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A reversible addition-fragmentation chain transfer agent, and preparation and applications thereof

A chain transfer reagent and addition-fragmentation technology, applied in organic chemistry and other fields, can solve problems such as the difficulty of purification restricting the large-scale use of RAFT polymerization, harsh preparation reaction conditions, and the influence of RAFT reagents, and achieve strong reversible addition-fragmentation capabilities , good control, low price effect

Active Publication Date: 2015-04-15
PETROCHINA CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, there is a problem of harsh preparation reaction conditions for highly active RAFT reagents. The most common dithioester RAFT reagents based on benzene rings are generally obtained through the Grignard reaction of halogenated benzenes. The yield is low and the stability is not high. Especially Its purification process is complicated, and it is usually separated by column chromatography
The purity of RAFT reagents has a great influence on the results of RAFT polymerization, and the difficulty of its purification greatly restricts the large-scale use of RAFT polymerization.

Method used

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  • A reversible addition-fragmentation chain transfer agent, and preparation and applications thereof
  • A reversible addition-fragmentation chain transfer agent, and preparation and applications thereof
  • A reversible addition-fragmentation chain transfer agent, and preparation and applications thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0020] At 0°C, add 6.2g of ethanethiol dropwise to the acetone suspension containing 8.0g of potassium hydride. After the dropwise addition, add 15.2g of carbon disulfide to the suspension. The molar ratio of the three components is 0.1 :0.2:0.2. Stir at 0°C for 0.5h. Then filter, wash the filter residue with acetone for 3 times, add acetonitrile to dissolve, filter, and obtain the filtrate to dry by rotary evaporation to obtain potassium ethyl trithiocarbonate.

[0021] Disperse 8.8 g of the obtained potassium ethyl trithiocarbonate in the ether solution, add dropwise 3.9 g of 2-chloro-2-phenylpropane, the molar ratio between the two is 0.05:0.025, at 10°C After stirring for 6 h, the obtained product was washed with water for 5 times, subjected to liquid separation treatment, and the organic solvent was removed to obtain cumyl ethyl trithiocarbonate with a yield of about 93%.

Embodiment 2

[0023] At 5°C, add 9.0g of butanethiol dropwise to the tetrahydrofuran suspension containing 6.0g of potassium hydride. After the addition is complete, add 15.2g of carbon disulfide to the suspension. The molar ratio of the three components is 0.1 :0.15:0.2. Stir at 5 °C for 1 h. Then it was filtered, and the filter residue was washed three times with tetrahydrofuran, dissolved in acetonitrile, filtered, and the obtained filtrate was dried by rotary evaporation to obtain butyl potassium trithiocarbonate.

[0024] Disperse 10.2 g of the obtained butyl potassium trithiocarbonate in an acetone solution, add dropwise 6.0 g of 2-bromo-2-phenylpropane, the molar ratio between the two is 0.05:0.03, and at 20°C After stirring for 4 hours, the obtained product was washed with water three times, subjected to liquid separation treatment, and the organic solvent was removed to obtain cumyl butyl trithiocarbonate with a yield of about 95%.

Embodiment 3

[0026] At 2°C, add 11.8g of hexanethiol dropwise to the suspension in tetrahydrofuran containing 3.0g of sodium hydride. After the addition is complete, add 11.4g of carbon disulfide to the suspension. The molar ratio of the three components is 0.1 :0.125:0.15. Stir at 2°C for 1.5h. Then filter, wash the filter residue three times with tetrahydrofuran, add acetonitrile to dissolve, filter, and obtain the filtrate by rotary evaporation and drying to obtain hexyl sodium trithiocarbonate.

[0027] Disperse 10.8 g of the obtained hexyl sodium trithiocarbonate in an acetone solution, add dropwise 5.4 g of 2-chloro-2-phenylpropane, the molar ratio between the two is 0.05:0.035, and stir at 50°C After 1 h, the obtained product was washed with water three times, subjected to liquid separation treatment, and the organic solvent was removed to obtain cumyl hexyl trithiocarbonate with a yield of about 90%.

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Abstract

The invention relates to preparation of a reversible addition-fragmentation chain transfer agent, and applications of the agent. The agent is cumyl alkyltrithiocarbonate having the following structure shown in the specification, wherein R is C2-12 n-alkyl. A preparation process of the agent includes: reacting n-alkyl thiol, sodium hydride or potassium hydride, and carbon disulfide to produce sodium alkyltrithiocarbonate or potassium alkyltrithiocarbonate; and reacting 2-chloro-2-phenylpropane or 2-bromo-2-phenylpropane with the sodium alkyltrithiocarbonate or the potassium alkyltrithiocarbonate to produce the cumyl alkyltrithiocarbonate that is the agent. The agent is simple in after-treatment and easy in purification, and has high addition-fragmentation capability in RAFT polymerization, and high reaction activity in RAFT polymerization. The agent can effectively control polymerization of a large scale of monomers, particularly monomers with high steric hindrance, and is rich in raw material source, low in cost, simple in process, short in period, free of special equipment, and easy in after-treatment.

Description

technical field [0001] The invention relates to a reversible addition fragmentation chain transfer reagent and its preparation and application, belonging to the field of living radical polymerization. Background technique [0002] Reversible addition-fragmentation chain transfer (RAFT) polymerization is one of the most widely used free radical living polymerization methods. Its biggest advantage is that it is suitable for a wide range of monomers. In addition to common monomers, acrylic acid, sodium p-vinylbenzenesulfonate , Aminoethyl methacrylate and other protic monomers as well as acid and basic monomers can be polymerized, which is very beneficial to the polymerization of ethylenic monomers containing special functional groups. This method does not require the use of expensive reagents such as 2,2,6,6-tetramethylpiperidine oxide, and does not lead to impurities or residual reagents (as in another living radical polymerization - atom transfer radical Transition metal io...

Claims

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Application Information

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IPC IPC(8): C08F2/38C07C329/00C08F112/08C08F120/06C08F120/14C08F220/14
Inventor 魏观为张东恒肖奇
Owner PETROCHINA CO LTD
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