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Carbon dioxide based high polymer material with crystallization performance

A technology of polymer materials and carbon dioxide, applied in the field of carbon dioxide-based polymer materials, can solve problems such as being limited within its glass transition temperature, and polycarbonate materials having no crystalline properties.

Inactive Publication Date: 2014-04-23
DALIAN UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0005] Polymers with crystallization ability largely depend on the symmetry of the repeating unit in the molecular chain, but unfortunately, although the terminal alkylene oxide and CO containing electron-donating groups in the molecule represented by propylene oxide 2 The tacticity of alternating copolymers has been improved to a near-perfect level (Sci. China Chem., 2010, 53, 1646–1652), but this type of polycarbonate material still does not have crystallization properties, making the use temperature of the polymer Can only be limited within its glass transition temperature

Method used

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  • Carbon dioxide based high polymer material with crystallization performance
  • Carbon dioxide based high polymer material with crystallization performance
  • Carbon dioxide based high polymer material with crystallization performance

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0046]

[0047] In a pre-dried stainless steel autoclave with an effective volume of 200mL and at ambient temperature, add in the following order: 0.5×10 -3 Mole of catalyst 1 in S configuration, X is 2,4-dinitrophenol anion), 0.5×10 -3 Mole of two-(triphenylphosphine, 2,4-dinitrophenol ammonium oxide, 0.25 mole of refined R-configuration styrene oxide, the temperature is controlled at -10 degrees, and then carbon dioxide gas is introduced and kept 2.0MPa constant pressure, react under magnetic stirring for 24 hours, slowly release unreacted carbon dioxide in the autoclave, add a large amount of ether to precipitate polycarbonate. Filter, wash with ether several times, vacuum dry to constant weight, and obtain 20 grams Polystyrene carbonate white solid.The average molecular weight of polymer is 18000 by gel permeation chromatography, and molecular weight distribution is 1.12; Measure its with Varian INOVA-400MHz nuclear magnetic resonance instrument 1 H-NMR, found that the...

Embodiment 2

[0049] In the same equipment used in Example 1, under the same conditions, only the temperature was lowered to -20 ° C for 48 hours to obtain 14 grams of polystyrene carbonate with a molecular weight of 12000 and a molecular weight distribution of 1.15. Polymerization The content of carbonate units in the product reaches 99%. pass 13 C-NMR analysis found that the isotactic structure of the polymer was more than 95%, and a small amount of polycarbonate hydrolyzed was analyzed by chiral gas phase column, and the enantioselectivity of the obtained 1-phenyl 1,2-ethylene glycol was 96% (S / R=98 / 2); After the obtained polymer was kept at a constant temperature of 130°C for 5 minutes, it was analyzed by DSC, and it was found that the glass transition temperature of the polymer was 93°C, and the maximum crystalline melting peak appeared at 148°C. The enthalpy is 27.1J / g; thermogravimetric analysis shows that the decomposition temperature of 50% of the material is 310°C; the wide-angl...

Embodiment 3

[0051]

[0052] In a pre-dried stainless steel autoclave with an effective volume of 200mL and at ambient temperature, add in the following order: 0.5×10 -3 moles of S-configuration catalyst 2, X and Y are 2,4-dinitrophenolate anion), 0.25 moles of refined R-configuration epichlorohydrin, the temperature is controlled at 0 degrees, and then carbon dioxide is introduced Gas and maintain a constant pressure of 2.0MPa, react under magnetic stirring for 24 hours, slowly release unreacted carbon dioxide in the autoclave, add a large amount of ether to precipitate polycarbonate. Filter, wash with ether several times, and dry in vacuum to constant weight to obtain 20 g of polycarbonate as a white solid. The average molecular weight of polymer measured by gel permeation chromatography is 18000, and molecular weight distribution is 1.12; Measure its with Varian INOVA-400MHz nuclear magnetic resonance instrument 1 H-NMR, found that the alternate structure exceeds 99%, by 13 C-NMR a...

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Abstract

The invention belongs to the field of the high polymer material, which relates to a class of carbon dioxide based high polymer material with the crystallization performance. The carbon dioxide based high polymer material with the crystallization performance is characterized in that end position alkyleneoxide containing an electrophilic group and carbon dioxide are copolymerized to form crystallizable polycarbonate material with an identical height structure under the action of catalyst. The polycarbonate has the following characteristics that the content of a carbonate ester unit in a polymer chain is 90-100%, and the identical structure of the polymer is between 80.0% and 99.9%; after the polymer is hydrolyzed by sodium hydroxide aqueous solution, the enantiomer selectivity of glycol obtained by measurement is 80.0% and 99.9%; and the polycarbonate with the crystallization performance can be obtained through carrying out simple thermal treatment on the polymer. The polycarbonate material provided by the invention has the advantages of big possibility of crystallizing, strong thermal deformation resistance and the like.

Description

technical field [0001] The invention discloses a class of carbon dioxide-based polymer materials with crystallization properties, belonging to the field of polymer materials. Background technique [0002] Carbon dioxide is the main gas that causes the greenhouse effect. At the same time, it is the most abundant and cheap carbon resource on the earth. Its reserves are more than the sum of oil, natural gas and coal. The chemical fixation of carbon dioxide is an important research field of green chemistry. Under the action of a catalyst, carbon dioxide and alkylene oxide can be copolymerized to prepare biodegradable polycarbonate materials. The polymer has excellent oxygen and water barrier properties, and can be used as food packaging materials, engineering plastics, rubber additives, adhesives and medical materials. [0003] At present, there are many patent reports on the preparation of polycarbonate by the copolymerization of carbon dioxide and alkylene oxide at home and ...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C08G64/10C08G64/02C08G64/34
Inventor 吕小兵伍广朋徐鹏翔任伟民祖玉萍
Owner DALIAN UNIV OF TECH
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