ARGET ATRP Research Articles

Amphiphilic zwitterionic-PDMS-based surface-modifying additives to tune fouling-release of siloxane-polyurethane marine coatings

Amphiphilic coatings have shown promising performance for marine applications to deter and limit biofouling. Hydrophobic marine coatings are unable to deter marine organisms that prefer hydrophobic surfaces for settlements, thus a series of amphiphilic additives were prepared and introduced to a hydrophobic system to attain surface amphiphilicity and improved performance without changing the base matrix. In this work, we report the successful synthesis of amphiphilic additives where highly incompatible blocks of hydrophobic polydimethylsiloxane (PDMS) and hydrophilic poly(sulfobetaine methacrylate) (poly(SBMA)) were connected, using ARGET ATRP (activators regenerated by electron transfer atom transfer radical polymerization) controlled radical polymerization technique. The surface characterization confirmed the presence of self-migrated amphiphilic additives to the surface of hydrophobic coating systems, and biological assessments indicated that the additives desirably improved fouling-release performance of the base hydrophobic system against macroalgal spores (Ulva linza) and barnacles (Amphibalanus amphitrite) while these additives had no detrimental effect on ability of the base matrix to release bacteria (Cellulophaga lytica), diatoms (Navicula incerta), and mussels (Geukensia demissa). Furthermore, this study not only reported the outstanding contribution of poly(SBMA)-PDMS additives towards contending with marine biofouling as well as the facile preparation of amphiphilic additives, but also concluded that several factors should be considered in the design of these additives for tailoring hydrophobic coatings: 1) PDMS block with a molecular weight of 1000 M¯n is preferred over higher molecular weights of PDMS; 2) hydrophilic portion between a range of 50% to 80% provides the desired amphiphilicity on a surface; and 3) poly(SBMA) block size does not necessarily impact the effectiveness of an additive.

Dual-functionalized block copolymer brush grafted on micron-sized polystyrene microsphere as recoverable sulfonic acid catalyst and nitroxide radical inhibitor for synthesis of MPEGMA

With 2,2,6,6-tetramethylpiperidin-4-yl methacrylate (TMPM) and styrene (St) as monomers, the block copolymer brush of PS-PSt-PTMPM was grafted on micro-sized polystyrene microsphere via the electron transfer regenerated catalyst atom transfer radical polymerization (ARGET ATRP). The piperidine groups of PTMPM block were then oxidized to nitroxide radicals by 3-chlorobenzoic acid and PSt block was sulfonated with sulfuric acid to give the dual-functionalized block copolymer brush of PS-PSH-PTMA containing both nitroxide radicals and sulfonic acid groups. PS-PSH-PTMA was used for the direct esterification of methacrylic acid (MAA) and methoxy poly(ethylene glycol) (MPEG) for synthesis of methoxy poly(ethylene glycol) methyl acrylates (MPEGMA) instead of free acid catalyst of p-toluene sulfonic acid and free inhibitor of 2,2,6,6-tetramethylpiperidine-1-oxyl radical (TEMPO), since the immobilized TEMPO units prevented the undesired radical self-polymerisation and the immobilized sulfonic acid residues catalyzed the esterification. The results showed that the esterification rate of MPEGMA with PS-PSH-PTMA as catalyst and inhibitor was over 99% and the reaction rate was twice as high as that with p-toluene sulfonic acid as catalyst and TEMPO as inhibitor. Furthermore, PS-PSH-PTMA could be easily recovered by filtration and the recycling performance was excellent.

Smart micelles self-assembled from four-arm star polymers as potential drug carriers for pH-triggered DOX release

A series of amphiphilic four-arm star polymers poly(e-caprolactone)-b-poly(2-(diethylamino)ethylmethacrylate) (4AS-PCL-b-PDMAEMA) were developed by a combination of ring opening polymerization (ROP) and continuous activators regenerated by electron transfer atom transfer radical polymerization (ARGET ATRP). The molecular structures of the copolymers were confirmed with 1H NMR, FT-IR and gel permeation chromatography (GPC). The critical micelle concentration (CMC) values of the star polymers in aqueous solution were extremely low (3.0–4.1 mg/L).In aqueous solution, the copolymers self-assemble into blank and doxorubicin (DOX)-loaded micelles with an average size of 56–150 nm measured by scanning electron microscopy (SEM) and dynamic light scattering (DLS), which consist of outer shell with blocks PDMAEMA and inner core with blocks PCL. The core block PCL was used to contain drug molecules and shell block PDMAEMA could protonize responding to acidic condition. The in vitro release behavior showed that the micelle structure remains basically unchanged, and the drug cumulative release was only 24.5% at pH 7.4, and at pH 5.0, PDMAEMA is protonated and the micelles swell, which accelerates the release rate of DOX and the cumulative release is higher than pH 7.4. Through the semi-empirical model, the mechanism of drug release process was analyzed, and the mechanism of drug release from polymer micelles was further explored. The in vitro cytotoxicity indicated that the 4AS-PCL-b-PDMAEMA materials had low toxicity, but the DOX-loaded micelles had an obvious inhibitory effect on the HepG2 cells. The results indicate the four-arm star polymers 4AS-PCL-b-PDMAEMA may be a potential drug carriers for pH-triggered DOX release.

Copper-Catalysed “Activators Regenerated by Electron Transfer” “Atom Transfer Radical Polymerisation” of Styrene from a Bifunctional Initiator in Ethyl Acetate/Ethanol, Using Ascorbic Acid/Sodium Carbonate as Reducing System

A new copper(II) chloride/tris(2-piridylmethyl)amine (1/1) catalysed “Activators Regenerated by Electron Transfer” “Atom Transfer Radical Polymerisation” (ARGET ATRP) process for the polymerisation of styrene is described. The salient features of the method are the simultaneous use of ascorbic acid (reducing agent) and Na2CO3 (basic agent), the employment of a bifunctional initiator (ethyl 2,2-dichloropropionate) and the utilisation of a green solvent mixture composed of ethyl acetate and ethanol (AcOEt/EtOH). Na2CO3 plays a central role since not only preserves the ligand from protonation, but it can also activate the reducing agent. The quantity of monomer in the reaction mixture, the AcOEt/EtOH ratio and the load of ascorbic acid/carbonate are important factors for achieving a regular transformation. Working at 100 °C and with a metal load of only 0.025 mol%, an almost perfectly controlled telechelic polystyrene is produced, provided that conversion is kept below 50%. If conversion is higher, the control is gradually lost due superimposition of a step-growth process to the main chain polymerisation process. Two interesting phenomena, encountered during this study, are activation of the redox complex by using only Na2CO3 and gelation of polystyrene at 60 °C.

Optimization of Cationic Nanogel PEGylation to Achieve Mammalian Cytocompatibility with Limited Loss of Gram-Negative Bactericidal Activity.

Tuning the composition of antimicrobial nanogels can significantly alter both nanogel cytotoxicity and antibacterial activity. This project investigated the extent to which PEGylation of cationic, hydrophobic nanogels altered their cytotoxicity and bactericidal activity. These biodegradable, cationic nanogels were synthesized by activators regenerated by electron transfer atom transfer radical polymerization (ARGET ATRP) emulsion polymerization with up to 13.9 wt % PEG (MW = 2000) MA, as verified by 1H NMR. Nanogel bactericidal activity was assessed against Gram-negative E. coli and P. aeruginosa and Gram-positive S. mutans and S. aureus by measuring membrane lysis with a LIVE/DEAD assay. E. coli and S. mutans viability was further validated by measuring metabolic activity with a PrestoBlue assay and imaging bacteria stained with a LIVE/DEAD probe. All tested nanogels decreased the membrane integrity (0.5 mg/mL dose) for Gram-negative E. coli and P. aeruginosa, irrespective of the extent of PEGylation. PEGylation (13.9 wt %) increased the cytocompatibility of cationic nanogels toward RAW 264.7 murine macrophages and L929 murine fibroblasts by over 100-fold, relative to control nanogels. PEGylation (42.8 wt %) reduced nanogel uptake by 43% for macrophages and 63% for fibroblasts. Therefore, PEGylation reduced nanogel toxicity to mammalian cells without significantly compromising their bactericidal activity. These results facilitate future nanogel design for perturbing the growth of Gram-negative bacteria.

Polysaccharide-enhanced ARGET ATRP signal amplification for ultrasensitive fluorescent detection of lung cancer CYFRA 21-1 DNA

An ultrasensitive fluorescence biosensor for detecting cytokeratin fragment antigen 21-1 (CYFRA 21-1) DNA of non-small cell lung carcinoma (NSCLC) is designed using polysaccharide and activator regenerated by electron transfer atom transfer radical polymerization (ARGET ATRP) signal amplification strategy. Thiolated peptide nucleic acid (PNA) is fixed on magnetic nanoparticles (MNPs) by a cross-linking agent and hybridized with CYFRA 21-1 DNA. Hyaluronic acid (HA) is linked to PNA/tDNA heteroduplexes in the form of carboxy-Zr4+-phosphate. Subsequently, multiple 2-bromo-2-methylpropionic acid (BMP) molecules are linked with HA to initiate ARGET ATRP reaction. Finally, a large number of fluorescein o-acrylate (FA) monomers are polymerized on the macro-initiators, and the fluorescence signal is significantly amplified. Under optimal conditions, this biosensor shows a significant linear correlation between the fluorescence intensity and logarithm of CYFRA 21-1 DNA concentration (0.1 fM to 0.1nM), and the limit of detection is as low as 78 aM. Furthermore, the sensor has a good ability to detect CYFRA 21-1 DNA in serum samples and to recognize mismatched bases. It suggests that the strategy has broad application in early diagnosis by virtue of its high sensitivity and selectivity. Graphical abstract A novel and highly sensitive fluorescence biosensor for quantitatively detecting CYFRA 21-1 DNA via dual signal amplification of hyaluronic acid and ARGET ATRP reaction was developed. This proposed method has a low detection limit, wide detection range, high selectivity, and strong anti-interference.

CuBr2/Me6TREN Mediated ARGET ATRP of Methyl acrylate in Polyethylene Glycol

CuBr2/Me6TREN Mediated ARGET ATRP of Methyl acrylate in Polyethylene Glycol

Natural catalyst mediated ARGET and SARA ATRP of N-isopropylacrylamide and methyl acrylate

An extract prepared from inexpensive, drumstick leaves having natural transition metals in ppm levels was exploited as a catalyst for a well-controlled synthesis of poly(N-isopropylacrylamide) and poly(methyl acrylate).

Research on a kind of biocompatible molecularly imprinted materials with silybin controlled release based on pH/temperature dual responses

Silybin, a hepatoprotective active natural ingredient, was used as the template, methyl acrylic acid (MAA) as the functional monomer, n-isopropyl acrylamide (NIPAm) as the thermal response monomer, magnetic core Fe3O4@CS@APTES@BiBB coated by biocompatible chitosan as the carrier, and a kind of silybin molecularly imprinted materials (MMIPs) based on pH/temperature dual responses were prepared by electron transfer activation regenerative catalyst atom transfer radical polymerization (ARGET ATRP). The synthesized material was characterized by FT-IR, TGA, SEM, XRD, VSM, and XPS, and the loading behavior of silybin in MMIPs could be explained by the pseudo-second-order kinetic model. The selectivity factor α (2.636) and the relative selectivity factor β (2.468) indicated MMIPs had good specific recognition ability for silybin. In addition, a series of experimental data displayed MMIPs had many other excellent characteristics such as adsorption property, swelling performance, biocompatibility, degradability, stability, reproducibility and so on. The cumulative release rates of MMIPs could reach 29%, 23% and 25% in the media of pH 1.0, 7.4 and 8.2 at 37.5 °C, resepectively, and when the temperature was raised to 43 °C, the release rate of MMIPs in solution (pH 7.4) reached 49%, which indicated that the carrier material had good pH/temperature dual responses.

PH-Sensitive micelles of adamantane-based random copolymer

pH-Sensitive adamantane-based random copolymer (Ad-P(EMA-co-MAA)4) was synthesized by electron transfer atom radical polymerization (ARGET ATRP). In aqueous solution, the copolymer could self-assembled into micelles (Dh = 146 nm). The pH-sensitiveness of the micelles was confirmed by dynamic light scattering (DLS) and transmission electron microscopy (TEM). In vitro drug release behavior of the paclitaxel (PTX)-loaded micelles suggested that the rate of PTX release could be influenced by the pH values of environment. The cytotoxicity assay indicated the low cytotoxicity of the blank micelles and significant drug efficacy of the PTX-loaded micelles. Thus, the as-made pH-sensitive micelles chould be used as nano-carriers for biomedical applications.

The toughening of polymeric glasses using cellulose without sacrificing transparency

The development of cellulose graft copolymers has been intensively studied during recent years. Our previous works have demonstrated that cellulose graft strategy can greatly improve the mechanical properties of thermoplastic elastomers. However, the effect of cellulose graft strategy on glassy polymers is still unknown. Herein, Cellulose-graft-poly(methyl methacrylate) (Cell-g-PMMA) copolymers were synthesized by activators regenerate by electron transfer atom transfer radical polymerization (ARGET ATRP). Two kinds of celluloses, microcrystalline cellulose (MCC) and wood pulp cellulose (Pulp) were used as starting materials. Thermal behavior, transparency, and mechanical properties of these graft copolymers were investigated. Compared with the brittle fracture of PMMA, a typical ductile fracture was observed in both MCC-g-PMMA and Pulp-g-PMMA copolymers, which showed similar transparency as linear PMMA film. The tensile toughness of MCC-g-PMMA copolymers was almost 7 times to that of linear PMMA. Furthermore, the toughness of Pulp-g-PMMA copolymers was even better than that of MCC-g-PMMA copolymers.

Smart pH-responsive polymeric micelles for programmed oral delivery of insulin

The development of intelligent oral drug delivery carrier aiming at efficiently bring insulin to intestine is of great significance for diabetes mellitus therapy. In the present study, a series of amphiphilic pH-sensitive block copolymer poly(methyl methacrylate-co-methacrylicacid)-b-poly(2-amino ethyl methacrylate) [P(MMA-co-MAA)-b-PAEMA] was synthesized via activators regenerated by electron transfer atom transfer radical polymerization (ARGET ATRP) and further self-assembled into pH-responsive cationic polymeric micelles (PCPMs) for oral insulin delivery. The structure and molecular weight were confirmed by proton nuclear magnetic resonance (1H-NMR), Fourier transforming infrared spectrum (FT-IR) and gel permeation chromatography (GPC), respectively. The critical micelle concentration (CMC) values of these copolymers were measured by fluorescent probe method at pH 1.2 (8–15 μg/mL) and pH 7.4 (22–42 μg/mL), respectively, demonstrating high stability at acidic environment. A decrease in the particle size of PCPMs was associated with an increased pH at beginning, which reached around 200 nm at neutral pH, while the particle size increased obviously with pH increase, indicating the pH-sensitivity of PCPMs. The insulin was entrapped into the core of PCPMs (Ins-loaded PCPMs) with high loading efficiency via diafiltration method. The in vitro experiments show Ins-loaded PCPMs have low toxicity and exhibit pH-triggered release profile with remitted initial burst release. The results indicate that the PCPMs self-assembled from P(MMA-co-MAA)-b-PAEMA may be potential carriers for efficient oral delivery of insulin with controlled release property.

Surface-Induced ARGET ATRP for Silicon Nanoparticles with Fluorescent Polymer Brushes.

Well-defined polymer brushes attached to nanoparticles offer an elegant opportunity for surface modification because of their excellent mechanical stability, functional versatility, high graft density as well as controllability of surface properties. This study aimed to prepare hybrid materials with good dispersion in different solvents, and to endow this material with certain fluorescence characteristics. Well-defined diblock copolymers poly (styrene)-b-poly (hydroxyethyl methyl acrylate)–co-poly (hydroxyethyl methyl acrylate- rhodamine B) grafted silica nanoparticles (SNPs-g-PS-b-PHEMA-co-PHEMA-RhB) hybrid materials were synthesized via surface-initiated activators regenerated by electron transfer atom transfer radical polymerization (SI-ARGET ATRP). The SNPs surfaces were modified by 3-aminopropyltriethoxysilane (KH-550) firstly, then the initiators 2-Bromoisobutyryl bromide (BIBB) was attached to SNPs surfaces through the esterification of acyl bromide groups and amidogen groups. The synthetic initiators (SNPs-Br) were further used for the SI-ARGET ATRP of styrene (St), hydroxyethyl methyl acrylate (HEMA) and hydroxyethyl methyl acrylate-rhodamine B (HEMA-RhB). The results indicated that the SI-ARGET ATRP initiator had been immobilized onto SNPs surfaces, the Br atom have located at the end of the main polymer chains, and the polymerization process possessed the characteristic of controlled/“living” polymerization. The SNPs-g-PS-b-PHEMA-co-PHEMA-RhB hybrid materials show good fluorescence performance and good dispersion in water and EtOH but aggregated in THF. This study demonstrates that the SI-ARGET ATRP provided a unique way to tune the polymer brushes structure on silica nanoparticles surface and further broaden the application of SI-ARGET ATRP.

Highly-reactive haloester surface initiators for ARGET ATRP readily prepared by radio frequency glow discharge plasma.

New surface initiators for ARGET ATRP (activators regenerated by electron transfer atomic transfer radical polymerization) have been prepared by the plasma deposition of haloester monomers. Specifically, methyl 3-bromopropionate (M3BP), methyl 2-chloropropionate, and ethyl 2-fluoropropionate (E2FP) were plasma deposited onto glass discs using RF glow discharge plasma. This technique creates surface coatings that are resistant to delamination and rich in halogen species making them good candidates for surface initiators for ARGET ATRP. Of all the plasma polymerized surface coatings, M3BP showed the highest halogen content and was able to grow 2-hydroxyethyl methacrylate (HEMA) polymer brushes on its surface via ARGET ATRP in as little as 15 min as confirmed by XPS. Surprisingly, E2FP, a fluoroester, was also able to grow HEMA polymer brushes despite fluorine being a poor leaving group for ARGET ATRP. The versatility of RF glow discharge plasma offers a clear advantage over other techniques previously used to immobilize ARGET ATRP surface initiators.

Moisture curable non-isocynated polyacrylate triblock copolymer elastomers: synthesis and properties

In this study, novel polyacrylate triblock copolymer elastomers containing methoxysilane groups, poly(methyl methacrylate-co - 3-methacryloxypropyl-methyldimethoxysilane)-b - poly(ethyl acrylate)-b - poly(methyl methacrylate-co - 3-methacryloxypropylmethyldimethoxy-silane) [(PMMA-co - PDMMSPMA)-b - PEA-b - (PMMA-co - PDMMSPMA)], are synthesized and investigated. The triblock copolymers are synthesized via ARGET ATRP using copper wire as the reducing agent and the copolymers can be crosslinked under moisture conditions due to the hydrolyzation of methoxysilane groups. Results show that the triblock copolymers are successfully synthesized in a good controlled way. Copper wire is a better reducing agent in the ARGET ATRP of the methoxysilane monomers than stannous octoate and ascorbic acid. The melt viscosity of the triblock copolymers can be obviously reduced after introducing the methoxysilane groups into the copolymers, which is beneficial for the processing. The triblock copolymers can be crosslinked under moisture and the tension strength and elongation at break of the cross-linked elastomers are greatly enhanced simultaneously.

β-Cyclodextrin-based Zwitterionic Polymers as Clay-Tolerance Sacrificial Agents of Polycarboxylate Superplasticizers

β-Cyclodextrin (β-CD)-based zwitterionic polymer (β-CD-PDMAPS) was synthesized via activators regenerated by electron transfer for atom transfer radical polymerization (ARGET ATRP). As a clay-tolerance sacrificial agent, β-CD-PDMAPS combined with common polycarboxylate superplasticizer (CPC) can result in modified polycarboxylate superplasticizer (MPC). The dispersion and the dispersive retention of MPC in a cement system in the absence and presence of clay were investigated. The results indicated that MPC possesses excellent dispersing ability and can effectively inhibit the preferential adsorption of CPC onto the surface of clay. Compared to CPC, MPC displayed enhanced robustness toward clay. This can be attributed to the easy adsorption of the β-CD-PDMAPS onto clay and the steric hindrance derived from β-CD, which can inhibit CPC from incorporating into the lattice structure of the clay. This work provides new insight into the development of polycarboxylate superplasticizers with enhanced clay tolerance.

Liposome-Surface-Initiated ARGET ATRP: Surface Softness Generated by "Grafting from" Polymerization.

Liposomes are self-assembled vesicles of amphiphilic lipid molecules, which have been investigated as models of cells, or tools for drug delivery systems. In these systems, the surface property of the liposomes plays an important role. In this study, we demonstrated a novel polymer modification of liposome surfaces using a controlled radical polymerization, "activators regenerated by electron transfer for atom transfer radical polymerization", in aqueous media without a deoxygenation step. Dynamic light scattering and 1H NMR measurement indicated the successful modification of the polymer on the liposome surface. The molecular weight of the grafted polymer chain was systematically controlled by changing the monomer concentrations in the "grafting from" polymerization. Moreover, the modification resulted in a notable increase in surface softness as indicated by electrophoretic behavior, which was comparable to the surface of cells. The preparation method and the characterization presented in this study would be a helpful guideline in designing the polymer/liposome hybrid having target surface properties.

Janus silica nanosheets-based MMIPs platform for synergetic selective capture and fast separation of 2′-deoxyadenosine: Two different components segmented on the surface of one object

There is a pressing need to develop Janus-like magnetic molecularly imprinted polymers (J-SNs-MMIPs) nanoplatforms that integrate recognition elements and fast separation for specific adsorption and separation of 2′-deoxyadenosine (dA). In this work, the Janus silica nanosheet (J-SNs) with a hydrophobic surface (capped with 3-chloropropyl groups) and a hydrophilic surface (capped with amino-groups) was firstly fabricated by crushing Janus composite hollow spheres resulting from self-organized sol-gel process at amphiphilic emulsion interface. Subsequently, the imprinted polymers using dA as template molecule and synthesized 5-(2-Carbomethoxyvinyl)-2′-deoxyuridine (AcrU) as functional monomer were grafted onto the hydrophobic surface of J-SNs by activators regenerated electron transfer atom transfer radical polymerization (ARGET ATRP). Finally, carboxyl modified Fe3O4 particles were attached onto the hydrophilic surface of as-prepared J-SNs-MIPs via the condensation reaction between amino and carboxyl groups. The J-SNs-MMIPs displayed the ability to specifically recognize and fast separate dA, whereas no imprinting effect was observed for 2′-deoxyguanosine (dG) or deoxycytidine (dC) or 5′-monophosphate disodium salt (AMP). And the formed hydrogen bonds between complementary base of AcrU and adenine base on the dA enhance the affinity. Moreover, the equilibrium time was 70 min, and the maximum monolayer adsorption was calculated to be 61.22 μmol g−1 at 25 °C. By evaluating the selective recognition of dA from spiked human urine samples, the J-SNs-MMIPs could be used for selective separation and analysis of target dA in complex biological samples.

A Novel Bacterial Cellulose Aerogel Modified with PGMA via ARGET ATRP Method for Catalase Immobilization

Formation of Poly(Glycidyl Methacrylate) (PGMA) films on bacterial cellulose (BC) supports (aerogels) was achieved via activators regenerated by electron transfer for atom transfer radical polymerization (ARGET ATRP). Epoxy groups on PGMA were used for covalent coupling with catalase. Immobilized catalases on BC@PGMA were characterized by Fourier transform infrared spectroscopy (FTIR) and Typical scanning electron microscopy (SEM). The immobilized catalase amount reached a high value of 116 mg/g. Furthermore, the thermal, pH and storage stabilities of the immobilized catalase were improved significantly. After 10 use cycles, the BC@PGMA-catalase still retained approximately 63.5 % of the initial activity. This work demonstrates the potential of hierarchical nanomaterials for improving enzyme performance, leveraging the benefits of both nano- and macroscale supports. These results demonstrate that the BC@PGMA-catalase has high stability and good reusability, suggesting that the BC aerogel modified with PGMA may find applications in biotechnology and as biocatalyst.

Evaluation of the effect of hydrophobically modified silica aerogel on the ARGET ATRP of styrene and butyl acrylate

Abstract Hydrophobically modified silica aerocgel was used for in situ random copolymerization of styrene and butyl acrylate by activators regenerated by electron transfer for atom transfer radical polymerization (ARGET ATRP) to synthesize tailor-made poly (styrene-co-butyl acrylate) nanocomposites. Nitrogen adsorption/desorption isotherm, SEM and TEM were employed to examine inherent characteristics of the hydrophobically modified silica aerogel. Conversion and molecular weight determinations were carried out using GC and SEC respectively. Addition of 3 wt% hydrophobically modified silica aerogel leads to decrement of conversion from 67 to 48%. Molecular weight of poly (styrene-co-butyl acrylate) chains also decreases from 15993 to 12401 g mol−1 by addition of only 3 wt% hydrophobically modified silica aerogel; however, polydispersity index values increases from 1.07 to 1.34. Linear increase of ln(M0/M) with time for all the samples shows that copolymerization proceeds in a living manner. TGA results indicate that by increasing hydrophobically modified silica aerogel content, slight improvements in thermal stability of the nanocomposites were obtained. DSC results show a decrease in Tg from 44.2 to 35.4 °C by addition of 3 wt% hydrophobically modified silica aerogel.