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Atom transfer radical polymerization method based on liquid/liquid two-phase catalysis system

A catalytic system and atom transfer technology, applied in the field of catalytic polymerization, can solve the problems of time-consuming, labor-intensive, high-cost, and large-scale application limitations, and achieve the effects of reducing the residual amount of metal salts, easy operation, and strong designability.

Active Publication Date: 2014-11-19
SUZHOU UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Although different catalyst separation and recovery methods have their own advantages, they also have many defects and deficiencies.
For example, the vast majority of polymerizations are conventional ATRP, which requires strict and cumbersome oxygen removal steps, and the reuse of catalysts requires reactivation under an inert atmosphere. Almost all ATRP catalyst recovery methods use ligands (a few is the initiator) modification and post-modification, the cost is high and time-consuming and labor-intensive, these problems have limited the large-scale application of ATRP (see Y. Q. Shen, H. D. Tang, S. J. Ding, Prog. Polym. Sci. ,2004, 29: 1053–1078)

Method used

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  • Atom transfer radical polymerization method based on liquid/liquid two-phase catalysis system
  • Atom transfer radical polymerization method based on liquid/liquid two-phase catalysis system
  • Atom transfer radical polymerization method based on liquid/liquid two-phase catalysis system

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0043] Example 1: Polymerization of MMA based on a liquid / liquid two-phase catalytic system.

[0044] according to n 单体 :n 引发剂 :n 催化剂 :n 配体 :n 还原剂 =200:1:2:2:0.2 initial molar ratio, monomer MMA (1.0 mL, 9.44 mmol), initiator EBrPA (8.25 μL, 0.0472 mmol), reducing agent AIBN (1.55 mg, 9.44×10 -3 mmol) was added to 2 mL of toluene, the catalyst CuBr 2 (21.2 mg, 0.0944 mmol), the ligand TPMA (27.4 mg, 0.0944 mmol) was added to 2 mL of purified water, and the two phases of water and organic solvent were mixed in a clean 10 mL ampoule, which was directly sealed without deoxygenation operation. Tube. Then the ampoule was transferred to an oil bath at a set temperature (75°C) and rotating speed (1800 rpm) for polymerization, after a given time (24 h), it was taken out and placed in ice water to cool and separate, and then Dilute the upper organic phase with THF, pour it into a large amount of methanol for precipitation, filter it with suction, and dry it in vacuum to obtain ...

Embodiment 2

[0045] Example 2: Polymerization of MMA based on a liquid / liquid two-phase catalytic system.

[0046] according to n 单体 :n 引发剂 :n 催化剂 :n 配体 :n 还原剂 =100:1:1:1:0.1 initial molar ratio, the monomer MMA (0.5 mL, 4.72 mmol), the initiator EBrPA (16.5 μL, 0.0944 mmol), the reducing agent AIBN (1.55 mg, 9.44×10 -3 mmol) into 1 mL of toluene, the catalyst CuBr 2 (21.2 mg, 0.0944 mmol), the ligand TPMA (27.4 mg, 0.0944 mmol) was added to 3 mL of purified water, and the two phases of water and organic solvent were mixed in a clean 10 mL ampoule. Tube. Then the ampoule was transferred to an oil bath at a set temperature (90°C) and rotating speed (1600 rpm) for polymerization, after a given time (30 h), it was taken out and placed in ice water to cool and separate, and then Dilute the upper organic phase with THF, pour it into a large amount of methanol for precipitation, filter it with suction, and dry it in vacuum to obtain the desired polymer.

Embodiment 3

[0047] Example 3: Effects of Different Initiator Types on Liquid / Liquid Two-phase Catalytic ATRP.

[0048] For ATRP polymerization, especially the ATRP polymerization of oil-soluble monomers in the water phase, the ATRP initiator plays a very critical role, which can affect the initiation efficiency, polymerization rate and terminal functionalization degree of the polymer in the entire polymerization stage, etc. . For this purpose, we follow the method recorded in Example 1, intending to use different initiators such as ethyl 2-bromoisobutyrate (EBiB), ethyl α-bromophenylacetate (EBrPA), 2-bromopropionitrile (BPN), MPEG550-Br, etc. prepared a series of polymers in parallel to investigate the effect of several conventional ATRP initiators on the polymerization of MMA under the liquid / liquid two-phase catalytic system. The results are shown in Table 1 below.

[0049]

[0050] Aggregation condition: except [MMA] 0 :[MPEG550-Br] 0 =100:1 other than [MMA] 0 :[Initiator] 0 :...

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Abstract

The invention discloses an atom transfer radical polymerization method based on a liquid / liquid two-phase catalysis system. The method comprises the following steps: mixing a monomer, an initiator, a catalyst, a ligand and a reducing agent respectively dissolved in water and an organic solvent, a polymerization is carried out for 12-60 hours under temperature of 60-90 DEG C and rotating speed of 1500-2000rpm; separating two phases after reaction is completed, the organic phase is dumped into methanol for deposition, pumping filtration and drying to obtain a required polymer; the monomer, the initiator and the reducing agent are added in the water phase, and then next polymerization is carried out. According to the invention, under existence of limit oxygen, any modification on the ligand is not required, high efficiency separation and recovery of ATRP and a transition-metal catalyst can be successfully realized by stirring mass transfer of diffusion in a simple mode, operation is simple, designability is strong, cost is low, labor saving and time saving are realized, and the invention provides a novel method for removing an ATRP catalyst in a simpleness, economy, high efficiency and environmental protection mode.

Description

technical field [0001] The invention belongs to the technical field of catalytic polymerization, and in particular relates to an atom transfer radical polymerization method carried out in a liquid / liquid two-phase system and capable of efficiently recovering and recycling a catalyst. Background technique [0002] Atom Transfer Radical Polymerization (ATRP) is a powerful "living" / controllable radical polymerization method, which can precisely design the macrostructure and microstructure of polymers. Since it was proposed in the 1990s, it has attracted great attention in academia and industry (see K. Matyjaszewski, J. Xia, Chem. Rev., 2001, 101: 2921-2990 and M. Kamigaito, T. Ando, ​​M. Sawamoto, Chem. Rev., 2001, 101: 3689-3746). Although ATRP can synthesize polymers with controllable molecular weight and narrow molecular weight distribution, it must use a large amount of transition metal salts as catalysts in order to regulate the growth process of polymerization. Thus, ...

Claims

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Application Information

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IPC IPC(8): C08F120/14C08F112/08C08F2/12C08F2/18C08F4/10
Inventor 程振平丁明强彭荩影姜孝武张丽芬朱秀林
Owner SUZHOU UNIV
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