Synthesis and characterization of amphiphilic graft copolymer poly(ethylene oxide)-graft-poly(methyl acrylate)

A novel well-defined amphiphilic graft copolymer of poly(ethylene oxide) as main chain and poly(methyl acrylate) as graft chains is successfully prepared by combination of anionic copolymerization with atom transfer radical polymerization (ATRP). The glycidol is protected by ethyl vinyl ether first, then obtained 2,3-epoxypropyl-1-ethoxyethyl ether (EPEE) is copolymerized with EO by initiation of mixture of diphenylmethyl potassium and triethylene glycol to give the well-defined poly(EO-co-EPEE), the latter is deprotected in the acidic conditions, then the recovered copolymer [(poly(EO-co-Gly)] with multi-pending hydroxyls is esterified with 2-bromoisobutyryl bromide to produce the ATRP macroinitiator with multi-pending activated bromides [poly(EO-co-Gly)_(ATRP)] to initiate the polymerization of methyl acrylate (MA). The object products and intermediates are characterized by NMR, MALDI-TOF-MS, FT-IR, and SEC in detail. In solution polymerization, the molecular weight distribution of the graft copolymers is rather narrow (M_w/M_n < 1.2), and the linear dependence of Ln [M₀]/[M] on time demonstrates that the MA polymerization is well controlled.     

Synthesis of poly(ethylene oxide)-block-poly(methyl methacrylate)-block-polystyrene triblock copolymers by two-step atom transfer radical polymerization

The synthesis of ABC triblock copolymer poly(ethylene oxide)-block-poly(methyl methacrylate)-block-polystyrene (PEO-b-PMMA-b-PS) via atom transfer radical polymerization (ATRP) is reported. First, a PEO-Br macroinitiator was synthesized by esterification of PEO with 2-bromoisobutyryl bromide, which was subsequently used in the preparation of halo-terminated poly(ethylene oxide)-block-poly(methyl methacrylate) (PEO-b-PMMA) diblock copolymers under ATRP conditions. Then PEO-b-PMMA-b-PS triblock copolymer was synthesized by ATRP of styrene using PEO-b-PMMA as a macroinitiator. The structures and molecular characteristics of the PEO-b-PMMA-b-PS triblock copolymers were studied by FT-IR, GPC and ¹H NMR.     

Synthesis and properties of polymer brush consisting of poly(phenylacetylene) main chain and poly(dimethylsiloxane) side chains

A novel polymer brush consisting of poly(phenylacetylene) (PPA) main chain and poly(dimethylsiloxane) (PDMS) side chains was synthesized by the polymerization of phenylacetylene-terminated PDMS macromonomer (M-PDMS). The macromonomer was prepared by the esterfication of monohydroxy-ended PDMS (PDMS-OH, degree of polymerization (DP) = 42) with p-ethynylbenzoic acid. The polymerization of M-PDMS using [(nbd)RhCl]₂/Et₃N catalyst led to polymer brush, poly(M-PDMS), with M_n up to 349?000 (DP of main chain 104). Poly(M-PDMS) with narrow molecular weight distribution (M_n = 39?900, M_w/M_n = 1.11) was obtained with a vinyl-Rh catalyst, [Rh{C(Ph)CPh₂}(nbd){P(4-FC₆H₄)₃}]/(4-FC₆H₄)₃P. Poly(M-PDMS)s were brown to orange viscous liquids and soluble in organic solvents such as toluene and CHCl₃. The UV-vis absorptions of poly(M-PDMS) were observed in the range of 350-525 nm, which are attributable to the PPA main chain.     

Poly(dimethylsiloxane) sealant-based blends with butadiene acrylonitrile elastomers and their adhesion and toughness behavior

A poly(dimethylsiloxane)-based sealant was modified by blending with three types of butadiene-acrylonitrile copolymers. The resulting blends containing 5, 10 and 15%, respectively, of the added component were heterogeneous, as indicated by evidence from SEM observations and energy dispersive X-ray analysis. The influence of the added component, substrate (California red-wood, aluminum and Portland cement mortar) and weathering (both artificial and natural) was assessed by stress-strain testing and toughness determinations.     

Syntheses of well-defined poly(siloxane)-b-poly(styrene) and poly(norbornene)-b-poly(styrene) block copolymers using functional alkoxyamines

Functional alkoxyamines, 1-[4-(4-lithiobutoxy)phenyl]-1-(2,2,6,6-tetramethylpiperidinyl-N-oxyl)ethane (2) and 1-[4-(2-vinyloxyethoxy)phenyl]-1-(2,2,6,6-tetramethylpiperidinyl-N-oxyl)ethane (3) were prepared, and well-defined poly(hexamethylcyclotrisiloxane)-b-poly(styrene)[poly(D₃)-b-poly(St)] and poly(norbornene)-b-poly(St) [poly(NBE)-b-poly(St)] were prepared using the alkoxyamines. The first step was preparation of poly(D₃) and poly(NBE) macroinitiators, which were obtained by the ring-opening anionic polymerization of D₃ using 2 as an initiator and the ring-opening metathesis polymerization of NBE using 3 as a chain transfer. The radical polymerization of St by the poly(D₃) and poly(NBE) macroinitiators proceeded in the ‘living’ fashion to give well-defined poly(D₃)-b-poly(St) and poly(NBE)-b-poly(St) block copolymers.     

Synthesis, characterization, and bulk crosslinking of polybutadiene-block-poly(2-vinyl pyridine)-block-poly(tert-butyl methacrylate) block terpolymers

We report on the synthesis and characterization of triblock terpolymers, polybutadiene-block-poly(2-vinyl pyridine)-block-poly(tert-butyl methacrylate) (PB-b-P2VP-b-PtBMA; BVT), via sequential living anionic polymerization in THF at low temperatures using sec-butyl lithium as initiator. In this work, 18 different BVT terpolymers were produced with volume fractions Φ_B : Φ_V : Φ_T in the range of 1 : 0.4…1.2 : 0.2…4.6. All polymers exhibit a very narrow molecular weight distribution (PDI < 1.1). They were characterized in terms of bulk morphology using small-angle X-ray scattering and transmission electron microscopy, unveiling mostly lamellar patterns or hexagonally arranged cylindrical structures. Some polymers displayed a partial gyroid structure coexisting with lamellar parts or cylinders with a non-continuous shell around the PB core and could serve as an interesting template for the facile generation of multi-compartmental self-assembled structures. In one case the middle block, P2VP, is forming a helix around the PB core. Crosslinking of the polybutadiene compartment of the bulk morphologies with an UV-photoinitiator was performed, followed by sonication-assisted dissolution of the aggregates to elucidate further use of the terpolymers for the generation of soft polymeric nanoparticles with controlled functionality. In that way, core-crosslinked cylindrical micelles could be generated and characterized.     

Structure-property behavior of poly(dimethylsiloxane) based segmented polyurea copolymers modified with poly(propylene oxide)

Poly(propylene oxide) (PPO) was incorporated in a controlled manner between poly(dimethylsiloxane) (PDMS) and urea segments in segmented polyurea copolymers and their solid state structure-property behavior was investigated. The copolymers contained PDMS segments of MW 3200 or 7000 g/mol and an overall hard segment content of 10-35 wt%. PPO segments of MW 450 or 2000 g/mol were utilized. Equivalent polyurea copolymers based on only PDMS as the soft segment (SS) component were used as controls. The materials (with or without PPO) utilized in this study were able to develop microphase morphology as determined from dynamic mechanical analysis (DMA) and small angle X-ray scattering (SAXS). DMA and SAXS results suggested that the ability of the PPO segments to hydrogen bond with the urea segments results in a limited inter-segmental mixing which leads to the formation of a gradient interphase, especially in the PPO-2000 co-SS containing copolymers. DMA also demonstrated that the polyureas based on only PDMS as the SS possessed remarkably broad and nearly temperature insensitive rubbery plateaus that extended up to ca. 175 °C, the upper temperature limit depending upon the PDMS MW. However, the incorporation of PPO resulted in more temperature sensitive rubbery plateaus. A distinct improvement in the Young's modulus, tensile strength, and elongation at break in the PPO-2000 and PDMS-7000 containing copolymers was observed due to inter-segmental hydrogen bonding and the formation of a gradient interphase. However, when PPO was incorporated as the co-SS, the extent of stress relaxation and mechanical hysteresis of the copolymers increased relative to the segmented polyureas based on the utilization of only PDMS as the soft segment component.     

Crystalline morphology of poly(dimethylsiloxane)

The crystalline morphology of poly(dimethylsiloxane) was studied using a scanning electron microscope equipped with a cold stage. Samples of two different molecular weights were used. In both cases, spherulitic morphology is seen, from −70 °C, with spherulites of about 100 μ in size. Small single crystals of about a micron in size are also seen, and these are attributed to the presence of cyclics.     

Synthesis and characterization of (star polystyrene)-block-(polyisoprene)-block-(star polystyrene) copolymers

A (star polystyrene)-block-(linear polyisoprene)-block-(star polystyrene) copolymer, (S)_nI(S)_n, was prepared. The star polystyrene was produced via anionic polymerization of polystyrene macromonomers each containing an unsaturated double bond (vinyl) at the chain end. This vinyl-terminated polystyrene macromonomer (SSTM) was obtained beforehand via the synthesis of a living polystyrene using alkyllithium and the termination with p-chloromethylstyrene (PCMS). The living site in the core of the star polystyrene enabled the construction of the succeeding polyisoprene block resulting in the living (star polystyrene)-block-(linear polyisoprene) copolymer, (S)_nI. This living diblock copolymer was then coupled with 1,2-dibromoethane (DBE) to form the well-defined (S)_nI(S)_n. Compared to a linear polystyrene-block-polyisoprene-block-polystyrene, SIS, with the same molecular weight, (S)_nI(S)_n had a higher T_g and exhibited a lamellae-forming phase separation in conjunction with many dislocation defects. The thermal stability appeared independent of the molecular structure, and the radius of gyration and viscosity of (S)_nI(S)_n were much smaller than SIS.     

Reactivity of poly(dimethylsiloxane) toward acidic permanganate

Poly(dimethylsiloxane) (PDMS) has been widely used in various microfluidic devices because it is considered to be one of the most inert materials available. A PDMS-based microfluidic system for the synthesis of manganese oxide (MO) nanoparticles is developed and tested. However, synthesis of MO nanoparticles in the PDMS-based microfluidic system is unsuccessful due to an unexpected reaction between acidic permanganate and PDMS. PDMS is pitted and coated with MnO₂ and opalized silica, which are confirmed by SEM and EDX. The products of the reaction between PDMS and acidic permanganate are mainly MnO₂, Cl₂, SiO₂ and CO₂, respectively. Here we report for the first time the reactivity of PDMS toward acidic permangante resulting in a new process to coat the channel walls with MnO₂.     

Phase behavior of linear polystyrene-block-poly(2-vinylpyridine)-block-poly(tert-butyl methacrylate) triblock terpolymers

Using sequential living anionic polymerization we synthesized well-defined linear ABC triblock terpolymers from polystyrene (PS), poly(2-vinylpyridine) (P2VP), and poly(tert-butyl methacrylate) (PtBMA). The length of the PtBMA block was systematically increased at constant block length ratios of the PS and P2VP blocks. The microdomain structures were characterized by transmission electron microscopy (TEM) and small angle X-ray scattering (SAXS). With increasing PtBMA block size we observe a systematic change in the bulk structure of the block copolymers.     

Synthesis, structure and morphology of poly(dimethylsiloxane) networks filled with in situ generated silica particles

The morphology of silica particles generated in situ in PDMS networks in the presence of two types of catalysts is evaluated by using different techniques including solid-state ²⁹Si MAS NMR, near-infrared spectroscopies and small-angle X-ray scattering. The interactions with the poly(dimethylsiloxane) chains are examined through the swelling properties and thermal characteristics (in particular crystallization process) of the composites. In addition, ¹H NMR is used to investigate the adsorption layer of reduced mobility on the particle surface.     

Epoxy resin containing poly(ethylene oxide)-block-poly(?-caprolactone) diblock copolymer: Effect of curing agents on nanostructures

An amphiphilic diblock copolymer, poly(ethylene oxide)-block-poly(?-caprolactone) (PEO-b-PCL) was synthesized via the ring-opening polymerization of ?-caprolactone in the presence of a hydroxyl-terminated poly(ethylene oxide) monomethyl ether. The diblock copolymer was incorporated into epoxy thermosets. It is found that the formation of nanostructures of thermosetting blends is quite dependent on the uses of aromatic amine hardeners. For 4,4′-methylenebis(2-chloroaniline) (MOCA)-cured thermosetting system, the homogeneous morphology was obtained at the compositions investigated. Nonetheless, the nanostructured thermosets were obtained when the blends were cured with 4,4′-diaminodiphenylsulfone (DDS). The differential scanning calorimetry (DSC) showed that the nanostructured thermosets did not displayed any crystallinity although the subchains of the diblock copolymer are crystalline. The nanostructures were evidenced by means of atomic force microscopy (AFM), small-angle X-ray scattering (SAXS) and transmission electron microscopy (TEM). The dependence of morphological structures on the types of aromatic amines for epoxy and PEO-b-PCL thermosetting blends were interpreted on the basis of the difference in hydrogen bonding interactions resulting from the structure of curing agents. Considering the complete miscibility of the subchains (viz. PEO and PCL) with the precursors of epoxy resin before curing, it is judged that the formation of the nanostructures in the thermosets follows the mechanism of reaction-induced microphase separation, which is in marked contrast to the mechanism of self-assembly, i.e., micelle structures of block copolymers are formed prior to curing, followed by fixing these nanostructures via curing.     

Surface properties of poly(dimethylsiloxane)-based inorganic/organic hybrid materials

Poly(dimethylsiloxane) (PDMS)-based hybrid materials were prepared by the sol-gel method on Si wafers, Al and polystyrene (PS) substrates. The reaction was monitored by attenuated total reflectance-infrared (ATR-IR) spectroscopy. The hybrid materials have always one surface made in contact with air and one with a substrate. These surfaces were investigated by using tapping mode atomic force microscopy (AFM), X-ray photo-electron spectroscopy (XPS), low-energy ion scattering (LEIS) and dynamic contact angle (DCA) analysis. The hybrid sample surfaces made in contact with air and substrates appeared to have different structures. The former have a silica-free PDMS top layer of ∼2 nm thick; while in the latter cases, SiO₂ are located at or just beneath the outermost atomic layer. In air and at room temperature, SiO₂ are likely beneath the outermost atomic layer. In contact with water, polar -OH groups at the surface of SiO₂ can easily stretch out to the outermost atomic layer. No correlation was found between the roughness of the surfaces and the amount of in situ formed SiO₂ present in the materials.     

Effect of filler amount on thermoelastic properties of poly(dimethylsiloxane) networks

End-linked poly(dimethylsiloxane) (PDMS) networks were prepared in the presence of fumed silica particles with hydroxyl groups at their surfaces. The silica particles were introduced into the polymer solution prior to end-linking. Hydroxyl ended PDMS chains were end-linked via the tetra functional crosslinker, tetraethoxysilane. The filler content varied in the range 0-5 wt%. Atomic Force Microscopy was used to image and characterize the silica particles. Swelling, stress-strain and thermoelasticity experiments were performed. The temperature coefficient and the energetic part of the force in uniaxial extension are found to increase with increasing silica amount. This observation is ascribed to effects contributed possibly by the adsorption layer around the silica particles.     

An investigation of the interaction of potassium ions with poly(dimethylsiloxane)

The interactions of potassium ions with , -hydroxy-terminated and , -trimethylsilyl-terminated poly(dimethylsiloxanes) (PDMS) have been investigated. After mixing with potassium hydroxide followed by partial extraction, the , -hydroxy-terminated PDMS samples gave elastomeric materials which are thought to result from aggregation of terminal potassium silanolate ion pairs. Uniaxial tensile testing of these materials was carried out at 298 K. The , -trimethylsilyl-terminated PDMS, when mixed with potassium hydroxide, however, gave completely soluble material following identical solvent extraction procedures.     

Synthesis of well-defined poly(styrene)-b-poly(p-tert-butoxystyrene) multiblock copolymer from poly(alkoxyamine) macroinitiator

The stepwise insertion reaction of styrene (St) and p-tert-butoxystyrene (BOSt) into poly(alkoxyamine) macroinitiator was carried out to provide well-defined poly(St)-b-poly(BOSt) multiblock copolymers. Structural confirmation of the multiblock copolymers was accomplished by NMR and IR measurements. The model reaction also supported that the monomer insertion into the macroinitiator proceeded in accordance with a living fashion.     

Poly(2,2-dimethyltrimethylene carbonate)-block-poly(dimethylsiloxane)-block-poly(2,2-dimethyltrimethylene carbonate). Synthesis and thermal properties

Lithium salts of hydroxytelechelic poly(dimethylsiloxane) [poly-(DMS)] were used as initiators for the anionic ring-opening polymerization of 2,2-dimethyltrimethylene carbonate (DTC). Triblock copolymers were obtained in high yields. Complexation of the active site in DTC polymerization by the poly(DMS) chain leads to a decrease in polymerization rate. The thermal properties of the copolymers of different compositions were determined. Catalysed thermal degradation of the block copolymers leads to cyclic oligomers D_n and DTC upon ring-closing depolymerization.     

Synthesis and characterization of poly(l-glutamic acid)-block-poly(l-phenylalanine)

Poly(γ-benzyl l-glutamate)-block-poly(l-phenylalanine) was prepared via the ring opening polymerization of γ-benzyl l-glutamate N-carboxyanhydride and l-phenylalanine N-carboxyanhydride using n-butylamine·HCl as an initiator for the living polymerization. Polymerization was confirmed by ¹H-nuclear magnetic resonance spectroscopy and matrix assisted laser desorption ionization time of flight mass spectroscopy. After deprotection, the vesicular nanostructure of poly(l-glutamic acid)-block-poly(l-phenylalanine) particles was examined by transmission electron microscopy and dynamic light scattering. The pH-dependent properties of the nanoparticles were evaluated by means of ζ-potential and transmittance measurements. The results showed that the block copolypeptide could be prepared using simple techniques. Moreover, the easily prepared PGA-PPA block copolypeptide showed pH-dependent properties due to changes in the PGA ionization state as a function of pH; this characteristic could potentially be exploited for drug delivery applications.     

Synthesis of poly(tetrafluoroethylene)/poly(butadiene) core-shell particles and their graft copolymerization

This article describes how to convert the unreactive surface of poly(tetrafluoroethylene) (PTFE) into poly(styrene-co-acrylonitrile) (SAN). Composite particles with a crosslinked poly(butadiene) (PB) shell covered over a PTFE core were prepared by an emulsifier-free seeded emulsion polymerization of butadiene in the presence of PTFE latex. It was found that the increase in the PB crosslink density resulted in depressing the formation of PB secondary particles. Then, styrene and acrylonitrile were able to graft onto PB shell in high efficiency of 70%. SAN-modified PTFE/PB core-shell particles could eventually be dispersed homogeneously in a SAN matrix. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68:185–190, 1998