RAFT Agent Research Articles

Stimuli-Responsive Track-Etched Membranes for Separation of Water–Oil Emulsions

In this work, we have developed a method for the preparation of pH-responsive track-etched membranes (TeMs) based on poly(ethylene terephthalate) (PET) with pore diameters of 2.0 ± 0.1 μm of cylindrical shape by RAFT block copolymerization of styrene (ST) and 4-vinylpyridine (4-VP) to be used in the separation of water–oil emulsions. The influence of the monomer concentration (1–4 vol%), the molar ratio of RAFT agent: initiator (1:2–1:100) and the grafting time (30–120 min) on the contact angle (CA) was studied. The optimal conditions for ST and 4-VP grafting were found. The obtained membranes showed pH-responsive properties: at pH 7–9, the membrane was hydrophobic with a CA of 95°; at pH 2, the CA decreased to 52°, which was due to the protonated grafted layer of poly-4-vinylpyridine (P4VP), which had an isoelectric point of pI = 3.2. The obtained membranes with controlled hydrophobic-hydrophilic properties were tested by separating the direct and reverse “oil–water” emulsions. The stability of the hydrophobic membrane was studied for 8 cycles. The degree of purification was in the range of 95–100%.

Photo‐RAFT Polymerization for Hydrogel Synthesis through Barriers and Development of Light‐Regulated Healable Hydrogels under NIR Irradiation

AbstractWe report an aqueous and near‐infrared (NIR) light mediated photoinduced reversible addition–fragmentation chain transfer (photo‐RAFT) polymerization system catalyzed by tetrasulfonated zinc phthalocyanine (ZnPcS4−) in the presence of peroxides. Taking advantage of its fast polymerization rates and high oxygen tolerance, this system is successfully applied for the preparation of hydrogels. Exploiting the enhanced penetration of NIR light, photoinduced gelation is effectively performed through non‐transparent biological barriers. Notably, the RAFT agents embedded in these hydrogel networks can be reactivated on‐demand, enabling the hydrogel healing under NIR light irradiation. In contrast to the minimal healing capability (<15 %) of hydrogels prepared by free radical polymerization (FRP), RAFT‐mediated networks display more than 80 % recovery of tensile strength. Although healable polymer networks under UV and blue lights have already been established, this work is the first photochemistry system using NIR light, facilitating photoinduced healing of hydrogels through thick non‐transparent barriers.

Photo-RAFT Polymerization for Hydrogel Synthesis through Barriers and Development of Light-Regulated Healable Hydrogels under NIR Irradiation.

We report an aqueous and near-infrared (NIR) light mediated photoinduced reversible addition-fragmentation chain transfer (photo-RAFT) polymerization system catalyzed by tetrasulfonated zinc phthalocyanine (ZnPcS4-) in the presence of peroxides. Taking advantage of its fast polymerization rates and high oxygen tolerance, this system is successfully applied for the preparation of hydrogels. Exploiting the enhanced penetration of NIR light, photoinduced gelation is effectively performed through non-transparent biological barriers. Notably, the RAFT agents embedded in these hydrogel networks can be reactivated on-demand, enabling the hydrogel healing under NIR light irradiation. In contrast to the minimal healing capability (< 15%) of hydrogels prepared by free radical polymerization (FRP), RAFT-mediated networks display more than 80% recovery of tensile strength. Although healable polymer networks under UV and blue lights have already been established, this work is the first photochemistry system using NIR light, facilitating photoinduced healing of hydrogels through thick non-transparent barriers.

Mechanical Property Modification of “Living” Networks via PET‐RAFT Photopolymerization

Abstract“Living” polymer networks have the ability to grow in size and mass after initial polymerization through the insertion of new monomers. In this work, a one‐pot method is used to prepare “living” polymer networks and modify their mechanical properties via the photo‐electron/energy transfer reversible addition‐fragmentation chain transfer (PET‐RAFT) photopolymerization method. The “living” networks are made from company‐bought constituents (N,N‐dimethylacrylamide [DMAm] monomer and poly(ethylene glycol) diacrylate [PEGDA] 700 crosslinker) so that no synthesis is involved. The study uses two different RAFT agents: asymmetric 2‐(n‐butyltrithiocarbonate) propionic acid (BTPA) and symmetric S,S‐dibenzyl trithiocarbonate (DBTTC). The study then modifies these parent networks with three monomers (acrylamide [AAm], DMAm, and methyl acrylate [MA]) by recommencing the PET‐RAFT process. Fourier transform infrared (FTIR) spectroscopy and thermogravimetric analysis (TGA) are conducted on the “living” networks to investigate the effects of monomer insertion after photo‐growth. The networks are also subjected to compression testing, where the daughter networks display modified mechanical properties dependent on both the choice of monomer and RAFT agent symmetry.

Chain-Extendable Crosslinked Hydrogels Using Branching RAFT Modification.

Functional crosslinked hydrogels were prepared from 2-hydroxyethyl methacrylate (HEMA) and acrylic acid (AA). The acid monomer was incorporated both via copolymerization and chain extension of a branching, reversible addition-fragmentation chain-transfer agent incorporated into the crosslinked polymer gel. The hydrogels were intolerant to high levels of acidic copolymerization as the acrylic acid weakened the ethylene glycol dimethacrylate (EGDMA) crosslinked network. Hydrogels made from HEMA, EGDMA and a branching RAFT agent provide the network with loose-chain end functionality that can be retained for subsequent chain extension. Traditional methods of surface functionalization have the downside of potentially creating a high volume of homopolymerization in the solution. Branching RAFT comonomers act as versatile anchor sites by which additional polymerization chain extension reactions can be carried out. Acrylic acid grafted onto HEMA-EGDMA hydrogels showed higher mechanical strength than the equivalent statistical copolymer networks and was shown to have functionality as an electrostatic binder of cationic flocculants.

Influence of thiocarbonylthio- RAFT agents on the homogeneity of polymer network and mechanical properties of 3D printed polymers

RAFT agents based on thiocarbonylthio- group were used in an acrylate formulation containing a phosphine oxide as photoinitiator. After optimization of the RAFT agent concentration, its effect on the polymer properties was studied. It turns out that the conversion at the gel point increases when RAFT agents are used. Similarly, a decrease in the relaxation temperature is noticed as well as an increase in the homogeneity of the polymer network. Due to the reduction of internal defects, this leads to better mechanical properties as exemplified by toughness measurement of 3D printed samples.

Silicon rubber grafted with hydrophilic and thermoresponsive poly(DEGMA‐co‐OEGMA) with improved hemo‐ and cyto‐compatibility

AbstractThe grafting of thermo‐responsive, hydrophilic, hemo‐ and biocompatible poly(DEGMA‐co‐OEGMA) onto silicone rubber was carried out by the gamma‐radiation pre‐irradiation method. The size of the grafted chains was controlled using 4‐cyano‐4‐(propylsulfanylthiocarbonyl)sulfanyl pentanoic acid as RAFT agent. Different graft parameters were evaluated to obtain an adequate grafting percentage which allows combining the features of both the matrix and the grafted polymers. The controlled process was confirmed by GPC analysis of the homopolymers formed during the grafting process as by‐products and their molar composition was determined by 1H‐NMR. Grafted materials were characterized by FTIR‐ATR, differential scanning calorimetry, thermogravimetric analysis, dynamic mechanical analysis, scanning electron microscopy, and optical profilometry, while hydrophilicity and temperature‐responsive behavior were evaluated by water absorbing capacity and contact angle measurements. The obtained materials showed enhanced hydrophilicity and excellent hemo‐ and cytocompatibility as evaluated in terms of hemolysis, thrombus formation, protein adsorption, cell viability, and cytotoxicity. The obtained materials showed potential to be applied in the biomedical field in devices in contact with blood.

Preparation of nanocomposite polymer electrolytes by incorporating poly[poly(ethylene glycol) methyl ether methacrylate]-grafted poly(amidoamine) dendrimer for high performance lithium ion batteries

Preparation of composite polymer electrolytes (CPEs) is one of the most effective ways to improve ionic conductivity and electrochemical properties in lithium ion batteries. Dendrimers as organic fillers can improve ionic conductivity, stability, and electrochemical properties of CPEs due to their specific branched structure, low glass transition temperature, and amorphous nature. In the present work, a poly(amidoamine) (PAMAM) dendrimer RAFT agent is synthesized and utilized to prepare CPEs based on poly[poly(ethylene glycol) methyl ether methacrylate] (p(PEGMA)) matrix. The resultant CPEs are electrochemically studied by exploring electrochemical impedance spectroscopy (ESI), linear sweep voltammetry (LSV), and cycling performance during the charge/discharge cycles. The CPEs demonstrated encouraging electrochemical characteristics to utilize in lithium ion batteries such as excellent ionic conductivity in the range of 10-3 S/cm, Li-ion transference number (t+) in the range of 0.39–0.45, great electrochemical stability window (ESW) up to 5 V vs Li/Li+, and insignificant interfacial resistance. Moreover, CPEs represented good cycling performance during 100 charge/discharge cycles and favorable specific capacity of 151 mAh/g in LCO||Gr cells.

Photoinduced RAFT Step‐Growth Polymerization toward Degradable Living Polymer Networks

Comprehensive SummaryThe application of reversible degenerative radical polymerization (RDRP) in the construction of polymer networks (PNs) provides a facile and convenient way to fabricate 3D objects with the ability to be posttransformed. However, the polymerization mechanism mainly relies on chain‐growth polymerization, which limits its wide application for various polymeric materials with different functionalities. Here, we present a method toward PNs by utilizing a photoinduced RAFT step‐growth polymerization, which is based on a RAFT single unit monomer insertion (SUMI) reaction between a xanthate and an alkyl vinyl group. Benefiting from this reaction, a pendant RAFT agent can be generated in each repeat unit of the backbone during the polymerization. These reactivatable dormant species can be further used for the postfunctionalization of PNs prepared by step‐growth polymerization of multifunctional monomers. Moreover, the prepared PNs are degradable owing to the introduction of ester groups, providing an avenue toward degradable and stimuli‐responsive materials.

Shape Control over the Polymer Molecular Weight Distribution and Influence on Rheological Properties

The shape, breadth, and average molecular weight of the overall molecular weight distribution (MWD) largely define polymer properties. In conventional free-radical polymerization, control over this distribution is through the many competing kinetic pathways dominated by radical termination events. “Living” radical polymerization mechanistically minimizes these termination events, providing a facile route to a desired Gaussian distribution with the distribution breadth dependent upon the activity of the catalyst or modulating agent. However, producing unusually shaped distributions can only be achieved through modeling of the complex polymerization kinetics and invoking feeding and other methods. Here, we construct square, slanted, and chair-like MWDs by blending two to four polymers made using a low-reactive RAFT agent with dispersities close to 2. The synthesis of these polymers, unlike that of polymers made with high-reactive RAFT agents, is simple, scalable, and importantly reproducible as the MWD is independent of conversion, making this polymerization method virtually and kinetically model-free. The blending method described here overcomes many of the difficulties in producing unusually shaped MWDs and allows control over the shape and breadth of the MWD. The concept further provides a general synthetic strategy for studying important structure–property relationships of polymers with desired processing and performance characteristics. This is demonstrated by measurement and modeling analysis of the linear viscoelastic properties of selected samples, which provides a way to tailor the properties of polymers by controlling the form of their MWD via blending. Unlike conventional approaches analyzing the effects of the MWD, its actual shape is considered and its effect on the properties is addressed.

Tethering inorganic luminous upconverting nanoparticles with macromolecular chppendixains using silica functionalized with RAFT agent

Upconversion nanoparticles (UCNPs) are superior next-generation nanomaterials due to their exclusive features, such as tunable emission, high quantum yield, and excellent stability against photo-blinking/bleaching/degradation. One can compel these UCNPs to target selective applications by surface functionalization of these nanocrystals with functional groups or polymers to make them chemically active, possessing colloidal stability, better biocompatibility as well as tunable emission region. Herein, we report the preparation of rare earth (Er 3+ , 0.5% mmol) doped upconversion nanoparticles (UCNPs) and their surface functionalization using RAFT agent primed silica followed by polymer functionalization. The polymer functionalization was performed using photo-induced electron/energy transfer-reversible addition-fragmentation chain transfer (PET-RAFT) polymerization in the presence of Eosin Y (EY) which act as a photocatalyst when exposed to blue light at room temperature. The polymer functionalization of UCNPs was performed with different types of polymers, for example, poly( N -isopropyl acrylamide), poly(acrylic acid), poly(ethylene glycol)methacrylate, and poly(methyl methacrylate) via “grafting-from” approach. Numerous characterizations were performed which confirm the successful grafting of polymers via PET-RAFT polymerization. The enhancement of photoluminescent efficiency towards the red region/window was observed after the grafting of polymers. The emission in the red region is marked as suitable for biological applications. Thus, indicating the potential use of the as-synthesized core@shell@shell system for various biological platforms. Interestingly, the cytocompatibility studies render the polymer functionalized UCNPs’ potential to be used in a variety of biological applications.

A novel approach to graft silicones onto waterborne polyacrylate for synthesizing anti‐graffiti coatings by polydimethylsiloxane‐functionalized RAFT agent

AbstractLinear organoalkoxysilane‐based RAFT agent functionalized polydimethylsiloxane (RAFT‐PDMS) has been prepared for the first time via co‐condensation of a new organoalkoxysilane based RAFT agent (RAFT‐Agent), 2‐((methyldimethoxysilyl)propyl)carbontrithio‐2‐methyl‐propanoicacidmethylester, with diethoxydimethylsilane (DDS) in an aqueous acidic solution. The RAFT‐Agent and RAFT‐PDMS was confirmed by FT‐IR and 1H NMR spectroscopy techniques. The obtained RAFT‐PDMS was used to prepare the silicone‐modified polyacrylate anti‐graffiti emulsions via RAFT polymerization with functional monomers. The living character of RAFT polymerization of RAFT‐PDMS and the narrow molecular weight distribution of the polymerization product were confirmed by GPC. The transformation of the particle state from a small micelle structure to a spherical core‐shell micelle structure during polymerization was verified by TEM and dynamic light scattering analysis. Moreover, DSC and TGA analysis disclosed that increasing the content of RAFT‐PDMS can reduce the glass transition temperature and improve the thermal stability of the resin. Finally, the effect of RAFT‐PDMS on the surface morphology and properties of coatings were examined by SEM and contact angle. These experimental results suggest that increasing the content of RAFT‐PDMS increases the surface porosity of the coating film and thus enhances its hydrophobic properties.

Facile Synthesis of Fluorinated Polyacrylate Elastomer via Emulsion Polymerization Using Adjustable Amphiphilic Star Macro‐RAFT Agent as Surfactant

AbstractNovel thermoplastic fluorinated polyacrylate films possessing excellent mechanical performance are prepared by emulsion polymerization latex using adjustable amphiphilic star macro‐reversible addition‐fragmentation chain‐transfer (macro‐RAFT) agent as surfactants in this work. First, star macro‐RAFT agent equipped with six amphiphilic arms is synthesized via two‐step RAFT polymerization of acrylic acid (AA) and 2,2,2‐trifluoroethyl acrylate (TFEA) in the presence of hexa‐functional RAFT agents. The surface activities of the as‐synthesized amphiphilic star macro‐RAFT agents in aqueous solutions are studied. Subsequently, various fluorinated polyacrylate latexes are obtained by conducting emulsion polymerization of 2,2,3,4,4,4‐hexafluorobutyl acrylate (HFBA) and butyl acrylate (BA) using the amphiphilic star macro‐RAFT agents as both RAFT agents and surfactants. The latex particle morphologies are studied by transmission electron microscope (TEM) and particle size is measured by dynamic light scattering (DLS). The effects of PAA segment length, HFBA/BA mole ratio, and TFEA segment length on the surface morphologies of the fluorinated polyacrylate films are illustrated by investigating the surface properties using water contact angle test and atomic force microscopy (AFM). Finally, the elastomeric films obtained by directly casting the prepared fluorinated polyacrylate latexes show excellent comprehensive properties such as tensile strength over 4 MPa, elongation at break ≈700%, permanent deformation below 25%. Water absorption test is also provided as a reference.

Thermoresponsive oligo(ethylene glycol) methyl ether methacrylate homopolymers via RAFT polymerization in 1-alkyl-3-methylimidazolium hexafluorophosphate ionic liquids

Responsive polymer-based materials vary their physicochemical properties upon external stimuli. In the past decades, these materials have been utilized in diverse applications such as drug delivery, tissue engineering, biosensors, and surface coatings. In these applications, stimuli-responsive polymers with narrow dispersity are ideal to ensure good sensitivity. RAFT polymerization remains one of the living polymerization techniques that affords great control over polymer size and dispersity. Herein, we investigated how the solvent size, RAFT agent choice, and monomer size affect the RAFT polymerization of thermoresponsive OEGMEMA in hexafluorophosphate-based RTILs. Gel permeation chromatography (GPC) results showed that increased RTIL chain length resulted in an increased polymerization rate, polymer size and dispersity. The RAFT agent CPDB provided better control over the polymerization kinetics. Moreover, GPC data revealed an inverse relationship between the monomer size and the dispersity of its polymer. Monomer size also restricted polymer growth with decreasing rate through time. Among the homopolymers, P(DEGMEMA) synthesized in [HMIM]PF6 and CPBD exhibited the highest percent conversion, fastest reaction rate, and relatively high size uniformity. Our findings demonstrate that a thermoresponsive P(DEGMEMA) can be rapidly obtained in high molecular weights and conversion in RTILs.

AIEgen-Terminated Charge-Switchable Zwitterionic Azo Polymer for Tumor Hypoxia Imaging

For fluorescent probes, getting over the obstacles encountered in an organism is an important prerequisite. A zwitterionic to cationic polymer is an attractive approach to realize long-term circulation and high cellular uptake efficiency at the same time. Here, we reported a hypoxia-activatable zwitterionic to cationic azo polymer for tumor imaging, which was composed of an AIEgen-decorated RAFT agent and an azo monomer unit with a carbonate linkage. The zwitterion group endowed it with great anti-fouling property, avoiding being captured by proteins in the blood stream. Under the hypoxic microenvironment, the azo bond was broken and changed into amine with positive charge, which enhanced the cellular uptake efficiency. Meanwhile, the fluorescence quenching effect was cut off because of the destruction of the azo units. Therefore, the probe achieved a “turn-on” process and could be used as a fluorescent probe for tumor hypoxia imaging.

Synthesis and sorption properties of organo-mineral sorbents based on poly(styrene-b-4-vinylpyridine) copolymer

New organo-mineral composites SiO2/poly(styrene-b-4-vinylpyridine) were obtained by adsorption of block- copolymers poly(styrene-b-4-vinylpyridine) with molar ratios of styrene (St) and 4-vinylpyridie (4-VP) St:4-VP = 1:4 and St:4-VP = 1:5 from THF solution onto silica gel surface. Block-copolymers were synthesized by controlled radical polymerization of styrene with RAFT agent and further copolymerization with 4-vinylpyridine. Also blok-copolymer with thiol end-group was obtained and has been employed for preparation of the composite. Composition of the block-copolymers and surface morphology of composites obtained were determined using 1H NMR and FT-IR spectroscopy, differential scanning calorimetry, thermogravimetric analysis and scanning electron microscopy. It was established that sorption capacity of the organo-mineral composites toward Pb(ІІ), Fe(ІІІ) and Cu(ІІ) ions is in 2–4 times higher in comparison with parent silica gel.

Preparation of Thermo- and pH-Responsive Microgels Based on Complementary Nucleobase Molecular Recognition.

Complementary interactions between the natural nucleobases is one of the important ways of biomolecular recognition. Although scientists have introduced such supramolecular noncovalent interactions into biomimetic materials through different approaches in recent years, further research is still needed to confer structural features of biomolecules into emerging stimuli-responsive microgels. In this study, a series of bis-thymine end decorated flexible poly (N-isopropyl acrylamide) (T-PNIPAM-T) are obtained through a thymine esterified RAFT agent. Meanwhile, a rigid polymeric backbone poly[1-(4-vinyl benzyl)] adenine (PS A), including several pendant adenines on the side chain is prepared. Through nucleobase complementary pairing subtle supramolecular cross-linked 3D networks are constructed, and further self-assembled to form microgels under the balance between hydrophilicity and block flexibility. More importantly, such supramolecular 3D microgels show volumetric shrinkage in different water content environments and the assembly behavior under thermo and pH stimulated conditions. This exploration is expected to play an important value and significance in the field of biomimetic controlled release of soft matter in the future.

Controlling polymer dispersity using switchable RAFT agents: Unravelling the effect of the organic content and degree of polymerization

Dispersity can significantly affect material properties and related applications and as such is a significant parameter to control in polymer design. Switchable RAFT agents were recently utilized as an efficient tool to tailor polymer dispersity. In this work, we investigate the effect of the organic solvent and targeted degree of polymerization (DP) in attaining dispersity-controlled homopolymers and block copolymers. By varying the addition of acid in pure aqueous media we found that a dispersity range between 1.16 and 1.58 could be obtained while the gradual incorporation of the organic content led to broader dispersity ranges. Pleasingly, when the polymerizations were performed in aqueous media, dispersity could be efficiently controlled regardless of the targeted degree of polymerization (from DP 50 to DP 800). Instead, in mixtures containing [DMF]:[H2O] = 4:1, dispersity could be successfully tailored only up to DP = 200 while for higher targeted DPs, a reduction in the final dispersity was not feasible. To expand the scope of our system, we subsequently exploited alternative organic solvents including DMAc, dioxane, DMSO, and ACN. While DMAc showed a side reaction attributed to the high amounts of acid employed, the other solvents successfully resulted in an efficient control over dispersity with ACN requiring the lowest amount of acid to achieve the lowest dispersity value (i.e. 2 equivalents of acid yielded Đ ∼ 1.19). Notably, the highest Đ polymers synthesized in the various solvents displayed very high end-group fidelity as characterized by mass-spectrometry and in-situ chain extensions. After establishing optimal reaction conditions, we also synthesized a range of exemplary diblock and triblock copolymers (with alternating low and high Đ) demonstrating excellent dispersity control upon subsequent block additions.

Methoxy-substituted carbazole-based polymers obtained by RAFT polymerization for solution-processable organic light-emitting devices

New electroactive vinyl monomers, i.e., 3,6-dimethoxy-9-(4-vinylphenyl)-9H-carbazole and 3,6-dimethoxy-9-(3-vinylphenyl)-9H-carbazole were prepared by palladium catalyzed reactions of dimethoxy-9H-carbazole with 1-bromo-4-vinylbenzene or 1-bromo-3-vinylbenzene, respectively. Living radical polymerization of these monomers was carried out using 2-(dodecylthiocarbonothioylthio)-2-methylpropionic acid as a RAFT agent affording polymers with controlled molecular weight (up to Mn = 20,000) and low polydispersity (Đ<1.5). The obtained polymers exhibited delayed fluorescence caused by relaxation of excimer states. The lifetimes of long-lived components up to 2.6 μs were obtained for the excimer emission by multi-exponential fitting of photoluminescence decay curves. The polymers were tested in solution-processed OLEDs. Green thermally-activated-delayed-fluorescence OLEDs with polymers as hole transporting materials demonstrated lower turn-on voltage and enhanced charge balance in emission layer compared to device fabricated using the commercial hole-transporting material. Additionally, the phosphorescent OLEDs based on red phosphor as dopant and the synthesized polymer as a host materials were fabricated and characterized. The best device showed external quantum efficiency of 10.6%.

Anti-UV and hydrophobic dual-functional coating fabrication for flame retardant polyester fabrics by surface-initiated PET RAFT technique

Inspired by the flourish of living radical polymerization (LRP), surface-initiated LPR technology shows great potential in good control and accurate tailoring of target polymer coatings. In this work, surface-initiated photoinduced electron transfer-reversible addition-fragmentation chain transfer polymerization (SI-PET-RAFT) was employed as a facile synthetic rout for the fabrication of surface-tethered polymeric brushes with anti-UV and hydrophobic properties for flame retardant polyester fabrics (FRPET). Firstly, RAFT agent 4-Cyano-4-[(dodecyl sulfanyl thiocarbonyl) sulfanyl] pentanoic acid (CDTPA) was grafted onto polydopamine (PDA) deposited FRPET, followed by the controlled growth of glycidyl methacrylate (GMA) onto polyester fabrics via SI-PET-RAFT method. Finally, benzotriazole anti-UV agents were grafted as secondary functionalization. According to SEM-EDS and XPS analysis, PGMA has been immobilized successfully onto the surface of FRPET fabrics. An efficient PET RAFT polymerization of GMA with low dispersity (Ð<1.2), temporal control, and chain-end fidelity was achieved under mild yellow light irradiation (λmax = 570 nm, 4 W/m2). It also exhibited the feasibility of polymerization under natural sunlight and oxygen tolerance. The flame retardant, UV resistant and hydrophobic properties of the treated fabrics were investigated. In the microscale combustion calorimetry test, the peak heat release rate (PHRR) effectively decreased by 59.50%. In the cone calorimetry test, the PHRR and total heat release also reduced. The melt-dripping was eliminated in the vertical flaming test and reached V-0 rating with LOI value of 28%. The UV transmittance of the fabric decreased to<4%, meeting the standard of UV resistant fabric and the water contact angle reached 125°, thus making flame retardant polyester fabric have good hydrophobicity. Besides, it also kept good durability in flame retardancy, UV shielding and water repellent. This study provides new insights into the surface engineering of photoregulated LRP techniques for multi-functional coating synthesis.