Polyester polymer, method for preparing polyester polymer, and molded article

Abstract

The present invention relates to a polyester polymer having a high bio-content and a high molecular weight and excellent optical properties, to a method for preparing the polyester polymer, and to a molded article.

Description

Polyester polymer, method for producing polyester polymer and molded article

[0001] Cross-citation with related applications

[0002] This application claims the benefit of priority to Republic of Korea Patent Application No. 10-2023-0119289, filed September 7, 2023, and Republic of Korea Patent Application No. 10-2024-0097522, filed July 23, 2024, the entire contents of which are incorporated herein by reference.

[0003]

[0004] The present invention relates to a polyester polymer, a method for producing a polyester polymer, and a molded article.

[0005] Unlike conventional petroleum-based resins like polystyrene, polyvinyl chloride, and polyethylene, biodegradable polyester polymers prevent depletion of petroleum resources and reduce carbon dioxide emissions, potentially reducing environmental pollution, a drawback of petroleum-based plastic products. Consequently, as environmental pollution caused by waste plastics becomes a growing social issue, efforts are being made to expand the scope of their application to products previously dominated by conventional plastics (petroleum-based resins), such as food packaging and containers, and electronic device cases.

[0006]

[0007] However, existing polyester polymers suffer from the problem of high yellowness after polymerization and the difficulty in obtaining high-molecular-weight polymers. To address these issues, color-enhancing additives such as toners or chain extenders can be used, but this can be burdensome in terms of raw material costs.

[0008]

[0009] In addition, with the recent depletion of petroleum resources and the increase in carbon dioxide emissions, global warming due to their accumulation is raising concerns about climate change, and there is a demand for polymers using raw materials obtained from biomass resources such as plants.

[0010] Conventional polyester polymers are manufactured using petroleum-based monomers and, because they are not polymerized using bio-based monomers, have low bio-contents, making carbon neutrality difficult to achieve. Furthermore, even when bio-based monomers are used in polyester polymer synthesis, conventional biosynthesis using microorganisms requires large amounts of solvent for separation and purification processes, making it neither environmentally friendly nor economical.

[0011]

[0012] Therefore, there is a need for research on eco-friendly polyester polymers with high bio-content and excellent physical properties and high molecular weight without the use of additional additives.

[0013]

[0014] The present invention provides a polyester polymer having a high bio-content and high molecular weight without using a chain extender, and excellent optical properties, a method for producing the polyester polymer, and a molded article thereof.

[0015]

[0016] According to one embodiment of the present invention, a polyester polymer is provided, which comprises a repeating unit represented by the following chemical formula 1, has a biomass content of 20% or more as measured according to ASTM D6866-22, and decomposes by 20% or more by weight based on the weight of the initial polymer when exposed to an external environment at room temperature for 90 days or more.

[0017] [Chemical Formula 1]

[0018]

[0019] In the above chemical formula 1, L1 is an ethylene group and L2 is an alkylene group having 1 to 10 carbon atoms.

[0020] According to another embodiment of the present invention, a method for producing a polyester polymer is provided, comprising: a step of introducing ethylene glycol and a dicarboxylic acid compound and reacting them under conditions of a temperature of 50° C. or more and 200° C. or less and a pressure of 10 torr or more and 760 torr or less to produce an oligomer; and a step of reacting the oligomer under conditions of a temperature of 50° C. or more and 200° C. or less and a pressure of 1 torr or less to produce a polyester polymer.

[0021] According to another embodiment of the invention, a molded article molded from a resin composition comprising the polyester polymer is provided.

[0022]

[0023] Hereinafter, a polyester polymer, a method for producing a polyester polymer, and a molded product according to specific embodiments of the invention will be described in more detail.

[0024]

[0025] Unless otherwise specified throughout this specification, the terms “include” or “comprising” refer to the inclusion of a component (or component) without limitation, and cannot be construed as excluding the addition of other components (or components).

[0026] In the present invention, terms such as first, second, etc. are used to describe various components, and the terms are used only for the purpose of distinguishing one component from another.

[0027] Furthermore, unless the steps constituting the manufacturing method described herein are explicitly stated to be sequential or consecutive, or there is another special order, the order of one step constituting a manufacturing method from another step is not limited to the order described in the specification. Accordingly, the order of the steps constituting the manufacturing method may be varied within a range readily understandable to those skilled in the art, and in such cases, any subsequent changes apparent to those skilled in the art are within the scope of the present invention.

[0028] In addition, unless otherwise stated herein, the number average molecular weight or weight average molecular weight can be measured using gel permeation chromatography (GPC). Specifically, the prepolymer or copolymer is dissolved in chloroform to a concentration of 1 mg / ml, 100 μl is injected into GPC, and GPC analysis is performed at 40°C. At this time, chloroform is used as the mobile phase of GPC, and it is introduced at a flow rate of 1.0 mL / min, two Agilent Mixed-B columns are used in series, and an RI Detector is used as the detector. The Mw value is derived using a calibration curve formed using a polystyrene standard sample. The weight average molecular weights of the polystyrene standard specimens were 12 types: 160 g / mol, 580 g / mol, 1180 g / mol, 4,880 g / mol, 9,310 g / mol, 22,790 g / mol, 75,050 g / mol, 217,900 g / mol, 479,200 g / mol, 1,069,000 g / mol, 3,022,000 g / mol, and 6,545,000 g / mol.

[0029] In this specification, copolymer is used to mean a copolymer including random copolymers, block copolymers, graft copolymers, etc.

[0030] In this specification, the term “block” means a polymer in which two or more repeating units are connected, and the term “block copolymer” means a copolymer in which two or more types of blocks are each connected by one or more direct bonds or linkages.

[0031] In this specification, , or means a bond that connects to another substituent.

[0032]

[0033] According to one embodiment of the invention, a polyester polymer can be provided, which comprises a repeating unit represented by the following chemical formula 1, has a biomass content of 20% or more as measured according to ASTM D6866-22, and decomposes by 20% or more by weight based on the weight of the initial polymer when exposed to an external environment at room temperature for 90 days or more.

[0034] [Chemical Formula 1]

[0035]

[0036] In the above chemical formula 1, L1 is an ethylene group and L2 is an alkylene group having 1 to 10 carbon atoms.

[0037] The polyester polymer of the above embodiment may be a polyester polymer produced by a method for producing a polyester polymer of another embodiment described below.

[0038] Since the polyester polymer of the above embodiment is produced by the method for producing the polyester polymer of the other embodiment described above, a polyester polymer having a high bio-content and high molecular weight, as well as excellent optical properties, can be provided.

[0039]

[0040] In the above chemical formula 1, L2 may be a functional group derived from a dicarboxylic acid compound.

[0041] The above L2 may be an alkylene group having 1 to 10 carbon atoms, an alkylene group having 1 to 5 carbon atoms, or an alkylene group having 1 to 3 carbon atoms, and may be, for example, an ethylene group.

[0042]

[0043] For example, the polyester polymer of the above embodiment may be polyethylene succinate.

[0044]

[0045] The polyester polymer may contain repeating units represented by the above chemical formula 1 in an amount of 90 mol % or more, 95 mol % or more, 99 mol % or more, 99.9 mol % or more, or 90 mol % or more and 100 mol % or less, 95 mol % or more and 100 mol % or less, 99 mol % or more and 100 mol % or less, or 99.9 mol % or more and 100 mol % or less, based on the total repeating units.

[0046] For example, the polyester polymer may be composed of repeating units represented by the above chemical formula 1. That is, the polyester polymer may contain only ethylene glycol and succinic acid as monomers, and may contain only repeating units derived from ethylene glycol and succinic acid, as no other monomers are included.

[0047]

[0048] The above polyester polymer may have a number average molecular weight (Mn) of 1,000 g / mol or more and 200,000 g / mol or less as measured using gel permeation chromatography (GPC).

[0049] Specifically, the polyester polymer may have a number average molecular weight (Mn) measured using gel permeation chromatography (GPC) of 1,000 g / mol or more, 1,500 g / mol or more, 2,000 g / mol or more, 2,500 g / mol or more, 200,000 g / mol or less, 100,000 g / mol or less, 80,000 g / mol or less, 60,000 g / mol or less, 1,000 g / mol or more and 200,000 g / mol or less, 1,500 g / mol or more and 200,000 g / mol or less, 2,000 g / mol or more and 200,000 g / mol or less, 2,500 g / mol or more and 200,000 g / mol or less, 1,000 g / mol or more 100,000 g / mol or less, 1,500 g / mol or more but 100,000 g / mol or less, 2,000 g / mol or more but 100,000 g / mol or less, 2,500 g / mol or more but 100,000 g / mol or less, 1,000 g / mol or more but 80,000 g / mol or less, 1,500 g / mol or more but 80,000 g / mol or less, 2,000 g / mol or more but 80,000 g / mol or less, 2,500 g / mol or more but 80,000 g / mol or less, 1,000 g / mol or more but 60,000 g / mol or less, 1,500 g / mol or more but 60,000 g / mol or less, 2,000 g / mol or more but 60,000 g / mol or less, 2,500 g / mol or more It may be less than 60,000 g / mol.

[0050] The polyester polymer of the above embodiment can have a high molecular weight and excellent optical properties without a chain extender by being manufactured by the above-described manufacturing method.

[0051]

[0052] The above polyester polymer may have a weight average molecular weight (Mw) measured using gel permeation chromatography (GPC) of 5,000 g / mol or more and 600,000 g / mol or less.

[0053] Specifically, the polyester polymer may have a weight average molecular weight (Mw) measured using gel permeation chromatography (GPC) of 5,000 g / mol or more, 5,500 g / mol or more, 6,000 g / mol or more, 6,500 g / mol or more, 600,000 g / mol or less, 300,000 g / mol or less, 250,000 g / mol or less, 200,000 g / mol or less, and 5,000 g / mol or more and 600,000 g / mol or less, 5,500 g / mol or more and 600,000 g / mol or less, 6,000 g / mol or more and 600,000 g / mol or less, 6,500 g / mol or more and 600,000 g / mol or less, 5,000 g / mol or more 300,000 g / mol or less, 5,500 g / mol or more but 300,000 g / mol or less, 6,000 g / mol or more but 300,000 g / mol or less, 6,500 g / mol or more but 300,000 g / mol or less, 5,000 g / mol or more but 250,000 g / mol or less, 5,500 g / mol or more but 250,000 g / mol or less, 6,000 g / mol or more but 250,000 g / mol or less, 6,500 g / mol or more but 250,000 g / mol or less, 5,000 g / mol or more but 200,000 g / mol or less, 5,500 g / mol or more but 200,000 g / mol or less, 6,000 g / mol or more but 200,000 g / mol or less, It can be between 6,500 g / mol and 200,000 g / mol.

[0054] The polyester polymer of the above embodiment can have a high molecular weight and excellent optical properties without a chain extender by being manufactured by the manufacturing method described below.

[0055]

[0056] Meanwhile, the polyester polymer may have a biomass content of 20% or more as measured according to ASTM D6866-22.

[0057] Specifically, the polyester polymer may have a biomass content of at least 20%, at least 50%, at least 90%, at least 95%, at least 98%, at least 99%, at least 100%, at most 99.9%, at least 20% but less than 100%, at least 50% but less than 100%, at least 90% but less than 100%, at least 95% but less than 100%, at least 98% but less than 100%, at least 99% but less than 100%, at least 20% but less than 99.9%, at least 50% but less than 99.9%, at least 90% but less than 99.9%, at least 95% but less than 99.9%, at least 98% but less than 99.9%, at least 99% but less than 99.9%.

[0058] The above polyester polymer can be manufactured from a bio-derived monomer and at the same time manufactured according to a method for manufacturing a polyester polymer of another embodiment described below, thereby manufacturing a polyester polymer having a high bio-content.

[0059] For example, when the polyester polymer is derived from one type of bio-derived monomer, the polyester polymer may have a biomass content of 20% or more and 100% or less, or 20% or more and 99.9% or less, as measured according to ASTM D6866-22.

[0060] Alternatively, when the polyester polymer is derived from two types of bio-derived monomers, the polyester polymer may have a biomass content of 90% or more, 95% or more, 98% or more, 99% or more, 100% or less, 99.9% or less, 90% or more but 100% or less, 95% or more but 100% or less, 98% or more but 100% or less, 99% or more but 100% or less, 90% or more but 99.9% or less, 95% or more but 99.9% or less, 98% or more but 99.9% or less, 99% or more but 99.9% or less, as measured according to ASTM D6866-22.

[0061]

[0062] The above biomass content is determined by radioisotope after graphitizing the polyester polymer. 14 The content of C may be calculated according to ASTM D6866-22.

[0063] Since the above polyester polymer has a biomass content of 90% or more as measured according to ASTM D6866-22, the effect of achieving carbon neutrality by not including petroleum-based monomers can be realized.

[0064] Specifically, bio-derived monomers may refer to monomers obtained from biomass resources such as plants.

[0065]

[0066] The polyester polymer of the above embodiment may be a biodegradable polyester polymer exhibiting biodegradability.

[0067] In this specification, a biodegradable resin or biodegradable (co)polymer means a resin or (co)polymer that undergoes natural decomposition when exposed to the outside, and specifically, may mean a resin or (co)polymer that undergoes decomposition by 20% or more by weight relative to the weight of the initial resin or (co)polymer when exposed to the outside environment at room temperature (10°C to 30°C) for 90 days or more.

[0068]

[0069] That is, the polyester polymer of the above embodiment can be decomposed by more than 20 wt% based on the weight of the initial polymer when exposed to an external environment at room temperature for more than 90 days. The method for measuring the biodegradability is not particularly limited, but can be measured according to, for example, ISO 14855-1.

[0070]

[0071] According to another embodiment of the invention, a method for producing a polyester polymer is provided, comprising: a step of introducing ethylene glycol and a dicarboxylic acid compound and reacting them under conditions of a temperature of 50° C. or more and 200° C. or less and a pressure of 10 torr or more and 760 torr or less to produce an oligomer; and a step of reacting the oligomer under conditions of a temperature of 50° C. or more and 200° C. or less and a pressure of 1 torr or less to produce a polyester polymer.

[0072] The present inventors have completed the present invention by finding that, when a polyester polymer is produced according to the method for producing a polyester polymer of the above embodiment, a polyester polymer having a high bio-content and high molecular weight, as well as excellent optical properties, can be produced without using a chain extender.

[0073] In the method for producing a polyester polymer of the above embodiment, the ethylene glycol and dicarboxylic acid compound may be bio-derived monomers.

[0074] The above bio-derived monomer may refer to a monomer obtained from biomass resources such as plants.

[0075]

[0076] Specifically, according to the method for producing a polyester polymer, a bio-based monomer is used, and since the equivalence ratio between monomers can be finely controlled, a polyester polymer having a high bio content and high molecular weight, as well as excellent optical properties, can be produced without using a chain extender.

[0077]

[0078] Specifically, the method for producing a polyester polymer of the above embodiment may include a step of introducing ethylene glycol and a dicarboxylic acid compound and reacting them under conditions of a temperature of 50° C. or more and 200° C. or less and a pressure of 10 torr or more and 760 torr or less to produce an oligomer; and a step of reacting the oligomer under conditions of a temperature of 50° C. or more and 200° C. or less and a pressure of 1 torr or less to produce a polyester polymer.

[0079] The method for producing a polyester polymer of the above embodiment can prevent yellowing by controlling side reactions between monomers since both the oligomer production step and the polymerization step are carried out at 200°C or lower, and at the same time, a polyester polymer having a high bio-content and high molecular weight and excellent optical properties can be produced without using a chain extender since a bio-based monomer is used and the equivalence ratio between monomers can be finely controlled.

[0080] The step of manufacturing the above oligomer can be specifically carried out at a temperature of 50°C or more and 200°C or less, 70°C or more and 200°C or less, or 90°C or more and 200°C or less.

[0081] In addition, the step of manufacturing the above oligomer may be performed at a pressure of 10 torr or more and 760 torr or less, 30 torr or more and 760 torr or less, 50 torr or more and 760 torr or less, 50 torr or more and 700 torr or less, 50 torr or more and 500 torr or less, or 50 torr or more and 400 torr or less.

[0082] Additionally, the step of manufacturing the above oligomer may be performed for a time of 1 hour or more and 30 hours or less, 1 hour or more and 20 hours or less, 1 hour or more and 10 hours or less, 2 hours or more and 10 hours or less, 2 hours or more and 8 hours or less, or 2 hours or more and 6 hours or less.

[0083] That is, the step of introducing ethylene glycol and a dicarboxylic acid compound and reacting them under conditions of a temperature of 50° C. or more and 200° C. or less and a pressure of 10 torr or more and 760 torr or less to produce an oligomer may include the step of introducing ethylene glycol and a dicarboxylic acid compound and reacting them under conditions of a temperature of 90° C. or more and 200° C. or less and a pressure of 50 torr or more and 700 torr or less to produce an oligomer for 1 hour or more and 30 hours or less.

[0084]

[0085] As the step of manufacturing the above oligomer proceeds under the above conditions, yellowing can be prevented by controlling side reactions between monomers, and at the same time, bio-based monomers can be used and the equivalence ratio between monomers can be finely controlled, so that a polyester polymer having a high bio content and high molecular weight and excellent optical properties can be manufactured without using a chain extender.

[0086]

[0087] In addition, the step of producing a polyester polymer by reacting the above oligomer under conditions of a temperature of 50°C or more and 200°C or less and a pressure of 1 torr or less; can be specifically performed at a temperature of 50°C or more and 200°C or less, 70°C or more and 200°C or less, or 90°C or more and 200°C or less.

[0088] In addition, the step of manufacturing a polyester polymer by reacting the above oligomer at a temperature of 50°C or more and 200°C or less and a pressure of 1 torr or less may be performed at a pressure of 1 torr or less, 0.1 torr or more and 1 torr or less, 0.1 torr or more and 0.5 torr or less, or 0.1 torr or more and 0.2 torr or less.

[0089] In addition, the step of producing a polyester polymer by reacting the above oligomer under conditions of a temperature of 50°C or more and 200°C or less and a pressure of 1 torr or less may be performed for a time of 1 hour or more and 30 hours or less, 1 hour or more and 20 hours or less, 10 hours or more and 30 hours or less, 10 hours or more and 20 hours or less, 12 hours or more and 20 hours or less, 15 hours or more and 20 hours or less, or 15 hours or more and 18 hours or less.

[0090] That is, the step of producing a polyester polymer by reacting the oligomer under conditions of a temperature of 50°C or more and 200°C or less and a pressure of 1 torr or less may include the step of producing a polyester polymer by reacting the oligomer under conditions of a temperature of 50°C or more and 200°C or less and a pressure of 1 torr or less for 10 hours or more and 30 hours or less.

[0091]

[0092] As the step of manufacturing a polyester polymer by reacting the above oligomer under conditions of a temperature of 50°C or more and 200°C or less and a pressure of 1 torr or less is carried out under the above conditions, side reactions between monomers can be controlled to prevent yellowing, and at the same time, a bio-based monomer can be used and the equivalence ratio between monomers can be finely controlled, so that a polyester polymer having a high bio content and high molecular weight and excellent optical properties can be manufactured without using a chain extender.

[0093] In particular, if the step of manufacturing a polyester polymer by reacting the above-mentioned oligomer at a temperature of 50°C or more and 200°C or less and a pressure of 1 torr or less is carried out at a temperature exceeding 200°C, a side reaction may occur, causing browning of the polyester polymer and a technical problem of excessively increasing the yellowness.

[0094]

[0095]

[0096] The polyester polymer produced by the method for producing a polyester polymer of the above embodiment may be a biodegradable polyester polymer exhibiting biodegradability.

[0097] In this specification, a biodegradable resin or biodegradable (co)polymer means a resin or (co)polymer that undergoes natural decomposition when exposed to the outside, and specifically, may mean a resin or (co)polymer that undergoes decomposition by 20% or more by weight relative to the weight of the initial resin or (co)polymer when exposed to the outside environment at room temperature (10°C to 30°C) for 90 days or more.

[0098]

[0099] That is, the polyester polymer produced by the method for producing a polyester polymer of the above embodiment can be decomposed by 20 wt% or more based on the weight of the initial resin or (co)polymer when exposed to an external environment at room temperature for 90 days or more. The method for measuring the biodegradability is not particularly limited, but can be measured according to ISO 14855-1, for example.

[0100]

[0101] Meanwhile, in the method for producing a polyester polymer of the above embodiment, a chain extender may be included in an amount of less than 0.0001 parts by weight based on a total of 100 parts by weight of the ethylene glycol and dicarboxylic acid compound.

[0102] Specifically, in the method for producing a polyester polymer of the above embodiment, the chain extender may be included in an amount of less than 0.0001 part by weight, less than 0.000001 part by weight, less than 0.00001 part by weight, or 0 part by weight, based on a total of 100 parts by weight of the ethylene glycol and the dicarboxylic acid compound.

[0103] That is, the method for producing a polyester polymer of the above embodiment may not include a chain extender.

[0104] The method for producing a polyester polymer of the above embodiment comprises the steps of introducing ethylene glycol and a dicarboxylic acid compound as described above, reacting them under conditions of a temperature of 50 to 200°C and a pressure of 10 torr to 760 torr to produce an oligomer; and reacting the oligomer under conditions of a temperature of 50 to 200°C and a pressure of 1 torr to produce a polyester polymer; thereby using a bio-based monomer and being able to finely control the equivalence ratio between monomers, it is possible to produce a polyester polymer having a high bio content and high molecular weight and excellent optical properties without a chain extender.

[0105]

[0106] The above polyester polymer may have a number average molecular weight (Mn) of 1,000 g / mol or more and 200,000 g / mol or less as measured using gel permeation chromatography (GPC).

[0107] Specifically, the polyester polymer may have a number average molecular weight (Mn) measured using gel permeation chromatography (GPC) of 1,000 g / mol or more, 1,500 g / mol or more, 2,000 g / mol or more, 2,500 g / mol or more, 200,000 g / mol or less, 100,000 g / mol or less, 80,000 g / mol or less, 60,000 g / mol or less, 1,000 g / mol or more and 200,000 g / mol or less, 1,500 g / mol or more and 200,000 g / mol or less, 2,000 g / mol or more and 200,000 g / mol or less, 2,500 g / mol or more and 200,000 g / mol or less, 1,000 g / mol or more 100,000 g / mol or less, 1,500 g / mol or more but 100,000 g / mol or less, 2,000 g / mol or more but 100,000 g / mol or less, 2,500 g / mol or more but 100,000 g / mol or less, 1,000 g / mol or more but 80,000 g / mol or less, 1,500 g / mol or more but 80,000 g / mol or less, 2,000 g / mol or more but 80,000 g / mol or less, 2,500 g / mol or more but 80,000 g / mol or less, 1,000 g / mol or more but 60,000 g / mol or less, 1,500 g / mol or more but 60,000 g / mol or less, 2,000 g / mol or more but 60,000 g / mol or less, 2,500 g / mol or more It may be less than 60,000 g / mol.

[0108] The method for producing a polyester polymer of the above embodiment comprises the steps of introducing ethylene glycol and a dicarboxylic acid compound as described above, reacting them under conditions of a temperature of 50 to 200°C and a pressure of 10 torr to 760 torr to produce an oligomer; and reacting the oligomer under conditions of a temperature of 50 to 200°C and a pressure of 1 torr to produce a polyester polymer; thereby using a bio-based monomer and being able to finely control the equivalence ratio between monomers, it is possible to produce a polyester polymer having a high molecular weight and excellent optical properties without a chain extender.

[0109]

[0110] The above polyester polymer may have a weight average molecular weight (Mw) measured using gel permeation chromatography (GPC) of 5,000 g / mol or more and 600,000 g / mol or less.

[0111] Specifically, the polyester polymer may have a weight average molecular weight (Mw) measured using gel permeation chromatography (GPC) of 5,000 g / mol or more, 5,500 g / mol or more, 6,000 g / mol or more, 6,500 g / mol or more, 600,000 g / mol or less, 300,000 g / mol or less, 250,000 g / mol or less, 200,000 g / mol or less, and 5,000 g / mol or more and 600,000 g / mol or less, 5,500 g / mol or more and 600,000 g / mol or less, 6,000 g / mol or more and 600,000 g / mol or less, 6,500 g / mol or more and 600,000 g / mol or less, 5,000 g / mol or more 300,000 g / mol or less, 5,500 g / mol or more but 300,000 g / mol or less, 6,000 g / mol or more but 300,000 g / mol or less, 6,500 g / mol or more but 300,000 g / mol or less, 5,000 g / mol or more but 250,000 g / mol or less, 5,500 g / mol or more but 250,000 g / mol or less, 6,000 g / mol or more but 250,000 g / mol or less, 6,500 g / mol or more but 250,000 g / mol or less, 5,000 g / mol or more but 200,000 g / mol or less, 5,500 g / mol or more but 200,000 g / mol or less, 6,000 g / mol or more but 200,000 g / mol or less, It can be between 6,500 g / mol and 200,000 g / mol.

[0112] The method for producing a polyester polymer of the above embodiment comprises the steps of introducing ethylene glycol and a dicarboxylic acid compound as described above, reacting them under conditions of a temperature of 50 to 200°C and a pressure of 10 torr to 760 torr to produce an oligomer; and reacting the oligomer under conditions of a temperature of 50 to 200°C and a pressure of 1 torr to produce a polyester polymer; thereby using a bio-based monomer and being able to finely control the equivalence ratio between monomers, it is possible to produce a polyester polymer having a high molecular weight and excellent optical properties without a chain extender.

[0113]

[0114] In the method for producing a polyester polymer according to the above embodiment, when introducing the ethylene glycol and the dicarboxylic acid compound, the ethylene glycol and the dicarboxylic acid compound may be introduced in an appropriate ratio. For example, the ethylene glycol may be included in an amount of 1.01 mol or more and 1.5 mol or less per 1 mol of the dicarboxylic acid compound.

[0115] Specifically, for 1 mole of the dicarboxylic acid compound, the ethylene glycol may be included in an amount of 1.01 mole or more, 1.5 mole or less, 1.4 mole or less, 1.3 mole or less, 1.25 mole or less, 1.2 mole or less, 1.1 mole or less, or 1.01 mole or more and 1.5 mole or less, 1.01 mole or more and 1.4 mole or less, 1.01 mole or more and 1.3 mole or less, 1.01 mole or more and 1.25 mole or less, 1.01 mole or more and 1.2 mole or less, or 1.01 mole or more and 1.1 mole or less.

[0116] By adding the dicarboxylic acid compound and ethylene glycol in the above ratio, a polyester polymer can be manufactured with excellent economic efficiency without additionally adding by-products.

[0117]

[0118] Meanwhile, the polyester polymer may include a repeating unit represented by the following chemical formula 1.

[0119] [Chemical Formula 1]

[0120]

[0121] In the above chemical formula 1, L1 is an ethylene group and L2 is an alkylene group having 1 to 10 carbon atoms.

[0122]

[0123] The above L1 is a functional group derived from ethylene glycol, and the above L2 may be a functional group derived from a dicarboxylic acid compound.

[0124] The above L2 may be an alkylene group having 1 to 10 carbon atoms, an alkylene group having 1 to 5 carbon atoms, or an alkylene group having 1 to 3 carbon atoms, and may be, for example, an ethylene group.

[0125]

[0126] The polyester polymer produced in the method for producing a polyester polymer of the above embodiment may be polyethylene succinate.

[0127]

[0128] The polyester polymer may contain repeating units represented by the above chemical formula 1 in an amount of 90 mol % or more, 95 mol % or more, 99 mol % or more, 99.9 mol % or more, or 90 mol % or more and 100 mol % or less, 95 mol % or more and 100 mol % or less, 99 mol % or more and 100 mol % or less, or 99.9 mol % or more and 100 mol % or less, based on the total repeating units.

[0129] For example, the polyester polymer may be composed of repeating units represented by the above chemical formula 1. That is, the polyester polymer may contain only ethylene glycol and succinic acid as monomers, and may contain only repeating units derived from ethylene glycol and succinic acid, as no other monomers are included.

[0130]

[0131] Meanwhile, the polyester polymer may have a biomass content of 20% or more as measured according to ASTM D6866-22.

[0132] Specifically, the polyester polymer may have a biomass content of at least 20%, at least 50%, at least 90%, at least 95%, at least 98%, at least 99%, at least 100%, at most 99.9%, at least 20% but less than 100%, at least 50% but less than 100%, at least 90% but less than 100%, at least 95% but less than 100%, at least 98% but less than 100%, at least 99% but less than 100%, at least 20% but less than 99.9%, at least 50% but less than 99.9%, at least 90% but less than 99.9%, at least 95% but less than 99.9%, at least 98% but less than 99.9%, at least 99% but less than 99.9%.

[0133] The above polyester polymer can be manufactured from a bio-derived monomer and at the same time manufactured according to a method for manufacturing a polyester polymer of another embodiment described below, thereby manufacturing a polyester polymer having a high bio-content.

[0134] For example, when the polyester polymer is derived from one type of bio-derived monomer, the polyester polymer may have a biomass content of 20% or more and 100% or less, or 20% or more and 99.9% or less, as measured according to ASTM D6866-22.

[0135] Alternatively, when the polyester polymer is derived from two types of bio-derived monomers, the polyester polymer may have a biomass content of 90% or more, 95% or more, 98% or more, 99% or more, 100% or less, 99.9% or less, 90% or more but 100% or less, 95% or more but 100% or less, 98% or more but 100% or less, 99% or more but 100% or less, 90% or more but 99.9% or less, 95% or more but 99.9% or less, 98% or more but 99.9% or less, 99% or more but 99.9% or less, as measured according to ASTM D6866-22.

[0136] The method for producing a polyester polymer of the above embodiment includes the steps of introducing ethylene glycol and a dicarboxylic acid compound as described above, reacting them under conditions of a temperature of 50° C. or more and 200° C. or less and a pressure of 10 torr or more and 760 torr or less to produce an oligomer; and reacting the oligomer under conditions of a temperature of 50° C. or more and 200° C. or less and a pressure of 1 torr or less to produce a polyester polymer; thereby using a bio-based monomer and being able to finely control the equivalence ratio between monomers, it is possible to produce a polyester polymer having a high bio content.

[0137] The above biomass content is determined by radioisotope after graphitizing the polyester polymer. 14 The content of C may be calculated according to ASTM D6866-22.

[0138] Since the above polyester polymer has a biomass content of 90% or more as measured according to ASTM D6866-22, the effect of achieving carbon neutrality by not including petroleum-based monomers can be realized.

[0139]

[0140] The polyester polymer of the above embodiment may be a biodegradable polyester polymer exhibiting biodegradability.

[0141] In this specification, a biodegradable resin or biodegradable (co)polymer means a resin or (co)polymer that undergoes natural decomposition when exposed to the outside, and specifically, may mean a resin or (co)polymer that undergoes decomposition by 20% or more by weight relative to the weight of the initial resin or (co)polymer when exposed to the outside environment at room temperature (10°C to 30°C) for 90 days or more.

[0142]

[0143] According to one embodiment of the invention, a molded article molded from a resin composition comprising the polyester polymer may be provided. The resin composition comprising the polyester polymer may further include other additives that improve physical properties in addition to the polyester polymer.

[0144] The above molded article may include at least one molded article selected from the group consisting of injection molded articles, extrusion molded articles, inflation molded articles, fibers, nonwovens, foams, films, and sheets.

[0145] The use of the above molded product is not particularly limited, but for example, the above molded product may be an electronic material, a building material, a food packaging, a food container (e.g., a disposable cup, a tray), an industrial product, an agricultural product (e.g., a mulching film), a non-woven fabric, a fiber, etc.

[0146]

[0147] Specifically, a film comprising the polyester polymer can be provided.

[0148] The film comprising the above polyester polymer may have a yellowness of 50 or less.

[0149] Specifically, the film comprising the polyester polymer may have a yellowness of 1 or more, 10 or more, 15 or more, 50 or less, 48 ​​or less, or 1 or more and 50 or less, 10 or more and 50 or less, 15 or more and 50 or less, 1 or more and 48 or less, 10 or more and 48 or less, or 15 or more and 48 or less.

[0150]

[0151] The polyester polymer of the above embodiment is manufactured by the above-described manufacturing method, and specifically, comprises the steps of: introducing ethylene glycol and a dicarboxylic acid compound, reacting them under conditions of a temperature of 50° C. or more and 200° C. or less and a pressure of 10 torr or more and 760 torr or less to manufacture an oligomer; and reacting the oligomer under conditions of a temperature of 50° C. or more and 200° C. or less and a pressure of 1 torr or less to manufacture a polyester polymer; As such, a bio-based monomer is used, and the equivalence ratio between monomers can be finely controlled, so that a polyester polymer having excellent optical properties can be manufactured.

[0152] The method for measuring the above yellowness is not particularly limited, but for example, it may be a value measured using Nippon Denshoku under the conditions of a light source of D65 and a viewing angle of 10 degrees for a film having a thickness of 180 ㎛ including the polyester polymer.

[0153]

[0154] According to the present invention, a method for producing a polyester polymer having high bio-content and high molecular weight, and excellent optical properties, without using a chain extender, and a polyester polymer can be provided.

[0155]

[0156] Hereinafter, embodiments of the present invention will be described in more detail in the following examples. However, the following examples are merely illustrative of embodiments of the present invention, and the content of the present invention is not limited by the following examples.

[0157]

[0158] Example 1

[0159] 20 g (0.322 mol) of bio-derived ethylene glycol, 37.3 g (0.316 mol) of bio-derived succinic acid, and 0.2 g (1.05 mmol) of p-toluenesulfonic acid were added to an oil bath reactor and mixed. Then, a polymerization reaction was performed at 90°C and 50 torr for 2 hours to produce an oligomer.

[0160] Afterwards, the above oligomer was reacted at 90°C and 0.2 torr for 18 hours to produce a polyester polymer.

[0161]

[0162] Example 2

[0163] A polyester polymer was prepared in the same manner as in Example 1, except that an oligomer was prepared by polymerization reaction at 110°C and 50 torr for 2 hours, and then the oligomer was further reacted at 110°C and 0.2 torr for 18 hours.

[0164]

[0165] Example 3

[0166] A polyester polymer was prepared in the same manner as in Example 1, except that an oligomer was prepared by polymerization reaction at 130°C and 50 torr for 2 hours, and then the oligomer was further reacted at 130°C and 0.2 torr for 18 hours.

[0167]

[0168] Example 4

[0169] A polyester polymer was prepared in the same manner as in Example 1, except that an oligomer was prepared by polymerization at 150°C and 50 torr for 2 hours, and then the oligomer was further reacted at 150°C and 0.2 torr for 18 hours.

[0170]

[0171] Example 5

[0172] A polyester polymer was prepared in the same manner as in Example 1, except that an oligomer was prepared by polymerization at 170°C and 50 torr for 2 hours, and then the oligomer was further reacted at 170°C and 0.2 torr for 18 hours.

[0173]

[0174] Example 6

[0175] A polyester polymer was prepared in the same manner as in Example 1, except that an oligomer was prepared by polymerization at 190°C and 50 torr for 2 hours, and then the oligomer was further reacted at 190°C and 0.2 torr for 18 hours.

[0176]

[0177] Example 7

[0178] A polyester polymer was prepared in the same manner as in Example 1, except that 0.438 g (1.288 mmol) of titanium butoxide (Ti(buO)4) was added instead of p-toluenesulfonic acid, polymerization was performed at 150°C and 400 torr for 2 hours, then the temperature was raised to 180°C and polymerization was performed at 400 torr for 2 hours and at 180°C and 10 torr for 2 hours to prepare an oligomer, and then the oligomer was further reacted at 180°C and 0.2 torr for 18 hours.

[0179]

[0180] Example 8

[0181] A polyester polymer was prepared in the same manner as in Example 1, except that 0.438 g (1.288 mmol) of titanium butoxide (Ti(buO)4) was added instead of p-toluenesulfonic acid, polymerization was performed at 150°C and 400 torr for 2 hours, then the temperature was raised to 190°C and polymerization was performed at 400 torr for 2 hours and at 190°C and 10 torr for 2 hours to prepare an oligomer, and then the oligomer was further reacted at 190°C and 0.2 torr for 18 hours.

[0182]

[0183] Example 9

[0184] A polyester polymer was prepared in the same manner as in Example 1, except that 0.438 g (1.288 mmol) of titanium butoxide (Ti(buO)4) was added instead of p-toluenesulfonic acid, polymerization was performed at 150°C and 400 torr for 2 hours, then the temperature was raised to 200°C and polymerization was performed at 400 torr for 2 hours and at 200°C and 10 torr for 2 hours to prepare an oligomer, and then the oligomer was further reacted at 200°C and 0.2 torr for 18 hours.

[0185]

[0186] Comparative Example 1

[0187] 17.36 g (0.279 mol) of non-biodegradable ethylene glycol, 23.6 g (0.199 mol) of non-biodegradable succinic acid, and 20.162 g (0.867 mmol) of SnCl were added to an oil bath reactor and mixed. Then, a polymerization reaction was performed at 120°C and 400 torr for 3 hours to produce an oligomer.

[0188] Afterwards, the above oligomer was reacted at 170°C and 10 torr for 10 hours, and then the temperature was raised to 230°C and reacted at 0.2 torr for 1 hour to produce a polyester polymer.

[0189]

[0190] Comparative Example 2

[0191] A polyester polymer was prepared in the same manner as in Example 1, except that the oligomer was reacted for an additional 18 hours at 220°C and 0.2 torr, using a non-biogenic monomer.

[0192]

[0193] Comparative Example 3

[0194] 20 g (0.322 mol) of bio-derived ethylene glycol, 0.316 mol of dimethyl terephthalate, and 0.438 g (1.288 mmol) of titanium butoxide (Ti(buO)4) were added to an oil bath reactor and mixed. Then, the temperature was raised to 240°C and a polymerization reaction was performed at 50 torr for 2 hours to produce an oligomer.

[0195] Afterwards, the above oligomer was reacted at 0.2 torr for 18 hours while heating to 290°C to produce a polyester polymer.

[0196] <Experimental Example>

[0197] The properties of the copolymers manufactured in the above examples and comparative examples were evaluated as follows.

[0198]

[0199] 1) GPC (gel permeation chromatography) molecular weight evaluation

[0200] For each copolymer manufactured in the above examples and comparative examples, the molecular weight was evaluated using a Water e2695 model equipment and Agilent Plgel mixed c and b columns. The sample was prepared at 1 mg / ml with chloroform as a solvent and 100 ul was injected. The weight-average molecular weights of the polystyrene standard specimens were 12 types: 160 g / mol, 580 g / mol, 1180 g / mol, 4,880 g / mol, 9,310 g / mol, 22,790 g / mol, 75,050 g / mol, 217,900 g / mol, 479,200 g / mol, 1,069,000 g / mol, 3,022,000 g / mol, and 6,545,000 g / mol. The weight average molecular weight, number average molecular weight, and polydispersity index were measured using gel permeation chromatography (GPC, Tosoh ECO SEC Elite), and the results are shown in Table 1 below.

[0201] Solvent: chloroform (eluent)

[0202] Flow rate: 1.0 ml / min

[0203] Column temperature: 40 ℃

[0204] Standard: Polystyrene (corrected to a cubic function)

[0205]

[0206] ClassificationMolecular weightCharacteristic evaluationMn (g / mol)Mw (g / mol)PDIExample 1262160512.31Example 2320188242.76Example 3432599002.29Example 410224165481.61Example 521209369881.74Example 622025400911.82Example 7428681142712.67Example 8457091148612.51Example 9472731110472.35Comparative example 19657180571.87Comparative example 212030270682.25

[0207] 2) Bio-content: After graphitizing the samples of the polyester polymers manufactured in the above examples and comparative examples, radioisotope 14 The content of C was analyzed and calculated according to ASTM D6866-22.

[0208]

[0209] 3) Yellowness

[0210] Polymer pellets of the polyester polymer manufactured in the above examples and comparative examples were melted in a hot press at 130°C for 3 minutes and formed into a film (thickness: 180 μm).

[0211] For the above polyester polymer film (thickness: 180 ㎛), yellowness was measured using Nippon Denshoku under the conditions of light source D65 and a viewing angle of 10 degrees.

[0212]

[0213] 4) Biodegradability

[0214] The polymer pellets of the polyester polymers manufactured in Examples 3, 4, and 9 and Comparative Examples 1 and 3 were cut into samples with a diameter of 5 mm or less, and placed in the sample holder of a freeze mill (freezer / mill), followed by insertion of a stainless steel rod. After filling the chamber with liquid nitrogen, the samples were ground at 60 revolutions per minute for 10 minutes. The freeze-milled powder was sieved through a 250 μm sieve to prepare samples for measuring biodegradability.

[0215] Using the above biodegradability measurement sample, biodegradability was measured at a temperature of 28°C using the analysis method of ISO 14855-1. At this time, the amount of CO2 generated was measured using an NDIR sensor, and a microbial respiration device (Respirometer) was used.

[0216]

[0217] Biocontent (%)YellownessBiodegradabilityExample 19915-Example 29917-Example 39932100 % (120 days)Example 49944100 % (148 days)Example 59948-Example 69945-Example 79917-Example 89920-Example 99920100 % (223 days)Comparative Example 1072100 % (148 days)Comparative Example 2075-Comparative Example 30210 %

[0218] According to Table 2 above, it was confirmed that the polyester polymer of the example had a bio-content of 99% and was carbon neutral by using a bio-derived monomer, and at the same time had a high bio-content and molecular weight without a chain extender and had low yellowness. On the other hand, it was confirmed that the polyester polymer of the comparative example had a bio-content of 0% and was not carbon neutral compared to the example, and at the same time had poor optical properties.

Claims

1. Contains a repeating unit represented by the following chemical formula 1, A biomass content of 20% or more as measured according to ASTM D6866-22; A polyester polymer that decomposes by more than 20% by weight based on the weight of the original polymer when exposed to an external environment at room temperature for more than 90 days: [Chemical Formula 1] In the above chemical formula 1, L1 is an ethylene group, L2 is an alkylene group having 1 to 10 carbon atoms.

2. In paragraph 1, The above polyester polymer is a polyester polymer having a number average molecular weight of 1,000 g / mol or more and 200,000 g / mol or less.

3. In paragraph 1, The above polyester polymer is a polyester polymer having a weight average molecular weight of 5,000 g / mol or more and 600,000 g / mol or less.

4. In paragraph 1, The above polyester polymer is a polyester polymer comprising at least 90 mol% of the repeating unit represented by the above chemical formula 1 with respect to the total repeating unit.

5. In paragraph 1, The above polyester polymer is a polyester polymer composed of repeating units represented by the above chemical formula 1.

6. A step of producing an oligomer by adding ethylene glycol and a dicarboxylic acid compound and reacting them under conditions of a temperature of 50°C or higher and 200°C or lower and a pressure of 10 torr or higher and 760 torr or lower; and A method for producing a polyester polymer, comprising: a step of producing a polyester polymer by reacting the above oligomer under conditions of a temperature of 50°C or more and 200°C or less and a pressure of 1 torr or less.

7. In paragraph 6, A method for producing a polyester polymer, wherein the polyester polymer decomposes by more than 20% by weight based on the weight of the initial polymer when exposed to an external environment at room temperature for more than 90 days.

8. In paragraph 6, A step of producing an oligomer by introducing the above ethylene glycol and dicarboxylic acid compound and reacting them under conditions of a temperature of 50°C or more and 200°C or less and a pressure of 10 torr or more and 760 torr or less; A method for producing a polyester polymer, comprising the steps of: introducing ethylene glycol and a dicarboxylic acid compound, and reacting them under conditions of a temperature of 90°C or higher and 200°C or lower and a pressure of 50 torr or higher and 700 torr or lower for 1 hour or longer and 30 hours or shorter to produce an oligomer.

9. In paragraph 6, A step of producing a polyester polymer by reacting the above oligomer under conditions of a temperature of 90°C or higher and 200°C or lower and a pressure of 1 torr or lower; A method for producing a polyester polymer, comprising: a step of reacting the above oligomer under conditions of a temperature of 50°C or more and 200°C or less and a pressure of 1 torr or less for 1 hour or more and 30 hours or less to produce a polyester polymer.

10. In paragraph 6, A method for producing a polyester polymer, wherein a chain extender is contained in an amount of less than 0.0001 parts by weight based on a total of 100 parts by weight of the ethylene glycol and dicarboxylic acid compound.

11. In paragraph 6, A method for producing a polyester polymer, wherein the polyester polymer has a number average molecular weight of 1,000 g / mol or more and 200,000 g / mol or less.

12. In paragraph 6, A method for producing a polyester polymer, wherein the polyester polymer has a weight average molecular weight of 5,000 g / mol or more and 600,000 g / mol or less.

13. In paragraph 6, A method for producing a polyester polymer, wherein 1.01 mol or more and 1.5 mol or less of ethylene glycol is contained per 1 mol of the dicarboxylic acid compound.

14. In paragraph 6, A method for producing a polyester polymer, wherein the polyester polymer comprises a repeating unit represented by the following chemical formula 1: [Chemical Formula 1] In the above chemical formula 1, L1 is an ethylene group, L2 is an alkylene group having 1 to 10 carbon atoms.

15. In paragraph 14, A method for producing a polyester polymer, wherein the polyester polymer comprises at least 90 mol% of a repeating unit represented by the chemical formula 1 based on the total repeating units:

16. In paragraph 14, The above polyester polymer is composed of a repeating unit represented by the above chemical formula 1, and a method for producing a polyester polymer:

17. In paragraph 6, A method for producing a polyester polymer, wherein the polyester polymer has a biomass content of at least 90% as measured according to ASTM D6866-22.

18. A molded article molded from a resin composition containing the polyester polymer of paragraph 1.

19. In paragraph 18, A molded product comprising at least one molded product selected from the group consisting of injection molded products, extrusion molded products, inflation molded products, fibers, non-woven fabrics, foams, adhesives, films, and sheets.

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