Composition for preparing polyester polyol, polyester polyol including naphthalene structure obtained therefrom and polyurethane foam applying the same

Abstract

A composition for preparing a polyester polyol comprises a dicarboxylic acid compound and an alcohol compound, wherein the dicarboxylic acid compound comprises a dicarboxylic acid compound containing a naphthalene structure and a dicarboxylic acid compound containing an aromatic structure other than naphthalene, and the alcohol compound comprises a linear alcohol compound and a non-linear alcohol compound.

Description

Technology Field

[0001] The present invention relates to a composition for manufacturing a polyester polyol, a polyester polyol containing a naphthalene structure produced therefrom, and a polyurethane foam to which the same is applied. Background Technology

[0003] Polyurethane foam can be manufactured by reacting a polyester polyol with a diisocyanate compound. Polyurethane foam with desired physical properties can be obtained by varying the types of polyester polyols or diisocyanate compounds used as raw materials.

[0004] Polyurethane foam can be used for various purposes, such as insulation materials for panels, boards, and sprays.

[0005] Since polyurethane foams used as insulation materials require high flame retardancy, various studies on polyols and compositions have been conducted to improve flame retardancy. The problem to be solved

[0007] The objective of the present invention is to provide a composition for manufacturing a polyester polyol capable of producing a polyester polyol having excellent strength and flame retardant performance and excellent storage stability.

[0008] The objective of the present invention is to provide a polyester polyol having excellent strength and flame retardant performance and excellent storage stability.

[0009] The objective of the present invention is to provide a polyurethane foam having excellent strength and flame-retardant properties using the above-mentioned polyester polyol.

[0010] The objects of the present invention are not limited to those mentioned above, and other unmentioned objects and advantages of the present invention may be understood from the following description and will be more clearly understood by the embodiments of the present invention. Furthermore, it will be readily apparent that the objects and advantages of the present invention can be realized by the means and combinations thereof set forth in the claims. means of solving the problem

[0012] In one embodiment of the present invention, a composition for preparing a polyester polyol is provided, comprising a dicarboxylic acid compound and an alcohol compound, wherein the dicarboxylic acid compound comprises a dicarboxylic acid compound containing a naphthalene structure and a dicarboxylic acid compound containing an aromatic structure other than naphthalene, and the alcohol compound comprises a linear alcohol compound and a non-linear alcohol compound.

[0013] The above dicarboxylic acid compound may contain 30 mol% or less of the naphthalene structure-containing dicarboxylic acid compound based on 100 mol% of the above dicarboxylic acid compound.

[0014] The above dicarboxylic acid compound may contain at least 70 mol% of an aromatic structure-containing dicarboxylic acid compound other than naphthalene, based on 100 mol% of the above dicarboxylic acid compound.

[0015] The above alcohol compound may contain at least 75 mol% of the non-linear alcohol compound based on 100 mol% of the above alcohol compound.

[0016] The above alcohol compound may contain 25 mol% or less of the linear alcohol compound based on 100 mol% of the above alcohol compound.

[0017] The above-mentioned naphthalene structure-containing dicarboxylic acid compound may include at least one selected from the group consisting of 2,6-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, and combinations thereof.

[0018] The dicarboxylic acid-based compound containing an aromatic structure other than the above naphthalene may include at least one selected from the group consisting of phthalic anhydride, terephthalic acid, isophthalic acid, trimellitic anhydride, tetrachlorophthalic anhydride, maleic anhydride, and combinations thereof.

[0019] The above non-linear alcohol compound may include at least one selected from the group consisting of dipropylene glycol, neopentyl glycol, and combinations thereof.

[0020] The above linear alcohol compound may include at least one selected from the group consisting of ethylene glycol, diethylene glycol, and combinations thereof.

[0022] In one embodiment of the present invention, a polyester polyol containing a naphthalene structure is provided by polymerizing the composition for producing the polyester polyol.

[0023] The hydroxyl value of the above naphthalene structure-containing polyester polyol is 220 mgKOH / g to 350 mgKOH / g, and the acid value may be 1 mgKOH / g or less.

[0024] The viscosity of the above naphthalene structure-containing polyester polyol can be 5,000 cps to 30,000 cps at 25°C.

[0026] In one embodiment of the present invention, a polyurethane foam is provided from a composition comprising a naphthalene structure-containing polyester polyol, a diisocyanate, a flame retardant, a foam stabilizer, a catalyst for manufacturing a foam, a foaming agent, and an additive. Effects of the invention

[0028] The naphthalene structure-containing polyester polyol produced by the composition for producing polyester polyol according to the present invention has excellent strength and flame retardant properties, as well as excellent storage stability.

[0029] In addition to the effects described above, the specific effects of the present invention are described together with the specific details for implementing the invention below. Specific details for implementing the invention

[0031] The aforementioned objectives, features, and advantages are described in detail below, and accordingly, a person skilled in the art to which the present invention pertains will be able to easily implement the technical concept of the present invention. In describing the present invention, detailed descriptions of known technologies related to the present invention are omitted if it is determined that such descriptions may unnecessarily obscure the essence of the present invention. Hereinafter, preferred embodiments according to the present invention will be described in detail.

[0033] In one embodiment of the present invention, a composition for preparing a polyester polyol is provided, comprising a dicarboxylic acid compound and an alcohol compound, wherein the dicarboxylic acid compound comprises a dicarboxylic acid compound containing a naphthalene structure and a dicarboxylic acid compound containing an aromatic structure other than naphthalene, and the alcohol compound comprises a linear alcohol compound and a non-linear alcohol compound.

[0034] The polyester polyol produced from the above-mentioned composition for manufacturing polyester polyol has excellent storage stability, and the polyurethane foam produced using it has excellent strength and flame retardant performance.

[0035] Increasing the aromatic content of the polyester polyol used as a raw material for manufacturing polyurethane foam can improve the strength and flame retardancy of the polyurethane foam obtained therefrom, but it can lead to crystallization, which may reduce storage stability.

[0036] The above composition for manufacturing a polyester polyol improves crystallization problems by designing a dicarboxylic acid compound and an alcohol compound in a predetermined mixed composition, thereby providing a polyester polyol containing an aromatic structure with excellent storage stability.

[0037] In one embodiment, the composition for manufacturing the polyester polyol is designed with a dicarboxylic acid compound and an alcohol compound in a predetermined mixed composition and a predetermined content, respectively, thereby improving crystallization problems, and thus the polyester polyol containing an aromatic structure has excellent storage stability.

[0038] The polyurethane foam manufactured using the polyester polyol obtained from the above-mentioned composition for manufacturing polyester polyol as a raw material has excellent strength and flame retardant performance.

[0040] By using dicarboxylic acid compounds containing aromatic structures, including naphthalene structures which are aromatic structures, the obtained polyester polyol is used as a raw material for polyurethane foam, thereby improving the strength and flame retardancy of the polyurethane foam.

[0041] In this specification, the term 'dicarboxylic acid-based compound' is a broader concept that includes dicarboxylic acid compounds, dicarboxylic acid anhydrides, etc.

[0042] The above-mentioned naphthalene structure-containing dicarboxylic acid compound may be, for example, 2,6-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, etc., but is not limited thereto, and may include at least one of these.

[0043] The above dicarboxylic acid compound containing an aromatic structure other than naphthalene may be a dicarboxylic acid compound containing an aromatic structure other than naphthalene, and may be, for example, phthalic anhydride, terephthalic acid, isophthalic acid, trimellitic anhydride, tetrachlorophthalic anhydride, maleic anhydride, etc., but is not limited thereto, and may include at least one of these.

[0044] In one embodiment, the dicarboxylic acid-based compound containing an aromatic structure other than naphthalene comprises two or more types.

[0045] In one embodiment, the dicarboxylic acid compound may contain 30 mol% or less, specifically 5 to 30 mol%, of the naphthalene structure-containing dicarboxylic acid compound based on 100 mol% of the dicarboxylic acid compound.

[0046] In one embodiment, the dicarboxylic acid compound may contain at least 70 mol%, specifically 70 to 95 mol%, of an aromatic structure-containing dicarboxylic acid compound other than naphthalene, based on 100 mol% of the dicarboxylic acid compound.

[0047] By mixing the dicarboxylic acid-based compound in the above-mentioned composition for manufacturing the polyester polyol within the above-mentioned content range, crystallization problems can be improved, and the storage stability of the obtained polyester polyol is improved.

[0048] By including a dicarboxylic acid compound containing an aromatic structure other than naphthalene among the dicarboxylic acid compounds in the above composition for manufacturing a polyester polyol, the aromaticity can be increased, thereby enabling the production of a highly aromatic polyester polyol, and a polyurethane foam produced from such a highly aromatic polyester polyol can exhibit improved strength properties.

[0050] The above alcohol compound is a mixed composition of linear alcohol compounds and non-linear alcohol compounds, and can improve the aforementioned crystallization problem. The above alcohol compound may be a mixture of linear alcohol compounds and non-linear alcohol compounds selected from alcohol compounds such as ethylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, butanediol, neopentyl glycol, 1,6-hexanediol, trimethylolpropane, glycerin, pentaerythritol, and sorbitol.

[0051] In one embodiment, to further increase the strength of the final polyurethane foam, the alcohol compound may have 6 or fewer carbon atoms.

[0052] In one embodiment, the linear alcohol compound may be, for example, ethylene glycol, diethylene glycol, etc., but is not limited thereto, and may include at least one of these.

[0053] In one embodiment, the linear alcohol compound comprises two or more types.

[0054] In one embodiment, the non-linear alcohol compound may be, for example, non-linear dipropylene glycol (cas no. 110-98-5), neopentyl glycol, etc., but is not limited thereto, and may include at least one of these.

[0055] In one embodiment, the non-linear alcohol compound comprises two or more types.

[0056] In one embodiment, the alcohol compound may contain at least 75 mol%, specifically 75 to 99 mol%, of the non-linear alcohol compound based on 100 mol% of the alcohol compound.

[0057] In one embodiment, the alcohol compound may contain 25 mol% or less, specifically 25 to 1 mol%, of the linear alcohol compound based on 100 mol% of the alcohol compound.

[0058] By mixing the alcohol compound in the above content range in the above composition for manufacturing the polyester polyol, the crystallization problem can be improved, and the storage stability of the obtained polyester polyol is improved.

[0060] A naphthalene structure-containing polyester polyol can be prepared by reacting the dicarboxylic acid compound and the alcohol compound in the above composition for preparing a polyester polyol according to a known equivalent ratio. The mixing ratio of the dicarboxylic acid compound and the alcohol compound in the above composition for preparing a polyester polyol can be appropriately mixed to a mixing ratio in which a reaction with the known equivalent ratio can take place.

[0061] In one embodiment, the equivalent ratio of the dicarboxylic acid compound and the alcohol compound may be about 1:0.9 to 1:1.3. The composition for manufacturing the polyester polyol may include the dicarboxylic acid compound and the alcohol compound in the above content ratio, which may help improve the storage stability of the polyester polyol obtained by improving crystallization problems.

[0063] In one embodiment of the present invention, a polyester polyol containing a naphthalene structure is provided by polymerizing the composition for producing the polyester polyol.

[0064] In one embodiment, the hydroxyl value of the naphthalene structure-containing polyester polyol is 220 mgKOH / g to 350 mgKOH / g, and the acid value may be 1 mgKOH / g or less.

[0065] In one embodiment, the viscosity of the naphthalene structure-containing polyester polyol may be 5,000 cps to 30,000 cps at 25°C.

[0067] In one embodiment of the present invention, a polyurethane foam is provided from a composition comprising a naphthalene structure-containing polyester polyol, a diisocyanate, a flame retardant, a foam stabilizer, a catalyst for manufacturing a foam, a foaming agent, and an additive. Since the naphthalene structure-containing polyester polyol contains an aromatic structure including naphthalene, the polyurethane foam obtained therefrom has excellent strength and flame retardancy.

[0068] The above diisocyanate, the above flame retardant, the above foam stabilizer, the above catalyst for manufacturing the foam, the above blowing agent, etc., may be any known materials used in manufacturing polyurethane foam without limitation.

[0069] The above additive may be added to the composition in an appropriate type and amount according to the known properties to be imparted to the polyurethane foam to be obtained.

[0070] The method of manufacturing the polyurethane foam from the above composition can be appropriately carried out according to a known process.

[0072] Examples and comparative examples of the present invention are described below. The following examples are merely embodiments of the present invention, and the present invention is not limited to the following examples.

[0074] (Example)

[0075] Example 1

[0076] A 4-neck flask equipped with a heating mantle, condenser, stirring device, and temperature controller was prepared. 200 g (1.35 mole) of phthalic anhydride, 32 g (0.15 mole) of 2,6-naphthalenedicarboxylic acid, 37 g (0.35 mole) of diethylene glycol and 423 g (3.15 mole) of dipropylene glycol as alcohols, and 0.099 g (0.015 wt%) of titanium isopropoxide as a catalyst were placed in a 1 L reaction flask, and the condensation polypolymerization reaction was carried out by increasing the temperature from 200°C to 240°C. Water and toluene were removed through azeotropy and vacuum to obtain a polyester polyol having a naphthalene structure.

[0077] The obtained polyester polyol has a hydroxyl value of 300 mgKOH / g, an acid value of 0.72 mgKOH / g, a viscosity of 8,500 cps (25℃), and excellent storage stability with no crystallization occurring for more than 3 months at 25℃.

[0079] Example 2

[0080] A polyester polyol having a naphthalene structure was prepared by the same method as in Example 1, except that the molar ratio of phthalic anhydride and 2,6-naphthalenedicarboxylic acid among the components described in Example 1 was changed to 70 / 30.

[0081] The obtained polyester polyol has a hydroxyl value of 290 mgKOH / g, an acid value of 0.86 mgKOH / g, a viscosity of 11,000 cps (25℃), and excellent storage stability with no crystallization occurring for more than 3 months at 25℃.

[0083] Example 3

[0084] A polyester polyol having a naphthalene structure was prepared by the same method as in Example 1, except that the molar ratio of diethylene glycol and dipropylene glycol among the components described in Example 1 was changed to 25 / 75.

[0085] The obtained polyester polyol has a hydroxyl value of 290 mgKOH / g, an acid value of 0.78 mgKOH / g, a viscosity of 12,000 cps (25℃), and excellent storage stability in which no crystallization occurs for more than 3 months at 25℃.

[0087] Example 4

[0088] A polyester polyol having a naphthalene structure was prepared by the same method as in Example 1, except that the molar ratio of phthalic anhydride and 2,6-naphthalenedicarboxylic acid among the components described in Example 1 was changed to 60 / 40.

[0089] The obtained polyester polyol has a hydroxyl value of 300 mgKOH / g, an acid value of 0.90 mgKOH / g, a viscosity of 9,000 cps (25℃), and crystallization occurred in 45 days at 25℃.

[0091] Example 5

[0092] A polyester polyol having a naphthalene structure was prepared by the same method as in Example 1, except that the molar ratio of diethylene glycol and dipropylene glycol among the components described in Example 1 was changed to 50 / 50.

[0093] The obtained polyester polyol has a hydroxyl value of 280 mgKOH / g, an acid value of 0.70 mgKOH / g, a viscosity of 9,500 cps (25℃), and crystallization occurred in 60 days at 25℃.

[0095] Comparative Example 1

[0096] A polyester polyol was prepared using the same method as in Example 1, except that 2,6-naphthalenedicarboxylic acid was not used among the components listed in Example 1, and only 222 g (1.50 mole) of phthalic anhydride was used.

[0097] The obtained polyester polyol has a hydroxyl value of 300 mgKOH / g, an acid value of 0.8 mgKOH / g, a viscosity of 3,000 cps (25℃), and excellent storage stability in which no crystallization occurs for more than 3 months at 25℃.

[0099] The physical properties of the polyester polyols having a naphthalene structure prepared in Examples 1 to 5 and the polyester polyol prepared in Comparative Example 1 are described in Table 1 below.

[0100] Examples Comparative example 1 2 3 4 5 1 Hydroxyl valence (mgKOH / g) 300 290 290 300 280 300 Acid value (mgKOH / g) 0.72 0.86 0.78 0.90 0.70 0.80 Viscosity (cps, @25℃) 8,500 11,000 12,000 9,000 9,500 3,000 Storage stability (25℃) 3 months or more (very excellent) 3 months or more (very excellent) 3 months or more (very excellent) 45 days 60 days 3 months or more (very excellent)

[0101] In the case of Examples 4 to 5, compared to the content ratio in the compositions of Examples 1 to 3, the content of 2,6-naphthalenedicarboxylic acid having a naphthalene structure was high, or the content of a linear alcohol compound (diethylene glycol) was high, showing even better storage stability results than in Examples 1-3.

[0102] In the case of Comparative Example 1, it was prepared in the same manner as Example 1 except that only phthalic anhydride was used as the dicarboxylic acid. It was confirmed that the viscosity was lower than that of Examples 1 to 5, which are polyester polyols containing a naphthalene structure, while the storage stability showed results equivalent to Examples 1 to 3. This appears to be an effect resulting from the structural characteristic that the aromatic benzene group included in the phthalic anhydride structure is not flat.

[0104] Examples 6 to 10 and Comparative Example 2

[0105] Polyurethane foams were prepared using the polyester polyols having a naphthalene structure prepared in Examples 1-5 and the polyester polyol prepared in Comparative Example 1. For each of the polyester polyols having a naphthalene structure prepared in Examples 1-5 and the polyester polyol prepared in Comparative Example 1, a composition was mixed with 4,4-diphenylmethane diisocyanate (MDI, Kumho Mitsui, Cosmonate M-200), a flame retardant, a foam stabilizer, a catalyst, a foaming agent, and an additive in the amounts listed in Table 2, heated in a water bath at 25°C, stirred at high speed at room temperature, and injected into a mold to prepare polyurethane foams.

[0107] Experimental example

[0108] The physical properties of the polyurethane foams prepared in Examples 6-10 and Comparative Example 2 were evaluated. The compressive strength of the foam was evaluated according to the ASTM D-1621 method.

[0110] The results of the polyurethane foam evaluated as above are listed in Table 2 below.

[0111] Classification (weight part) Example 6 Example 7 Example 8 Example 9 Example 10 Comparative Example 2 Polyester polyol Example 1 100 Example 2 100 Example 3 100 Example 4 100 Example 5 100 Comparative Example 1 100 catalyst 1.5 1.5 1.5 1.5 1.5 1.5 Jeongpoje 2.0 2.0 2.0 2.0 2.0 2.0 flame retardant 10 10 10 10 10 10 blowing agent 25 25 25 25 25 25 MDI Index 200 200 200 200 200 200 Density (kg / m³) 3 ) 39.6 39.2 40.1 39.5 40.3 39.7 Compressive strength (kgf / cm²) 2 ) 26.2 27.6 27.5 28.3 26.3 23.2

[0112] - MDI : Cosmonate M-200 (Kumho Mitsui)

[0113] - Catalyst: Polycat-8 (N,N-dimethylcyclohexylamine)

[0114] - Standardized Form: B-8462 (Evonik)

[0115] - Flame retardant: TCPP (tris(1-chloro-2-propyl)phosphate)

[0116] - Foaming agent: HCFC-141b

[0118] In Examples 6 to 10 and Comparative Example 2, it was confirmed that the compressive strength of the polyurethane foam tended to increase as the content of 2,6-naphthalenedicarboxylic acid having a naphthalene structure increased. It was also confirmed that crystallization improvement effects could be obtained more effectively by controlling the content of dicarboxylic acid compounds (anhydrides) having a naphthalene structure and non-linear alcohols. In conclusion, using the composition for manufacturing a polyester polyol according to one embodiment of the present invention, it was possible to synthesize a polyester polyol capable of producing a foam with excellent storage stability, high strength, and excellent flame retardancy.

[0120] Although the present invention has been described above with reference to embodiments, the present invention is not limited by the embodiments disclosed in this specification, and it is obvious that various modifications can be made by a person skilled in the art within the scope of the technical concept of the present invention. Furthermore, even if the effects of the configuration of the present invention were not explicitly described while describing the embodiments of the present invention above, it is natural to acknowledge that the effects predictable by said configuration should also be recognized.

Claims

Claim 1 A composition for preparing a polyester polyol comprising a dicarboxylic acid compound and an alcohol compound, wherein the dicarboxylic acid compound comprises a dicarboxylic acid compound containing a naphthalene structure and a dicarboxylic acid compound containing an aromatic structure other than naphthalene, the alcohol compound comprises a linear alcohol compound and a non-linear alcohol compound, and the non-linear alcohol compound comprises at least one selected from the group consisting of dipropylene glycol, neopentyl glycol, and combinations thereof, and wherein the alcohol compound comprises at least 75 mol% of the non-linear alcohol compound based on 100 mol% of the alcohol compound. Claim 2 A composition for manufacturing a polyester polyol according to claim 1, wherein the dicarboxylic acid compound comprises 30 mol% or less of the naphthalene structure-containing dicarboxylic acid compound based on 100 mol% of the dicarboxylic acid compound. Claim 3 A composition for manufacturing a polyester polyol according to claim 1, wherein the dicarboxylic acid compound comprises 70 mol% or more of an aromatic structure-containing dicarboxylic acid compound other than naphthalene, based on 100 mol% of the dicarboxylic acid compound. Claim 4 delete Claim 5 A composition for manufacturing a polyester polyol according to claim 1, wherein the alcohol compound comprises 25 mol% or less of the linear alcohol compound based on 100 mol% of the alcohol compound. Claim 6 A composition for producing a polyester polyol according to claim 1, wherein the naphthalene structure-containing dicarboxylic acid compound comprises at least one selected from the group consisting of 2,6-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, and combinations thereof. Claim 7 A composition for producing a polyester polyol according to claim 1, wherein the aromatic structure-containing dicarboxylic acid compound other than naphthalene comprises at least one selected from the group consisting of phthalic anhydride, terephthalic acid, isophthalic acid, trimellitic anhydride, tetrachlorophthalic anhydride, maleic anhydride, and combinations thereof. Claim 8 delete Claim 9 A composition for manufacturing a polyester polyol according to claim 1, wherein the linear alcohol compound comprises at least one selected from the group consisting of ethylene glycol, diethylene glycol, and combinations thereof. Claim 10 A naphthalene structure-containing polyester polyol produced by polymerizing a composition for producing a polyester polyol according to claim 1. Claim 11 In claim 10, the naphthalene structure-containing polyester polyol has a hydroxyl value of 220 mgKOH / g to 350 mgKOH / g and an acid value of 1 mgKOH / g or less. Claim 12 In claim 10, the viscosity of the above naphthalene structure-containing polyester polyol is 5,000 cps to 30,000 cps at 25°C. Claim 13 Polyurethane foam prepared from a composition comprising a naphthalene structure-containing polyester polyol according to claim 10, a diisocyanate, a flame retardant, a foam stabilizer, a catalyst for foam manufacturing, a foaming agent, and additives.

Images