KR102522366B1 - Polyester polyol, manufacturing method thereof and manufacturing method polyurethane using the same - Google Patents

Abstract

The present invention relates to polyester polyols and methods for their preparation. In addition, the present invention relates to a method for producing polyurethane using the polyester polyol and a polyurethane produced by the method. The polyester polyol according to the present invention has excellent storage properties, and the polyurethane prepared using the polyester polyol has excellent flame retardancy.

Description

Polyester polyol, method for producing the same, and method for producing polyurethane using the same

The present invention relates to polyester polyols and methods for their preparation. In addition, the present invention relates to a method and polyurethane for producing polyurethane using the polyester polyol.

As energy saving policies for greenhouse gas reduction are strengthened globally, the role of insulation materials among building materials is becoming more important. In addition, due to the successive building fires, interest in materials that can satisfy not only insulation properties but also flame retardancy is increasing. Polyurethane foam has excellent insulation properties compared to other materials (EPS, XPS, Rockwool) and has recently attracted a lot of attention as an insulation material, but its use has slowed down due to flame retardancy issues.

Among the polyols that are essential components of polyurethane, polyether polyol and polyester polyol are known as the most common polyols. These polyols have a significant effect on the properties of the polyurethane or polyurethane foam to be produced.

In general, a polyol having a high molecular weight and a low functional group number is used to prepare a soft urethane foam, and a polyol having a small molecular weight and a high number of functional groups is used to prepare a rigid urethane foam.

On the other hand, polyurethane foam (polyurethane foam), especially rigid polyurethane foam is used in various fields, there is a difference in physical properties required depending on the applicable field. When used as an insulation material for interior and exterior construction materials, flame retardancy, dimensional stability, formability, insulation, and eco-friendliness are particularly required.

Phthalic anhydride (PA)-based backbone structure polyester polyol was used as the main resin of the universally used rigid polyurethane foam (PUR/PIR), but recently high-purity terephthalic acid (PTA)-based backbone was used due to poor flame retardancy. was developed with However, when polyester polyol having a PTA structure alone is used, the flame retardancy of the polyurethane produced as a raw material is secured, but the crystallinity of the polyester polyol is high, and solidification problems occur at room temperature, resulting in poor storability. Although it was developed as a PTA / PA base to compensate for these disadvantages, difficulties in market application are likely to occur if flame retardancy regulations are strengthened.

Korean Patent Publication No. 2009-0095889

The present invention is to solve the above problems to provide a polyester polyol with excellent storage stability and a polyurethane with excellent flame retardancy prepared using the polyester polyol.

An exemplary embodiment of the present invention provides a polyester polyol represented by Formula 1 below.

[Formula 1]

In Formula 1,

중 적어도 하나로 치환되거나 비치환된 직쇄 또는 분지쇄의 탄소수 2 내지 6의 알킬렌기; 또는 히드록시기 및

중 적어도 하나로 치환되거나 비치환된 직쇄 또는 분지쇄의 탄소수 2 내지 6의 에테르기이고, L ₁ is a hydroxy group and

a linear or branched alkylene group having 2 to 6 carbon atoms, unsubstituted or substituted with at least one of; or a hydroxyl group and

A linear or branched chain ether group having 2 to 6 carbon atoms, which is unsubstituted or substituted with at least one of,

L ₂ is a straight-chain or branched-chain alkylene group having 1 to 5 carbon atoms unsubstituted or substituted with a hydroxyl group; Or a straight-chain or branched-chain ether group having 1 to 5 carbon atoms unsubstituted or substituted with a hydroxyl group,

m is an integer from 1 to 50;

n is an integer from 3 to 21;

Another embodiment of the present invention, a first step of preparing a polyester polyol represented by the following formula (3) by reacting isophthalic acid and an alcohol represented by the following formula (2); and a second step of preparing a compound represented by the following Chemical Formula 1 by reacting the polyester polyol represented by Chemical Formula 3 with a compound represented by Chemical Formula 4 below.

[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

In Formulas 1 to 4,

중 적어도 하나로 치환되거나 비치환된 직쇄 또는 분지쇄의 탄소수 2 내지 6의 알킬렌기; 또는 히드록시기 및

중 적어도 하나로 치환되거나 비치환된 직쇄 또는 분지쇄의 탄소수 2 내지 6의 에테르기이고, L ₁ is a hydroxy group and

a linear or branched alkylene group having 2 to 6 carbon atoms, unsubstituted or substituted with at least one of; or a hydroxyl group and

A linear or branched chain ether group having 2 to 6 carbon atoms, which is unsubstituted or substituted with at least one of,

L ₂ is a straight-chain or branched-chain alkylene group having 1 to 5 carbon atoms unsubstituted or substituted with a hydroxyl group; Or a straight-chain or branched-chain ether group having 1 to 5 carbon atoms unsubstituted or substituted with a hydroxyl group,

L ₃ is a straight 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 hydroxyl group,

m is an integer from 1 to 50;

n is an integer from 3 to 21;

Finally, another embodiment of the present invention provides a polyurethane production method comprising the step of reacting the polyester polyol with one or more compounds containing two or more isocyanate groups.

The polyester polyol according to an exemplary embodiment of the present invention has storage stability. In addition, the polyurethane produced using the polyester polyol according to the present invention has excellent flame retardancy.

Hereinafter, the present invention will be described in detail.

In this specification, when a part is said to "include" a certain component, it means that it may further include other components without excluding other components unless otherwise stated.

In the present specification, the term "substitution" means that a hydrogen atom bonded to a carbon atom of a compound is replaced with another substituent, and the position to be substituted is not limited as long as the hydrogen atom is substituted, that is, the position where the substituent can be substituted, When two or more substituents are substituted, two or more substituents may be the same as or different from each other.

In addition, the term “alkyl group” as used herein refers to a monovalent straight-chain, branched-chain or cyclic-chain saturated hydrocarbon group composed of only carbon and hydrogen atoms, and includes a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and an isobutyl group. group, t-butyl group, pentyl group, hexyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, and the like, but are not limited thereto.

In the present specification, "alkylene group" means a divalent straight-chain, branched-chain or cyclic saturated hydrocarbon group composed of only carbon and hydrogen atoms, and is the same as the examples of the above alkyl group, but is not limited thereto.

In this specification, "ether group" means a divalent organic group having at least one ether bond (-O-).

는 화합물의 골격에 결합되는 부위를 의미한다. in this specification

means a site bonded to the backbone of the compound.

In one embodiment of the present specification, a polyester polyol represented by Formula 1 is provided.

[Formula 1]

In Formula 1,

중 적어도 하나로 치환되거나 비치환된 직쇄 또는 분지쇄의 탄소수 2 내지 6의 알킬렌기; 또는 히드록시기 및

중 적어도 하나로 치환되거나 비치환된 직쇄 또는 분지쇄의 탄소수 2 내지 6의 에테르기이고, L ₁ is a hydroxy group and

a linear or branched alkylene group having 2 to 6 carbon atoms, unsubstituted or substituted with at least one of; or a hydroxyl group and

A linear or branched chain ether group having 2 to 6 carbon atoms, which is unsubstituted or substituted with at least one of,

L ₂ is a straight-chain or branched-chain alkylene group having 1 to 5 carbon atoms unsubstituted or substituted with a hydroxyl group; Or a straight-chain or branched-chain ether group having 1 to 5 carbon atoms unsubstituted or substituted with a hydroxyl group,

m is an integer from 1 to 50;

n is an integer from 3 to 21;

As in one embodiment of the present specification, the polyester polyol represented by Formula 1 is composed of an isophthalic acid (PIA)-based backbone instead of a phthalic anhydride (PA)-based, high-purity terephthalic acid (PTA)-based backbone. . In this case, the steric hindrance is lower than that of the PA or PA/PTA-based backbone, resulting in excellent reactivity with isocyanates and increased flame retardancy of the prepared polyurethane.

In one embodiment of the present specification, 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 -;

;

;

;

;

; 또는

이고, n은 3 내지 21의 정수이다. 본 명세서의 일 실시상태에 있어서, L₁은 -CH₂-CH₂-이다.

;

;

;

;

; or

And, n is an integer from 3 to 21. In one embodiment of the present specification, L ₁ is -CH ₂ -CH ₂ -.

In one embodiment of the present specification, 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 -O-CH ₂ -CH ₂ -; or -CH ₂ -O-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -. In one embodiment of the present specification, L ₂ is -CH ₂ -.

In one embodiment of the present specification, L ₁ is -CH ₂ -CH ₂ -, and L ₂ is -CH ₂ -. As in one embodiment of the present specification, when L ₁ is -CH ₂ -CH ₂ - and L ₂ is -CH ₂ -, by including a linear structure, the crystallinity of polyester polyol is increased, increase the viscosity.

Polyester polyol according to an exemplary embodiment of the present invention has a structure including ester and ether bonds at the same time. Specifically, the polyester polyol of the present invention includes an ester linkage in the main chain and an ether linkage in the side chain.

In the case of a compound containing only an ether bond, flexibility (flexibility) is excellent and mobility is good, but it tends to be well thermally oxidized. Therefore, the polyester polyol according to an exemplary embodiment of the present invention includes both an ester bond and an ether bond, thereby securing the flexibility and mobility of the polyester polyol, increasing the thermal decomposition temperature, and preventing oxidation to secure storage stability. Ester polyols can be provided.

Therefore, the polyester polyol according to an exemplary embodiment of the present invention has high storage stability, and polyurethane prepared using the polyester polyol has excellent flame retardancy.

In one embodiment of the present specification, the hydroxyl value (OH Value) of the polyester polyol represented by Formula 1 is 10 mgKOH/g to 500 mgKOH/g. Hard polyurethane required within the above range can be obtained.

In another embodiment, the weight average molecular weight of the polyester polyol represented by Formula 1 is 200 g/mol to 10,000 g/mol.

In one embodiment, the polyester polyol represented by Formula 1 has a viscosity at 25 ° C of 500 cP to 1,000,000 cP.

In one embodiment of the present invention, a first step of preparing a polyester polyol represented by the following Chemical Formula 3 by reacting isophthalic acid with an alcohol represented by the following Chemical Formula 2; and a second step of preparing a polyester polyol represented by the following Chemical Formula 1 by reacting the polyester polyol represented by Chemical Formula 3 with a compound represented by Chemical Formula 4 below.

[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

In Formulas 1 to 4,

중 적어도 하나로 치환되거나 비치환된 직쇄 또는 분지쇄의 탄소수 2 내지 6의 알킬렌기; 또는 히드록시기 및

중 적어도 하나로 치환되거나 비치환된 직쇄 또는 분지쇄의 탄소수 2 내지 6의 에테르기이고, L ₁ is a hydroxy group and

a linear or branched alkylene group having 2 to 6 carbon atoms, unsubstituted or substituted with at least one of; or a hydroxyl group and

A linear or branched chain ether group having 2 to 6 carbon atoms, which is unsubstituted or substituted with at least one of,

L ₂ is a straight-chain or branched-chain alkylene group having 1 to 5 carbon atoms unsubstituted or substituted with a hydroxyl group; Or a straight-chain or branched-chain ether group having 1 to 5 carbon atoms unsubstituted or substituted with a hydroxyl group,

L ₃ is a straight 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 hydroxyl group,

m is an integer from 1 to 50;

n is an integer from 3 to 21;

In the present specification, the polyester polyol represented by Chemical Formula 1 may be applied in the same manner as the polyester polyol represented by Chemical Formula 1 described above as long as they do not contradict each other.

The first step of preparing the polyester polyol represented by Chemical Formula 3 by reacting isophthalic acid according to an exemplary embodiment of the present specification with an alcohol represented by Chemical Formula 2 may be performed by an ester reaction.

In one embodiment of the present invention, the first step is performed at a temperature of 140 ℃ to 240 ℃ at normal pressure. More specifically, the first step is performed by reacting at atmospheric pressure at a temperature of 140 °C to 240 °C for 8 hours to 12 hours.

In one embodiment of the present specification, 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 -;

;

;

;

;

; 또는

이고, n은 3 내지 21의 정수이다. 본 명세서의 일 실시상태에 있어서, L₁은 -CH₂-CH₂-이다.

;

;

;

;

; or

And, n is an integer from 3 to 21. In one embodiment of the present specification, L ₁ is -CH ₂ -CH ₂ -.

In one embodiment of the present invention, the compound represented by Formula 2 may be an alcohol selected from the group consisting of monoethyl glycol, diethyl glycol, neopentyl glycol, methyl propanediol, trimethylol propane and triethylene glycol there is. In one embodiment of the present invention, when the compound represented by Formula 2 is monoethyl glycol, it may be preferable in terms of increasing crystallinity, increasing viscosity, increasing thermal decomposition temperature, and preventing oxidation.

In one embodiment of the present specification, 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 -O-CH ₂ -CH ₂ -; or -CH ₂ -O-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -. In one embodiment of the present specification, L ₂ is -CH ₂ -.

In one embodiment of the present specification, L ₁ is -CH ₂ -CH ₂ -, and L ₂ is -CH ₂ -.

In one embodiment of the present specification, the L ₃ 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 -; or -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -. In one embodiment of the present specification, L ₃ is -CH ₂ -CH ₂ -.

In one embodiment of the present specification, in the first step, the compound represented by Chemical Formula 2 is added in an amount of 1.1 to 2.5 moles based on 1 mole of isophthalic acid.

In one embodiment of the present invention, the polyester polyol represented by Formula 3 has a weight average molecular weight of 200 g/mol to 10,000 g/mol.

In one embodiment of the present invention, in the second step, the compound represented by Formula 4 is added at a rate of 0.01 mol to 0.1 mol based on 1 mol of polyester polyol represented by Formula 3. It may be excellent in terms of storage stability and flame retardancy of polyurethane prepared using the same. Specifically, when the compound represented by Formula 4 is added in an amount of less than 0.01 mol with respect to 1 mol of polyester polyol represented by Formula 3, the storage effect of the polyester polyol may be reduced, and at a rate exceeding 0.1 mol When added, flame retardancy of polyurethane prepared using polyester polyol may deteriorate.

In one embodiment of the present invention, the weight average molecular weight of the compound represented by Formula 4 is preferably from 200 g / mol to 1,000 g / mol in terms of storage properties of polyester polyol and flame retardancy of polyurethane prepared using the same. do. Specifically, when the weight average molecular weight of the compound represented by Formula 4 is less than 200 g/mol, it is difficult to prepare, and when the weight average molecular weight of the compound represented by Formula 4 exceeds 1,000 g/mol, the reactivity of the second step is rapid. The storage properties of the polyester polyol and the flame retardancy of the polyurethane prepared therefrom may be deteriorated.

In one embodiment of the present invention, the second step of preparing the compound represented by Formula 1 by reacting the polyester polyol represented by Formula 3 with the compound represented by Formula 4 in the presence of an acid-base catalyst is carried out

In the present specification, the acid-base catalyst is a catalyst involved in reactions including accepting hydrogen ions or donating electron pairs, and includes potassium tert-butoxide, triethyl 2-phosphono propionate ), diphenylprolinol silyl ether, (S)-1-(2-pyrrolidinylmethyl)pyrrolidine ((S)-1-(2-pyrrolidinylmethyl)pyrrolidine) and (S) It may be one or two or more catalysts selected from the group consisting of -2-(morpholinomethyl)pyrrolidine ((S)-2-(morpholinomethyl)pyrrolidine), but is not limited thereto.

The acid-base catalyst is added in an amount of 0.005% by weight to 0.1% by weight based on the weight of the compound represented by Formula 4.

In one embodiment of the present invention, the second step is performed at a temperature of 100 °C to 220 °C under normal pressure. More specifically, the second step is performed by reacting for 2 hours to 6 hours at a temperature of 100 ℃ to 220 ℃ at atmospheric pressure.

In one embodiment of the present invention, a polyester polyol prepared by the above production method is provided.

Polyester polyol according to an exemplary embodiment of the present invention is very useful in the production of polyurethane having excellent flame retardancy. The production of polyurethane can be made by generally known techniques. It usually involves a reaction between the isocyanate component and the polyol component in the presence of a catalyst, a blowing agent.

Another embodiment of the present invention provides a method for producing a polyurethane comprising the step of reacting the polyester polyol with one or more compounds containing two or more isocyanate groups.

In the present specification, the polyester polyol represented by Chemical Formula 1 may be applied in the same manner as the polyester polyol represented by Chemical Formula 1 described above as long as they do not contradict each other.

In the present specification, the at least one compound containing two or more isocyanate groups is a compound containing two or more isocyanate groups (-N=C=O), for example, 1,12-dodecane diisocyanate, 2-ethyltetramethylene 1 ,4-diisocyanate, 2-methylpentamethylene 1,5-diisocyanate, tetramethylene 1,4-diisocyanate, hexamethylene 1,6-diisocyanate; Cyclohexane 1,3-diisocyanate, cyclohexane 1,4-diisocyanate, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (IPDI), 2,4- Hexahydrotolylene diisocyanate, 2,6-hexahydrotolylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 2,2'-dicyclohexylmethane diisocyanate, 2,4'-dicyclohexylmethane di Isocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), 2,4'-diphenylmethane diisocyanate, 2,2'- Diphenylmethane diisocyanate, polyphenylpolymethylene polyisocyanate, 1,5-naphthylene diisocyanate (NDI), 3,3'-dimethylbiphenyl diisocyanate, 1,2-diphenylethane diisocyanate, p-phenylene Diisocyanate (PPDI), trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, 2-methylpentamethylene 1,5-diisocyanate, 2- Ethylbutylene 1,4-diisocyanate, pentamethylene 1,5-diisocyanate, butylene 1,4-diisocyanate, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl -Cyclohexane (isophorone diisocyanate, IPDI), 1,4-bis (isocyanatomethyl) cyclohexane, 1,3-bis (isocyanatomethyl) cyclohexane (HXDI), 1,4-cyclo Hexane diisocyanate, isomers thereof, or mixtures thereof, but is not limited thereto.

In one embodiment of the present invention, additional additives may be further included as needed during the preparation of the polyurethane. For example, it may include, but is not limited to, commonly used additives such as foaming agents, flame retardants, foam stabilizers, catalysts, surface active materials, foam stabilizers, cell control agents, fillers, dyes, pigments, and hydrolysis control agents.

In the present specification, the foaming agent includes water, carboxylic acid, a fluorocarbon-based foaming agent, carbon dioxide, and a hydrocarbon foaming agent such as a linear or branched chain alkane hydrocarbon, but is not limited thereto.

In the present specification, the flame retardant may use a commonly used flame retardant, for example, brominated ester, brominated ether (Ixol) or brominated alcohol, such as dibromoneopentyl alcohol, tribromoneopentyl alcohol and PHT-4-diol, and also chlorinated phosphates such as tris(2-chloroethyl) phosphate, tris(2-chloropropyl)phosphate (TCPP), tris(1,3-dichloropropyl)phosphate, tricresyl phosphate, tris(2,3-di bromopropyl) phosphate, tetrakis(2-chloroethyl) ethylenediphosphate, dimethyl methanephosphonate, diethyl diethanolaminomethylphosphonate and also commercially available halogenated flame retardant polyols. With additional phosphates or phosphonates, diethyl ethanephosphonate (DEEP), triethyl phosphate (TEP), dimethyl propylphosphonate (DMPP) or diphenyl cresyl phosphate (DPK) as liquid flame retardants, It is not limited to this.

In the present specification, the foam control agent is a silicone foam control agent, a nonionic foam control agent, a non-silicone foam control agent, etc. Specifically, a foam control agent such as dinonyl phenol, methyl glucoside, methyl propanediol, vinyl ether maleic acid, Si-copolymer series, etc. and is not limited thereto.

In the present specification, commonly used catalysts may be used as the catalyst, for example, triethylamine, tributylamine, dimethylbenzylamine, dicyclohexylmethylamine, dimethylcyclohexylamine, N,N,N',N' -Tetramethyldiaminodiethyl ether, bis(dimethylaminopropyl) urea, N-methylmorpholine, N-ethylmorpholine, N-cyclohexylmorpholine, N,N,N',N'-tetramethylethylenediamine , N,N,N,N-tetramethylbutanediamine, N,N,N,N-tetramethylhexane-1,6-diamine, pentamethyldiethylenetriamine, bis(2-dimethylaminoethyl) ether, dimethyl Piperazine, N-dimethylaminoethylpiperidine, 1,2-dimethylimidazole, 1-azabicyclo[2.2.0]octane, 1,4-diazabicyclo[2.2.2]octane (Dabco), triethanol Amine, triisopropanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, dimethylaminoethanol, 2-(N,N-dimethylaminoethoxy) ethanol, N,N',N"-tris(dialkyl aminoalkyl) hexahydrotriazine, N,N',N"-tris(dimethylaminopropyl)-s-hexahydrotriazine, triethylenediamine, iron(II) chloride, zinc chloride, lead octoate, tin dioctoate , tin diethylhexoate, dibutyltin dilaurate, tetraisopropyl titanate, butylstanonic acid, butylcrotin dihydroxide, tetrabutyl titanate, and mixtures thereof, but is not limited thereto.

Another embodiment of the present invention provides a polyurethane prepared by the above production method. Polyurethane prepared using the polyester polyol according to an exemplary embodiment of the present invention has excellent flame retardancy.

Hereinafter, examples will be described in detail to explain the present invention in detail. However, embodiments according to the present invention can be modified in many different forms, and the scope of the present invention is not construed as being limited to the embodiments described below. The embodiments herein are provided to more completely explain the present invention to those skilled in the art.

Comparative Example 1

Phthalic anhydride (PA; SigmaAldrich) 488.7 g, diethylene glycol (DEG; diethylene glycol, Lotte Chemical Co., Ltd.) 549.7 g, Fascat 4100 ( butylstannoic acid, Arkema) 0.519 g was added and the temperature was first raised to 160 ° C (3 hours). Water was removed while stirring at a stirring speed of 200 rpm in the process of raising the temperature. After 2 hours, the second temperature was raised to 240 °C for 3 hours. Water was removed by vacuuming for 3 hours to prepare Polyol 1 having an acid value (mg KOH/g resin) of 0.5 and a hydroxyl value (mg KOH/g resin) of 211.

Comparative Examples 2 to 8

Polyols 2 to 8 were prepared in the same manner as in Comparative Example 1, except for changing some of the conditions described in Table 1 below.

Example 1

PIA (pure isophthalic acid, Lotte Chemical Co., Ltd.) 664.4 g, MEG (monoethylene glycol, Lotte Chemical Co., Ltd.) 352.2 g, Fascat 4100 (butylstannoic acid, Arkema) 0.528 g was added and the temperature was first raised to 160 ° C (3 hours). Water was removed while stirring at a stirring speed of 200 rpm in the process of raising the temperature. After 2 hours, the second temperature was raised to 240 °C for 3 hours. After removing water by vacuuming for 3 hours, lowering the temperature to 160 ℃, adding 40 g of VPEG-200 (alcohol, Lotte Chemical Co., Ltd.) and 0.020 g of potassium tert-butoxide (catalyst, SigmaAldrich). By reacting for 2 hours, Polyol 9 having an acid value (mg KOH/g resin) of 0.8 and a hydroxyl value (mg KOH/g resin) of 207 was prepared.

Example 2 and Example 3

Polyols 10 and 11 were prepared in the same manner as in Example 1, except for changing some of the conditions described in Table 2 below.

The polyester polyols of Comparative Examples 1 to 8 are shown in Table 1 below.

ingredient compound comparative example Polyol 1 Polyol 2 Polyol 3 Polyol 4 Polyol 5 Polyol 6 Polyol 7 Polyol 8 acid PA
(phthalic anhydride) 488.7g 651.6g 237.0g PTA
(pure terephthalic acid) 514.9g 681.0g 265.8g PIA (pure isophthalic acid) 514.9g 681.0g 564.7g alcohol DEG
(diethylene glycol) 549.7g 516.4g 533.0g 516.4g MEG
(monoethylene glycol) 387.4g 361.0g 361.0g MPO (2-Methyl 1, 3-Propanediol) 465.6g catalyst Fascat 4100 0.519g 0.520g 0.516g 0.521g 0.518g 0.516g 0.521g 0.515g total 1038.9 1039.5 1031.8 1042.5 1036.3 1031.8 1057.1 1042.5 Properties OH value 211 205 204 200 207 204 205 207 Acid value 0.5 0.6 1.5 2.0 0.9 1.0 0.8 0.8 Viscosity (25℃_cP) 750 100,000 25,000 - 18,000 15,000 250,000 150,000 Storage (20℃) 3 months (O) 2 days
(X) 3 weeks
(X) -
(X) 2 months
(Δ-O) 2 months
(Δ-O) 1 day
(X) 1 week
(X)

The polyester polyols of Examples 1 to 3 are shown in Table 2 below.

ingredient compound Example Polyol 9 Polyol 10 Polyol 11 acid PA PTA PIA 664.4g 631.2g 548.1g alcohol DEG MEG 352.2g 332.2g MPO 449g VPEG-200 40g 76g 39.6g catalyst Fascat 4100 0.528g 0.520g 0.518g Potassium
tert-butoxide 0.020g 0.038g 0.020g total 1038.9 1057.1 1037.2 Properties OH value 207 209 208 Acid value 0.8 0.7 0.8 Viscosity (25 ℃_cP) 130,000 70,000 80,000 Storage (20℃) 2 months (Δ-O) 3 months
(O) 3 months
(O)

In Tables 1 and 2, the storage stability of the samples in a constant temperature chamber at 20 ° C. for 3 months was evaluated as follows.

X: Gelation or solidification within 2 weeks

△: Gelation or solidification within 1.5 months

○: maintained in a liquid state for more than 3 months, indicated by the number of months

In Tables 1 and 2, the viscosity was evaluated by selecting a spindle so that the resistance was in the range of 40% to 70% by measuring samples based on 25 ° C. with a Brookfield viscometer DV-II + Pro meter did

Looking at the results of Tables 1 and 2, it can be seen that the polyester polyol represented by Formula 1 according to an exemplary embodiment of the present invention has excellent storability compared to Comparative Examples 2 to 4, Comparative Examples 7 and 8.

Manufacture of polyurethane

Polyester polyol 200 g, TCPP (Tris(1-Chloro-2-Propyl)Phosphate, SigmaAldrich) 10 g, TEGOSTAB®B8462 (silicone surfactant, Evonik) 3 g, cyclopentane (foaming agent, SigmaAldrich) 40 g, Polycat® 41 (catalyst, Evonik) 2.0 g, and DMCHA (N,N-dimethylcyclohexylamine, Huntsman) 2.0 g were put into a 2 liter can and mixed with a high-speed stirrer to obtain a mixture as shown in Tables 3 and 4 below. Polyurethane was prepared.

Polyurethanes prepared using the polyester polyols prepared in Comparative Examples 1 to 3 and Comparative Examples 5 to 8 are shown in Table 3 below.

ingredient compound unit comparative example A B C D E F G profit Polyol 1 g 200 Polyol 2 g 200 Polyol 3 g 200 Polyol 5 g 200 Polyol 6 g 200 Polyol 7 g 200 Polyol 8 g 200 flame retardant TCPP g 10 10 10 10 10 10 5 antifoaming agent TEGSTAB®
B8462 g 3 3 3 3 3 3 3 blowing agent cyclopentane g 40 40 40 40 40 40 40 catalyst Polycat® 41 g 2.0 2.0 2.0 2.0 2.0 2.0 2.0 DMCHA g 2.0 2.0 2.0 2.0 2.0 2.0 2.0 curing agent COSMONATE
SR-500 g 121.6 121.6 121.6 121.6 121.6 121.6 121.6 index 120 120 120 120 120 120 120 Properties combustibility mm 121 110 72 93 75 31 30

Polyurethanes prepared using the polyester polyols prepared in Examples 1 to 3 are shown in Table 4 below.

ingredient compound unit Example H I J profit Polyol 9 g 200 Polyol 10 g 200 Polyol 11 g 200 flame retardant TCPP g 10 10 10 antifoaming agent TEGSTAB®
B8462 g 3 3 3 blowing agent cyclopentane g 40 40 40 catalyst Polycat® 41 g 2.0 2.0 2.0 DMCHA g 2.0 2.0 2.0 curing agent COSMONATE
SR-500 g 121.6 121.6 121.6 index 120 120 120 Properties combustibility mm 32 42 31

In Tables 3 and 4, the combustibility is ignited by a small flame in the horizontal direction with at least 5 specimens with a size of 150 ± 10 mm in length and 50 ± 1 mm in width according to the measurement of horizontal flammability (KS M ISO 9772) in the KS standard The combustion behavior of the foamed plastic material was evaluated when it was burned, and the damaged length was evaluated as the damaged length (mm) within 120 seconds of burning time.

Through the results of Tables 1 to 4, in the case of polyurethane made of polyester polyol represented by Formula 1 according to an exemplary embodiment of the present invention, compared to Comparative Examples 1 to 3 and Comparative Examples 5 to 8, polyester It was confirmed that the polyol was excellent in terms of storage properties and flame retardancy of polyurethane prepared therefrom.

Specifically, comparing Comparative Examples 1 to 3, Comparative Example 5 and Examples 1 to 3, it was confirmed that the polyurethane prepared using the polyester polyol according to the present invention had excellent flame retardancy. As in Comparative Examples 1 to 3 and Comparative Example 5, polyurethane prepared from polyester polyol having PA and/or PTA as a backbone has poor flame retardancy. In particular, Comparative Examples 1 and 5 are polyester polyols having high storage stability using PA as a backbone, but polyurethanes prepared therefrom have a problem of low flame retardancy. It was confirmed that additionally introducing a side chain into the PIA backbone, such as the polyester polyol represented by Formula 1 according to an exemplary embodiment of the present invention, improves storage stability and improves flame retardancy of polyurethane prepared using the same.

In addition, comparing Comparative Examples 6 to 8 with PIA as the backbone and Examples 1 to 3, the polyester polyol according to the present invention has high storage stability, and the polyurethane prepared using the polyester polyol has excellent flame retardancy. It was confirmed that it has In particular, in the case of Comparative Examples 7 and 8, it can be confirmed that the flame retardancy of polyurethane is excellent, but the storage property of polyester polyol is poor. It can be confirmed that the storage stability of the polyester polyol is improved and the flame retardancy of the polyurethane prepared using the same is improved by additionally introducing a side chain into the PIA backbone, such as the polyester polyol represented by Formula 1 according to an embodiment of the present invention. there was.

Therefore, the polyester polyol according to one embodiment of the present specification can provide a polyurethane foam having high storage stability and excellent flame retardancy.

Claims (14)

A polyester polyol represented by Formula 1 below:
[Formula 1]

In Formula 1,
L ₁ is a hydroxy group and

a linear or branched alkylene group having 2 to 6 carbon atoms, unsubstituted or substituted with at least one of; or a hydroxyl group and

A linear or branched chain ether group having 2 to 6 carbon atoms, which is unsubstituted or substituted with at least one of,
L ₂ is a straight-chain or branched-chain alkylene group having 1 to 5 carbon atoms unsubstituted or substituted with a hydroxyl group; Or a straight-chain or branched-chain ether group having 1 to 5 carbon atoms unsubstituted or substituted with a hydroxyl group,
m is an integer from 1 to 50;
n is an integer from 3 to 21; The method of claim 1,
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

ego,
n is an integer from 3 to 21 polyester polyol. The method of claim 1,
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 -O-CH ₂ -CH ₂ -; or -CH ₂ -O-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ - polyester polyol. The method of claim 1,
A polyester polyol having a hydroxyl value (OH Value) of the polyester polyol represented by Formula 1 of 10 mgKOH/g to 500 mgKOH/g. The method of claim 1,
A polyester polyol having a weight average molecular weight of 200 g/mol to 10,000 g/mol of the polyester polyol represented by Formula 1. The method of claim 1,
The polyester polyol represented by Formula 1 has a viscosity at 25 ° C of 500 cP to 1,000,000 cP. The method of claim 1,
L ₁ is -CH ₂ -CH ₂ -;
A polyester polyol wherein L ₂ is -CH ₂ -. A first step of preparing a polyester polyol represented by the following Chemical Formula 3 by reacting isophthalic acid with an alcohol represented by the following Chemical Formula 2; and
A second step of preparing a polyester polyol represented by the following Chemical Formula 1 by reacting the polyester polyol represented by the above Chemical Formula 3 with a compound represented by the following Chemical Formula 4; Method for producing a polyester polyol comprising:
[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

In Formulas 1 to 4,
L ₁ is a hydroxy group and

a linear or branched alkylene group having 2 to 6 carbon atoms, unsubstituted or substituted with at least one of; or a hydroxyl group and

A linear or branched chain ether group having 2 to 6 carbon atoms, which is unsubstituted or substituted with at least one of,
L ₂ is a straight-chain or branched-chain alkylene group having 1 to 5 carbon atoms unsubstituted or substituted with a hydroxyl group; Or a straight-chain or branched-chain ether group having 1 to 5 carbon atoms unsubstituted or substituted with a hydroxyl group,
L ₃ is a straight 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 hydroxyl group,
m is an integer from 1 to 50;
n is an integer from 3 to 21; The method of claim 8,
In the first step, the compound represented by Formula 2 is added in an amount of 1.1 to 2.5 moles based on 1 mole of isophthalic acid. The method of claim 8,
In the second step, the compound represented by Formula 4 is added in a ratio of 0.01 mol to 0.1 mol based on 1 mol of the polyester polyol represented by Formula 3. The method of claim 8,
The second step of preparing the compound represented by Formula 1 by reacting the polyester polyol represented by Formula 3 with the compound represented by Formula 4 is carried out in the presence of an acid-base catalyst. method. The method of claim 11,
The acid base catalyst is potassium tert-butoxide, triethyl 2-phosphono propionate, diphenylprolinol silyl ether, (S)- 1-(2-pyrrolidinylmethyl)pyrrolidine ((S)-1-(2-pyrrolidinylmethyl)pyrrolidine) and (S)-2-(morpholinomethyl)pyrrolidine ((S)-2- (morpholinomethyl) pyrrolidine) a method for producing a polyester polyol that is one or two or more catalysts selected from the group consisting of. The method of claim 11,
The acid-base catalyst is a method for producing a polyester polyol that is added in a ratio of 0.005% to 0.1% by weight based on the weight of the compound represented by Formula 4. A method for producing a polyurethane comprising reacting the polyester polyol according to any one of claims 1 to 7 with at least one compound containing at least two isocyanate groups.