Macromolecular Chain Transfer Agent Research Articles

Differences between ab initio emulsion and miniemulsion polymerization of styrene mediated by an alkenyl-functionalized amphiphilic RAFT agent

An alkenyl (butene)-functionalized amphiphilic macromolecular reversible addition fragmentation chain transfer (macro-RAFT) agent was designed as both surfactant and polymerization mediator for ab initio emulsion and miniemulsion polymerization of styrene (St), intending to synthesize polymer nanoparticles with alkenyl-enriched surfaces. However, the pendent alkenyl units exhibited unexpectedly higher reactivity in ab initio emulsion polymerization than they did in solution polymerization. Their copolymerization with St resulted in depletion of alkenyl groups, positive deviation of molecular weights, broad molecular weight distributions, and limiting conversions. Miniemulsion polymerization was superior to ab initio emulsion polymerization in its ability to prepare alkenyl-functionalized nanoparticles. Consumption of alkenyl groups happened, but only within the nucleation period. In spite of positive deviation of molecular weights and broad molecular weight distributions, the final particles were characteristics of alkenyl functionalities confined to the particle surfaces. Thus, PSt nanoparticles with alkenyl-enriched surface were obtained via miniemulsion polymerization.

Synthesis of Film-Forming Photoactive Latex Particles by Emulsion Polymerization-Induced Self-Assembly to Produce Singlet Oxygen.

The design of photoactive polymer substrates producing singlet oxygen under visible light irradiation has great technological potential. Aqueous dispersion of novel photoactive core-shell particles was synthesized by surfactant-free reversible addition-fragmentation chain transfer (RAFT) emulsion polymerization of n-butyl acrylate. The surface of the nanoparticles is directly decorated thanks to the polymerization-induced self-assembly process using a hydrophilic macromolecular chain transfer agent (macro-CTA) functionalized with the organic photosensitizer. The macro-CTA was synthesized by statistical copolymerization of acrylic acid and 2-Rose Bengal ethyl acrylate (RBEA) at 80 °C mediated with 4-cyano-4-[(dodecylsulfanylthiocarbonyl)sulfanyl]pentanoic acid. Monitoring polymerization kinetics of RAFT polymerization highlights that increasing amount of RBEA induces retardation, still more pronounced when using the vinylbenzyl Rose Bengal comonomer. The present work provides insight into the quantum yield of singlet oxygen production in water (ΦΔ = 0.2-0.6) for the three types of synthesized polymers (hydrophilic polymer, latex particles, and polymer film). The photoactive core-shell latex particles enabled the easy preparation of photoactive polymer film by simple casting.

Polymer Side-Chain Conjugates를 위한 전구체인 Polydiacetone Acrylamide

Polydiacetone acrylamide (PDAAM), a reactive polymer containing pendant ketone groups was synthesized via reversible addition-fragmentation chain transfer (RAFT) polymerization. Kinetic studies indicated a well-controlled behavior of this RAFT polymerization. The characteristics of this RAFT polymerization was also confirmed by a wellcontrolled chain-extending RAFT polymerization using the above-synthesized PDAAM as a macromolecular chain transfer agent. Acid-catalyzed ketalization of PDAAM with trimethylol propane (TMP) was carried out to obtain the polymer containing pendant cyclic ketal groups and hydroxyl groups, PDAAM-TMP. PCL was grafted from PDAAM-TMP by ring-opening polymerization (ROP) in the presence of tin 2-ethylhexanoate as a catalyst to obtain graft copolymer. Basecatalyzed aldol condensation of PDAAM with benzaldehyde was also used to obtain poly[N-(1,1-dimethyl-3-oxo-5-phenyl-pent-4-enyl)-acrylamide] (PDMOPPEAM) having cinnamoyl groups, and the photoreactivity of polymer with cinnamoyl group was studied by UV-visible and IR absorption spectroscopy. Both of these two polymers prepared from PDAAM were characterized by FTIR and 1H NMR spectroscopy. PDAAM can be a multifunctional platform that can undergo further polymerization by ketalization and aldol condensation.

Topology Affecting Block Copolymer Nanoassemblies: Linear Block Copolymers versus Star Block Copolymers under PISA Conditions

Linear and star block copolymer (BCP) nanoassemblies of [poly(4-vinylpyridine)-block-polystyrene]n ([P4VP-b-PS]n) with different arm numbers have been synthesized by RAFT dispersion polymerization under formulation of polymerization-induced self-assembly (PISA). All RAFT dispersion polymerizations employing mono- and multifunctional macromolecular chain transfer agents proceed with similar polymerization kinetics. The size and/or morphology of [P4VP-b-PS]n nanoassemblies are firmly correlative to arm number n, and star [P4VP-b-PS]n BCPs have more complex morphology than the linear counterpart. Several interesting morphologies of star BCPs including small-sized vesicles and porous nanospheres have been synthesized, and they are compared with those of the linear counterpart. Our research indicates that topology is a significant parameter to dedicate the size and morphology of star BCP nanoassemblies under PISA conditions.

Reactive Polymorphic Nanoparticles: Preparation via Polymerization‐Induced Self‐Assembly and Postsynthesis Thiol–para‐Fluoro Core Modification

The use of 2,3,4,5,6-pentafluorobenzyl methacrylate (PFBMA) as a core-forming monomer in ethanolic reversible addition-fragmentation chain transfer dispersion polymerization formulations is presented. Poly[poly(ethylene glycol) methyl ether methacrylate] (pPEGMA) macromolecular chain transfer agents were chain-extended with PFBMA leading to nanoparticle formation via polymerization-induced self-assembly (PISA). pPEGMA-pPFBMA particles exhibited the full range of morphologies (spheres, worms, and vesicles), including pure and mixed phases. Worm phases formed gels that underwent a thermo-reversible degelation and morphological transition to spheres (or spheres and vesicles) upon heating. Postsynthesis, the pPFBMA cores were modified through thiol-para-fluoro substitution reactions in ethanol using 1,8-diazabicyclo[5.4.0]undec-7-ene as the base. For monothiols, conversions were 64% (1-octanethiol) and 94% (benzyl mercaptan). Spherical and worm-shaped nano-objects were core cross-linked using 1,8-octanedithiol, which prevented their dissociation in nonselective solvents. For a temperature-responsive worm sample, cross-linking additionally resulted in the loss of the temperature-triggered morphological transition. The use of the reactive monomer PFBMA in PISA formulations presents a simple method to prepare well-defined nano-objects similar to those produced with nonreactive monomers (e.g., benzyl methacrylate) and to retain morphologies independent of solvent and temperature.

CO2 -Breathing Polymer Assemblies via One-Pot Sequential RAFT Dispersion Polymerization.

ABC triblock copolymer assemblies with reversible "breathing" behaviors based on poly[oligo(ethylene glycol) methyl ether methacrylate]-b-poly(benzyl methacrylate)-b-poly[2-(diethylamino)ethyl methacrylate] (POEGMA-b-PBnMA-b-PDEA) are fabricated via one-pot sequential reverisble addition-fragmentation chain transfer dispersion polymerization. Using a POEGMA as the macromolecular chain transfer agent, chain extension with BnMA and DEA is conducted in ethanol, where PBnMA acts as the core-forming block, and the PDEA block endows the solvophilicity and CO2 -responsiveness. With the increment of the DP of PBnMA, the morphology of the assemblies evolves from spheres to worms, and to vesicles, while it degenerates from conglutinated vesicles to spheres as the DP of PDEA increases. After replacing ethanol with water, the morphologies of these assemblies remain unchanged, while their size decreases due to the collapse of the hydrophobic PDEA chains. Interestingly, due to the protonation and deprotonation of PDEA blocks, both the spheres and vesicles manifest a reversible expansion/shrinkage upon alternative CO2 /Ar stimulation, exhibiting distinctive breathing feature.

Beyond Simple AB Diblock Copolymers: Application of Bifunctional and Trifunctional RAFT Agents to PISA in Water.

The influence of the macromolecular reversible addition-fragmentation chain transfer (macro-RAFT) agent architecture on the morphology of the self-assemblies obtained by aqueous RAFT dispersion polymerization in polymerization-induced self-assembly (PISA) is studied by comparing amphiphilic AB diblock, (AB)2 triblock, and triarm star-shaped (AB)3 copolymers, constituted of N,N-dimethylacrylamide (DMAc = A) and diacetone acrylamide (DAAm = B). Symmetrical triarm (AB)3 copolymers could be synthesized for the first time in a PISA process. Spheres and higher order morphologies, such as worms or vesicles, could be obtained for all types of architectures and the parameters that determine their formation have been studied. In particular, we found that the total DPn of the PDMAc and the PDAAm segments, i.e., the same overall molar mass, at the same Mn (PDMAc)/Mn (PDAAm) ratio, rather than the individual length of the arms determined the morphologies for the linear (AB)2 and star shaped (AB)3 copolymers obtained by using the bi- and trifunctional macro-RAFT agents.

Poly(vinylidene fluoride)-block-poly(N-vinylpyrrolidone) diblock copolymers: Synthesis via sequential RAFT/MADIX polymerization and self-assembly behavior

In this contribution, we reported the synthesis of poly(vinylidene fluoride)-block-poly(N-vinylpyrrolidone) (PVDF-b-PVPy) diblock copolymers via a sequential reversible addition-fragmentation chain transfer / macromolecular design via the interchange of xanthate (RAFT/MADIX) approach. First, the radical polymerization of vinylidene fluoride (VDF) was carried out with O-ethyl-S-(1-methoxycarbonyl)ethyldithiocarbonate as the starting chain transfer agent and a xanthate-terminated PVDF was obtained. The xanthate-terminated PVDF was then used as the macromolecular chain transfer agent further to mediate the radical polymerization of N-vinylpyrrolidone (NVP) and the PVDF-b-PVPy diblock copolymers were successfully synthesized. The kinetics of NVP polymerization was investigated by means of gel permeation chromatography (GPC). By controlling the molar ratios of the macromolecular chain transfer agent to NVP, a series of PVDF-b-PVPy diblock copolymers with variable lengths of PVPy were obtained. The PVDF-b-PVPy diblock copolymers displayed the interesting self-assembly behavior. It was found that for the PVDF-b-PVPy diblock copolymers no self-assembly behavior was exhibited in bulks. Nonetheless, the diblock copolymers were capable of self-assembling into the nanoobjects in aqueous solutions. In addition, the diblock copolymers displayed composition-dependent microphase-separated morphologies in their blends with poly(hydroxyether of bisphenol A). The different self-assembly behaviors have been interpreted in terms of differential scanning calorimetry (DSC), transmission electron microscopy (TEM) and atomic force microscopy (AFM).

A Novel Hydrophobic Associative Polymer by RAFT-MADIX Copolymerization for Fracturing Fluids with High Thermal Stability

Hydrophobic associative water-soluble polymers (HAWSP) are widely used as thickening agents for fracturing fluids due to their excellent viscoelastic properties. However, the HAWSP products synthesized by conventional methods are generally poor in resisting higher temperatures. In order to solve this problem, the effects of molecular weight and amount of hydrophobic monomer on the rheological properties of hydrophobic were investigated carefully. The macromolecular chain transfer agent was prepared through the process of reversible addition–fragmentation chain transfer polymerization (RAFT)/macromolecular designed by the interchange of xanthates (MADIX), and then the terpolymer of AM-co-AA-co-N-(3-methacrylamidopropyl)-N,N-dimethyldodecan-1-aminium (MAO-12DMA) was synthesized. The polymer has a narrow molecular-weight distribution giving rise to a good solubility even when the molecular-weight and the content of hydrophobic monomer are relatively high. Our study shows that the increase of molecular-weight...

Expanding the Scope of Polymerization-Induced Self-Assembly: Z-RAFT-Mediated Photoinitiated Dispersion Polymerization.

In this communication, we developed the first well-controlled Z-RAFT (RAFT = reversible addition-fragmentation chain transfer) mediated polymerization-induced self-assembly (PISA) formulation based on photoinitiated RAFT dispersion polymerization of tert-butyl acrylate (tBA) in ethanol/water (60/40, w/w) at room temperature using a Z-type macromolecular chain transfer agent (macro-CTA). Polymerizations proceeded rapidly via the exposure of visible-light irradiation (405 nm, 0.45 mW/cm2) with high monomer conversion (>95%) being achieved within 1 h. A variety of polymer nano-objects (spheres, worms, and vesicles) with narrow molar mass distributions were prepared by this Z-RAFT mediated PISA formulation. Silver nanoparticles were loaded with the vesicles via in situ reduction, which can be used as a catalyst for the reduction of methylene blue (MB) in the presence of NaBH4. Finally, gel permeation chromatography (GPC) analysis demonstrated that the corona block and the core-forming block could be cleaved by treating with excess initiator. This novel PISA formulation will greatly expand the scope of PISA and provide more mechanistic insights into the PISA research.

Highly Efficient One-Pot Synthesis of COS-Based Block Copolymers by Using Organic Lewis Pairs.

A one-pot synthesis of block copolymer with regioregular poly(monothiocarbonate) block is described via metal-free catalysis. Lewis bases such as guanidine, quaternary onium salts, and Lewis acid triethyl borane (TEB) were equivalently combined and used as the catalysts. By using polyethylene glycol (PEG) as the macromolecular chain transfer agent (CTA), narrow polydispersity block copolymers were obtained from the copolymerization of carbonyl sulfide (COS) and propylene oxide (PO). The block copolymers had a poly(monothiocarbonate) block with perfect alternating degree and regioregularity. Unexpectedly, the addition of CTA to COS/PO copolymerization system could dramatically improve the turnover frequency (TOF) of PO (up to 240 h−1), higher than that of the copolymerization without CTA. In addition, the conversion of CTA could be up to 100% in most cases, as revealed by 1H NMR spectra. Of consequence, the number-average molecular weights (Mns) of the resultant block copolymers could be regulated by varying the feed ratio of CTA to PO. Oxygen-sulfur exchange reaction (O/S ER), which can generate randomly distributed thiocarbonate and carbonate units, was effectively suppressed in all of the cases in the presence of CTA, even at 80 °C. This work presents a versatile method for synthesizing sulfur-containing block copolymers through a metal-free route, providing an array of new block copolymers.

Overcoming Surfactant-Induced Morphology Instability of Noncrosslinked Diblock Copolymer Nano-Objects Obtained by RAFT Emulsion Polymerization.

RAFT emulsion polymerization techniques including polymerization-induced self-assembly (PISA) and temperature-induced morphological transformation (TIMT) are widely used to produce noncrosslinked nano-objects with various morphologies. However, the worm, vesicle and lamellar morphologies produced by these techniques typically cannot tolerate the presence of added surfactants, thus limiting their potential applications. Herein we report the surfactant tolerance of noncrosslinked worms, vesicles, and lamellae prepared by RAFT emulsion polymerizations using poly(di(ethylene glycol) ethyl ether methacrylate-co-N-(2-hydroxypropyl) methacrylamide) (P(DEGMA-co-HPMA)) as a macromolecular chain transfer agent (macro-CTA). Significantly, these P(DEGMA-co-HPMA) nanoparticles are highly stable in concentrated solutions of surfactants (e.g., sodium dodecyl sulfate (SDS)). We also demonstrate that the surfactant tolerance is related to the limited binding of SDS to the main-chain of the P(DEGMA-co-HPMA) macro-CTA constituting the particle shell. This work provides new insight into the interactions between surfactants and thermoresponsive copolymers and expands the scope of RAFT emulsion polymerization techniques for the preparation of noncrosslinked and surfactant-tolerant nanomaterials.

Thermoreversible crystallization-driven aggregation of diblock copolymer nanoparticles in mineral oil.

A poly(behenyl methacrylate)37 (PBeMA37) macromolecular chain transfer agent is utilized for the reversible addition-fragmentation chain transfer (RAFT) dispersion polymerization of benzyl methacrylate (BzMA) directly in mineral oil at 90 °C. Polymerization-induced self-assembly (PISA) occurs under these conditions, yielding a series of sterically-stabilized PBeMA37-PBzMA x diblock copolymer spheres of tunable diameter as confirmed by dynamic light scattering (DLS) and transmission electron microscopy (TEM) studies. Rheological studies indicate that a relatively transparent, free-flowing, concentrated dispersion of non-interacting 32 nm PBeMA37-PBzMA100 spheres at 50 °C forms a turbid, paste-like dispersion on cooling to 20 °C. Turbidimetry and differential scanning calorimetry (DSC) studies conducted on solutions of PBeMA37 homopolymer in mineral oil suggest that this switchable colloidal stability is linked to crystallization-induced phase separation exhibited by this stabilizer block. Indeed, variable-temperature small-angle X-ray scattering (SAXS) indicates that a loose mass fractal network of strongly interacting spheres is formed on cooling to 20 °C, which accounts for this thermoreversible sol-gel transition. Moreover, SAXS, DSC and wide-angle X-ray scattering (WAXS) analyses indicate that the behenyl (C22H45) side-chains first form crystalline domains comprising adjacent stabilizer chains within individual spherical nanoparticles, with subsequent crystallization between neighboring nanoparticles leading to the formation of the mass fractal aggregates.

2-(Methylthio)ethyl Methacrylate: A Versatile Monomer for Stimuli Responsiveness and Polymerization-Induced Self-Assembly in the Presence of Air.

In this communication, we investigate the photoinduced electron/energy transfer-reversible addition-fragmentation chain transfer (PET-RAFT) polymerization of 2-(methylthio)ethyl methacrylate (MTEMA) using 5,10,15,20-tetraphenylporphine zinc (ZnTPP) as a photocatalyst under visible red light (λmax = 635 nm). Interestingly, the polymerization kinetics were not affected by the presence of air as near identical polymerization kinetics were observed for non-deoxygenated and deoxygenated systems, which is attributed to the singlet oxygen quenching ability of MTEMA. In both cases, well-defined polymers were obtained with good control over the molecular weight and molecular weight distribution (MWD). Furthermore, we have demonstrated that MTEMA can undergo the polymerization-induced self-assembly (PISA) process from a poly(oligo(ethylene glycol) methyl ether methacrylate) (POEGMA) macromolecular chain transfer agent (macro-CTA) to yield well-defined polymeric nanoparticles of various morphologies. These nanoparticles were rapidly disassembled after exposure to visible light due to the formation of singlet oxygen by the encapsulated ZnTPP and subsequent rapid oxidation of the thioether group.

Temperature-Induced Morphological Transitions of Poly(dimethylacrylamide)–Poly(diacetone acrylamide) Block Copolymer Lamellae Synthesized via Aqueous Polymerization-Induced Self-Assembly

Aqueous dispersion polymerization of diacetone acrylamide (DAAM) by chain extension from a hydrophilic poly(N,N-dimethylacrylamide) (PDMA30) macromolecular chain transfer agent (macro-CTA) to produce PDMA30–PDAAMx block copolymer nano-objects was investigated in detail by systematically varying solids content and degree of polymerization of the core-forming PDAAM, leading to the formation of pure lamellae, mixed lamellae/vesicles, and pure vesicles as revealed by dynamic light scattering (DLS), transmission electron microscopy (TEM), atomic force microscopy (AFM), and scanning electron microscopy (SEM). PDMA30–PDAAMx lamellae were found to span an unprecedented wide space in the morphology phase diagram. Moreover, in situ cross-linking of lamellae via statistical copolymerization of DAAM with an asymmetric cross-linker allyl acrylamide and the effect of cross-linking density on the colloidal and morphological stabilities were studied, representing the first report on in situ cross-linking of lamellae duri...

Polystyrene-block-polyethylene-block-polystyrene triblock copolymers: Synthesis and crystallization-driven self-assembly behavior

In this work, we reported the synthesis of a series of novel semicrystalline ABA triblock copolymers with polyethylene midblock and polystyrene endblocks via the combination of ring-opening metathesis polymerization (ROMP), hydrogenation and reversible addition-fragmentation chain transfer (RAFT) polymerization. First, an α,ω-dihydroxyl-terminated polycyclooctadiene (PCOD) was synthesized via the ROMP of cyclooctadiene by the use of the Grubbs second generation catalyst and with cis-2-butene-1,4-diol as the chain transfer agent. The α,ω-dihydroxyl-terminated PCOD was then hydrogenated into an α,ω-dihydroxyl-terminated polyethylene (PE); the latter was allowed to react with 2-methyl-2-[(dodecylsulfanylthiocarbonyl) sulfanyl]propanoic acid to afford a macromolecular chain transfer agent (i.e., Macro-CTA) for the RAFT polymerization of styrene. By controlling the lengths of PS endblocks, a series of polystyrene-block-polyethylene-block-polystyrene (PS-b-PE-b-PS) triblock copolymers were obtained. The successful synthesis of the ABA triblock copolymers were demonstrated by means of nuclear magnetic resonance (NMR) spectroscopy and gel permeation chromatography (GPC). The results of differential scanning calorimetry (DSC) and atomic force microscopy (AFM) indicate that the PS-b-PE-b-PS triblock copolymers were microphase-separated in bulks and their morphologies were quite dependent on the mass ratios of PE to PS blocks. Transmission electron microscopy (TEM), atomic force microscopy (AFM) and dynamic light scattering (DLS) showed that the triblock copolymers displayed crystallization-driven self-assembly (CDSA) behavior in selective solvent (viz. 1,4-dioxane). Depending on the lengths of PS blocks, the CDSA behavior of all the triblock copolymers generated spherical and cylindrical micelles. It was found that the quantity of the cylindrical micelles increased with decreasing the lengths of PS blocks.

Polymerization-Induced Self-Assembly: The Effect of End Group and Initiator Concentration on Morphology of Nanoparticles Prepared via RAFT Aqueous Emulsion Polymerization.

Polymerization-induced self-assembly (PISA) is a widely used technique for the synthesis of nanoparticles with various morphologies including spheres, worms, and vesicles. The development of a PISA formulation based on reversible addition-fragmentation chain transfer (RAFT) aqueous emulsion polymerization offers considerable advantages such as enhanced rate of polymerization, high conversion and environmentally friendly conditions. However, this formulation has typically produced spheres as opposed to worms and vesicles. Herein, we report the formation of vesicle morphology by increasing the RAFT end-group hydrophobicity of the macromolecular chain transfer agent or manipulating the radical initiator concentration used in the aqueous emulsion polymerization PISA formulation. Additionally, decreasing the molecular weight of the hydrophobic polystyrene domain in these vesicles leads to the formation of worms. This work demonstrates that RAFT end-group hydrophobicity and radical initiator concentration are key parameters which can be exploited to enable access to sphere, worm, and vesicle morphologies via the RAFT aqueous emulsion polymerization.

Synthesis of Photocrosslinkable and Amine Containing Multifunctional Nanoparticles via Polymerization-Induced Self-Assembly.

Photo-crosslinkable and amine-containing block copolymer nanoparticles are synthesized via reversible addition-fragmentation chain transfer (RAFT) polymerization-induced self-assembly of a multifunctional core-forming monomer, 2-((3-(4-(diethylamino)phenyl)acryloyl)oxy)ethyl methacrylate (DEMA), using poly(2-hydroxypropyl methacrylate) macromolecular chain transfer agent as a steric stabilizer in methanol at 65 °C. By tuning the chain length of PDEMA, a range of nanoparticle morphologies (sphere, worm, and vesicle) can be obtained. Since cinnamate groups can easily undergo a [2 + 2] cycloaddition of the carbon-carbon double bonds upon UV irradiation, the as-prepared block copolymer nanoparticles are readily stabilized by photo-crosslinking to produce anisotropic nanoparticles. The crosslinked block copolymer nanoparticles can be used as templates for in situ formation polymer/gold hybrid nanoparticles.

Controlled synthesis and microstructure tuning of PEG-containing side-chain discotic liquid crystalline block copolymers via RAFT polymerization

Liquid crystalline block copolymers (LCBCPs) are fascinating for their combining molecular level liquid crystalline orders and microphase separated multidomain morphologies. Here in this article, a series of PEG-containing side-chain discotic LCBCPs of PEG-b-Pm-n with variant spacer length m = 6, 10 and degree of polymerization (DP) of discotic LC block from n = 10 to 45, have been well-synthesized via reversible addition-fragmentation chain-transfer (RAFT) polymerization. The RAFT process mediated by macromolecular chain transfer agent (macroCTA) shows remarkable monomer concentration dependence. The influence of the introduced PEG block on the nano-scale microphase-segregation and mesophase organization is closely related to the side-chain triphenylene (TP) discogens stacking mode dependent on the spacer length. Wherein, the PEG-b-P6-n series with a six-methylene spacer exhibit consistent microphase separation with slightly disturbed yet ordered columnar structures. While for PEG-b-P10-n series with a longer ten-methylene spacer, the columnar organization in the copolymers is even improved in contrast with the low order of randomly TP stacking in their corresponding homopolymers. This work offers a viable and inspiring pathway for controlled synthesis of block copolymers with bulky side groups, as well as enhances in-depth understanding of the hierarchical superstructure organization in discotic units involved complex block copolymers. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017, 55, 2544–2553

Star Architecture Promoting Morphological Transitions during Polymerization-Induced Self-Assembly.

Polymerization-induced self-assembly (PISA) via reversible addition-fragmentation chain transfer (RAFT) dispersion polymerization is an effective method to produce block copolymer nano-objects of various morphologies at high solids. However, current PISA formulations have been limited to linear block copolymers. We report the synthesis of AB2 star block copolymers via RAFT aqueous dispersion polymerization of diacetone acrylamide using a poly(ethylene glycol) methyl ether bearing two chain transfer agents as the difunctional macromolecular chain transfer agent (macro-CTA), which was efficiently synthesized using 2,4,6-trichloro-1,3,5-triazine and activated esters to afford a high end functionality (97%). The star polymer architecture can significantly promote morphological transitions to obtain higher-order morphologies at both lower solids and lower degrees of polymerization of the core-forming block in comparison with its linear counterpart. This work demonstrates that polymer architecture is another important parameter that should be considered when conducting PISA synthesis to obtain complex morphologies.