KR102058153B1 - Manufacturing Method Of Polyesther Polyol Using Terephthalic Acid - Google Patents

Abstract

The present invention relates to a method for manufacturing polyester polyol which improves flame retardancy and strength of polyester polyol and improves production efficiency by using terephthalic acid. More specifically, the present invention relates to a method for manufacturing polyester polyol by using terephthalic acid, which comprises a first reaction step of making a mixture of 50-70 wt% of diethylene glycol (DEG), 20-30 wt% of phthalic acid (PA), and 10-20 wt% of terephthalic acid (TPA) at 160-180°C for 7-9 hours; a second reaction step of making the mixture through the first reaction react at 220-240°C for 7-9 hours; and a step of filtering the mixture through the second reaction.

Description

Manufacturing Method Of Polyesther Polyol Using Terephthalic Acid

The present invention relates to a method for producing a polyester polyol with improved production efficiency while improving the flame retardancy and strength of the polyester polyol using terephthalic acid, and more specifically, 50 to 70% by weight of diethylene glycol (DEG) and phthalic acid (PA). ) A first reaction step of reacting a mixture of 20 to 30% by weight and 10 to 20% by weight of terephthalic acid (TPA) at 160 to 180 ° C. for 7 to 9 hours, and the mixture at which the first reaction is performed at 220 to 240 ° C. It relates to a secondary reaction step of reacting for ˜9 hours, and a method for producing a polyester polyol using terephthalic acid, comprising filtering the mixture made of the secondary reaction.

Polyurethane is a high molecular compound having a urethane bond obtained by chemical reaction between an isocyanate group-containing substance and an active hydrogen-containing substance, and according to raw materials and applied technologies, cushioning materials for automobiles and furniture, insulation materials for buildings, adhesives, waterproofing agents, flooring materials, It is a polymer material widely used in all industries such as artificial leather, coating agent, sealing agent and artificial fiber.

In general, polyol may be used as a material having active hydrogen used in the synthesis of polyurethane, and such polyol may be amine (Amine), phenol (Phenol), alcohol (Alcohol), water (H 2 O), or active methylene. It can be prepared using a compound (Active Methylene Compound) and the like as an initiator.

Polyols may be classified into various types according to chemical structures, and the most commonly used ones thereof include polyester polyols and polyether polyols. In particular, polyester polyols are generally produced by condensation reaction between phthalic acid (PA) and glycol, but in recent years, various modifications such as addition of functional materials have been made to improve the flame retardancy and strength of polyols produced. It is done.

However, these attempts have the advantage of adding functionality, such as improving the flame retardancy and strength of the polyol, but has a disadvantage in that it is difficult to control the quality, such that the overall production efficiency is poor and the quality control such as acid value and viscosity of the resulting polyol is difficult.

In the present invention, in order to improve the overall physical properties, such as flame retardancy and strength of the polyol produced by using a combination of phthalic acid and terephthalic acid in general, in order to overcome the disadvantages that the overall reactivity is poor and difficult to control the physical properties of the polyol, New polyol production methods with controlled reaction steps and conditions have been developed.

Republic of Korea Patent Publication KR 10-2019-0009815 A Republic of Korea Patent Application Publication KR 10-2018-0137938 A

The present invention is to solve the above problems, the polyester polyol to improve the overall physical properties such as the flame retardancy and strength of the polyol prepared using terephthalic acid and at the same time to overcome the disadvantages of difficult to control and control the physical properties of the polyol produced An object of the present invention is to provide a manufacturing method.

In order to achieve the above object, the present invention is a mixture of 50 to 70% by weight of diethylene glycol (DEG), 20 to 30% by weight of phthalic acid (PA) and 10 to 20% by weight of terephthalic acid (TPA) at 160 to 180 ℃ 7 A first reaction step of reacting for ˜9 hours, a second reaction step of reacting the mixture made with the first reaction at 220-240 ° C. for 7-9 hours, and filtering the mixture made with the secondary reaction To provide a method for producing a polyester polyol using terephthalic acid. At this time, it is preferable that the tin catalyst is added in the secondary reaction step.

The polyester polyol prepared according to the present invention uses terephthalic acid to improve overall physical properties such as flame retardancy and strength of the polyol, and to control reaction steps and conditions, thereby improving overall production efficiency.

1 is a process chart showing the manufacturing process of the polyester polyol of the present invention.

Hereinafter, with reference to the drawings and embodiments of the present invention will be described in detail. These examples are only presented by way of example only to more specifically describe the present invention, it will be apparent to those skilled in the art that the scope of the present invention is not limited by these examples. .

Also, unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs, and in the case of conflict, the specification including definitions The description of will prevail.

In the polyester polyol of the present invention, a polyester polyol is prepared through a condensation reaction of phthalic acid, terephthalic acid, and diethylene glycol, but the condensation reaction is composed of two steps having different temperature conditions, and a tin catalyst is introduced in the second step. It features. Take a closer look below.

First, 50 to 70% by weight of diethylene glycol (DEG), 20 to 30% by weight of phthalic acid (PA) and 10 to 20% by weight of terephthalic acid (TPA) are added thereto, and reacted at 160 to 180 ° C for 7 to 9 hours. . Thereafter, the mixture is secondly reacted again at 220-240 ° C. for 7-9 hours, in which a tin catalyst is preferably added to increase the production rate of the polyester polyol.

At this time, the tin catalyst may be used a variety of commonly used tin catalyst, in the present invention, i) to increase the production efficiency, i) a gel by heating and mixing the metal precursor solution and maleic acid at 80 ~ 90 ℃ for 1 to 3 hours Obtaining the compound and ii) it is preferable to use the tin-zinc catalyst prepared through the step of calcining the gel compound at 700 ~ 900 ℃ for 5 to 7 hours.

In detail, first, the metal precursor is dissolved in a solvent to prepare a metal precursor solution. At this time, the metal precursor may be oxides, nitrates, sulfur oxides of tin and zinc, the solvent is dimethylformamide, gamma butyrolactone, N-methylpyrrolidone, dimethyl sulfoxide and aprotic solvent Chloroethylene, trichloroethylene, chloroform, chlorobenzene, dichloro benzene, styrene, dimethylformamide, dimethyl sulfoxide, xylene, toluene, cyclohexene, isopropyl alcohol, etc. may be used, but is not limited thereto. In a preferred embodiment, distilled water may be used.

Maleic acid is mixed and stirred in the prepared metal precursor solution, and heated to a constant temperature in order to volatilize the solvent. As the solvent is volatilized, a gelled compound is obtained. At this time, it is preferable that the mixing ratio of a metal precursor and maleic acid is 2: 1-5: 1 by mass ratio.

The heating temperature is preferably 80 ~ 90 ℃, if the heating temperature is less than 80 ℃ the time required to obtain a gel-like compound is long, if it exceeds 90 ℃ solvent is too volatilized to obtain the desired gel compound I can't. The heating and stirring time is preferably 1 to 3 hours, and when less than 1 hour, volatilization of the solvent is insufficient, and when more than 3 hours, the solvent is excessively volatilized to obtain a desired gelled compound.

When the gel-like compound is prepared as described above, the firing process is performed. The firing temperature at this time is 700 to 900 ° C, and the firing time is preferably 5 to 7 hours. If the firing temperature and the firing time are less than or exceed the above range, the catalyst crystal structure may not be sufficiently produced or lost, resulting in insufficient catalytic effect.

The tin-zinc catalyst prepared as described above is preferably added in an amount of 0.1 to 1 parts by weight based on 100 parts by weight of the raw material mixture for polyol production.

Meanwhile, although the tin-zinc catalyst prepared as described above may be used as it is, preferably, in order to further increase the efficiency of the catalyst, the tin-zinc catalyst may be reworked in a form in which tin particles are dispersed on the surface of the tin-zinc catalyst.

That is, the prepared tin-zinc catalyst serves as a stable support, and tin is dispersed therein with a high dispersion so that high catalytic activity is possible while having strong interaction with the support. At this time, the dispersed tin is preferably added 1 to 10 parts by weight based on 100 parts by weight of tin-zinc catalyst serving as a support.

Specifically, this process, iii) by impregnating the tin-zinc catalyst prepared in the tin precursor solution for 2 to 5 hours by rotary evaporation at 50 ~ 60 ℃, then drying for 10 to 12 hours at 70 ~ 80 ℃, and iv ) Under a hydrogen and nitrogen atmosphere (hydrogen: nitrogen = 1: 1) at a temperature of 800-900 ° C. for 5-7 hours. The solvent used in the tin precursor solution is the same as described above.

Meanwhile, the tin catalyst may be optionally used with the bismuth catalyst in a weight ratio of 10: 1 to 1: 1 (tin catalyst: bismuth catalyst) to improve efficiency. The bismuth catalyst may be used a variety of commercially available bismuth catalyst, preferably a) bismuth oxide (Bi ₂ O ₃ ), distilled water and octanoic acid (C ₈ H ₁₆ O ₂ ) solution of 90 ℃ ~ 110 ℃ Reacting for 1 to 2 hours at a temperature to form a composition for preparing a catalyst, b) distilling the composition for preparing a catalyst under reduced pressure to remove a solvent and water generated during the reaction, and c) filtering the product to form a bismuth salt catalyst compound It can be prepared through the step of obtaining.

It is preferable that the said composition for catalyst manufacture contains 36-44 weight% of bismuth oxides, 4-6 weight% of distilled water, and 50-60 weight% of an octanoic acid solution based on the total weight of a composition. This is because when the bismuth oxide is included in less than 36% by weight and the octanoic acid solution is included in less than 50% by weight, the process yield and the purity of the catalyst to be produced are lowered. In addition, when bismuth oxide is included in excess of 44% by weight and octanoic acid solution in excess of 60% by weight, only the material cost is increased without further effect in terms of process yield or purity. Therefore, it is most preferable that the said composition for catalyst manufacture contains 40 weight% of bismuth oxide, 5 weight% of distilled water, and 55 weight% of an octanoic acid solution.

In addition, the step of forming the composition for preparing the catalyst is preferably carried out for 1 to 2 hours at a temperature of 90 ~ 110 ℃. When carried out at a temperature below 90 ° C., the reaction does not proceed sufficiently to reduce the process yield and lower the purity of the catalyst produced, and when carried out at temperatures above 110 ° C., the reaction proceeds too fast and the solvent rapidly Evaporation may result in failure to obtain the desired catalytic compound. In addition, when the reaction time is less than 1 hour, the reaction does not proceed sufficiently, the process yield is lowered, the purity of the catalyst produced is lowered, and if it exceeds 2 hours, it causes only fuel consumption without any further effect.

Thereafter, the catalyst composition is distilled under reduced pressure to remove the solvent and water generated during the reaction. At this time, the solvent and most of the water generated during the reaction are removed to form a paste-like product.

Thereafter, the bismuth salt catalyst compound is finally obtained by performing the step of filtering the product in the form of a paste to obtain a bismuth salt catalyst compound. If necessary, the step of drying after filtration may be further performed.

After the catalyst prepared as described above is finished until the second reaction, the catalyst is finally filtered and finally a polyester polyol product is obtained.

Hereinafter, the configuration and effects of the present invention will be described in more detail with reference to specific preparation examples and examples. However, this embodiment is intended to illustrate the present invention in more detail, and the scope of the present invention is not limited to these examples.

 [Examples and Comparative Examples]

1) (Example 1) A metal precursor solution was prepared by dissolving 30 g of tin oxide (SnO ₂ ) and 30 g of zinc oxide (ZnO) in distilled water. 20 g of maleic acid was added to the metal precursor solution, followed by stirring at room temperature for 2 hours, followed by volatilization of distilled water while the temperature was raised to 90 ° C. The gel compound thus obtained was calcined at 800 ° C. for 6 hours to obtain a tin-zinc catalyst.

Next, a mixture of 120 g of diethylene glycol (DEG), 50 g of phthalic acid (PA), and 30 g of terephthalic acid (TPA) was reacted at 170 ° C. for 8 hours, and then 0.3 part by weight of the catalyst prepared above was added to 230 parts by weight of the mixture. The reaction was carried out for 8 hours at ℃. Thereafter, a polyester polyol was obtained after filtration.

2) Example 2 A metal precursor solution was prepared by dissolving 30 g of tin oxide (SnO ₂ ) and 30 g of zinc oxide (ZnO) in distilled water. 20 g of maleic acid was added to the metal precursor solution, followed by stirring at room temperature for 2 hours, followed by volatilization of distilled water while the temperature was raised to 90 ° C. The gel compound thus obtained was calcined at 800 ° C. for 6 hours to obtain a tin-zinc catalyst.

The catalyst obtained was impregnated in a tin oxide (SnO 2) aqueous solution and rotary evaporated at 50 ° C. for 3 hours, dried at 75 ° C. for 10 hours, and then heated at 800 ° C. under hydrogen and nitrogen atmosphere (hydrogen: nitrogen = 1: 1) for 6 hours. Calcination gave a tin-zinc catalyst in which tin was dispersed on the surface.

Next, a mixture of 120 g of diethylene glycol (DEG), 50 g of phthalic acid (PA), and 30 g of terephthalic acid (TPA) was reacted at 170 ° C. for 8 hours, and then 0.3 part by weight of the catalyst prepared above was added to 230 parts by weight of the mixture. The reaction was carried out for 8 hours at ℃. Thereafter, a polyester polyol was obtained after filtration.

3) Example 3 A polyester polyol was prepared in the same manner as in Example 2, except that 10 parts by weight of the bismuth catalyst was used based on 100 parts by weight of the tin-zinc catalyst.

The bismuth catalyst was mixed with 300 g of octanoic acid and 130 g of toluene to prepare an octanoic acid solution. 4 g of distilled water and 60 g of the octanoic acid solution were added to the reactor, and 36 g of bismuth oxide was slowly added thereto while reacting at 90 ° C. for 2 hours. The product was distilled under reduced pressure to remove water produced during the reaction with toluene and filtered to obtain a bismuth salt catalyst compound (bismuth tris 2-ethylhexanoate).

(Comparative Example 1) A mixture of 120 g of diethylene glycol (DEG), 50 g of phthalic acid (PA) and 30 g of terephthalic acid (TPA) was reacted at 170 ° C. for 8 hours, followed by dibutyltin di, a commercially available tin catalyst. 0.1 parts by weight of laurate (Dibutyltin dilaurate) was added to the mixture and reacted at 230 ° C. for 8 hours. Thereafter, a polyester polyol was obtained after filtration.

(Comparative Example 2) A mixture of 120 g of diethylene glycol (DEG), 50 g of phthalic acid (PA) and 30 g of terephthalic acid (TPA) was reacted at 170 ° C. for 8 hours, followed by dibutyltin di, a commercially available tin catalyst. 0.3 parts by weight of laurate (Dibutyltin dilaurate) was added to the mixture and reacted at 230 ° C. for 8 hours. Thereafter, a polyester polyol was obtained after filtration.

Experimental Example

The quality of the polyester polyol was evaluated by measuring the acid value (mgKOH / g) and the viscosity of the polyester polyol prepared according to Examples 1 to 3 and Comparative Examples 1 and 2, and according to the following formula The recovery is calculated and shown in the table below. (X is the dosage of PA and TPA, Y is the dosage of DEG, and Z is the production of polyester polyol.)

Recovery (%) = (Z / X + Y) X 100

As can be seen from the table, it was confirmed that the quality of the polyol becomes homogeneous and the recovery rate increased from 3 to Example 1.

In the present specification, only a few examples of various embodiments performed by the present inventors are described, but the technical idea of the present invention is not limited thereto, but may be variously modified and implemented by those skilled in the art.

Claims (2)

First reaction step of reacting a mixture of 50 to 70% by weight of diethylene glycol (DEG), 20 to 30% by weight of phthalic acid (PA) and 10 to 20% by weight of terephthalic acid (TPA) at 160 to 180 ° C for 7 to 9 hours. ; A second reaction step of reacting the mixture in which the first reaction is performed at 220-240 ° C. for 7-9 hours; And filtering the mixture in which the secondary reaction is made.
In the second reaction step, the tin-zinc catalyst is added 0.1 to 1 parts by weight based on 100 parts by weight of the mixture,
The tin-zinc catalyst may include: i) heating and mixing the metal precursor solution and maleic acid at 80 to 90 ° C. for 1 to 3 hours to obtain a gel compound; And ii) calcining the gel compound at 700 to 900 ° C. for 5 to 7 hours.
The metal precursor solution is an oxide, nitrate or sulfur oxides of tin and zinc dimethylformamide, gamma butyrolactone, N-methylpyrrolidone, dimethylsulfoxide, dichloroethylene, trichloroethylene, chloroform, chlorobenzene, Prepared by dissolving in dichloro benzene, styrene, dimethylformamide, dimethylsulfoxide, xylene, toluene, cyclohexene, isopropyl alcohol or distilled water,
The mixing ratio of the metal precursor and maleic acid is 2: 1 to 5: 1 (mass ratio), the method for producing a polyester polyol using terephthalic acid, characterized in that.
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