Polymerization-induced Self-assembly Research Articles

Reverse Sequence Polymerization-Induced Self-Assembly in Aqueous Media.

We report a new aqueous polymerization‐induced self‐assembly (PISA) formulation that enables the hydrophobic block to be prepared first when targeting diblock copolymer nano‐objects. This counter‐intuitive reverse sequence approach uses an ionic reversible addition–fragmentation chain transfer (RAFT) agent for the RAFT aqueous dispersion polymerization of 2‐hydroxypropyl methacrylate (HPMA) to produce charge‐stabilized latex particles. Chain extension using a water‐soluble methacrylic, acrylic or acrylamide comonomer then produces sterically stabilized diblock copolymer nanoparticles in an aqueous one‐pot formulation. In each case, the monomer diffuses into the PHPMA particles, which act as the locus for the polymerization. A remarkable change in morphology occurs as the ≈600 nm latex is converted into much smaller sterically stabilized diblock copolymer nanoparticles, which exhibit thermoresponsive behavior. Such reverse sequence PISA formulations enable the efficient synthesis of new functional diblock copolymer nanoparticles.

Reverse Sequence Polymerization‐Induced Self‐Assembly in Aqueous Media

We report a new aqueous polymerization-induced self-assembly (PISA) formulation that enables the hydrophobic block to be prepared first when targeting diblock copolymer nano-objects. This counter-intuitive reverse sequence approach uses an ionic reversible addition–fragmentation chain transfer (RAFT) agent for the RAFT aqueous dispersion polymerization of 2-hydroxypropyl methacrylate (HPMA) to produce charge-stabilized latex particles. Chain extension using a water-soluble methacrylic, acrylic or acrylamide comonomer then produces sterically stabilized diblock copolymer nanoparticles in an aqueous one-pot formulation. In each case, the monomer diffuses into the PHPMA particles, which act as the locus for the polymerization. A remarkable change in morphology occurs as the ≈600 nm latex is converted into much smaller sterically stabilized diblock copolymer nanoparticles, which exhibit thermoresponsive behavior. Such reverse sequence PISA formulations enable the efficient synthesis of new functional diblock copolymer nanoparticles.

Polymerization-Induced Self-Assembly Toward Micelle-Crosslinked Tough and Ultrastretchable Hydrogels

As a promising class of tough and ultrastretchable hydrogels, micelle-crosslinked hydrogels have been restrained by the scarcity of micellar crosslinkers with a high concentration, controlled nanostructure, and uniform size distribution. Herein, polymerization-induced self-assembly (PISA) was demonstrated to be a general and powerful platform for micellar crosslinkers, affording micelle-crosslinked hydrogels with tailorable chemical structures, mechanics, and functionality. Poly(N,N-dimethylacrylamide)-b-poly(diacetone acrylamide) (PDMAc-b-PDAAM) micellar crosslinkers with a controlled nanostructure and uniform size distribution were prepared via PISA and one-step post-polymerization modification at high concentrations. Copolymerization of these micellar crosslinkers with acrylamide generated tough and ultrastretchable hydrogels, whose mechanical properties were found correlated with the concentration, nanostructure, and chemical composition of the micelles. The energy dissipation mechanism of these micelle-crosslinked hydrogels was analyzed via cyclic mechanical tests and stress relaxation experiments. The general feasibility of PISA toward micelle-crosslinked hydrogels was verified by systematic evaluation of both aqueous (including 2-methoxyethyl acrylate, tetrahydro-2-furanylmethyl acrylate, and 4-hydroxybutyl acrylate) and alcoholic (including benzyl methacrylate, lauryl methacrylate, styrene, and benzyl acrylate) PISA formulations, producing hydrogels with diverse chemical structures, mechanics, and functionalities depending on the micellar crosslinkers. The modularity of this strategy was further demonstrated by the fabrication of fluoro-functionalized hydrogels with fluoro-containing micellar crosslinkers. This strategy has significantly enlarged the scope and application of micelle-crosslinked hydrogels.

Physical Adsorption of Graphene Oxide onto Polymer Latexes and Characterization of the Resulting Nanocomposite Particles.

Polymer/graphene oxide (GO) nanocomposite particles were prepared via heteroflocculation between 140–220 nm cationic latex nanoparticles and anionic GO nanosheets in either acidic or basic conditions. It is demonstrated that nanocomposite particles can be formed using either poly(2-vinylpyridine)-b-poly(benzyl methacrylate) (P2VP–PBzMA) block copolymer nanoparticles prepared by reversible-addition chain-transfer (RAFT)-mediated polymerization-induced self-assembly (PISA), or poly(ethylene glycol)methacrylate (PEGMA)-stabilized P2VP latexes prepared by traditional emulsion polymerization. These two latexes are different morphologically as the P2VP–PBzMA block copolymer latexes have P2VP steric stabilizer chains in their corona, whereas the PEGMA-stabilized P2VP particles have a P2VP core and a nonionic steric stabilizer. Nevertheless, both the P2VP–PBzMA and PEGMA-stabilized P2VP latexes are cationic at low pH. Thus, the addition of GO to these latexes causes flocculation to occur immediately due to the opposite charges between the anionic GO nanosheets and cationic latexes. Control heteroflocculation experiments were conducted using anionic sterically stabilized poly(potassium 3-sulfopropyl methacrylate)-b-poly(benzyl methacrylate) (PKSPMA–PBzMA) and nonionic poly(benzyl methacrylate) (PBzMA) nanoparticles to demonstrate that polymer/GO nanocomposite particles were not formed. The degree of flocculation and the strength of electrostatic interaction between the cationic polymer latexes and GO were assessed using disc centrifuge photosedimentometry (DCP), transmission electron microscopy (TEM), and UV–visible spectrophotometry. These studies suggest that the optimal conditions for the formation of polymer/GO nanocomposite particles were GO contents between 10% and 20% w/w relative to latex, with the latexes containing P2VP in their corona having a stronger electrostatic attraction to the GO sheets.

(Bio)degradable and Biocompatible Nano-Objects from Polymerization-Induced and Crystallization-Driven Self-Assembly.

Polymerization-induced self-assembly (PISA) and crystallization-driven self-assembly (CDSA) techniques have emerged as powerful approaches to produce a broad range of advanced synthetic nano-objects with high potential in biomedical applications. PISA produces nano-objects of different morphologies (e.g., spheres, vesicles and worms), with high solids content (∼10-50 wt %) and without additional surfactant. CDSA can finely control the self-assembly of block copolymers and readily forms nonspherical crystalline nano-objects and more complex, hierarchical assemblies, with spatial and dimensional control over particle length or surface area, which is typically difficult to achieve by PISA. Considering the importance of these two assembly techniques in the current scientific landscape of block copolymer self-assembly and the craze for their use in the biomedical field, this review will focus on the advances in PISA and CDSA to produce nano-objects suitable for biomedical applications in terms of (bio)degradability and biocompatibility. This review will therefore discuss these two aspects in order to guide the future design of block copolymer nanoparticles for future translation toward clinical applications.

One‐For‐All Polyolefin Functionalization: Active Ester as Gateway to Combine Insertion Polymerization with ROP, NMP, and RAFT

AbstractThis work develops the Polyolefin Active‐Ester Exchange (PACE) process to afford well‐defined polyolefin–polyvinyl block copolymers. α‐Diimine PdII‐catalyzed olefin polymerizations were investigated through in‐depth kinetic studies in comparison to an analog to establish the critical design that facilitates catalyst activation. Simple transformations lead to a diversity of functional groups forming polyolefin macroinitiators or macro‐mediators for various subsequent controlled polymerization techniques. Preparation of block copolymers with different architectures, molecular weights, and compositions was demonstrated with ring‐opening polymerization (ROP), nitroxide‐mediated polymerization (NMP), and photoiniferter reversible addition–fragmentation chain transfer (PI‐RAFT). The significant difference in the properties of polyolefin–polyacrylamide block copolymers was harnessed to carry out polymerization‐induced self‐assembly (PISA) and study the nanostructure behaviors.

One-For-All Polyolefin Functionalization: Active Ester as Gateway to Combine Insertion Polymerization with ROP, NMP, and RAFT.

This work develops the Polyolefin Active-Ester Exchange (PACE) process to afford well-defined polyolefin-polyvinyl block copolymers. α-Diimine PdII -catalyzed olefin polymerizations were investigated through in-depth kinetic studies in comparison to an analog to establish the critical design that facilitates catalyst activation. Simple transformations lead to a diversity of functional groups forming polyolefin macroinitiators or macro-mediators for various subsequent controlled polymerization techniques. Preparation of block copolymers with different architectures, molecular weights, and compositions was demonstrated with ring-opening polymerization (ROP), nitroxide-mediated polymerization (NMP), and photoiniferter reversible addition-fragmentation chain transfer (PI-RAFT). The significant difference in the properties of polyolefin-polyacrylamide block copolymers was harnessed to carry out polymerization-induced self-assembly (PISA) and study the nanostructure behaviors.

Double-bond-containing polyallene-based composite nanofibers

Composite nanofibers have attracted increasing attention due to their applications in a variety of fields, such as biomedicine, nanoelectronic and drug delivery systems. Particularly, the introduction of customizable reactive segments to composite nanofibers is proven efficient to generate novel nanomaterials with extra functionalities. However, the preparation of reactive composite nanofibers unavoidably involves multiple-step and tedious manipulations. In addition, these nanofibers are generally prepared at high dilution, which restricts their potential applications. Herein, a new method of producing reactive composite nanofibers was reported through the polymerization-induced self-assembly (PISA) formulation of poly(phenoxyallene) (PPOA)-containing diblock copolymers. Reversible addition-fragmentation chain transfer (RAFT) block copolymerization of styrene and POA was chosen as a model reaction to explore the polymerization and PISA conditions. It was found that a chain transfer agent (CTA) consisting of C12H25S as Z segment and –COOH in R moiety allows for the preparation of well-defined double-bond-containing poly(styrene)-b-poly(phenoxyallene) (PS-b-PPOA), poly(methyl acrylate)-b-poly(phenoxyallene) (PMA-b-PPOA) and poly(methyl methacrylate)-b-poly(phenoxyallene) (PMMA-b-PPOA) diblock copolymers with controlled molecular weights and narrow dispersities. Specifically, on the basis of as-prepared poly(ethylene glycol) (PEG) macro-CTA, we demonstrated the in situ formation of unique composite nanofibers of PEG-b-PPOA via PISA process in methanol. Our work provides a facile synthetic approach toward attractive one-dimensional composite nanofibers with controlled dimension and a capacity for post-functionalization.

Synthesis of a dual UCST-type thermosensitive and acid-degradable nanogel based on poly(N-acryloyl glycinamide) and a ketal-containing crosslinker

In the present study, we designed a dual upper critical solution temperature (UCST) type thermosensitive and acid-degradable nanogel via UV-light initiated RAFT-mediated polymerization-induced thermal self-assembly (PITSA). The dual stimuli-triggered nanogel was prepared with N-acryloyl glycinamide as the precursor monomer of a hydrogen-bonding UCST-type thermosensitive polymer, a new pH-sensitive ketal-containing crosslinker, and poly(poly(ethylene glycol) methyl ether acrylate) acting as both a macromolecular chain transfer agent and a surfactant, called macro-transurf. The resulting spherical nanogel exhibits dual thermo- and pH-sensitive properties, as determined by UV–Vis spectrophotometry and/or dynamic light scatterring measurements at different values of pH (4, 6 and 9) and temperature (5 and 55 °C). The nanogel displays a UCST phase transition at 41 °C in buffer solution (pH = 9) and is degraded rapidly (25 and 45 min) in acidic environments (pH 4 and pH 6).

Multicompartment Vesicles: A Key Intermediate Structure in Polymerization-Induced Self-Assembly of Graft Copolymers

The morphological evolution of graft copolymer-based nano-objects was monitored by light scattering and electron microscopy during their formulation in water by polymerization induced self-assembly using a photo-mediated reversible addition–fragmentation chain transfer mechanism. The copolymer models used were composed of a dextran backbone bearing poly(2-hydroxypropyl methacrylate) grafts of two degrees of polymerization (X). At a full monomer conversion, unilamellar vesicles (ULVs) and large compound nano-objects (LCNs) were formed when targeting X = 100 and 500, respectively. For X = 100, some spherical, worm-like, then jellyfish-like structures were progressively observed before the ULVs formation. For X = 500, electron cryotomography revealed an unprecedented intermediate morphology formed from the onset of self-assembly called a multicompartment vesicle (MCV) that fused to form LCN. The formation of MCV was attributed to a local phase separation between dextran and the residual 2-hydroxypropyl methacrylate inducing the appearance of multiple hydrophilic cores.

Tuning the Glass Transition Temperature of a Core-Forming Block during Polymerization-Induced Self-Assembly: Statistical Copolymerization of Lauryl Methacrylate with Methyl Methacrylate Provides Access to Spheres, Worms, and Vesicles.

A series of poly(lauryl methacrylate)–poly(methyl methacrylate-stat-lauryl methacrylate) (PLMAx–P(MMA-stat-LMA)y) diblock copolymer nanoparticles were synthesized via RAFT dispersion copolymerization of 90 mol % methyl methacrylate (MMA) with 10 mol % lauryl methacrylate (LMA) in mineral oil by using a poly(lauryl methacrylate) (PLMA) precursor with a mean degree of polymerization (DP) of either 22 or 41. In situ1H NMR studies of the copolymerization kinetics suggested an overall comonomer conversion of 94% within 2.5 h. GPC analysis confirmed a relatively narrow molecular weight distribution (Mw/Mn ≤ 1.35) for each diblock copolymer. Recently, we reported an unexpected morphology constraint when targeting PLMA22–PMMAy nano-objects in mineral oil, with the formation of kinetically trapped spheres being attributed to the relatively high glass transition temperature (Tg) of the PMMA block. Herein we demonstrate that this limitation can be overcome by (i) incorporating 10 mol % LMA into the core-forming block and (ii) performing such syntheses at 115 °C. This new strategy produced well-defined spheres, worms, or vesicles when using the same PLMA22 precursor. Introducing the LMA comonomer not only enhances the mobility of the core-forming copolymer chains by increasing their solvent plasticization but also reduces their effective glass transition temperature to well below the reaction temperature. Copolymer morphologies were initially assigned via transmission electron microscopy (TEM) studies and subsequently confirmed via small-angle X-ray scattering analysis. The thermoresponsive behavior of PLMA22–P(0.9MMA-stat-0.1LMA)113 worms and PLMA22–P(0.9MMA-stat-0.1LMA)228 vesicles was also studied by using dynamic light scattering (DLS) and TEM. The former copolymer underwent a worm-to-sphere transition on heating from 20 to 170 °C while a vesicle-to-worm transition was observed for the latter. Such thermal transitions were irreversible at 0.1% w/w solids but proved to be reversible at 20% w/w solids.

Novel Near‐Infrared Fluorescent Nanoprobe Synthesized by the RAFT‐Mediated PISA Strategy for Hypoxia‐Triggered Tumor Imaging and Azoreductase‐Responsive Drug Release

AbstractDrug carriers and visual tracking play an important role in accurate and efficient drug delivery systems for targeted drug therapy. Polymerization‐induced self‐assembly (PISA), a powerful strategy for the fabrication of stimuli‐responsive polymeric nanoparticles has been a focus over the past decade due to its promising applications in biomedical fields such as targeted drug delivery and fluorescent nanoprobes used for tumor imaging. Herein, hypoxia‐responsive near‐infrared (NIR) fluorescent nanoprobes of amphiphilic block copolymers (PPEGMA14‐ADP‐Azo‐PBzMAx) are reported, the first example synthesized by RAFT‐mediated PISA strategy in situ to realize synchronous drug release and cell imaging. First, a series of nanoparticles with different morphologies and sizes, including spheres and vesicles, are synthesized by the PISA strategy using PPEGMA14‐ADP‐Azo‐CDPA as macro‐RAFT agents link with near‐infrared Aza‐BODIPY fluorogen and azobenzene groups. Hypoxia‐triggered dissociation of the nanoprobes and NIR fluorescence emission is then observed because of the cleavage of azo bonds. Meanwhile, the in situ DOX‐loaded nanoprobes by the PISA demonstrate synchronous drug release and NIR fluorescence enhancement against mouse colon cancer cells (CT26) under hypoxia (1% O2) compared with under normoxia (16% O2).

Polymeric Nanofibers of Various Degrees of Cross‐Linking as Fillers in Poly(styrene‐stat‐n‐butyl acrylate) Nanocomposites: Overcoming the Trade‐Off between Tensile Strength and Stretchability

Synthesis of light polymer nanocomposites with high strength and toughness has been a significant interest for its potential applications in industry. Herein, the authors have synthesized polymerization-induced self-assembly (PISA) derived nanodimensional polymeric worm (fiber) reinforced polymer nanocomposites by a simple and environmentally friendly synthesis process without the addition of volatile organic compounds. PISA-derived worms with a core-forming block of low glass transition temperature (Tg ≈27.1°C) comprising poly(styrene-stat-n-butyl acrylate) have been employed as reinforcing filler. The influence of core-segment cross-linking on reinforcement efficiency has been explored by comparing noncross-linked worms, and worms cross-linked with a small amount of ethylene glycol diacrylate introduced at t=0h or t=2h of polymerization. Upon addition of 1wt% of noncross-linked, t=0h cross-linked, and t=2h cross-linked worms, toughness of polymer nanocomposites can be enhanced by 62%, 114%, and 120%, respectively. The results suggest that the reinforcement efficiency of worms is significantly influenced by the cross-linking of core-segments regardless of cross-linking methods. This work broadens the understanding in application of PISA-derived worms as reinforcing filler by demonstrating the efficient reinforcement with low Tg worms.

Stimuli-Responsive Pickering Emulsions Regulated via Polymerization-Induced Self-Assembly Nanoparticles.

With the development of reversible deactivated radical polymerization techniques, polymerization-induced self-assembly (PISA) is emerging as a facile method to prepare block copolymer nanoparticles in situ with high concentrations, providing wide potential applications in different fields, including nanomedicine, coatings, nanomanufacture, and Pickering emulsions. Polymeric emulsifiers synthesized by PISA have many advantages comparing with conventional nanoparticle emulsifiers. The morphologies, size, and amphiphilicity can be readily regulated via the synthetic process, post-modification, and external stimuli. By introducing stimulus responsiveness into PISA nanoparticles, Pickering emulsions stabilized with these nanoparticles can be endowed with "smart" behaviors. The emulsions can be regulated in reversible emulsification and demulsification. In this review, the authors focus on recent progress on Pickering emulsions stabilized by PISA nanoparticles with stimuli-responsiveness. The factors affecting the stability of emulsions during emulsification and demulsification are discussed in details. Furthermore, some viewpoints for preparing stimuli-responsive emulsions and their applications in antibacterial agents, diphase reaction platforms, and multi-emulsions are discussed as well. Finally, the future developments and applications of stimuli-responsive Pickering emulsions stabilized by PISA nanoparticles are highlighted.

RAFT Polymerization of Semifluorinated Monomers Mediated by a NIR Fluorinated Photocatalyst.

Near-infrared (NIR) light plays an increasingly important role in the field of photoinduced electron/energy transfer-reversible addition-fragmentation chain transfer (PET-RAFT) polymerization due to its unique properties. Yet, the NIR photocatalyst with good stability for PET-RAFT polymerization remains promising. Here, a strategy of NIR PET-RAFT polymerization of semifluorinated monomers using fluorophenyl bacteriochlorin as a photocatalyst with strong absorption at the NIR light region (710-780nm) is reported. In which, the F atoms are used to modify reduced tetraphenylporphyrin structure with enhanced photostability of photocatalyst. Under the irradiation of NIR light (λmax = 740nm), the PET-RAFT polymerization of semifluorinated methylacrylic monomers presents living/control characteristics and temporal modulation. By the PET-RAFT polymerization-induced self-assembly (PISA) strategy, stable fluorine-containing micelles are constructed in various solvents. In addition, the fluorinated hydrophobic surface is fabricated via a surface-initiated PET-RAFT (SI-PET-RAFT) polymerization using silicon wafer bearing RAFT agents with tunable surface hydrophobicity. This strategy not only enlightens the application of further modified compounds based on porphyrin structure in photopolymerization, but also shows promising potential for the construction of well-defined functional fluoropolymers.

Polymerization-Induced Self-Assembly (PISA) for in situ drug encapsulation or drug conjugation in cancer application

HypothesisWe describe the possibility of using the same block copolymer carriers prepared by PISA for in situ drug encapsulation or drug conjugation. ExperimentsBlock copolymers containing poly((ethylene glycol) methacrylate)–co-poly(pentafluorophenyl methacrylate)-b-poly(hydroxypropyl methacrylate) (P((PEGMA-co-PFBMA)-b-PHPMA)) were synthesized at 10 wt% using PISA. The first approach involved in situ Doxorubicin (DOX) loading during PISA, while the second exhibited surface functionalization of PISA-made vesicles with dual drug therapies, N-acetyl cysteine (NAC) and DOX using para-fluoro-thiol reaction (PFTR) and carbodiimide chemistry, respectively. Cytotoxicity, cell uptake, and cell apoptosis were assessed on MDA-MB-231 cell lines. FindingsP((PEGMA-co-PFBMA)-b-PHPMA) nanocarriers were prepared, showing size and shape transformations from spheres, cylinders to raspberry-forming vesicles. DOX was readily loaded into NPs during PISA with relatively high encapsulation efficiency of 70 %, whereas the plain PISA-made vesicles could be functionalized with NAC and DOX at high yields. DOX-free NPs showed biocompatibility, whilst DOX-conjugated NPs imparted a concentration-dependent cytotoxicity, as well as an enhanced cell uptake compared to free DOX. The results demonstrated that the same PISA-derived self-assemblies enabled either in situ drug encapsulation, or post-polymerization surface engineering with useful functionalities upon tuning the macro-CTA block, thus holding promises for future drug delivery and biomedical applications.

Polymeric nanocomposites based on high aspect ratio polymer fillers: Simultaneous improvement in tensile strength and stretchability

We have prepared polymer nanocomposite films reinforced with polymer worms synthesized via polymerization induced self-assembly (PISA). Films were prepared by mixing a soap-free polymer latex (base matrix) and an aqueous worm dispersion, followed by solvent casting. Three types of worms with different core-forming blocks were used as nanofillers. Uniaxial tensile testing was conducted to study the effect of worms on the mechanical properties of the films. The effects of core-forming block as well as amount of worms on the film reinforcement were investigated. It is demonstrated that the worms can improve the mechanical properties of the films at very low loading (1 wt% relative to the polymer matrix), and the glass transition temperature (Tg) of the core-forming block plays an important role for effective reinforcement.

Simultaneous Synthesis and Self-Assembly of Bottlebrush Block Copolymers at Room Temperature via Photoinitiated RAFT Dispersion Polymerization.

Bottlebrush polymers exhibiting unique properties have attracted considerable attention for applications in many research areas. Herein, the first simultaneous synthesis and self-assembly of bottlebrush block copolymers at room temperature via photoinitiated polymerization-induced self-assembly (photo-PISA) using multifunctional macromolecular chain transfer agents (macro-CTAs) is reported. Comparing with linear block copolymers, the bottlebrush block copolymers can promote the formation of higher-order morphologies (e.g., vesicles) when targeting similar degrees of polymerization (DPs). Moreover, a higher polymerization rate is observed in the case of bottlebrush block copolymers. Gel permeation chromatography (GPC) analysis shows that good polymerization control is maintained when synthesizing bottlebrush block copolymers by photo-PISA. Finally, the obtained bottlebrush block copolymer vesicles are used as seeds for further chain extension and multicompartment nanoparticles with a sponge internal structure are formed. It is expected that this study will not only expand polymer architectures employed in PISA, but also provide a new strategy to synthesize polymer nanoparticles with unique structures.

Synthesis of Cross-Linked Block Copolymer Nanoassemblies and their Coating Application.

Since the discovery of polymerization-induced self-assembly (PISA), convenient synthesis of concentrated block copolymer nanoassemblies dispersed in solvent has been achieved. Now, application of block copolymer nanoassemblies should be paid more attention. In this study, corona-cross-linked block copolymer nanoparticles of poly[dimethylacrylamide-co-(diacetone acrylamide)]-b-polystyrene [P(DMA-co-DAAM)-b-PS] containing the poly(DAAM) segment in the hydrophilic P(DMA-co-DAAM) block are synthesized initially by PISA following dispersion reversible addition-fragmentation chain transfer polymerization and then by covalent intraparticle cross-linking through the poly(DAAM) segment and adipic acid dihydrazide. Coating application of the corona-cross-linked block copolymer nanoassemblies is tried, and much higher water resistance of the corona-cross-linked block copolymer nanoassemblies than that of the linear block copolymer nanoassemblies is demonstrated.

Preparation and applications of the polymeric micelle by polymerization-induced self-assembly (PISA)

Polymerization induced self-assembly (PISA) has a high solid content, simple operating steps, and can generally achieve high conversion to monomers in a short time, which has been widely used in the preparation and adjusting to morphologies of polymer micelles self-assembly. In this article, the preparation and applications of the polymeric micelle synthesized by PISA were reviewed. The particle morphology can be adjusted by a variety of active polymerizations with different initiation mechanisms in the preparation of polymer micelles. Among them, free radical active polymerization is more practical. The reversible addition-fragmentation chain transfer (RAFT) and atom transfer radical polymerization (ATRP) were highlighted. Additionally, different shapes such as spheres, worms, and vesicles can be obtained by RAFT in the preparation of nano-objects fields. Researchers construct the phase diagram to get the pure phase for applications. As one form produced by PISA, polymeric micelles are usually artificial nanoreactors for a series of organic and inorganic catalysis and can be used as drug delivery and target agents. Due to the increase in the ultimate tensile strength, RAFT is an optimal technique to produce thermoplastic elastomers.