Controlling Molecular Weight Distributions through Photoinduced Flow Polymerization

Corrigan, Nathaniel; Almasri, Abdulrahman; Taillades, Werner; Xu, Jiangtao; Boyer, Cyrille

doi:10.1021/acs.macromol.7b01890

Cited by 144 publications

(147 citation statements)

References 78 publications

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“…Although PET‐RAFT polymerization has been demonstrated to exhibit remarkable oxygen tolerance, its application in SUMI process has not yet been confirmed. By using a handmade continuous flow reaction system based on our previous experience, a series of discrete oligomers with up to five monomer units (Scheme ) were synthesized through sequential and alternating insertions of N ‐phenyl maleimide (PMI)/indene (Ind) monomers to a trithiocarbonate RAFT agent. The purification after each monomer insertion involves an automated flash chromatography, which provides high isolation efficiency and effectively reduces the total production time.…”

Section: Introductionsupporting

confidence: 82%

Upscaling single unit monomer insertion to synthesize discrete oligomers

Huang

Corrigan

Lin

et al. 2019

J. Polym. Sci. Part A: Polym. Chem.

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As one of the emerging techniques for preparing discrete oligomers, the photo‐RAFT single unit monomer insertion (SUMI) process has shown its uniqueness and superiority in the control of both monomer sequence and stereochemistry. However, current precision polymer synthesis techniques are still burdened by the scalability challenges, such as low reaction yields, small product quantities, and long production times. Herein, we successfully established a practical protocol to address scalability problems in the photo‐RAFT SUMI processes. A series of discrete oligomers containing up to five monomer units were synthesized in batch and flow reactors by sequential and alternating SUMI of two monomers into a trithiocarbonate RAFT agent under mild reaction conditions and purified by automated flash chromatography. This protocol offers the process with large quantity (grams scale), excellent isolated yields (82%–95% for each step and 59% for five iterations), and short production time (several days for a pentamer). © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 1947–1955

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Section: Introductionsupporting

confidence: 82%

Upscaling single unit monomer insertion to synthesize discrete oligomers

Huang

Corrigan

Lin

et al. 2019

J. Polym. Sci. Part A: Polym. Chem.

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“…[7][8][9][10][11][12] However,p olymers with large values are occasionally desired for improved physical properties such as miscibility and processability,a nd the manipulation of in LRP is an important topic but still challenging. [23,24] However, the pumpassisted method is always inapplicable to heterogeneous systems,s uch as polymer brush synthesis from solid substrates,a nd thus limits applications.We have developed an organocatalyzed LRP,t hat is, reversible complexation mediated polymerization (RCMP) that uses alkyl iodides (RÀI) as dormant species and organic catalysts such as Bu 4 N + I À (BNI;s ee Scheme S1 in the Supporting Information). [13][14][15] Thep olymers need to be prepared in multiple independent runs,a nd the blended polymers often have multimodal molecular weight distribution.…”

mentioning

confidence: 99%

“…[13][14][15] Thep olymers need to be prepared in multiple independent runs,a nd the blended polymers often have multimodal molecular weight distribution. [23,24] However, the pumpassisted method is always inapplicable to heterogeneous systems,s uch as polymer brush synthesis from solid substrates,a nd thus limits applications. [16][17][18] However,t he attained large usually arose from inefficient control in LRP.…”

mentioning

confidence: 99%

Polymer Dispersity Control by Organocatalyzed Living Radical Polymerization

2019

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Molecular weight distribution of polymers,t ermed dispersity (), is af undamental parameter for determining polymer material properties.T his paper reports an ovel approach for controlling by exploiting at emperatureselective radical generation in organocatalyzed living radical polymerization. The polymers with tailored were synthesized in ab atch system without the assistance of an external pump.Aunique aspect of this approach is that was tuneable from 1.11 to 1.50 in any segment in diblock, triblock, and multiblock copolymers and in any form of star and brush polymer without segmental or topological restriction. This approach is amenable to various monomers and free from metals and thus attractive for applications.T he approach also generated polymer brushes on surfaces with tailored .A n interesting finding was that the polymer brushes exhibited unique interaction with external molecules,d epending on the value.Molecular weight distribution of polymers,t ermed dispersity ( = M w /M n ), is afundamental parameter in determining polymer properties such as processability,viscoelasticity,and self-assembly behaviors,w here M w and M n are the weightand number-average molecular weights,r espectively. [1][2][3][4][5][6] Living radical polymerization (LRP) facilitates the synthesis of polymers with small values,a sw ell as pre-determined molecular weights and sophisticated architectures. [7][8][9][10][11][12] However,p olymers with large values are occasionally desired for improved physical properties such as miscibility and processability,a nd the manipulation of in LRP is an important topic but still challenging. Several approaches have been developed to manipulate values.Blending polymers with different molecular weights is often applied. [13][14][15] Thep olymers need to be prepared in multiple independent runs,a nd the blended polymers often have multimodal molecular weight distribution. By optimizing the polymerization conditions such as catalyst loadings, initiators,temperatures,and additional chain-transfer agents, the was modulated at 1.1-2.0 in LRP. [16][17][18] However,t he attained large usually arose from inefficient control in LRP. Thus,t he obtained polymers hardly undergo further chain extension. Recently,F ors et al. elegantly varied and molecular weight distribution "shapes" by metering the addition of an initiator using af eeding pump in anionic and nitroxide-mediated polymerizations. [19][20][21][22] This approach was applied to homopolymers and the first segment of block copolymers but not to the other segments of block copolymers.B oyer et al. recently metered the addition of the polymeric initiator (macro-initiator) in ap hotocontrolled LRP and successfully obtained block copolymers with tailored in the second segment. [23,24] However, the pumpassisted method is always inapplicable to heterogeneous systems,s uch as polymer brush synthesis from solid substrates,a nd thus limits applications.We have developed an organocatalyzed LRP,t hat is, reversible complexation mediated polymerization (RCMP) t...

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“…Thed iscrete oligo(methyl acrylate)s are expected to behave substantially differently from their disperse high-molecular-weight polymeric counterparts,o wing to being monodisperse,b ut mostly also to not having reached the length yet that is required to form ideal polymer coils.T he transition between oligomers and polymers is not precisely defined, but the general consensus is that this point is located around 50 to 100 monomer units when chains switch from ap ure Rouse motion towards more reptation-like behavior according to the Edwards tube model in polymer melts. [18,19] Furthermore,artificial distributions can potentially be used to encode information in as imple fashion in ab arcode-like manner. [17] With discrete oligomers at hand it is also possible to create precisely defined artificial oligomer distributions.T he design of tailored molecular weight distributions (MWD) has found substantial interest over the years as the MWD governs the resulting thermal and mechanical properties.…”

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confidence: 99%

Deconstructing Oligomer Distributions: Discrete Species and Artificial Distributions

et al. 2019

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The separation of an oligo(methyl acrylate) distribution, obtained from reversible addition-fragmentation chain transfer (RAFT) polymerization, in ad iscrete (dispersity = 1) oligomeric library (degree of polymerization between 1a nd 22) is presented. The properties of this library in terms of diffusivity,g lass transition temperature,a nd viscosity are determined, filling as ignificant knowledge gap associated with these materials.T he obtained oligomer library is used to construct artificial oligomer distributions on demand. These artificial oligomer distributions are used to highlight the potential to tailor physical properties of am aterial, while concomitantly demonstrating the limitations associated with size-exclusion chromatography analysis of molecular weight and dispersity in particular.Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.

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Controlling Molecular Weight Distributions through Photoinduced Flow Polymerization

Cited by 144 publications

References 78 publications

Upscaling single unit monomer insertion to synthesize discrete oligomers

Upscaling single unit monomer insertion to synthesize discrete oligomers

Polymer Dispersity Control by Organocatalyzed Living Radical Polymerization

Deconstructing Oligomer Distributions: Discrete Species and Artificial Distributions

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