Preparation and characterization of phenyl and undecyl oxazoline block copolymers

Undecyl and phenyl oxazolines were synthesized. They were copolymerized in different mole ratios using methyl nosylate as initiator. A series of di- and triblock copolymers with narrow molecular weight distributions as indicated by GPC were obtained. A three-armed block copolymer was also obtained by using 1,3,5-tris(bromomethyl)benzene as initiator. When the nonpolar undecyl block crystallized as a coating, the critical surface energy approached 21.0 dyn/cm, and the contact angle of water on the surface could be higher than 107°. The melting point increased as the chain length of crystallizable undecyl block increased, and the melting peak on DSC was very sharp when the length was equal to or longer than 25 monomer units. When these copolymers were coated on substrates, the work of adhesion with pressure sensitive adhesives was greatly reduced.     

Dendritic homopolymers and block copolymers: Tuning the morphology and properties

The synthesis and characterization of dendritic homopolymers and block copolymers of ?‐caprolactone and lactide (L ‐lactide and racemic lactide) were performed with multifunctional initiators in combination with living polymerization and the selective placement of branching junctures in a divergent growth strategy. A hexahydroxy‐functional 2,2‐bis(hydroxymethyl) propionic acid derivative was used as an initiator for the stannous‐2‐ethylhexanoate‐catalyzed living ring‐opening polymerization of ?‐caprolactone, L ‐lactide, and racemic L ,D ‐lactide. Branching junctions at the chain ends were introduced with benzylidene‐protected 2,2‐bis(hydroxymethyl) propionic acid. Subsequent generations were then polymerized, after deprotection, from these star‐shaped macroinitiators. Successive chain end capping and initiation produced three generations of polymers with molecular weights in excess of 130,000 g/mol and narrow polydispersities (<1.20). It was possible to prepare diblock and triblock copolymers with phase‐separated morphologies, and with L ‐lactide or D ,L ‐lactide, semicrystalline and amorphous morphologies were demonstrated. The polymers were characterized by ¹H NMR, ¹³C NMR, size exclusion chromatography, and differential scanning calorimetry. The compositions of the block copolymers and the conformational structures of the optically active polymers were also confirmed by optical rotation measurements. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1174–1188, 2004     

Poly(N-acylethylenimine) copolymers containing pendant pentamethyldisiloxanyl groups. III. Surface properties and abhesion

The surface properties and abhesion of both N/Si and U/Si series of random copolymers were studied by contact angle and peel strength measurements. When these copolymers are coated on clean glass slides, the contact angles of water on the polymer films are over 105° for copolymers with less than 50 mol % of Si , and 98-104° for those with more than 50 mol % of Si. All the polymers have similar critical surface energies, 21 dyn/cm (from hydrocarbon probes) and 20 dyn/cm (from EtOH/H₂O probes), within the experimental error. This demonstrates that the amide groups in the polymer backbones are buried and all the polymers have methyl surfaces. The copolymers with less than 50 mol % Si (for N/Si copolymers) or 20 mol % (for U/Si copolymers) are stable and show good abhesive properties toward Scotch magic tape at or below 50°C. The peel strengths of Scotch magic tape with the copolymer coated slides rise dramatically as the annealing temperatures approach to the melting points of the polymers.     

Selective hydrolysis of oxazoline block copolymers

Block copolymers, composed of a hydrophobic block [poly(N-t-butylbenzoyl ethylenimine) or poly(N-lauroyl ethylenimine)] and a hydrophilic block [poly(N-propionyl ethylenimine)], synthesized by cationic ring-opening polymerization of 2-substituted Δ2-oxazolines, were selectively deacylated by acid hydrolysis. The hydrolysis process was monitored by using ¹H-NMR. The results show that the propionyl groups could be removed from the hydrophilic block of the polymer chain without touching the hydrophobic block, if appropriate reaction conditions were used.     

Monte-Carlo simulation of ternary blends of block copolymers and homopolymers

We perform a theoretically informed coarse grain Monte-Carlo simulation in the nPT-ensemble and the Gibbs ensemble on symmetric ternary mixtures of AB-diblock copolymers with the corresponding homopolymers. We study the lamellar period by varying the length and amount of homopolymers. The homopolymer distribution within the lamellar morphology is determined as is the maximum amount of homopolymer within the lamellae. Gibbs ensemble simulations are used to locate the three-phase coexistence between two homopolymer-rich phases and a lamellar phase.     

Synthesis and characterization of biodegradable homopolymers and block copolymers based on adipic anhydride

Homopolymers of adipic anhydride (AA) and block copolymers of ϵ-caprolactone (ϵ-CL) and AA have been synthesized with aluminum triisopropoxide as an initiator. Homopolymerization was studied at 20°C in toluene and methylene chloride (CH₂Cl₂). The end-group analysis agrees with a coordination insertion mechanism based on the acyl-oxygen cleavage of the AA ring. Living poly(ϵ-caprolactone) (PCL) chains are very efficient macro-initiators for the polymerization of AA, with formation of diblock copolymers of a narrow molecular weight distribution. At our best knowledge, low molecular weight ω-aluminum alkoxide PCL macroinitiators (M_n < 1000) allow the first valuable synthesis of PAA with a molecular weight as high as 58,000 and a quite narrow polydispersity (M_w/M_n = 1.2). Size-exclusion chromatography (SEC) and ¹³C NMR confirm the blocky structure of the copolymers, in agreement with DSC that shows two melting endotherms and two glass transitions characteristic of the crystalline and amorphous phases of PCL and PAA, respectively. Block copolymers of ϵ-CL and AA are also sensitive to hydrolysis, which makes them possible candidates for biomedical applications. Initiation of the AA polymerization in bulk with aluminum triisopropoxide in the presence of various ligands is also discussed. © 1997 John Wiley & Sons, Inc.     

Star-shaped block copolymers. III. Surface and interfacial properties

Surface and interfacial activities of A(B)₂ star-shaped block copolymers, where B is a polyoxirane block and A a polydiene or polyvinyl block, have been measured at 20°C. The surface tension of organic solvents is only slightly lowered by these copolymers, whereas a significant surface activity is noted in water. Interfacial tensions are dependent on both the nature of the organic solvent (aliphatic or aromatic hydrocarbons) and the molecular parameters of the copolymers; 50% polyoxirane seems to be the composition of maximum surface activity. The role played by the molecular architecture [A-B or A(B)₂] of the copolymers is demonstrated. The same limiting interfacial tension is obtained on increasing the concentration of diblock [A-B] or star-shaped block [A(B)₂] copolymer. The limiting value is, however, attained at significantly lower concentration with the star-shaped copolymers. Their ability to fill the interface is accordingly higher.     

Surface and adhesion properties of poly(imide-siloxane) block copolymers

Poly(imide-siloxane) (PIS) block copolymers were studied with respect to their structure surface and adhesive properties relationship. The study of the morphology of PIS copolymers characterized by Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), and Atomic Force Microscopy (AFM) shows a growth of the surface roughness by increase of the content of siloxane. With an increase of siloxane content Attenuated Total Reflection-Fourier Transform Infra Red (ATR-FTIR) spectroscopy detected a growth of the absorption bands near 1100 cm⁻¹ characteristic for siloxane group, and a decrease at 1700-1800 cm⁻¹ corresponding to carbonyl groups of polyimide moieties. The X-ray Photoelectron Spectroscopy (XPS) and Time-of-Flight-Secondary Ion Mass Spectroscopy (TOF-SIMS) analysis showed an excessive increase of Si on surface of the copolymer. The relatively small amount of siloxane in PIS block copolymer, 10-20 wt.%, increased significantly the contact angle of water due to the surface hydrophobization of the copolymer and the significant decrease of the surface energy of the PIS copolymer has been observed. The polar component of surface energy shows an intense decrease, whereas its dispersive component increases. The increase of the surface hydrophobicity reduced the peel as well as shear strengths of epoxy adhesive joints. The relationship between peel strength of adhesive joint to epoxy and polar fraction of PIS copolymer can be described by exponential decay dependence.     

Surface properties of styrene–ethylene oxide block copolymers

Hydrophobic–hydrophilic block copolymers were prepared by “living” anionic polymerization. They consist of polystyrene and poly(ethylene oxide) blocks, and are soluble in water. Their interfacial properties were investigated, employing aqueous solutions. The block copolymers lowered the surface tension of water in analogy with the low molecular weight surfactants such as sodium lauryl sulfate and heptaethylene oxide n-dodecyl ether. Their aqueous solutions exhibited solubilization properties differing from those of polyethylene glycol. Therefore, it is thought that the polystyrene blocks produce solubilization phenomena. In samples of the same styrene content, the precipitation temperature of a high molecular weight copolymer in water was lower than that of a low molecular weight copolymer at the same concentration in the same solvent. The surface tension and precipitation temperature of aqueous solutions seem to be influenced by molecular weight and composition.     

Optic and catalytic properties of gold nanoparticles tuned by homopolymers

Gold nanoparticles (GNs) are prepared through in situ reduction using NaBH₄ in the presence of homopolymer PDMAEMA. The sizes of the GNs can be adjusted by alternating the molar ratio of gold to DMAEMA. Pure PDMAEMA aqueous solution shows a phase-transition at 50°C at pH 10 and 25°C at pH 14, while PDMAEMA-supported GNs aqueous solution shows a phase-transition at 47°C at pH 10 because of the increasing hydrophobic property resulting from GNs. Due to the pH and temperature-responsible characteristics of PDMAEMA, the resulting PDMAEMA-supported GNs exhibit pH adjustable temperature-responsive characteristics in optic and catalytic aspects. Under an acidic condition (pH 2), the GNs show unchanged surface Plasmon absorbance with a peak of 518 nm in a temperature range from 20 to 65°C. Under a basic condition (pH 10), the GNs first show the same absorbance with a peak at 518 nm in a temperature range from 20 to 40°C, and then the absorbance red shifts from 518 to 545 nm as temperature increases from 40 to 65°C. When the GNs are used as catalysts to catalyze the reduction of p-nitrophenol, the catalytic activity can be adjusted by changing the permeation of reactants in the PDMAEMA layer at low and high temperatures, respectively.     

Controlling the size of nanostructures in thin films via blending of block copolymers and homopolymers

The effects of molecular weight and concentration of poly (methyl methacrylate) (PMMA) homopolymer or symmetric short polystyrene-block-poly (methyl methacrylate) (PS-b-PMMA) diblock copolymer on the size of the nanostructures of its blends with symmetric long PS-b-PMMA diblock copolymer have been investigated by atomic force microscopy. By careful controlling of the film thickness, solvent selectivity, and annealing time, PMMA cylindrical microdomains oriented normal to the film surface were obtained in all thin films. With the addition of both low- and high-molecular-weight PMMA homopolymers, the cylindrical domain sizes increased although it was less obvious for the lower molecular weight homopolymer. In contrast to the homopolymer, adding the short chain diblock copolymer resulted in a decrease in the cylindrical domain size, which was ascribed to the reduction of the interfacial tension and increase in the stretching energy.     

Dynamic scattering properties of mixtures of cyclic and linear homopolymers and copolymers

The dynamic scattering properties of mixtures of cyclic copolymers and homopolymers are discussed. These properties are compared with those characterizing linear chain mixtures in similar conditions. The differences between cyclic and linear chains are introduced through the form factors only. The interaction parameter between different monomer species are assumed to be the same whether they belong to cyclic or linear chains. The dynamical model is based upon a generalization of the random phase approximation neglecting hydrodynamic interaction and mode coupling effects. Despite these simplifications, substantial differences are found in the dynamics of mixtures containing cyclic copolymers and homopolymers when compared to those of linear chain systems in similar conditions of temperature, concentration, and molecular weight. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35 : 1191–1200, 1997     

Reaction of undecyl radicals with aromatic hydrocarbons

A competition method (R^.+O₂RO ₂ ^. , R^.+XHRH+X^.) is proposed to measure the relative rate constants for the interaction of alkyl radicals with different organic compounds. Partial (per C–H bond) rate constants have been determined for the reaction of undecyl radicals with cumene, ethylbenzene and toluene.

---

(R^.+O₂RO ₂ ^. , R^.+XHRH+X^.), . ( C–H ) , .

     

New fluorinated oxazoline block copolymer lowers the adhesion of platelets on polyurethane surfaces

We have prepared an amphiphilic oxazoline block copolymer of hydrophilic poly(2-methyl-2-oxazoline) and hydrophobic poly[2-(2-perfluorooctyl)ethyl-2-oxazoline] chains. By controlling the length and composition of polymer chains, we found that this fluorinated block copolymer can be readily dissolved in water. Furthermore, we can achieve a stable surface coating of the fluorinated block copolymer by dissolving the copolymer in water, then coating the aqueous copolymer solution onto surfaces of nonwater-soluble polymers. This is a simple and useful method of modifying the surface character of polymer substrates. We have found that the polyether urethane (PEU) coated by block copolymer has a different surface chemistry and biological reactivity than the uncoated PEU. From XPS analysis, we found the fluorinated copolymer was coated on PEU (atomic % of F: 31.3 on coated PEU, 0.3 on uncoated). The two surfaces have different affinities for biological molecules. Specifically, the fibrinogen adsorption on the fluorinated copolymer-coated PEU was 62 ± 39 ng/cm², compared to a value of 156 ± 99 ng/cm² for uncoated PEU. In an ex vivo evaluation of platelet adhesion, the surface of coated PEU attached a few white cells while uncoated PEU was covered with activated platelets. © 1994 John Wiley & Sons, Inc.     

Synthesis of phenylenevinylene and naphthylenevinylene homopolymers and block copolymers by ring‐opening metathesis polymerization

Homopolymers and copolymers containing phenylenevinylenes and naphthylenevinylenes can be synthesized by ring‐opening metathesis polymerization of strained monomers such as tetraoctyloxy‐substituted cyclophanedienes and naphthalenophanedienes initiated by the third‐generation Grubbs’ initiator. The resulting homopolymers exhibited low polydispersities. The block copolymers can also be synthesized by the sequential ring‐opening metathesis polymerization of two individual monomers. The structures of homopolymers and block copolymers were fully characterized by nuclear magnetic resonance spectroscopy. The molecular weight distribution of the block copolymers is relatively broad compared to their parent homopolymers possibly due to chain transfer reaction. The molar ratio of the two blocks can be tailored by the ratio of the monomers employed. The block copolymers exhibited a more efficient energy transfer in the solid state between the different blocks than those carried out in solution. The optical and electrochemical properties of the polymers were investigated and exhibited the potential uses in optoelectronics devices. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 67–74     

Spinodal decomposition of two homopolymers with their block copolymer: A comparison of models

The dynamics of phase separation in the presence of a diblock copolymer have been studied using ternary and quaternary models of spinodal decomposition. The ternary model treats the block copolymer as a third component that is compatible with each of the mutually incompatible homopolymers. The quaternary model treats the block copolymer as a pair of specially constrained homopolymers. Both models predict core-shell morphologies with the copolymer concentrated at the interface. Both models predict larger domain sizes and less sharp phase boundaries in the early stages of spinodal decomposition. In the late stages, domain sizes are largest for the system of homopolymers without copolymer and smallest when a system containing copolymer is modeled as a quaternary blend. The scaling exponent observed for the quaternary model was s = 0.25 ± 0.02 compared to s ≅ 0.3 for the homopolymers without copolymer and for the ternary model. The quaternary model predicts internal phase separation within a pure diblock copolymer, whenever the corresponding homopolymers are sufficiently incompatible. © 1996 John Wiley & Sons, Inc.     

Synthesis of homopolymers and block copolymers of methacrylates using a mixed Al/Li alkyl initiator

We report the use of a triisobutylaluminium/tert-butyllithium initiator in the preparation of living methacrylate homopoloymers and a wide range of methacrylic block copolymers. The system, which we have referred to as Screened Anionic Polymerisation (SAP), is very tolerant of impurities and is effective in hydrocarbon solution with reaction rates such that high molecular weight polymers can be produced at temperatures readily accessible for large scale industrial use. A mechanism for the reaction is proposed based on preliminary spectroscopic evidence.     

Non-ionic amphiphilic homopolymers: synthesis, solution properties, and biochemical validation

A novel type of nonionic amphipols for handling membrane proteins in detergent-free aqueous solutions has been obtained through free-radical homo-telomerization of an acrylamide-based monomer comprising a C(11) alkyl chain and two glucose moieties, using a thiol as transfer reagent. By controlling the thiol/monomer ratio, the number-average molecular weight of the polymers was varied from 8 to 63 kDa. Homopolymeric nonionic amphipols were found to be highly soluble in water and to self-organize, within a large concentration range, into small, compact particles of ~6 nm diameter with a narrow size distribution, regardless of the molecular weight of the polymer. They proved able to trap and stabilize two test membrane proteins, bacteriorhodopsin from Halobium salinarum and the outer membrane protein X of Escherichia coli, under the form of small and well-defined complexes, whose size, composition, and shape were studied by aqueous size-exclusion chromatography, analytical ultracentrifugation, and small-angle neutron scattering. As shown in a companion paper, nonionic amphipols can be used for membrane protein folding, cell-free synthesis, and solution NMR studies (Bazzacco et al. 2012, Biochemistry, DOI: 10.1021/bi201862v).     

Control of the microdomain orientation in block copolymer thin films with homopolymers for lithographic application

Block copolymer lithography is a promising method for fabricating periodical nanopatterns of less than 20 nm by self-assembly and can be applicable for fabricating patterned magnetic media with a recording density over 1 Tb/in.2. We found a simple technique to control the orientation of cylindrical microdomains in thin films. Simply by mixing polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) diblock copolymers with the homopolymer (PS or PMMA) of the major component, we could align the cylindrical microdomains perpendicular to the film surface. The added homopolymer induces conformational entropic relaxation of the block chains in microdomain space and stabilizes the perpendicular orientation of hexagonally packed cylindrical microdomains. Thus formed perpendicular cylinders can be readily aligned in a regular array with a grating substrate.