second flask. is the amount (ml) of the 0.02N potassium hydroxide (KOH) consumed, N is the normal concentration of the potassium hydroxide (KOH), and F is the factor of the 0.02N potassium hydroxide (KOH), The M is the weight (g) of the polyol composition added to the first flask.)

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

In one embodiment of the present invention, the active oxygen content of the polyol composition may be 100 ppm or less.

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

In one embodiment of the present invention, the antioxidant may be included in an amount of 0.03% by weight to 1.00% by weight, 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 300 g/mol to 12,000 g/mol.

In one embodiment of the present invention, the polyol composition may have a viscosity of 300 cPs to 600 cPs at 25°C.

In one embodiment of the present invention, the second unit derived from 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 branched alkylene group may be bonded to the first unit derived from 1,4:3,6-dianhydrohexitol.

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 linear alkylene group may be bonded to the branched alkylene group.

The composition for producing polyurethane according to the present invention includes at least one first unit derived from 1,4:3,6-dianhydrohexitol and a second unit derived from alkylene oxide, and the following measurement method A polyol composition having an acid value of less than 0.02 mgKOH/g; and isocyanate-based compositions.

<Measurement method>

1) Prepare a first flask containing the polyol composition and a second flask without the polyol composition, add 50 ml of methanol to each of the first flask and the second flask, and then stir for 30 minutes.

2) Add 0.5 ml of 1% phenolphthalein indicator to each of the first flask and the second flask, and mix with 0.02N potassium hydroxide (KOH) until the composition of the first flask and the second flask turns pink for 30 seconds. Titrate.

3) Calculate the acid value according to Equation 1 below.

[Equation 1]

Acid value (mgKOH/g) = [(V _s - V _b ) × 56.1 × N × F]/M

(In Equation 1, V _s is the amount (ml) of the 0.02N potassium hydroxide (KOH) consumed to titrate the composition of the first flask, and V _b is the amount (ml) consumed to titrate the composition of the second flask. is the amount (ml) of the 0.02N potassium hydroxide (KOH) consumed, N is the normal concentration of the potassium hydroxide (KOH), and F is the factor of the 0.02N potassium hydroxide (KOH), The M is the weight (g) of the polyol composition added to the first flask.)

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

<Measurement method>

1) Prepare a first flask containing the polyol composition and a second flask without the polyol composition, add 50 ml of methanol to each of the first flask and the second flask, and then stir for 30 minutes.

2) Add 0.5 ml of 1% phenolphthalein indicator to each of the first flask and the second flask, and mix with 0.02N potassium hydroxide (KOH) until the composition of the first flask and the second flask turns pink for 30 seconds. Titrate.

3) Calculate the acid value according to Equation 1 below.

[Equation 1]

Acid value (mgKOH/g) = [(V _s - V _b ) × 56.1 × N × F]/M

(In Equation 1, V _s is the amount (ml) of the 0.02N potassium hydroxide (KOH) consumed to titrate the composition of the first flask, and V _b is the amount (ml) consumed to titrate the composition of the second flask. is the amount (ml) of the 0.02N potassium hydroxide (KOH) consumed, N is the normal concentration of the potassium hydroxide (KOH), and F is the factor of the 0.02N potassium hydroxide (KOH), The M is the weight (g) of the polyol composition added to the first flask.)

The polyol composition according to the present invention contains isosorbide that can be produced from renewable natural resources, so it is environmentally friendly and has the effect of saving energy.

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

The polyol composition according to the present invention can exhibit mechanical properties equivalent to or better than those of polyol compositions manufactured from petroleum-based raw materials.

The polyol composition according to the present invention has a low active oxygen content, so side reactions that may occur due to active oxygen can be reduced, the odor of polyurethane foam manufactured from the polyol composition can be reduced, and moldability can be improved. there is.

1 is a flow chart briefly showing the manufacturing process of the polyol composition according to the present invention.
Figure 2 is a cross-sectional view briefly showing a battery module according to the present invention.

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

In addition, when it is said that a certain element is 'included' in this specification or application, this means that other elements may be further included rather than excluding other elements, unless specifically stated to the contrary. In addition, all numerical ranges representing physical property values, dimensions, etc. of components described in this specification or application should be understood as modified by the term 'about' in all cases unless otherwise specified.

Hereinafter, the polyol composition, the composition for producing polyurethane, and the battery module containing the same according to the present invention will be described.

<Polyol composition>

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

<Measurement method>

1) Prepare a first flask containing the polyol composition and a second flask without the polyol composition, add 50 ml of methanol to each of the first flask and the second flask, and then stir for 30 minutes.

2) Add 0.5 ml of 1% phenolphthalein indicator to each of the first flask and the second flask, and mix with 0.02N potassium hydroxide (KOH) until the composition of the first flask and the second flask turns pink for 30 seconds. Titrate.

3) Calculate the acid value according to Equation 1 below.

[Equation 1]

Acid value (mgKOH/g) = [(V _s - V _b ) × 56.1 × N × F]/M

In Equation 1, V _s is the amount (ml) of 0.02N potassium hydroxide (KOH) consumed to titrate the composition of the first flask, and V _b is the amount (ml) consumed to titrate the composition of the second flask. is the amount (ml) of the 0.02N potassium hydroxide (KOH) consumed, N is the normal concentration of the potassium hydroxide (KOH), F is the factor of the 0.02N potassium hydroxide (KOH), and M is the weight (g) of the polyol composition added to the first flask.

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

The isosorbide can be obtained through a dehydration reaction of D-sorbitol, a renewable natural resource. The polyol composition of the present invention is environmentally friendly and energy-saving by containing the isosorbide, which can be manufactured from renewable natural resources.

The polyol composition is based on the total weight of the polyol composition. The first unit derived from the 1,4:3,6-dianhydrohexitol is 5% to 50% by weight, 10% to 50% by weight, 10% to 45% by weight, and 15% to 45% by weight. It may be included in weight percent, or from 20 weight percent to 45 weight percent. When the above range is satisfied, the viscosity of the composition increases when producing polyurethane foam from the polyol composition, which does not cause problems of smooth foaming, and the molding density and hardness of the produced polyurethane foam can be improved.

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

The branched alkylene group may be bonded to the first unit derived from 1,4:3,6-dianhydrohexitol.

The branched alkylene group may be propylene oxide.

The polyol composition has 20% to 90% by weight, 25% to 90% by weight, 30% to 90% by weight, and 35% to 90% by weight of the branched alkylene group, based on the total weight of the polyol composition. , 35% by weight to 85% by weight, or 40% by weight to 85% by weight.

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

The linear alkylene group may be bonded to the branched alkylene group.

The linear alkylene group may be ethylene oxide.

The polyol composition has, based on the total weight of the polyol composition, the linear alkylene group in an amount of more than 0% by weight to 40% by weight, more than 0% by weight to 35% by weight, more than 0% by weight to 30% by weight, and more than 0% by weight. 25% by weight, or greater than 0% to 20% by weight.

In general, polyol compositions manufactured from petroleum-based raw materials exhibit a high acid value, and the activity of the catalyst is reduced due to a neutralization effect between the amine catalyst used in polyurethane foam production and the polyol composition, and the polyol composition and There was a problem of reduced reactivity with isocyanate-based compositions. This caused a problem in that the manufacturing process efficiency of the polyurethane foam was reduced and the moldability was deteriorated.

Accordingly, the polyol composition according to the present invention can be manufactured from renewable natural resources, has a lower acid value compared to polyol compositions manufactured from petroleum-based raw materials, is environmentally friendly, and does not reduce the activity of the catalyst used in polyurethane foam production. , the reactivity between the polyol composition and the isocyanate-based composition can be improved. Because of this, the manufacturing process efficiency and moldability of polyurethane foam can be improved.

The polyol composition according to the present invention has an acid value of less than 0.02 mgKOH/g according to the following measurement method.

<Measurement method>

1) Prepare a first flask containing the polyol composition and a second flask without the polyol composition, add 50 ml of methanol to each of the first flask and the second flask, and then stir for 30 minutes.

2) Add 0.5 ml of 1% phenolphthalein indicator to each of the first flask and the second flask, and mix with 0.02N potassium hydroxide (KOH) until the composition of the first flask and the second flask turns pink for 30 seconds. Titrate.

3) Calculate the acid value according to Equation 1 below.

[Equation 1]

Acid value (mgKOH/g) = [(V _s - V _b ) × 56.1 × N × F]/M

In Equation 1, V _s is the amount (ml) of 0.02N potassium hydroxide (KOH) consumed to titrate the composition of the first flask, and V _b is the amount (ml) consumed to titrate the composition of the second flask. is the amount (ml) of the 0.02N potassium hydroxide (KOH) consumed, N is the normal concentration of the potassium hydroxide (KOH), F is the factor of the 0.02N potassium hydroxide (KOH), and M is the weight (g) of the polyol composition added to the first flask.

The polyol composition may have an acid value of less than 0.02 mgKOH/g, less than 0.019 mgKOH/g, less than 0.018 mgKOH/g, less than 0.015 mgKOH/g, or less than 0.012 mgKOH/g according to the measurement method, and the lower limit value of the acid value is There is no need to specifically limit it, but may be greater than 0 mgKOH/g, greater than 0.005 mgKOH/g, or greater than 0.010 mgKOH/g. When the above range is satisfied, the acid resistance of the polyurethane foam manufactured from the polyol composition can be strengthened, and the reactivity between the polyol composition and the isocyanate-based composition can be improved.

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

The polyol composition may have a viscosity at 25°C of 200 cPs to 800 cPs, 250 cPs to 800 cPs, 300 cPs to 800 cPs, 300 cPs to 700 cPs, or 300 cPs to 600 cPs. The viscosity can be measured using a known method, for example, using a non-contact viscometer. When the above range is satisfied, the storage stability of the polyol composition can be improved, the generation of bubbles can be prevented when manufacturing polyurethane foam, and uneven curing can be prevented, thereby improving workability.

The polyol composition according to the present invention has an APHA (American Public Health Association) 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. You can. When the above range is satisfied, the polyol composition is colorless and transparent, and polyurethane foam with low yellowness can be manufactured using the polyol.

The number average molecular weight (Mn) of the polyol composition is 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 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. When the above range is satisfied, the reactivity between the polyol composition and isocyanate may be improved.

The polyol composition may further include an antioxidant. The antioxidant can improve the heat resistance stability of the polyurethane foam obtained from the polyol composition and reduce the generation of odor. The antioxidants include 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.) can be used. The content of the antioxidant is 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. It may be weight percent.

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. The CRP is an indicator of the amount of alkaline substances in the polyol composition, and can be measured by mixing 30 g of the polyol composition with 50 ml of methanol and quantifying the amount of hydrochloric acid (concentration: 0.001N) appropriate for neutralization according to the test method of ASTM D6437. . If the above range is satisfied, reactivity control is easy during the product manufacturing process and product specifications can be met.

The active oxygen content of the 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 can be measured using a known method, for example, using a spectrophotometer and a calibration curve of the change in absorbance according to the active oxygen content. When the above range is satisfied, side reactions are reduced, the odor of polyurethane foam manufactured from the polyol composition is reduced, and moldability can be improved.

The polyol composition may include a compound represented by Formula 1 below.

[Formula 1]

In Formula 1, R ₁ and R ₄ are each independently a substituted or unsubstituted linear alkylene group having 2 to 10 carbon atoms, and R ₂ and R ₃ are each independently a substituted or unsubstituted branched alkylene group having 3 to 10 carbon atoms. is an alkylene group, 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 am.

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

R ₁ to R ₄ may be a second unit derived from alkylene oxide.

R ₁ and R ₄ may each independently be a substituted or unsubstituted ethylene group. R ₁ and R ₄ may be derived from a substituted or unsubstituted linear alkylene group oxide having 2 to 10 carbon atoms. Preferably, R ₁ and R ₄ may each independently be an ethylene group.

R ₂ and R ₃ may each independently be a substituted or unsubstituted propylene group.

R ₂ and R ₃ may be derived from a substituted or unsubstituted branched alkylene group oxide having 3 to 10 carbon atoms. Preferably, R ₂ and R ₃ may each independently be a propylene group.

The compound represented by Formula 1 has a parent core structure, which is a first unit derived from at least one type of 1,4:3,6-dianhydrohexitol, and a propylene group derived from the branched alkylene group as a second unit. It may be in the form of a block copolymer in which the propylene group and the ethylene group derived from the linear alkylene group are polymerized to form a block.

Since blocks in which ethylene groups are polymerized are formed at both ends of the compound represented by Formula 1, the hydroxyl group (-OH) content of the primary alcohol is higher compared to conventional polyol compounds, and the reactivity with isocyanate may be excellent. In addition, polyurethane foam containing the above compound can realize mechanical properties and processability equivalent to or better than polyurethane foam manufactured from a conventional petroleum-based polyol composition.

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) may each independently be 3 to 50. Preferably, (a+b) and (c+d) may each independently be 3 to 30, 3 to 20, 5 to 20, 5 to 10, or 5 to 9.

When the above range is satisfied, the polyurethane foam containing the compound has improved hardness, reduced compression set, and a smooth surface, so that it can have an excellent appearance. In addition, by achieving an appropriate level of CFD (Compression Force Deformation), when polyurethane foam is applied to a battery module, the volume change caused by the expansion of the battery cell is buffered and the volume is kept constant, thereby improving product stability. . The CFD is a parameter that represents the repulsion force when the measurement object is compressed.

The CFD can be evaluated by measuring the repulsion force when polyurethane foam is cut to a size of 5 cm × 5 cm at room temperature and compressed using a device such as a UTM (Universal Testing Machine). For example, the repulsion force when the polyurethane foam is compressed by 25% can be evaluated by the CFD 25% value, and the preferred CFD 25% value ranges from about more than 0.06 kg/cm ² to less than 0.15 kg/cm ² You can have it. In addition, the repulsion force when the polyurethane foam is compressed by 50% can be evaluated by the CFD 50% value, and the preferred CFD 50% value can range from about more than 0.10 kg/cm ² to less than 0.20 kg/cm ² there is.

The compound represented by Formula 1 may be a compound represented by Formula 2 below.

[Formula 2]

In Formula 2, 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.

Specifically, the type of compound represented by Formula 2 may be represented by compounds of Formula A to Formula I below.

[Formula A]

[Formula B]

[Formula C]

[Formula D]

[Formula E]

[Formula F]

[Formula G]

[Formula H]

[Formula I]

[Formula J]

[Formula K]

[Formula L]

The content of the compound represented by Formula 1 may be 50% to 99% by weight based on the total weight of the polyol composition. Preferably, the content of the compound represented by Formula 1 is 60% to 99% by weight, 70% to 99% by weight, 75% to 99% by weight, and 77% to 99% by weight based on the total weight of the polyol composition. %, or from 80% to 99% by weight. When the above range is satisfied, the viscosity of the composition increases when producing polyurethane foam from the polyol composition, which does not cause problems of smooth foaming, and the molding density and hardness of the produced polyurethane foam can be improved.

<Method for producing polyol composition>

The method for producing a polyol composition according to the present invention includes the steps of (a) mixing at least one type of 1,4:3,6-dianhydrohexitol and a catalyst to perform a dehydration process, (b) dehydrating the at least one preparing a first polymer by reacting at least one kind of 1,4:3,6-dianhydrohexitol with a substituted or unsubstituted branched alkylene oxide having 3 to 10 carbon atoms, and (c) above (b) After the preparation of the first polymer in the step is completed, it may include the step of reacting the first polymer with a substituted or unsubstituted linear alkylene oxide having 2 to 10 carbon atoms to prepare a second polymer, wherein the polyol composition The acid value according to the measurement method below may be less than 0.02 mgKOH/g.

<Measurement method>

1) Prepare a first flask containing the polyol composition and a second flask without the polyol composition, add 50 ml of methanol to each of the first flask and the second flask, and then stir for 30 minutes.

2) Add 0.5 ml of 1% phenolphthalein indicator to each of the first flask and the second flask, and mix with 0.02N potassium hydroxide (KOH) until the composition of the first flask and the second flask turns pink for 30 seconds. Titrate.

3) Calculate the acid value according to Equation 1 below.

[Equation 1]

Acid value (mgKOH/g) = [(V _s - V _b ) × 56.1 × N × F]/M

In Equation 1, V _s is the amount (ml) of 0.02N potassium hydroxide (KOH) consumed to titrate the composition of the first flask, and V _b is the amount (ml) consumed to titrate the composition of the second flask. is the amount (ml) of the 0.02N potassium hydroxide (KOH) consumed, N is the normal concentration of the potassium hydroxide (KOH), F is the factor of the 0.02N potassium hydroxide (KOH), and M is the weight (g) of the polyol composition added to the first flask.

1 is a flow chart briefly showing the manufacturing process of the polyol composition according to the present invention. Referring to Figure 1, the manufacturing method of the present invention may include a dehydration step (S10). In S10, at least one type of 1,4:3,6-dianhydrohexitol can be mixed with a catalyst to dehydrate the at least one type of 1,4:3,6-dianhydrohexitol.

The 1,4:3,6-dianhydrohexitol may exist in three isomers: isomannide, isoidide, and isosobide. The three isomers can be distinguished by differences in the relative configuration of the two hydroxy groups (-OH) in each compound. The isomannide can be obtained through a dehydration reaction of D-mannitol. The isoidide can be obtained through a dehydration reaction of L-iditol. Considering the manufacturing process and efficiency aspects, it is preferable to use isosorbide among the three 1,4:3,6-dianhydrohexitol isomers in S10.

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

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

The acid catalyst may be added in an amount of 0.01 to 15.00 parts by weight, 0.01 to 10.00 parts by weight, or 0.01 to 5.00 parts by weight, based on 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 remaining catalyst can be minimized.

The D-sorbitol may be in powder form or in the form of an aqueous solution containing D-sorbitol at a concentration of 50% by weight to 90% by weight. Additionally, the D-sorbitol can be obtained through a synthetic process by extracting it from nature or reducing it from glucose.

The isosorbide forms 1,4-sorbitan, an intermediate product in which one water molecule is removed from D-sorbitol, and then one water molecule is additionally removed from the 1,4-sorbitan. It can be obtained by a removal process.

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

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

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. When the temperature of the dehydration process in which the 1,4-sorbitan is formed is adjusted to be lower than the temperature of the dehydration process in which the isosorbide is obtained, isosorbide can be obtained in high yield even if an acid catalyst is not used.

The isosorbide can be obtained by Scheme 1 below.

[Scheme 1]

The at least one type of 1,4:3,6-dianhydrohexitol may 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.

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

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

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

The purity of the 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 diameter of the 1,4:3,6-dianhydrohexitol is 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. It can be. The average particle size is measured using a laser diffraction method, and can be defined as the particle size corresponding to 50% of the cumulative volume in the particle size distribution curve.

The moisture content of the 1,4:3,6-dianhydrohexitol may be less than about 5% by weight, less than about 4% by weight, less than about 3% by weight, less than about 2% by weight, or less than about 1% by weight. The moisture content is calculated by subtracting the weight after drying of 1,4:3,6-dianhydrohexitol from the weight before drying of 1,4:3,6-dianhydrohexitol. It can be calculated by dividing by the weight of dianhydrohexitol before drying and then multiplying by 100. The drying involves raising the temperature from room temperature to about 150°C and then maintaining it at 150°C, and the total drying time can be set to 20 minutes, including 5 minutes for the temperature increase step.

The 1,4:3,6-dianhydrohexitol may be added to the batch reactor in the form of an aqueous solution. The 1,4:3,6-dianhydrohexitol is added to the batch reactor in an amount of about 70% by weight to about 90% by weight, about 75% by weight to about 90% by weight, or about 75% by weight to about 85% by weight. It can be administered at a concentration of .

The 1,4:3,6-dianhydrohexitol can be added to the batch reactor in batches. The 1,4:3,6-dianhydrohexitol may be added to 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 1,4:3,6-dianhydrohexitol is divided into equal amounts in 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. can be put in.

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.

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

The catalyst may be introduced into the batch reactor as an aqueous solution. For example, an aqueous potassium hydroxide solution may be added to the batch reactor. The catalyst may be added after the at least one type of 1,4:3,6-dianhydrohexitol is added to the batch reactor. The catalyst may be added to the batch reactor in batches. The catalyst may be added to 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 is reacted in 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. It can be divided into doses and administered.

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

The dehydration process of 1,4:3,6-dianhydrohexitol may 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 1,4:3,6-dianhydrohexitol may be performed 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 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.

The dehydration process of 1,4:3,6-dianhydrohexitol may be performed for about 1 hour to about 5 hours at a temperature of about 80°C to about 120°C. Preferably, the dehydration process of 1,4:3,6-dianhydrohexitol is performed at a temperature of about 80°C to about 120°C and a pressure of about 0.1 torr to about 20.0 torr for about 2 hours to about 4 hours. It can take place over time.

After step S10, 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. The 1,4:3,6-dianhydrohexitol can improve the yield of the polyol composition due to its low moisture content.

The production method of the present invention may include a step (S20) of producing the first polymer. In S20, the first polymer can be prepared by reacting the dehydrated at least one type of 1,4:3,6-dianhydrohexitol 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 propylene oxide may be added to the batch reactor.

The process of adding propylene oxide may 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 process of introducing propylene oxide may 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 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 at a temperature of about 80°C to about 120°C and a pressure of about 2 torr to about 8 torr.

The input rate of the 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 1,4:3,6-dianhydrohexitol, the propylene oxide is present 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 150 parts by weight. 450 parts by weight can be added to the batch reactor.

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

The addition reaction of the 1,4:3,6-dianhydrohexitol and the propylene oxide is 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. It can proceed.

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

S20 may further include a step of removing the remaining branched alkylene oxide after preparing the first polymer. The remaining branched alkylene oxide may be propylene oxide. By removing the remaining branched alkylene oxide, reactivity with isocyanate can be improved, hardness and appearance of polyurethane foam can be improved, and manufacturing economics can be improved.

The remaining propylene oxide removal process may be performed at 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 remaining propylene oxide removal process may be performed 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 remaining propylene oxide removal process may 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 remaining propylene oxide may be performed for about 20 minutes to about 40 minutes at a temperature of about 100°C to about 140°C and a pressure of about 0.1 torr to about 20.0 torr.

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

The weight ratio of the branched alkylene oxide of S20 and the linear alkylene oxide of S30 is 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 increases, and the hardness and appearance quality of polyurethane foam manufactured from the polyol composition can be improved.

The substituted or unsubstituted linear alkylene oxide having 2 to 10 carbon atoms may be ethylene oxide. The ethylene oxide may be added to the batch reactor in which the production of the first polymer has been completed.

The process of adding 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 process of adding ethylene oxide may 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 process of adding ethylene oxide may 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 process of adding ethylene oxide may be carried out for about 2 to about 3 hours at a temperature of about 120°C to about 130°C and a pressure of about 0.1 torr to about 30.0 torr.

The input 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.

Based on 100 parts by weight of 1,4:3,6-dianhydrohexitol, the ethylene oxide is present in an amount of about 10 parts by weight to about 100 parts by weight, about 20 parts by weight to about 100 parts by weight, and about 20 parts by weight to about 80 parts by weight. Parts by weight, or about 20 parts by weight to about 60 parts by weight, may be added to the batch reactor.

The ethylene oxide may undergo an addition reaction with the first polymer in the batch reactor. Through the addition reaction, a second polymer including the ethylene oxide-derived repeating unit in the first polymer can be produced. Additionally, a second polymer comprising the propylene oxide-derived repeating unit and the ethylene oxide-derived repeating unit as a block-type copolymer can be produced. The derived repeating unit may refer to a component or structure derived from ethylene oxide or ethylene oxide itself.

The addition reaction of the 1,4:3,6-dianhydrohexitol and the ethylene oxide is 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. It can proceed.

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

S30 may further include a step of removing linear alkylene oxide remaining after preparing the second polymer. The remaining linear alkylene oxide may be ethylene oxide.

The remaining ethylene oxide removal process may be carried out 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.

The remaining propylene oxide removal process may be performed 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 remaining ethylene oxide removal process may 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 remaining ethylene oxide removal process may be performed for about 40 minutes to about 80 minutes at a temperature of about 100°C to about 140°C and a pressure of about 0.1 torr to about 20.0 torr.

The manufacturing method of the present invention may further include removing and filtering residual metal ions (S40) and adding an antioxidant (S50). In S40, residual metal ions in the polyol composition are removed and filtered, and in S50, a process of adding an antioxidant to the polyol composition may be performed.

In S40, an additive may be added to the polyol composition in which the reaction has been completed to remove the remaining metal ions. The additive may be one or more selected from the group consisting of diatomaceous earth, alumina, MAGNESOL, CELITE, AMBOSOL, and silica gel.

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

Thereafter, in S40, a neutralization process of the polyol composition into which the additive is added may proceed. The neutralization process may last about 1 hour to about 4 hours, about 1 hour to about 3 hours, or about 1 hour to about 2 hours. Thereafter, the polyol composition for which the neutralization process has been completed may undergo a moisture removal process. 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, a process for detecting the residual metal ion may be performed in S40, and if the residual metal ion is not detected, the polyol composition is heated to about 50°C to about 90°C, about 50°C to about 80°C. , or it can be maintained under temperature conditions of about 60°C to about 80°C. In S40, the polyol composition from which the moisture has been removed can be filtered. The additives and by-products may be filtered out by the filtering.

In S50, the polyol composition contains a phenolic antioxidant (dibutylhydroxytoluene, etc.), a sulfur-based antioxidant (mercaptopropionic acid derivative, etc.), and a phosphorus-based antioxidant (9,10-dihydro-9-oxa-10-phos). Antioxidants containing one or more types selected from the group consisting of paphenanthrene-10-oxide, etc. may be added. The antioxidant is present in an amount of 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. It can be put into . The antioxidant can improve the heat resistance stability of the polyurethane foam obtained from the polyol composition and reduce the generation of odor.

The polyol composition prepared according to the above production method may have an acid value of less than 0.02 mgKOH/g, less than 0.019 mgKOH/g, less than 0.018 mgKOH/g, less than 0.015 mgKOH/g, or less than 0.012 mgKOH/g according to the following measurement method. , the lower limit value of the acid value does not need to be specifically limited, but may be greater than 0 mgKOH/g, greater than 0.005 mgKOH/g, or greater than 0.010 mgKOH/g.

<Measurement method>

1) Prepare a first flask containing the polyol composition and a second flask without the polyol composition, add 50 ml of methanol to each of the first flask and the second flask, and then stir for 30 minutes.

2) Add 0.5 ml of 1% phenolphthalein indicator to each of the first flask and the second flask, and mix with 0.02N potassium hydroxide (KOH) until the composition of the first flask and the second flask turns pink for 30 seconds. Titrate.

3) Calculate the acid value according to Equation 1 below.

[Equation 1]

Acid value (mgKOH/g) = [(V _s - V _b ) × 56.1 × N × F]/M

In Equation 1, V _s is the amount (ml) of 0.02N potassium hydroxide (KOH) consumed to titrate the composition of the first flask, and V _b is the amount (ml) consumed to titrate the composition of the second flask. is the amount (ml) of the 0.02N potassium hydroxide (KOH) consumed, N is the normal concentration of the potassium hydroxide (KOH), F is the factor of the 0.02N potassium hydroxide (KOH), and M is the weight (g) of the polyol composition added to the first flask.

When the above range is satisfied, the acid resistance of the polyurethane foam manufactured from the polyol composition can be strengthened, and the reactivity between the polyol composition and the isocyanate-based composition can be improved.

<Composition for producing polyurethane>

The composition for producing polyurethane according to the present invention includes at least one first unit derived from 1,4:3,6-dianhydrohexitol and a second unit derived from alkylene oxide, and the following measurement method A polyol composition having an acid value of less than 0.02 mgKOH/g; and isocyanate-based compositions.

<Measurement method>

1) Prepare a first flask containing the polyol composition and a second flask without the polyol composition, add 50 ml of methanol to each of the first flask and the second flask, and then stir for 30 minutes.

2) Add 0.5 ml of 1% phenolphthalein indicator to each of the first flask and the second flask, and mix with 0.02N potassium hydroxide (KOH) until the composition of the first flask and the second flask turns pink for 30 seconds. Titrate.

3) Calculate the acid value according to Equation 1 below.

[Equation 1]

Acid value (mgKOH/g) = [(V _s - V _b ) × 56.1 × N × F]/M

In Equation 1, V _s is the amount (ml) of 0.02N potassium hydroxide (KOH) consumed to titrate the composition of the first flask, and V _b is the amount (ml) consumed to titrate the composition of the second flask. is the amount (ml) of the 0.02N potassium hydroxide (KOH) consumed, N is the normal concentration of the potassium hydroxide (KOH), F is the factor of the 0.02N potassium hydroxide (KOH), and M is the weight (g) of the polyol composition added to the first flask.

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

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

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

The polyisocyanate is methylene diisocyanate, ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1-12-dodecane diisocyanate, cyclobutane-1,3-diisocyanate, cyclo Hexane-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' -It may include at least one selected from the group consisting of diisocyanate, diphenylmethane-4,4'-diisocyanate, polymeric methylene diphenyl diisocyanate (PMDI), and naphthalene-1,5-diisocyanate. .

The polyisocyanate is toluene diisocyanate (2,4-/2,6-isomer ratio = 80/20), which is a mixture of 2,4-toluene diisocyanate and 2,6-toluene diisocyanate, or polymeric methylene diisocyanate. Phenyl diisocyanate may be used.

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

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

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

If the isocyanate index is less than 70, the gelling reaction may be delayed due to low reactivity, which may cause a problem of curing, and if the isocyanate index is more than 130, the hard segment may increase excessively, causing shrinkage. Problems may arise.

The composition for producing 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 serve to promote the reaction between the polyol composition and the isocyanate composition.

The type of the amine catalyst is not particularly limited, and preferably one type or a mixture of two or more types selected from tertiary amine catalysts can be used. For example, at least one selected from the group consisting of triethylene diamine, triethylamine, N-Methyl morpholine, and N-Ethylmorpholine may be used. You can.

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

The content of the curing catalyst is about 0.01 parts by weight to about 5 parts by weight, 0.01 parts by weight to about 4 parts by weight, 0.01 parts by weight to about 3 parts by weight, and 0.1 parts by weight to about 3 parts by weight based on 100 parts by weight of the polyol composition. , or it may be included from 0.1 parts by weight to about 2.5 parts by weight. When the above range is satisfied, curing failure, shrinkage, or the phenomenon of polyurethane foam collapsing during formation can be reduced.

The composition for producing polyurethane may include a foaming agent. The foaming agent prevents the cells from coalescing or being destroyed when cells are formed inside the polyurethane foam, and can play a role in controlling the formation of cells with uniform shapes and sizes.

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

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

The composition for producing polyurethane may include a foaming agent. The foaming agent can typically be water, and in addition to water, methylene chloride, n-butane, isobutane, n-pentane, isopentane, dimethyl ether, acetone, carbon dioxide, and 1,1-dichloro1-fluoroethane. At least one selected from the group consisting of can be used. The foaming agent can be used according to normal usage methods and can be used appropriately depending on the density or other characteristics of the required foam.

The content of the blowing agent is about 0.1 parts by weight to about 60 parts by weight, about 0.2 parts by weight to about 60 parts by weight, about 0.3 parts by weight to about 60 parts by weight, and about 0.3 parts by weight to about 50 parts by weight, based on 100 parts by weight of the polyol composition. parts by weight, or about 1 part by weight to about 30 parts by weight.

The composition for producing polyurethane may not contain the foaming agent. That is, in the process of manufacturing polyurethane foam using the composition for producing polyurethane, a gaseous foaming agent such as nitrogen gas may be directly injected into the composition for producing polyurethane, thereby forming fine cells.

The composition for producing polyurethane may further include auxiliary additives selected from the group consisting of flame retardants, colorants, UV stabilizers, thickeners, foam stabilizers, fillers, or combinations thereof.

The composition for producing polyurethane may be one-component or two-component. If the composition for producing polyurethane is a two-component type, it may be divided into two components and stored, and then the two components may be mixed immediately before the polyurethane resin production process.

When the composition for producing polyurethane is a two-component type, the composition for producing polyurethane may include a first component mainly containing the polyol composition and a second component mainly containing the isocyanate composition.

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

The second component may include the isocyanate composition.

<Manufacturing method of polyurethane foam>

Polyurethane foam can be manufactured from the composition for producing polyurethane. The method for producing the polyurethane foam includes (a) an isocyanate supplier supplying the second component, (b) a gas supply stage in which a gas supplier supplies a foaming gas, and (c) a polyol supplier supplying the first component. supplying, (d) mixing the first component, the second component, and the foaming gas by a mixer to produce a polyurethane foam composition, and (e) curing the polyurethane foam composition. It can be included.

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

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

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

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

The average diameter of the fine closed cells is 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 It may be 50 μm to about 100 μm.

<Battery module>

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

<Measurement method>

1) Prepare a first flask containing the polyol composition and a second flask without the polyol composition, add 50 ml of methanol to each of the first flask and the second flask, and then stir for 30 minutes.

2) Add 0.5 ml of 1% phenolphthalein indicator to each of the first flask and the second flask, and mix with 0.02N potassium hydroxide (KOH) until the composition of the first flask and the second flask turns pink for 30 seconds. Titrate.

3) Calculate the acid value according to Equation 1 below.

[Equation 1]

Acid value (mgKOH/g) = [(V _s - V _b ) × 56.1 × N × F]/M

In Equation 1, V _s is the amount (ml) of 0.02N potassium hydroxide (KOH) consumed to titrate the composition of the first flask, and V _b is the amount (ml) consumed to titrate the composition of the second flask. is the amount (ml) of the 0.02N potassium hydroxide (KOH) consumed, N is the normal concentration of the potassium hydroxide (KOH), F is the factor of the 0.02N potassium hydroxide (KOH), and M is the weight (g) of the polyol composition added to the first flask.

Figure 2 is a cross-sectional view briefly showing 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 that accommodates a plurality of battery cells 102 and protects them from external shocks, etc. The housing 101 may be made of a metal material with high mechanical rigidity. However, the housing 101 is not limited to a metallic material and may be made of a non-metallic material to ensure insulation.

The battery module 100 may include a thermally conductive adhesive 104. The thermally conductive adhesive 104 can fix the plurality of battery cells 102 in the housing 101 and ensure that the heat of the plurality of battery cells 102 is well transmitted to the housing 101. . The thermally conductive adhesive 104 may be made of various organic or inorganic resins, such as thermally conductive epoxy adhesive, thermally conductive silicone adhesive, and thermally conductive urethane adhesive.

The plurality of battery cells 102 may be provided in a pouch type in which the number of stacked cells per unit area can be maximized. The plurality of battery cells 102 provided in the pouch type can be manufactured by storing an electrode assembly including an anode, a cathode, and a separator in a cell case of a laminate sheet, and then heat-sealing the sealing portion of the cell case. However, the plurality of battery cells 102 do not necessarily have to be provided in a pouch shape, and may be provided in a prismatic shape, a cylindrical shape, or other various shapes, provided that the storage capacity required for devices to be installed in the future is achieved.

The battery module 100 includes a plurality of battery cells 102 accommodated inside a housing 101 and polyurethane foam 103 disposed between the plurality of battery cells 102. The polyurethane foam 103 has excellent vibration absorption and repulsion due to compression, and thus dimensional stability can be maintained even if swelling occurs in the plurality of battery cells 102. Additionally, damage to the battery module 100 due to expansion of the plurality of battery cells 102 can be prevented. The degree of expansion of the plurality of battery cells 102 may vary depending on chemical properties and usage environment. Considering this, the maximum compressible thickness range of the polyurethane foam 103 is the range of the plurality of battery cells 102. It can be selected within a range that can accommodate the thickness of the expansion of the back.

Below, the present invention will be described in more detail based on examples and comparative examples. However, the following examples and comparative examples are only examples to explain the present invention in more detail, and the present invention is not limited by the following examples and comparative examples.

Preparation Example - Preparation of polyol composition

Manufacturing Example 1

800 g of isosorbide and 22 g of potassium hydroxide were added to a reactor capable of pressurization and heating. Afterwards, the inside of the reactor was replaced with nitrogen, heated to 112°C, and moisture in the reactor was removed under vacuum and reduced pressure conditions.

While 1,880 g of propylene oxide was added to the reactor at a constant rate, the reaction proceeded for 6 hours at a temperature of about 115°C. At this time, the reactor temperature was adjusted not to exceed 115°C.

The reactor was stirred until all propylene oxide remaining in the reactor reacted, and after the reaction was completed, the reactor temperature was heated to about 120°C. Afterwards, 275 g of ethylene oxide was added to the reactor at a constant rate, and the reaction proceeded for 1 hour and 30 minutes at a temperature of about 120°C. At this time, the reactor temperature was adjusted not to exceed 125°C.

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

After confirming that no metal ions remaining in the reactant were detected, the reactor temperature was lowered to 70°C, the remaining by-products were removed through a filter, and antioxidant (SN-1076, Songwon Industrial Co., Ltd.) was added based on the total weight of the reactant. ) After adding 300 ppm and proceeding with the reaction for 10 minutes, 3,000 g of polyol composition was obtained.

Production example 2

A polyol composition was obtained through the same process as Preparation Example 1, except that 2,0500 g of propylene oxide was added to the reactor instead of 1,880 g of propylene oxide.

Production example 3

A polyol composition was obtained through the same process as Preparation Example 1, except that 290 g of ethylene oxide was added to the reactor instead of 275 g of ethylene oxide.

Production example 4

A polyol composition was produced through the same process as Preparation Example 1, except that 2,000 g of propylene oxide was added to the reactor instead of 1,880 g of propylene oxide, and 300 g of ethylene oxide was added instead of 275 g of ethylene oxide. was obtained.

Production example 5

A polyol composition was obtained through the same process as Preparation Example 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.

Production example 6

A polyol composition was obtained through the same process as Preparation Example 1, except that instead of adding 800 g of isosorbide and 22 g of potassium hydroxide to the reactor, 810 g of isosorbide and 24 g of potassium hydroxide were added to the reactor.

Comparative Manufacturing Example 1

388 g of monopropylene glycol (MPG) and 18 g of potassium hydroxide were added to a reactor capable of pressurization and heating. Afterwards, the inside of the reactor was replaced with nitrogen, heated to 112°C, and moisture in the reactor was removed under vacuum and reduced pressure conditions.

While 2,100 g of propylene oxide was added to the reactor at a constant rate, the reaction proceeded for 7 hours at a temperature of about 110°C. At this time, the reactor temperature was adjusted not to exceed 115°C.

The reactor was stirred until all propylene oxide remaining in the reactor reacted, and after the reaction was completed, the reactor temperature was heated to about 122°C. Afterwards, 270 g of ethylene oxide was added to the reactor at a constant rate, and the reaction proceeded for 1 hour and 30 minutes at a temperature of about 120°C. At this time, the reactor temperature was adjusted not to exceed 125°C.

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

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

Comparative Manufacturing Example 2

A polyol composition was obtained through the same process as Comparative Preparation Example 1, except that 388 g of dipropylene glycol (DPG) was added to the reactor instead of 386 g of monopropylene glycol (MPG).

Comparative Manufacturing Example 3

A polyol composition was obtained through the same process as Comparative Preparation Example 1, except that 400 g of monopropylene glycol (MPG) was added to the reactor instead of 388 g of MPG.

Comparative Manufacturing Example 4

A polyol composition was obtained through the same process as Comparative Preparation Example 2, except that 400 g of dipropylene glycol (DPG) was added to the reactor instead of 388 g of DPG.

Example - Polyurethane foam production

Example 1

30 g of the polyol composition prepared in Preparation Example 1 was added to a plastic beaker. Afterwards, 4.0 g of distilled water, 0.3 g of B-8629 (Evonik) and 1.2 g of L-1501 (Momentive) as a silicone foaming agent were added to the beaker, and 0.5 g of D-33LV (Air Products) as an amine catalyst. 0.2 g of M-50 (Tosoh) and 0.6 g of diethanolamine as a cross-linking agent were added. Afterwards, the mixture was obtained by mixing for 3 minutes at 4,000 rpm using a high-speed stirrer.

Afterwards, 58 g of methylenediphenyl isocyanate (CG-3701S, Kumho Co., Ltd.) was added to the mixture and foamed to prepare polyurethane foam.

Examples 2 to 6 and Comparative Examples 1 to 4

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

Experiment example

Experimental Example 1 - Acid value measurement

15 g of the polyol composition prepared in Preparation Examples 1 to 6 and Comparative Preparation Examples 1 to 4 were added to each 100 ml first flask. Separately, for blank testing, a second flask of 100 ml was prepared. Thereafter, 50 ml of methanol and a magnetic bar were added to each of the first and second flasks to remove impurities, and the stoppers of the first and second flasks were sealed and left for 30 minutes. The mixture was stirred.

Thereafter, 0.5 ml of 1% phenolphthalein indicator was added to each of the first flask and the second flask, and 0.02N (normal concentration) potassium hydroxide (KOH) was added until the pink color was maintained for 30 seconds at the end point when observed with the naked eye. ) was titrated. The acid value was calculated using Equation 1 below, and the results are shown in Table 1 below.

[Equation 1]

Acid value (mgKOH/g) = [(V _s - V _b ) × 56.1 × N × F]/M

In Equation 1, V _s is the amount (ml) of 0.02N potassium hydroxide (KOH) consumed to titrate the composition of the first flask, and V _b is the amount (ml) consumed to titrate the composition of the second flask. is the amount (ml) of the 0.02N potassium hydroxide (KOH) consumed, N is the normal concentration of the potassium hydroxide (KOH), F is the factor of the 0.02N potassium hydroxide (KOH), and M is the weight (g) of the polyol composition added to the first flask.

Experimental Example 2 - Number average molecular weight measurement

2.75 g of the polyol composition prepared in Preparation Examples 1 to 6 and Comparative Preparation Examples 1 to 4 was added to each container containing the phthalic anhydride solution, and then reacted at 115°C for 30 minutes. Afterwards, the pH was observed while titrating with a 0.5N aqueous sodium hydroxide (NaOH) solution, and the volume (ml) of sodium hydroxide (NaOH) required to reach the 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. Afterwards, the acid value (mgKOH/g) of the polyol composition was calculated based on the measured value. Thereafter, the number average molecular weight of the polyol composition prepared in Preparation Examples 1 to 6 and Comparative Preparation Examples 1 to 4 was calculated using the acid value and the relational formula 1 below, 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 - Measurement of active oxygen content

After purging the 25 ml first flask with nitrogen for 2 minutes, 3 g of the polyol composition prepared in Preparation Examples 1 to 6 and Comparative Preparation Examples 1 to 4 were added to the first flask, and then purged again with nitrogen. did. Separately, a second flask of 25 ml was prepared for blank testing.

Thereafter, 20 ml of ferrous thiocyanate was added to each of the first and second flasks, diluted with methanol, and reacted for 5 minutes. Using a UV-Vis spectrophotometer (Cary50conc, Varian) and a quartz cell (10mm × 10mm), the absorbance of distilled water at a wavelength of 500 nm, the absorbance of the material added to the first flask, and the The absorbance of each added material was measured. The actual absorbance was calculated from the difference between the absorbance of the material added to the first flask and the absorbance of the material added to the second flask. Afterwards, the amount of active oxygen was calculated using the calibration curve, and the results are shown in Table 1 below.

Experimental Example 4 - Viscosity measurement

The viscosity of each polyol composition prepared in Preparation Examples 1 to 6 and Comparative Preparation Examples 1 to 4 was measured using Brookfield's DV-Ⅲ at 25°C, and the results are shown in Table 1 below.

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

Experimental Example 5 - Process Time

The total process time for manufacturing the polyurethane foam of Examples 1 to 6 and Comparative Examples 1 to 4 was measured, and the results are shown in Table 2 below.

Experimental Example 6 - Formability Evaluation

When manufacturing the polyurethane foam of Examples 1 to 6 and Comparative Examples 1 to 4, the time at which the polyurethane foam begins to swell (Cream Time; CT) and the time at which the polyurethane foam expands and swells (Rise Time; RT) ) were measured respectively. If the CT of the polyurethane foam is 7 to 10 seconds and the RT is 90 to 100 seconds, the moldability can be evaluated as good, and the results are shown in Table 2 below.

Experimental Example 7 - Evaluation of polyurethane foam physical properties

Samples were prepared by cutting the polyurethane foams prepared in Examples 1 to 6 and Comparative Examples 1 to 4 into a size of 5 cm × 5 cm, respectively. Afterwards, based on ASTM D3574-86, the compression hardness, elongation, compression set, and repeated compression set of the sample were measured using UTM (Universal Testing Machine), and the results are shown in Table 2 below. It was.

polyol
composition process time Formability 25% compression hardness ³⁾ 50% compression hardness ⁴⁾ elongation compression
everlasting
reduction rate repeat
compression
reduction rate CT ¹⁾ RT ²⁾ unit - hour sec kgf/ ^cm2 % Example 1 Manufacturing Example 1 20 8 92 0.08 0.16 65 7 8 Example 2 Production example 2 20 8 92 0.09 0.16 66 8 7 Example 3 Production example 3 20 8 93 0.08 0.16 64 8 10 Example 4 Production example 4 20 8 92 0.09 0.16 66 7 10 Example 5 Production example 5 20 8 93 0.08 0.15 66 7 8 Example 6 Production example 6 20 8 93 0.09 0.16 65 8 8 Comparative Example 1 Comparative Manufacturing Example 1 30 12 110 0.07 0.15 62 8 9 Comparative Example 2 Comparative Manufacturing Example 2 31 14 125 0.06 0.13 63 10 12 Comparative Example 3 Comparative Manufacturing Example 3 30 12 115 0.07 0.15 61 8 10 Comparative Example 4 Comparative Manufacturing Example 4 31 14 124 0.06 0.14 62 10 12 1) CT: Cream Time
2) RT: Rise Time
3) 25% compression hardness: Repulsion force when the sample is compressed by 25%
4) 50% compression hardness: Repulsion force when the sample is compressed by 25%

As can be seen in Tables 1 and 2 above, the polyol compositions according to Preparation Examples 1 to 6, which can be manufactured from renewable natural resources, show a lower acid value compared to the polyol compositions according to Comparative Preparation Examples 1 to 4. there was.

Accordingly, the polyol composition according to Preparation Examples 1 to 6 has improved reactivity with the isocyanate-based composition compared to the polyol composition according to Comparative Preparation Examples 1 to 4, the process time for producing polyurethane foam is reduced, and 6 6 moldability is improved. This improvement could be confirmed.

In addition, it was confirmed that the polyurethane foams of Examples 1 to 6 manufactured from Preparation Examples 1 to 6 exhibited mechanical properties equal to or better than those of the polyurethane foams of Comparative Examples 1 to 4 manufactured from petroleum-based raw materials.

Therefore, the polyol composition according to the present invention and the polyurethane foam containing it are environmentally friendly because they do not use petroleum-based raw materials, and have a low acid value, improving the efficiency of process time and moldability, and having mechanical properties that are equivalent to or better than those of petroleum-based raw materials. It was confirmed that it represents .

100: Battery module
101: housing
102: battery cell
103: Polyurethane foam
104: Thermal conductive adhesive

Claims (13)

A first unit derived from at least one type of 1,4:3,6-dianhydrohexitol; and
comprising a second unit derived from an alkylene oxide,
A polyol composition having an acid value of less than 0.02 mgKOH/g according to the following measurement method:
<Measurement method>
1) Prepare a first flask containing the polyol composition and a second flask without the polyol composition, add 50 ml of methanol to each of the first flask and the second flask, and then stir for 30 minutes.
2) Add 0.5 ml of 1% phenolphthalein indicator to each of the first flask and the second flask, and mix with 0.02N potassium hydroxide (KOH) until the composition of the first flask and the second flask turns pink for 30 seconds. Titrate.
3) Calculate the acid value according to Equation 1 below.
[Equation 1]
Acid value (mgKOH/g) = [(V _s - V _b ) × 56.1 × N × F]/M
(In Equation 1, V _s is the amount (ml) of the 0.02N potassium hydroxide (KOH) consumed to titrate the composition of the first flask, and V _b is the amount (ml) consumed to titrate the composition of the second flask. is the amount (ml) of the 0.02N potassium hydroxide (KOH) consumed, N is the normal concentration of the potassium hydroxide (KOH), and F is the factor of the 0.02N potassium hydroxide (KOH), The M is the weight (g) of the polyol composition added to the first flask.) According to paragraph 1,
A polyol composition wherein the at least one type of 1,4:3,6-dianhydrohexitol includes isosorbide. According to paragraph 1,
A polyol composition wherein the active oxygen content of the polyol composition is 100 ppm or less. According to paragraph 1,
The polyol composition further includes an antioxidant. According to paragraph 4,
A polyol composition comprising 0.03% by weight to 1.00% by weight of the antioxidant, based on the total weight of the polyol composition. According to paragraph 1,
The polyol composition has a number average molecular weight (Mn) of 300 g/mol to 12,000 g/mol. According to paragraph 1,
The polyol composition has a viscosity of 300 cPs to 600 cPs at 25°C. According to paragraph 1,
A polyol composition wherein the second unit derived from the alkylene oxide includes a substituted or unsubstituted branched alkylene group having 3 to 10 carbon atoms. According to clause 8,
A polyol composition wherein the branched alkylene group is bonded to the first unit derived from the 1,4:3,6-dianhydrohexitol. According to clause 9,
A polyol composition wherein the second unit derived from the alkylene oxide includes a substituted or unsubstituted linear alkylene group having 2 to 10 carbon atoms. According to clause 10,
A polyol composition wherein the linear alkylene group is bonded to the branched alkylene group. It contains at least one first unit derived from 1,4:3,6-dianhydrohexitol and a second unit derived from alkylene oxide, and has an acid value of 0.02 according to the following measurement method. polyol composition less than mgKOH/g; and a composition for producing polyurethane comprising an isocyanate-based composition:
<Measurement method>
1) Prepare a first flask containing the polyol composition and a second flask without the polyol composition, add 50 ml of methanol to each of the first flask and the second flask, and then stir for 30 minutes.
2) Add 0.5 ml of 1% phenolphthalein indicator to each of the first flask and the second flask, and mix with 0.02N potassium hydroxide (KOH) until the composition of the first flask and the second flask turns pink for 30 seconds. Titrate.
3) Calculate the acid value according to Equation 1 below.
[Equation 1]
Acid value (mgKOH/g) = [(V _s - V _b ) × 56.1 × N × F]/M
(In Equation 1, V _s is the amount (ml) of the 0.02N potassium hydroxide (KOH) consumed to titrate the composition of the first flask, and V _b is the amount (ml) consumed to titrate the composition of the second flask. is the amount (ml) of the 0.02N potassium hydroxide (KOH) consumed, N is the normal concentration of the potassium hydroxide (KOH), and F is the factor of the 0.02N potassium hydroxide (KOH), The M is the weight (g) of the polyol composition added to the first flask.)
housing;
a plurality of battery cells accommodated within the housing; and
A battery module comprising polyurethane foam disposed between the plurality of battery cells,
The polyurethane foam includes a composition for producing polyurethane including a polyol composition and an isocyanate-based composition,
The polyol composition includes at least one first unit derived from 1,4:3,6-dianhydrohexitol, and a second unit derived from alkylene oxide, and has an acid value (Acid) according to the following measurement method. A battery module having a Value of less than 0.02 mgKOH/g:
<Measurement method>
1) Prepare a first flask containing the polyol composition and a second flask without the polyol composition, add 50 ml of methanol to each of the first flask and the second flask, and then stir for 30 minutes.
2) Add 0.5 ml of 1% phenolphthalein indicator to each of the first flask and the second flask, and mix with 0.02N potassium hydroxide (KOH) until the composition of the first flask and the second flask turns pink for 30 seconds. Titrate.
3) Calculate the acid value according to Equation 1 below.
[Equation 1]
Acid value (mgKOH/g) = [(V _s - V _b ) × 56.1 × N × F]/M
(In Equation 1, V _s is the amount (ml) of the 0.02N potassium hydroxide (KOH) consumed to titrate the composition of the first flask, and V _b is the amount (ml) consumed to titrate the composition of the second flask. is the amount (ml) of the 0.02N potassium hydroxide (KOH) consumed, N is the normal concentration of the potassium hydroxide (KOH), and F is the factor of the 0.02N potassium hydroxide (KOH), The M is the weight (g) of the polyol composition added to the first flask.)