Nanostructured thermotropic PBLG-PDMS-PBLG block copolymers

We report on the nano-organization and the thermal behavior of a series of triblock copolymers composed of a central soft polydimethylsiloxane (PDMS) and two polypeptide (poly-γ-benzyl-l-glutamate) blocks. Peptide blocks with varied lengths and therefore different secondary structures (β-sheet or α-helical) were attached to the PDMS central block. These two blocks are incompatible and microphase separate into different morphologies elucidated by polarized optical microscopy (POM), small-angle light scattering (SALS), X-ray spectroscopy (SAXS, WAXS) and atomic force microscopy (AFM). We demonstrate that the relative ratio of PBLG to PDMS direct both the type of nanodomain morphologies formed and also modifies the transition temperature. Each of these block copolymers have shown a reversible transition associated to its thermotropic liquid crystal behavior. At temperatures above the transition, the self-assembled structures are disrupted and prevented the organization at larger scales.     

Synthesis of block copolymers for surface functionalization with stimuli-responsive macromolecules

Using block copolymers with poly(n-butyl acrylate) (PBA) as anchor block being capable to tether the temperature-responsive block poly(N-isopropylacrylamide) (PNIPAAm) to the surface, polysulfone (PSf) films were functionalized applying an adsorption/surface entrapment process. Homo and block copolymer synthesis was investigated applying atom transfer radical polymerization (ATRP) using tris(2-(dimethylamino)ethyl)amine (Me₆TREN), CuCl and N,N-dimethylformamide (DMF). On basis of the determined critical micelle concentration of the block copolymers, surface functionalization of PSf was performed from an aqueous solution containing 25 vol% dimethylacetamide. These functionalized surfaces exhibit reversible temperature dependent properties due to the lower critical solution temperature (LCST) of PNIPAAm as can be proven by contact angle measurement. Furthermore, the beneficial effect of the PBA block with adjusted molecular weight on the stability of these coatings was proven. This surface functionalization method has various potential applications and the resulting surfaces are anticipated to exhibit actively triggerable ‘chaotic’ properties as basis of an efficient anti-biofouling strategy.     

Melt strength of blends of linear low density polyethylene and comb polymers

The melt strength of a metallocene linear low-density polyethylene (m-LLDPE) can be enhanced significantly by blending in less than 10 wt% of long chain branched comb polymer. The extent of the enhancement could be ten-fold and depends on the architectural details of the comb polymer. Comb polymers primarily affect melt strength and have little effect on other properties such as shear thinning, melt index, melt index ratio, and intrinsic tear.Balancing melt strength properties against shear-thinning properties is important in LLDPE fabrication processes. One approach would be to augment the effect of comb polymer by blending in another component, namely an easy processing (also known as sparsely long chain branched) LLDPE. In the examples given here, the enhancements in melt strength and shear thinning properties of the base polymer were found to be additive, i.e. a simple weighted sum of component properties matched the blend properties within 10%.     

Designing block copolymer architectures for targeted membrane performance

Using a combination of block copolymer self-assembly and non-solvent induced phase separation, isoporous ultrafiltration membranes were fabricated from four poly(isoprene-b-styrene-b-4-vinylpyridine) triblock terpolymers with similar block volume fractions but varying in total molar mass from 43 kg/mol to 115 kg/mol to systematically study the effect of polymer size on membrane structure. Small-angle X-ray scattering was used to probe terpolymer solution structure in the dope. All four triblocks displayed solution scattering patterns consistent with a body-centered cubic morphology. After membrane formation, structures were characterized using a combination of scanning electron microscopy and filtration performance tests. Membrane pore densities that ranged from 4.53 × 10¹⁴ to 1.48 × 10¹⁵ pores/m² were observed, which are the highest pore densities yet reported for membranes using self-assembly and non-solvent induced phase separation. Hydraulic permeabilities ranging from 24 to 850 L m⁻² h⁻¹ bar⁻¹ and pore diameters ranging from 7 to 36 nm were determined from permeation and rejection experiments. Both the hydraulic permeability and pore size increased with increasing molar mass of the parent terpolymer. The combination of polymer characterization and membrane transport tests described here demonstrates the ability to rationally design macromolecular structures to target specific performance characteristics in block copolymer derived ultrafiltration membranes.     

Crystallization assisted self-assembly of semicrystalline block copolymers

The self-assembly of block copolymers (BCPs) in the presence of crystallization as the second driving force is reviewed, for BCPs in the bulk, thin films, single crystals and micelles. The crystallization of semicrystalline BCPs in the bulk is introduced briefly and the unique morphologies of semicrystalline BCPs at various levels due to crystallization are discussed. The thin film morphologies shown by crystalline BCPs are summarized in terms of the factors affecting the relative strengths of various driving forces. Special attention is paid to the thin film morphologies of functional BCPs containing crystalline poly(3-alkylthiophene) and perylene bisimide units. The single crystal morphologies of semicrystalline BCPs are also presented. Finally, the micellar morphologies of BCPs with a semicrystalline core are reviewed. The controlled and living growth of crystalline micelles, which is the unique characteristic of such micelle, is then discussed.     

Poly(l-lactide) comb polymer brushes on the surface of clay layers

Poly(l-lactide) (PLLA) comb polymers on poly(hydroxyethyl methacrylate) (PHEMA) backbone were prepared on the surface of clay layers by a combination of in situ atom transfer radical polymerization (ATRP) and ring-opening polymerization. An ATRP initiator with a quaternary ammonium salt end group was intercalated into the interlayer spacing of clay. PHEMA polymer brushes on the surface of clay layers were prepared by in situ ATRP. PLLA comb polymers on PHEMA backbone were prepared by ring-opening polymerization. X-ray diffraction (XRD) and transmission electron microscopy (TEM) results showed that with the increase of comb chain length more and more exfoliated structure was created. Aggregation of wormlike comb polymer brushes on the surface of clay layers was observed by TEM. Differential scanning calorimeter (DSC) results indicated that both the melting points and glass transition temperatures of the comb polymer brushes increase with the increase of comb chain length. The equilibrium melting temperature of the comb polymer brush on the surface of clay layers is lower than cleaved polymer. An atomic force microscopy (AFM) image proves the formation of wormlike structure by cleaved comb polymers.     

The effect of radiation on comb block copolymers

In order to increase the plasma etch resistance of photoresists, comb-shaped block copolymers have been prepared with radiation resistant sidechains and radiation sensitive backbones. The sidechains were polystyrene, and the backbones were poly(methyl methacrylate) or poly(alkene sulphones). It was found possible to synthesize these block copolymers with up to 50% of the radiation resistant sidechains by anionic grafting for poly(methyl methacrylate). In the case of the polysulphones, an initial polystyrene containing a terminal alkene group was synthesized. This was copolymerized with the alkene and sulphur dioxide by a radical reaction. The radiation sensitivity of the copolymers was then studied.     

Synthesis, characterization and self-assembly behavior of six-armed star block copolymers with triphenylene core

Hexa-armed star block copolymers, s-[poly(l-lactide)-b-poly(styrene-co-N-acryloxysuccinimide)]₆ (s-[PLLA-b-poly(St-co-NAS)]₆) with triphenylene core have been successively prepared by the combination of ring-opening polymerization and atom transfer radical copolymerization, and they were used in the self-assembly in tetrahydrofuran, and the micelles with triphenylene core and PLLA as inner layer as well as poly(St-co-NAS) as shell were formed. After shell was cross-linked, PLLA was hydrolyzed in aqueous NaOH solution, the hollow spheres were formed. The structures, molecular weight and polydispersity index of the polymers were characterized by their ¹H NMR and FT-IR spectra, as well as GPC. Their morphologies were studied by TEM. The influence factors on the formation of various morphologies are under investigation.     

Self-organization of stack-up block copolymers into polymeric supramolecules

Polyethylene oxide –b– polypropylene oxide -b- polyethylene oxide (EO₁₀₆PO₇₀EO₁₀₆) block copolymer self-organizes into polymeric supramolecules, characterized by NMR as phase transition from the isotropic stack-up block structure to the ordered cubic polymeric supramolecular structure. Its dependence on both temperature and copolymer concentration is clearly shown by the changes in line shape and chemical shift of the PO₇₀ block β, γ resonances.     

Synthesis of novel block copolymers containing polyhedral oligomeric silsesquioxane (POSS) pendent groups via ring-opening metathesis polymerization (ROMP)

Ring-opening metathesis copolymerization of norbornene ethyl polyhedral oligomeric silsesquioxane monomer (NBEPOSS) and 2-endo-3-exo-5-norbornene-2,3-dicaboxylic acid trimethyl ester (NBETMS) was performed using a Ru-based catalyst, RuCl₂(CHPh)(PCy₃)₂. The block copolymers poly(NBETMS-b-NBEPOSS) were then converted to poly(NBECOOH-b-NBEPOSS) by hydrolysis and precipitation. The polymers were characterized by NMR and GPC and the actual NBEPOSS contents were found in good correspondence with the theoretical values. A linear dependence of M_n on conversion and a linear dependence of ln([M₀]/[M]) on reaction time observed in the polymerization of NBETMS suggest that chain breaking reactions such as termination and chain transfer are minimal. Low PDI values and smooth GPC peak shifts during polymerization after addition of a second batch of the same monomer or a NBEPOSS monomer also reflect a living process.     

Synthesis and self-assembly behaviors of three-armed amphiphilic block copolymers via RAFT polymerization

The novel trifunctional reversible addition-fragmentation chain transfer (RAFT) agent, tris(1-phenylethyl) 1,3,5-triazine-2,4,6-triyl trithiocarbonate (TTA), was synthesized and used to prepare the three-armed polystyrene (PS₃) via RAFT polymerization of styrene (St) in bulk with thermal initiation. The polymerization kinetic plot was first order and the molecular weights of polymers increased with the monomer conversions with narrow molecular weight distributions (M_w/M_n ≤ 1.23). The number of arms of the star PS was analyzed by gel permeation chromatography (GPC), ultraviolet visible (UV-vis) and fluorescence spectra. Furthermore, poly(styrene-b-N-isopropylacrylamide)₃ (PS-b-PNIPAAM)₃, the three-armed amphiphilic thermosensitive block copolymer, with controlled molecular weight and well-defined structure was also successfully prepared via RAFT chain extension method using the three-armed PS obtained as the macro-RAFT agent and N-isopropylacrylamide as the second monomer. The copolymers obtained were characterized by GPC and ¹H nuclear magnetic resonance (NMR) spectra. The self-assembly behaviors of the three-armed amphiphilic block copolymers (PS-b-PNIPAAM)₃ in mixed solution (DMF/CH₃OH) were also investigated by high performance particle sizer (HPPS) and transmission electron microscopy (TEM). Interestingly, the lower critical solution temperature (LCST) of aqueous solutions of the three-armed amphiphilic block copolymers (PS-b-PNIPAAM)₃ decreased with the increase of relative length of PS in the block copolymers.     

Synthesis and characterization of itaconic anhydride and stearyl methacrylate copolymers

The free-radical copolymerization and the properties of comb-like copolymers derived from renewable resources, itaconic anhydride (ITA) and stearyl methacrylate (SM), are described. The ITA-SM copolymers were nearly random with a slight alternating tendency. The copolymers exhibited a nanophase-separated morphology, with the stearate side-chains forming a bilayer, semi-crystalline structure. The melting point (T_m) of the side-chains and the crystallinity decreased with increasing ITA concentration. The crystalline side-chains suppressed molecular motion of the main chain, so that a glass transition temperature (T_g) was not resolved unless the ITA concentration was sufficiently high so that T_g > T_m. The softening point and modulus of the copolymers increased with the increasing ITA concentration, but the thermal stability decreased.     

New self-assembling biocompatible-biodegradable amphiphilic block copolymers

New biodegradable-biocompatible amphiphilic block copolymers were prepared in good yields by SnOct₂ catalyzed ring opening polymerization of ε-caprolactone initiated by monomethoxy-terminated poly(ethylene glycol) (MPEG). Coupling of the AB copolymers with hexamethylene diisocyanate afforded ABA (formally ABBA) block copolymers. Both AB and ABA copolymers were thoroughly characterized by IR and NMR spectroscopy, size exclusion chromatography, TGA and DSC thermal analysis. In particular, DSC measurements evidenced that the copolymer hydrophilic-lipophilic balance appreciably affected the state of adsorbed water. Polarized optical microscopy of bulk materials and pyrene fluorescence emission of polymer water solutions highlighted the copolymer tendency to phase separation and self-organization, respectively. Most of the prepared materials formed micelles in water and the copolymer structure appreciably affected their critical micellar concentration. In vitro cytocompatibility tests confirmed the low toxicity of the prepared polymeric materials which enhances their potential for biomedical applications.     

Synthesis and self-assembly of comb oligomers having rigid racemic or chiral binaphthyl macrocyclic pendant groups

In this article, we described the synthesis of comb oligomers having rigid racemic or chiral binaphthyl macrocyclic pendant groups via the free radical polymerization. Oligomers obtained were well characterized by MALDI-TOF-MS, ¹H NMR, FT-IR, UV, CD and SEC. These comb oligomers having macrocyclic pendant groups showed very good solubility in common organic solvents at room temperature. Furthermore, the oligomers could self-assemble into different morphologies by dropping their THF solutions of different concentrations on the surface of water. At a relatively low concentration, the oligomers self-aggregated into hollow spheres. When the concentration was increased, the aggregates changed into solid spheres. The morphologies of the hollow or solid spheres were observed by TEM and ESEM.     

偶氮嵌段共聚物合成、自组装与光响应性

含偶氮苯基团的嵌段共聚物兼具偶氮聚合物和嵌段共聚物的特点,可自组装形成具有特殊光响应性能的各种纳米/亚微米结构,在光信息存储、传感器、药物输送、光控智能材料等领域有重要的应用前景。本文对本课题组近年来在含强推拉电子型偶氮生色团的嵌段共聚物合成、自组装与光响应性方面的研究工作进行简要综述。     

Conjugated rod-coil block copolymers: Synthesis, morphology, photophysical properties, and stimuli-responsive applications

Conjugated rod-coil block copolymers have been accorded great importance since they provide a powerful route towards supramolecular objects with novel architectures, functions and physical properties. This review summarizes recent progress on the synthesis, morphology, optoelectronic properties and applications of such block copolymers. The combination of the precise condensation and living polymerization through the grafting-from or grafting-onto methodology produce various architectures of conjugated rod-coil block copolymers, including rod-coil, coil-rod-coil, rod-coil-coil, and rod-coil-rod. In the following, the relationships between polymer morphologies and photophysical properties in different phases are reviewed, as classified by solution micelles, thin films or bulk samples, polymer brushes and electrospun nanofibers. The effects of the rod/coil ratio and polymer architecture on the morphology and optoelectronic properties are discussed. The control of nanosize domain and the aligned direction of conjugated rods are the key issues for enhancing the optoelectronic device performance. Moreover, novel multifunctional sensory materials based on combining the tunable photophysical properties of the π-conjugated rod and the stimuli-responsive coil are also highlighted. It is believed that conjugated rod-coil block copolymers could spark the future evolution of nanostructured polymers for multifunctional device applications.     

Self-assembly of POSS-containing block copolymers: Fixing the hierarchical structure in networks

A series of P(MMA-co-GMA)-b-PMAPOSS block copolymers (BCPs) were synthesized by ATRP. The BCPs contain POSS (polyhedral oligomeric silsesquioxane) as a pendant unit on a particular polymer block chain. In selective solvents, the BCPs self-assemble to form ordered micellar-like structures. Spherical, cylindrical or vesicle-like morphologies were produced by tuning the BCP and mixed solvent compositions. Crosslinking of the BCP by the reaction of the glycidyl groups in the P(MMA-co-GMA) block of the micelle shell (GMA = glycidyl methacrylate) with a diamine results in a long-range structure ordering. The hexagonally packed cylindrical arrangement of the BCP networks was revealed by SAXS and TEM. The hierarchical, ordered structure of the POSS-containing hybrids was fixed by crosslinking. In addition, transient physical gels were prepared from triblock copolymers with outer MAPOSS blocks, and their rheological behavior was investigated.     

Synthesis of polyesters-perfluoropolyethers block copolymers

Summary Multiblock-(A-B)_n-copolymers containing polyester segments together with perfluoropolyether (PFPE) segments have been prepared by polymerizing dimethyl terephthalate (DMT), or an equimolar mixture of DMT and dimethyl isophthalate (DMI), with ethylene glycol (EG) in the presence of different telechelic perfluoropolyethers in various amounts (5–30 wt%), using Tl(OBu)₄ as the catalyst. Fomblin ZDEAL (a-COOCH₃ terminated PFPE), Fomblin ZDOL (a PFPE having-CH₂OH terminal groups), and Fomblin ZDOLTX (a PFPE having-CH₂O(CH₂CH₂O)_yH terminal groups) were used as telechelic PFPEs. Fomblin ZDOLTX gave the best results: the highest yield in block copolymer (less sensitive to hydrolysis with respect to block copolymers prepared from the other PFPEs), a longer average length of polyester segments, and a relatively low fraction of PFPE lost by distillation during polymerization.     

Self-assembly of amphiphilic liquid crystal block copolymers containing a cholesteryl mesogen: Effects of block ratio and solvent

We report on the self-assembly, in water and in bulk, of amphiphilic liquid crystal block copolymers consisting of a cholesterol-based smectic LC polymer block (PAChol) and poly(ethylene glycol) (PEG) block. Two series of block copolymers, PEG₄₅-b-PAChol and PEG₁₁₄-b-PAChol (45 and 114 are the degree of polymerization of PEG blocks) with different hydrophilic/hydrophobic weight ratios were synthesized and characterized in detail. Depending on the diblock composition, smectic polymer vesicles and/or nanofibers were formed by adding water into a dilute solution of copolymers in dioxane. If THF is used instead of dioxane as solvent, solid spherical aggregates were obtained upon water addition for PEG₄₅-b-PAChol series, while macroscopic precipitation occurred for PEG₁₁₄-b-PAChol series. The mesomorphic and microphase segregation structures of the block copolymers in bulk were studied by X-ray scattering, DSC and POM. The interdigital smectic A (SmA_d) phase with a lamellar period of 4.25 nm was detected in all block copolymers. For PEG₁₁₄-b-PAChol₅ (PEG/PAChol weight ratio = 66/34) and PEG₁₁₄-b-PAChol₁₂ (45/55), lamellar type of microphase segregation was observed.