Poly(3-hydroxypropionate) composition and method for preparing same

Abstract

The present invention provides: a poly(3-hydroxypropionate) composition which comprises poly(3-hydroxypropionate) having a linear structure and poly(3-hydroxypropionate) having a branched structure, and has a predetermined slope (α) of the Mark-Houwink-Sakurada formula; and a method for preparing same.

Description

Poly(3-hydroxypropionate) composition and method for preparing the same

[0001] The present invention relates to a poly(3-hydroxypropionate) composition and a method for producing the same.

[0002] Poly(3-hydroxypropionic acid) is biodegradable, and due to its environmentally friendly properties, research on its use has been actively conducted recently. There are two main methods for producing poly(3-hydroxypropionic acid): a petrochemical-based polymerization using β-propiolactone (PL), and a bio-based method using 3-hydroxypropinic acid (3HP).

[0003] When using β-propiolactone, multiple synthetic steps using ethylene oxide are required, so there is a disadvantage in terms of economic feasibility compared to when using 3-hydroxypropionic acid, and there is the problem of 0% bio-content.

[0004] Meanwhile, in the case of polymerization using the synthesis of 3-hydroxypropionic acid, several steps such as freeze-drying, ultrasonication, and solvent elution must be performed to obtain poly(3-hydroxypropionic acid), and a large amount of solvent must be used at this time.

[0005] To solve this problem, there have been attempts to polycondense 3-hydroxypropionic acid, but there are limitations in obtaining high molecular weight poly(3-hydroxypropionic acid) because byproducts in the form of cyclic oligomers are generated and the moisture generated as a byproduct is not removed as the viscosity increases during polycondensation.

[0006] Accordingly, attempts have been made to increase the molecular weight by ROP of low-molecular-weight cyclic oligomers, but separation and purification are difficult. Furthermore, attempts have been made to increase the reaction temperature and time to improve the molecular weight, but only the weight-average molecular weight increased, not the number-average molecular weight. Furthermore, there was a problem in that the production rate of byproducts, which consisted of vinyl groups at the polymer terminals, also increased. Therefore, a method for producing poly(3-hydroxypropionic acid) with a high number-average molecular weight from 3-hydroxypropionic acid is required.

[0007] The present invention relates to a composition comprising poly(3-hydroxypropionate) having biodegradability, high number average molecular weight and weight average molecular weight, and a very narrow PDI value, and a method for producing the same.

[0008] According to one embodiment of the present invention, a method for producing a poly(3-hydroxypropionate) composition is provided, comprising: a step of reacting a 3-hydroxypropionic acid monomer or polymer at a temperature of 160°C or higher to produce a high-temperature reacted 3-hydroxypropionic acid oligomer or polymer; and a step of polymerizing the high-temperature reacted 3-hydroxypropionic acid oligomer or polymer to produce a poly(3-hydroxypropionate) composition.

[0009] According to another embodiment of the present invention, a poly(3-hydroxypropionate) composition is provided, which comprises a mixture comprising a linear poly(3-hydroxypropionate) and a branched poly(3-hydroxypropionate), wherein the slope (α) of the Mark-Houwink-Sakurada equation for the mixture is 0.10 or more and 0.45 or less.

[0010] Hereinafter, a poly(3-hydroxypropionate) composition and a method for producing the same according to a specific embodiment of the invention will be described in more detail.

[0011] 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.

[0012] Additionally, in this specification, the terms first and second are used to describe various components, and the terms are used only for the purpose of distinguishing one component from another.

[0013] Additionally, unless otherwise stated herein, the weight average molecular weight of a polymer can be measured using gel permeation chromatography (GPC). Specifically, the (co)polymer is dissolved in chloroform to a concentration of 2 mg / ml, 20 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 the solution is introduced at a flow rate of 1.0 mL / min. Two Agilent Mixed-B columns are connected 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. Nine weight-average molecular weights of polystyrene standard specimens were used: 2,000 g / mol, 10,000 g / mol, 30,000 g / mol, 70,000 g / mol, 200,000 g / mol, 700,000 g / mol, 2,000,000 g / mol, 4,000,000 g / mol, and 10,000,000 g / mol.

[0014] In the present invention, 3-hydroxypropionic acid means including 3-hydroxypropionic acid and / or 3-hydroxypropionate.

[0015]

[0016] According to one embodiment of the invention, there is provided a method comprising: reacting a 3-hydroxypropionic acid monomer or polymer at a temperature of 160°C or higher to produce a high-temperature reacted 3-hydroxypropionic acid oligomer or polymer; and

[0017] A method for producing a poly(3-hydroxypropionate) composition is provided, comprising a step of producing a poly(3-hydroxypropionate) composition by polymerizing the above-described high-temperature reacted 3-hydroxypropionic acid oligomer or polymer.

[0018] The present inventors have confirmed that a poly(3-hydroxypropionate)-containing composition having a high molecular weight, such as a number average molecular weight, can be manufactured through a process of reacting a 3-hydroxypropionic acid monomer or polymer at a temperature of 160°C or higher and then further polymerizing the same, and have completed the invention.

[0019]

[0020] The method for producing a poly(3-hydroxypropionate) composition according to the above embodiment comprises a step of reacting a 3-hydroxypropionic acid monomer or polymer at a temperature of 160°C or higher to produce a high-temperature reacted 3-hydroxypropionic acid oligomer or polymer.

[0021] The step of reacting the above 3-hydroxypropionic acid monomer or polymer at a temperature of 160°C or higher to produce a high-temperature reacted 3-hydroxypropionic acid oligomer or polymer may be a step of polymerizing the above 3-hydroxypropionic acid monomer at a temperature of 160°C or higher to produce a high-temperature reacted 3-hydroxypropionic acid oligomer.

[0022] By polymerizing the above 3-hydroxypropionic acid at a high temperature of 160°C or higher, the vinyl group content of the 3-hydroxypropionate oligomer can be increased. The terminal groups of the 3-hydroxypropionate oligomer may include a hydroxyl group, a carboxyl group, a vinyl group, etc. In the past, attempts were made to reduce the content of vinyl groups generated as a side reaction during the polymerization of 3-hydroxypropionic acid, as this was seen as the cause of difficulty in obtaining a high molecular weight polymer.

[0023] However, the inventors of the present invention have confirmed that when the vinyl group at the terminal of a 3-hydroxypropionate oligomer participates in an additional polymerization reaction, the molecular weight of the polymer finally produced increases and a branched polymer can be produced, and have completed the invention. Specifically, in the process of polymerizing the 3-hydroxypropionate oligomer, an addition polymerization reaction of the vinyl group at the terminal of the 3-hydroxypropionate oligomer, for example, radical polymerization and / or ionic polymerization, can additionally occur, and due to this addition polymerization reaction of the vinyl group, a composition containing poly(3-hydroxypropionate) having a large number average molecular weight and a branched structure can be produced.

[0024] That is, through a process of polymerizing 3-hydroxypropionic acid at a high temperature of 160°C or higher, the content of terminal vinyl groups capable of subsequent addition polymerization increases, and by further polymerizing such oligomers, a composition including poly(3-hydroxypropionate) that is branched and has a large number average molecular weight can be manufactured.

[0025] For example, the 3-hydroxypropionate oligomer may have a terminal vinyl group content of 5% or more and 40% or less, for example, 6% or more, 8% or more, 10% or more, 20% or more, 25% or more, 30% or more, 39% or less, 38% or less, 37% or less, 36% or less, 35% or less, 34% or less, 33% or less, 32% or less.

[0026] In addition, since the vinyl group participates in the reaction in the process of polymerizing the 3-hydroxypropionate oligomer, the poly(3-hydroxypropionate) may have a terminal vinyl group content of 35% or less, for example, 0%, 0.01% or more, 0.1% or more, 0.5% or more, 1% or more, 3% or more, 5% or more, 30% or less, 25% or less, 20% or less, 15% or less, 10% or less, 8% or less, 7% or less, or 6% or less.

[0027] The vinyl group content of the oligomer and / or polymer terminals was determined using NMR (Buker 500MHz NMR model instrument). 1 The ratio of vinyl groups to total end groups can be calculated using H-NMR measurements. Specifically, the polymer is dissolved in d-CDCl3 at a concentration of 8 mg / ml, and the measurement is performed using the following mathematical formula 1.

[0028] [Mathematical Formula 1]

[0029]

[0030] In the above mathematical formula 1,

[0031] a is 6.3 ppm of C=C 1 is the area value of H,

[0032] b is 3.8 ppm of HO-CH2- 2 It can be the area value of H.

[0033] C=C 1The area value of H is the area value of one of the hydrogens (H) of the double bond of the vinyl group, and HO-CH2- 2 The area value of H may be the area value of two hydrogens substituted on the carbon connected to the hydroxyl group terminal.

[0034]

[0035] In the step of polymerizing the above 3-hydroxypropionic acid at a temperature of 160°C or higher, the polymerization temperature may be 165°C or higher and 230°C or lower, 170°C or higher and 220°C or lower, 175°C or higher and 210°C or lower, or 180°C or higher and 200°C or lower. If the polymerization temperature is too low, the vinyl group content at the terminal of the 3-hydroxypropionate oligomer may not increase, so that the number average molecular weight of the final polymer may be low, and if the heat treatment temperature is too high, it may be difficult for the polymerization of 3-hydroxypropionate to proceed.

[0036] In addition, the reaction can be carried out in the absence of a catalyst at a temperature of 160°C or higher. That is, the polymerization of the 3-hydroxypropionic acid can be carried out in the absence of a catalyst. Since the polymerization of the 3-hydroxypropione is carried out at a high temperature without using a catalyst, the content of terminal vinyl groups can be improved. If the polymerization is carried out in the presence of a catalyst, the polydispersity index becomes very wide, making it difficult to control the molecular weight.

[0037]

[0038] In addition, the method for producing a poly(3-hydroxypropionate) composition according to the above embodiment may include a step of producing a poly(3-hydroxypropionate) composition by polymerizing the high-temperature reacted 3-hydroxypropionic acid oligomer or polymer.

[0039] In addition, the reaction for polymerizing the 3-hydroxypropionic acid oligomer reacted at high temperature may be a melt polymerization reaction, and melt polymerization means that the reactants and products remain in a liquid state. In addition, the polymerization reaction may also include an addition reaction of the vinyl group, as described above.

[0040] The polymerization may be carried out at a pressure of 4 torr or less and a temperature of 70°C or more and 120°C or less. For example, the temperature for polymerizing the high-temperature reacted 3-hydroxypropionic acid oligomer may be 75°C or more, 80°C or more, or 85°C or more, and 115°C or less, 110°C or less, 105°C or less, or 100°C or less. In addition, the pressure of the polymerization may be 0.01 torr or more, 0.1 torr or more, 0.5 torr or more, or 1.0 torr or more, and 3.5 torr or less, 3.0 torr or less, or 2.5 torr or less. The above polymerization reaction time can be appropriately considered in consideration of the molecular weight, yield, etc. of the polymer produced, and can preferably be performed for 1 hour to 60 hours, 5 hours to 50 hours, 10 hours to 40 hours, or 15 hours to 30 hours.

[0041] In addition, the polymerization reaction may be carried out in the presence of a sulfonic acid catalyst. The sulfonic acid catalyst is not particularly limited as long as it contains at least one sulfonic group, but may be, for example, p-toluenesulfonic acid, m-xylene-4-sulfonic acid, 2-mesitylenesulfonic acid, or p-xylene-2-sulfonic acid. The above catalyst may be used in an amount of 0.01 mol% or more and 20 mol% or less relative to poly(3-hydroxypropionic acid), for example, 0.05 mol% or more, 0.10 mol% or more, 0.20 mol% or more, 0.30 mol% or more, 0.40 mol% or more, 0.50 mol% or more, 0.70 mol% or more, 1.00 mol% or more, 3.00 mol% or more, and 18 mol% or less, 15 mol% or less, 13 mol% or less, 10 mol% or less, 8 mol% or less, or 5 mol% or less.

[0042] In addition, the polymerization reaction can proceed without a separate coupling agent, crosslinking agent, or initiator in addition to the catalyst. Conventionally, the use of crosslinking agents, etc. increased molecular weight, but there were problems such as toxicity or increased process costs. However, the method for producing a poly(3-hydroxypropionic acid) composition does not use crosslinking agents, coupling agents, or initiators, and thus can prevent problems resulting from the addition of these agents.

[0043]

[0044] In addition, the high temperature reacted 3-hydroxypropionic acid oligomer may have a number average molecular weight of 8,000 or less, 1,500 or more and 7,000 or less, 1,700 or more and 6,500 or less, 1,900 or more and 6,000 or less, or 2,000 or more and 55,000 or less.

[0045] In addition, the high temperature reacted 3-hydroxypropionate oligomer may have a weight average molecular weight of 20,000 or less, 1,000 or more and 15,000 or less, 1,500 or more and 13,000 or less, 2,000 or more and 10,000 or less, 2,500 or more and 9,000 or less, or 30,000 or more and 8,000 or less.

[0046]

[0047] In addition, in the method for producing a poly(3-hydroxypropionate) composition according to the above embodiment, the step of reacting the 3-hydroxypropionic acid monomer or polymer at a temperature of 160° C. or higher to produce a high-temperature-reacted 3-hydroxypropionic acid oligomer or polymer may be a step of heat-treating the 3-hydroxypropionic acid polymer at a temperature of 160° C. or higher to produce a high-temperature-reacted 3-hydroxypropionic acid polymer.

[0048] At this time, before the step of heat-treating the 3-hydroxypropionic acid polymer at a temperature of 160°C or higher to produce a high-temperature reacted 3-hydroxypropionic acid polymer, a step of removing a catalyst included in the 3-hydroxypropionic acid polymer may be included.

[0049] The method for removing the catalyst contained in the above 3-hydroxypropionic acid polymer is not limited thereto, but for example, the catalyst may be removed by dissolving the 3-hydroxypropionic acid polymer in a solvent and then precipitating the polymer. Specifically, the catalyst contained in the 3-hydroxypropionic acid polymer may be removed through a process of dissolving the 3-hydroxypropionic acid polymer in a solvent such as chloroform, forming 3-hydroxypropionic acid polymer crystals using isopropanol (IPA), precipitating the crystals, and separating the crystals into solid and liquid. Thereafter, the 3-hydroxypropionic acid polymer crystals from which the catalyst has been removed may be dried to recover the 3-hydroxypropionic acid polymer from which the catalyst and moisture have been removed.

[0050]

[0051] In the step of producing a high-temperature reacted 3-hydroxypropionic acid polymer by heat-treating the 3-hydroxypropionic acid polymer at a temperature of 160°C or higher, the content of vinyl groups at the terminals of the 3-hydroxypropionic acid polymer can be improved by heat-treating the 3-hydroxypropionic acid polymer at a temperature of 160°C or higher. Poly(3-hydroxypropionic acid) may have terminal groups such as hydroxyl groups, carboxyl groups, and vinyl groups. In the past, attempts were made to reduce the content of vinyl groups generated as a side reaction during the polymerization of 3-hydroxypropionic acid into poly(3-hydroxypropionic acid) as a cause of difficulty in obtaining a polymer with a high molecular weight.

[0052] However, the inventors of the present invention have confirmed that when the vinyl group at the terminal of the 3-hydroxypropionic acid polymer participates in the polymerization reaction, the molecular weight of the polymer finally produced, particularly the number average molecular weight, increases and a branched polymer can be produced, and have completed the invention. Specifically, in the process of additionally polymerizing the 3-hydroxypropionic acid polymer reacted at high temperature, an addition polymerization reaction of the vinyl group at the terminal, for example, radical polymerization and / or ionic polymerization, can additionally occur, and due to this addition polymerization reaction of the vinyl group, a composition containing poly(3-hydroxypropionate) having a large number average molecular weight and a branched structure can be produced.

[0053] That is, through a process of heat-treating a 3-hydroxypropionic acid polymer at a high temperature of 160°C or higher, the content of vinyl groups at the terminals that can undergo subsequent addition polymerization increases, and by further polymerizing the 3-hydroxypropionic acid polymer reacted at such a high temperature, a composition including poly(3-hydroxypropionate) that is branched and has a large number average molecular weight can be manufactured.

[0054] For example, the high temperature reacted 3-hydroxypropionic acid polymer may have a terminal vinyl group content of 5% or more and 40% or less, for example, 6% or more, 8% or more, 10% or more, 20% or more, 25% or more, 30% or more, 39% or less, 38% or less, 37% or less, 36% or less, 35% or less, 34% or less, 33% or less, or 32% or less.

[0055] In addition, since the vinyl group participates in the reaction in the subsequent polymerization process, the poly(3-hydroxypropionate) may have a terminal vinyl group content of 35% or less, for example, 0%, 0.01% or more, 0.1% or more, 0.5% or more, 1% or more, 3% or more, 5% or more, 30% or less, 25% or less, 20% or less, 15% or less, 10% or less, 8% or less, 7% or less, or 6% or less.

[0056]

[0057] In the step of heat-treating the above 3-hydroxypropionic acid polymer at a temperature of 160°C or higher, the heat-treatment temperature may be 165°C or higher and 230°C or lower, 170°C or higher and 220°C or lower, 175°C or higher and 210°C or lower, or 180°C or higher and 200°C or lower. If the heat-treatment temperature is too low, the vinyl group content at the terminal of the 3-hydroxypropionic acid polymer may not increase, so that the number average molecular weight of the final polymer may be low, and if the heat-treatment temperature is too high, thermal decomposition of the polymer may proceed, so that a large amount of by-products may be produced.

[0058] In addition, the heat treatment may be performed for a period of 30 minutes to 12 hours, 1 hour to 10 hours, or 2 hours to 8 hours. If the heat treatment is performed for too short a time, the vinyl group content at the terminal of the 3-hydroxypropionic acid polymer may not increase, resulting in a low number average molecular weight of the final polymer produced. In addition, if the heat treatment is performed for too long, thermal decomposition of the polymer may occur, resulting in the generation of a large amount of byproducts.

[0059] Additionally, the heat treatment of the 3-hydroxypropionic acid polymer may be performed in the absence of a catalyst. Since the heat treatment of the 3-hydroxypropionic acid polymer is performed at a high temperature without using a catalyst, the content of terminal vinyl groups can be improved. If the heat treatment is performed in the presence of a catalyst, the polydispersity index may become very wide, making it difficult to control the molecular weight.

[0060] In addition, as described above, by additionally performing a process of removing the catalyst before heat-treating the 3-hydroxypropionic acid polymer, problems arising from the use of the catalyst can be prevented.

[0061]

[0062] In addition, the method for producing a poly(3-hydroxypropionic acid) composition according to the above embodiment may include a step of producing a poly(3-hydroxypropionate) composition by polymerizing the high-temperature reacted 3-hydroxypropionic acid polymer.

[0063] The above polymerization reaction may be a melt polymerization reaction, and melt polymerization means that the reactants and products remain in a liquid state. In addition, the polymerization reaction may be accompanied by an addition reaction of a vinyl group as described above. The polymerization may be carried out at a pressure of 4 torr or less and a temperature of 70°C or more and 120°C or less. For example, the polymerization may be carried out at a temperature of 75°C or more, 78°C or more, 80°C or more, or 85°C or more, and 115°C or less, 110°C or less, 105°C or less, or 100°C or less. In addition, the pressure of the polymerization may be 0.01 torr or more, 0.1 torr or more, 0.5 torr or more, or 1.0 torr or more, and 3.5 torr or less, 3.0 torr or less, or 2.5 torr or less. The above polymerization reaction time can be appropriately considered in consideration of the molecular weight, yield, etc. of the polymer produced, and can preferably be performed for 1 hour to 60 hours, 5 hours to 50 hours, 10 hours to 40 hours, or 15 hours to 30 hours.

[0064] In addition, the polymerization reaction may be carried out in the presence of a sulfonic acid catalyst. The sulfonic acid catalyst is not particularly limited as long as it contains at least one sulfonic group, but may be, for example, p-toluenesulfonic acid, m-xylene-4-sulfonic acid, 2-mesitylenesulfonic acid, or p-xylene-2-sulfonic acid. The above catalyst may be used in an amount of 0.01 mol% or more and 20 mol% or less relative to poly(3-hydroxypropionic acid), for example, 0.05 mol% or more, 0.10 mol% or more, 0.20 mol% or more, 0.30 mol% or more, 0.40 mol% or more, 0.50 mol% or more, 0.70 mol% or more, 1.00 mol% or more, 3.00 mol% or more, and 18 mol% or less, 15 mol% or less, 13 mol% or less, 10 mol% or less, 8 mol% or less, or 5 mol% or less.

[0065] In addition, the polymerization reaction can proceed without a separate coupling agent, crosslinking agent, or initiator in addition to the catalyst. Conventionally, the use of crosslinking agents, etc. increased molecular weight, but there were problems such as toxicity or increased process costs. However, the method for producing a poly(3-hydroxypropionic acid) composition does not use a crosslinking agent, coupling agent, or initiator, and thus can prevent problems resulting from the addition of these agents.

[0066]

[0067] The above 3-hydroxypropionic acid polymer may have a number average molecular weight of 20,000 or less, 2,000 or more and 18,000 or less, 4,000 or more and 16,000 or less, 6,000 or more and 14,000 or less, or 8,000 or more and 12,000 or less.

[0068] In addition, the 3-hydroxypropionic acid polymer may have a weight average molecular weight of 80,000 or less, 10,000 or more and 70,000 or less, 12,000 or more and 60,000 or less, 14,000 or more and 50,000 or less, 16,000 or more and 40,000 or less, or 18,000 or more and 30,000 or less.

[0069] Additionally, the number average molecular weight of the poly(3-hydroxypropionate) composition may be at least 1.5 times the number average molecular weight of the 3-hydroxypropionic acid polymer, for example, at least 2.0 times, at least 3.0 times, at least 4.0 times, at least 5.0 times, at least 6.0 times, and at most 50 times, at most 40 times, at most 30 times, at most 25 times, at most 20 times.

[0070] The poly(3-hydroxypropionate) composition may comprise a poly(3-hydroxypropionate) having a branched structure; or a mixture of a poly(3-hydroxypropionate) having a branched structure and a poly(3-hydroxypropionate) having a linear structure, so that the molecular weight of the composition may be the molecular weight of the poly(3-hydroxypropionate) having a branched structure or a molecular weight measured for the mixture.

[0071]

[0072] Meanwhile, the method for producing the 3-hydroxypropionic acid polymer may be produced by a general polymerization process, but may be produced by, for example, a step of producing an oligomer by polymerizing 3-hydroxypropionic acid (step 1) and a step of producing a 3-hydroxypropionic acid polymer by polymerizing the oligomer (step 2).

[0073] The polymerization reaction of the above step 1 may be a melt polymerization reaction, and may be carried out at a temperature of 50°C or more and 150°C or less and a pressure of 1 torr or more and 200 torr or less. The reaction time of the above step 1 may be appropriately considered in consideration of the molecular weight, yield, etc. of the oligomer produced, and is preferably carried out for 1 to 10 hours, 1.5 to 8 hours, or 2 to 5 hours.

[0074] In addition, the polymerization reaction may be carried out in the presence of a sulfonic acid catalyst. The sulfonic acid catalyst is not particularly limited as long as it contains at least one sulfonic group, but may be, for example, p-toluenesulfonic acid, m-xylene-4-sulfonic acid, 2-mesitylenesulfonic acid, or p-xylene-2-sulfonic acid. The catalyst may be used in an amount of 0.1 to 0.5 mol% relative to 3-hydroxypropionic acid.

[0075] The polymerization reaction of the above step 2 may also be a melt polymerization reaction, and may be carried out at a temperature of 70°C or more and 150°C or less. The reaction temperature of the above step 2 may be 75°C or more, 80°C or more, 85°C or more, 90°C or more, or 95°C or more, and 140°C or less, 130°C or less, 120°C or less, or 110°C or less. The reaction time of the above step 2 may be appropriately considered in consideration of the molecular weight, yield, etc. of the polymer produced, and may preferably be carried out for 1 hour to 60 hours, 5 hours to 50 hours, 10 hours to 40 hours, or 15 hours to 30 hours.

[0076] Meanwhile, since step 2 is performed subsequent to step 1, the catalyst added in each step 1 can also participate in the reaction in step 2. In addition, steps 1 and 2 can be performed sequentially.

[0077]

[0078] The method for producing a poly(3-hydroxypropionic acid) composition according to the above embodiment comprises the steps of: polymerizing the high-temperature reacted 3-hydroxypropionic acid oligomer or polymer to produce a poly(3-hydroxypropionate) composition;

[0079] A step of crystallizing the above poly(3-hydroxypropionate) composition may be included.

[0080] By crystallizing the poly(3-hydroxypropionate) composition and precipitating the crystals to separate the solid and liquid, the catalyst, byproducts, etc. contained in the poly(3-hydroxypropionate) composition other than the branched and / or linear poly(3-hydroxypropionate) composition are removed and dried, thereby manufacturing high-purity poly(3-hydroxypropionate) from which the catalyst and moisture, etc. are removed.

[0081] Meanwhile, the slope, weight average molecular weight, etc. of the Mark-Houwink-Sakurada equation for poly(3-hydroxypropionate) described later may be for poly(3-hydroxypropionate) composition crystals recovered after the crystallization step.

[0082]

[0083] According to another embodiment of the invention, a mixture comprising a linear poly(3-hydroxypropionate) and a branched poly(3-hydroxypropionate) is provided.

[0084] A poly(3-hydroxypropionate) composition is provided, wherein the slope (α) of the Mark-Houwink-Sakurada equation represented by the following mathematical equation 1 for the above mixture is 0.10 or more and 0.45 or less.

[0085] [Mathematical Formula 1]

[0086] log[η] = αlogM + logK

[0087] In the above mathematical formula 1,

[0088] [η] is the intrinsic viscosity (㎗ / g) of the mixture,

[0089] M is the absolute molecular weight (Absolute MW) of the mixture,

[0090] K is a constant.

[0091] The present inventors have completed the invention by confirming that, in the case of a composition comprising two types of poly(3-hydroxypropionates) having different structures, linear and / or branched, and having a slope (α) of the Mark-Houwink-Sakurada equation of 0.10 or more and 0.45 or less, both the number average molecular weight and the weight average molecular weight are high, while the glass transition temperature is high and the melting temperature is low or similar to that of conventional poly(3-hydroxypropionates).

[0092]

[0093] In addition, the slope (α) of the Mark-Houwink-Sakurada equation represented by the above mathematical equation 1 for the above mixture may be 0.10 or more and 0.45 or less, 0.13 or more and 0.40 or less, 0.15 or more and 0.35 or less, 0.17 or more and 0.30 or less, 0.18 or more and 0.29 or less, or 0.19 or more and 0.28 or less.

[0094] If the slope (α) of the Mark-Houwink-Sakurada equation for the above mixture is too small, the melting temperature may be too low, and if the slope (α) is too large, the poly(3-hydroxypropionic acid) composition may contain little branched poly(3-hydroxypropionic acid) structure, so that the glass transition temperature may be low or a high molecular weight may not be obtained.

[0095] The slope (α) of the above Mark-Houwink-Sakurada equation refers to the slope value in a log-log graph where the logarithm (log) of the measured absolute molecular weight is plotted on the horizontal axis and the logarithm (log) of the measured intrinsic viscosity is plotted on the vertical axis, by measuring the intrinsic viscosity and absolute molecular weight of the mixture through GPC / MALS (Gel Permeation Chromatography / Multi-Angle Light Scattering). The closer the slope is to 1, the more linear the polymer has a structure. If the slope is 0.10 or more and 0.45 or less, it may include a branched polymer. If the slope value is closer to 0, the degree of branching may increase.

[0096] At this time, the mobile phase of GPC / MALS may be chloroform, and the measurement temperature may be 40°C.

[0097]

[0098] The mixture included in the poly(3-hydroxypropionic acid) composition according to the above other embodiments may have a bimodal molecular weight distribution when measured by GPC / MALS. In addition, the weight average molecular weight, etc., may be measured by GPC / MALS for the mixture having a bimodal molecular weight distribution.

[0099] For example, the weight average molecular weight for the above mixture may be 30,000 or more and 200,000 or less, 40,000 or more and 150,000 or less, 50,000 or more and 100,000 or less, 60,000 or more and 90,000 or less, or 65,000 or more and 850,000 or less.

[0100] Additionally, the number average molecular weight of the mixture may be 8,000 or more and 100,000 or less, 9,000 or more and 90,000 or less, 10,000 or more and 80,000 or less, 11,000 or more and 70,000 or less, or 12,000 or more and 60,000 or less.

[0101] Additionally, the polydispersity index (PDI) for the mixture may be 2.5 or more and 10.0 or less, 3.0 or more and 9.0 or less, 4.0 or more and 8.0 or less, or 5.0 or more and 7.0 or less.

[0102] The poly(3-hydroxypropionic acid) composition having the above bimodal molecular weight distribution may include a first monomodal poly(3-hydroxypropionic acid) and a second monomodal poly(3-hydroxypropionic acid), and the first monomodal poly(3-hydroxypropionic acid) may have a number average molecular weight of 25,000 or less, 2,000 or more and 18,000 or less, 4,000 or more and 16,000 or less, 5,000 or more and 14,000 or less, or 5,500 or more and 12,000 or less. In addition, the poly(3-hydroxypropionic acid) of the first single-piece may have a weight average molecular weight of 40,000 or less, 8,000 or more and 30,000 or less, 9,000 or more and 25,000 or less, 10,000 or more and 20,000 or less, 11,000 or more and 19,000 or less, or 12,000 or more and 18,000 or less. In addition, the poly(3-hydroxypropionic acid) of the first single-piece may have a polydispersity index (PDI) of 2.5 or less, 1.1 or more and 2.4 or less, 1.2 or more and 2.3 or less, or 1.3 or more and 2.2 or less.

[0103] In addition, the poly(3-hydroxypropionic acid) of the second daily dose may have a number average molecular weight of 30,000 or more, 40,000 or more and 200,000 or less, 50,000 or more and 180,000 or less, 55,000 or more and 170,000 or less, 60,000 or more and 160,000 or less, 63,000 or more and 150,000 or less, 65,000 or more and 140,000 or less, or 66,000 or more and 130,000 or less. In addition, the poly(3-hydroxypropionic acid) of the second daily dose may have a weight average molecular weight of 50,000 or more, 70,000 or more and 900,000 or less, 90,000 or more and 850,000 or less, 100,000 or more and 800,000 or less, 110,000 or more and 700,000 or less, 120,000 or more and 600,000 or less, 130,000 or more and 500,000 or less, or 140,000 or more and 400,000 or less. In addition, the poly(3-hydroxypropionic acid) of the second daily dose may have a polydispersity index (PDI) of 1.0 or more and 3.5 or less, 1.1 or more and 3.3 or less, 1.2 or more and 3.1 or less, 1.3 or more and 3.0 or less, 1.4 or more and 2.9 or less, 1.5 or more and 2.8 or less, or 1.6 or more and 2.7 or less.

[0104]

[0105] According to the above-described embodiment, a mixture having a bimodal molecular weight distribution in a poly(3-hydroxypropionic acid) composition can be deconvoluted into a linear poly(3-hydroxypropionate) and a branched poly(3-hydroxypropionate). After deconvoluting, the molecular weights, etc. of each linear poly(3-hydroxypropionate) and branched poly(3-hydroxypropionate) can be measured.

[0106] For example, the poly(3-hydroxypropionate) of the linear structure may have a number average molecular weight of 25,000 or less, 2,000 or more and 18,000 or less, 4,000 or more and 16,000 or less, 5,000 or more and 14,000 or less, or 5,500 or more and 12,000 or less.

[0107] In addition, the poly(3-hydroxypropionate) of the linear structure may have a weight average molecular weight of 40,000 or less, 8,000 or more and 30,000 or less, 9,000 or more and 25,000 or less, 10,000 or more and 20,000 or less, 11,000 or more and 19,000 or less, or 12,000 or more and 18,000 or less.

[0108] In addition, the poly(3-hydroxypropionate) of the linear structure may have a polydispersity index (PDI) of 2.5 or less, 1.1 or more and 2.4 or less, 1.2 or more and 2.3 or less, or 1.3 or more and 2.2 or less.

[0109]

[0110] In addition, the poly(3-hydroxypropionate) of the branched structure may have a number average molecular weight of 30,000 or more, 40,000 or more and 200,000 or less, 50,000 or more and 180,000 or less, 55,000 or more and 170,000 or less, 60,000 or more and 160,000 or less, 63,000 or more and 150,000 or less, 65,000 or more and 140,000 or less, or 66,000 or more and 130,000 or less.

[0111] In addition, the poly(3-hydroxypropionate) having the branched structure may have a weight average molecular weight of 50,000 or more, 70,000 or more and 900,000 or less, 90,000 or more and 850,000 or less, 100,000 or more and 800,000 or less, 110,000 or more and 700,000 or less, 120,000 or more and 600,000 or less, 130,000 or more and 500,000 or less, or 140,000 or more and 400,000 or less.

[0112] In addition, the poly(3-hydroxypropionate) having the branched structure may have a polydispersity index (PDI) of 1.0 or more and 3.5 or less, 1.1 or more and 3.3 or less, 1.2 or more and 3.1 or less, 1.3 or more and 3.0 or less, 1.4 or more and 2.9 or less, 1.5 or more and 2.8 or less, or 1.6 or more and 2.7 or less.

[0113]

[0114] The above branched structure is not limited thereto, and may be a star type structure, a comb type structure, etc.

[0115] For example, the poly(3-hydroxypropionate) having the branched structure may include a repeating unit represented by the following chemical formula 1.

[0116] [Chemical Formula 1]

[0117]

[0118] In the above chemical formula 1,

[0119] A is a substituent represented by the following chemical formula 2,

[0120] [Chemical Formula 2]

[0121]

[0122] In the above chemical formula 2

[0123] * is the part that connects to A,

[0124] n is an integer between 10 and 700.

[0125] Meanwhile, in the above chemical formula 2, n may be 10 or more, 15 or more, 20 or more, 30 or more, 40 or more, 50 or more, 60 or more, 70 or more, 80 or more, 90 or more, 100 or more, and may be 700 or less, 650 or less, 600 or less, 550 or less, 500 or less, 450 or less, or 400 or less.

[0126] The repeating unit represented by the above chemical formula 1 may be included in a repeating number of 2 or more and 800 or less, for example, it may be included in a repeating number of 3 or more, 10 or more, 20 or more, 30 or more, 40 or more, 50 or more, or it may be included in a repeating number of 750 or less, 700 or less, 650 or less, 600 or less, 550 or less, 500 or less.

[0127] Additionally, n of chemical formula 2 included in each repeating unit may be different or the same.

[0128]

[0129] The poly(3-hydroxypropionate) having the above branched structure is not limited thereto, but can be represented by the following chemical formula 3.

[0130] [Chemical Formula 3]

[0131]

[0132] In the above chemical formula 3,

[0133] m, o, and p can each independently be an integer from 10 to 700.

[0134] For example, m, o, and p can each independently be 10 or more, 15 or more, 20 or more, 30 or more, 40 or more, 50 or more, 60 or more, 70 or more, 80 or more, 90 or more, 100 or more, 700 or less, 650 or less, 600 or less, 550 or less, 500 or less, 450 or less, 400 or less, and m, o, and p can be the same or different. When m, o, and p are the same, the polymer can have a symmetrical structure, and when m, o, and p are different, the polymer can have an asymmetrical structure.

[0135]

[0136] Additionally, in the poly(3-hydroxypropionate) composition according to the other embodiment, the weight ratio of the linear poly(3-hydroxypropionate) and the branched poly(3-hydroxypropionate) may be 1:9 to 9:1. If the linear poly(3-hydroxypropionate) is included in excessive amounts compared to the branched poly(3-hydroxypropionate), the weight average molecular weight and the number average molecular weight may decrease.

[0137] Additionally, in the mixture, the branched poly(3-hydroxypropionate) and the linear poly(3-hydroxypropionate) may be reacted. The reaction may be formed through proton transfer polymerization, oxa-michael addition, or radical reaction.

[0138] As described above, a composition including poly(3-hydroxypropionate) having biodegradability, high number average molecular weight and weight average molecular weight, and a very narrow PDI value, and a method for producing the same can be provided.

[0139] Figure 1 is a Mark-Houwink-Sakurada graph calculated using GPC / MALS for poly(3-hydroxypropionate) of Examples 5 and 10 and Comparative Example 3.

[0140] 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.

[0141]

[0142] Manufacturing Example 1

[0143] 50 g of 3-hydroxypropionic acid aqueous solution (purity 50%) and 0.15 mg of toluenesulfonic acid monohydrate (p-TSA) catalyst were added to a three-necked glass reactor, distilled and concentrated under vacuum conditions of 80 to 90°C and 80 torr, and further polymerized at the same temperature and 2 torr pressure for 18 hours to produce a 3-hydroxypropionic acid polymer (number average molecular weight: 8,878, weight average molecular weight: 23,718).

[0144]

[0145] Example 1

[0146] 80 g of 3-hydroxypropionic acid aqueous solution (purity 74.3%) was added to a 3-necked glass reactor, and the temperature of the oil bath was raised to 180°C, and a polymerization reaction was performed under nitrogen reflux for 4 hours while removing water, thereby producing a 3-hydroxypropionate oligomer (number average molecular weight: 1,919, weight average molecular weight: 2,936).

[0147] After the reaction was completed, the mixture was cooled to 100°C, 251 mg of p-toluenesulfonic acid monohydrate (p-TSA) catalyst was added to the oil bath, and a polymerization reaction was performed at 80°C and 2 torr pressure for 21 hours to produce a poly(3-hydroxypropionate) composition. Afterwards, the composition was dissolved in chloroform, precipitated using isopropanol (IPA), crystallized, and dried to recover the crystallized poly(3-hydroxypropionate) composition.

[0148]

[0149] Example 2

[0150] 80 g of 3-hydroxypropionic acid aqueous solution (purity 74.3%) was added to a three-necked glass reactor, and the temperature of the oil bath was raised to 180°C, and a polymerization reaction was performed under nitrogen reflux for 5.5 hours while removing water, thereby producing a 3-hydroxypropionate oligomer (number average molecular weight: 2,410, weight average molecular weight: 4,036).

[0151] After the reaction was completed, the mixture was cooled to 100°C, 251 mg of p-toluenesulfonic acid monohydrate (p-TSA) catalyst was added to the oil bath, and a polymerization reaction was performed at 85°C and 3 torr pressure for 21 hours to produce a poly(3-hydroxypropionate) composition. Afterwards, the composition was dissolved in chloroform, precipitated using isopropanol (IPA), crystallized, and dried to recover the crystallized poly(3-hydroxypropionate) composition.

[0152]

[0153] Example 3

[0154] 80 g of 3-hydroxypropionic acid aqueous solution (purity 74.3%) was added to a 3-necked glass reactor, and the temperature of the oil bath was raised to 180°C, and a polymerization reaction was performed under nitrogen reflux for 8 hours while removing water, thereby producing a 3-hydroxypropionate oligomer (number average molecular weight: 1,919, weight average molecular weight: 2,936).

[0155] After the reaction was completed, the mixture was cooled to 100°C, 251 mg of p-toluenesulfonic acid monohydrate (p-TSA) catalyst was added to the oil bath, and a polymerization reaction was performed at 90°C and 2 torr pressure for 19 hours to produce a poly(3-hydroxypropionate) composition. Afterwards, the composition was dissolved in chloroform, precipitated using isopropanol (IPA), crystallized, and dried to recover the crystallized poly(3-hydroxypropionate) composition.

[0156]

[0157] Example 4

[0158] 80 g of 3-hydroxypropionic acid aqueous solution (purity 74.3%) was added to a 3-necked glass reactor, the temperature of the oil bath was raised to 180°C while removing water for 2 hours, and then the temperature was raised to 200°C for 1 hour under nitrogen reflux to carry out a polymerization reaction, thereby producing a 3-hydroxypropionate oligomer (number average molecular weight: 2,035, weight average molecular weight: 3,305).

[0159] After the reaction was completed, the mixture was cooled to 100°C, 251 mg of p-toluenesulfonic acid monohydrate (p-TSA) catalyst was added to the oil bath, and a polymerization reaction was performed at 90°C and 2 torr pressure for 23 hours to produce a poly(3-hydroxypropionate) composition. Afterwards, the composition was dissolved in chloroform, precipitated using isopropanol (IPA), crystallized, and dried to recover the crystallized poly(3-hydroxypropionate) composition.

[0160]

[0161] Example 5

[0162] 100 g of 3-hydroxypropionic acid (68% aqueous solution) was added to an oil bath, and polymerization was performed under nitrogen reflux for 4 hours while removing water at a temperature of 180°C, thereby producing a 3-hydroxypropionate oligomer (number average molecular weight: 2,340, weight average molecular weight: 4,056).

[0163] After the reaction was completed, the mixture was cooled to 100°C, 300 mg of p-toluenesulfonic acid (p-TSA) catalyst was added to the oil bath, and a polymerization reaction was performed at 85°C and 1 torr pressure for 30 hours to produce a poly(3-hydroxypropionate) composition. Afterwards, the composition was dissolved in chloroform, precipitated using isopropanol (IPA), crystallized, and dried to recover the crystallized poly(3-hydroxypropionate) composition.

[0164]

[0165] Example 6

[0166] The 3-hydroxypropionic acid polymer manufactured in the above Manufacturing Example 1 was dissolved in chloroform, precipitated using isopropanol (IPA), and crystallized to remove the p-TSA catalyst.

[0167] 20 g of 3-hydroxypropionic acid polymer from which the catalyst had been removed was added to an oil bath, and a heat treatment reaction was performed for 5 hours at 180°C under nitrogen reflux.

[0168] After the heat treatment reaction was completed, it was cooled to 100 ℃, 0.12 mg of p-toluenesulfonic acid (p-TSA) catalyst was added to the oil bath, and a polymerization reaction was performed at 80 ℃ and 1 torr pressure for 17 hours. After that, it was dissolved in chloroform, precipitated using isopropanol (IPA), crystallized, and dried to recover the poly(3-hydroxypropionate) composition.

[0169]

[0170] Example 7

[0171] The 3-hydroxypropionic acid polymer manufactured in the above Manufacturing Example 1 was dissolved in chloroform, precipitated using isopropanol (IPA), and crystallized to remove the p-TSA catalyst.

[0172] 20 g of 3-hydroxypropionic acid polymer from which the catalyst had been removed was added to an oil bath, and a heat treatment reaction was performed for 4 hours at 180°C under nitrogen reflux.

[0173] After the heat treatment reaction was completed, it was cooled to 100 ℃, 0.12 mg of p-toluenesulfonic acid (p-TSA) catalyst was added to the oil bath, and a polymerization reaction was performed at 80 ℃ and 1 torr pressure for 40 hours. After that, it was dissolved in chloroform, precipitated using isopropanol (IPA), crystallized, and dried to recover the poly(3-hydroxypropionate) composition.

[0174]

[0175] Example 8

[0176] The 3-hydroxypropionic acid polymer manufactured in the above Manufacturing Example 1 was dissolved in chloroform, precipitated using isopropanol (IPA), and crystallized to remove the p-TSA catalyst.

[0177] 20 g of 3-hydroxypropionic acid polymer from which the catalyst had been removed was added to an oil bath, and a heat treatment reaction was performed for 8 hours at 180°C under nitrogen reflux.

[0178] After the heat treatment reaction was completed, it was cooled to 100 ℃, 0.40 mg of p-toluenesulfonic acid (p-TSA) catalyst was added to the oil bath, and a polymerization reaction was performed at 80 ℃ and 2 torr pressure for 30 hours. After that, it was dissolved in chloroform, precipitated using isopropanol (IPA), crystallized, and dried to recover the poly(3-hydroxypropionate) composition.

[0179]

[0180] Example 9

[0181] The 3-hydroxypropionic acid polymer manufactured in the above Manufacturing Example 1 was dissolved in chloroform, precipitated using isopropanol (IPA), and crystallized to remove the p-TSA catalyst.

[0182] 20 g of 3-hydroxypropionic acid polymer from which the catalyst had been removed was added to an oil bath, and a heat treatment reaction was performed for 5 hours at 180°C under nitrogen reflux.

[0183] After the heat treatment reaction was completed, it was cooled to 100 ℃, 0.50 mg of p-toluenesulfonic acid (p-TSA) catalyst was added to the oil bath, and a polymerization reaction was performed at 80 ℃ and 2 torr pressure for 40 hours. After that, it was dissolved in chloroform, precipitated using isopropanol (IPA), crystallized, and dried to recover the poly(3-hydroxypropionate) composition.

[0184]

[0185] Example 10

[0186] 200 g of 3-hydroxypropionic acid aqueous solution (purity 50%) and 550 mg of toluenesulfonic acid monohydrate (p-TSA) catalyst were added to a three-necked glass reactor, and concentrated at a temperature of 70°C and a pressure of 65 torr for 3 hours, followed by polymerization at a temperature of 85°C and a pressure of 1 torr for 25 hours to produce a 3-hydroxypropionic acid polymer.

[0187] The above 3-hydroxypropionic acid polymer was dissolved in chloroform, precipitated using isopropanol (IPA), and crystallized to remove the p-TSA catalyst.

[0188] 50 g of 3-hydroxypropionic acid polymer from which the catalyst had been removed was added to an oil bath, and a heat treatment reaction was performed at 180°C under nitrogen reflux for 4 hours. After completion of the heat treatment reaction, the mixture was cooled to 100°C, and 300 mg of p-toluenesulfonic acid (p-TSA) catalyst was added to the oil bath, and a polymerization reaction was performed at 85°C and 1 torr pressure for 25 hours. Afterwards, the mixture was dissolved in chloroform, precipitated using isopropanol (IPA), crystallized, and dried to recover the poly(3-hydroxypropionate) composition.

[0189]

[0190] Example 11

[0191] 3-hydroxypropionic acid 30 g (60% aqueous solution) was added to an oil bath, and polymerization was performed under nitrogen reflux for 4 hours while removing water at a temperature of 180°C, thereby producing a 3-hydroxypropionate oligomer (number average molecular weight: 2,050, weight average molecular weight: 3,320).

[0192] After the reaction was completed, the mixture was cooled to 100°C, 100 mg of p-toluenesulfonic acid (p-TSA) catalyst was added to the oil bath, and a polymerization reaction was performed at 80°C and 4 torr pressure for 17 hours to produce a poly(3-hydroxypropionate) composition. Afterwards, the composition was dissolved in chloroform, precipitated using isopropanol (IPA), crystallized, and dried to recover the poly(3-hydroxypropionate) composition.

[0193]

[0194] Example 12

[0195] 100 g of 3-hydroxypropionic acid (60% aqueous solution) was added to an oil bath, and polymerization was performed under nitrogen reflux for 4 hours while removing water at a temperature of 180°C, thereby producing a 3-hydroxypropionate oligomer (number average molecular weight: 1,740, weight average molecular weight: 2,980).

[0196] After the reaction was completed, the mixture was cooled to 100°C, 100 mg of p-toluenesulfonic acid (p-TSA) catalyst was added to the oil bath, and a polymerization reaction was performed at 80°C and 4 torr pressure for 20 hours to produce a poly(3-hydroxypropionate) composition. Afterwards, the composition was dissolved in chloroform, precipitated using isopropanol (IPA), crystallized, and dried to recover the poly(3-hydroxypropionate) composition.

[0197]

[0198] Example 13

[0199] 100 g of 3-hydroxypropionic acid (68% aqueous solution) was added to an oil bath, and polymerization was performed under nitrogen reflux for 8 hours while removing water at a temperature of 180°C, thereby producing a 3-hydroxypropionate oligomer (number average molecular weight: 2,540, weight average molecular weight: 4,456).

[0200] After the reaction was completed, the mixture was cooled to 100°C, 200 mg of p-toluenesulfonic acid (p-TSA) catalyst was added to the oil bath, and a polymerization reaction was performed at 80°C and 2 torr pressure for 21 hours to produce a poly(3-hydroxypropionate) composition. Afterwards, the composition was dissolved in chloroform, precipitated using isopropanol (IPA), crystallized, and dried to recover the poly(3-hydroxypropionate) composition.

[0201]

[0202] Comparative Example 1

[0203] 80 g of 3-hydroxypropionic acid aqueous solution (purity 74.3%) was added to a three-necked glass reactor, and the temperature of the oil bath was raised to 80°C and 60 torr, and polymerization was performed while removing water, thereby producing a 3-hydroxypropionate oligomer (number average molecular weight: 985, weight average molecular weight: 1,034).

[0204] After completion of the reaction, 251 mg of p-toluenesulfonic acid monohydrate (p-TSA) catalyst was added, and polymerization was performed at 85 ℃ and 1.5 torr pressure for 21 hours to produce and purify poly(3-hydroxypropionate).

[0205]

[0206] Comparative Example 2

[0207] 80 g of 3-hydroxypropionic acid aqueous solution (purity 74.3%) was added to a 3-necked glass reactor, the temperature of the oil bath was raised, and polymerization was performed under nitrogen reflux for 3 hours while removing water at a temperature of 120°C, and then polymerization was further performed under nitrogen reflux for 1.5 hours at a temperature of 130°C, thereby producing a 3-hydroxypropionate oligomer (number average molecular weight: 2,365, weight average molecular weight: 3,665).

[0208] After the reaction was completed, the temperature was cooled to 100°C, 251 mg of p-toluenesulfonic acid monohydrate (p-TSA) catalyst was added to the oil bath, and a polymerization reaction was performed at 85°C and 2 torr pressure for 17 hours to produce and purify poly(3-hydroxypropionate).

[0209]

[0210] Comparative Example 3

[0211] 80 g of 3-hydroxypropionic acid (75% aqueous solution) was added to a three-necked glass reactor, the temperature of the oil bath was increased, and the mixture was concentrated at 86°C and 70 torr. 25 mg of p-toluenesulfonic acid monohydrate (p-TSA) catalyst was added, and polymerization was performed at 85°C and 0.8 torr for 15 hours. After completion of the reaction, the mixture was dissolved in chloroform, precipitated using isopropanol (IPA), crystallized, and dried to recover poly(3-hydroxypropionate).

[0212]

[0213] Comparative Example 4

[0214] The 3-hydroxypropionic acid polymer manufactured in the above Manufacturing Example 1 was dissolved in chloroform, precipitated using isopropanol (IPA), and crystallized to remove the p-TSA catalyst.

[0215] 20 g of 3-hydroxypropionic acid polymer from which the catalyst was removed was added to an oil bath, and a heat treatment reaction was performed for 5 hours at 180°C under nitrogen reflux, and the heat-treated 3-hydroxypropionic acid polymer was recovered.

[0216]

[0217] Comparative Example 5

[0218] 80 g of 3-hydroxypropionic acid (75% aqueous solution) was added to a three-necked glass reactor, the temperature of the oil bath was increased, and the mixture was concentrated at 90°C and 60 torr. 300 mg of p-toluenesulfonic acid monohydrate (p-TSA) catalyst was added, and a polymerization reaction was performed at 90°C and 1 torr pressure for 30 hours to produce and purify poly(3-hydroxypropionate).

[0219]

[0220] Comparative Example 6

[0221] 80 g of 3-hydroxypropionic acid (75% aqueous solution) was charged into a three-necked glass reactor, the temperature of the oil bath was increased, and the mixture was concentrated at 80°C and 60 torr. 251 mg of p-toluenesulfonic acid monohydrate (p-TSA) catalyst was added, and polymerization was performed at 80°C and 1 torr for 20 hours. Afterwards, the reaction was continued at 180°C for 2 hours under nitrogen reflux to produce poly(3-hydroxypropionate).

[0222]

[0223] Experimental example

[0224] The physical properties of the polymers manufactured in the above examples and comparative examples were evaluated using the following methods, and the results are shown in Tables 1 and 2 below.

[0225]

[0226] 1. Molecular weight measurement

[0227] For the compositions of the above examples and comparative examples, the weight average molecular weight (Mw), number average molecular weight (Mn), maximum peak molecular weight (Mp), and polydispersity index (PDI) were measured by gel permeation chromatography (GPC, Waters Alliance e2695).

[0228] Meanwhile, Examples 1 to 10 measured the molecular weight, etc., of the entire poly(3-hydroxypropionate) composition (mixture) having a bimodal molecular weight distribution, and the results are shown in Table 1, and Examples 11 to 13 measured the first poly(3-hydroxypropionic acid) of each monomodal and the second poly(3-hydroxypropionic acid) of each monomodal in the bimodal molecular weight distribution, and these results are shown as first P3HP and second P3HP in Table 2, respectively, and the weight ratio of the first P3HP and the second P3HP is shown in “Composition ratio (GPC area).”

[0229] - Solvent: chloroform (eluent)

[0230] - Flow rate: 1.0 ml / min

[0231] - Column temperature: 35 ℃

[0232] - Standard: Polystyrene

[0233]

[0234] 2. Slope (α) of the Mark-Houwink-Sakurada equation

[0235] The slope (α) of the Mark-Houwink-Sakurada equation for the compositions of the examples and comparative examples was measured using the following GPC / MALS, and the results are shown in 'MHS slope (α)' in Table 1 below.

[0236] GPC: Alliance e2695 (Manufacturer: Waters),

[0237] MALS:

[0238] - RI: DAWN8 (Manufacturer: Wyatt)

[0239] - RI: Viscostar III (Manufacturer: Wyatt)

[0240] - RI: Optilab T-rEX (Manufacturer: Wyatt)

[0241] Specifically, the sample was prepared by dissolving it in chloroform (Stabilized with ETOH) at a concentration of 3 mg / mL, and the mobile phase was prepared by filtering 1000 mL of chloroform (Stabilized with ETOH) using a solvent clarification system.

[0242] Additionally, the measurement conditions of GPC / MALS are as follows.

[0243] - Stationary phase: 2x Agilent PLgel MIXED-B and C, 7.5 x 300 mm, 5 μm

[0244] - Mobile phase: A; Chloroform (stablized with ETOH) = 100(v / v, %)

[0245] - Flow rate: 1.0 mL / min

[0246] - Fixed temperature: 40 ℃

[0247] - Injection volume: 100 ㎕ (0.45 μm filtered)

[0248] - Analysis time: 45 minutes

[0249] - System calibration: Polystyrene (Mp:32700)

[0250] - Chloroform refractive index: 1.45

[0251] For reference, the molecular weights, such as the number average molecular weight in Table 1 below, are relative molecular weights calculated using a standard material (polystyrene), whereas the molecular weights, such as the number average molecular weight in Table 2 below, are absolute molecular weights calculated from molecular size measured using MALS (magnetic aggregation).

[0252]

[0253] Number average molecular weight (Mn) Weight average molecular weight (Mw) Maximum peak molecular weight (Mp) Polydispersity index (PDI) MHS slope (α) Example 136, 251 192, 583 - 5.31 Example 225, 142 84, 858 - 3.34 Example 342, 844 245, 001 - 5.71 Example 433, 010 140, 708 - 4.26 Example 512, 600 67, 200 12, 400 5.30.25 Example 648, 377 134, 002 - 2.76 Example 750, 200187,001-3.73-Example 855,002160,200-2.91-Example 987,002215,460-2.47-Example 1013,30081,7009,4006.20.28Comparative Example 27,85916,875-2.1Comparative Example 36,30011,30011,5001.80.70Comparative Example 46,08913,311-2.19-

[0254] Example 11 Example 12 Example 13 Comparative Example 1 Comparative Example 5 Comparative Example 6 First P3HP Number average molecular weight (Mn) 7,9215,6219,890 14,300 15,2104,297 Weight average molecular weight (Mw) 13,603 12,301 17,650 24,510 26,5018,577 Polydispersity index (PDI) 1.702.191.781.711.741.99 Second P3HP Number average molecular weight (Mn) 88,110 66,320 90,981 --- Weight average molecular weight (Mw) 190,704 156,870 161,248 --- Polydispersity index (PDI) 2.162.361.77 --- Composition ratio (GPC area)4:67:33:7--

[0255] Referring to Table 1 above, it was confirmed that Examples 1 to 5, in which 3-hydroxypropionic acid was polymerized at a temperature of 160°C or higher to produce an oligomer and then polymerized, and Examples 6 to 10, in which 3-hydroxypropionic acid polymers were heat-treated at a temperature of 160°C or higher and then polymerized, had significantly higher number-average molecular weights and weight-average molecular weights than the comparative examples.

[0256] Meanwhile, Examples 5 and 10 had a higher molecular weight than Comparative Example 3, but the slope (α) value of the MHS formula was smaller, confirming that Examples 5 and 10 had a structure with a higher degree of branching than Comparative Example 3.

[0257] In addition, referring to Table 2 above, it was confirmed that Examples 11 to 13 had a bimodal molecular weight distribution while the second P3HP had a high molecular weight, etc., whereas Comparative Examples 1, 5, and 6 had a unimodal molecular weight distribution while having a low molecular weight.

Claims

A step of producing a high-temperature reacted 3-hydroxypropionic acid oligomer or polymer by reacting a 1.3-hydroxypropionic acid monomer or polymer at a temperature of 160°C or higher; and A step of preparing a poly(3-hydroxypropionate) composition by polymerizing the 3-hydroxypropionic acid oligomer or polymer reacted at high temperature; Method for preparing a poly(3-hydroxypropionate) composition.

2. In paragraph 1, The step of reacting the above 3-hydroxypropionic acid monomer or polymer at a temperature of 160°C or higher to produce a high-temperature reacted 3-hydroxypropionic acid oligomer or polymer is as follows: A method for producing a poly(3-hydroxypropionate) composition, which is a step of producing a high-temperature reacted 3-hydroxypropionic acid oligomer by polymerizing the above 3-hydroxypropionic acid monomer at a temperature of 160°C or higher.

3. In paragraph 1, The step of reacting the above 3-hydroxypropionic acid monomer or polymer at a temperature of 160°C or higher to produce a high-temperature reacted 3-hydroxypropionic acid oligomer or polymer is as follows: A method for producing a poly(3-hydroxypropionate) composition, comprising the step of heat-treating the above 3-hydroxypropionic acid polymer at a temperature of 160°C or higher to produce a high-temperature reacted 3-hydroxypropionic acid polymer.

4. In paragraph 3, Before the step of heat-treating the above 3-hydroxypropionic acid polymer at a temperature of 160°C or higher to produce a high-temperature reacted 3-hydroxypropionic acid polymer, A method for producing a poly(3-hydroxypropionate) composition, further comprising a step of removing a catalyst included in the 3-hydroxypropionic acid polymer.

5. In paragraph 1, After the step of polymerizing the above high temperature reacted 3-hydroxypropionic acid oligomer or polymer to prepare a poly(3-hydroxypropionate) composition, A method for producing a poly(3-hydroxypropionate) composition, further comprising a step of crystallizing the poly(3-hydroxypropionate) composition.

6. In paragraph 1, A method for producing a poly(3-hydroxypropionate) composition, wherein the reaction is carried out in the absence of a catalyst at a temperature of 160°C or higher.

7. In paragraph 1, A method for producing a poly(3-hydroxypropionate) composition, wherein the above polymerization is performed at a pressure of 4 torr or less and a temperature of 70°C or more and 120°C or less.

8. In paragraph 2, A method for producing a poly(3-hydroxypropionate) composition, wherein the 3-hydroxypropionic acid oligomer reacted at high temperature has a number average molecular weight of 8,000 or less.

9. In paragraph 3, A method for producing a poly(3-hydroxypropionate) composition, wherein the above 3-hydroxypropionic acid polymer has a number average molecular weight of 20,000 or less.

10. In paragraph 3, A method for producing a poly(3-hydroxypropionate) composition, wherein the number average molecular weight of the poly(3-hydroxypropionate) composition is at least 1.5 times that of the 3-hydroxypropionic acid polymer.

11. A mixture comprising a linear poly(3-hydroxypropionate) and a branched poly(3-hydroxypropionate), The slope (α) of the Mark-Houwink-Sakurada equation represented by the following mathematical equation 1 for the above mixture is 0.10 or more and 0.45 or less, Poly(3-hydroxypropionate) composition: [Mathematical Formula 1] log[η] = αlogM + logK In the above mathematical formula 1, [η] is the intrinsic viscosity (㎗ / g) of the mixture, M is the absolute molecular weight (Absolute MW) of the mixture, K is a constant.

12. In paragraph 11, The weight average molecular weight of the above mixture is 30,000 or more and 200,000 or less, The number average molecular weight of the above mixture is 8,000 or more and 100,000 or less, A poly(3-hydroxypropionate) composition having a polydispersity index (PDI) of 2.5 or more and 10.0 or less for the above mixture.

13. In paragraph 11, The poly(3-hydroxypropionate) of the above linear structure has a number average molecular weight of 25,000 or less, A poly(3-hydroxypropionate) composition having a linear structure and a weight average molecular weight of 40,000 or less.

14. In paragraph 11, The poly(3-hydroxypropionate) of the above branched structure has a number average molecular weight of 30,000 or more, The poly(3-hydroxypropionate) of the above branched structure has a weight average molecular weight of 50,000 or more, A poly(3-hydroxypropionate) composition having a branched structure, wherein the poly(3-hydroxypropionate) has a polydispersity index (PDI) of 1.0 or more and 3.5 or less.

15. In paragraph 11, The poly(3-hydroxypropionate) having the above branched structure is a poly(3-hydroxypropionate) composition comprising a repeating unit represented by the following chemical formula 1: [Chemical Formula 1] In the above chemical formula 1, A is a substituent represented by the following chemical formula 2, [Chemical Formula 2] In the above chemical formula 2 * is the part that connects to A, n is an integer between 10 and 700.

16. In paragraph 11, A poly(3-hydroxypropionate) composition, wherein the weight ratio of the linear poly(3-hydroxypropionate) and the branched poly(3-hydroxypropionate) is 1:9 to 9:1.

Images