Polyalkylene carbonate-based 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 same, and provides a polyalkylene carbonate-based resin and a method for preparing same, the resin comprising: a repeating unit represented by chemical formula 1; a repeating unit represented by chemical formula 2; and an organic acid anhydride-derived unit, wherein a peak is present in the region of 6.3 ppm to 6.7 ppm in the 1H NMR spectrum.

Description

Polyalkylene carbonate resin and its manufacturing method

[0001] Cross-citation with related applications

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

[0003] Technology field

[0004] The present invention relates to a polyalkylene carbonate resin having excellent thermal stability and a method for producing the same.

[0005] Since the Industrial Revolution, humanity has built modern society through massive consumption of fossil fuels. However, environmental destruction, such as deforestation, has also led to increased atmospheric carbon dioxide concentrations. Since rising carbon dioxide concentrations contribute to the greenhouse effect, reducing atmospheric carbon dioxide, a significant contributor to global warming, is crucial. Various research projects are underway, including regulating carbon dioxide emissions and sequestering it.

[0006] Recently, polyalkylene carbonate resins produced by carbon dioxide and epoxide polymerization have attracted significant attention as a type of biodegradable resin. In particular, the process of manufacturing polyalkylene carbonate resins using carbon dioxide has the potential to mitigate global warming by fixing atmospheric carbon dioxide, and is also actively being researched from the perspective of utilizing it as a carbon resource.

[0007] However, due to its low thermal stability, it undergoes thermal decomposition at temperatures above 180℃, which greatly limits its industrial application.

[0008] Therefore, research is needed to improve the thermal stability of polyalkylene carbonate.

[0009]

[0010] Prior art literature

[0011] (Patent Document 1) CN 103842406 B (November 2, 2016)

[0012]

[0013] The purpose of the present invention is to provide a polyalkylene carbonate resin having excellent thermal stability.

[0014] The purpose of the present invention is to provide a method for producing the above polyalkylene carbonate resin.

[0015] To solve the above problem, the present invention provides a polyalkylene carbonate resin and a method for producing the same.

[0016] More specifically, (1) the present invention comprises a repeating unit represented by the following chemical formula 1; a repeating unit represented by the following chemical formula 2; and a maleic anhydride-derived unit, 1 Provided is a polyalkylene carbonate resin having a peak in the 6.3 ppm to 6.7 ppm region in the H NMR spectrum:

[0017] [Chemical Formula 1]

[0018]

[0019] [Chemical Formula 2]

[0020]

[0021] In the above chemical formulas 1 and 2,

[0022] R1 to R8 are each independently hydrogen, a linear 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,

[0023] * indicates a connection between repeating units,

[0024] x and y are mole fractions, x is 0.70 to 1.00, y is 0.00 to 0.30, and x+y is 1.

[0025] (2) The present invention provides a polyalkylene carbonate resin characterized in that, in the above (1), the melting index measured under the conditions of 190°C and 6.835 kg according to ASTM D1238 is 1 g / 10 min or more and 25 g / 10 min or less.

[0026] (3) The present invention provides a polyalkylene carbonate resin characterized in that, in the above (1) or (2), the mass change rate when stored at 240°C for 60 minutes is 80 wt% or less.

[0027] (4) The present invention provides a polyalkylene carbonate resin characterized in that the glass transition temperature is -10°C or higher and 50°C or lower in any one of the above (1) to (3).

[0028] (5) The present invention provides a polyalkylene carbonate resin characterized in that the thermal decomposition temperature (Td50) is 290°C or higher in any one of the above (1) to (4).

[0029] (6) The present invention provides a polyalkylene carbonate resin, wherein the maleic anhydride-derived unit is included in an amount of 1 to 50 parts by weight relative to 100 parts by weight of the polyalkylene carbonate resin in any one of the above (1) to (5).

[0030] (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.

[0031] (8) In the present invention, in the above (7), the antioxidant is tetrakis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane, triethylene glycol-bis-3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionate, thiodiethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 1,2-bis(3,5-di-t-butyl-4-hydroxyhydrocinnamoyl)hydrazine, octadecyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, A polyalkylene carbonate resin composition is provided, wherein the composition comprises at least one selected from the group consisting of 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 2,4-di-t-pentyl-6-(1-(3,5-di-t-pentyl-2-hydroxyphenyl)ethyl)phenyl acrylate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, α-tocopherol, and 2,6-di-t-butyl-p-cresol.

[0032] (9) The present invention provides a polyalkylene carbonate resin composition, wherein the antioxidant is included in an amount of 0.01 to 3.00 parts by weight based on 100 parts by weight of the polyalkylene carbonate resin in the above (7) or (8).

[0033] (10) The present invention provides a method for producing a polyalkylene carbonate resin, which comprises a step of polymerizing an alkylene oxide compound, carbon dioxide, and maleic anhydride in a solvent in the presence of a catalyst.

[0034] (11) The present invention provides a method for producing a polyalkylene carbonate resin, wherein, in the above (10), the maleic anhydride is used in an amount of 0.1 to 25 parts by weight relative to 100 parts by weight of the alkylene oxide compound.

[0035] (12) The present invention provides a method for producing a polyalkylene carbonate resin, wherein, in the above (10) or (11), the polymerization is performed at a temperature of 30°C to 120°C for less than 24 hours.

[0036] (13) The present invention provides a method for producing a polyalkylene carbonate resin, wherein the catalyst comprises a double metal cyanide compound and a complexing agent in any one of the above (10) to (12).

[0037] (14) The present invention provides a method for producing a polyalkylene carbonate resin, wherein in any one of the above (10) to (13), the double metal cyanide compound includes a metal cyanide complex-derived component and a metal salt-derived component, the metal cyanide complex is represented by the following chemical formula 3, and the metal salt is represented by the following chemical formula 4:

[0038] [Chemical Formula 3]

[0039] Y a M`(CN) b

[0040] In the above chemical formula 3,

[0041] M` is at least one selected from the group consisting 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),

[0042] Y is an alkali metal ion or alkaline earth metal ion,

[0043] a is an integer from 1 to 4, b is an integer from 4 to 6, and the values ​​of a and b are selected so that the metal cyanide complex is electrically neutral,

[0044] [Chemical Formula 4]

[0045] M(X) n

[0046] In the above chemical formula 4,

[0047] M is at least one selected from the group consisting 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),

[0048] X is any one anion selected from the group consisting of halides, hydroxides, sulfates, carbonates, cyanates, oxalates, thiocyanates, isocyanates, isothiocyanates, carboxylates, and nitrates,

[0049] n is the number of M atoms that satisfy the condition.

[0050] (15) The present invention provides a method for producing a polyalkylene carbonate resin, wherein in any one of the above (10) to (14), the metal cyanide complex salt is potassium hexacyanocobaltate(III), potassium hexacyanoferrate(II), potassium hexacyanoferrate(III), calcium hexacyanocobaltate(III), or lithium hexacyanoiridate(III).

[0051] (16) The present invention provides a method for producing a polyalkylene carbonate resin, wherein in any one of the above (10) to (15), the metal salt is at least one selected from the group consisting of zinc(II) chloride, zinc(III) chloride, zinc bromide, zinc iodide, zinc acetate, zinc acetylacetonate, zinc benzoate, zinc nitrate, iron(II) sulfate, iron(II) bromide, cobalt(II) chloride, cobalt(II) thiocyanate, nickel(II) formate, and nickel(II) nitrate.

[0052] (17) The present invention is any one of the above (10) to (16), wherein the complexing agent is cyclobutanol, cyclopentanol, cyclohexanol, cycloheptanol, cyclooctanol, 1-methyl cyclopentanol, 2-methyl cyclopentanol, 3-methyl cyclopentanol, 1-ethyl cyclopentanol, 2-ethyl cyclopentanol, 3-ethyl cyclopentanol, 1-propyl cyclopentanol, 2-propyl cyclopentanol, 3-propyl cyclopentanol, 1-butyl cyclopentanol, 2-butyl cyclopentanol, 3-butyl cyclopentanol, 1-isopropyl cyclopentanol, 2-isopropyl cyclopentanol, 3-isopropyl cyclopentanol, 1-(propan-2-yl) cyclopentanol, 2,2-dimethyl cyclopentanol, 2,3-dimethyl cyclopentanol, 3,3-dimethyl Cyclopentanol (3,3-dimethyl cyclopentanol), 1,2-dimethyl cyclopentanol, 1,3-dimethyl cyclopentanol (1,3-dimethyl cyclopentanol), 1-methyl cyclohexanol, 1-ethyl cyclohexanol, 1-propyl cyclohexanol, 1-butyl cyclohexanol, 2-methyl-1-cyclohexanol, 2-ethyl-1-cyclohexanol, 3-ethyl-1-cyclohexanol, 4-ethyl-1-cyclohexanol, 2-propy-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-cyclohexanolA method for producing a polyalkylene carbonate resin is provided, wherein the polyalkylene carbonate resin comprises at least one selected from the group consisting of 4-dimethyl-1-cyclohexanol, 1-methyl cycloheptanol, 2-methyl cycloheptanol, 3-methyl cycloheptanol, and 4-methyl cycloheptanol.

[0053] The polyalkylene carbonate resin according to the present invention is manufactured by polymerizing alkylene oxide and carbon dioxide together with maleic anhydride, and has the effect of improving thermal stability by including maleic anhydride-derived units in the polymer chain, thereby increasing the glass transition temperature and increasing the thermal decomposition temperature.

[0054] The following drawings attached to this specification illustrate specific embodiments of the present invention, and serve to further understand the technical idea of ​​the present invention together with the contents of the invention described above, and therefore the present invention should not be interpreted as being limited to matters described in such drawings.

[0055] Figure 1 shows the NMR analysis results of polyethylene carbonate resins manufactured in examples and comparative examples.

[0056] Figures 2 and 3 are graphs showing the results of mass change analysis using a thermogravimetric analyzer for polyethylene carbonate resins manufactured in examples and comparative examples.

[0057] Hereinafter, the present invention will be described in more detail to help understand the present invention.

[0058]

[0059] The terms or words used in the description and claims of the present invention should not be interpreted as limited to their usual or dictionary meanings, and should be interpreted as meanings and concepts that conform to the technical idea of ​​the present invention, based on the principle that the inventor can appropriately define the concept of the term to explain his or her own invention in the best way.

[0060]

[0061] Definition of terms

[0062] In this specification, the term 'thermal decomposition temperature (Td 50 )' means the temperature at which the polyalkylene carbonate resin is decomposed by heat and the mass is reduced to 50% of the mass before applying heat.

[0063] The term “alkyl group” in this specification may mean a monovalent aliphatic saturated hydrocarbon.

[0064] The term "aryl group" in this specification may mean a cyclic aromatic hydrocarbon, and may also mean a monocyclic aromatic hydrocarbon in which one ring is formed, or a polycyclic aromatic hydrocarbon in which two or more rings are combined.

[0065] The term “alkenyl group” in this specification may mean a monovalent aliphatic unsaturated hydrocarbon containing one or more double bonds.

[0066] The term "cycloalkyl group" in this specification may mean both a cyclic saturated hydrocarbon and a cyclic unsaturated hydrocarbon containing one or more unsaturated bonds.

[0067]

[0068] measurement method

[0069] In this specification, the thermal decomposition temperature (Td 50) was measured using a TGA (thermogravimetric analyzer), and specifically, the temperature at which the mass decreased by 50% was measured while increasing the temperature (10°C / min) from 30°C to 400°C using TGA (TGA2, Mettler Toledo).

[0070] In this specification, the mass change rate was measured using TGA, similar to the thermal decomposition temperature, and the mass change rate when stored for 60 minutes under isothermal conditions at 240°C was confirmed.

[0071] In this specification, the glass transition temperature was measured using DSC (differential scanning calorimetry). Specifically, the sample was heated (10°C / min) from -40°C to 250°C using DSC (Q20, TA instrument) in a nitrogen atmosphere. The Tg (glass transition temperature) was confirmed based on the endothermic curve results.

[0072] In this specification, the melt index was measured using a melt flow indexer (MFI), and was measured under the conditions of 190℃ and 6.835kg according to ASTM D1238, and the discharge amount was calculated as g / 10min. More specifically, using MFI (QM280A, QMESYS), the evaluation material was placed in a piston heated to the above temperature, the piston to apply the load of the above weight was placed in position, and the discharge amount was cut off after 4 minutes, and the average value of the discharge amount cut off 4 times every 30 seconds was confirmed.

[0073]

[0074] polyalkylene carbonate resin

[0075] The present invention provides a polyalkylene carbonate resin having improved thermal stability by suppressing thermal decomposition.

[0076] A polyalkylene carbonate resin according to one embodiment of the present invention comprises a repeating unit represented by the following chemical formula 1; a repeating unit represented by the following chemical formula 2; and a maleic anhydride-derived unit; 1It is characterized by the presence of a peak in the 6.3 ppm to 6.7 ppm region in the H NMR spectrum.

[0077] [Chemical Formula 1]

[0078]

[0079] [Chemical Formula 2]

[0080]

[0081] In the above chemical formulas 1 and 2,

[0082] R1 to R8 are each independently hydrogen, a linear 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,

[0083] * indicates a connection between repeating units,

[0084] x and y are mole fractions, x is 0.70 to 1.00, y is 0.00 to 0.30, and x+y is 1.

[0085] Meanwhile, when the chemical formula 1 or chemical formula 2 is the terminal of the initiation site of the polymer chain constituting the polyalkylene carbonate resin, the terminal may have a methyl group (-CH3) as a terminal group, and when the chemical formula 1 or chemical formula 2 is the terminal of the termination site of the polymer chain, the terminal may have a hydroxyl group (-OH) as a terminal group.

[0086]

[0087] Polyalkylene carbonate resins are manufactured using carbon dioxide as a raw material and are attracting significant attention as biodegradable resins. However, their low thermal stability significantly limits their industrial application, as they undergo thermal decomposition at temperatures above 180°C. Research has focused on improving thermal stability by mixing acid anhydrides as terminal capping agents with polyalkylene carbonate resins or by extruding them after mixing. However, the improvement in thermal stability has been minimal.

[0088] However, a polyalkylene carbonate-based resin according to one embodiment of the present invention is manufactured by reacting maleic anhydride with a monomer component during polymerization thereof, and the maleic anhydride can improve thermal stability by suppressing thermal decomposition by being introduced into the polymer chain structure. The thermal decomposition behavior of polyalkylene carbonate is a back-biting reaction in which hydrogen contained in a hydroxyl group at the resin terminal is released under high temperature conditions, thereby activating the resin terminal, and the activated resin terminal continuously attacks a carbonate group in a nearby polymer chain to continuously create a single molecule such as an alkylene carbonate, and the polymer chain length is shortened by a back-biting reaction and random chain scission in which a portion of the carbonate group in the polymer chain is broken and divided into chains including terminals such as carbon dioxide, hydroxyl groups, and double bonds, thereby causing the polymer chain length to be shortened in a cascade manner. However, it is difficult to prevent thermal decomposition of short polymer chains that are sequentially generated in the terminal-capped polyalkylene carbonate resin, whereas in the case of introducing maleic anhydride into the polymer chain structure as in the present invention, the maleic anhydride-derived units in the polymer chain structure form a polymer network cross-linked with terminally activated polymer chains, thereby improving the thermal stability of the polymer chain structure.

[0089]

[0090] In the present invention, the polyalkylene carbonate resin is a polymer manufactured by polymerizing an alkylene oxide compound, carbon dioxide, and an organic acid anhydride, and may include a repeating unit represented by the following chemical formula 1, a repeating unit represented by the following chemical formula 2, and a maleic anhydride-derived unit.

[0091] [Chemical Formula 1]

[0092]

[0093] [Chemical Formula 2]

[0094]

[0095] In the above chemical formulas 1 and 2,

[0096] R1 to R8 are each independently hydrogen, a linear 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, * denotes a linking site between repeating units, x and y are mole fractions, x is 0.70 to 1.00, y is 0.00 to 0.30, and x+y is 1.

[0097] In addition, the above x may be 0.80 to 1.00, and y may be 0.00 to 0.20, and preferably the above x may be 0.90 to 1.00, and y may be 0.00 to 0.10. When the above-described range is satisfied, the fixed ratio of carbon dioxide is high, which is effective in reducing greenhouse gases and is advantageous in biodegradation characteristics. In addition, when the polyalkylene carbonate resin according to the present invention is manufactured into a film, the film exhibits low oxygen permeability, thereby exhibiting excellent barrier characteristics.

[0098]

[0099] In addition, in the above chemical formula 1, R1 to R8 are each independently hydrogen, a linear 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 may be selected as an appropriate functional group in consideration of the properties of the resin to be ultimately obtained.

[0100] Additionally, the repeating unit represented by the above chemical formula 1 may be represented by the following chemical formula 5.

[0101] [Chemical Formula 5]

[0102]

[0103] In the above chemical formula 5, R1 to R4 are each independently hydrogen or a linear alkyl group having 1 to 10 carbon atoms, and x and * are as defined in the above chemical formula 1.

[0104] More specifically, the repeating unit represented by the above chemical formula 1 may be represented by the following chemical formula 6 or chemical formula 7.

[0105] [Chemical Formula 6]

[0106]

[0107] [Chemical Formula 7]

[0108]

[0109] In the above chemical formulas 6 and 7, x and * are as defined in the above chemical formula 1.

[0110]

[0111] Additionally, the repeating unit represented by the above chemical formula 2 may be represented by the following chemical formula 8.

[0112] [Chemical Formula 8]

[0113]

[0114] In the above chemical formula 8, R5 to R8 are each independently hydrogen or a linear alkyl group having 1 to 10 carbon atoms, and y and * are as defined in the above chemical formula 2.

[0115] More specifically, the repeating unit represented by the above chemical formula 2 may be represented by the following chemical formula 9 or chemical formula 10.

[0116] [Chemical Formula 9]

[0117]

[0118] [Chemical Formula 10]

[0119]

[0120] In the above chemical formulas 9 and 10, y and * are as defined in the above chemical formula 4.

[0121]

[0122] In addition, the maleic anhydride-derived unit is a component derived from maleic anhydride and bonded to a polymer chain of a polyalkylene carbonate resin, and may be maleic anhydride itself or a structure, functional group or component derived from maleic anhydride.

[0123]

[0124] In addition, the polyalkylene carbonate resin according to one embodiment of the present invention 1 In the H NMR spectrum, a peak exists in the region of 6.3 ppm to 6.7 ppm, and the presence of a peak in the region indicates the presence of a maleic anhydride-derived unit in the polymer chain structure. More specifically, the peak in the region can be confirmed only when a maleic anhydride-derived unit exists in the polymer chain structure, and the peak may not exist when the polymer formed by the completion of the polymerization reaction is mixed with maleic anhydride, or when the maleic anhydride is used as a terminal capping agent.

[0125] Here, the above 1 H NMR spectrum 1 It can be measured by dissolving 10 mg of a polyalkylene carbonate resin sample in chloroform-d6 solvent using a H-NMR spectrometer (500 MHz Spectrometer, Jeol Co.).

[0126]

[0127] In addition, the polyalkylene carbonate resin according to one embodiment of the present invention may have a melting index measured under the conditions of 190°C and 6.835 kg according to ASTM D1238 of 1 g / 10 min or more and 25 g / 10 min or less, and more preferably 1 g / 10 min to 10 g / 10 min.

[0128] In addition, the polyalkylene carbonate resin according to one embodiment of the present invention may have a mass change rate of 80 wt% or less, preferably 10 wt% to 80 wt%, and particularly preferably 15 wt% to 50 wt% when stored at 240°C for 60 minutes.

[0129] In addition, the polyalkylene carbonate resin according to one embodiment of the present invention may have a glass transition temperature of -10°C or higher and 50°C or lower, and preferably 5°C or higher and 50°C or lower.

[0130] In addition, the polyalkylene carbonate resin according to one embodiment of the present invention may have a thermal decomposition temperature (Td50) of 290°C or higher, and preferably 290°C or higher and 400°C or lower.

[0131] The polyalkylene carbonate resin according to one embodiment of the present invention can have the melting index, mass change rate, glass transition temperature, and thermal decomposition temperature described above by including the chemical formula 1, chemical formula 2, and maleic anhydride-derived unit, and thus can have excellent thermal stability and processability.

[0132]

[0133] In addition, the polyalkylene carbonate-based resin according to one embodiment of the present invention may contain a maleic anhydride-derived unit in an amount of 0.1 parts by weight or more and 50 parts by weight or less, based on 100 parts by weight of the polyalkylene carbonate-based resin, and specifically, may contain a unit in an amount of 0.5 parts by weight to 45 parts by weight, and when the maleic anhydride-derived unit is within the above-described range, the melting index of the polyalkylene carbonate-based resin may be lower and the thermal stability may be better.

[0134]

[0135] In addition, the polyalkylene carbonate resin of the present invention may have a cyclic carbonate content of 0.5 wt% to 15.0 wt%, 0.5 wt% to 10.0 wt%, or 0.5 wt% to 5.0 wt% based on the total weight. When the above-described range is satisfied, the problem of the glass transition temperature being lowered due to the cyclic carbonate acting as a softener can be minimized, thereby providing excellent mechanical properties.

[0136] The above cyclic carbonate content is 1 H-NMR spectrometer (500 MHz Spectrometer, Jeol Co.) can be used to measure 10 mg of polyalkylene carbonate resin sample dissolved in chloroform-d6 solvent. Specifically, 1 From the results measured by the H-NMR spectrometer, it was confirmed that a peak appeared around 4.5 ppm, which is a cyclic carbonate peak, and the cyclic carbonate content can be calculated using the carbonate peak area and ether peak area values, as in the following mathematical equation 1.

[0137] [Mathematical Formula 1]

[0138]

[0139] In the above mathematical expression 1, the contents of A, B, C, N and CO2 can be defined as follows.

[0140] A = cyclic carbonate peak area, B = carbonate peak area, C = ether peak area, N = [alkylene oxide molar mass / (44 + alkylene oxide molar mass)], CO2 content = (mole fraction of carbonate unit X 44) / [(mole fraction of carbonate unit X 44) + (alkylene oxide molar mass X 100)]

[0141]

[0142] Polyalkylene carbonate resin composition

[0143] The present invention provides a polyalkylene carbonate resin composition comprising the polyalkylene carbonate resin described above.

[0144] More specifically, the present invention provides a polyalkylene carbonate resin composition comprising the above-described polyalkylene carbonate resin; and an antioxidant.

[0145] The above antioxidant is for removing radicals that may remain in the polyalkylene carbonate resin, and more specifically, the above antioxidant is tetrakis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane, triethylene glycol-bis-3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionate, thiodiethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 1,2-bis(3,5-di-t-butyl-4-hydroxyhydrocinnamoyl)hydrazine, octadecyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, It may be at least one selected from the group consisting of 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 2,4-di-t-pentyl-6-(1-(3,5-di-t-pentyl-2-hydroxyphenyl)ethyl)phenyl acrylate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, α-tocopherol, and 2,6-di-t-butyl-p-cresol.

[0146] The above antioxidant may be included in an amount of 0.01 to 3.00 parts by weight based on 100 parts by weight of the polyalkylene carbonate resin, and preferably 0.05 to 1.50 parts by weight. When the antioxidant is included within the above-described range, the thermal stability of the polyalkylene carbonate resin can be effectively improved.

[0147]

[0148] Method for manufacturing polyalkylene carbonate resin

[0149] The present invention provides a method for producing the above polyalkylene carbonate resin.

[0150] A method for producing a polyalkylene carbonate resin according to one embodiment of the present invention includes a step of polymerizing an alkylene oxide compound, carbon dioxide, and maleic anhydride in a solvent in the presence of a catalyst.

[0151] The above polymerization can obtain a polymer including a polyalkylene carbonate-based resin in which a maleic anhydride-derived unit is introduced into the polymer chain, and the maleic anhydride can be included in an amount of 0.1 to 40 parts by weight based on 100 parts by weight of the alkylene oxide compound. More specifically, the maleic anhydride can be included in an amount of 0.5 to 35 parts by weight based on 100 parts by weight of the alkylene oxide compound. In this case, the maleic anhydride-derived unit can be included in an amount of 1 to 50 parts by weight based on 100 parts by weight of the finally produced polyalkylene carbonate-based resin, so that the thermal stability of the resin can be further improved.

[0152]

[0153] In addition, the antioxidant described above may be added to the polymer manufactured above, and the added antioxidant may increase the glass transition temperature and thermal decomposition temperature of the polyalkylene carbonate resin, thereby improving thermal stability and processability. The antioxidant may be added in an amount of 0.01 to 3.00 parts by weight based on 100 parts by weight of the polyalkylene carbonate resin.

[0154]

[0155] The above catalyst comprises a double metal cyanide compound and a complexing agent, and the double metal cyanide compound and the complexing agent can be used without limitation as long as they are conventional in the art.

[0156] For example, the double metal cyanide compound may include a metal cyanide complex-derived component and a metal salt-derived component, and the metal cyanide complex may be represented by the following chemical formula 3, and the metal salt may be represented by the following chemical formula 4.

[0157] [Chemical Formula 3]

[0158] Y a M`(CN) b

[0159] In the above chemical formula 3, M` is at least one selected from the group consisting 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, b is an integer from 4 to 6, and the values ​​of a and b are selected so that the metal cyanide complex is electrically neutral,

[0160] [Chemical Formula 4]

[0161] M(X) n

[0162] In the above chemical formula 4,

[0163] M is at least one selected from the group consisting 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 anion selected from the group consisting of halide, hydroxide, sulfate, carbonate, cyanate, oxalate, thiocyanate, isocyanate, isothiocyanate, carboxylate, and nitrate, and n is a number that satisfies the state of the M atom.

[0164] As another example, the metal cyanide complex salt may be potassium hexacyanocobaltate(III), potassium hexacyanoferrate(II), potassium hexacyanoferrate(III), calcium hexacyanocobaltate(III) or lithium hexacyanoiridate(III), and preferably potassium hexacyanocobaltate(III).

[0165] The above metal salt may exhibit water solubility. Specifically, the metal salt may be represented by the following chemical formula 11.

[0166] [Chemical Formula 11]

[0167] M(X) n

[0168] In the above chemical formula 11, M is a transition metal, and preferably may be at least one selected from the group consisting 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), and more preferably may be at least one selected from the group consisting of Zn(II), Fe(II), Co(II) and Ni(II). X is an anion selected from halide, hydroxide, sulfate, carbonate, cyanate, oxalate, thiocyanate, isocyanate, isothiocyanate, carboxylate, and nitrate. The value of n is a number that satisfies the valence state of M.

[0169] As another example, the metal salt may be zinc(II) chloride, zinc(III) chloride, zinc bromide, zinc iodide, zinc acetate, zinc acetylacetonate, zinc benzoate, zinc nitrate, iron(II) sulfate, iron(II) bromide, cobalt(II) chloride, cobalt(II) thiocyanate, nickel(II) formate, nickel(II) nitrate, and mixtures thereof, and preferably zinc(II) chloride, zinc(III) chloride, zinc bromide, or zinc iodide.

[0170] The catalyst according to the present invention can be represented by the following chemical formula 12.

[0171] [Chemical Formula 12]

[0172] M 2 p [M 1 (CN)6] q ·dM 2 (X) r ·eL·fH2O

[0173] In the above chemical formula 12, M 1 and M 2 are each independently a transition metal, X is an anion, and L is cyclobutanol, cyclopentanol, cyclohexanol, cycloheptanol, or cyclooctanol. p, q, d, r, e, and f are each independently an integer from 1 to 6.

[0174] More specifically, the catalyst according to the present invention can be represented by the following chemical formula 13.

[0175] [Chemical Formula 13]

[0176] Zn3[Co(CN)6]2·gZnCl2·hL·iH2O

[0177] In the above chemical formula 13, L is cyclobutanol, cyclopentanol, cyclohexanol, cycloheptanol, or cyclooctanol, and g, h, and i are each independently an integer from 1 to 6.

[0178] In addition, the complexing agent may be used without particular limitation as long as it is generally used in the art, but may be at least one selected from the group consisting of ethanol, isopropanol, normal butanol, isobutanol, sec-butanol, and tert-butanol.

[0179] As another example, the complexing agent may be a compound represented by the following chemical formula 14.

[0180] [Chemical Formula 14]

[0181]

[0182] In the above chemical formula 14, R 9a and R 9b are independently a single bond or an alkylene group having 1 to 5 carbon atoms, R 9a and R 9b At least one of them is an alkylene group having 1 to 5 carbon atoms, and R 9c and R 9d are independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and n is an integer from 0 to 2.

[0183] Specifically, in the above chemical formula 14, R 9a and R 9b are independently a single bond or an alkylene group having 1 to 3 carbon atoms, R 9a and R 9b At least one of R is an alkylene group having 1 to 3 carbon atoms, 9c and R 9d are independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and n can be an integer from 0 to 2.

[0184] As another example, in the above chemical formula 14, R 9s and R 9b are independently a single bond or an alkylene group having 1 to 3 carbon atoms, R 9a and R 9b At least one of R is an alkylene group having 1 to 3 carbon atoms, 9cis a hydrogen atom, and n can be 0.

[0185] As another example, the complexing agent may be a cycloalkyl alcohol having 3 to 12 carbon atoms, specifically a cycloalkyl alcohol having 4 to 10 carbon atoms, or 5 to 7 carbon atoms.

[0186] More specifically, the complexing agent is cyclobutanol, cyclopentanol, cyclohexanol, cycloheptanol, cyclooctanol, 1-methyl cyclopentanol, 2-methyl cyclopentanol, 3-methyl cyclopentanol, 1-ethyl cyclopentanol, 2-ethyl cyclopentanol, 3-ethyl cyclopentanol, 1-propyl cyclopentanol, 2-propyl cyclopentanol, 3-propyl cyclopentanol, 1-butyl cyclopentanol, 2-butyl cyclopentanol, 3-butyl cyclopentanol, 1-isopropyl cyclopentanol, 2-isopropyl cyclopentanol, 3-isopropyl cyclopentanol, 1-(propan-2-yl) cyclopentanol, 2,2-dimethyl cyclopentanol, 2,3-dimethyl cyclopentanol, 3,3-dimethyl cyclopentanol, 1,2-dimethyl 1,2-dimethyl cyclopentanol, 1,3-dimethyl cyclopentanol,1-methyl cyclohexanol, 1-ethyl cyclohexanol, 1-propyl cyclohexanol, 1-butyl cyclohexanol, 2-methyl-1-cyclohexanol, 2-ethyl-1-cyclohexanol, 3-ethyl-1-cyclohexanol, 4-ethyl-1-cyclohexanol, 2-propy-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,It may be at least one selected from the group consisting of 1-methyl cycloheptanol, 2-methyl cycloheptanol, 3-methyl cycloheptanol, and 4-methyl cycloheptanol. Specifically, the complexing agent may be at least one selected from the group consisting of cyclobutanol, cyclopentanol, cyclohexanol, cycloheptanol, and cyclooctanol.

[0187] As another example, the complexing agent may be at least one selected from the group consisting of cyclobutanol, cyclopentanol, cyclohexanol, cycloheptanol, and cyclooctanol.

[0188]

[0189] Meanwhile, when the catalyst includes a compound represented by chemical formula 14 as a complexing agent, the crystal structure of the catalyst can be configured in various ways, such as cubic, amorphous, and monoclinic, by using a cycloalkane alcohol having a bulky structure as a complexing agent, and thus, by appropriately controlling the reaction rate of the epoxide compound and carbon dioxide, the proportion of repeating units containing carbon dioxide in the polyalkylene carbonate produced increases, and the content of cyclic carbonate as a by-product decreases, so that a polyalkylene carbonate having superior thermal stability and processability can be obtained.

[0190]

[0191] In addition, the catalyst may further include an attaching agent as needed, and the attaching agent may be a compound having a hydroxyl group, an amine group, an ester group, or an ether group at a terminal.

[0192] The above-mentioned adhesive can improve the activity of the catalyst, and for example, is at least one selected from the group consisting of polyacrylamide, poly(acrylamide-co-acrylic acid), polyacrylic acid, poly(acrylic acid-co-maleic acid), polyacrylonitrile, polyalkyl acrylate, polyalkyl methacrylate, 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, polyalkyleneimine, maleic acid, maleic anhydride copolymer, hydroxyethyl cellulose, polyacetal, glycidyl ether, glycoside, carboxylic acid ester of polyhydric alcohol, gallic acid, ester and amide. Can be.

[0193] In addition, the adhesive may be a compound prepared by ring-opening polymerization of a cyclic ether compound, an epoxy polymer, or an oxetane polymer, and may be, for example, at least one selected from the group consisting of polyether, polyester, polycarbonate, polyalkylene glycol, polyalkylene glycol sorbitan ester, and polyalkylene glycol glycidyl ether.

[0194]

[0195] In addition, the polymerization is not particularly limited, but may preferably be carried out as a solution polymerization. Solution polymerization allows for appropriate control of the heat of reaction, and can facilitate control of the weight average molecular weight or viscosity of the polyalkylene carbonate to be obtained.

[0196] The above catalyst and alkylene oxide compound can be used in a weight ratio of 1:100 to 1:8000, 1:300 to 1:6000, or 1:1000 to 1:4000. Within the above-described range, high catalytic activity can be exhibited while minimizing by-products, and there is an effect of minimizing the back-biting phenomenon of polyalkylene carbonate produced by heating.

[0197]

[0198] In addition, the polymerization can be carried out at a temperature range of 30°C to 120°C, 40°C to 110°C, or 50°C to 100°C. When the above-described range is satisfied, the polymerization time of the alkylene oxide compound and carbon dioxide can be managed within 24 hours, thereby improving manufacturing productivity.

[0199] In addition, the polymerization can be carried out at a pressure range of 5 bar to 50 bar, 10 bar to 40 bar, or 15 bar to 30 bar. When the above-described range is satisfied, the ratio of repeating units containing carbon dioxide in the produced polyalkylene carbonate is high, and the content of cyclic carbonate as a by-product is reduced.

[0200] The above alkylene oxide compound is an alkylene oxide having 2 to 20 carbon atoms, substituted or unsubstituted with a halogen or an alkyl group having 1 to 5 carbon atoms; a cycloalkylene oxide having 4 to 20 carbon atoms, substituted or unsubstituted with a halogen or an alkyl group having 1 to 5 carbon atoms; And at least one compound selected from the group consisting of styrene oxide having 8 to 20 carbon atoms substituted or provided with a halogen or an alkyl group having 1 to 5 carbon atoms may be used, and examples thereof include ethylene oxide, propylene oxide, butene oxide, pentene oxide, hexene oxide, octene oxide, decene oxide, dodecene oxide, tetradecene oxide, hexadecene oxide, octadecene oxide, butadiene monoxide, 1,2-epoxy-7-octene, epifluorohydrin, epichlorohydrin, epibromohydrin, isopropyl glycidyl ether, butyl glycidyl ether, t-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, cyclopentene oxide, cyclohexene oxide, cyclooctene oxide, Any one or more compounds selected from the group consisting of cyclododecene oxide, alpha-pinene oxide, 2,3-epoxynorbornene, limonene oxide, dieldrin, 2,3-epoxypropylbenzene, styrene oxide, phenylpropylene oxide, stilbene oxide, chlorostilbene oxide, dichlorostilbene oxide, 1,2-epoxy-3-phenoxypropane, benzyloxymethyl oxirane, glycidyl-methylphenyl ether, chlorophenyl-2,3-epoxypropyl ether, epoxypropyl methoxyphenyl ether, biphenyl glycidyl ether, and glycidyl naphthyl ether may be used.

[0201] In addition, when the above alkylene oxide compound and carbon dioxide are carried out by solution polymerization, the alkylene oxide compound and the solvent may be mixed, and the solvent may include methylene chloride, ethylene dichloride, trichloroethane, tetrachloroethane, chloroform, acetonitrile, propionitrile, dimethylformamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, nitromethane, 1,3-dioxalane (dioxolane), 1,4-dioxane, hexane, toluene, tetrahydrofuran, methyl ethyl ketone, methyl amine ketone, methyl isobutyl ketone, acetone, cyclohexanone, trichloroethylene, methyl acetate, vinyl acetate, ethyl acetate, propyl acetate, butyrolactone, caprolactone, nitropropane, benzene, styrene, xylene, and Any one or more selected from the group consisting of methyl propasol may be used.

[0202] The solvent and the alkylene oxide compound may be used in a weight ratio of 1:0.1 to 1:100, 1:1 to 1:100, or 1:1 to 1:10. Within this range, the solvent can function appropriately as a reaction medium, thereby improving the productivity of the polyalkylene carbonate resin and minimizing byproducts generated during the manufacturing process.

[0203]

[0204] After the above polymerization, a step of removing the solvent may be further performed, and the solvent removal may be performed by any means common in the art without particular limitation as long as the purpose of removing the solvent can be achieved, and for example, it may be performed by applying heat at a temperature of 30°C to 150°C for 30 minutes to 10 hours.

[0205]

[0206] Example

[0207] Hereinafter, the present invention will be described in more detail by way of examples. However, the following examples are intended to illustrate the present invention and are not intended to limit the scope of the present invention solely to these examples.

[0208]

[0209] Manufacturing example

[0210] A first mixed solution was prepared by mixing 11.45 g of zinc chloride, 30 ml of distilled water, and 39 g of cyclohexanol in a first 500 ml beaker. A second mixed solution was prepared by dissolving 4 g of potassium hexacyanocobaltate in 100 ml of distilled water in a second 250 ml beaker. A third mixed solution was prepared by dissolving 5 g of polypropylene glycol (Mw=3,000) and 23 g of cyclohexanol in 2 ml of distilled water in a third 100 ml beaker. The second mixed solution was added dropwise to the first mixed solution using a mechanical stirrer at 25°C for 1 hour, and then the third mixed solution was added all at once and reacted for 1 hour. Thereafter, the mixed product was separated using a high-speed centrifuge, and the separated precipitate was washed twice using a mixture of 70 ml of distilled water and 70 ml of cyclohexanol. After additional washing using 140 ml of cyclohexanol, the washed precipitate was dried in a vacuum oven at 80°C for 12 hours, ultimately obtaining 6.2 g of a double metal cyanide catalyst.

[0211]

[0212] Example 1

[0213] In a high-pressure reactor, 11 mg of the double metal cyanide catalyst prepared in the manufacturing example, 30 g of ethylene oxide, 10 g of dioxolane solvent, and 5 g of maleic anhydride were placed. Then, carbon dioxide was introduced into the reactor and the pressure was increased to 30 bar. The polymerization reaction was carried out at 75°C for 24 hours, and after the reaction was completed, unreacted carbon dioxide was removed, and a polymer including a polyethylene carbonate resin was prepared. Thereafter, the polymer was diluted with a dioxolane solvent so that the solid content of the polyethylene carbonate resin in the polymer became 20 wt%, and then 0.1 part by weight of citric acid was added based on 100 parts by weight of the polyethylene carbonate resin solid content to deactivate the remaining catalyst, stirred, poured onto a tray, and dried in a vacuum oven at 40°C for 6 hours to prepare a polyethylene carbonate resin. 6 g of the manufactured resin was placed in a micro twin extruder (HAAKE Mini CTW, Thermo Scientific), kept at 170°C for 20 minutes, and then extruded.

[0214]

[0215] Example 2

[0216] In the above Example 1, a polyethylene carbonate resin was manufactured in the same manner as in Example 1, except that 0.1 part by weight of an antioxidant (Irganox 1010, BASF) was added together with citric acid per 100 parts by weight of polyethylene carbonate resin solids.

[0217]

[0218] Example 3

[0219] In the above Example 1, a polyethylene carbonate resin was manufactured in the same manner as Example 1, except that 10 g of maleic anhydride was added.

[0220]

[0221] Example 4

[0222] In the above Example 1, a polyethylene carbonate resin was manufactured in the same manner as Example 1, except that 0.66 g of maleic anhydride was added.

[0223]

[0224] Comparative Example 1

[0225] In the above Example 1, a polyethylene carbonate resin was manufactured in the same manner as Example 1, except that maleic anhydride was not added.

[0226]

[0227] Comparative Example 2

[0228] The same process as in Comparative Example 1 was followed to manufacture the resin, but 1 g of maleic anhydride was mixed with 6 g of polyethylene carbonate resin before being fed into the ultra-small twin extruder, and then the resin was fed into the ultra-small twin extruder and extruded under the same conditions to manufacture a polyethylene carbonate resin end-capped with maleic anhydride.

[0229]

[0230] Experimental example

[0231] The polymerization chain structure, melt index, mass loss rate, glass transition temperature, thermal decomposition temperature, and crosslinking rate of the polyalkylene carbonate resins manufactured in the above examples and comparative examples were measured. The results are shown in Table 1 and Figures 1 to 3 below.

[0232] (1) Structural analysis

[0233] Analysis of the polymer chain structure of the resin 1 A 10 mg sample of polyalkylene carbonate resin was dissolved in chloroform-d6 solvent and measured using a H-NMR spectrometer (500 MHz Spectrometer, Jeol Co.), and the results are shown in Figure 1.

[0234] (2) Melting index (g / 10 min)

[0235] The melt index was measured using a melt flow indexer (MFI), and was measured under the conditions of 190℃ and 6.835kg according to ASTM D1238, and the discharge amount was calculated as g / 10min. More specifically, using MFI (QM280A, QMESYS), the evaluation material was placed in a piston heated to the above temperature, the piston to apply the above weight was placed in position, and the discharge amount was cut off after 4 minutes, and the average value of the discharge amount cut off 4 times every 30 seconds was confirmed, and the results are shown in Table 1.

[0236] (3) Thermal decomposition temperature (Td) 50 , ℃) and mass reduction rate (weight%)

[0237] The thermal decomposition temperature and mass loss rate were measured using a thermogravimetric analyzer (TGA). Specifically, the temperature at which the mass decreased by 50% was measured while increasing the temperature (10°C / min) from 30°C to 400°C using TGA (TGA2, Mettler Toledo). The mass change rate was measured using TGA, similar to the thermal decomposition temperature, and the mass change rate when stored for 60 minutes under isothermal conditions at 240°C was confirmed. The measurement results are shown in Table 1, Figs. 2 and 3.

[0238] (4) Glass transition temperature (℃)

[0239] The glass transition temperature was measured using a differential scanning calorimeter (DSC). Specifically, the sample was heated (10°C / min) from -40°C to 250°C using a DSC (Q20, TA instrument) in a nitrogen atmosphere. The Tg (glass transition temperature) was determined based on the endothermic curve results. The results are shown in Table 1.

[0240] (5) Cross-linking degree (%)

[0241] Crosslinking degree analysis was performed using a Soxhlet extractor as a solvent extraction method under chloroform solvent conditions for 24 hours. After removing the solvent, the crosslinking degree was calculated as the weight ratio of the sample before extraction to the sample after extraction. The results are shown in Table 1. Meanwhile, the area marked with a hyphen in Table 1 below is where measurement was omitted.

[0242] Classification Preliminary Comparative Example 123412 Melting Index (g / 10min) 2.08.1-1.9-30.7 Mass Reduction Rate (Wt%) 494712-8986 Thermal Decomposition Temperature (Td 50 , ℃)304312378-281287Glass transition temperature(℃)8.818.2-12.53.92.1Crosslinking degree(%)128-5<0<0

[0243] As can be seen from Table 1 above, both Comparative Example 1, which did not use maleic anhydride, and Comparative Example 2, which was terminally capped with maleic anhydride, exhibited higher melting index, mass loss rate, and lower thermal decomposition temperature and glass transition temperature compared to the polyalkylene carbonate resins manufactured in the examples of the present invention. This means that the examples of the present invention, in which maleic anhydride was introduced into the polymerization chain, exhibited superior thermal stability and processability compared to Comparative Example 2, in which maleic anhydride was terminally capped.

[0244] In addition, in the case of crosslinking, the polyalkylene carbonate resin manufactured in the examples of the present invention showed a higher value than the polyalkylene carbonate resin of the comparative example, which means that the introduced maleic anhydride-derived unit formed a polymer network crosslinked with terminally activated polymer chains, thereby improving the thermal stability of the polymer chain structure.

Claims

1. A repeating unit represented by the following chemical formula 1; A repeating unit represented by the following chemical formula 2; and Contains a maleic anhydride derived unit, 1 A polyalkylene carbonate resin having a peak in the region of 6.3 ppm to 6.7 ppm in the H NMR spectrum: [Chemical Formula 1] [Chemical formula 2] In the above chemical formulas 1 and 2, R 1 Inland R 8 are each independently hydrogen, a linear 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 a connection 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. In paragraph 1, A polyalkylene carbonate resin characterized by having a melting index of 1 g / 10 minutes or more and 25 g / 10 minutes or less as measured under the conditions of 190°C and 6.835 kg according to ASTM D1238.

3. In paragraph 1, A polyalkylene carbonate resin characterized in that the mass change rate when stored at 240°C for 60 minutes is 80 wt% or less.

4. In paragraph 1, A polyalkylene carbonate resin characterized by a glass transition temperature of -10°C or higher and 50°C or lower.

5. In paragraph 1, A polyalkylene carbonate resin characterized by a thermal decomposition temperature (Td50) of 290°C or higher.

6. In paragraph 1, A polyalkylene carbonate resin, wherein the maleic anhydride derived unit is contained in an amount of 1 to 50 parts by weight per 100 parts by weight of the polyalkylene carbonate resin.

7. Polyalkylene carbonate resin according to any one of clauses 1 to 6; and A polyalkylene carbonate resin composition comprising an antioxidant.

8. In paragraph 7, The above antioxidants are tetrakis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane, triethylene glycol-bis-3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionate, thiodiethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 1,2-bis(3,5-di-t-butyl-4-hydroxyhydrocinnamoyl)hydrazine, octadecyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, A polyalkylene carbonate resin composition comprising at least one selected from the group consisting of 2,4-di-t-pentyl-6-(1-(3,5-di-t-pentyl-2-hydroxyphenyl)ethyl)phenyl acrylate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, α-tocopherol, and 2,6-di-t-butyl-p-cresol.

9. In paragraph 7, A polyalkylene carbonate resin composition, 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 producing a polyalkylene carbonate resin, comprising a step of polymerizing an alkylene oxide compound, carbon dioxide and maleic anhydride in a solvent in the presence of a catalyst.

11. In paragraph 10, A method for producing a polyalkylene carbonate resin, wherein the maleic anhydride is used in an amount of 0.1 to 25 parts by weight relative to 100 parts by weight of an alkylene oxide compound.

12. In paragraph 10, A method for producing a polyalkylene carbonate resin, wherein the above polymerization is performed at a temperature of 30°C to 120°C within 24 hours.

13. In paragraph 10, A method for producing a polyalkylene carbonate resin, wherein the catalyst comprises a double metal cyanide compound and a complexing agent.

14. In paragraph 13, The above double metal cyanide compound comprises a metal cyanide complex derived component and a metal salt derived component, The above metal cyanide complex is represented by the following chemical formula 3: The above metal salt is represented by the following chemical formula 4: A method for producing a polyalkylene carbonate resin: [Chemical Formula 3] Y a M`(CN) b In the above chemical formula 3, M` is at least one selected from the group consisting 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 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 selected so that the metal cyanide complex is electrically neutral, [Chemical Formula 4] M(X) n In the above chemical formula 4, M is at least one selected from the group consisting 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 anion selected from the group consisting of halides, hydroxides, sulfates, carbonates, cyanates, oxalates, thiocyanates, isocyanates, isothiocyanates, carboxylates, and nitrates, n is the number of M atoms satisfying the state.

15. In paragraph 13, A method for producing a polyalkylene carbonate resin, wherein the metal cyanide complex salt is potassium hexacyanocobaltate(III), potassium hexacyanoferrate(II), potassium hexacyanoferrate(III), calcium hexacyanocobaltate(III), or lithium hexacyanoiridate(III).

16. In paragraph 13, A method for producing a polyalkylene carbonate resin, wherein the metal salt is at least one selected from the group consisting of zinc (II) chloride, zinc (III) chloride, zinc bromide, zinc iodide, zinc acetate, zinc acetylacetonate, zinc benzoate, zinc nitrate, iron (II) sulfate, iron (II) bromide, cobalt (II) chloride, cobalt (II) thiocyanate, nickel (II) formate, and nickel (II) nitrate.

17. In paragraph 13, The above complexing agent is cyclobutanol, cyclopentanol, cyclohexanol, cycloheptanol, cyclooctanol, 1-methyl cyclopentanol, 2-methyl cyclopentanol, 3-methyl cyclopentanol, 1-ethyl cyclopentanol, 2-ethyl cyclopentanol, 3-ethyl cyclopentanol, 1-propyl cyclopentanol, 2-propyl cyclopentanol, 3-propyl cyclopentanol, 1-butyl cyclopentanol, 2-butyl cyclopentanol, 3-butyl cyclopentanol, 1-isopropyl cyclopentanol, 2-isopropyl cyclopentanol, 3-isopropyl cyclopentanol, 1-(propan-2-yl) cyclopentanol, 2,2-dimethyl cyclopentanol, 2,3-dimethyl cyclopentanol, 3,3-dimethyl cyclopentanol, 1,2-dimethyl 1,2-dimethyl cyclopentanol, 1,3-dimethyl cyclopentanol,1-methyl cyclohexanol, 1-ethyl cyclohexanol, 1-propyl cyclohexanol, 1-butyl cyclohexanol, 2-methyl-1-cyclohexanol, 2-ethyl-1-cyclohexanol, 3-ethyl-1-cyclohexanol, 4-ethyl-1-cyclohexanol, 2-propy-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,A method for producing a polyalkylene carbonate resin, wherein the polyalkylene carbonate resin comprises at least one selected from the group consisting of 1-methyl cycloheptanol, 2-methyl cycloheptanol, 3-methyl cycloheptanol, and 4-methyl cycloheptanol.

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