Polycarbonate with optical activity and preparation method thereof

A polycarbonate and optically active technology, applied in the field of polymer synthesis, can solve problems such as the greenhouse effect, harsh reaction conditions, and single product types, and achieve the effects of broad industrial promotion value, mild reaction conditions, and high optical selectivity

Active Publication Date: 2014-09-24
郑州裕昌建筑节能科技有限公司
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Although carbon dioxide is the raw material for photosynthesis of plants, the sharp increase of carbon dioxide not only destroys the carbon cycle in nature, but also leads to the greenhouse effect, causing drastic changes in global climate
However, there are still many problems to be solved in the preparation of polycarbonate by alternating copolymerization of carbon dioxide and epoxy compounds, such as: the types of products obtained are relatively single, unable to meet different industrial needs; for polycarbonate with optical activity , the selectivity of the catalytic system is low, and the ideal optical purity cannot be obtained yet; usually higher carbon dioxide pressure is required, and the reaction conditions are harsh

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0018] (1) Add chiral ligand A (Ar=Ph) 0.061 g, 0.1 mmol) and 2 mL toluene into the Schlenk reaction tube, and replace the air in the tube with nitrogen. Slowly add ZnEt dropwise at 0°C (ice-water bath) under nitrogen protection 2 (organometallic; 0.2 mL, 1.0 M, 0.2 mmol), and stirred at room temperature for 30 min. Then add absolute ethanol (0.04 mL, 1 M, 0.04 mmol), continue stirring at room temperature for 15 min, then add 2 mmol of 7-oxobicyclo[4.1.0]-3-heptene (1a), and bubble with carbon dioxide , stirred at 30 °C for 36 h.

[0019] Add 40 mL of dichloromethane to the reaction system for dilution, the organic phase was washed with 1 M hydrochloric acid (3×20 mL) and saturated sodium chloride solution (2×20 mL), and the organic phase was dried over anhydrous magnesium sulfate. Concentrate under reduced pressure to about 3 mL, add 40 mL of methanol to precipitate the polymer, filter, wash with methanol, and dry the product to constant weight to obtain a white solid poly ...

Embodiment 2

[0023] (1) Add chiral ligand A (Ar=Ph) 0.061 g, 0.1 mmol) and 2 mL toluene into the Schlenk reaction tube, and replace the air in the tube with nitrogen. Slowly add ZnEt dropwise at 0°C (ice-water bath) under nitrogen protection 2 (organometallic; 0.2 mL, 1.0 M, 0.2 mmol), and stirred at room temperature for 30 min. Then absolute ethanol (0.04 mL, 1 M, 0.04 mmol) was added, stirring was continued at room temperature for 15 min, then 2 mmol of cyclopentene oxide (1b) was added, carbon dioxide was bubbled, and the reaction was stirred at 30 °C for 36 h.

[0024] Add 40 mL of dichloromethane to the reaction system for dilution, the organic phase was washed with 1 M hydrochloric acid (3×20 mL) and saturated sodium chloride solution (2×20 mL), and the organic phase was dried over anhydrous magnesium sulfate. Concentrate under reduced pressure to about 3 mL, add 40 mL of methanol to precipitate the polymer, filter, wash with methanol, and dry the product to constant weight to obtai...

Embodiment 3

[0028] (1) Add chiral ligand A (Ar=Ph) 0.061 g, 0.1 mmol) and 2 mL toluene into the Schlenk reaction tube, and replace the air in the tube with nitrogen. Slowly add ZnEt dropwise at 0°C (ice-water bath) under nitrogen protection 2 (organometallic; 0.2 mL, 1.0 M, 0.2 mmol), and stirred at room temperature for 30 min. Then add absolute ethanol (0.04 mL, 1 M, 0.04 mmol), continue stirring at room temperature for 15 min, and then add 2 mmol of 4,4-dimethyl-3,5,8-trioxobicyclo[5.1.0 ] octane (1c), carbon dioxide bubbles, 30 ℃ stirring reaction for 36 h.

[0029] Add 40 mL of dichloromethane to the reaction system for dilution, the organic phase was washed with 1 M hydrochloric acid (3×20 mL) and saturated sodium chloride solution (2×20 mL), and the organic phase was dried over anhydrous magnesium sulfate. Concentrate under reduced pressure to about 3 mL, add 40 mL of methanol to precipitate the polymer, filter, wash with methanol, and dry the product to constant weight. 0.321 g ...

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Abstract

The invention discloses polycarbonate with optical activity and a preparation method thereof, and belongs to the technical field of polymer synthesis, wherein a repetitive unit of the polycarbonate has a formula as shown in the specification, wherein R1-R3 are -H or alkyl. The preparation method of the polycarbonate comprises the following steps: dispersing an epoxy compound and a catalyst into an organic solvent, and carrying out carbon dioxide bubbling reaction for 30-40 hours to obtain the polycarbonate; the epoxy compound has a formula as shown in the specification. The polycarbonate prepared by the preparation method disclosed by the invention has optical activity, number-average molecular weight of over 3000, a glass-transition temperature of over 150 DEG C, which can be as high as 272 DEG C, can be used as a high temperature-resistant polymer material and is applied to the field with a more harsh working environment. The preparation method disclosed by the invention can be carried out at the room temperature, is very low in pressure requirements of carbon dioxide, gentle in reaction conditions and high in optical selectivity; the prepared polycarbonate has extremely high optical purity, and a wide industrial popularization value.

Description

technical field [0001] The invention belongs to the technical field of macromolecule synthesis, and in particular relates to a class of optically active polycarbonates and a synthesis method thereof. Background technique [0002] Carbon dioxide is one of the final products of most energy release processes, including combustion and metabolic processes. As a carbon resource, the reserves of carbon dioxide on the earth are greater than the sum of natural gas, oil and coal. Since the Industrial Revolution, the amount of carbon dioxide in the atmosphere has skyrocketed. Although carbon dioxide is the raw material for photosynthesis of plants, the sharp increase of carbon dioxide not only destroys the natural carbon cycle, but also leads to the greenhouse effect, causing drastic changes in the global climate. Reducing the content of carbon dioxide in the atmosphere can reduce the greenhouse effect and help improve the environment. In view of the characteristics of stable, non-to...

Claims

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Application Information

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Patent Type & AuthorityApplications(China)
IPC IPC(8): C08G64/34
Inventor刘绍文任金霞华远照黄培进王敏灿王涵
Owner郑州裕昌建筑节能科技有限公司