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Atom transition free radical polymerization initiation system under supercritical state

An initiation system and polymerization initiation technology, applied in the production of bulk chemicals, etc., can solve the problems of difficult recycling of catalysts, high treatment costs, toxicity of amine ligands, etc., and achieve the effect of eliminating the post-treatment process

Inactive Publication Date: 2007-09-12
HANGZHOU NORMAL UNIVERSITY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Using organic solvents as the medium will pollute the environment, and the added amine ligands are toxic
After the polymerization of small molecular ligand catalysts of transition metals, the catalysts can only be separated after cumbersome treatment. The treatment costs are too high, and the catalysts are difficult to recycle.

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0015] Example 1: Supercritical CO 2 Atom transfer radical polymerization (ATRP) of methacrylate (MMA) in the system

[0016] Take by weighing 18.80g (188mmol) MMA methyl methacrylate monomer, after passing nitrogen to remove oxygen, weigh 1.400g (1.88mmol) triphenylphosphine nickel bromide catalyst, add in MMA to heat, stir, continue passing nitrogen to remove Oxygen, seal, keep the temperature at 75°C for 20 minutes, inject 277μL (1.88mmol) of the initiator α-bromoisobutyrate ethyl ester, replace it with carbon dioxide three times, press into the carbon dioxide, set the pressure to 24-26MPa, and the temperature at 75~80℃. React for 1 hour, cool to room temperature, slowly depressurize and discharge carbon dioxide, and then extract three times with supercritical carbon dioxide to obtain powdery white solid polymethyl methacrylate, PMMA. Mn = 13998, PDI = 1.09.

Embodiment 2

[0017] Example 2: Supercritical CO 2 Atom Transfer Radical Polymerization of Methyl Methacrylate (MMA) Catalyzed by Ferrous Chloride in System

[0018] Weigh 18.80 g (188 mmol) of methyl methacrylate, and pass nitrogen to remove oxygen. Add 0.048g (0.376mmol) of ferrous chloride and 0.227g (0.752mmol) of triphenylphosphorus, continue to pass nitrogen to remove oxygen, heat and stir to raise the temperature to 80°C until ferrous chloride and triphenylphosphorus are dissolved , adding the solution to supercritical CO 2 The reactor was kept at 80° C. for half an hour, and the pressure was controlled at 24-26 MPa. 55.3 μL (0.376 mmol) of ethyl α-bromoisobutyrate was injected and reacted for 1 hour. Cool to room temperature, slowly depressurize and release CO 2 , then supercritical CO 2 Extracted three times to obtain polymethyl methacrylate, Mn=132600, PDI=1.41.

Embodiment 3

[0019] Example 3: Supercritical CO 2 Cuprous Bromide Catalyzed Atom Transfer Radical Polymerization of Methyl Methacrylate (MMA) in the System

[0020] Weigh 18.80 g (188 mmol) of methyl methacrylate, and pass nitrogen to remove oxygen. Add 0.054g (0.376mmol) of cuprous bromide and 0.114g (0.376mmol) of triphenylphosphorus, continue to pass through nitrogen to remove oxygen, heat and stir to raise the temperature to 50°C until cuprous bromide and triphenylphosphorus are dissolved , adding the solution to supercritical CO 2 The reactor was kept at 50° C. for half an hour, and the pressure was controlled at 30-32 MPa. 55.3 μL (0.376 mmol) of ethyl α-bromoisobutyrate was injected and reacted for 2 hours. Cool to room temperature, slowly depressurize and release CO 2 , then supercritical CO 2 Extracted three times to obtain polymethyl methacrylate, Mn=61600, PDI=1.37.

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PUM

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Abstract

This invention relates to a new atom group transfer radical polymerization initiating system taking the supercritical CO2 as polymerization medium. The problem it needs to solve is to provide an initiating system which mineral salt catalyst solubility is adjustable, medium is cheap, non-polluting, safe, and product polymerization is easy for purification. The general formula is SCF-CO2 / RX / MXn / L, in which, SCF- CO2 is supercritical carbon dioxide, RX is a initiator of alpha-bromoisobutyrate ethyl, MXn is catalyst- transition metal salt, and L is the ligand of triphenylphosphine. The molar ratio of RX, MXn and L is 1:0.33~1:0.66~ 2.

Description

technical field [0001] The invention relates to the field of organic chemistry, specifically a supercritical CO 2 A new atomic group transfer radical polymerization initiation system as a polymerization medium, suitable for preparing polymers such as polymethyl methacrylate. Background technique [0002] In 1995, Wang Jinshan (J.Am.chem.Sot., 1995, 117, 5614) reported for the first time in the atomic group transfer radical polymerization (abbreviated ATRP) initiation system that the alkyl halide hydrocarbon R-X was used as the initiator. Wherein X is Cl, Br, and R is an organic group with conjugation inducing effect. In the first-generation ATRP initiation system, CuX and organic ligands were mainly used as catalysts; Anbo and Granel (Macromolecules, 1996, 29: 8576, 1074) used Ru and Ni complexes such as RuCl 2 (PPh) 3 / Al(OR) 3 , Ni(NCN)Br, Ni[O, 0'(CH 2 NMe 2 ) 2 C 6 H] Br is the catalyst and the alkyl halide hydrocarbon initiator together constitutes the ATRP init...

Claims

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Application Information

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IPC IPC(8): C08F4/44C08F4/70C08F2/00C08F20/14
CPCY02P20/54
Inventor 来国桥陈利民蒋剑雄邱化玉罗蒙贤
Owner HANGZHOU NORMAL UNIVERSITY
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