Polyalkylene carbonate resin and method for producing same

Abstract

The present invention relates to a polyalkylene carbonate-based resin having excellent thermal stability and a method for preparing the same, and provides a polyalkylene carbonate-based resin and a method for preparing the same, the polyalkylene carbonate-based resin comprising: a repeating unit represented by chemical formula 1; a repeating unit represented by Chemical Formula 2; and a unit derived from an organic acid anhydride, in which the polyalkylene carbonate-based resin has a peak in the region of 6.3 ppm to 6.7 ppm in the 1H NMR spectrum.

Description

Technical Field

[0001] Cross-reference to related applications

[0002] This application claims priority to Korean Patent Application No. 10-2023-0173506, filed on December 4, 2023, the entire contents of which are incorporated herein by reference for all purposes.

[0003] This invention relates to a polyalkylene carbonate resin with excellent thermal stability and its preparation method. Background Technology

[0004] Since the Industrial Revolution, humanity has built modern society by consuming vast amounts of fossil fuels, but the concentration of carbon dioxide in the atmosphere has increased due to environmental destruction such as deforestation. Since this increase in carbon dioxide concentration is a major contributor to the greenhouse effect, it is crucial to reduce atmospheric carbon dioxide levels, which have a significant impact on global warming, and various studies are underway on the regulation or sequestration of carbon dioxide emissions.

[0005] Recently, polyalkylene carbonate resins produced by the polymerization of carbon dioxide and epoxides have attracted much attention as a biodegradable resin. In particular, the method of producing polyalkylene carbonate resins using carbon dioxide can reduce global warming by fixing carbon dioxide in the atmosphere, and it has also been actively studied from the perspective of its use as a carbon resource.

[0006] However, due to their low thermal stability, they undergo thermal decomposition at temperatures above 180°C, which greatly limits their industrial applications.

[0007] Therefore, research is needed to improve the thermal stability of polyalkylene carbonates.

[0008] [Existing Technical Documents]

[0009] (Patent Document 1) CN 103842406 B (November 2, 2016) Summary of the Invention

[0010] Technical issues

[0011] One object of the present invention is to provide a polyalkylene carbonate resin with excellent thermal stability.

[0012] Another object of the present invention is to provide a method for preparing polyalkylene carbonate resins.

[0013] Technical solution

[0014] To address the above problems, this invention provides a polyalkylene carbonate resin and a method for preparing the same.

[0015] More specifically, (1) the present invention provides a polyalkylene carbonate resin comprising: repeating units represented by the following chemical formula 1; repeating units represented by the following chemical formula 2; and units derived from maleic anhydride, wherein the polyalkylene carbonate resin in 1 The 1H NMR spectrum shows peaks in the region of 6.3 ppm to 6.7 ppm: [Chemical Formula 1]

[0016] [Chemical Formula 2]

[0017] in: R1 to R8 are each independently hydrogen, a straight-chain alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or a cycloalkyl group having 3 to 20 carbon atoms. Indicates the connection sites between repeating units. x and y are mole fractions, where x is from 0.70 to 1.00, y is from 0.00 to 0.30, and x+y is 1.

[0018] (2) The present invention provides a polyalkylene carbonate resin according to (1) above, characterized in that the melt index measured according to ASTM D1238 at 190°C and 6.835 kg is 1 g / 10 min or more and 25 g / 10 min or less.

[0019] (3) The present invention provides a polyalkylene carbonate resin according to (1) or (2) above, characterized in that the mass change rate when stored at 240°C for 60 minutes is less than 80% by weight.

[0020] (4) The present invention provides a polyalkylene carbonate resin according to any one of (1) to (3) above, characterized in that the glass transition temperature is above -10°C and below 50°C.

[0021] (5) The present invention provides a polyalkylene carbonate resin according to any one of (1) to (4) above, characterized in that the thermal decomposition temperature (Td) is 50 The temperature is above 290℃.

[0022] (6) The present invention provides a polyalkylene carbonate resin according to any one of (1) to (5) above, wherein, based on 100 parts by weight of the polyalkylene carbonate resin, the unit derived from maleic anhydride is contained in an amount of 1 to 50 parts by weight.

[0023] (7) The present invention provides a polyalkylene carbonate resin composition comprising: a polyalkylene carbonate resin according to any one of (1) to (6) above; and an antioxidant.

[0024] (8) The present invention provides a polyalkylene carbonate resin composition according to (7) above, wherein the antioxidant is at least one selected from the group consisting of: tetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane, triethylene glycol bis-3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate, thiodiethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 1,2-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyl)hydrazine, 3- Octadecyl (3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 2,4-di-tert-pentyl-6-(1-(3,5-di-tert-pentyl-2-hydroxyphenyl)ethyl)phenyl acrylate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, α-tocopherol, and 2,6-di-tert-butyl-p-cresol.

[0025] (9) The present invention provides a polyalkylene carbonate resin composition according to (7) or (8) above, wherein, based on 100 parts by weight of the polyalkylene carbonate resin, an antioxidant is included in an amount of 0.01 parts by weight to 3.00 parts by weight.

[0026] (10) The present invention provides a method for preparing polyalkylene carbonate resins, comprising the step of polymerizing an alkylene oxide compound, carbon dioxide and maleic anhydride in a solvent in the presence of a catalyst.

[0027] (11) The present invention provides a method for preparing polyalkylene carbonate resin according to (10) above, wherein the maleic anhydride is used in an amount of 0.1 parts by weight to 25 parts by weight relative to 100 parts by weight of the alkylene oxide compound.

[0028] (12) The present invention provides a method for preparing polyalkylene carbonate resin according to (10) or (11) above, wherein the polymerization is carried out at a temperature of 30°C to 120°C for 24 hours.

[0029] (13) The present invention provides a method for preparing polyalkylene carbonate resin according to any one of (10) to (12) above, wherein the catalyst comprises a bimetallic cyanide and a complexing agent.

[0030] (14) The present invention provides a method for preparing polyalkylene carbonate resins according to any one of (10) to (13) above, wherein the bimetallic cyanide comprises a component derived from a metal cyanide complex salt and a component derived from a metal salt, wherein the metal cyanide complex salt is represented by the following chemical formula 3, and the metal salt is represented by the following chemical formula 4: [Chemical Formula 3] Y a M`(CN) b in: M' is selected from at least one of Fe(II), Fe(III), Co(II), Co(III), Cr(II), Cr(III), Mn(II), Mn(III), Ir(III), Ni(II), Rh(III), Ru(II), V(V) and V(IV). Y is an alkali metal ion or an alkaline earth metal ion. a is an integer from 1 to 4, and b is an integer from 4 to 6. Choose the values ​​of a and b such that the metal cyanide complex salt is electroneutrally neutral. [Chemical Formula 4] M(X) n in: M is selected from at least one of Zn(II), Fe(II), Ni(II), Mn(II), Co(II), Sn(II), Pb(II), Fe(III), Mo(IV), Mo(VI), Al(III), V(V), V(IV), Sr(II), W(IV), W(VI), Cu(II), and Cr(III). X is any anion selected from halides, hydroxides, sulfates, carbonates, cyanates, oxalates, thiocyanates, isocyanates, isothiocyanates, carboxylates, and nitrates. n is a number that satisfies the valence state of M.

[0031] (15) The present invention provides a method for preparing polyalkylene carbonate resin according to any one of (10) to (14) above, wherein the metal cyanide complex salt is potassium hexacyanocobalt(III), potassium hexacyanoferrate(II), potassium hexacyanoferrate(III), calcium hexacyanocobalt(III), or lithium hexacyanoiridium(III).

[0032] (16) The present invention provides a method for preparing polyalkylene carbonate resin according to any one of (10) to (15) above, wherein the metal salt is at least one selected from zinc chloride (II), zinc chloride (III), zinc bromide, zinc iodide, zinc acetate, zinc acetylacetone, zinc benzoate, zinc nitrate, ferrous sulfate (II), ferrous bromide (II), cobalt chloride (II), cobalt thiocyanate (II), nickel formate (II), and nickel nitrate (II).

[0033] (17) The present invention provides a method for preparing polyalkylene carbonate resins according to any one of (10) to (16) above, wherein the complexing agent is selected from at least one of the following: cyclobutanol, cyclopentanol, cyclohexanol, cycloheptanol, cyclooctanol, 1-methylcyclopentanol, 2-methylcyclopentanol, 3-methylcyclopentanol, 1-ethylcyclopentanol, 2-ethylcyclopentanol, 3-ethylcyclopentanol, 1-propylcyclopentanol, 2-Propylcyclopentanol, 3-Propylcyclopentanol, 1-Butylcyclopentanol, 2-Butylcyclopentanol, 3-Butylcyclopentanol, 1-Isopropylcyclopentanol, 2-Isopropylcyclopentanol, 3-Isopropylcyclopentanol, 1-(Prop-2-yl)cyclopentanol, 2,2-Dimethylcyclopentanol, 2,3-Dimethylcyclopentanol, 3,3-Dimethylcyclopentanol, 1,2-Dimethylcyclopentanol, 1,3-Dimethylcyclopentanol, 1-Methylcyclohexane Alcohols, 1-ethylcyclohexanol, 1-propylcyclohexanol, 1-butylcyclohexanol, 2-methyl-1-cyclohexanol, 2-ethyl-1-cyclohexanol, 3-ethyl-1-cyclohexanol, 4-ethyl-1-cyclohexanol, 2-propyl-1-cyclohexanol, 3-propyl-1-cyclohexanol, 4-propyl-1-cyclohexanol, 2-butyl-1-cyclohexanol, 3-butyl-1-cyclohexanol, 4-butyl-1-cyclohexanol, 2-isopropyl -1-Cyclohexanol, 3-Isopropyl-1-Cyclohexanol, 4-Isopropyl-1-Cyclohexanol, 2-tert-butyl-1-Cyclohexanol, 3-tert-butyl-1-Cyclohexanol, 4-tert-butyl-1-Cyclohexanol, 2,3-Dimethyl-1-Cyclohexanol, 2,4-Dimethyl-1-Cyclohexanol, 3,4-Dimethyl-1-Cyclohexanol, 1-Methylcycloheptanol, 2-Methylcycloheptanol, 3-Methylcycloheptanol, and 4-Methylcycloheptanol.

[0034] Beneficial effects

[0035] The polyalkylene carbonate resin according to the present invention is prepared by polymerizing alkylene oxide and carbon dioxide with maleic anhydride, thus including units derived from maleic anhydride in the polymer chain, which increases the glass transition temperature and the thermal decomposition temperature, thereby improving thermal stability. Attached Figure Description

[0036] The accompanying drawings illustrate specific embodiments of the invention and are used to further understand the technical concept of the invention and the above-described content of the invention. Therefore, the invention should not be construed as limited to the content described in these drawings.

[0037] Figure 1 The NMR analysis results of the polyethylene carbonate resins prepared in the examples and comparative examples are shown.

[0038] Figure 2 and Figure 3 This is a graph showing the mass change analysis results of the polyethylene carbonate resins prepared in the examples and comparative examples using a thermogravimetric analyzer. Detailed Implementation

[0039] The invention will be described in more detail below to aid in understanding it.

[0040] Based on the principle that inventors may appropriately define the concepts of terms to best describe their inventions, the terms or words used in the specification and claims of this invention should not be construed as limited to their ordinary or dictionary meanings, but should be construed as having meanings and concepts consistent with the technical concept of this invention.

[0041] Definition of terminology

[0042] In this specification, the term "thermal decomposition temperature (Td)" is used. 50 "" refers to the temperature at which polyalkylene carbonate resin decomposes due to heat and its mass decreases to 50% of its original mass before heating.

[0043] In this specification, the term "alkyl" may refer to a monovalent aliphatic saturated hydrocarbon.

[0044] In this specification, the term "aryl" may refer to cyclic aromatic hydrocarbons, and may also refer to monocyclic aromatic hydrocarbons that form one ring and polycyclic aromatic hydrocarbons that bond two or more rings.

[0045] In this specification, the term "alkenyl" may refer to a monovalent aliphatic unsaturated hydrocarbon containing one, two, or more double bonds.

[0046] In this specification, the term "cycloalkyl" may refer to cyclic saturated hydrocarbons and cyclic unsaturated hydrocarbons containing one or two or more unsaturated bonds.

[0047] Measurement methods

[0048] In this manual, a TGA (Thermogravimetric Analysis) instrument is used to measure the thermal decomposition temperature (Td). 50Specifically, the temperature at which the mass decreased by 50% while the temperature (10°C / min) was increased from 30°C to 400°C was measured using a TGA (TGA2, Mettler Toledo).

[0049] In this specification, similar to the thermal decomposition temperature, the rate of mass change is measured using a TGA, and the rate of mass change is confirmed when stored at an isothermal temperature of 240°C for 60 minutes.

[0050] In this specification, the glass transition temperature was measured using a DSC (differential scanning calorimeter), specifically a DSC (Q20, TA instrument) under a nitrogen atmosphere while heating the sample from -40°C to 250°C (10°C / min). The glass transition temperature (Tg) was confirmed based on the endothermic curve results.

[0051] In this specification, the melt flow index was measured using a melt flow indexer (MFI) at 190°C and 6.835 kg according to ASTM D1238, and the discharge rate was calculated in g / 10 min. More specifically, the evaluation material was placed in a piston heated to the aforementioned temperature using an MFI (QM280A, QMESYS), and the piston was positioned to apply the aforementioned weight load. After 4 minutes, the discharge rate was cut off, and the discharge rate was cut off again 4 times every 30 seconds to confirm the average value.

[0052] Polyalkylene carbonate resins

[0053] This invention provides a polyalkylene carbonate resin with improved thermal stability by inhibiting thermal decomposition.

[0054] A polyalkylene carbonate resin according to one embodiment of the present invention is characterized by comprising: repeating units represented by the following chemical formula 1; repeating units represented by the following chemical formula 2; and units derived from maleic anhydride, wherein the polyalkylene carbonate resin in 1 The 1H NMR spectrum shows peaks in the region of 6.3 ppm to 6.7 ppm: [Chemical Formula 1]

[0055] [Chemical Formula 2]

[0056] in: R1 to R8 are each independently hydrogen, a straight-chain alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or a cycloalkyl group having 3 to 20 carbon atoms. Indicates the connection sites between repeating units. x and y are mole fractions, where x is from 0.70 to 1.00, y is from 0.00 to 0.30, and x+y is 1.

[0057] Meanwhile, when the above chemical formula 1 or chemical formula 2 is the starting point end of the polymer chain constituting polyalkylene carbonate resin, the end may have a methyl (-CH3) terminal group, and when the above chemical formula 1 or chemical formula 2 is the ending point end of the polymer chain, the end may have a hydroxyl (-OH) terminal group.

[0058] Polyalkylene carbonate resins are prepared using carbon dioxide as a raw material and have attracted much attention as biodegradable resins. However, due to their low thermal stability, they undergo thermal decomposition at temperatures above 180°C, which greatly limits their industrial applications. Therefore, methods have been investigated to improve thermal stability by mixing or extruding anhydrides as end-capping agents into polyalkylene carbonate resins, but the effect on improving thermal stability has not been significant.

[0059] However, according to one embodiment of the invention, polyalkylene carbonate resins are prepared by reacting maleic anhydride with monomer components during their polymerization, wherein the maleic anhydride can be introduced into the polymer chain structure to improve thermal stability by inhibiting thermal decomposition. The thermal decomposition behavior of polyalkylene carbonates manifests as follows: under high-temperature conditions, hydrogen contained in the hydroxyl groups at the resin ends is released, the resin ends are activated, and the activated resin ends attack carbonate groups in nearby polymer chains, causing a bite-like reaction and random chain scission that reduces the polymer chain length. Simultaneously, individual molecules such as alkylene carbonates are continuously formed, thereby partially breaking the carbonate groups within the polymer chain and separating into chains containing ends such as carbon dioxide, hydroxyl groups, and double bonds, thus shortening the polymer chain length in a chain-like manner. However, in the case of end-capped polyalkylene carbonate resins, it is difficult to prevent the thermal decomposition of the short polymer chains generated in a chain-like manner. However, in the case of introducing maleic anhydride into the polymer chain structure as in the present invention, the units derived from maleic anhydride within the polymer chain structure form a polymer network crosslinked with the end-activated polymer chains, thereby improving the thermal stability of the polymer chain structure.

[0060] In this invention, the polyalkylene carbonate resin is a polymer prepared by polymerizing an alkylene oxide compound, carbon dioxide, and an organic acid anhydride, and may contain repeating units represented by Chemical Formula 1 below, repeating units represented by Chemical Formula 2 below, and units derived from maleic anhydride: [Chemical Formula 1]

[0061] [Chemical Formula 2]

[0062] in: R1 to R8 are each independently hydrogen, a straight-chain alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or a cycloalkyl group having 3 to 20 carbon atoms. The connection sites between repeating units are indicated by x and y, which are mole fractions, where x is from 0.70 to 1.00, y is from 0.00 to 0.30, and x+y is 1.

[0063] Additionally, x can be from 0.80 to 1.00, and y can be from 0.00 to 0.20. Preferably, x can be from 0.90 to 1.00, and y can be from 0.00 to 0.10. When the above ranges are met, the carbon dioxide fixation rate is high, which is effective in reducing greenhouse gases and advantageous in terms of biodegradability. Furthermore, when the polyalkylene carbonate resin according to the invention is used to make a membrane, the membrane exhibits low oxygen permeability, thereby possessing excellent barrier properties.

[0064] Furthermore, R1 to R8 in the above chemical formula 1 are each independently hydrogen, a straight-chain alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or a cycloalkyl group having 3 to 20 carbon atoms, and the appropriate functional group can be selected based on the properties of the final resin obtained.

[0065] Furthermore, the repeating unit represented by the above chemical formula 1 can be represented by the following chemical formula 5: [Chemical Formula 5]

[0066] In the above chemical formula 5, R1 to R4 are each independently hydrogen or a straight-chain alkyl group having 1 to 10 carbon atoms, and x and As defined in Chemical Formula 1 above.

[0067] More specifically, the repeating unit represented by the above chemical formula 1 can be represented by the following chemical formula 6 or chemical formula 7: [Chemical Formula 6]

[0068] [Chemical Formula 7]

[0069] In the above chemical formulas 6 and 7, x and As defined in Chemical Formula 1 above.

[0070] Furthermore, the repeating unit represented by the above chemical formula 2 can be represented by the following chemical formula 8: [Chemical Formula 8]

[0071] In the above chemical formula 8, R5 to R8 are each independently hydrogen or a straight-chain alkyl group having 1 to 10 carbon atoms, and y and As defined in chemical formula 2 above.

[0072] More specifically, the repeating unit represented by the above chemical formula 2 can be represented by the following chemical formula 9 or chemical formula 10: [Chemical Formula 9]

[0073] [Chemical Formula 10]

[0074] In the aforementioned chemical formulas 9 and 10, y and As defined in chemical formula 4 above.

[0075] Furthermore, the unit derived from maleic anhydride is a component of a polymer chain derived from maleic anhydride and bonded to a polyalkylene carbonate resin, and can be maleic anhydride itself or a structure, functional group or component derived from maleic anhydride.

[0076] Furthermore, according to one embodiment of the present invention, the polyalkylene carbonate resin in... 1 The 1H NMR spectrum shows a peak in the region of 6.3 ppm to 6.7 ppm, the presence of which indicates the presence of maleic anhydride-derived units in the polymer chain structure. More specifically, this peak can only be confirmed if maleic anhydride-derived units are present in the polymer chain structure; it may not be present when the polymer formed by the polymerization reaction is mixed with maleic anhydride, or when maleic anhydride is used as a capping agent.

[0077] Here, 1 H NMR spectroscopy can be used 1 The 10 mg polycarbonate alkylene resin sample was dissolved in chloroform-d6 solvent and measured using a 500 MHz spectroscopy spectrometer (Jeol).

[0078] Furthermore, the polyalkylene carbonate resin according to one embodiment of the present invention may have a melt index of more than 1 g / 10 min and less than 25 g / 10 min, more preferably 1 g / 10 min to 10 g / 10 min, as measured according to ASTM D1238 at 190 °C and 6.835 kg.

[0079] Furthermore, the polyalkylene carbonate resin according to one embodiment of the present invention can have a mass change rate of less than 80% by weight, preferably from 10% to 80% by weight, and particularly preferably from 15% to 50% by weight when stored at 240°C for 60 minutes.

[0080] Furthermore, the polyalkylene carbonate resin according to one embodiment of the present invention may have a glass transition temperature of -10°C to 50°C, preferably 5°C to 50°C.

[0081] Furthermore, the polyalkylene carbonate resin according to one embodiment of the present invention may have a thermal decomposition temperature (Td) of 290°C or higher, preferably 290°C or higher and 400°C or lower. 50 ).

[0082] The polyalkylene carbonate resin according to one embodiment of the present invention comprises chemical formula 1, chemical formula 2 and units derived from maleic anhydride as described above, and thus can have melt index, mass change rate, glass transition temperature and thermal decomposition temperature as described above, thereby exhibiting excellent thermal stability and processability.

[0083] Furthermore, based on 100 parts by weight of the polyalkylene carbonate resin, the polyalkylene carbonate resin according to one embodiment of the present invention may contain 0.1 parts by weight and 50 parts by weight and less, specifically 0.5 parts by weight and 45 parts by weight, of units derived from maleic anhydride. When the units derived from maleic anhydride are within the above range, the polyalkylene carbonate resin may have a lower melt index and better thermal stability.

[0084] Furthermore, based on total weight, the polyalkylene carbonate resin of the present invention may have a content of 0.5% to 15.0% by weight, 0.5% to 10.0% by weight, or 0.5% to 5.0% by weight of cyclic carbonate. When the above ranges are met, the problem of the glass transition temperature being reduced due to the cyclic carbonate acting as a softener can be minimized, thereby resulting in excellent mechanical properties.

[0085] The content of cyclic carbonates can be determined by using 1 A 10 mg polyalkylene carbonate resin sample was dissolved in chloroform-d6 solvent and measured using a 500 MHz ¹H NMR spectrometer (Jeol). Specifically, measurements were performed by dissolving the sample in chloroform-d6 solvent using a 10 mg ¹H NMR spectrometer (500 MHz Spectrometer). 1 The results of H-NMR spectroscopy confirmed that the peak appeared around 4.5 ppm, which is the cyclic carbonate peak. The cyclic carbonate content can be calculated using the carbonate peak area and ether peak area values, as shown in the following mathematical equation 1: [Mathematical Equation 1]

[0086] The contents of A, B, C, N, and CO2 can be defined as follows: A = Peak area of ​​cyclic carbonate, B = Peak area of ​​carbonate, C = Peak area of ​​ether, N = [Molar mass of epoxide / (44 + Molar mass of epoxide)], CO2 content = (Molar fraction of carbonate unit x 44) / [(Molar fraction of carbonate unit x 44) + (Molar mass of epoxide x 100)] Polyalkylene carbonate resin compositions The present invention provides a polyalkylene carbonate resin composition comprising the above-mentioned polyalkylene carbonate resin.

[0087] More specifically, the present invention provides a polyalkylene carbonate resin composition comprising the above-mentioned polyalkylene carbonate resin and an antioxidant.

[0088] Antioxidants are used to remove free radicals that may remain in polyalkylene carbonate resins. More specifically, the antioxidant may be at least one selected from the following: tetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane, triethylene glycol bis-3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate, thiodiethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 1,2-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyl)hydrazine, 3-( Octadecyl 3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 2,4-di-tert-pentyl-6-(1-(3,5-di-tert-pentyl-2-hydroxyphenyl)ethyl)phenyl acrylate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, α-tocopherol, and 2,6-di-tert-butyl-p-cresol.

[0089] Based on 100 parts by weight of polyalkylene carbonate resin, an antioxidant may be included in an amount of 0.01 parts by weight to 3.00 parts by weight, preferably in an amount of 0.05 parts by weight to 1.50 parts by weight. When the antioxidant is included within the above range, the thermal stability of the polyalkylene carbonate resin can be effectively improved.

[0090] Methods for preparing polyalkylene carbonate resins

[0091] This invention provides a method for preparing the above-mentioned polyalkylene carbonate resin.

[0092] A method for preparing polyalkylene carbonate resin according to one embodiment of the present invention includes the step of polymerizing an alkylene oxide compound, carbon dioxide and maleic anhydride in a solvent in the presence of a catalyst.

[0093] Through the above polymerization, a polymer containing units derived from maleic anhydride introduced into the polymer chain can be obtained, wherein maleic anhydride can be included in an amount of 0.1 parts by weight to 40 parts by weight relative to 100 parts by weight of the epoxide compound. More specifically, maleic anhydride can be included in an amount of 0.5 parts by weight to 35 parts by weight relative to 100 parts by weight of the epoxide compound. In this case, the units derived from maleic anhydride are included in an amount of 1 part by weight to 50 parts by weight relative to 100 parts by weight of the finally prepared polyalkylene carbonate resin, thereby further improving the thermal stability of the resin.

[0094] Furthermore, the aforementioned antioxidants can be added to the polymer prepared above. The added antioxidants can increase the glass transition temperature and thermal decomposition temperature of the polyalkylene carbonate resin, thereby improving its thermal stability and processing performance. Based on 100 parts by weight of the polyalkylene carbonate resin, the antioxidant can be included in an amount from 0.01 parts by weight to 3.00 parts by weight.

[0095] The catalyst comprises a bimetallic cyanide and a complexing agent, and any conventional bimetallic cyanide and complexing agent in the art can be used without limitation.

[0096] For example, a bimetallic cyanide can contain components derived from a metal cyanide complex salt and components derived from a metal salt, wherein the metal cyanide complex salt can be represented by the following chemical formula 3, and the metal salt can be represented by the following chemical formula 4: [Chemical Formula 3] Y a M`(CN) b Wherein, M' is at least one selected from Fe(II), Fe(III), Co(II), Co(III), Cr(II), Cr(III), Mn(II), Mn(III), Ir(III), Ni(II), Rh(III), Ru(II), V(V), and V(IV), Y is an alkali metal ion or an alkaline earth metal ion, a is an integer from 1 to 4, b is an integer from 4 to 6, and the values ​​of a and b are chosen such that the metal cyanide complex salt is electrically neutral. [Chemical Formula 4] M(X) n in: M is at least one of Zn(II), Fe(II), Ni(II), Mn(II), Co(II), Sn(II), Pb(II), Fe(III), Mo(IV), Mo(VI), Al(III), V(V), V(IV), Sr(II), W(IV), W(VI), Cu(II), and Cr(III), X is any one of the anions selected from halides, hydroxides, sulfates, carbonates, cyanates, oxalates, thiocyanates, isocyanates, isothiocyanates, carboxylates, and nitrates, and n is the number of valence states that satisfy M.

[0097] As another example, the metal cyanide complex salt can be potassium hexacyanocobalt(III), potassium hexacyanoferrate(II), potassium hexacyanoferrate(III), calcium hexacyanocobalt(III) or lithium hexacyanoiridium(III), preferably potassium hexacyanocobalt(III).

[0098] Metal salts can exhibit water solubility. Specifically, metal salts can be represented by the following chemical formula 11: [Chemical Formula 11] M(X) n Wherein M is a transition metal, and may be at least one selected from Zn(II), Fe(II), Ni(II), Mn(II), Co(II), Sn(II), Pb(II), Fe(III), Mo(IV), Mo(VI), Al(III), V(V), V(IV), Sr(II), W(IV), W(VI), Cu(II), and Cr(III), and more preferably at least one selected from Zn(II), Fe(II), Co(II), and Ni(II). X is an anion selected from halides, hydroxides, sulfates, carbonates, cyanates, oxalates, thiocyanates, isocyanates, isothiocyanates, carboxylates, and nitrates. The value of n is the number of valence states that satisfy M.

[0099] As another example, the metal salt may be at least one selected from zinc(II), zinc(III), zinc bromide, zinc iodide, zinc acetate, zinc acetylacetone, zinc benzoate, zinc nitrate, ferrous sulfate(II), ferrous bromide(II), cobalt(II), cobalt(II) thiocyanate(II), nickel(II) formate(II), nickel(II) nitrate, and mixtures thereof, and preferably may be zinc(II), zinc(III), zinc bromide, or zinc iodide.

[0100] The catalyst according to the present invention can be represented by the following chemical formula 12: [Chemical Formula 12] M 2 p [M1 (CN)6] q dM 2 (X) r ·eL·fH2O Among them, M 1 and M 2 Each of these elements is an independent transition metal, X is an anion, and L is cyclobutanol, cyclopentanol, cyclohexanol, cycloheptanol, or cyclooctanol. p, q, d, r, e, and f are each independent integers from 1 to 6.

[0101] More specifically, the catalyst according to the invention can be represented by the following chemical formula 13: [Chemical Formula 13] Zn3[Co(CN)6]2·gZnCl2·hL·iH2O Where L is cyclobutanol, cyclopentanol, cyclohexanol, cycloheptanol, or cyclooctanol, and g, h, and i are each independent integers from 1 to 6.

[0102] Furthermore, the complexing agent can be any commonly used in the art without particular limitation, but can be at least one selected from ethanol, isopropanol, n-butanol, isobutanol, sec-butanol and tert-butanol.

[0103] As another example, a complexing agent can be a compound represented by the following chemical formula 14: [Chemical Formula 14]

[0104] Among them, R 9a and R 9b Each is independently a single bond or an alkylene group having 1 to 5 carbon atoms, provided that R 9a and R 9b At least one of them is an alkylene group having 1 to 5 carbon atoms, R 9c and R 9d Each is independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and n is an integer from 0 to 2.

[0105] Specifically, in the above chemical formula 14, R 9a and R 9b Each can be an independent single bond or an alkylene group having 1 to 3 carbon atoms, provided that R 9a and R 9b At least one of them is an alkylene group having 1 to 3 carbon atoms, R 9c and R 9d Each can be a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and n can be an integer from 0 to 2.

[0106] As yet another example, in the aforementioned chemical formula 14, R 9sand R 9b Each can be an independent single bond or an alkylene group having 1 to 3 carbon atoms, provided that R 9a and R 9b At least one of them is an alkylene group having 1 to 3 carbon atoms, R 9c It can be a hydrogen atom, and n can be 0.

[0107] As another example, the complexing agent can be a cycloalkyl alcohol having 3 to 12 carbon atoms, particularly a cycloalkyl alcohol having 4 to 10 carbon atoms or 5 to 7 carbon atoms.

[0108] More specifically, the complexing agent may be selected from at least one of the following: cyclobutanol, cyclopentanol, cyclohexanol, cycloheptanol, cyclooctanol, 1-methylcyclopentanol, 2-methylcyclopentanol, 3-methylcyclopentanol, 1-ethylcyclopentanol, 2-ethylcyclopentanol, 3-ethylcyclopentanol, 1-propylcyclopentanol, 2-propylcyclopentanol, 3-propylcyclopentanol, 1-butylcyclopentanol, 2-butylcyclopentanol, 3-butylcyclopentanol, 1-isopropylcyclopentanol, 2-isopropylcyclopentanol, 3-isopropylcyclopentanol, 1-(propyl-2-yl)cyclopentanol, 2,2-dimethylcyclopentanol, 2,3-dimethylcyclopentanol, 3,3-dimethylcyclopentanol, 1,2-dimethylcyclopentanol, 1,3-dimethylcyclopentanol, 1-methylcyclohexanol, 1-ethylcyclohexanol, 1-propylcyclohexanol, 1-butylcyclopentanol, 1-ethylcyclohexanol, 1-propylcyclohexanol, 1-ethylcyclopentanol, 1-propylcyclohexanol, 1-ethylcyclopentanol, 1-ethylcyclopentanol, 1-propylcyclohexanol, 1-ethylcyclopentanol, 1-ethylcyclopentanol, 1-ethylcyclohex ...pentanol, 1-ethylcyclohexanol, 1-ethylcyclopentanol, 2-methyl-1-cyclohexanol, 2-ethyl-1-cyclohexanol, 3-ethyl-1-cyclohexanol, 4-ethyl-1-cyclohexanol, 2-propyl-1-cyclohexanol, 3-propyl-1-cyclohexanol, 4-propyl-1-cyclohexanol, 2-butyl-1-cyclohexanol, 3-butyl-1-cyclohexanol, 4-butyl-1-cyclohexanol, 2-isopropyl-1-cyclohexanol, 3-isopropyl-1-cyclohexanol The complexing agent may be any one or more selected from cyclobutanol, 4-isopropyl-1-cyclohexanol, 2-tert-butyl-1-cyclohexanol, 3-tert-butyl-1-cyclohexanol, 4-tert-butyl-1-cyclohexanol, 2,3-dimethyl-1-cyclohexanol, 2,4-dimethyl-1-cyclohexanol, 3,4-dimethyl-1-cyclohexanol, 1-methylcycloheptanol, 2-methylcycloheptanol, 3-methylcycloheptanol, and 4-methylcycloheptanol. Specifically, the complexing agent may be any one or more selected from cyclobutanol, cyclopentanol, cyclohexanol, cycloheptanol, and cyclooctanol.

[0109] As another example, the complexing agent can be any one or more selected from cyclobutanol, cyclopentanol, cyclohexanol, cycloheptanol, and cyclooctanol.

[0110] Meanwhile, when the catalyst contains a compound represented by chemical formula 14 as a complexing agent, by using a cycloalkanol with a large volume structure as a complexing agent, the crystal structure of the catalyst can be configured in various forms such as cubic, amorphous and monoclinic crystal systems. This allows for appropriate control of the reaction rate between the epoxy compound and carbon dioxide to increase the proportion of repeating units of carbon dioxide in the prepared polyalkylene carbonate and reduce the content of cyclic carbonates as byproducts, thereby obtaining polyalkylene carbonates with excellent thermal stability and processing properties.

[0111] Furthermore, the catalyst may, as needed, further include an auxiliary complexing agent, which may be a compound having a hydroxyl, amino, ester, or ether group at the end.

[0112] The auxiliary complexing agent can improve the activity of the catalyst, and may be, for example, selected from at least one of the following: polyacrylamide, poly(acrylamide-co-acrylic acid), polyacrylic acid, poly(acrylic acid-co-maleic acid), polyacrylonitrile, alkyl polyacrylate, alkyl polymethacrylate, polyvinyl methyl ether, polyvinyl ethyl ether, polyvinyl acetate, polyvinyl alcohol, poly-N-vinylpyrrolidone, poly(N-vinylpyrrolidone-co-acrylic acid), polyvinyl methyl ketone, poly(4-vinylphenol), poly(acrylic acid-co-styrene), oxazoline polymer, polyalkylimide, maleic acid, maleic anhydride copolymer, hydroxyethyl cellulose, polyacetal, glycidyl ether, glycoside, carboxylic acid ester of polyol, gallic acid, ester and amide.

[0113] In addition, the auxiliary complexing agent can be a compound prepared by ring-opening polymerization of cyclic ether compounds, epoxy polymers or oxetane polymers, for example, it can be at least one selected from polyethers, polyesters, polycarbonates, polyalkylene glycols, polyalkylene glycol dehydrated sorbitol esters and polyalkylene glycol glycidyl ethers.

[0114] Furthermore, there are no particular restrictions on polymerization, but solution polymerization is preferred. Solution polymerization allows for appropriate control of the heat of reaction and easy control of the weight-average molecular weight or viscosity of the polyalkylene carbonate to be obtained.

[0115] The catalyst and the alkylene oxide compound can be used in weight ratios of 1:100 to 1:8000, 1:300 to 1:6000, or 1:1000 to 1:4000. Within these ranges, it has the effect of minimizing byproducts while exhibiting high catalytic activity, and minimizing the backbiting phenomenon of polyalkylene carbonates prepared by heating.

[0116] Furthermore, polymerization can be carried out within temperature ranges of 30°C to 120°C, 40°C to 110°C, or 50°C to 100°C. When these ranges are met, the polymerization time of the alkyl epoxide compound with carbon dioxide can be controlled within 24 hours, thereby improving manufacturing productivity.

[0117] Furthermore, polymerization can be carried out within pressure ranges of 5 to 50 bar, 10 to 40 bar, or 15 to 30 bar. When these ranges are met, there is an effect of increasing the proportion of repeating units containing carbon dioxide in the prepared polyalkylene carbonate and reducing the content of cyclic carbonates as byproducts.

[0118] The epoxide compound can be selected from at least one of the following: unsubstituted or halogenated alkylene oxides having 2 to 20 carbon atoms, substituted with halogens or alkyl groups having 1 to 5 carbon atoms; unsubstituted or halogenated cycloalkylene oxides having 4 to 20 carbon atoms, substituted with halogens or alkyl groups having 1 to 5 carbon atoms; and unsubstituted or halogenated styrene oxides having 8 to 20 carbon atoms, substituted with halogens or alkyl groups having 1 to 5 carbon atoms. For example, it can be selected from at least one of the following: ethylene oxide, propylene oxide, butane oxide, pentane oxide, hexane oxide, octane oxide, decane oxide, dodecane oxide, tetradecane oxide, hexadecane oxide, octadecane oxide, and butadiene oxide. Monooxide, 1,2-epoxy-7-octene, epifluoropropane, epichlorohydrin, epibromopropane, isopropyl glycidyl ether, butyl glycidyl ether, tert-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, cyclopentene oxide, cyclohexene oxide, cyclooctene oxide, cyclododecene oxide, α-pinene oxide, 2,3-epoxynorbornene, limonene oxide, dieldrin, 2,3-epoxypropylbenzene, styrene oxide, phenylepoxypropane, styrene oxide, chlorostilbene oxide, dichlorostilbene oxide, 1,2-epoxy-3-phenoxypropane, benzyloxymethyl ethylene oxide, glycidyl-methylphenyl ether, chlorophenyl-2,3-epoxypropyl ether, epichloropropyl methoxyphenyl ether, biphenyl glycidyl ether, and glycidyl naphthyl ether.

[0119] Furthermore, when alkyl oxidants are polymerized with carbon dioxide solution, the alkyl oxidants and solvents can be mixed, wherein the solvent can be at least one selected from the following: dichloromethane, dichloroethane, trichloroethane, tetrachloroethane, chloroform, acetonitrile, propionitrile, dimethylformamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, nitromethane, 1,3-dioxolane, 1,4-dioxane, hexane, toluene, tetrahydrofuran, methyl ethyl ketone, methyl ketone, methyl isobutyl ketone, acetone, cyclohexanone, trichloroethylene, methyl acetate, vinyl acetate, ethyl acetate, propyl acetate, butyrolactone, caprolactone, nitropropane, benzene, styrene, xylene, and methyl propasol.

[0120] Solvents and alkylene oxides can be used in weight ratios of 1:0.1 to 1:100, 1:1 to 1:100, or 1:1 to 1:10. Within this range, the solvent can be suitably used as a reaction medium, thereby improving the productivity of polyalkylene carbonate resins and minimizing byproducts generated during the manufacturing process.

[0121] Following the polymerization described above, a solvent removal step can be performed. The solvent removal can be carried out by conventional methods in the art without any particular limitation, as long as it achieves the purpose of removing the solvent. For example, it can be carried out by heating at a temperature of 30°C to 150°C for 30 minutes to 10 hours.

[0122] Example

[0123] The invention will be described in more detail below by way of examples. However, the examples below are intended to illustrate the invention, and the scope of the invention is not limited thereto.

[0124] Preparation Example

[0125] In a first 500 ml beaker, 11.45 g of zinc chloride, 30 ml of distilled water, and 39 g of cyclohexanol were mixed to prepare a first mixed solution. In a second 250 ml beaker, 4 g of potassium hexacyanocobaltate was dissolved in 100 ml of distilled water to prepare a second mixed solution. In a third 100 ml beaker, 5 g of polypropylene glycol (Mw=3,000) and 23 g of cyclohexanol were dissolved in 2 ml of distilled water to prepare a third mixed solution. Using a mechanical stirrer, the second mixed solution was added dropwise to the first mixed solution at 25 °C for 1 hour, followed by the addition of the third mixed solution, and the reaction was allowed to proceed for 1 hour. Subsequently, the mixture was separated using a high-speed centrifuge, and the separated precipitate was washed twice with a mixture of 70 ml of distilled water and 70 ml of cyclohexanol. It was then washed again with 140 ml of cyclohexanol, and the washed precipitate was dried in a vacuum oven at 80 °C for 12 hours to obtain 6.2 g of the bimetallic cyanide catalyst.

[0126] Example 1

[0127] 11 mg of the bimetallic cyanide catalyst prepared in the preparation example, 30 g of ethylene oxide, 10 g of dioxolane solvent, and 5 g of maleic anhydride were placed in a high-pressure reactor. Carbon dioxide was then injected into the reactor and the pressure was increased to 30 bar. The polymerization reaction was carried out at 75°C for 24 hours. After the reaction was complete, unreacted carbon dioxide was removed to prepare a polymer containing polyethylene carbonate resin. Subsequently, the polymer was diluted with dioxolane solvent to reduce the polyethylene carbonate resin solids content to 20% by weight. Then, based on 100 parts by weight of polyethylene carbonate resin solids content, 0.1 parts by weight of citric acid was added to deactivate the remaining catalyst. The mixture was stirred, poured into a pan, and dried in a vacuum oven at 40°C for 6 hours to prepare the polyethylene carbonate resin. 6 g of the prepared resin was placed in a micro dual extruder (HAAKEMini CTW, Thermo Scientific), held at 170°C for 20 minutes, and then extruded.

[0128] Example 2

[0129] Except for the addition of 0.1 parts by weight of antioxidant (Irganox 1010, BASF) and citric acid relative to 100 parts by weight of polyethylene carbonate resin solids, the polyethylene carbonate resin was prepared in the same manner as in Example 1.

[0130] Example 3

[0131] Except for the addition of 10g of maleic anhydride, polyethylene carbonate resin was prepared in the same manner as in Example 1.

[0132] Example 4

[0133] Except for the addition of 0.66g of maleic anhydride, polyethylene carbonate resin was prepared in the same manner as in Example 1.

[0134] Comparative Example 1

[0135] Polyethyl carbonate resins were prepared in the same manner as in Example 1, except that maleic anhydride was not added.

[0136] Comparative Example 2

[0137] The same method as in Comparative Example 1 was performed, except that 1 g of maleic anhydride was mixed with 6 g of polyethylene carbonate resin before being fed into the micro twin extruder. The mixture was then fed into the micro twin extruder and extruded under the same conditions to prepare polyethylene carbonate resin with maleic anhydride end-capping.

[0138] Experimental Example

[0139] The polymerization chain structure, melt index, mass loss rate, glass transition temperature, thermal decomposition temperature, and crosslinking rate of the polyalkylene carbonate resins prepared in the above examples and comparative examples were measured. The results are shown in Table 1 below. Figures 1 to 3 middle.

[0140] (1) Structural analysis

[0141] By using 1 The polymerization chain structure of a 10 mg polyalkylene carbonate resin sample was analyzed using a 500 MHz spectroscopy (Jeol) instrument dissolved in chloroform-d6 solvent. The results are shown below. Figure 1 middle.

[0142] (2) Melt index (g / 10min)

[0143] Melt index was measured using a melt flow indexer (MFI) according to ASTM D1238 at 190°C and 6.835 kg, and discharge rate was calculated in g / 10 min. More specifically, the evaluation material was placed in a piston heated to the above temperature using an MFI (QM280A, QMESYS), and the piston was positioned to apply the above weight load. After 4 minutes, the discharge rate was cut off, and the discharge rate was cut off again 4 times every 30 seconds to confirm the average value. The results are shown in Table 1.

[0144] (3) Thermal decomposition temperature (Td) 50 (℃) and mass loss rate (weight %)

[0145] Thermogravimetric analyzer (TGA) was used to measure the thermal decomposition temperature and mass loss rate. Specifically, a TGA (TGA2, Mettler Toledo) was used to measure the temperature at which the mass decreased by 50% while the temperature was increased (10°C / min) from 30°C to 400°C. Similar to the thermal decomposition temperature, the mass change rate was measured using the TGA to confirm the mass change rate after storage at an isothermal temperature of 240°C for 60 minutes. The measurement results are shown in Table 1. Figure 2 and Figure 3 middle.

[0146] (4) Glass transition temperature

[0147] The glass transition temperature was measured using a differential scanning calorimeter (DSC). Specifically, a DSC (Q20, TA instrument) was used to measure the temperature in a nitrogen atmosphere while heating the sample from -40°C to 250°C (10°C / min). The glass transition temperature (Tg) was confirmed based on the endothermic curve results. The results are shown in Table 1.

[0148] (5) Degree of crosslinking (%)

[0149] Crosslinking degree analysis was performed using a Soxhlet extractor with solvent extraction in chloroform for 24 hours. After solvent removal, the crosslinking degree was calculated as the weight ratio of the extracted sample to the unextracted sample. The results are shown in Table 1. Measurements marked with a hyphen (-) in Table 1 below are omitted.

[0150] [Table 1]

[0151] As can be seen from Table 1 above, compared with the polyalkylene carbonate resins prepared in the embodiments of the present invention, Comparative Example 1 without maleic anhydride and Comparative Example 2 with maleic anhydride end-capping both exhibit higher melt index, higher mass loss rate, lower thermal decomposition temperature, and lower glass transition temperature. That is, this means that compared with Comparative Example 2 with maleic anhydride end-capping, the embodiments of the present invention that introduce maleic anhydride into the polymer chain exhibit better thermal stability and processing performance.

[0152] Furthermore, in terms of crosslinking degree, the polyalkylene carbonate resin prepared in the embodiments of the present invention exhibits a higher value than the polyalkylene carbonate resin of the comparative example. This means that the introduced units derived from maleic anhydride form a crosslinked polymer network with the terminal activated polymer chains, thereby improving the thermal stability of the polymer chain structure.

Claims

1. A polyalkylene carbonate resin, comprising: Repeating units represented by the following chemical formula 1; The repeating unit represented by the following chemical formula 2; and Units derived from maleic anhydride in, The polycarbonate alkylene resin in 1 The 1H NMR spectrum shows peaks in the region of 6.3 ppm to 6.7 ppm: [Chemical Formula 1] [Chemical Formula 2] in: R1 to R8 are each independently hydrogen, a straight-chain alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or a cycloalkyl group having 3 to 20 carbon atoms. Indicates the connection sites between repeating units. x and y are mole fractions, where x is from 0.70 to 1.00, y is from 0.00 to 0.30, and x+y is 1.

2. The polyalkylene carbonate resin according to claim 1, characterized in that, According to ASTM D1238, the melt index, measured at 190°C and 6.835 kg, is greater than 1 g / 10 min and less than 25 g / 10 min.

3. The polyalkylene carbonate resin according to claim 1, characterized in that, The rate of mass change after storage at 240°C for 60 minutes is less than 80% by weight.

4. The polyalkylene carbonate resin according to claim 1, characterized in that, The glass transition temperature is above -10℃ and below 50℃.

5. The polyalkylene carbonate resin according to claim 1, characterized in that, Thermal decomposition temperature (Td) 50 The temperature is above 290℃.

6. The polyalkylene carbonate resin according to claim 1, wherein, Based on 100 parts by weight of the polyalkylene carbonate resin, the unit derived from maleic anhydride is included in an amount of 1 to 50 parts by weight.

7. A polyalkylene carbonate resin composition comprising: a polyalkylene carbonate resin according to any one of claims 1 to 6; and an antioxidant.

8. The polyalkylene carbonate resin composition according to claim 7, wherein, The antioxidant is selected from at least one of the following: tetra[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane, triethylene glycol bis-3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate, thiodiethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 1,2-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyl)hydrazine, 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate Octadecyl ester, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 2,4-di-tert-pentyl-6-(1-(3,5-di-tert-pentyl-2-hydroxyphenyl)ethyl)phenyl acrylate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, α-tocopherol, and 2,6-di-tert-butyl-p-cresol.

9. The polyalkylene carbonate resin composition according to claim 7, wherein, The antioxidant is contained in an amount of 0.01 to 3.00 parts by weight based on 100 parts by weight of the polyalkylene carbonate resin.

10. A method for preparing polyalkylene carbonate resins, comprising the step of polymerizing an alkylene oxide compound, carbon dioxide, and maleic anhydride in a solvent in the presence of a catalyst.

11. The method for preparing polyalkylene carbonate resin according to claim 10, wherein, The maleic anhydride is used in an amount of 0.1 to 25 parts by weight relative to 100 parts by weight of the epoxide compound.

12. The method for preparing polyalkylene carbonate resin according to claim 10, wherein, The polymerization is carried out over 24 hours at a temperature of 30°C to 120°C.

13. The method for preparing polyalkylene carbonate resin according to claim 10, wherein, The catalyst comprises a bimetallic cyanide and a complexing agent.

14. The method for preparing polyalkylene carbonate resin according to claim 13, wherein, The bimetallic cyanide comprises components derived from metal cyanide complex salts and components derived from metal salts. The metal cyanide complex salt is represented by the following chemical formula 3. The metal salt is represented by the following chemical formula 4: [Chemical Formula 3] Y a M`(CN) b in: M' is selected from at least one of Fe(II), Fe(III), Co(II), Co(III), Cr(II), Cr(III), Mn(II), Mn(III), Ir(III), Ni(II), Rh(III), Ru(II), V(V) and V(IV). Y is an alkali metal ion or an alkaline earth metal ion. a is an integer from 1 to 4, and b is an integer from 4 to 6. Choose the values ​​of a and b such that the metal cyanide complex salt is electroneutrally neutral. [Chemical Formula 4] M(X) n in: M is selected from at least one of Zn(II), Fe(II), Ni(II), Mn(II), Co(II), Sn(II), Pb(II), Fe(III), Mo(IV), Mo(VI), Al(III), V(V), V(IV), Sr(II), W(IV), W(VI), Cu(II), and Cr(III). X is any anion selected from halides, hydroxides, sulfates, carbonates, cyanates, oxalates, thiocyanates, isocyanates, isothiocyanates, carboxylates, and nitrates. n is a number that satisfies the valence state of M.

15. The method for preparing polyalkylene carbonate resin according to claim 13, wherein, The metal cyanide complex salt is potassium hexacyanocobalt(III), potassium hexacyanoferrate(II), potassium hexacyanoferrate(III), calcium hexacyanocobalt(III), or lithium hexacyanoiridium(III).

16. The method for preparing polyalkylene carbonate resin according to claim 13, wherein, The metal salt is selected from at least one of zinc chloride (II), zinc trichlorozinc (III), zinc bromide, zinc iodide, zinc acetate, zinc acetylacetone, zinc benzoate, zinc nitrate, ferrous sulfate (II), ferrous bromide (II), cobalt chloride (II), cobalt thiocyanate (II), nickel formate (II), and nickel nitrate (II).

17. The method for preparing polyalkylene carbonate resin according to claim 13, wherein, The complexing agent is selected from at least one of the following: cyclobutanol, cyclopentanol, cyclohexanol, cycloheptanol, cyclooctanol, 1-methylcyclopentanol, 2-methylcyclopentanol, 3-methylcyclopentanol, 1-ethylcyclopentanol, 2-ethylcyclopentanol, 3-ethylcyclopentanol, 1-propylcyclopentanol, 2-propylcyclopentanol, 3-propylcyclopentanol, 1-butylcyclopentanol, 2-butylcyclopentanol, 3-butylcyclopentanol, 1-isopropylcyclopentanol, 2-isopropylcyclopentanol, 3-isopropylcyclopentanol, 1-(propyl-2-yl)cyclopentanol, 2,2-dimethylcyclopentanol, 2,3-dimethylcyclopentanol, 3,3-dimethylcyclopentanol, 1,2-dimethylcyclopentanol, 1,3-dimethylcyclopentanol, 1-methylcyclohexanol, 1-ethylcyclohexanol, 1-propylcyclohexanol, 1-butylcyclohexanol. Alcohols, 2-methyl-1-cyclohexanol, 2-ethyl-1-cyclohexanol, 3-ethyl-1-cyclohexanol, 4-ethyl-1-cyclohexanol, 2-propyl-1-cyclohexanol, 3-propyl-1-cyclohexanol, 4-propyl-1-cyclohexanol, 2-butyl-1-cyclohexanol, 3-butyl-1-cyclohexanol, 4-butyl-1-cyclohexanol, 2-isopropyl-1-cyclohexanol, 3-isopropyl -1-Cyclohexanol, 4-Isopropyl-1-Cyclohexanol, 2-tert-butyl-1-Cyclohexanol, 3-tert-butyl-1-Cyclohexanol, 4-tert-butyl-1-Cyclohexanol, 2,3-Dimethyl-1-Cyclohexanol, 2,4-Dimethyl-1-Cyclohexanol, 3,4-Dimethyl-1-Cyclohexanol, 1-Methylcycloheptanol, 2-Methylcycloheptanol, 3-Methylcycloheptanol, and 4-Methylcycloheptanol.

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