KR20230057261A - Rigid polyurethane foam and method for preparing the same - Google Patents

Abstract

A rigid polyurethane foam of the present invention is the rigid polyurethane foam manufactured by mixing and reacting a polyol composition comprising isophthalic acid-based polyester polyol, expanded graphite, melamine, and 1-chloro-3,3,3-trifluoropropene, and diphenylmethane diisocyanate, wherein a polyisocyanurate ratio (PIR ratio) according to formula 1 is 5 to 6.5, and a residual diphenylmethane diisocyanate ratio (MDI ratio) according to formula 2 is 0.1 to 0.5. The rigid polyurethane foam has excellent semi-incombustibility, thermal insulation, and compressive strength.

Description

Rigid polyurethane foam and its manufacturing method {RIGID POLYURETHANE FOAM AND METHOD FOR PREPARING THE SAME}

The present invention relates to a rigid polyurethane foam and a manufacturing method thereof. More specifically, the present invention relates to a rigid polyurethane foam having excellent semi-incombustibility, heat insulation, compressive strength, and the like, and a method for manufacturing the same.

Rigid polyurethane foam is one of the most popular insulators in terms of industrial and thermal insulation. However, since the insulation material is the most vulnerable to fire, heat, etc. among building materials, in order to prevent the spread of fire in the event of a fire, the voice that the standards for quasi-incombustibility (flammability and harmful gas reduction) of the insulation material should be strengthened is gradually increasing.

In order to satisfy the reinforced quasi-incombustibility evaluation criteria for insulators, the heat release amount of the core material itself, excluding the face material (Al-GF film, etc.) surrounding the core material (hard polyurethane foam, etc.), must satisfy the quasi-incombustibility evaluation criteria. However, existing rigid urethane foams cannot obtain a heat release amount that satisfies the semi-incombustible evaluation criteria.

Therefore, it is necessary to develop a rigid polyurethane foam having excellent semi-incombustibility (flame retardancy and harmful gas reduction), heat insulation, compressive strength, and the like.

The background art of the present invention is disclosed in Korean Patent Publication No. 10-2009-0095889 and the like.

An object of the present invention is to provide a rigid polyurethane foam having excellent semi-incombustibility, heat insulation, compressive strength, and the like.

Another object of the present invention is to provide a method for producing the rigid polyurethane foam.

The above and other objects of the present invention can all be achieved by the present invention described below.

1. One aspect of the present invention relates to rigid polyurethane foam. The rigid polyurethane foam may include a polyol composition including isophthalic acid-based polyester polyol, expanded graphite, melamine, and 1-chloro-3,3,3-trifluoropropene; And diphenylmethane diisocyanate; It is a rigid polyurethane foam prepared by mixing and reacting, the polyisocyanurate ratio (PIR ratio) according to the following formula 1 is 5 to 6.5, and the residual diphenylmethanedi according to the following formula 2 Characterized in that the isocyanate ratio (MDI ratio) is 0.1 to 0.5:

[Equation 1]

Polyisocyanurate ratio (PIR ratio) = PIR / (PUR + Urea + PIR + MDI)

[Equation 2]

Residual diphenylmethane diisocyanate ratio (MDI ratio) = MDI / (PUR + Urea + PIR + MDI)

In the above formulas 1 and 2, PUR + Urea + PIR + MDI is the FT-IR absorbance of a phenyl group (1,565 to 1,625 cm ^-1 range) commonly included in polyurethane, urea, polyisocyanurate and diphenylmethane diisocyanate value, PIR is the FT-IR absorbance value of the isocyanurate group-containing polyisocyanurate structure (1,340 to 1,465 cm ^-1 range), and MDI is the isocyanate group (2,200 to 2,317 cm ^-1 range) FT-IR is the absorbance value.

2. In the first embodiment, the isophthalic acid-based polyester polyol may be represented by Formula 1 below:

[Formula 1]

중 적어도 하나로 치환되거나 비치환된 직쇄 또는 분지쇄의 탄소수 1 내지 6의 알킬렌기; 또는 히드록시기 및

중 적어도 하나로 치환되거나 비치환된 직쇄 또는 분지쇄의 탄소수 2 내지 6의 에테르기;이고, L₂는 히드록시기로 치환 또는 비치환된 직쇄 또는 분지쇄의 탄소수 1 내지 5의 알킬렌기; 또는 히드록시기로 치환 또는 비치환된 직쇄 또는 분지쇄의 탄소수 1 내지 5의 에테르기;이며, m은 1 내지 50의 정수이고, n은 1 내지 21의 정수이다.In Formula 1, L ₁ is a hydroxy group and

a linear or branched alkylene group having 1 to 6 carbon atoms, which is unsubstituted or substituted with at least one of; or a hydroxyl group and

A straight-chain or branched-chain ether group having 2 to 6 carbon atoms, substituted or unsubstituted with at least one of; and, L ₂ is a hydroxy group-substituted or unsubstituted straight-chain or branched-chain alkylene group having 1 to 5 carbon atoms; Or a straight-chain or branched chain ether group having 1 to 5 carbon atoms unsubstituted or substituted with a hydroxy group; m is an integer of 1 to 50, and n is an integer of 1 to 21.

3. In the embodiment 1 or 2, the isophthalic acid-based polyester polyol may have a hydroxyl value (OH value) of 10 to 500 mgKOH/g.

4. In the above 1 to 3 embodiments, the isophthalic acid-based polyester polyol may have a weight average molecular weight of 200 to 10,000 g/mol.

5. In the embodiments 1 to 4, the polyol composition includes 100 parts by weight of the isophthalic acid-based polyester polyol; 0.5 to 5 parts by weight of the expanded graphite; 10 to 40 parts by weight of the melamine; and 5 to 40 parts by weight of the 1-chloro-3,3,3-trifluoropropene.

6. In embodiments 1 to 5, the weight ratio of the isophthalic acid-based polyester polyol and the diphenylmethane diisocyanate may be 1:1.5 to 1:3.

7. In the embodiments 1 to 6, the rigid polyurethane foam may have a heat release rate of 2 to 8 MJ/m ² as measured by a cone calorimeter according to KS F ISO 5660-1.

8. In the embodiments 1 to 6, the rigid polyurethane foam may have a gas generation amount of 50 to 100 m ² /m ² measured by a cone calorimeter according to KS F ISO 5660-1.

9. In the embodiments 1 to 8, the rigid polyurethane foam may have a thermal conductivity of 0.018 to 0.022 W/m·K measured according to KS M 3809.

10. In the embodiments 1 to 9, the rigid polyurethane foam may have a compressive strength of 10 to 40 N/cm ² measured according to KS M 3809.

11. Another aspect of the present invention relates to a method for producing rigid polyurethane foam. The manufacturing method includes mixing an isophthalic acid-based polyester polyol, a polyol composition including expanded graphite, melamine, and 1-chloro-3,3,3-trifluoropropene, and diphenylmethane diisocyanate; And reacting such that the polyisocyanurate ratio (PIR ratio) according to the following formula 1 is 5 to 6.5 and the residual diphenylmethane diisocyanate ratio (MDI ratio) according to the following formula 2 is 0.1 to 0.5:

[Equation 1]

Polyisocyanurate ratio (PIR ratio) = PIR / (PUR + Urea + PIR + MDI)

[Equation 2]

Residual diphenylmethane diisocyanate ratio (MDI ratio) = MDI / (PUR + Urea + PIR + MDI)

In the above formulas 1 and 2, PUR + Urea + PIR + MDI is the FT-IR absorbance of a phenyl group (1,565 to 1,625 cm ^-1 range) commonly included in polyurethane, urea, polyisocyanurate and diphenylmethane diisocyanate value, PIR is the FT-IR absorbance value of the isocyanurate group-containing polyisocyanurate structure (1,340 to 1,465 cm ^-1 range), and MDI is the isocyanate group (2,200 to 2,317 cm ^-1 range) FT-IR is the absorbance value.

12. In the 11th embodiment, the reaction may be performed under a temperature condition of 30 to 70° C. and a pressure condition of 0.8 to 1.5 kgf/cm ² in the presence of a catalyst including an organometallic catalyst.

13. In the 11th or 12th embodiment, the polyol composition comprises 100 parts by weight of the isophthalic acid-based polyester polyol; 0.5 to 5 parts by weight of the expanded graphite; 10 to 40 parts by weight of the melamine; and 5 to 40 parts by weight of the 1-chloro-3,3,3-trifluoropropene.

14. In the embodiments 10 to 13, the weight ratio of the isophthalic acid-based polyester polyol and the diphenylmethane diisocyanate may be 1:1.5 to 1:3.

The present invention has the effect of providing a rigid polyurethane foam having excellent semi-incombustibility, heat insulation, compressive strength, and the like, and a manufacturing method thereof.

Hereinafter, the present invention will be described in detail as follows.

The rigid polyurethane foam according to the present invention includes (A) a polyol composition comprising isophthalic acid-based polyester polyol, expanded graphite, melamine, and 1-chloro-3,3,3-trifluoropropene; And (B) diphenylmethane diisocyanate; it is prepared by mixing and reacting.

In this specification, "a to b" representing a numerical range is defined as "≥a and ≤b".

(A) polyol composition

The polyol composition according to one embodiment of the present invention can form a rigid polyurethane foam by reacting with diphenylmethane diisocyanate, (a) isophthalic acid-based polyester polyol, (b) expanded graphite, (c) melamine and (d) 1-chloro-3,3,3-trifluoropropene.

(a) isophthalic acid-based polyester polyol

Isophthalic acid-based polyester polyol according to one embodiment of the present invention has excellent reactivity with diphenylmethane isocyanate and can improve semi-incombustibility, heat insulation, compressive strength, etc. of rigid polyurethane foam, and is represented by the following formula (1) The isophthalic acid-based polyester polyols shown can be used.

[Formula 1]

중 적어도 하나로 치환되거나 비치환된 직쇄 또는 분지쇄의 탄소수 1 내지 6의 알킬렌기; 또는 히드록시기 및

중 적어도 하나로 치환되거나 비치환된 직쇄 또는 분지쇄의 탄소수 2 내지 6의 에테르기;이고, L₂는 히드록시기로 치환 또는 비치환된 직쇄 또는 분지쇄의 탄소수 1 내지 5의 알킬렌기; 또는 히드록시기로 치환 또는 비치환된 직쇄 또는 분지쇄의 탄소수 1 내지 5의 에테르기;이며, m은 1 내지 50의 정수이고, n은 1 내지 21의 정수이다.In Formula 1, L ₁ is a hydroxy group and

a linear or branched alkylene group having 1 to 6 carbon atoms, which is unsubstituted or substituted with at least one of; or a hydroxyl group and

A straight-chain or branched-chain ether group having 2 to 6 carbon atoms, substituted or unsubstituted with at least one of; and, L ₂ is a hydroxy group-substituted or unsubstituted straight-chain or branched-chain alkylene group having 1 to 5 carbon atoms; Or a straight-chain or branched chain ether group having 1 to 5 carbon atoms unsubstituted or substituted with a hydroxy group; m is an integer of 1 to 50, and n is an integer of 1 to 21.

;

;

;

;

; 또는

이고, n은 3 내지 21의 정수이다.In embodiments, L ₁ is -CH ₂ -CH ₂ -; -CH ₂ -C(CH ₃ ) ₂ -CH ₂ -; -CH ₂ -C(CH ₂ CH ₃ )(CH ₂ OH)-CH ₂ -; -CH ₂ -CH(CH ₃ )-CH ₂ -; -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -; -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -;

;

;

;

;

; or

And, n is an integer from 3 to 21.

In an embodiment, L ₂ is -CH ₂ -; -C(CH ₃ ) ₂ -CH ₂ -; -C(CH ₂ CH ₃ )(CH ₂ OH)-CH ₂ -; -CH(CH ₃ )-CH ₂ -; -CH ₂ -OCH ₂ -CH ₂ -; or -CH ₂ -O-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -.

In embodiments, L ₁ may be -CH ₂ -CH ₂ -, and L ₂ may be -CH ₂ -.

In an embodiment, the isophthalic acid-based polyester polyol is prepared by reacting isophthalic acid with an alcohol represented by the following Chemical Formula 2 to prepare a polyol represented by the following Chemical Formula 3, and the polyol represented by the following Chemical Formula 3 is represented by the following Chemical Formula 4 It can be prepared by reacting with a compound.

[Formula 2]

[Formula 3]

[Formula 4]

In Formulas 2 to 4, L ₃ is a linear or branched chain alkylene group having 2 to 6 carbon atoms, unsubstituted or substituted with a hydroxyl group; Or a straight or branched chain ether group having 2 to 6 carbon atoms unsubstituted or substituted with a hydroxy group, m is an integer of 1 to 50, and n is an integer of 3 to 21.

In an embodiment, the compound represented by Formula 2 may be added in an amount of 1.1 to 2.5 moles based on 1 mole of isophthalic acid, and the reaction between isophthalic acid and the alcohol represented by Formula 2 is carried out at normal pressure and 140 to 2.5 moles. It can be carried out at 240 ℃ conditions.

In an embodiment, the compound represented by Formula 4 may be added in an amount of 0.01 mol to 0.1 mol based on 1 mol of the polyol represented by Formula 3, and the compound represented by Formula 4 and the compound represented by Formula 3 may be added. The reaction of the polyol to be is in the presence of an acid base catalyst, the reaction may be carried out under normal pressure and 100 to 220 ℃ conditions.

In embodiments, the isophthalic acid-based polyester polyol may have a hydroxyl value (OH value) of 10 to 500 mgKOH/g measured in accordance with JIS K1557-1:2007. Within this range, the required rigid polyurethane foam can be formed.

In embodiments, the isophthalic acid-based polyester polyol may have a weight average molecular weight of 200 to 10,000 g/mol as measured by gel permeation chromatography (GPC).

(b) expanded graphite

Expanded graphite according to one embodiment of the present invention is applied as a polyol composition, such as isophthalic acid-based polyester polyol, melamine, and 1-chloro-3,3,3-trifluoropropene, etc., to improve semi-incombustibility of rigid urethane foam. As an improvement, ordinary expanded graphite can be used.

In embodiments, the expanded graphite may use expanded graphite having an expansion start temperature of 200°C or higher, for example, 200 to 260°C. Within this range, semi-incombustibility of the rigid polyurethane foam may be excellent.

In a specific embodiment, the expanded graphite has an average particle size (D50, particle diameter at the point where the distribution ratio is 50%) measured by a particle size analyzer (LS 13 320 (Beckman Coulter)) of 20 to 120 μm, for example, 50 to may be 90 μm. Within the above range, the stability of the liquid may be excellent, and the quasi-incombustibility of the rigid polyurethane foam may be excellent even with a small content.

In embodiments, the content of the expanded graphite may be 0.5 to 5 parts by weight, for example, 1 to 3 parts by weight, based on 100 parts by weight of the isophthalic acid-based polyester polyol. Within this range, semi-incombustibility of the rigid urethane foam may be excellent.

(c) melamine

Melamine according to one embodiment of the present invention is applied as a polyol composition with isophthalic acid-based polyester polyol, expanded graphite and 1-chloro-3,3,3-trifluoropropene, etc. , harmful gas reduction), etc., it is possible to use ordinary melamine (1,3,5-triazine-2,4,6-triamine).

In embodiments, the content of the melamine may be 10 to 40 parts by weight, for example, 15 to 35 parts by weight, based on 100 parts by weight of the isophthalic acid-based polyester polyol. Within this range, semi-incombustibility of the rigid polyurethane foam may be excellent.

(d) 1-chloro-3,3,3-trifluoropropene

The 1-chloro-3,3,3-trifluoropropene of the present invention can act as a blowing agent without impairing thermal insulation properties, formability, and processability, and is commercially available 1-chloro-3,3,3-trifluoropropene. Fluoropropene may be used.

In embodiments, the content of 1-chloro-3,3,3-trifluoropropene is 5 to 40 parts by weight, for example 10 to 35 parts by weight, based on 100 parts by weight of the isophthalic acid-based polyester polyol. can The amount (content) of the 1-chloro-3,3,3-trifluoropropene may be varied in order to control the free foaming density of the rigid polyurethane foam, and within the above range, the insulation properties and foaming efficiency are improved. can be excellent

The polyol composition according to one embodiment of the present invention may further include additives used in conventional polyol compositions within a range that does not impair the objects and effects of the present invention. Examples of the additive include flame retardants, foam stabilizers, surface active materials, foam stabilizers, cell control agents, fillers, dyes, pigments, and combinations thereof, but are not limited thereto. When using the additive, the content thereof may be 0.001 to 40 parts by weight, for example, 0.05 to 25 parts by weight, based on 100 parts by weight of the isophthalic acid-based polyester polyol.

(B) diphenylmethane diisocyanate

Diphenylmethane diisocyanate (MDI) of the present invention can react with the polyol composition to form a rigid polyurethane foam, and 4,4'-diphenylmethane diisocyanate (P-MDI) can be used.

In embodiments, the weight ratio of the isophthalic acid-based polyester polyol and the diphenylmethane diisocyanate may be 1:1.5 to 1:3, for example, 1:1.7 to 1:2.3. In the above range, rigid polyurethane having the polyisocyanurate ratio (PIR ratio) and residual diphenylmethane diisocyanate ratio (MDI ratio) of the present invention, gas hazards are reduced, and excellent semi-incombustibility, heat insulation, compressive strength, etc. form can be formed.

Rigid polyurethane foam according to one embodiment of the present invention is a polyurethane structure (urethane reaction), isocyanurate structure (trimerization reaction), urea structure ( urea reaction), etc., the polyisocyanurate ratio (PIR ratio) according to the following formula 1 is 5 to 6.5, for example, 5.1 to 6.2, and the residual diphenylmethane diisocyanate ratio according to the following formula 2 ( MDI ratio) is 0.1 to 0.5, for example, 0.1 to 0.3.

[Equation 1]

Polyisocyanurate ratio (PIR ratio) = PIR / (PUR + Urea + PIR + MDI)

[Equation 2]

Residual diphenylmethane diisocyanate ratio (MDI ratio) = MDI / (PUR + Urea + PIR + MDI)

In the above formulas 1 and 2, PUR + Urea + PIR + MDI is the FT-IR absorbance of a phenyl group (1,565 to 1,625 cm ^-1 range) commonly included in polyurethane, urea, polyisocyanurate and diphenylmethane diisocyanate value, PIR is the FT-IR absorbance value of the isocyanurate group-containing polyisocyanurate structure (1,340 to 1,465 cm ^-1 range), and MDI is the isocyanate group (NCO) (2,200 to 2,317 cm ^-1 range) is the FT-IR absorbance value.

When the polyisocyanurate ratio (PIR ratio) is less than 5, there is a concern that the semi-incombustibility and compressive strength of the rigid polyurethane foam may decrease, and when the PIR ratio exceeds 6.5, the heat insulation property of the rigid polyurethane foam decreases, There is a risk of increased gas hazards.

If the residual diphenylmethane diisocyanate ratio (MDI ratio) is less than 0.1, there is a concern that the semi-incombustibility, compressive strength, etc. of rigid polyurethane foam may decrease, and if it exceeds 0.5, the gas hazard of rigid polyurethane foam increases. there is a risk of

Rigid polyurethane foam according to one embodiment of the present invention may be prepared according to a known rigid polyurethane foam manufacturing method. For example, mixing the polyol composition and the diphenylmethane diisocyanate; And it can be prepared by reacting the polyol composition and the diphenylmethane diisocyanate to have the polyisocyanurate ratio (PIR ratio) and the residual diphenylmethane diisocyanate ratio (MDI ratio).

In embodiments, the reaction is carried out at a temperature of 30 to 70 °C, for example, 40 to 50 °C, and 0.8 to 1.5 kgf/cm ² , for example 0.9 to 1.2 kgf/cm, in the presence of a catalyst including an organometallic catalyst. It can be performed under ² pressure conditions. In the above range, it is possible to obtain a rigid polyurethane foam having the polyisocyanurate ratio (PIR ratio) and the residual diphenylmethane diisocyanate ratio (MDI ratio), and the semi-incombustibility, heat insulation, and compressive strength of the rigid polyurethane foam etc. can be excellent.

In embodiments, the organometallic catalyst includes potassium-2-ethylhexanoate, tin(II)2-ethylhexanoate, a combination thereof, and the like. can be used In addition, as a catalyst that can be used together with the organometallic catalyst, pentamethyldiethylenetriamine (PMDETA), N,N-dimethylcyclohexylamine (DMCHA), etc. are amine-based catalysts. can be exemplified.

The rigid polyurethane foam according to one embodiment of the present invention may have a density of 20 to 50 kg/m ³ , for example, 35 to 45 kg/m ³ as measured in accordance with JIS K7222.

In embodiments, the rigid polyurethane foam may have a heat release rate of 2 to 8 MJ/m ² , for example 4 to 8 MJ/m ² , as measured by a cone calorimeter, in accordance with KS F ISO 5660-1. .

In a specific embodiment, the rigid polyurethane foam has a gas generation amount of 50 to 100 m ² /m ² , for example 60 to 90 m ² /m, as measured by a cone calorimeter, in accordance with KS F ISO 5660-1 can be ²

In a specific embodiment, the rigid polyurethane foam may have a thermal conductivity of 0.018 to 0.022 W/m·K, for example, 0.019 to 0.021 W/m·K, measured according to KS M 3809.

In embodiments, the rigid polyurethane foam may have a compressive strength of 10 to 40 N/cm ² , for example 13 to 30 N/cm ² , as measured in accordance with KS M 3809.

Hereinafter, the present invention will be described in more detail through examples, but these examples are only for the purpose of explanation and should not be construed as limiting the present invention.

Example

Hereinafter, specifications of each component used in Examples and Comparative Examples are as follows.

(A) polyester polyol

(A1) Isophthalic acid-based polyester polyol (manufacturer: Lotte Chemical, product name: FIP-2160) was used.

(A2) A terephthalic acid-based polyester polyol (manufacturer: Woozo Hitech, product name: W7204) was used.

(B) expanded graphite

Expanded graphite (manufacturer: Seongha, product name: Expandable Graphite) was used.

(C) Melamine

Melamine (manufacturer: Samjeon Pure Medicine, product name: Melamine) was used.

(D) blowing agent

(D1) 1-chloro-3,3,3-trifluoropropene (manufacturer: Honeywell, product name: Solstice LBA) was used.

(D2) Cyclopentane (CP, manufacturer: Yeochun NCC, product name: cyclo pentane) was used.

(E) diphenylmethane diisocyanate

4,4'-diphenylmethane diisocyanate (P-MDI, manufacturer: BASF, product name: LUPRANATE M50, viscosity: 450 to 650 cP) was used.

Example 1 and Comparative Examples 1 to 3

A polyisocyanate compound ( E) was mixed, and then reacted (free foaming) in the presence of a catalyst containing potassium-2-ethylhexanoate at a temperature of 50°C and a pressure of 1.0 kgf/cm ² to form a rigid poly A urethane foam was prepared. For the prepared rigid polyurethane foam, physical properties were evaluated by the following method, and the results are shown in Table 1 below.

How to measure physical properties

(1) Polyisocyanurate ratio (PIR ratio) and residual diphenylmethane diisocyanate ratio (MDI ratio): according to the following formulas 1 and 2, polyisocyanurate ratio and residual diphenylmethane diisocyanate of rigid polyurethane foam rain was calculated.

[Equation 1]

Polyisocyanurate ratio (PIR ratio) = PIR / (PUR + Urea + PIR + MDI)

[Equation 2]

Residual diphenylmethane diisocyanate ratio (MDI ratio) = MDI / (PUR + Urea + PIR + MDI)

In the above formulas 1 and 2, PUR + Urea + PIR + MDI is the FT-IR absorbance of a phenyl group (1,565 to 1,625 cm ^-1 range) commonly included in polyurethane, urea, polyisocyanurate and diphenylmethane diisocyanate value, PIR is the FT-IR absorbance value of the isocyanurate group-containing polyisocyanurate structure (1,340 to 1,465 cm ^-1 range), and MDI is the isocyanate group (2,200 to 2,317 cm ^-1 range) FT-IR is the absorbance value.

Here, the FT-IR measurement was performed using the ATR mode of an iS50 model IR measuring device manufactured by Thermo Scientific, and a range from 400 to 4,000 cm ^-1 at a resolution of 8 cm ^-1 was measured at room temperature. Specifically, after contacting the cross-section of the polyurethane foam specimen with the diamond cell of the ATR, turning the screw at the top so that the cross-section adheres to the measuring instrument, measurement was performed, and FT-IR measurement Then, after measuring the spectrum with OMNIC Spectra software, an absorbance peak value (FT-IR absorbance value) in a designated wavelength range was measured.

(2) Heat release rate (unit: MJ/m ² ): In accordance with KS F ISO 5660-1, the heat release rate of the rigid polyurethane foam specimen was measured with a cone calorimeter (manufacturer: FESTEC, device name: Cone Calorimeter).

(3) Gas generation amount (unit: m ² /m ² ): In accordance with KS F ISO 5660-1, gas generation amount was measured with a cone calorimeter (manufacturer: FESTEC, device name: Cone Calorimeter).

(4) Thermal conductivity (unit: W/m K): According to KS M 3809, the thermal conductivity of the rigid polyurethane foam specimen was measured.

(5) Compressive strength (unit: N/cm ² ): In accordance with KS M 3809, the compressive strength of rigid polyurethane foam specimens was measured.

Example comparative example One One 2 3 (A1) (parts by weight) 100 - 100 100 (A2) (parts by weight) - 100 - - (B) (parts by weight) 1.5 1.5 1.5 1.5 (C) (parts by weight) 30 30 30 - (D1) (parts by weight) 30 30 - 30 (D2) (parts by weight) - - 30 - (E) (parts by weight) 200 200 200 200 PIR ratio 5.2 4.5 3.8 5.1 MDI ratio 0.2 0.6 0.2 0.2 Heat release rate (MJ/m ² ) 6.8 11.8 15.1 6.5 Gas generation (m ² /m ² ) 70 110 80 120 Thermal conductivity (W/m K) 0.020 0.020 0.024 0.020 Compressive Strength (N/cm ² ) 15 14 12 14

From the above results, it can be seen that the rigid polyurethane foam of the present invention is excellent in semi-incombustibility (reduced heat release rate, reduced gas emission), heat insulation (thermal conductivity), compressive strength, and the like.

On the other hand, in the case of Comparative Example 1 in which terephthalic acid-based polyester polyol (A2) was applied instead of the isophthalic acid-based polyester polyol of the present invention, the PIR ratio and MDI ratio were out of the scope of the present invention, and semi-inflammable (reduced heat release rate, It can be seen that the gas emission reduction) and the like are reduced, and in the case of Comparative Example 2 in which cyclopentane (D2) is applied instead of 1-chloro-3,3,3-trifluoropropene (D1) of the present invention, PIR It can be seen that the ratio is out of the scope of the present invention, semi-incombustibility (reduced heat release rate), insulation, etc. are lowered, and the compressive strength is relatively lowered. In the case of Comparative Example 3 in which melamine is not applied, reduction), etc., can be seen.

So far, the present invention has been looked at mainly through embodiments. Those skilled in the art to which the present invention pertains will be able to understand that the present invention can be implemented in a modified form without departing from the essential characteristics of the present invention. Therefore, the disclosed embodiments should be considered from an illustrative rather than a limiting point of view. The scope of the present invention is shown in the claims rather than the foregoing description, and all differences within the equivalent scope will be construed as being included in the present invention.

Claims (14)

a polyol composition comprising isophthalic acid-based polyester polyol, expanded graphite, melamine, and 1-chloro-3,3,3-trifluoropropene; And diphenylmethane diisocyanate; a rigid polyurethane foam prepared by mixing and reacting,
Rigid polyurethane foam, characterized in that the polyisocyanurate ratio (PIR ratio) according to the following formula 1 is 5 to 6.5, and the residual diphenylmethane diisocyanate ratio (MDI ratio) according to the following formula 2 is 0.1 to 0.5:
[Equation 1]
Polyisocyanurate ratio (PIR ratio) = PIR / (PUR + Urea + PIR + MDI)
[Equation 2]
Residual diphenylmethane diisocyanate ratio (MDI ratio) = MDI / (PUR + Urea + PIR + MDI)
In the above formulas 1 and 2, PUR + Urea + PIR + MDI is the FT-IR absorbance of a phenyl group (1,565 to 1,625 cm ^-1 range) commonly included in polyurethane, urea, polyisocyanurate and diphenylmethane diisocyanate value, PIR is the FT-IR absorbance value of the isocyanurate group-containing polyisocyanurate structure (1,340 to 1,465 cm ^-1 range), and MDI is the isocyanate group (2,200 to 2,317 cm ^-1 range) FT-IR is the absorbance value.
The rigid polyurethane foam according to claim 1, wherein the isophthalic acid-based polyester polyol is represented by Formula 1 below:
[Formula 1]

In Formula 1, L ₁ is a hydroxy group and

a linear or branched alkylene group having 1 to 6 carbon atoms, which is unsubstituted or substituted with at least one of; or a hydroxyl group and

A straight-chain or branched-chain ether group having 2 to 6 carbon atoms, substituted or unsubstituted with at least one of; and, L ₂ is a hydroxy group-substituted or unsubstituted straight-chain or branched-chain alkylene group having 1 to 5 carbon atoms; Or a straight-chain or branched chain ether group having 1 to 5 carbon atoms unsubstituted or substituted with a hydroxy group; m is an integer of 1 to 50, and n is an integer of 1 to 21.
The rigid polyurethane foam according to claim 1, wherein the isophthalic acid-based polyester polyol has an OH value of 10 to 500 mgKOH/g.
The rigid polyurethane foam according to claim 1, wherein the isophthalic acid-based polyester polyol has a weight average molecular weight of 200 to 10,000 g/mol.
The method of claim 1, wherein the polyol composition comprises 100 parts by weight of the isophthalic acid-based polyester polyol; 0.5 to 5 parts by weight of the expanded graphite; 10 to 40 parts by weight of the melamine; and 5 to 40 parts by weight of the 1-chloro-3,3,3-trifluoropropene.
The rigid polyurethane foam according to claim 1, wherein the isophthalic acid-based polyester polyol and the diphenylmethane diisocyanate have a weight ratio of 1:1.5 to 1:3.
The rigid polyurethane foam according to claim 1, wherein the rigid polyurethane foam has a heat release rate of 2 to 8 MJ/m ² as measured by a cone calorimeter in accordance with KS F ISO 5660-1.
The rigid polyurethane foam according to claim 1, wherein the rigid polyurethane foam has a gas generation amount of 50 to 100 m ² /m ² as measured by a cone calorimeter in accordance with KS F ISO 5660-1.
The rigid polyurethane foam according to claim 1, wherein the rigid polyurethane foam has a thermal conductivity of 0.018 to 0.022 W/m·K measured in accordance with KS M 3809.
The rigid polyurethane foam according to claim 1, wherein the rigid polyurethane foam has a compressive strength of 10 to 40 N/cm ² measured according to KS M 3809.
mixing an isophthalic acid-based polyester polyol, a polyol composition comprising expanded graphite, melamine and 1-chloro-3,3,3-trifluoropropene, and diphenylmethane diisocyanate; and
Characterized by comprising the step of reacting such that the polyisocyanurate ratio (PIR ratio) according to the following formula 1 is 5 to 6.5 and the residual diphenylmethane diisocyanate ratio (MDI ratio) according to the following formula 2 is 0.1 to 0.5 Method for producing rigid polyurethane foam to:
[Equation 1]
Polyisocyanurate ratio (PIR ratio) = PIR / (PUR + Urea + PIR + MDI)
[Equation 2]
Residual diphenylmethane diisocyanate ratio (MDI ratio) = MDI / (PUR + Urea + PIR + MDI)
In the above formulas 1 and 2, PUR + Urea + PIR + MDI is the FT-IR absorbance of a phenyl group (1,565 to 1,625 cm ^-1 range) commonly included in polyurethane, urea, polyisocyanurate and diphenylmethane diisocyanate value, PIR is the FT-IR absorbance value of the isocyanurate group-containing polyisocyanurate structure (1,340 to 1,465 cm ^-1 range), and MDI is the isocyanate group (2,200 to 2,317 cm ^-1 range) FT-IR is the absorbance value.
The method of claim 11, wherein the reaction is performed under a temperature condition of 30 to 70° C. and a pressure condition of 0.8 to 1.5 kgf/cm ² in the presence of a catalyst including an organometallic catalyst. .
12. The method of claim 11, wherein the polyol composition comprises 100 parts by weight of the isophthalic acid-based polyester polyol; 0.5 to 5 parts by weight of the expanded graphite; 10 to 40 parts by weight of the melamine; and 5 to 40 parts by weight of the 1-chloro-3,3,3-trifluoropropene.
The method of claim 11, wherein the isophthalic acid-based polyester polyol and the diphenylmethane diisocyanate have a weight ratio of 1:1.5 to 1:3.