Polyetherester copolymer and method for producing same

Abstract

The present invention relates to a polyetherester copolymer comprising a polymer matrix containing polyether repeating units and polyester repeating units; and a monometallic salt of an inorganic acid and a multimetallic salt of an inorganic acid remaining in the polymer matrix; and a method for producing the same.

Description

[Technical field]

[0001] (CROSS REFERENCE TO RELATED APPLICATIONS) This application claims the benefit of priority based on Korean Patent Application No. 10-2022-0168705 dated December 6, 2022, and all contents disclosed in the documents of that Korean patent application are incorporated herein by reference.

[0002] The present invention relates to a polyetherester copolymer that can significantly reduce the polymerization time and increase productivity while maintaining excellent physical properties of the copolymer, and a method for producing the same. [Background technology]

[0003] Thermoplastic poly(ether ester) elastomer (TPEE) is a highly functional material that combines the elasticity of rubber with the moldability of plastics, and is used in a wide range of fields such as automobiles, home appliances, building materials, IT, and everyday items, replacing vulcanized rubber and PVC (polyvinyl chloride). A representative example of the TPEE is a polyether ester block copolymer resin composition.

[0004] The polyether ester copolymer has the properties of an elastomer, consisting of a hard segment composed of a diol and a dicarboxylic acid derivative and a soft segment composed of a polyether diol and a dicarboxylic acid derivative. The hard segment provides the mechanical properties of the elastomer, and the soft segment provides the elasticity and flexibility of the elastomer.

[0005] Such thermoplastic polyetherester copolymers are commercially produced by a two-step reaction of a diol, a dicarboxylate and a polyetherdiol as raw materials, which comprises an ester exchange reaction and then a polycondensation reaction of the reaction product.

[0006] As an example, polybutylene terephthalate (PBT)-poly(tetramethylene ether glycol) (PTMG) copolymer, which is one of the widely known TPEEs, is produced through an ester exchange reaction and a condensation polymerization step using 1,4-butylene glycol (BG), dimethyl terephthalate (DMT) and PTMG as starting materials.

[0007] Meanwhile, in the polycondensation step, in order to improve productivity, a co-catalyst can be additionally applied in addition to the main catalyst, and as such a co-catalyst, an alkali metal salt or an alkaline earth metal salt such as sodium acetate (Na-acetate), magnesium acetate (Mg acetate), calcium acetate (Ca acetate) has been mainly used.

[0008] However, in the process using the existing cocatalyst, it is difficult to sufficiently shorten the polymerization time, and the productivity still decreases, making it unsuitable for mass production.

[0009] Therefore, there is a need for a method for producing polyetherester copolymers that maintains similar thermal and mechanical properties to conventional methods while shortening the polymerization time sufficiently to make it suitable for mass production. Summary of the Invention [Problem to be solved by the invention]

[0010] The present invention provides a polyether ester copolymer that can significantly reduce the polymerization time and increase productivity while maintaining excellent physical properties of the copolymer.

[0011] The present invention also provides a method for producing the polyetherester copolymer. [Means for solving the problem]

[0012] In order to solve the above problems, the present specification provides a polyetherester copolymer comprising: a polymer matrix including polyether-based repeating units and polyester-based repeating units; and a monometal salt of an inorganic acid and a multimetal salt of an inorganic acid remaining in the polymer matrix.

[0013] The present specification also provides a method for producing a polyether ester copolymer, comprising: a) an esterification reaction step of reacting a diol, a dicarboxylic acid or a derivative thereof, and a polyether diol in the presence of a catalyst and a co-catalyst; b) a first condensation polymerization step of adding a catalyst to the reaction mixture after the completion of the a) step and carrying out condensation polymerization under reduced pressure to produce a prepolymer; and c) a second condensation polymerization step of condensing the prepolymer under a pressure condition lower than that of the b) step; wherein the co-catalyst comprises a monometallic salt of an inorganic acid and a multimetallic salt of an inorganic acid.

[0014] The polyetherester copolymer and the method for producing the same according to specific embodiments of the invention will be described in more detail below.

[0015] Unless otherwise expressly stated herein, the terminology used is for the purpose of referring to particular embodiments only and is not intended to be limiting of the invention.

[0016] As used herein, the singular forms "a," "an," and "the" include the plural forms unless the context clearly dictates to the contrary.

[0017] As used herein, the meaning of "comprising" is to embody certain features, regions, integers, steps, operations, elements, components and / or components, and does not exclude the presence or addition of other certain features, regions, integers, steps, operations, elements, components and / or groups.

[0018] In this specification, terms including ordinal numbers, such as "first" and "second," are used for the purpose of distinguishing one component from another component, and are not limited by the ordinal number. For example, within the scope of the present invention, a first component may be named a second component, and similarly, a second component may be named the first component.

[0019] In this specification, examples of the substituents are described below, but the present invention is not limited thereto.

[0020] In this specification, the term "substituted" means that another functional group is bonded in place of a hydrogen atom in a compound, and the position of the substitution is not limited as long as it is a position at which a hydrogen atom is substituted, that is, a position at which a substituent can be substituted, and when two or more substituents are substituted, the two or more substituents may be the same or different.

[0021] In the present specification, the term "substituted or unsubstituted" means that the group is substituted or unsubstituted with one or more substituents selected from the group consisting of deuterium, halogen, cyano, nitro, hydroxy, carbonyl, ester, imide, amide, primary amino, carboxy, sulfonic acid, sulfonamide, phosphine oxide, alkoxy, aryloxy, alkylthio, arylthio, alkylsulfoxy, arylsulfoxy, silyl, boron, alkyl, cycloalkyl, alkenyl, aryl, aralkyl, aralkenyl, alkylaryl, alkoxysilylalkyl, arylphosphine, or heterocyclic groups containing one or more of N, O, and S atoms, or that the group is substituted or unsubstituted with two or more of the above-listed substituents. For example, the "substituent with two or more substituents connected" may be a biphenyl group. In other words, the biphenyl group may be an aryl group, and may be interpreted as a substituent with two phenyl groups connected.

[0022] In this specification, [ka] or [ka] means a bond connected to another substituent, and a direct bond means that there is no other atom present in the moiety represented by L.

[0023] In this specification, aromaticity refers to a property that satisfies the Huckels Rule, and according to the Huckels Rule, a compound can be defined as aromatic if it satisfies all of the following three conditions:

[0024] 1) There must be 4n+2 electrons present that are fully conjugated through hollow p-orbitals, unsaturated bonds, unpaired electron pairs, etc.

[0025] 2) The 4n+2 electrons must form a planar isomer and form a ring structure.

[0026] 3) All atoms of the ring must be able to participate in conjugation.

[0027] In this specification, aliphatic can be defined as aliphatic when it does not satisfy the above-mentioned aromaticity.

[0028] In this specification, the alkyl group is a monovalent functional group derived from an alkane, which may be linear or branched, and the number of carbon atoms in the linear alkyl group is not particularly limited, but is preferably 1 to 20. Also, the number of carbon atoms in the branched alkyl group is 3 to 20. Exemplary alkyl groups include, but are not limited to, methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n-heptyl, 1-methylhexyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, 2,6-dimethylheptan-4-yl, and the like. The alkyl group may be substituted or unsubstituted, and when substituted, examples of the substituents are as described above.

[0029] In the present specification, a cycloalkyl group is a monovalent functional group derived from a cycloalkane, which may be monocyclic or polycyclic, and has 3 to 20 carbon atoms, but is not limited thereto. According to another embodiment, the cycloalkyl group has 3 to 10 carbon atoms. Specific examples include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, and bicyclo[2,2,1]heptyl. The cycloalkyl group may be substituted or unsubstituted, and if substituted, examples of the substituent are as described above.

[0030] In the present specification, the aryl group is a monovalent functional group derived from arene, and is not particularly limited, but preferably has 6 to 20 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. The aryl group may be a monocyclic aryl group such as a phenyl group, a biphenyl group, a terphenyl group, etc., but is not limited thereto. The polycyclic aryl group may be a naphthyl group, anthracenyl group, a phenanthrenyl group, a pyrenyl group, a perylenyl group, a chrysenyl group, a fluorenyl group, etc., but is not limited thereto. The aryl group may be substituted or unsubstituted, and if substituted, examples of the substituent are as described above.

[0031] In this specification, the alkylene group is a divalent functional group derived from an alkane, and the above description of the alkyl group is applicable except that it is a divalent functional group. For example, it may be linear or branched, and may be a methylene group, an ethylene group, a propylene group, an isobutylene group, a sec-butylene group, a tert-butylene group, a pentylene group, a hexylene group, etc. The alkylene group may be substituted or unsubstituted, and if substituted, examples of the substituent are as described above.

[0032] In this specification, the arylene group is a divalent functional group derived from arene, and the above description of the aryl group is applicable except that it is a divalent functional group. For example, it may be a phenylene group, a biphenylene group, a terphenylene group, a naphthalene group, a fluorenyl group, a pyrenyl group, a phenanthrenyl group, a perylene group, a tetracenyl group, an anthracenyl group, etc. The arylene group may be substituted or unsubstituted, and if substituted, examples of the substituent are as described above.

[0033] In this specification, the cycloalkylene group is a divalent functional group derived from a cycloalkane, and the above description of the cycloalkyl group is applicable except that it is a divalent functional group. The cycloalkylene group may be substituted or unsubstituted, and if substituted, examples of the substituent are as described above.

[0034] In this specification, a derivative compound means a compound that has been modified from a certain organic compound by introducing a functional group, oxidizing, reducing, substituting an atom, or the like, within the limits that do not significantly change the structure and properties of the parent compound.

[0035] The present invention will now be described in more detail.

[0036] 1. Polyetherester copolymer According to one embodiment of the invention, there is provided a polyetherester copolymer comprising: a polymeric matrix including polyether-based repeating units and polyester-based repeating units; and a monometallic salt of an inorganic acid and a multimetallic salt of an inorganic acid remaining in the polymeric matrix.

[0037] The present inventors have confirmed through experiments that, as in the case of the polyetherester copolymer of the above embodiment, when a monometallic salt of an inorganic acid and a multimetallic salt of an inorganic acid are added as co-catalysts during synthesis of the polyetherester copolymer, the production efficiency of the polyetherester copolymer can be improved while maintaining excellent physical properties, and thus completed the invention.

[0038] The monometallic salt of an inorganic acid and the multimetallic salt of an inorganic acid can be added as a co-catalyst together with the monomers diol, dicarboxylic acid or derivatives thereof, and polyether diol, and the main catalyst in the synthesis process of the polyether ester copolymer, and can remain in part or in whole in the final synthesized polyether ester copolymer.

[0039] In particular, the polyetherester copolymer can include a polymeric matrix that includes polyether-based repeating units and polyester-based repeating units.

[0040] The polyether repeating unit means a repeating unit containing a polyether functional group in the repeating unit structure, and specifically, may have a structure represented by the following Chemical Formula 1.

[0041] [ka]

[0042] In the above Chemical Formula 1, R1 is one of an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 3 to 10 carbon atoms, or an arylene group having 6 to 20 carbon atoms, R2 is an alkylene group having 1 to 10 carbon atoms, and n is an integer of 1 to 100.

[0043] As a more specific example, in the above Chemical Formula 1, R1 may be a phenylene group which is an arylene group having 6 to 20 carbon atoms, and R2 may be a butylene group which is an alkylene group having 1 to 10 carbon atoms.

[0044] The polyether repeating unit may include a reaction product of a dicarboxylic acid or a derivative thereof and a polyether diol. An example of the dicarboxylic acid or a derivative thereof is terephthalic acid, which is an aromatic dicarboxylic acid, and an example of the polyether diol is poly(tetramethylene ether) glycol.

[0045] The polyester repeating unit means a repeating unit containing a polyester functional group in the repeating unit structure, and specifically, may have a structure represented by the following Chemical Formula 2.

[0046] [ka]

[0047] In the above Chemical Formula 2, R3 is one of an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 3 to 10 carbon atoms, or an arylene group having 6 to 20 carbon atoms, and R4 is an alkylene group having 1 to 10 carbon atoms.

[0048] As a more specific example, in the above Chemical Formula 2, R3 may be a phenylene group which is an arylene group having 6 to 20 carbon atoms, and R4 may be a butylene group which is an alkylene group having 1 to 10 carbon atoms.

[0049] The polyester repeating unit may include a reaction product of a dicarboxylic acid or a derivative thereof and a diol. An example of the dicarboxylic acid or a derivative thereof is terephthalic acid, which is an aromatic dicarboxylic acid, and an example of the diol is 1,4-butanediol, which is an aliphatic diol.

[0050] The polyether repeating units can constitute soft segments that provide elasticity and flexibility in the polyetherester copolymer, and the polyester repeating units can constitute hard segments that provide mechanical properties in the polyetherester copolymer.

[0051] That is, the polyether ester contains both the polyether repeating units and the polyester repeating units, and thus has hard segments and soft segments and has the properties of an elastomer.

[0052] Meanwhile, the polyetherester copolymer may contain monometallic salts of inorganic acids and multimetallic salts of inorganic acids remaining in the polymer matrix. The monometallic salts of inorganic acids and multimetallic salts of inorganic acids may be added as cocatalysts together with monomers (diol, dicarboxylic acid or derivatives thereof, polyetherdiol, and main catalyst) during the synthesis of the polyetherester copolymer, and may remain partially or entirely in the final synthesized polyetherester copolymer.

[0053] This can be confirmed by inductively coupled plasma (ICP) analysis of the final synthesized polyetherester copolymer. Specifically, the presence of two types of inorganic acid metal salt promoters remaining in the polyetherester copolymer can be confirmed by quantitative analysis of metal elements (e.g., Na and S) using ICP. In addition, the content and ratio of two types of inorganic acid metal salt promoters can be confirmed by ion chromatography analysis or a combination of ICP and ion chromatography analysis.

[0054] The multiple metal salt of an inorganic acid means a salt obtained by an acid-base neutralization reaction between a base compound containing a metal component and an inorganic acid, and particularly refers to a final salt compound containing 2(di) or more metal components. In other words, if the number of metal components in the chemical formula of a metal salt of an inorganic acid is 2 or more, it is defined as a multiple metal salt of an inorganic acid.

[0055] The multimetal salt of an inorganic acid may include a dimetal salt of an inorganic acid, a trimetal salt of an inorganic acid, a tetrametal salt of an inorganic acid, or a pentametal salt of an inorganic acid, depending on the number of metal components.

[0056] Examples of dimetal salts of inorganic acids among the multiple metal salts of inorganic acids include sodium sulfate (Na2SO4), disodium hydrogen phosphate (Na2HPO4), and trisodium phosphate (Na3PO4).

[0057] The inorganic acid multimetal salt acts as a co-catalyst during the synthesis of the polyetherester copolymer, thereby shortening the polymerization time of the polyetherester copolymer.

[0058] The monometallic salt of an inorganic acid means a salt obtained by an acid-base neutralization reaction between a base compound containing a metal component and an inorganic acid, and particularly refers to a case where the final salt compound contains one (mono) metal component. In other words, if the number of metal components in the chemical formula of a metal salt of an inorganic acid is one, it is defined as a monometallic salt of an inorganic acid. Examples of the monometallic salt of an inorganic acid include sodium bisulfate (NaHSO4) and sodium dihydrogen phosphate (NaH2PO4).

[0059] The monometallic salt of an inorganic acid acts as a co-catalyst during the synthesis of the polyetherester copolymer, and helps to shorten the polymerization time of the polyetherester copolymer by the multimetallic salt of an inorganic acid. Therefore, even a smaller amount of the multimetallic salt of an inorganic acid can sufficiently shorten the polymerization time, thereby improving the process efficiency.

[0060] Therefore, when a mixture of a monometallic salt of an inorganic acid and a multimetallic salt of an inorganic acid is used, a sufficient polymerization time shortening effect can be achieved even with a smaller amount of the multimetallic salt of an inorganic acid, due to the monometallic salt of the inorganic acid. On the other hand, when only one monometallic salt of an inorganic acid is used, the polymerization time of the polyetherester copolymer increases to more than 140 minutes, which is a problem in that the polymerization time is not shortened sufficiently, and when only one multimetallic salt of an inorganic acid is used, an excess of the multimetallic salt of an inorganic acid must be added to shorten the polymerization time to a sufficient level, which is a problem in that the efficiency of the process is difficult to ensure.

[0061] Specifically, the weight ratio of the multiple metal salt of an inorganic acid to 1 part by weight of the monometal salt of an inorganic acid may be 10 parts by weight or more, or 20 parts by weight or more, or 50 parts by weight or more, or 100 parts by weight or more, or 1000 parts by weight or less, or 200 parts by weight or less, or 10 parts by weight to 1000 parts by weight, or 20 parts by weight to 1000 parts by weight, or 50 parts by weight to 1000 parts by weight, or 100 parts by weight to 1000 parts by weight, or 10 parts by weight to 200 parts by weight, or 20 parts by weight to 200 parts by weight, or 50 parts by weight to 200 parts by weight, or 100 parts by weight to 200 parts by weight.

[0062] If the weight ratio of the inorganic acid multimetal salt to 1 part by weight of the inorganic acid monometal salt is too low, such as less than 10 parts by weight, the effect of shortening the polymerization time of the polyetherester copolymer by the inorganic acid multimetal salt is difficult to fully achieve.If the weight ratio of the inorganic acid multimetal salt to 1 part by weight of the inorganic acid monometal salt is too high, such as more than 1000 parts by weight, an excessive amount of the inorganic acid multimetal salt must be added, which makes it difficult to ensure the efficiency of the process.

[0063] More specifically, the inorganic acid multiple metal salt is contained in an amount of 10 ppm to 10,000 ppm, or 10 ppm to 5,000 ppm, or 10 ppm to 4,000 ppm, or 100 ppm to 10,000 ppm, or 100 ppm to 5,000 ppm, or 100 ppm to 4,000 ppm, or 500 ppm to 10,000 ppm, or 500 ppm to 5,000 ppm, or 500 ppm to 4,000 ppm, or 1000 ppm to 10,000 ppm, or 1000 ppm to 5,000 ppm, or 1000 ppm to 4,000 ppm.

[0064] The monometal salt of an inorganic acid is contained in a content of 0.1 ppm to 150 ppm, or 0.1 ppm to 100 ppm, or 0.1 ppm to 80 ppm, or 0.1 ppm to 50 ppm, or 1 ppm to 150 ppm, or 1 ppm to 100 ppm, or 1 ppm to 80 ppm, or 1 ppm to 50 ppm, or 10 ppm to 150 ppm, or 10 ppm to 100 ppm, or 10 ppm to 80 ppm, or 10 ppm to 50 ppm, based on the weight of the polyetherester copolymer.

[0065] The inorganic acid may include a polyvalent inorganic acid. The polyvalent inorganic acid is a polyprotic acid that can release more than one hydrogen ion among inorganic acids, and may include divalent inorganic acids, trivalent inorganic acids, tetravalent inorganic acids, pentavalent inorganic acids, etc. depending on the number of hydrogen ions. More specifically, examples of the inorganic acid may include sulfuric acid or phosphoric acid.

[0066] The metal may include an alkali metal or an alkaline earth metal, and specific examples of the metal include sodium, potassium, calcium, magnesium, or mixtures thereof.

[0067] The polyetherester copolymer may have a yellowness index (YI) measured using a color meter of 24 or less, or 23 or less, or 22 or less, or 1 or more, or 1 to 24, or 1 to 23, or 1 to 22. If the polyetherester copolymer has a yellowness index measured using a color meter that is excessively increased to more than 24, there is a problem that it is difficult to ensure a high level of transparency due to excessive yellowing.

[0068] The polyether ester copolymer has a melting point (T m) may be 150°C or more, or 200°C or more, or 201°C or more, or 202°C or more, or 203°C or more, or 250°C or less, or 210°C or less, or 150°C to 250°C, or 200°C to 250°C, or 201°C to 250°C, or 202°C to 250°C, or 203°C to 250°C, or 200°C to 210°C, or 201°C to 210°C, or 202°C to 210°C, or 203°C to 210°C. An example of a differential scanning calorimeter for measuring the melting point is Differential Scanning Calorimetry, device name: DSC2920, manufacturer: TA instrument. The melting point is obtained from a temperature-heat flow graph obtained by scanning at a heating rate of 5°C / min to 15°C / min in a temperature range of 0°C to 250°C or less, or at a cooling rate of 5°C / min to 15°C / min. More specifically, the melting point (T m ) was obtained by peak analysis of the heat flow heating curve during the second temperature rise.

[0069] The polyether ester copolymer has a melting point (T m If the temperature is too low, such as below 150° C., the efficiency of the molding process for the polyether ester copolymer may decrease.

[0070] The polyether ester copolymer may have a crystallization temperature measured by a differential scanning calorimeter of 70°C or more, or 151°C or more, or 152°C or more, or 153°C or more, or 154°C or more, or 155°C or more, or 156°C or more, or 200°C or less, or 160°C or less, or 70°C to 200°C, or 151°C to 200°C, or 152°C to 200°C, or 153°C to 200°C, or 154°C to 200°C, or 155°C to 200°C, or 156°C to 200°C, or 70°C to 160°C, or 151°C to 160°C, or 152°C to 160°C, or 153°C to 160°C, or 154°C to 160°C, or 155°C to 160°C, or 156°C to 160°C. An example of a differential scanning calorimeter for measuring the crystallization temperature is a Differential Scanning Calorimetry, device name: DSC2920, manufacturer: TA Instrument. The crystallization temperature is determined from a temperature-heat flow graph obtained by scanning at a heating rate of 5°C / min to 15°C / min or a cooling rate of 5°C / min to 15°C / min in a temperature range of 0°C to 250°C. More specifically, the crystallization temperature (T c ) is determined by peak analysis of the heat flow cooling curve during the first cooling.

[0071] If the polyetherester copolymer has a crystallization temperature measured by a differential scanning calorimeter that is too low, below 70° C., the efficiency of the molding process for the polyetherester copolymer may decrease.

[0072] The polyether ester copolymer may have a melt index of 30 g / 10 min or less, or 29 g / 10 min or less, or 28 g / 10 min or less, or 27 g / 10 min or less, or 26 g / 10 min or less, or 10 g / 10 min or more, or 10 g / 10 min to 30 g / 10 min, or 10 g / 10 min to 29 g / 10 min, or 10 g / 10 min to 28 g / 10 min, or 10 g / 10 min to 27 g / 10 min, or 10 g / 10 min to 26 g / 10 min, as measured by ASTM D1238 at 230°C and a load of 2.16 kg for a maintenance time of 4 minutes, using a sample obtained by drying the polyether ester copolymer. The drying conditions for the polyether ester copolymer are not particularly limited, but for example, drying can be carried out at a temperature of 50° C. or higher and 100° C. or lower for 6 hours or longer.

[0073] The polyether ester copolymer is not particularly limited in its application, and can be used in any application field of conventionally known thermoplastic polyester elastomers (TPEEs), but can be used in a variety of applications, such as automobile parts, automobile interior materials, automobile exterior materials, cables, wires, hoses, tubes, antenna covers, leisure goods, and sporting goods, for example.

[0074] The molding process for such applications is not limited, and various conventional molding processes for thermoplastic polyester elastomers (TPEE) can be applied without limitation.

[0075] 2. Method for producing polyether ester copolymer According to another embodiment of the invention, there is provided a method for producing a polyether ester copolymer, comprising: a) an esterification reaction step of reacting a diol, a dicarboxylic acid or a derivative thereof, and a polyether diol in the presence of a catalyst and a co-catalyst; b) a first condensation polymerization step of producing a prepolymer by adding a catalyst to the reaction mixture after the completion of the a) step and carrying out condensation polymerization under reduced pressure; and c) a second condensation polymerization step of condensing the prepolymer under a pressure condition lower than that of the b) step; wherein the co-catalyst comprises a monometal salt of an inorganic acid and a multimetal salt of an inorganic acid.

[0076] Specifically, the method for producing the polyetherester copolymer may include a) an esterification reaction step of reacting a diol, a dicarboxylic acid or a derivative thereof, and a polyetherdiol in the presence of a catalyst and a cocatalyst.

[0077] In the present invention, the diol is preferably an aliphatic or alicyclic diol having 2 to 10 carbon atoms and a molecular weight of 300 g / mol or less, in terms of realizing the effects of the present invention. Specifically, examples of diols that can be used in the present invention include aliphatic diols such as 1,4-butylene glycol (1,4-butanediol), monoethylene glycol, diethylene glycol, propylene glycol, and neopentyl glycol; and alicyclic diols such as 1,1-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, and tricyclodecane dimethanol; but are not limited thereto. Specifically, in the present invention, the diol may be 1,4-butanediol, which is an aliphatic diol.

[0078] Examples of dicarboxylic acids that can be used in the present invention include, but are not limited to, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, adipic acid, and sebacic acid. Specifically, the dicarboxylic acid may be terephthalic acid. Examples of dicarboxylic acid derivatives that can be used in the present invention include, but are not limited to, dialkyl terephthalate, dialkyl isophthalate, dialkyl naphthalenedicarboxylate, dialkyl adipic acid ester, and dialkyl sebacic acid ester. Specifically, the dicarboxylic acid or its derivative may be dimethyl terephthalate, which is a derivative of an aromatic dicarboxylic acid.

[0079] The polyether diol usable in the present invention may be in the form of a homopolymer or copolymer, and specific examples thereof include, but are not limited to, one or more selected from the group consisting of polytetramethylene glycol, polyethylene glycol, polypropylene glycol, polyethylene glycol-polypropylene glycol-polyethylene glycol, and polyhexamethylene glycol. Specifically, the polyether diol may be polytetramethylene glycol.

[0080] At this time, the number average molecular weight (Mn) of the polyether diol is not particularly limited, but may be 500 g / mol to 3000 g / mol, or 500 g / mol to 2000 g / mol, or 500 g / mol to 1500 g / mol. The number average molecular weight can be determined, for example, by gel permeation chromatography (GPC) or end titration method (a method including acetylating the end of polyether diol using acetic anhydride, decomposing unreacted acetic anhydride into acetic acid, measuring the OH value of the acetylated polyether diol by back titration using an alkali, and determining the number average molecular weight of the polyether diol from the OH value) or -OH end group analysis method by 1H NMR analysis.

[0081] The esterification reaction of reacting diol, dicarboxylic acid or its derivative and polyether diol is carried out in the presence of a catalyst (main catalyst) and a cocatalyst, and the catalyst (main catalyst) may be any suitable material known in the art. Specifically, the catalyst (main catalyst) may be a catalyst containing titanium or tin as an active metal, and more specifically, the catalyst may be a titanium-based catalyst such as tetrabutyl titanate (TBT), tetraethyl titanate or tetra(isopropyl) titanate; or a tin-based catalyst such as n-butylstannic acid, octylstannic acid, dimethyltin oxide, dibutyltin oxide, dioctyltin oxide, diphenyltin oxide, tri-n-butyltin acetate, tri-n-butyltin chloride or tri-n-butyltin fluoride. In addition to the above-mentioned catalysts, catalysts such as oxides or acetates containing Mg, Ca, Mn, Zn, Pb, Zr, etc. as active metals may be used alone or in combination. Of these, a titanium-based catalyst such as TBT can be preferably used.

[0082] Meanwhile, in the present invention, the catalyst is added not only in the esterification reaction but also in the polycondensation step. In general, when preparing a polyetherester copolymer, the catalyst for the esterification (or transesterification) reaction and the polycondensation reaction is the same, and no separation step is required between the two reactions. Therefore, after adding a certain amount of catalyst at the start or during the initial esterification (or transesterification) reaction, it is not necessary to add additional catalyst in the polycondensation step.

[0083] The co-catalyst may include a monometal salt of an inorganic acid and a dimetal salt of an inorganic acid. The multimetal salt of an inorganic acid means a salt obtained by an acid-base neutralization reaction between a base compound containing a metal component and an inorganic acid, and particularly refers to a final salt compound containing 2(di) or more metal components. In other words, if the number of metal components in the chemical formula of a metal salt of an inorganic acid is 2 or more, it is defined as a multimetal salt of an inorganic acid.

[0084] The multimetal salt of an inorganic acid may include a dimetal salt of an inorganic acid, a trimetal salt of an inorganic acid, a tetrametal salt of an inorganic acid, or a pentametal salt of an inorganic acid, depending on the number of metal components.

[0085] Examples of dimetal salts of inorganic acids among the multiple metal salts of inorganic acids include sodium sulfate (Na2SO4), disodium hydrogen phosphate (Na2HPO4), and trisodium phosphate (Na3PO4).

[0086] The inorganic acid multimetal salt acts as a co-catalyst during the synthesis of the polyetherester copolymer, thereby shortening the polymerization time of the polyetherester copolymer.

[0087] The monometallic salt of an inorganic acid means a salt obtained by an acid-base neutralization reaction between a base compound containing a metal component and an inorganic acid, and particularly refers to a case where the final salt compound contains one (mono) metal component. In other words, if the number of metal components in the chemical formula of a metal salt of an inorganic acid is one, it is defined as a monometallic salt of an inorganic acid. Examples of the monometallic salt of an inorganic acid include sodium bisulfate (NaHSO4) and sodium dihydrogen phosphate (NaH2PO4).

[0088] The monometallic salt of an inorganic acid acts as a co-catalyst during the synthesis of the polyetherester copolymer, and helps to shorten the polymerization time of the polyetherester copolymer by the multimetallic salt of an inorganic acid. Therefore, even a smaller amount of the multimetallic salt of an inorganic acid can sufficiently shorten the polymerization time, thereby improving the process efficiency.

[0089] Therefore, when a mixture of a monometallic salt of an inorganic acid and a multimetallic salt of an inorganic acid is used, a sufficient polymerization time shortening effect can be achieved even with a smaller amount of the multimetallic salt of an inorganic acid, due to the monometallic salt of the inorganic acid. On the other hand, when only one monometallic salt of an inorganic acid is used, the polymerization time of the polyetherester copolymer increases to more than 140 minutes, which is a problem in that the polymerization time is not shortened sufficiently, and when only one multimetallic salt of an inorganic acid is used, an excess of the multimetallic salt of an inorganic acid must be added to shorten the polymerization time to a sufficient level, which is a problem in that the efficiency of the process is difficult to ensure.

[0090] Specifically, the weight ratio of the multiple metal salt of an inorganic acid to 1 part by weight of the monometal salt of an inorganic acid may be 10 parts by weight or more, or 20 parts by weight or more, or 50 parts by weight or more, or 100 parts by weight or more, or 1000 parts by weight or less, or 200 parts by weight or less, or 10 parts by weight to 1000 parts by weight, or 20 parts by weight to 1000 parts by weight, or 50 parts by weight to 1000 parts by weight, or 100 parts by weight to 1000 parts by weight, or 10 parts by weight to 200 parts by weight, or 20 parts by weight to 200 parts by weight, or 50 parts by weight to 200 parts by weight, or 100 parts by weight to 200 parts by weight.

[0091] If the weight ratio of the inorganic acid multimetal salt to 1 part by weight of the inorganic acid monometal salt is too low, such as less than 10 parts by weight, the effect of shortening the polymerization time of the polyetherester copolymer by the inorganic acid multimetal salt is difficult to fully achieve.If the weight ratio of the inorganic acid multimetal salt to 1 part by weight of the inorganic acid monometal salt is too high, such as more than 1000 parts by weight, an excessive amount of the inorganic acid multimetal salt must be added, which makes it difficult to ensure the efficiency of the process.

[0092] More specifically, the inorganic acid multimetal salt is contained in an amount of 10 ppm to 10,000 ppm, or 10 ppm to 5,000 ppm, or 10 ppm to 4,000 ppm, or 100 ppm to 10,000 ppm, or 100 ppm to 5,000 ppm, or 100 ppm to 4,000 ppm, or 500 ppm to 10,000 ppm, or 500 ppm to 5,000 ppm, or 500 ppm to 4,000 ppm, or 1000 ppm to 10,000 ppm, or 1000 ppm to 5,000 ppm, or 1000 ppm to 4,000 ppm.

[0093] In addition, the monometal salt of an inorganic acid is contained in a content of 0.1 ppm to 150 ppm, or 0.1 ppm to 100 ppm, or 0.1 ppm to 80 ppm, or 0.1 ppm to 50 ppm, or 1 ppm to 150 ppm, or 1 ppm to 100 ppm, or 1 ppm to 80 ppm, or 1 ppm to 50 ppm, or 10 ppm to 150 ppm, or 10 ppm to 100 ppm, or 10 ppm to 80 ppm, or 10 ppm to 50 ppm, based on the weight of the reaction mixture after completion of step a).

[0094] The inorganic acid may include a polyvalent inorganic acid. The polyvalent inorganic acid is a polyprotic acid that can release more than one hydrogen ion among inorganic acids, and may include divalent inorganic acids, trivalent inorganic acids, tetravalent inorganic acids, pentavalent inorganic acids, etc. depending on the number of hydrogen ions. More specifically, examples of the inorganic acid may include sulfuric acid or phosphoric acid.

[0095] The metal may include an alkali metal or an alkaline earth metal, and specific examples of the metal include sodium, potassium, calcium, magnesium, or a mixture thereof. Meanwhile, in the present invention, the co-catalyst may be added in a certain amount at the start of the initial esterification (or transesterification) reaction, at the initial stage of the reaction, or at the final stage of the reaction, and may also be added additionally in the polycondensation step as necessary.

[0096] The reaction temperature in step a) is suitably in the range of 150° C. to 300° C., or 200° C. to 240° C., and the reaction pressure may be in the range of 100 torr to 760 torr. Specifically, the starting materials and the catalyst are charged into a reactor, and the temperature is increased at 0.1° C. / min to 10° C. / min under stirring until the temperature reaches the above range, and the esterification reaction can be carried out for about 30 minutes to 4 hours, or 1 to 2 hours.

[0097] After the step a) is completed, the polycondensation steps b) and c) are carried out. The polycondensation step is carried out in a reactor separate from the esterification reactor, and may be carried out without a distillation column. Specifically, the polycondensation step is carried out after adding an active metal-based catalyst of 50 ppm or more to the reaction mixture after the step a) is completed.

[0098] In the present invention, the polycondensation step is divided into two steps, b) and c). The steps b) and c) are carried out substantially continuously, but there is a difference in pressure conditions. Specifically, the step b) is a process for removing excess diol, and the step c) is a process for increasing the viscosity of the polyether ester copolymer.

[0099] Specifically, the method for preparing the polyetherester copolymer may include a first condensation polymerization step of preparing a prepolymer by adding a catalyst to the reaction mixture obtained by the step a) and condensing the mixture under reduced pressure.

[0100] Step b) of the present invention is a first polycondensation step carried out under relatively mild conditions, in which a catalyst is additionally added to the reaction mixture after the completion of step a), and the mixture is stirred under reduced pressure to obtain a prepolymer.

[0101] The step b) is carried out at a temperature of 180°C to 250°C and a pressure of 5 torr to 100 torr. Under these conditions, the excess diol that is not reacted in the step a) is vaporized and removed. The reaction time of the step b) is not particularly limited, but may be 20 minutes to 1 hour, or 20 minutes to 40 minutes.

[0102] If the polycondensation is immediately carried out at a high vacuum of 5 torr or less without carrying out the step b), the unreacted diol may be rapidly vaporized, causing bumping in the reactor and a rapid drop in temperature of the reactants. In addition, the polyether ester copolymer may not be obtained due to its high viscosity. Therefore, in the present invention, a first polycondensation step is preliminarily carried out under relaxed conditions before the full-scale polycondensation reaction.

[0103] Meanwhile, in step a) or b), one or more commonly used additives may be added together to improve the reaction efficiency and adjust the physical properties of the polyetherester copolymer to be produced.

[0104] Examples of additives that can be used include branching agents (e.g., glycerol, sorbitol, pentaerythritol, 1,1,4,4-tetrakis(hydroxymethyl)cyclohexane, trimethylolpropane, pyromellitic acid, 1,1,2,2-ethanetetracarboxylic acid, etc.) for increasing the melt strength of the polyetherester copolymer, photoinhibiting agents (e.g., TiO2, zinc sulfide or zinc oxide) for improving color properties, colorants (e.g., dyes), stabilizers (e.g., antioxidants, ultraviolet light stabilizers, heat stabilizers, etc.), fillers, flame retardants, pigments, antimicrobial agents, antistatic agents, optical brighteners, extenders, processing aids, or viscosity enhancers, including, but not limited to, any one or mixtures of two or more of these. As an example, a stabilizer in the form of a hindered phenol (e.g., Irganox 1330) can be added to increase the thermal stability of the polyetherester copolymer.

[0105] These additives can be used in an appropriate content within a range that ensures the intended effect and does not deteriorate the physical properties of the polyetherester copolymer produced; specifically, 0.1 to 10% by weight can be used relative to 100% by weight of the total raw materials.

[0106] Also, the method for preparing the polyetherester copolymer may include a second polycondensation step of polycondensing the prepolymer under a pressure condition lower than that of step c) or b).

[0107] Step c) is a reaction subsequent to step b), in which the prepolymer is polycondensed in the same reactor, only at a lower pressure.

[0108] In step c), the time from the start of the reaction to the time when the torque value attached to the mechanical stirrer reaches 0.8 Nm and the reaction is stopped may be 100 minutes or less, or 95 minutes or less, or 94 minutes or less, or 90 minutes or less, or 50 minutes or more, or 50 minutes to 100 minutes, or 50 minutes to 95 minutes, or 50 minutes to 94 minutes, or 50 minutes to 90 minutes. In step c), if the time from the start of the reaction to the time when the torque value attached to the mechanical stirrer reaches 0.8 Nm and the reaction is stopped is excessively increased, there is a problem that the polymerization time is difficult to sufficiently shorten, resulting in a decrease in productivity.

[0109] The step c) is carried out under the conditions of a temperature of 180° C. to 250° C. and a pressure of 5 torr or less. Under these conditions, the polycondensation is carried out for about 30 minutes to 5 hours or 1 to 3 hours, and the reaction is completed when the torque value reaches a range of 0.5 Nm to 2.0 Nm, finally producing a polyether ester copolymer. Effect of the Invention

[0110] According to the present invention, there are provided a polyether ester copolymer which maintains excellent physical properties of the copolymer and can significantly reduce the polymerization time to increase productivity, and a method for producing the same. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0111] The present invention will be described in more detail with reference to the following examples, however, the following examples are merely illustrative of the present invention and are not intended to limit the scope of the present invention.

[0112] <Examples, Comparative Examples and Reference Examples: Production of Polyetherester Copolymer> Example 1 In a 2L glass reactor, 120g of terephthalic acid, 200g of 1,4-butanediol, 80g of poly(tetramethylene ether) glycol (PTMG, Mn=1,000), 50ppm (Ti element basis) of tetrabutyl titanate (TBT) catalyst, 800ppm (total raw material input basis) of sodium sulfate (Na2SO4) and 30ppm (total raw material input basis) of sodium bisulfate (NaHSO4) as cocatalysts were added, stirred at 230℃ for 2 hours under nitrogen, and the temperature was raised to 100~760torr to carry out the esterification (ES) reaction.

[0113] After the ES reaction, 50 ppm (Ti element basis) of tetrabutyl titanate (TBT) catalyst and 3000 ppm of Irganox1330 as an antioxidant were added to the reactor, and the mixture was stirred for 10 minutes. After removing the liquid by-products generated in the Dean-Stark trap, the pressure was reduced to 10 torr for 30 minutes at a temperature of 230°C, and the first polycondensation (PP) reaction was carried out.

[0114] The second polycondensation (PC) reaction was carried out at 240℃ and 1 torr. During the PC reaction, the torque value attached to the mechanical stirrer increased continuously, and when the torque reached 0.8 Nm, the reaction was stopped, pressurized and discharged into cold water to cool the product, which was then dried to obtain a PBT-PTMG copolymer.

[0115] (Examples 2 to 3, Comparative Examples 1 to 4, Reference Examples 1 to 2) As shown in Table 1 below, a PBT-PTMG copolymer was obtained in the same manner as in Example 1, except that the contents of the cocatalysts sodium sulfate (Na2SO4) 800 ppm (based on the total amount of raw materials input) and sodium bisulfate (NaHSO4) 30 ppm (based on the total amount of raw materials input) were changed.

[0116] <Experimental example: Measurement of physical properties of polyether ester copolymer> The physical properties of the polyether ester copolymers obtained in the above Examples and Comparative Examples were measured by the following methods, and the results are shown in Table 1.

[0117] 1. Secondary polycondensation (PC) reaction time (unit: min) In the above examples and comparative examples, the time from the start of the second polycondensation (PC) reaction to the termination of the reaction when the torque value attached to a mechanical stirrer reached 0.8 Nm was measured.

[0118] 2. Melting index (unit: g / 10 min) The polyetherester copolymers obtained in the examples and comparative examples were vacuum dried in an oven at 60°C for 6 hours or more, and the melt index of the samples was measured in the same manner as ASTM D1238 (230°C, 2.16 kg load, 4 minutes maintenance time).

[0119] 3. Melting point, crystallization temperature (unit: °C) The polyether ester copolymers obtained in the above examples and comparative examples were scanned twice at a heating rate or cooling rate of 10°C / min in the temperature range of 0°C to 250°C using a differential scanning calorimetry (DSC2920, manufacturer: TA Instruments). The melting points (T m ) and crystallization temperature (T c ) was measured.

[0120] The crystallization temperature (T c ) is obtained by peak analysis of the cooling curve of the heat flow during the first cooling stage, and the melting point (T m ) was obtained by peak analysis of the heat flow heating curve during the second temperature rise.

[0121] 4.Yellow index The polyether ester copolymers obtained in the above examples and comparative examples were measured using a color meter ZE6000 (NIPPON DENSHOKU).

[0122] [Table 1]

[0123] As shown in Table 1, the polyetherester copolymers of Examples 1 to 3 exhibit the same levels of melt index, melting point, crystallization temperature, and yellow index properties as the Comparative Examples and Reference Examples, but have a PC reaction time of 87 to 95 minutes, which is shorter than the PC reaction times of 100 minutes or more in Comparative Examples 1, 2, 3, and 4 and Reference Examples 1 and 2, and therefore can improve process efficiency.

Claims

1. A polymeric matrix comprising polyether-based repeat units and polyester-based repeat units; and A polyetherester copolymer comprising a monometallic salt of an inorganic acid and a multimetallic salt of an inorganic acid remaining in the polymeric matrix.

2. The polyetherester copolymer of claim 1, wherein the polyetherester copolymer has a yellowness index of 24 or less as measured using a color meter.

3. The polyetherester copolymer according to claim 1 , wherein the polyetherester copolymer has a melting point of 150° C. or higher as measured by a differential scanning calorimeter.

4. The polyetherester copolymer according to claim 1, wherein the polyetherester copolymer has a crystallization temperature of 70° C. or higher as measured by a differential scanning calorimeter.

5. The polyetherester copolymer of claim 1 , wherein the inorganic acid comprises sulfuric acid or phosphoric acid.

6. 2. The polyetherester copolymer of claim 1, wherein the metal of the metal salt comprises an alkali metal or an alkaline earth metal.

7. The multimetal salt of an inorganic acid is sodium sulfate; 2. The polyetherester copolymer of claim 1, wherein said monometallic salt of an inorganic acid is sodium hydrogen sulfate.

8. 2. The polyetherester copolymer of claim 1, wherein the weight ratio of said multimetal salt of an inorganic acid to 1 part by weight of said monometal salt of an inorganic acid is 10 parts by weight or more.

9. 2. The polyetherester copolymer according to claim 1, wherein the inorganic acid multimetal salt is present in an amount of 10 ppm to 10,000 ppm based on the weight of the polyetherester copolymer.

10. 2. The polyetherester copolymer according to claim 1, wherein the monometallic salt of an inorganic acid is present in an amount of 0.1 ppm to 150 ppm based on the weight of the polyetherester copolymer.

11. The polyether ester copolymer according to claim 1, wherein the polyether repeating unit has a structure represented by the following chemical formula 1: 【Chemistry 5】 In the above Chemical Formula 1, R 1 is one of an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 3 to 10 carbon atoms, or an arylene group having 6 to 20 carbon atoms, R 2 is an alkylene group having 1 to 10 carbon atoms, n is an integer from 1 to 100.

12. The polyether ester copolymer according to claim 1, wherein the polyester repeating unit has a structure represented by the following chemical formula 2: 【Chemistry 6】 In the above Chemical Formula 2, R 3 is one of an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 3 to 10 carbon atoms, or an arylene group having 6 to 20 carbon atoms, R 4 is an alkylene group having 1 to 10 carbon atoms.

13. a) an esterification step in which a diol, a dicarboxylic acid or a derivative thereof, and a polyether diol are reacted in the presence of a catalyst and a cocatalyst; b) a first polycondensation step of preparing a prepolymer by adding a catalyst to the reaction mixture obtained after the step a) and polycondensing the mixture under reduced pressure; and c) a second polycondensation step in which the prepolymer is polycondensed under a pressure condition lower than that of the step b); The method for producing a polyetherester copolymer, wherein the cocatalyst comprises a monometallic salt of an inorganic acid and a multimetallic salt of an inorganic acid.

14. 14. The method for producing a polyetherester copolymer according to claim 13, wherein in step c), the time from the start of the reaction to the time when the torque value attached to a mechanical stirrer reaches 0.8 Nm and the reaction is terminated is 100 minutes or less.

15. The method for producing a polyether ester copolymer according to claim 13, wherein the weight ratio of the multimetal salt of an inorganic acid to 1 part by weight of the monometal salt of an inorganic acid is 10 parts by weight or more.

16. The method for producing a polyetherester copolymer according to claim 13, wherein the inorganic acid multimetal salt is added in an amount of 10 ppm to 10,000 ppm based on the weight of the reaction mixture after the step a) is completed.

17. The method for producing a polyetherester copolymer according to claim 13, wherein the monometallic salt of an inorganic acid is added in an amount of 0.1 ppm to 150 ppm based on the weight of the reaction mixture after the completion of step a).

18. The multimetal salt of an inorganic acid is sodium sulfate; The method for producing a polyetherester copolymer according to claim 13, wherein the monometallic salt of an inorganic acid is sodium hydrogen sulfate.

19. The method for producing a polyetherester copolymer according to claim 13, wherein the step b) is carried out under conditions of a temperature of 180° C. to 250° C. and a pressure of 5 torr to 100 torr.

20. The method for producing a polyetherester copolymer according to claim 13, wherein the step c) is carried out under conditions of a temperature of 180° C. to 250° C. and a pressure of 5 torr or less.

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