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CN-122003454-A - Polyalkylene carbonate resin and process for producing the same

CN122003454ACN 122003454 ACN122003454 ACN 122003454ACN-122003454-A

Abstract

The present invention relates to a polyalkylene carbonate resin having excellent thermal stability and a method for preparing the same, and provides a polyalkylene carbonate resin and a method for preparing the same, the polyalkylene carbonate 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, wherein the polyalkylene carbonate resin has a peak in a region of 6.3ppm to 6.7ppm in 1 H NMR spectrum.

Inventors

  • REN SHUYAN
  • Shen baola
  • JIN XIANGYOU
  • Pu Luzhen
  • XU JUNZHI

Assignees

  • 株式会社LG化学

Dates

Publication Date
20260508
Application Date
20241129
Priority Date
20231204

Claims (17)

  1. 1. A polyalkylene carbonate resin comprising: a repeating unit represented by the following chemical formula 1; A repeating unit represented by the following chemical formula 2, and Units derived from maleic anhydride and the like, Wherein the polyalkylene carbonate resin has a peak in the region of 6.3ppm to 6.7ppm in 1 H NMR spectrum: [ chemical formula 1] [ Chemical formula 2] Wherein: R 1 to 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, Represents the site of attachment between the repeating units, X and y are mole fractions, where x is 0.70 to 1.00, y is 0.00 to 0.30, and x+y is 1.
  2. 2. The polyalkylene carbonate resin according to claim 1, wherein the melt index measured according to ASTM D1238 at 190 ℃ and 6.835kg is 1g/10min or more and 25g/10min or less.
  3. 3. The polyalkylene carbonate resin according to claim 1, wherein the mass change rate at 60 minutes of storage at 240 ℃ is 80% by weight or less.
  4. 4. The polyalkylene carbonate resin according to claim 1, wherein the glass transition temperature is from-10 ℃ to 50 ℃.
  5. 5. The polyalkylene carbonate resin according to claim 1, wherein the thermal decomposition temperature (Td 50 ) is 290 ℃ or higher.
  6. 6. The polyalkylene carbonate resin according to claim 1, wherein the unit derived from maleic anhydride is contained in an amount of 1 to 50 parts by weight based on 100 parts by weight of the polyalkylene carbonate resin.
  7. 7. A polyalkylene carbonate resin composition comprising the polyalkylene carbonate resin according to any one of claims 1 to 6, and an antioxidant.
  8. 8. The polyalkylene carbonate resin composition according to claim 7, wherein the antioxidant is at least one selected from the group consisting of tetrakis [ methylene-3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ] methane, triethylene glycol-bis-3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionate, thiodiethylene bis [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, 2, 4-di-t-amyl-6- (1- (3, 5-di-t-amyl-2-hydroxyphenyl) ethyl) acrylate, 1, 5-trimethyl-2, 6-di-t-butyl-4-hydroxyphenyl) propionate, and tocopheryl-1, 3, 5-tri-t-butyl-3, 6-di-t-butylphenyl (α -4-hydroxybenzyl) propionate.
  9. 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. 10. A method for preparing a polyalkylene carbonate resin, comprising the step of polymerizing an alkylene oxide compound, carbon dioxide and maleic anhydride in a solvent in the presence of a catalyst.
  11. 11. The method for producing a polyalkylene carbonate-based 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 alkylene oxide compound.
  12. 12. The method for preparing a polyalkylene carbonate-based resin according to claim 10, wherein the polymerization is performed at a temperature of 30 ℃ to 120 ℃ within 24 hours.
  13. 13. The method for preparing a polyalkylene carbonate resin according to claim 10, wherein the catalyst comprises a double metal cyanide compound and a complexing agent.
  14. 14. The method for producing a polyalkylene carbonate-based resin according to claim 13, wherein the double metal cyanide compound 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, The metal salt is 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, the values of a and b being selected such that the metal cyanide complex salt is electrically neutral, [ Chemical formula 4] M(X) n Wherein: M is 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), X is any one anion selected from halide, hydroxide, sulfate, carbonate, cyanate, oxalate, thiocyanate, isocyanate, isothiocyanate, carboxylate and nitrate, N is a number satisfying the valence of M.
  15. 15. The method for producing a polyalkylene carbonate resin according to claim 13, wherein the metal cyanide complex salt is potassium hexacyanocobaltate (III), potassium hexacyanoferric (II), potassium hexacyanoferric (III), calcium hexacyanocobaltate (III) or lithium hexacyanoiridium (III).
  16. 16. The method for preparing a polyalkylene carbonate resin according to claim 13, wherein the metal salt is at least one selected from zinc (II) chloride, zinc (III) trichloride, 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. 17. The method for producing a polyalkylene carbonate-based resin according to claim 13, wherein the complexing agent is at least one selected from the group consisting of: the process comprises the steps of (a) carrying out the reaction of a mixture of (a) a solvent selected from the group consisting of (a) a butanol, cyclopentanol, cyclohexanol, cycloheptanol, cyclooctanol, 1-methylcyclopentanol, 2-methylcyclopentanol, 3-methylcyclopentanol, 1-ethylcyclopentanol, 2-ethylcyclopentanol, 3-ethylcyclopentanol, 1-propylcyclopentanol, 2-propylcyclopentanol, 1-butylcyclopentanol, 3-butylcyclopentanol, 1-isopropylcyclopentanol, 2-isopropylcyclopentanol, 3-isopropylcyclopentanol, 1- (propan-2-yl) cyclopentanol, 2-dimethylcyclopentanol, 2, 3-dimethylcyclopentanol, 3-dimethylcyclopentanol, 1, 2-dimethylcyclohexanol, 1, 3-dimethylcyclohexanol, 1-methylcyclohexanol, 1-ethylcyclohexanol, 1-propylcyclohexanol, 1-butylcyclohexanol, 2-methyl-1-cyclohexanol, 2-ethyl-1-cyclohexanol, 3-ethyl-1-cyclohexanol, 4-ethyl-cyclohexanol, 2-propyl-1-cyclohexanol, 2-isopropyl-cyclohexanol, 3-isopropyl-cyclohexanol, 1-propyl-2-cyclohexanol, 3-propyl-1-2-propyl-cyclohexanol, 1-propyl-2-isopropyl-cyclohexanol, 1-propyl-2-isopropyl-cyclohexanol, 1-isopropyl-1-2-propyl-2-isopropyl-1-cyclohexanol, 1-isopropyl-2-n 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.

Description

Polyalkylene carbonate resin and process for producing the same Technical Field Cross Reference to Related Applications The present application claims priority from korean patent application No. 10-2023-0173506 filed on 4/12/2023, the entire contents of which are incorporated herein by reference for all purposes. The present invention relates to a polyalkylene carbonate resin having excellent thermal stability and a method for preparing the same. Background Since the industrial revolution, humans have established modern society by consuming large amounts of fossil fuels, but the concentration of carbon dioxide in the atmosphere has increased due to environmental damage such as deforestation. Since an increase in carbon dioxide concentration is a cause of increasing greenhouse effect, it is important to reduce the concentration of carbon dioxide in the atmosphere, which has a high contribution rate to global warming, and various studies are being made on regulation or fixation of carbon dioxide emissions. Recently, polyalkylene carbonate resins produced by polymerization of carbon dioxide with epoxides have received much attention as a biodegradable resin. In particular, a method of producing a polyalkylene carbonate resin using carbon dioxide can reduce the global warming problem by fixing carbon dioxide in the atmosphere, and active researches have also been conducted from the viewpoint of use as a carbon resource. However, due to low thermal stability, they undergo thermal decomposition at temperatures above 180 ℃, which greatly limits their industrial application. Therefore, research is required to improve the thermal stability of polyalkylene carbonates. [ Prior Art literature ] (Patent document 1) CN 103842406B (2016, 11, 02) Disclosure of Invention Technical problem It is an object of the present invention to provide a polyalkylene carbonate-based resin having excellent thermal stability. It is another object of the present invention to provide a method for preparing a polyalkylene carbonate-based resin. Technical proposal In order to solve the above problems, the present invention provides a polyalkylene carbonate resin and a method for preparing the same. More specifically, (1) the present invention provides a polyalkylene carbonate-based resin comprising a repeating unit represented by the following chemical formula 1, a repeating unit represented by the following chemical formula 2, and a unit derived from maleic anhydride, wherein the polyalkylene carbonate-based resin has a peak in the region of 6.3ppm to 6.7ppm in 1 H NMR spectrum: [ chemical formula 1] [ Chemical formula 2] Wherein: R 1 to 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, Represents the site of attachment between the repeating units, X and y are mole fractions, where x is 0.70 to 1.00, y is 0.00 to 0.30, and x+y is 1. (2) The polyalkylene carbonate resin according to the above (1), which has a melt index of 1g/10min or more and 25g/10min or less as measured according to ASTM D1238 under conditions of 190 ℃ and 6.835 kg. (3) The present invention provides the polyalkylene carbonate resin according to the above (1) or (2), wherein the mass change rate of the polyalkylene carbonate resin when stored at 240℃for 60 minutes is 80% by weight or less. (4) The present invention provides the polyalkylene carbonate resin according to any one of the above (1) to (3), characterized in that the glass transition temperature is from-10 ℃ to 50 ℃. (5) The present invention provides the polyalkylene carbonate resin according to any one of the above (1) to (4), characterized in that the thermal decomposition temperature (Td 50) is 290 ℃ or higher. (6) The present invention provides the polyalkylene carbonate resin according to any one of the above (1) to (5), wherein the unit derived from maleic anhydride is contained in an amount of 1 to 50 parts by weight based on 100 parts by weight of the polyalkylene carbonate resin. (7) The present invention provides a polyalkylene carbonate resin composition comprising the polyalkylene carbonate resin according to any one of the above (1) to (6), and an antioxidant. (8) The present invention provides the polyalkylene carbonate resin composition according to the above (7), wherein the antioxidant is at least one selected from the group consisting of tetrakis [ methylene-3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ] methane, triethylene glycol-bis-3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionate, thiodiethylene bis [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) -