Synthesis of ABA‐triblock and star‐diblock copolymers with poly(2‐adamantyl vinyl ether) and poly(n‐butyl vinyl ether) segments: New thermoplastic elastomers composed solely of poly(vinyl ether) backbones

ABA‐type triblock copolymers and AB‐type star diblock copolymers with poly(2‐adamantyl vinyl ether) [poly(2‐AdVE)] hard outer segments and poly(n‐butyl vinyl ether) [poly(NBVE)] soft inner segments were synthesized by sequential living cationic copolymerization. Although both the two polymer segments were composed solely of poly(vinyl ether) backbones and hydrocarbon side chains, they were segregated into microphase‐separated structure, so that the block copolymers formed thermoplastic elastomers. Both the ABA‐type triblock copolymers and the AB‐type star diblock copolymers exhibited rubber elasticity over wide temperature range. For example, the ABA‐type triblock copolymers showed rubber elasticity from about ?53 °C to about 165 °C and the AB‐type star diblock copolymer did from about ?47 °C to 183 °C with a similar composition of poly(2‐AdVE) and poly(NBVE) segments in the dynamic mechanical analysis. The AB‐type star diblock copolymers exhibited higher tensile strength and elongation at break than the ABA‐type triblock copolymers. The thermal decomposition temperatures of both the block copolymers were as high as 321–331 °C, indicating their high thermal stability. © 2013 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

The synthesis and solution behaviors of novel amphiphilic block copolymers based on d-galactopyranose and 2-(dimethylamino)ethyl methacrylate

A series of novel stimuli-responsive AB, ABA, and BAB type block copolymers based on 6-O-methacryloyl-1,2:3,4-di-O-isopropylidene-d-galactopyranose (MAIpGP:A block) and 2-(N,N-dimethylamino)ethyl methacrylate (DMAEMA: B block) were synthesized via ATRP techniques using ethyl 2-bromoisobutyrate (EBiB) as monofunctional ATRP initiator in the case of diblock copolymer and diethyl meso-2,5-dibromoadipate (DEDBA) as bifunctional ATRP initiator in the case of triblock copolymers. The PMAIpGP blocks of the AB, ABA, and BAB type linear block copolymers were converted to water soluble PMAGP blocks via deprotection process under mild acidic conditions. Both proton NMR and DLS studies demonstrated that block copolymers were temperature-sensitive, whereby the lower critical solution temperature (LCST) of polymers varied with the polymerization degrees of comonomers in the block copolymers. LCST was determined to be between ∼35 °C and 55 °C depending on the type and the comonomer compositions of the block copolymers. It was observed that an increase on the percentage of hydrophilic PMAGP block in block copolymer caused an increase on the LCST value as expected.     

Azobenzene‐Containing Block Copolymers as Light‐Induced Reworkable Adhesives: Effects of Molecular Weight,Composition, and Block Copolymer Architectures on the Adhesive Properties

We previously reported that ABA‐type triblock copolymers with azobenzene‐containing terminal blocks can be utilized as a light‐induced reworkable adhesive that enables repeatable bonding and debonding on demand. The reworkability was based on the photoisomerization of the azobenzene moiety and concomitant softening and hardening of the azo blocks. Our aim in this study is to investigate the effect of the composition, molecular weight, and block copolymer architectures on the reworkable adhesive properties. For this purpose, we prepared AB diblock, ABA triblock, and 4‐arm (AB)₄ star‐block copolymers consisting of polymethacrylates bearing an azobenzene moiety (A block) and 2‐ethylhexyl (B block) side chains and performed adhesion tests by using these block copolymers. As a result, among the ABA block copolymers with varied compositions and molecular weights, the ABA triblock copolymers with an azo block content of about 50 wt % and relatively low molecular weight could achieve an appropriate balance between high adhesion strength and low residual adhesion strength upon UV irradiation. Furthermore, the 4‐arm star‐block structure not only enhances the adhesion strength, but also maintains low residual adhesion strength when exposed to UV irradiation. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 806–813     

Synthesis of sterically stabilized polystyrene latex particles using cationic block copolymers and macromonomers and their application as stimulus-responsive particulate emulsifiers for oil-in-water emulsions

2-(Dimethylamino)ethyl methacrylate (DMA) was block copolymerized with methyl methacrylate (MMA) using group transfer polymerization to give four AB diblock, ABA triblock, and BAB triblock copolymers of low polydispersity (Mw/Mn < 1.20). In addition, a near-monodisperse styrene-functionalized DMA-based macromonomer was synthesized via oxyanionic polymerization using a potassium 4-vinylbenzyl alcoholate initiator. These five well-defined, tertiary amine methacrylate-based copolymers were evaluated as steric stabilizers for the synthesis of polystyrene latexes via emulsion and dispersion polymerization. The most efficient steric stabilizers proved to be the DMA-MMA diblock copolymer and the DMA-based macromonomer. The polystyrene latexes were characterized in terms of their particle size and morphology, stabilizer content, surface charge, and surface activity using dynamic light scattering, scanning electron microscopy, 1H NMR spectroscopy, aqueous electrophoresis measurements, and surface tensiometry, respectively. The pH-dependent surface activity exhibited by selected latexes suggests potential applications as stimulus-responsive particulate emulsifiers for oil-in-water emulsions.     

Thermoresponsive gels based on ABA triblock copolymers: Does the asymmetry matter?

The aim of this study was to investigate the effect of the asymmetry of the triblock copolymers on their thermoresponsive self‐assembly behavior. To this end, nine ABA‐type triblock copolymers with n‐butyl methacrylate and 2‐(dimethylamino)ethyl methacrylate (DMAEMA) consisting of the A and the B blocks, respectively, were synthesized. Polymers of three different DMAEMA contents (50, 60, and 70 wt %) were synthesized while varying the length ratio of the two hydrophobic A blocks. Specifically, one symmetric ABA triblock copolymer and two asymmetric ABA′ triblock copolymers with the length of the second A block to be twice or four times bigger than the length of the first A block (AB2A and AB4A triblock copolymer) were synthesized for each DMAEMA composition. Three statistical copolymers were also synthesized for comparison. The thermoresponsive behavior of the copolymers was studied and it was found that the cloud point and rheological properties of the polymers were strongly affected by the architecture (statistical vs. block) and less strongly by the DMAEMA composition and the asymmetry of the polymers. Nevertheless, interestingly the asymmetry of the ABA triblock copolymers did influence the thermoresponsive behavior with the more symmetric polymers presenting a sol–gel transition at lower temperatures. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 2850–2859.     

Topological “interfacial” polymer chemistry: Dependency of polymer “shape” on surface morphology and stability of layer structures when heating organized molecular films of cyclic and linear block copolymers of n‐butyl acrylate‐ethylene oxide

The “topological polymer chemistry” of amphiphilic linear and cyclic block copolymers at an air/water interface was investigated. A cyclic copolymer and two linear copolymers (AB‐type diblock and ABA‐type triblock copolymers) synthesized from the same monomers were used in this study. Relatively stable monolayers of these three copolymers were observed to form at an air/water interface. Similar condensed‐phase temperature‐dependent behaviors were observed in surface pressure–area isotherms for these three monolayers. Molecular orientations at the air/water interface for the two linear block copolymers were similar to that of the cyclic block copolymer. Atomic force microscopic observations of transferred films for the three polymer types revealed the formation of monolayers with very similar morphologies at the mesoscopic scale at room temperature and constant compression speed. ABA‐type triblock linear copolymers adopted a fiber‐like surface morphology via two‐dimensional crystallization at low compression speeds. In contrast, the cyclic block copolymer formed a shapeless domain. Temperature‐controlled out‐of‐plane X‐ray diffraction (XRD) analysis of Langmuir–Blodgett (LB) films fabricated from both amphiphilic linear and cyclic block copolymers was performed to estimate the layer regularity at higher temperatures. Excellent heat‐resistant properties of organized molecular films created from the cyclic copolymer were confirmed. Both copolymer types showed clear diffraction peaks at room temperature, indicating the formation of highly ordered layer structures. However, the layer structures of the linear copolymers gradually disordered when heated. Conversely, the regularity of cyclic copolymer LB multilayers did not change with heating up to 50 °C. Higher‐order reflections (d₀₀₂, d₀₀₃) in the XRD patterns were also unchanged, indicative of a highly ordered structure. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 486–498     

Atrp synthesis of abc lipophilic–hydrophilic–fluorophilic triblock copolymers

New ABC triblock copolymers that contain lipophilic, hydrophilic, and fluorophilic blocks are reported. These new block copolymers were synthesized via sequential controlled/living atom transfer radical polymerization. The formation of block copolymers was confirmed by size exclusion chromatography, ¹H, and ¹⁹F NMR. In direct comparison to the ABC copolymer, the corresponding ABA′ polymer did not produce a gel up to 45 wt % polymer. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2601–2608, 2007     

Synthesis and characterization of side‐chain liquid crystalline ABC triblock copolymers with p‐methoxyazobenzene moieties by atom transfer radical polymerization

A series of novel side‐chain liquid crystalline ABC triblock copolymers composed of poly(ethylene oxide) (PEO), polystyrene (PS), and poly[6‐(4‐methoxy‐4′‐oxy‐azobenzene) hexyl methacrylate] (PMMAZO) were synthesized by atom transfer radical polymerization (ATRP) using CuBr/1,1,4,7,7‐pentamethyldiethylenetriamine (PMDETA) as a catalyst system. First, the bromine‐terminated diblock copolymer poly(ethylene oxide)‐block‐polystyrene (PEO‐PS‐Br) was prepared by the ATRP of styrene initiated with the macro‐initiator PEO‐Br, which was obtained from the esterification of PEO and 2‐bromo‐2‐methylpropionyl bromide. An azobenzene‐containing block of PMMAZO with different molecular weights was then introduced into the diblock copolymer by a second ATRP to synthesize the novel side‐chain liquid crystalline ABC triblock copolymer poly(ethylene oxide)‐block‐polystyrene‐block‐poly[6‐(4‐methoxy‐4′‐oxy‐azobenzene) hexyl methacrylate] (PEO‐PS‐PMMAZO). These block copolymers were characterized using proton nuclear magnetic resonance (¹H NMR) and gel permeation chromatograph (GPC). Their thermotropic phase behaviors were investigated using differential scanning calorimetry (DSC) and polarized optical microscope (POM). These triblock copolymers exhibited a smectic phase and a nematic phase over a relatively wide temperature range. At the same time, the photoresponsive properties of these triblock copolymers in chloroform solution were preliminarily studied. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4442–4450, 2008     

Water-soluble ABC triblock copolymers based on vinyl ethers: Synthesis by living cationic polymerization and solution characterization

Water-soluble ABC triblock copolymers of methyl vinyl ether (MVE), ethyl vinyl ether (EVE), and methyl tri(ethylene glycol) vinyl ether (MTEGVE) of various block sequences and carrying 20 monomer units in each block were synthesized by living cationic polymerization. In addition to the triblocks, one AB diblock, one BA diblock, and one statistical copolymer of MVE and MTEGVE carrying 20 units of each type of monomer were synthesized as controls. Moreover, three homopolymers each carrying 20 units of MVE and end groups of varying hydrophobicity were synthesized using three different initiators. The molecular weights and molecular weight distributions of all the polymers were determined by gel permeation chromatography (GPC) in tetrahydrofuran (THF). The number average degrees of polymerization (DP_ns) and composition of all the polymers were calculated by proton nuclear magnetic resonance (¹H-NMR) spectroscopy. The molecular weights and degrees of polymerization corresponded to the values expected from the monomer/initiator ratios. The calculated polydispersities were reasonably narrow at 1.3. Aqueous GPC studies at room temperature on the triblock copolymers showed that the polymers exist as isolated chains (unimers) in solution but they tend to assemble and form micelles in the presence of a sufficiently high salt concentration apparently due to the insolubility of the EVE units under the latter conditions. Triblocks with a different block sequence exhibited a different susceptibility to salt-induced micellization, as indicated by the retention volume of the micelles and the relative micelle/unimer peak areas. Similarly, the cloud points of the triblock copolymers covered a relatively wide temperature range from 56 to 72°C. These differences in micellization and cloud points suggest a profound effect of the location of the hydrophilic MTEGVE block on copolymer association. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 1181–1195, 1997     

Well‐defined phosphonate‐functional copolymers through RAFT copolymerization of dimethyl‐p‐vinylbenzylphosphonate

Dibenzyltrithiocarbonate‐mediated RAFT polymerization of dimethyl‐p‐vinylbenzylphosphonate and its copolymerization with styrene are studied in order to access well‐defined statistical and block copolymers containing controlled amounts of dimethylphosphonate groups. NMR and SEC analysis of the (co)polymers confirm the controlled character of the polymerizations. ABA triblock copolymers are treated with TMSiBr/MeOH in order to transform the dimethylphosphonate groups into phosphonic acids while keeping the midchain trithiocarbonate group and triblock nature unaffected. Alternatively, the combination of trithiocarbonate aminolysis with TMSiBr/MeOH treatment of the same triblock copolymers leads to phosphonic acid‐functional diblock copolymer counterparts. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 2616‐2624     

ABA triblock copolymers from two mechanistic techniques: Polycondensation and atom transfer radical polymerization

ABA triblock copolymers were synthesized using two polymerization techniques, polycondensation, and atom transfer radical polymerization (ATRP). A telechelic polymer was synthesized via polycondensation, which was then functionalized into a difunctional ATRP initiator. Under ATRP conditions, outer blocks were polymerized to form the ABA triblock copolymer. Six types of samples were prepared based on a poly(ether ether ketone) or poly(arylene ether sulfone) center block with either poly(methyl methacrylate), poly(pentafluorostyrene), or poly(ionic liquid) outer blocks. As polycondensation results in polymers with broad molecular weight distribution (MWD), the center of these triblock copolymers are disperse, while the outside blocks have narrow MWD due to the control afforded from ATRP. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 228–238     

Syntheses and characterizations of poly[2‐(dimethylamino)ethyl methacrylate]–poly(propylene oxide)–poly[2‐(dimethylamino)ethyl methacrylate] ABA triblock copolymers

A novel, near‐monodisperse, well‐defined ABA triblock copolymer, poly[2‐(dimethylamino)ethyl methacrylate]‐b‐poly(propylene oxide)‐b‐poly[2‐(dimethylamino)ethyl methacrylate], was synthesized via oxyanion‐initiated polymerization. The initiator was a telechelic‐type potassium alcoholate prepared from poly(propylene glycol) and KH in dry tetrahydrofuran. The copolymers produced were characterized by Fourier transform infrared, ¹H NMR, and gel permeation chromatography (GPC). GPC and ¹H NMR analyses showed that the products obtained were the desired copolymers, with narrow molecular weight distributions (ca. 1.09–1.11) very close to that of the original poly(propylene glycol). ¹H NMR, surface tension measurements, and dynamic light scattering all indicated that the triblock copolymer led to interesting aqueous solution behaviors, including temperature‐induced micellization and very high surface activity. © 2002 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 40: 624–631, 2002; DOI 10.1002/pola.10144     

Development of organotellurium‐mediated and organostibine‐mediated living radical polymerization reactions

Organotellurium‐mediated living radical polymerizations (TERPs) and organostibine‐mediated living radical polymerizations (SBRPs) provide well‐defined polymers with a variety of polar functional groups via degenerative chain‐transfer polymerization. The high controllability of these polymerizations can be attributed to the rapid degenerative‐transfer process between the polymer‐end radicals and corresponding dormant species. The versatility of the methods allows the synthesis of AB diblock, ABA triblock, and ABC triblock copolymers by the successive addition of different monomers. This review summarizes the current status of TERP and SBRP. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1–12, 2006     

Thermoreversible gelation of poly(ethylene oxide) biodegradable polyester block copolymers. II

Poly(ethylene oxide)-b-poly(L-lactic acid) (PEO-PLLA) diblock copolymers were synthesized via a ring opening polymerization from poly(ethylene oxide) and l -lactide. Stannous octoate was used as a catalyst in a solution polymerization with toluene as the solvent. Their physicochemical properties were investigated by using infrared spectroscopy, ¹H-NMR spectroscopy, gel permeation chromatography, and differential scanning calorimetry, as well as the observational data of gel-sol transitions in aqueous solutions. Aqueous solutions of PEO-PLLA diblock copolymers changed from a gel phase to a sol phase with increasing temperature when their polymer concentrations are above a critical gel concentration. As the PLLA block length increased, the gel-sol transition temperature increased. For comparison, diblock copolymers of poly(ethylene oxide)-b-poly(l -lactic acid-co-glycolic acid) [PEO-P(LLA/GA)] and poly(ethylene oxide)-b-poly(dl -lactic acid-co-glycolic acid) [PEO-P(DLLA/GA)] were synthesized by the same methods, and their gel-sol transition behaviors were also investigated. The gel-sol transition properties of these diblock copolymers are influenced by the hydrophilic/hydrophobic balance of the copolymer, block length, hydrophobicity, and stereoregularity of the hydrophobic block of the copolymer. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 2207–2218, 1999     

嵌段序列对聚合物囊泡形成过程影响的Monte Carlo模拟

采用Monte Carlo模拟方法研究了具有相同链长和组分比的不同嵌段序列的AB两嵌段共聚物与ABA三嵌段共聚物在选择性溶剂中形成囊泡的动力学过程. 模拟结果表明, AB两嵌段共聚物囊泡的形成与ABA三嵌段共聚物囊泡的形成的动力学过程不同. 在慢速退火条件下, ABA三嵌段共聚物囊泡是通过亲水链段向胶束的表面和中心扩散而形成的, 而AB两嵌段共聚物囊泡则由片层弯曲闭合而形成. 相对而言, 退火速度对AB两嵌段共聚物囊泡形成的动力学过程没有显著影响, 其改变仅影响亲水链段与疏水链段发生相分离的难易程度. 当退火速度较快时, 亲水链段和疏水链段发生相分离的速度较快且相分离发生在囊泡形成之前; 而当退火速度较慢时亲水链段和疏水链段之间的相分离在囊泡形成之后仍在进行.     

Monte-carlo simulations of the order–disorder transition depression in ABA triblock copolymers with a short terminal block

Although most ABA triblock copolymers are molecularly symmetric (i.e., the terminal blocks possess the same mass), molecularly asymmetric A1BA2 triblock copolymers are of greater fundamental interest in that they can be used to explore the transition from diblock to triblock copolymer in systematic fashion. In this study, we use a lattice Monte Carlo method known as the cooperative motion algorithm to simulate molten ABA triblock copolymers possessing a short terminal block to explore the effect of molecular asymmetry on the copolymer order–disorder transition (ODT). Reduced ODT temperatures, discerned by simultaneously analyzing several features of the simulation results, are found to compare favorably with experimental data. Of particular interest here is the initial depression in the ODT temperature for A1BA2 copolymers possessing a relatively short terminal (A2) block. This signature feature is successfully captured by the simulations and is found to be strongly dependent on composition, but weakly dependent on copolymer chain length. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2013     

Synthesis and characterization of well‐defined diblock and triblock copolymers of poly(N‐isopropylacrylamide) and poly(ethylene oxide)

Well‐defined diblock and triblock copolymers composed of poly(N‐isopropylacrylamide) (PNIPAM) and poly(ethylene oxide) (PEO) were successfully synthesized through the reversible addition–fragmentation chain transfer polymerization of N‐isopropylacrylamide (NIPAM) with PEO capped with one or two dithiobenzoyl groups as a macrotransfer agent. ¹H NMR, Fourier transform infrared, and gel permeation chromatography instruments were used to characterize the block copolymers obtained. The results showed that the diblock and triblock copolymers had well‐defined structures and narrow molecular weight distributions (weight‐average molecular weight/number‐average molecular weight < 1.2), and the molecular weight of the PNIPAM block in the diblock and triblock copolymers could be controlled by the initial molar ratio of NIPAM to dithiobenzoate‐terminated PEO and the NIPAM conversion. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4873–4881, 2004     

Synthesis of novel oligoester‐block‐polyacrylate‐block‐oligoester ABA triblock copolymers by coupling methods

An original approach based on coupling methodology was used to prepare novel well‐defined ABA triblock copolymers, made of polyester‐type chain ends (A) associated with a polyacrylate midblock (B). Poly(ethylene terephthalate)‐block‐poly(lauryl acrylate)‐block‐poly(ethylene terephthalate) (PET‐b‐PLAc‐b‐PET) copolymers were achieved from poly(ethylene terephthalate)‐b‐poly(lauryl acrylate) (PET‐b‐PLAc) diblock ones. The first step consisted in the synthesis of diblock copolymers by atom transfer radical polymerization of lauryl acrylate starting from PET segment as a macroinitiator. In the second step, the coupling of diblock copolymers was achieved using four different methods, which were evaluated and compared: atom transfer radical coupling, “click” chemistry using the Huisgen's reaction, and coupling via a dithiol reagent or a diisocyanate molecule. Coupling using the Huisgen's reaction or a diisocyanate spacer proved to be the most efficient techniques. Even if these methods showed limitation and were only adapted for copolymers with low molecular weights, we managed to successfully prepare ABA triblock copolymers involving a polyester segment as end blocks and a polyacrylate moiety as midblock. To our knowledge, such kind of chemical structure has never been reported before and would be useful, possibly affording physical networks leading to rheological modification, for instance. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Synthesis,characterization, and property of amphiphilic fluorinated abc‐type triblock copolymers

Novel amphiphilic fluorinated ABC‐type triblock copolymers composed of hydrophilic poly(ethylene oxide) monomethyl ether (MeOPEO), hydrophobic polystyrene (PSt), and hydrophobic/lipophobic poly(perfluorohexylethyl acrylate) (PFHEA) were synthesized by atom transfer radical polymerization (ATRP) using N,N,N′,N″,N″‐pentamethyldiethylenetriamine (PMDETA)/CuBr as a catalyst system. The bromide‐terminated diblock copolymers poly(ethylene oxide)‐block‐polystyrene (MeOPEO‐b‐PSt‐Br) were prepared by the ATRP of styrene initiated with the macroinitiator MeOPEO‐Br, which was obtained by the esterification of poly(ethylene oxide) monomethyl ether (MeOPEO) with 2‐bromoisobutyryl bromide. A fluorinated block of poly(perfluorohexylethyl acrylate) (PFHEA) was then introduced into the diblock copolymer by a second ATRP process to synthesize a novel ABC‐type triblock copolymer, poly(ethylene oxide)‐block‐polystyrene‐block‐poly(perfluorohexylethyl acrylate) (MeOPEO‐b‐PSt‐b‐PFHEA). These block copolymers were characterized by means of proton nuclear magnetic resonance (¹H NMR) and gel permeation chromatography (GPC). Water contact angle measurements revealed that the polymeric coating of the triblock copolymer (MeOPEO‐b‐PSt‐b‐PFHEA) shows more hydrophobic than that of the corresponding diblock copolymer (MeOPEO‐b‐PSt). Bovine serum albumin (BSA) was used as a model protein to evaluate the protein adsorption property and the triblock copolymer coating posseses excellent protein‐resistant character prior to the corresponding diblock copolymer and polydimethylsiloxane. These amphiphilic fluoropolymers can expect to have potential applications for antifouling coatings and antifouling membranes. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Effect of network connectivity on the mechanical and transport properties of block copolymer gels

Establishing the independent tunability of transport and mechanical properties in polymer gels would significantly contribute to their implementation as transdermal drug delivery media, among other things. The work conducted herein uses facile changes in the formulation of physically crosslinked styrenic ABA/AB block copolymer organogels to alter their mechanical properties independently from the mass transport of an internally-loaded nanocarrier. Such independent tunability is made possible by altering the relative amounts of ABA triblock and AB diblock copolymers while holding total copolymer concentration fixed. Specifically, three series of gels each with a fixed total copolymer concentration (10, 20, or 30 wt%) comprised of varying triblock copolymer concentration are studied. Small angle x-ray scattering confirms that, at the nanoscale, only gel network connectivity changes within each series, while mechanical and release experiments show that increasing network connectivity leads to significant growth of gel moduli, but little change in nanocarrier release rate.