Radical Addition-Coupling Polymerization (RACP) toward Periodic Copolymers

Zhang, Chengyu; Ling, Jun; Wang, Qi

doi:10.1021/ma201843n

Cited by 47 publications

(44 citation statements)

References 30 publications

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“…The basic Monte Carlo algorithm applied in this work is the same as reported except a slight modification described as follows. In every “elemental reaction,” known as a single Monte Carlo step, an active free radical is randomly selected to carry out propagation (with a monomer), chain transfer (with a further randomly selected CTA) or termination (with another randomly selected active radical) according to the reaction probabilities calculated by the set of Equations (1),

\begin{matrix} true \\ left P_{p} = \frac{N (normalM)}{N (M) + C_{tr} \cdot N (Z) + C_{term} \cdot N (R)} \\ left P_{tr} = \frac{C_{tr} \cdot N (Z)}{N (M) + C_{tr} \cdot N (Z) + C_{term} \cdot N (R)} \\ left P_{term} = \frac{C_{term} \cdot N (R)}{N (M) + C_{tr} \cdot N (Z) + C_{term} \cdot N (R)} \\ left C_{tr} = \frac{k_{tr}}{k_{p}} \\ left C_{term} = \frac{k_{term}}{k_{p}} \end{matrix}

where P , N , k , M, Z, and R stand for reaction probability, species amount, reaction rate constant, monomer, CTA and active radical, respectively.…”

Section: Resultsmentioning

confidence: 99%

Revival of the R‐Group Approach: A “CTA‐shuttled” Grafting from Approach for Well‐Defined Cylindrical Polymer Brushes via RAFT Polymerization

Zheng

Ling

Müller

2013

Macromol. Rapid Commun.

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The synthesis of well-defined cylindrical polymer brushes (CPBs) from a linear polymer backbone with a high density of RAFT functionalities ("grafting from" approach) is challenging when the chain transfer agent (CTA) is attached to the backbone via its R-group. It is proposed that the difficulties of the R-group approach in controlling the grafting polymerization are induced by the "entrapment" of active free radicals within individual growing CPBs. A facile "CTA-shuttled" R-group approach overcoming this entrapment effect is developed, and used to synthesize well-defined CPBs with polystyrene or poly(tert-butyl acrylate) branches and core-shell CPBs with polystyrene-block-poly(N-isopropylacrylamide) branches. The polydispersity index (PDI = 1.23) of the obtained CPBs with polystyrene branches is much lower than that from the conventional R-group approach (PDI = 2.18). Monte Carlo simulations confirm that the advantage of the "CTA-shuttled" R-group approach consists in the release of the active radicals from the trapping CPB systems.

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\begin{matrix} true \\ left P_{p} = \frac{N (normalM)}{N (M) + C_{tr} \cdot N (Z) + C_{term} \cdot N (R)} \\ left P_{tr} = \frac{C_{tr} \cdot N (Z)}{N (M) + C_{tr} \cdot N (Z) + C_{term} \cdot N (R)} \\ left P_{term} = \frac{C_{term} \cdot N (R)}{N (M) + C_{tr} \cdot N (Z) + C_{term} \cdot N (R)} \\ left C_{tr} = \frac{k_{tr}}{k_{p}} \\ left C_{term} = \frac{k_{term}}{k_{p}} \end{matrix}

where P , N , k , M, Z, and R stand for reaction probability, species amount, reaction rate constant, monomer, CTA and active radical, respectively.…”

Section: Resultsmentioning

confidence: 99%

Revival of the R‐Group Approach: A “CTA‐shuttled” Grafting from Approach for Well‐Defined Cylindrical Polymer Brushes via RAFT Polymerization

Zheng

Ling

Müller

2013

Macromol. Rapid Commun.

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“…As an alternative of ATRC, to suppress the existing side reactions, the polymerizations of SMMS and SAAS were further carried out in the presence of MNP as a spin trap agent . The two MSUs can both be polymerized successfully, and two polymers (P(SMMS‐NO) and P(SAAS‐NO)) with lower PDIs were obtained (Figure , Figure S25, S26, Supporting Information).…”

Section: Resultsmentioning

confidence: 99%

Combination of ATRA and ATRC for the Synthesis of Periodic Vinyl Copolymers

Wang

Song

Deng

et al. 2013

Macromol. Rapid Commun.

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A new approach to periodic vinyl copolymers via combination of atom transfer radical addition (ATRA) and atom transfer radical coupling (ATRC) is reported. The two examples are methyl methacrylate (MMA) and styrene (St) periodic copolymer (P(SMMS)) and acrylonitrile (AN) and St periodic copolymer (P(SAAS)). First, two monomer sequence units (MSU) with built-in sequence, SMMS and SAAS, are synthesized through the controlled ATRA of two ATRP initiators with St. Then, the ATRC of SMMS and SAAS are conducted at high radical conditions to generate two types of high-molecular-weight copolymers, P(SMMS) and P(SAAS). Though side reactions can not be totally avoided, characterizations of the polymer structure with a variety of means confirm that the main chain structures of P(SMMS) and (PSAAS) are predominantly with the periodic sequences from the MSUs. Attempts to suppress the side reactions are successful via the MNP-mediated ATRC of SMMS and SAAS.

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“…Wang and coworkers [30,31] reported a special strategy which utilized radical addition-coupling polymerization. As shown in Figure 5, ,-dibromo compound reacted with equivalent nitroso through two elementary steps, e.g., the addition of carbon-centered radical generated by copper catalyst to nitroso and the subsequent coupling between the resulting nitroxy radical and another carbon-centered radical.…”

Section: Figurementioning

confidence: 99%

Recent developments in the synthesis of sequence controlled polymers

2015

Sci. China Chem.

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Radical Addition-Coupling Polymerization (RACP) toward Periodic Copolymers

Abstract: We synthesize periodic copolymers possessing [ABAC], [ABCD], and [ABCDBCAD] repeating structure by radical addition-coupling polymerization (RACP) based on the reaction between α,ω-biradicals derived from α,α 0 -dibromo compound and 2-methyl-2-nitrosopropane.

Cited by 47 publications

References 30 publications

Revival of the R‐Group Approach: A “CTA‐shuttled” Grafting from Approach for Well‐Defined Cylindrical Polymer Brushes via RAFT Polymerization

Revival of the R‐Group Approach: A “CTA‐shuttled” Grafting from Approach for Well‐Defined Cylindrical Polymer Brushes via RAFT Polymerization

Combination of ATRA and ATRC for the Synthesis of Periodic Vinyl Copolymers

Recent developments in the synthesis of sequence controlled polymers

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