KR102190327B1 - Method for preparing poly(ether ester) copolymer - Google Patents

Abstract

The present invention relates to a method for producing a polyether ester copolymer capable of significantly reducing side reactions during the production process. According to the method for preparing a polyether ester copolymer of the present invention, side reactions during the manufacturing process are significantly reduced, and thus, a polyether ester copolymer of excellent quality with improved purity and color can be obtained.

Description

Method for preparing polyether ester copolymer {Method for preparing poly(ether ester) copolymer}

The present invention relates to a method for producing a polyether ester copolymer capable of significantly reducing side reactions during the production process.

Thermoplastic poly(ether ester) elastomer (TPEE) is a high-performance material that combines the elasticity of rubber and the molding processability of plastic. It replaces vulcanized rubber and polyvinyl chloride (PVC), and is used for home appliances, construction materials, including automobiles. It is used in a wide range of fields such as IT and daily goods. The TPEE is typically a polyether ester-based block copolymer resin composition.

The polyether ester copolymer is composed of a hard segment composed of a diol and a dicarboxylic acid and a soft segment composed of a polyether polyol and a dicarboxylic acid, and has the characteristics of an elastomer. The hard segment provides mechanical properties of the elastomer, and the soft segment provides elasticity and flexibility of the elastomer.

These thermoplastic polyether ester copolymers are commercially made of diol, dicarboxylate (or dicarboxylic acid), and polyalkylene glycol as raw materials, and are then subjected to an ester exchange reaction or esterification. , It is prepared through a two-step reaction of polycondensation of the reaction product. The transesterification reaction (or esterification reaction) and condensation polymerization reaction are generally carried out under a titanium-based catalyst. On the other hand, when a higher molecular weight or higher viscosity product is to be manufactured, a solid-phase polymerization reaction step may be additionally performed.

However, in the conventional method for preparing a polyether ester copolymer as described above, side reactions occur, thereby generating a significant amount of unwanted end groups such as -COOH and by-products such as tetrahydrofuran (THF). These unnecessary end groups and by-products have a problem of deteriorating the quality of the final product, such as generating odor and causing discoloration.

The present invention is to solve the above problem, and an object of the present invention is to provide a method for producing a polyether ester copolymer capable of producing a product of excellent quality by significantly reducing side reactions.

In order to solve the above problems, the present invention

a) diol; Dicarboxylate or dicarboxylic acid; And transesterification or esterification reaction of the polyether polyol in the presence of a titanium-based catalyst, and

b) Injecting a magnesium-based catalyst and a zinc-based catalyst into the reaction mixture in which step a) has been completed, and condensation polymerization is provided to prepare a polyether ester copolymer.

The titanium-based catalyst may include tetraalkyl titanate and partial hydrolyzate thereof; Titanyl oxalate compound; Titanium halides and hydrolysates thereof; Titanium composite oxide; A reaction product of a titanium alkoxide and a phosphorus compound; And combinations thereof.

The content of the titanium-based catalyst is diol; Dicarboxylate or dicarboxylic acid; And based on the total weight of the polyether polyol, it may be 0.1 to 1000 ppm.

The magnesium-based catalyst may be at least one selected from the group consisting of magnesium acetate, magnesium oxide, magnesium nitrate, and magnesium carbonate.

The zinc-based catalyst may be at least one selected from the group consisting of zinc acetate, zinc oxide, and zinc nitrate.

The total content of the magnesium-based catalyst and the zinc-based catalyst is diol; Dicarboxylate or dicarboxylic acid; And based on the total weight of the polyether polyol, it may be 0.1 to 1000 ppm.

The content of the magnesium-based catalyst and the zinc-based catalyst may be less than 500 ppm, respectively.

The titanium-based catalyst may be used in an amount greater than the weight of each of the magnesium-based catalyst and the zinc-based catalyst.

The weight ratio of the titanium-based catalyst: magnesium-based catalyst: zinc-based catalyst may be 1 to 2: 0.5 to 1: 0.5 to 1.

According to the method for preparing a polyether ester copolymer of the present invention, side reactions during the manufacturing process are significantly reduced, and thus, a polyether ester copolymer of excellent quality with improved purity and color can be obtained.

The terms used in the present specification are only used to describe exemplary embodiments, and are not intended to limit the present invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. In the present specification, terms such as "comprises", "includes" or "have" are intended to designate the existence of a feature, step, component, or combination of the implemented features, one or more other features or steps, It is to be understood that the possibility of the presence or addition of components, or combinations thereof, is not excluded in advance.

The present invention will be described in detail below and exemplify specific embodiments, as various changes can be made and various forms can be obtained. However, this is not intended to limit the present invention to a specific form disclosed, it should be understood to include all changes, equivalents, and substitutes included in the spirit and scope of the present invention.

Hereinafter, the present invention will be described in detail.

The present invention is a) diol; Dicarboxylate or dicarboxylic acid; And transesterification or esterification reaction of the polyether polyol in the presence of a titanium-based catalyst, and

b) Injecting a magnesium-based catalyst and a zinc-based catalyst into the reaction mixture in which step a) has been completed, and condensation polymerization is provided to prepare a polyether ester copolymer.

According to the above configuration, the condensation polymerization reaction in the present invention proceeds in the presence of a titanium-based, magnesium-based and zinc-based catalyst. Accordingly, according to the present invention, the occurrence of side reactions is significantly reduced compared to the conventional polyether ester copolymer manufacturing method, and the final polyether ester copolymer has fewer by-products such as THF, and has a terminal group content such as -COOH. There is little, no odor, and excellent color and purity. Since the manufacturing method of the present invention does not require modification of existing facilities or addition of other additives, it has excellent effects in terms of economic efficiency and efficiency of the process.

In the present invention, the thermoplastic polyether ester elastomer is a diol; Dicarboxylate or dicarboxylic acid; And transesterification or esterification reaction of polyalkylene glycol in the presence of a catalyst, and then transfer of the obtained reaction mixture to a separate condensation polymerization pot and condensation polymerization in the presence of a catalyst.

In the present invention, the diol is an aliphatic or alicyclic diol having 2 to 10 carbon atoms, and preferably has a molecular weight of 300 g/mol or less in terms of implementing the effects of the present invention. Specifically, examples of diols that can be used in the present invention include ethylene glycol, propylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6- Hexanediol or 1,4-cyclohexanedimethanol may be used, but is not limited thereto. Specifically, in the present invention, the diol may be 1,4-butanediol.

The diol is used in an amount of 10 to 60 parts by weight, preferably 14 to 40 parts by weight, based on a total of 100 parts by weight of the starting material, that is, diol, dicarboxylate (or dicarboxylic acid) and polyalkylene glycol. If the diol content is less than 10 parts by weight or more than 60 parts by weight, the reaction balance is not correct and the reaction does not proceed.

Examples of dicarboxylic acids that can be used in the present invention include terephthalic acid, isophthalic acid, 2,6-naphthalene dicarboxylic acid, 1,5-naphthalene dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid, and the like. Can be lifted. The dicarboxylate that can be used in the present invention may be, for example, an aromatic dicarboxylate, specifically dimethyl terephthalate, dimethyl isophthalate, 2,6-dimethyl naphthalene dicarboxylate, dimethyl 1,4-cylate Lohexane dicarboxylate, etc. are mentioned. These may be used alone or in combination. According to a preferred embodiment of the present invention, dimethyl terephthalate may be used as the dicarboxylic acid or dicarboxylate.

The dicarboxylate or dicarboxylic acid is used in an amount of 15 to 70 parts by weight, preferably 18 to 60 parts by weight, based on 100 parts by weight of the total starting material. If dicarboxylate or dicarboxylic acid is used in an amount of less than 15 parts by weight or more than 70 parts by weight of the starting material, it is preferable to satisfy the above range because it may result in a decrease in the moldability and heat resistance of the product. Do.

Specific examples of the polyether polyol that can be used in the present invention include one or more selected from the group consisting of polytetramethylene glycol, polyethylene glycol, polypropylene glycol, and polyhexamethylene glycol, but is not limited thereto. Specifically, the polyether polyol may be polytetramethylene glycol.

At this time, the number average molecular weight (Mn) of the polyether polyol is not particularly limited, but polymerization reactivity and product properties in the range of 400 to 6,000 g/mol, or 800 to 3,000 g/mol, or 1,500 to 2,400 g/mol. It is appropriate in terms of If the molecular weight of the polyether polyol is less than 400 g/mol, the blockiness of the polyether ester copolymer decreases, resulting in lower melting and softening points, and if it exceeds 6,000 g/mol, the hard segment and the soft segment of the polyether ester copolymer There is a problem that it becomes opaque and becomes pearly after being separated.

The number average molecular weight can be determined by, for example, gel permeation chromatography (GPC) or terminal titration (acetylating the end of the polyether polyol using acetic anhydride, decomposing unreacted acetic anhydride with acetic acid, and using an alkali. It can be determined by a method including measuring the OH number of the acetylated polyether polyol by reverse titration and determining the number average molecular weight of the polyether polyol from the OH number).

The polyether polyol is used in an amount of 5 to 70 parts by weight, preferably 13 to 67 parts by weight, based on 100 parts by weight of the total starting material. If the polyether polyol is less than 5 parts by weight, the hardness of the polyether ester copolymer may be too high and there may be a problem with flexibility, and if it exceeds 70 parts by weight, the mechanical strength of the product may decrease and heat resistance and compatibility may be problems. It is desirable to satisfy the range.

Step a) of the present invention comprises a diol; Dicarboxylate or dicarboxylic acid; And a transesterification reaction or esterification reaction step of reacting the polyether polyol. The step a) is performed in the presence of a catalyst, and in this case, a material known in the art may be used without limitation, as the catalyst includes titanium as an active ingredient.

Specifically, examples of the titanium-based catalyst that can be used in step a) include tetraalkyl titanate and partial hydrolyzate thereof, titanyl oxalate compound, titanium halide and hydrolyzate thereof, titanium composite oxide, titanium alkoxide and And reactants of phosphorus compounds, and these may be used alone or in combination.

Examples of the tetraalkyl titanate and partial hydrolyzate thereof include tetraethyl titanate, tetraisopropyl titanate, tetra-n-propyl titanate, tetra-n-butyl titanate (TBT), and the like.

Examples of the titanyl oxalate compound include titanium acetate, titanyl oxalate, titanyl ammonium oxalate, sodium titanyl oxalate, titanyl potassium oxalate, calcium titanyl oxalate, strontium titanyl oxalate, and the like.

Examples of the titanium halide and hydrolyzate thereof include titanium trimellitate, titanium sulfate, titanium fluoride, and titanium chloride.

Examples of the titanium composite oxide include titanium silicide, potassium 6-fluoride titanate, ammonium 6-fluoride titanate, cobalt 6-fluoride titanate, manganese 6-fluoride titanate, and titanium acetyl acetonate.

In a preferred embodiment of the present invention, TBT may be used as the titanium-based catalyst.

The amount of catalyst introduced in step a) is preferably 0.1 to 1000 ppm, or 0.1 to 700 ppm, or 0.1 to 500 ppm, based on the total weight of the starting material. If the amount of catalyst added in step a) is less than 0.1 ppm, the time required for polymerization is long, resulting in a decrease in productivity or thermal decomposition due to long-term reaction.If it exceeds 1000 ppm, it causes decomposition and odor due to side reactions. There is a possibility of the formation of substances.

The reaction conditions in step a) are not particularly limited, and may be appropriately adjusted according to the type, content and combination of starting materials, and physical properties of the polyether ester copolymer to be prepared.

For example, step a) may be performed under normal pressure or 500 to 760 torr, and may be performed under a temperature condition of 150 to 300°C, 150 to 250°C, or 150 to 210°C, but is not limited thereto. In addition, the reaction in step a) is preferably performed under stirring, and the reaction time is not limited, but may range from 60 to 200 minutes. When the above conditions are satisfied, the reaction conversion rate can be increased.

When the step a) is completed, the condensation polymerization step of b) is then performed. Step b) may be performed in a separate reactor from step a).

The titanium-based catalyst used in the transesterification reaction or the esterification reaction can also be used as a catalyst for the condensation polymerization reaction. In addition, since the titanium-based catalyst remains in the reaction mixture after transesterification or esterification, it may act as a catalyst in the subsequent condensation polymerization reaction. Therefore, in the conventional method for preparing a polyether ester copolymer, it is common to perform a condensation polymerization reaction after adding a catalyst to the condensation polymerization reaction step or after adding the same titanium-based catalyst.

However, when transesterification and condensation reactions are performed using only a titanium-based catalyst as described above, side reactions occur at a considerable level, resulting in a large amount of by-products and unwanted functional groups, and the resulting polyether ester copolymer has an odor. There is a problem in which quality deterioration occurs, such as loss or discoloration.

In order to improve the above problem, the present inventors studied a combination of a preferred catalyst, and as a result, a titanium-based catalyst was used in the transesterification reaction or the esterification reaction, but magnesium-based and zinc-based catalysts were used as catalysts added to the polycondensation reaction step. When used, it was confirmed that the above problem was greatly improved.

Accordingly, in the present invention, a magnesium-based catalyst and a zinc-based catalyst are used as catalysts added in step b). Accordingly, in the present invention, the condensation polymerization reaction includes titanium-based catalyst remaining after step a) and includes titanium, magnesium and zinc as catalytic active components.

The magnesium-based catalyst usable in the present invention is not particularly limited, and may be at least one selected from the group consisting of magnesium acetate, magnesium oxide, magnesium nitrate, and magnesium carbonate. According to a preferred embodiment of the present invention, the magnesium-based catalyst may be magnesium acetate. By including the magnesium-based catalyst as described above, it is possible to reduce the amount of odor-causing substances by suppressing side reactions.

In addition, the zinc-based catalyst usable in the present invention may include at least one selected from the group consisting of zinc acetate, zinc oxide, and zinc nitrate, but is not limited thereto. According to a preferred embodiment of the present invention, the zinc-based catalyst may be zinc acetate. When the zinc-based catalyst is included, the amount of odor-causing substances can be reduced, and the color tone of the produced polyether ester copolymer can be greatly improved.

The catalytic amount of step b) is the starting material, that is, diol; Dicarboxylate or dicarboxylic acid; And 0.1 to 1000 ppm, or 0.1 to 700 ppm, or 0.1 to 500 ppm, based on the total weight of the polyether polyol. If the amount of catalyst is less than 0.1 ppm, the time required for the reaction may be lengthened and productivity may decrease. If it exceeds 1000 ppm, there is a possibility of decomposition and generation of odor-causing substances due to side reactions.

In the present invention, the weight ratio of the titanium-based catalyst used in steps a) and b): the magnesium-based catalyst: the zinc-based catalyst is preferably in the range of 1 to 2: 0.5 to 1: 0.5 to 1. When the above range is satisfied, there is an effect of improving color and reducing odor without impairing productivity.

In addition, in order to secure the effect of the present invention, step b) may be performed under high vacuum conditions of 1 torr or less, or 0.3 torr or less, and may be performed under a temperature condition of 200 to 300 °C, or 200 to 250 °C. . Step b) is preferably carried out under stirring, and by observing the torque, when the value no longer increases, the stirring speed is gradually reduced to complete the reaction, thereby finally preparing a polyether ester copolymer. Although not limited, the reaction time of step b) may range from about 30 minutes to 5 hours, or 1 to 3 hours.

Meanwhile, in the production method of the present invention, an additive may be further included in step a) or b) in order to improve the reaction efficiency of each step and adjust the properties of the polyether ester elastomer to be produced.

Examples of additives that can be used include branching agents for increasing the melt strength of the polyether ester copolymer (e.g., glycerol, sorbitol, pentaerythritol, 1,1,4,4-tetrakis(hydroxymethyl)cyclohexane , Trimethylol propane, pyromellitic acid, 1,1,2,2-ethanetetracarboxylic acid, etc.), matting agents for improving color properties (eg, TiO ₂ , zinc sulfide or zinc oxide), coloring agents (E.g., dyes), stabilizers (e.g., antioxidants, ultraviolet light stabilizers, heat stabilizers, etc.), fillers, flame retardants, pigments, antimicrobial agents, antistatic agents, light brighteners, extenders, processing aids or viscosity enhancers And the like, and any one or a mixture of two or more of them may be used, but the present invention is not limited thereto. As an example, 1,3,5-trimethyl-2,4,6'-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene as an antioxidant is added with the catalyst in step b). I can.

Each of these additives secures the desired effect, but can be used in an appropriate amount within a range that does not deteriorate the physical properties of the polyether ester copolymer to be produced, specifically 0.1 to 10 based on 100% by weight of the total starting material. It can be used in weight percent.

According to the manufacturing method of the present invention described above, side reactions during the manufacturing process of the polyether ester copolymer can be significantly reduced without any additional additives or changes in manufacturing equipment. Accordingly, the content of end groups such as -COOH or by-products such as THF that causes odor and discoloration in the final product is significantly reduced, and thus a polyether ester copolymer of improved quality can be prepared.

Specifically, the polyether ester copolymer prepared according to an embodiment of the present invention may preferably have a THF content of about 2000 ug/g or less, or 1600 ug/g or less, or 1550 ug/g or less. In addition, the polyether ester copolymer may preferably have a -COOH end group content of 40 eq/ton or less, or 35 eq/ton or less, or 30 eq/ton or less. The THF content and the -COOH end group content may be measured in the same manner as in Experimental Examples to be described later.

Hereinafter, preferred embodiments are presented to aid the understanding of the present invention, but the following examples are only illustrative of the present invention, and it is obvious to those skilled in the art that various changes and modifications are possible within the scope and spirit of the present invention. It is natural that changes and modifications fall within the scope of the appended claims.

[Example]

Example 1

323 parts of dimethyl terephthalate (DMT), 633 parts of polytetramethylene glycol (PTMG, Mn=2000), 217 parts of 1,4-butylene glycol (BG) and tetrabutyl titanate (TBT) 0.43 weight in a transesterification kettle Part (366ppm) was added and transesterification was performed at 140 to 210°C for 120 minutes at atmospheric pressure (760 torr).

To the reaction mixture in which the transesterification reaction was completed, 0.3 parts by weight (255 ppm) of magnesium acetate and zinc acetate were added respectively, and then the transesterification reaction product was transferred to a condensation polymerization pot, the temperature was raised from 210 to 245°C, and the degree of vacuum in the reaction part was adjusted. Condensation polymerization was carried out at 0.3 torr or less. When the torque value of the reactant was observed and reached the maximum value, the reaction was stopped, pressurized, and discharged into cold water to obtain a pelletized polyether ester copolymer.

Example 2

In a transesterification pot, 330 parts of dimethyl terephthalate (DMT), 180 parts of polytetramethylene glycol (PTMG, Mn=1000), 200 parts of 1,4-butylene glycol (BG) and 0.3 weight of tetrabutyl titanate (TBT) Part (423ppm) was added and transesterification was performed at 140 to 210°C for 120 minutes at atmospheric pressure.

To the reaction mixture in which the transesterification reaction was completed, 0.2 parts by weight (282 ppm) and 0.4 parts by weight (563 ppm) of magnesium acetate and zinc acetate were added, respectively, and the transesterification reaction was transferred to a condensation polymerization pot from 210 to 245°C. The temperature was raised and condensation polymerization was carried out with a vacuum degree of 0.3 torr or less in the reaction part. When the torque value of the reactant was observed and reached the maximum value, the reaction was stopped, pressurized, and discharged into cold water to obtain a pelletized polyether ester copolymer.

Example 3

Polyether ester copolymer in the same manner as in Example 2, except that 0.3 parts by weight of TBT (423 ppm) and 0.4 (563 ppm) and 0.2 parts by weight (282 ppm) of magnesium acetate and zinc acetate were added as a catalyst for the transesterification reaction. Was prepared.

Example 4

A polyether ester copolymer was prepared in the same manner as in Example 2, except that 0.3 parts by weight (423 ppm) of TBT and 0.3 parts by weight (423 ppm) of magnesium acetate and zinc acetate were added as a catalyst for the transesterification reaction.

Comparative Example 1

A polyether ester copolymer was prepared in the same manner as in Example 1, except that 1.3 parts by weight of TBT (1108 ppm) as a catalyst for transesterification and 0.5 parts by weight (426 ppm) of TBT as a catalyst for the condensation polymerization reaction were added.

Comparative Example 2

A polyether ester copolymer was prepared in the same manner as in Example 2, except that 0.3 parts by weight of TBT (423 ppm) as a catalyst for the transesterification reaction and 0.8 parts by weight (1127 ppm) of TBT as a catalyst for the condensation polymerization reaction were added.

Comparative Example 3

As a catalyst for the transesterification reaction, 0.43 parts by weight (366 ppm) of TBT magnesium acetate and 0.3 parts by weight (255 ppm) of zinc acetate were added respectively, and the polyether ester was copolymerized in the same manner as in Example 1, except that a condensation polymerization catalyst was not added. The coalescence was prepared.

As a result, it was found that the torque (viscosity) did not increase at all even after the condensation polymerization reaction time elapsed for 3 hours, and a sufficient degree of polymerization could not be obtained under the above conditions.

[Experimental Example]

For each copolymer of Examples and Comparative Examples, THF content, -COOH end group content, and yellowness were measured by the following method. The results are shown in Table 1 below.

(1) THF content measurement

Put 0.2g of sample into a 22mL Headspace vial, close the cap, and leave it in an oven at 110°C for 90 minutes, and analyze with HS-GC/FID.

(2) -COOH end group content measurement

Take 0.150 ± 0.002g of the finely ground sample and put it in a 30mL vial. After quantifying o-cresol and chloroform into a vial containing the polymer with a micropipette, 10 mL each, close the cap tightly, and stir until the polymer is completely dissolved at room temperature. After all the polymer is dissolved, add 2-3 drops of 0.1% phenol red, titrate with 0.04N KOH/ethanol until the color of the indicator turns from yellow to orange, and record the volume of the consumed KOH/ethanol solution. In the same way, after performing the blank test without the copolymer sample, the acid value is calculated through Equation 1 below.

[Equation 1]

V: Volume (mL) of KOH/ethanol solution consumed for titration of the sample

VO: Volume of KOH/ethanol solution consumed in the titration of the blank test (mL)

M: Molar concentration of KOH/ethanol solution (0.04 mol/L)

F: titer of KOH/ethanol solution

(3) Measurement of yellow index

Each copolymer was in a pallet state, and the yellowness was measured using a Colorflex colorimeter.

THF content (ug/g) COOH content (eq/ton) Yellowness Example 1 1059 16 2 Example 2 1530 30 9 Example 3 1606 32 11 Example 4 2000 38 10 Comparative Example 1 2393 42 13 Comparative Example 2 2580 73 29

Referring to Table 1, when magnesium-based and zinc-based catalysts are added as catalysts in the condensation polymerization step, the amount of THF produced as a by-product and the content of -COOH end groups are compared with the case of using only a titanium-based catalyst as in the conventional method. It was found to be significantly reduced, and it can be seen that the yellowness was also greatly improved. However, it can be seen from Comparative Example 3 that when the magnesium-based and zinc-based catalysts are used together with the titanium-based catalyst from the transesterification step, a sufficient degree of polymerization is not obtained, and the effect of the present invention cannot be obtained.

The effect was found to be more excellent when a titanium-based catalyst is mainly used, but magnesium and zinc-based catalysts are additionally used. That is, in the case of Example 1 in which the content of TBT was higher than that of magnesium acetate and zinc acetate, the contents of THF and -COOH were smaller than those of Examples 2 to 4, and the yellowness was also greatly improved Appeared.

From the above results, in order to obtain the effect of the present invention, a titanium-based catalyst and a magnesium-based and zinc-based catalyst are used together with a titanium-based catalyst when preparing the polyether ester copolymer, but the magnesium-based and zinc-based catalyst is a condensation polymerization step rather than a transesterification step It can be seen that it should be put in. In addition, in order to obtain more excellent results, it can be seen that it is preferable to use a titanium-based catalyst in a higher ratio.

Claims (9)

a) diol; Dicarboxylate; And transesterification of the polyether polyol in the presence of a titanium-based catalyst, and
b) Injecting a magnesium-based catalyst and a zinc-based catalyst into the reaction mixture in which step a) has been completed and condensation polymerization as a method for producing a polyether ester copolymer,
The diol is ethylene glycol, propylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, or 1,6-hexanediol,
The dicarboxylate is at least one selected from the group consisting of dimethyl terephthalate, dimethyl isophthalate, 2,6-dimethylnaphthalenedicarboxylate, and dimethyl 1,4-cyclohexanedicarboxylate,
The polyether polyol is at least one selected from the group consisting of polytetramethylene glycol, polyethylene glycol, polypropylene glycol, and polyhexamethylene glycol,
The titanium-based catalyst is at least one selected from the group consisting of tetraethyl titanate, tetraisopropyl titanate, tetra-n-propyl titanate, and tetra-n-butyl titanate,
The magnesium-based catalyst is at least one selected from the group consisting of magnesium acetate, magnesium oxide, magnesium nitrate, and magnesium carbonate,
The zinc-based catalyst is at least one selected from the group consisting of zinc acetate, zinc oxide, and zinc nitrate,
Method for producing a polyether ester copolymer.
delete The method of claim 1,
The content of the titanium-based catalyst is diol; Dicarboxylate; And 0.1 to 1000 ppm, based on the total weight of the polyether polyol, for producing a polyether ester copolymer.
delete delete The method of claim 1,
The total content of the magnesium-based catalyst and the zinc-based catalyst is diol; Dicarboxylate; And 0.1 to 1000 ppm, based on the total weight of the polyether polyol, for producing a polyether ester copolymer.
The method of claim 6,
The content of the magnesium-based catalyst and the zinc-based catalyst are each less than 500 ppm, the method of producing a polyether ester copolymer.
The method of claim 1,
The titanium-based catalyst is used in an amount greater than the weight of each of the magnesium-based catalyst and the zinc-based catalyst, a method for producing a polyether ester copolymer.
The method of claim 1,
The weight ratio of the titanium-based catalyst: magnesium-based catalyst: zinc-based catalyst is 1 to 2: 0.5 to 1: 0.5 to 1, a method for producing a polyether ester copolymer.