Patent Application
20240026060
The present invention relates to a polyester polyol for preparing a semi-incombustible rigid polyurethane and a polyurethane prepared therefrom.
As energy saving policies for greenhouse gas reduction are strengthened globally, the role of heat insulation materials among building materials is becoming more important. In addition, due to a series of building fires, interest in materials that can satisfy not only heat insulation properties but also flame retardancy is increasing. Polyurethane foam has excellent heat insulation properties compared to other materials (EPS, XPS, Rockwool) and has recently attracted a lot of attention as a heat insulation material, but its use has slowed down due to flame retardancy issues.
Among polyols that are an essential component of polyurethane, a polyether polyol and a 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 prepared.
In general, a polyol having a high molecular weight and low functionality is used to prepare a soft urethane foam, and a polyol having a small molecular weight and high functionality is used to prepare a rigid urethane foam.
Meanwhile, since the polyurethane foam, especially the rigid polyurethane foam, is used in various fields, there is a difference in required physical properties depending on the application field. When used as a heat insulation material for interior and exterior building materials, it particularly requires flame retardancy, dimensional stability, formability, heat insulation, and eco-friendliness.
A polyester polyol with a phthalic anhydride (PA)-based backbone structure was used as the main resin of the universally used rigid polyurethane foam (PUR/PIR), but due to its poor flame retardancy, the polyol was recently developed with a high-purity terephthalic acid (PTA)-based backbone. However, when the polyester polyol having a PTA structure alone is used, the flame retardancy of the polyurethane produced from this 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 with a PTA/PA base to compensate for these disadvantages, difficulties in market application are likely to occur when flame retardancy regulations are strengthened. Meanwhile, when high-purity isophthalic acid (PIA: Purified Isophthalic Acid) is used as a base, flame retardancy is excellent, but there are problems of compatibility and an increase in viscosity.
In order to solve the above problems, the present invention is directed to providing a polyester polyol with low viscosity, excellent storage stability and compatibility, and a polyurethane with excellent flame retardancy prepared using the polyester polyol.
The present invention provides a polyester polyol prepared from:
HO-L3-OH [Chemical Formula 1]
The present invention also provides a polyurethane prepared by reacting the polyester polyol with one or more compounds including two or more isocyanate groups.
The present invention can provide a polyester polyol having excellent storage stability, low viscosity, and excellent reactivity with isocyanate. In addition, a polyurethane prepared using the polyester polyol according to the present invention has excellent flame retardancy and dimensional stability.
In the present invention, for preparation of a polyester polyol, an acid component selected from the group consisting of purified isophthalic acid (PIA) and phthalic anhydride (PA), and an alcohol component represented by Chemical Formula 1 below are used:
HO-L3-OH [Chemical Formula 1]
To prepare an aromatic polyester polyol with compatibility, low viscosity, and excellent storage stability, the present invention suggests the type and mixing ratio of an acid component, uses a specific alcohol component, and has an optimal OH value and an acid value therefrom to provide an aromatic polyester polyol having excellent reactivity with isocyanate by lowering crystallinity and controlling low viscosity (low molecular weight distribution increase). Furthermore, the present invention provides a flame-retardant polyurethane prepared therefrom.
In the present invention, purified isophthalic acid (PIA) or phthalic anhydride (PA) may be used as the acid component, which may be used alone or in combination. In particular, the present invention provides a polyol including PIA as the acid component, wherein PIA may be included in an amount of 80 to 100 mol %.
As in one embodiment of the present specification, a polyester polyol represented by Chemical Formula 1 is composed of a phthalic anhydride (PA)-based and a purified isophthalic acid (PIA)-based backbone instead of a high-purity terephthalic acid (PTA)-based backbone. PIA has a low steric hindrance compared to the PTA-based backbone, so that it has excellent reactivity with isocyanate and can increase the flame retardancy of the prepared polyurethane. Therefore, in the present invention, PIA is included as an acid component of the polyester polyol, and the PIA is included in an amount of 80 to 100 mol % in the acid component to obtain desired effects.
In addition, when a certain amount of PA is mixed and used as the acid component, it is possible to provide a semi-incombustible aromatic polyester polyol having excellent reactivity with isocyanate by lowering crystallinity and controlling low viscosity (low molecular weight distribution increase).
Meanwhile, an alcohol component represented by Chemical Formula 1 in the present invention may include monoethyl glycol, diethylene glycol, neopentyl glycol, methyl propanediol, and trimethylol propane, and in particular, neopentyl glycol (NPG) or diethylene glycol (DEG).
NPG has an effect of increasing solubility due to its bulky structure, and has a methyl group (short chain), so that NPG has an effect of improving flame retardancy and compatibility compared to DEG due to the van der Waals interaction effect. In addition, since NPG includes tertiary carbon atoms, it has relatively high thermal stability and has an effect of lowering crystallinity. Therefore, in one embodiment of the present invention, NPG is used as the alcohol component of the polyester polyol, and at this time, it is proposed to use it together with DEG.
When NPG and DEG are used together as the alcohol component, a mixing ratio is preferably in a range of 1:2 to 1:20 in terms of a molar ratio in order to obtain an effect of using NPG.
The polyester polyol of the present invention is prepared using the acid component and the alcohol component in a mixing ratio of 1.0:1.4 to 2.0 mol. In addition, for a reaction of the acid component and the alcohol component, the reaction is carried out at a temperature of 170 to 240° C. at atmospheric pressure in the presence of a catalyst such as butylstannonic acid, butyltin tris-2-ethylhexanoate, tertabutyl titanate, or the like for 7 to 12 hours.
The polyester polyol of the present invention preferably has a weight average molecular weight of 300 g/mol to 3,000 g/mol in terms of storage stability and flame retardancy of polyurethane prepared using the same. Specifically, when the weight average molecular weight of the polyester polyol is less than 300 g/mol, preparation is difficult, and when the weight average molecular weight exceeds 3,000 g/mol, the storage properties and urethane reactivity of the polyester polyol are lowered, so that the flame retardancy of the polyurethane may be reduced.
As the polyester polyol of the present invention uses PIA or PA as the acid component, especially includes PIA, and uses DEG or a mixture of DEG and NPG as the alcohol component, low viscosity is controlled to increase a low molecular weight distribution, and reactivity with isocyanate is excellent. Therefore, it is advantageous in terms of preparation of the polyurethane.
The present invention provides a polyurethane prepared by reacting the polyester polyol with one or more compounds including two or more isocyanate groups. The preparation of the polyurethane may be made by generally known techniques. It usually involves a reaction between an isocyanate component and a polyol component in the presence of a catalyst and a foaming agent.
The one or more compounds including two or more isocyanate groups are compounds including two or more isocyanate groups (—N═C═O), and may include, 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 diisocyanate, 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-cyclohexane diisocyanate, isomers thereof, or mixtures thereof, but are 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, the additives may include, but are not limited to, commonly used additives such as foaming agents, flame retardants, foam stabilizers, catalysts, surface active materials, cell control agents, fillers, dyes, pigments, and hydrolysis control agents.
In the present specification, the foaming agent includes water, a 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, as the flame retardant, a commonly used flame retardant may be used, and the flame retardant may include, 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-dibromopropyl) phosphate, tetrakis(2-chloroethyl) ethylenediphosphate, dimethyl methanephosphonate, diethyl diethanolaminomethylphosphonate, and also commercially available halogenated flame retardant polyols. With additional phosphates or phosphonates, a liquid flame retardant includes, but is not limited to, diethyl ethanephosphonate (DEEP), triethyl phosphate (TEP), dimethyl propylphosphonate (DMPP), or diphenyl cresyl phosphate (DPK).
In the present specification, the foam stabilizer includes, but is not limited to, a silicone foam stabilizer, a non-ionic foam stabilizer, a non-silicone foam stabilizer, and the like, and specifically includes dinonyl phenol, methyl glucoside, methyl propanediol, vinyl ether maleic acid, an Si-copolymer series, and the like.
In the present specification, as the catalyst, a commonly used catalyst may be used, and the catalyst may include, but is not limited to, 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.
The polyurethane prepared using the polyester polyol according to one embodiment of the present invention has excellent flame retardancy and dimensional stability.
Hereinafter, examples will be given to describe the present invention in detail. However, the examples according to the present invention may be modified into various other forms, and the scope of the present invention is not to be construed as being limited to the examples described below. The examples of the present specification are provided to more completely explain the present invention to those of ordinary skill in the art.
4.6 mol of phthalic anhydride (PA, SigmaAldrich), 8.38 mol of diethylene glycol (DEG, Lotte Chemical Co., Ltd.), and 0.0008 mol of butylstannoic acid (Fascat 4100, Arkema) were added to a 2 L reactor equipped with a stirrer, a packing column, and a stirring bar, and the temperature was primarily raised to 170° C. (2 hours). A stirring speed during the temperature increase process was 200 rpm, and an ES reaction was performed for 2 hours. The temperature was secondarily raised to 230° C. for 3 hours. After holding for 1 hour, a vacuum was set at 200 mmHg, and then a reaction was performed for 2 hours to prepare a resin having an acid value (mg KOH/g resin) of 0.4 and a hydroxyl value (mg KOH/g resin) of 276.
A resin was prepared in the same manner as in Comparative Example 1, except for changing some of the conditions described in Table 1 below.
4.6 mol of purified isophthalic acid (PIA, Lotte Chemical Co., Ltd.), 7.58 mol of diethylene glycol (DEG, Lotte Chemical Co., Ltd.), 0.84 mol of neopentyl glycol (NPG, LG Chem Co., Ltd.), and 0.0008 mol of butylstannoic acid (Fascat 4100, Arkema) were added to a 2 L reactor equipped with a stirrer, a packing column, and a stirring bar, and the temperature was primarily raised to 170° C. (2 hours). A stirring speed during the temperature increase process was 200 rpm, and an ES reaction was performed for 2 hours. The temperature was secondarily raised to 230° C. for 3 hours. After holding for 1 hour, a vacuum was set at 200 mmHg, and then a reaction was performed for 2 hours to prepare a resin having an acid value (mg KOH/g resin) of 0.5 and a hydroxyl value (mg KOH/g resin) of 281.
A resin was prepared in the same manner as in Example 1, except for changing some of the conditions described in Table 1 below.
Next, polyurethanes were prepared from the polyols. 100 g of resin, 10 g of tris(1-chloro-2-propyl)phosphate (TCPP, flame retardant, SigmaAldrich), 1 g of TEGOSTAB®B8462 (foam stabilizer, silicone surfactant, Evonik), 12 g of cyclopentane (foaming agent, SigmaAldrich), 3.5 g of Dabco k-15 (Catalyst, Evonik), and 1.0 g of N,N-dimethylcyclohexylamine (DMCHA, catalyst, Huntsman), were put into a 2 liter can and then mixed using a high-speed stirrer to prepare a system polyol.
The physical properties of the prepared polyurethanes are shown in Table 3 below.
The polyols of Examples 1 to 3 had excellent storage stability and compatibility, and flame retardancy of the polyurethane prepared therefrom was also excellent. On the other hand, the polyol of Comparative Example 2 had significantly poor storage stability and compatibility, and Comparative Examples 1, 4 and 5 showed poor results in terms of flame retardancy. In addition, the PIA/DEG polyol of Comparative Example 3 had good physical properties such as flame retardancy and water absorption, but was difficult to use due to poor compatibility with raw materials used in the system polyol.
More specifically, since the polyols of Comparative Examples 1 to 3 are results of using DEG as an alcohol component and the same amount of other acid components, it was possible to compare effects depending on the type of acid component. When PA was used (Comparative Example 1), storage stability and compatibility were maintained excellently, but flame retardancy was greatly reduced. When PTA was used (Comparative Example 2), storage stability and compatibility were greatly reduced. When PIA was used (Comparative Example 3), compatibility was slightly reduced. However, compared to Example 1 in which NPG was mixed as the alcohol component under the same conditions, storage stability and compatibility were reduced, and the total heat release and total smoke generation increased, indicating poor physical properties. That is, when PIA was used alone as the acid component, a much better polyol was obtained when NPG was mixed and used as the alcohol component. In addition, when Comparative Example 3 was compared with Example 3 in which PIA and PA were mixed as acid components, it was confirmed that storage stability and compatibility were significantly improved. That is, when only DEG was used as the alcohol component, polyols having excellent physical properties were obtained when PIA and PA were used together.
Next, the polyols of Example 1 and Comparative Example 3 show different results by using NPG as the alcohol component when PIA was used alone as the acid component, and when NPG was used in combination, storage stability and compatibility were better than when DEG was used alone.
On the other hand, the polyols of Example 3 and Comparative Example 5 are cases in which the mixing ratio was changed when PA and PIA were used as acid components, and flame retardancy was poor in Comparative Example 5 in which the amount of PA was increased.
Therefore, like polyester polyols according to the practice of the present invention, by using PIA alone as the acid component or using PA and PIA in a certain mixing ratio, and using DEG or a mixture of DEG and NPG as the alcohol component, it was confirmed that the storage stability and the compatibility of the polyol were improved, and the flame retardancy and the dimensional stability of the polyurethane prepared using the same could be improved.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10-2020-0165222 | Nov 2020 | KR | national |
| 10-2021-0068094 | May 2021 | KR | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/KR2021/017881 | 11/30/2021 | WO |
