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Acetylacetone manganese-initiated RAFT (reversible addition fragmentation chain transfer) polymerization method

A technology of manganese acetylacetonate and RAFT, applied in the field of RAFT polymerization initiated by manganese acetylacetonate, can solve the problems of low conversion rate, high polymerization temperature, poor molecular weight controllability and the like

Active Publication Date: 2015-06-17
ZHEJIANG KELI NEW MATERIAL TECH CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

For example, at higher temperatures (60°C or 80°C), Mn(acac) 3 Under the condition of cooperating with RX, the control of the molecular weight of PMMA polymer is realized, but the molecular weight distribution is wide, M w / M n Between 2.0 and 3.0 (K.Endo and A.Yachi, Polym.J., 2002, 34, 320); at 80°C, Mn(acac) 3 Combined with BzBr, the molecular weight of PSt polymer can also be controlled, but the conversion rate is lower than 60%, M w / M n Between 2.0 and 3.0 (K. Endo and A. Yachi, Polym. Bull. 2001, 46, 363)
The above acetylacetonate (Mt(acac) x ) The polymerization reaction initiated by ) has poor control over the molecular weight, and the polymerization temperature is high
So far, acetylacetonate (Mt(acac) x ) has not been reported as an initiator of RAFT polymerization, and the initiation of polymerization at low temperature (room temperature) has not been reported

Method used

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  • Acetylacetone manganese-initiated RAFT (reversible addition fragmentation chain transfer) polymerization method
  • Acetylacetone manganese-initiated RAFT (reversible addition fragmentation chain transfer) polymerization method
  • Acetylacetone manganese-initiated RAFT (reversible addition fragmentation chain transfer) polymerization method

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0038] Embodiment one Mn (acac) 3 Under the combined action of / MECTP, the bulk synthesis of polyvinyl acetate (PVAc)

[0039] By ratio [VAc] 0 :[MECTP] 0 :[Mn(acac) 3 ] 0 =200:(0,0.5,1,2):(0,0.05,0.1,0.2,1,4), add Mn(acac) in turn 3 , VAc (1.0mL) and MECTP in a 5mL ampoule bottle, add a stirrer, and seal the tube in an oxygen-free atmosphere after 6 standard freeze-pump-thaw-aeration cycles. The sealed ampoules were placed in an RCT basic S25 magnetic stirrer (80° C.) of IKA company for a predetermined time, and the rotation speed was 900 rpm. After the reaction, take out the sealed tube, open the sealed tube, dissolve with 2-5 mL of tetrahydrofuran, pour it into 250 mL of n-hexane, put it overnight, filter it with suction, and dry it to obtain PVAc.

[0040] The data in the 1st to 3rd rows in Table 1 are [MECTP] in Example 1 0 :[Mn(acac) 3 ] 0 Aggregation results when =1:0.05 and 1:0.1; the data in the 8th to 11th rows are respectively without Mn(acac) 3 or the agg...

Embodiment 2

[0046] Embodiment 2 Under the combined action of AIBN / MECTP, the bulk synthesis of PVAc

[0047] By ratio [VAc] 0 :[MECTP] 0 :[AIBN] 0 =200:1:(0.05,0.1,0.2,1,4), add AIBN, VAc (1.0mL) and MECTP into a 5mL ampoule in turn, add a stirrer, and go through 6 times of standard freezing-pumping-thawing After the gassing cycle, the tube was sealed in an oxygen-free atmosphere. The sealed ampoules were placed in an RCT basic S25 magnetic stirrer (80° C.) of IKA company for a predetermined time, and the rotation speed was 900 rpm. After the reaction, take out the sealed tube, open the sealed tube, dissolve with 2-5 mL of tetrahydrofuran, pour it into 250 mL of n-hexane, put it overnight, filter it with suction, and dry it to obtain PVAc.

[0048] The data in rows 4 to 7 in Table 1 are [MECTP] in Example 2 0 :[AIBN] 0 Aggregation results of VAc at =1:0.05 and 1:0.1.

[0049] Figure 5 It is the kinetic diagram of the controllable radical polymerization reaction of VAc monomer und...

Embodiment 3

[0055] Embodiment three Mn (acac) 3 Synthesis of polymethyl methacrylate (PMMA) under the combined action of / CPDN

[0056] By ratio [MMA] 0 :[CPDN] 0 :[Mn(acac) 3 ] 0 =200:(0,0.5,1,2):(0,0.5,1,2), add Mn(acac) in turn 3 , CPDN, ​​MMA (1.0mL) and solvent (0.5mL dimethyl sulfoxide (DMSO), N,N-dimethylformamide (DMF), toluene or bulk) in a 5mL ampoule bottle, add a stirring bar, pass through After 6 standard freeze-pump-thaw gassing cycles, the tubes were sealed in an oxygen-free atmosphere. The sealed ampoules were placed in a magnetic water bath at a constant temperature (25°C) for a predetermined time to react. After the reaction, take out the sealed tube, open the sealed tube, dissolve with 2-5 mL of tetrahydrofuran, pour it into 250 mL of methanol, put it overnight, filter it with suction, and dry it to obtain PMMA.

[0057] The data in the 1st, 3rd and 4th rows in Table 2 are that DMSO is used as the solvent in Example 3, and Mn (acac) is not added. 3 or the polyme...

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Abstract

The invention discloses an acetylacetone manganese-initiated RAFT (reversible addition fragmentation chain transfer) polymerization method which comprises the following steps of: preparing a bulk polymerization reaction system comprising a vinyl monomer, an initiator and a chain transfer agent or a solution polymerization reaction system comprising a vinyl monomer, an initiator, a chain transfer agent and a solvent; and performing a polymerization reaction at 25-100 DEG C to obtain a polymer, wherein the molar ratio of the vinyl monomer to the initiator to the chain transfer agent is 200:(0.2-4):(0.5-2), the molar ratio of the vinyl monomer to the solvent is (0.5-3):1, and the initiator is acetylacetone manganese. The method disclosed by the invention adopts acetylacetone manganese as an RAFT polymerization initiator for the first time, is suitable for a wide range of monomers, and is effective to methacrylates, vinyl acetates and styrene monomers; the temperature application range is wider, and the application universality is enhanced; and as an initiator, the acetylacetone manganese can realize a higher end group functional degree of the tail end of the polymer.

Description

technical field [0001] The invention belongs to the technical field of polymer synthesis, relates to a method for reversible addition-fragmentation chain transfer polymerization (Reversible Addition Fragmentation chain Transfer polymerization, RAFT for short), in particular to a manganese acetylacetonate (Mn(acac) 3 ) initiated RAFT polymerization method. Background technique [0002] Over the past few decades, there has been a growing interest in polymer engineering. For the synthesis of novel polymeric materials with well-defined molecular parameters, controlled radical polymerization is a suitable method due to its mild reaction conditions and certain water resistance. At present, nitroxide-mediated polymerization (NMP), Atom Transfer Radical Polymerization (ATRP) and RAFT polymerization are the most popular and polymerizable monomers. Controlled free radical polymerization method. Among them, RAFT polymerization is usually carried out under the action of traditional f...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C08F118/08C08F120/14C08F112/08C08F2/38C08F4/80
Inventor 张正彪王文香朱秀林周媛周年琛朱健程振平
Owner ZHEJIANG KELI NEW MATERIAL TECH CO LTD
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