iCVD growth of poly(N-vinylimidazole) and poly(N-vinylimidazole-co-N-vinylpyrrolidone)

The imidazole group plays an important role in α-chymotrypsin catalysis, metal-ion complexation, counterion or dye binding. Poly(N-vinylimidazole), PVI, is also a good model polymer interacting with neutral salts. The poly(N-vinylimidazole-co-N-vinylpyrrolidone) copolymer P(VI-co-VP), can be used to produce highly functionalized polymers.PVI and P(VI-co-VP) thins films were achieved via initiated chemical vapor deposition (iCVD), a solvent-free process to form films under mild conditions. The polymerization was initiated by hot wire heated tert-butyl peroxide (TBPO). The chemical structure and compositions of the polymers were analyzed using FTIR and XPS. The growth rate of PVI as a function of the pressure inside the iCVD reactor was measured to be 1 nm/h mTorr. The XPS results show that the functional groups were retained in the polymer deposited. For the P(VI-co-VP) deposition, there are more VI groups found in the co-polymer chain even when the reacting monomers were fed in the same ratio.     

Polymeric nanomedicines based on poly(lactide) and poly(lactide-co-glycolide)

Small molecule chemotherapeutics often have undesired physiochemical and pharmacological properties, such as low solubility, severe side effect and narrow therapeutic index. To address these challenges, polymeric nanomedicine drug delivery technology has been routinely employed, in particular with the use of biodegradable and biocompatible polyesters, such as poly(lactide) (PLA) and poly(lactide-co-glycolide) (PLGA). Here we review the development and use of PLA and PLGA for the delivery of chemotherapeutic agents in the forms of polymer–drug conjugates and nanoconjugates.     

Reinforcement of elastomeric poly(dimethylsiloxane) by glassy poly(diphenylsiloxane)

Some novel approaches were taken to provide the improvements in mechanical properties that are almost always necessary to prepare a commercially useful elastomer from poly(dimethylsiloxane) (PDMS) [-Si(CH₃)₂O-]. The reinforcement was provided by poly(diphenylsiloxane) (PDPS) [-Si(C₆H₅)₂O-], a hard glassy polymer, which was introduced into the PDMS by two rather different techniques. In the first, the PDPS was prepared separately by condensation polymerization of diphenylsilanediol and then solution-blended into the PDMS. In the second, it was generated by in situ polymerization of the same monomer absorbed into the PDMS network. The resulting materials were characterized by scanning electron microscopy and by stress-strain isotherms in elongation. At least under some conditions both techniques were found to be successful, leading to increases in ultimate strength by a factor of two or more.     

聚乙二醇改性聚乳酸的合成与性能表征

以外消旋乳酸(D,L-LA)和不同数均分子量(Mn)的聚乙二醇(PEG)为原料,通过熔融缩聚法,合成了系列聚乳酸聚乙二醇(PLEG)。最佳工艺条件为:以(Sn(Oct)2)为催化剂,m(Sn(Oct)2)为0.8%,n(PEG)∶n(D,L-LA)=1∶600,聚合温度170℃,压力0.096 MPa条件下,反应8h。用特性粘度测试、FT-IR、XRD、接触角等对其进行表征,实验结果表明系列PLEG中PLEG-800接触角为63°,表明其亲水性能最好;PEG-800和乳酸共聚合成的PLEG的粘均分子量最大,可达48997,与PDLLA相比,结晶度有较大提高,亲水性得到改善。     

Plasma surface treatments of poly(l-lactic acid) (PLLA) and poly(hydroxybutyrate-co-hydroxyvalerate) (PHBV)

The surfaces of poly(l-lactic acid) (PLLA) and poly(hydroxybutyrate-co-hydroxyvalerate) (PHBV) were modified by oxygen and nitrogen plasma treatments. The physical and chemical surface characteristics were evaluated by contact angle tests, scanning electron microscopy (SEM), atomic force microscopy (AFM), and X-ray photoelectron spectroscopy (XPS). The plasma treatments caused an increase in both contact angle and roughening, altered the surface morphology, inserted polar groups, and, consequently, enhanced the hydrophilicity for both PLLA and PHBV polymers.     

Interphase transfer of tackifier between poly(butadiene) and poly(styrene-co-butadiene)

The interphase transfer behavior of poly(styrene-co-α-methyl styrene), which is known as a tackifier in rubber industry, is investigated using poly(butadiene) rubber (BR) and poly(styrene-co-butadiene) rubber (SBR). The films of pure rubbers and the blends with the tackifier were prepared by a solution-cast method using toluene as a solvent. Two sheets composed of different rubbers, in which the tackifier was mixed at least in one rubber sheet, were piled together and annealed beyond the glass transition temperature T _g of the tackifier. The transfer phenomenon of the tackifier between the sheets was evaluated by the peak shift in the tensile loss modulus E″ curve, ascribed to T _g of the rubbers, which was measured by the dynamic mechanical analysis. Moreover, crystallization temperature of BR was also employed as a measure of the transfer, because the tackifier retards the crystallization of BR. It is found that the tackifier moves from one rubber to another during annealing procedure to reduce severe localization. When the content is the same in each rubber, the tackifier immigrates from BR to SBR, suggesting a better miscibility with SBR. This behavior is attributed to the small difference in the solubility parameter between SBR and the tackifier as compared to that between BR and the tackifier.     

Properties of magnetic poly(glycidyl methacrylate) and poly(N-isopropylacrylamide) microspheres

Iron oxide colloids were prepared by coprecipitation of Fe(II) and Fe(III) salts in alkaline media and stabilized by perchloric acid, oleic acid, or poly(acrylic acid). In an attempt to obtain magnetic polymer microspheres differing in size, dispersion polymerization of glycidyl methacrylate (GMA) in ethanol containing HClO₄-stabilized magnetite, dispersion copolymerization of GMA and 2-hydroxyethyl methacrylate (HEMA) in toluene/2-methylpropan-1-ol mixture in the presence of oleic acid-coated magnetite, and inverse suspension copolymerization of N-isopropylacrylamide (NIPAAm) and N,N′-methylenebisacrylamide (MBAAm) in cyclohexane in the presence of poly(acrylic acid)-coated maghemite were compared. The microspheres were characterized by morphology, size, polydispersity, and some magnetic properties.     

Environmentally-affected indentation fracture in poly(ethersulphone) and poly(methyl methacrylate)

The effect of plasticization on the ductile-to-brittle fracture transitions (DBFT) in the ball indentation of poly (ethersulphone) (PES) and poly(methyl methacrylate) (PMMA) has been studied. The DBFT in various organic liquids are governed by a size effect related to the indenter radius, in accordance with the Puttick theory of fracture transitions. In addition, abrasive wear rates of the polymers in these liquids are shown to correlate with the critical indenter radius needed to produce a fracture transition, owing to the connection with fracture toughness.     

NMR analysis of poly(ethylene naphthalate) + poly(butylene terephthalate) blends

Melt blends of poly (butylene terephthalate) (PBT) and poly (ethylene naphthalate) (PEN) with 30, 40, 50, 60 and 70 wt% PEN were prepared using a single screw extruder and injection moulding machine. ¹³C and ¹H nuclear magnetic resonance (NMR) spectra were obtained with a Bruker DRX-400 instrument, on solutions prepared by dissolving samples of the homopolymers and each blend in deuterated trifluoroacetic acid + chloroform mixtures (1:1 by volume). The absence of new signals in ¹H and ¹³C spectra, that would be expected to result from transesterification reactions in the PBT + PEN blend system, provides convincing evidence that such reactions do not occur in these blends under the melt processing conditions that were used. In the light of published work on solid-state NMR studies of these and related blend systems, and our observations of partial miscibility with a very small domain size, together with substantial enhancement of the mechanical properties of PBT by blending with PEN, we conclude that the improvement in mechanical properties arises from molecular scale mixing of the homopolymers and strong but non-covalent bonding interactions over the very large interfacial area between the PBT-rich and PEN-rich phases.     

Synthesis and characterization of conducting poly (1-aminonaphthalene), poly (2-aminonaphthalene) and poly (aniline-co-1-aminonaphthalene)

Poly (1&2)-aminonaphthalene and poly (aniline-co-1-aminonaphthalene) have been synthesized in high yields by chemical oxidative polymerization method. The polymers are soluble in polar solvents such as DMSO, NMP etc. In PNA-2 as head-to-tail coupling cannot occur, the electrical conductivity is lower than PNA-1. The copolymer exhibits distinct morphology, higher viscosity, characteristic exciton peak, appreciable thermal stability and electrical conductivity compared to PNA-1.     

Dynamic mechanical characterization of hydrogel blends of poly(vinyl alcohol-vinyl acetate) with poly(acrylic acid) or poly(vinyl pyrrolidone)

Transparent hydrogels were prepared by blending solutions of poly(vinyl alcohol-vinyl acetate) with either poly(acrylic acid) or poly(vinyl pyrrolidone) in the presence of glutaraldehyde as a crosslinking agent. The network obtained from the poly(vinyl pyrrolidone) system was subjected to various thermal treatments, the effects of which have been studied. Dynamic mechanical analysis was used to characterize the hydrogels and to establish the suitability of these blends for use in biomedical applications. The swelling behaviour was followed under dynamic loads as well as by mass difference. Different frequencies were used to study the dynamic properties of the hydrogel blends which showed an increase in storage modulus with increasing frequency. A comparison of modulus values obtained dynamically were in agreement with data obtained mechanically in tension.This paper was accepted for publication after the 1995 Conference of the European Society of Biomaterials. Oporto, Portugal, 10–13 September.     

Amphiphilic zwitterionic poly(dimethylsiloxane) (PDMS)-contained poly(ether amine) (Z-SiPEA) as the responsive polymeric dispersant

We demonstrated here a novel concept of the responsive dispersant based on the amphiphilic zwitterionic poly(ether amine) (Z-SiPEAs), which can control the dispersion of dyes and pigments in water. Z-SiPEAs are composed of short poly (dimethylsiloxane) (PDMS) chain in the backbone and Jeffamine L100 as graft chain. The amino groups in the backbone and carboxyl groups grafted to the backbone make the obtained Z-SiPEAs zwitterionic. Transmission electron microscopy (TEM) and dynamic light scattering (DLS) results revealed that the obtained Z-SiPEAs can self-assemble into nanoparticles in water, which possessed sharp response to temperature, pH, and ionic strength with the tunable clouding point (CP). In the presence of Z-SiPEAs, not only hydrophobic dyes such as Nile Red can be dispersed in water, but the hydrophilic dye Rose Bengal (RB) can be dispersed in unpolar solvents. Further more, Z-SiPEAs can enhance the dispersion of inorganic pigments Titanium White, Iron Red and Chrome Yellow very efficiently in most solvents. It should be noted that the dispersion of organic dyes and inorganic pigments in water can be controlled by temperature in the presence of Z-SiPEAs. 1H NMR and FT-IR revealed the strong coordination between carboxyl groups in Z-SiPEAs and metal atoms of inorganic pigments. These characteristics will give Z-SiPEAs potential as the novel responsive polymeric dispersant.     

Surface modification of polystyrene and poly(ethylene terephtalate) by grafting poly(N-isopropylacrylamide)

In this work, poly(N-isopropylacrylamide) (PNIPAAm) was incorporated into previously oxidized PS and PET surfaces by grafting using two photo-initiation pathways. The incorporation of PNIPAAm was observed by drop water contact angle measurements, dyeing with Methylene Blue and AFM images analysis of the virgin and modified polymers. It was verified that the grafting process depends on the chemical surface environment. The grafted surfaces are hydrophilic below 32 °C and hydrophobic above this temperature. The transition is due to the incorporated PNIPAAm. This characteristic gives to the grafted materials potential to be applied as biomaterials.     

A qualitative in vitro evaluation of the degradable materials poly(caprolactone), poly(hydroxybutyrate) and a poly(hydroxybutyrate)-(hydroxyvalerate) copolymer

A qualitative in vitro evaluation of poly(caprolactone) (PCL), poly(hydroxybutyrate) (PHB) and a poly(hydroxybutyrate)-(hydroxyvalerate) (PHB-PHV) copolymer was carried out using primary human osteoblasts (HOB) and a human osteosarcoma (HOS) cell line. The cells were grown on films of these polymers and cultured for 2 and 4 days with cells grown on Thermanox as a control. The cells on each of the polymers exhibited different cellular morphologies with different rates of cell proliferation. Results from a preliminary degradation study demonstrated that biodegradable materials can be partially degraded using enzymes such as papain and trypsin. Of the solutions tested, papain caused the greatest degradation, with phosphate-buffered saline (PBS) a physiological buffer having very little effect over a six week period. The bone cells were grown on partially degraded polymers and no differences in the performance of HOS and HOB cells on the materials were observed.     

Mechanical properties of blends of poly(methyl methacrylate) and poly(vinylidene fluoride)

The mechanical properties of blends of the crystallizable polymer poly(vinylidene fluoride) and the amorphous material poly(methyl methacrylate) have been investigated as a function of composition both for glassy amorphous materials and for partially crystalline materials. The data obtained were interpreted in terms of the molecular and super-molecular structure of the blends and in terms of their dynamic properties.The main conclusions were that the mechanical properties are not strongly dependent on details of the distribution of the two components in the material nor on the crystal modifications present. The mechanical properties were found to depend primarily on the location of the glass transition temperature relative to the elongation temperature and on the presence or absence of crystalline regions. The degree of crystallinity was found to play an important role in determining the properties only at lower values of this quantity. The advantage of these blends is that the important parameters, namely, the degree of crystallinity and the location of the glass transition temperature, can be adjusted at will by varying the composition appropriately. This allows well-defined variations of the mechanical properties to be achieved.     

The actuation of a biomimetic poly(vinyl alcohol)poly(acrylic acid) gel

Active polymer gels expand and contract in response to certain environmental stimuli, such as the application of an electric field or a change in the pH level of the surroundings. This ability to achieve large, reversible deformations with no external mechanical loading has generated much interest in the use of these gels as biomimetic actuators and "artificial muscles". In previous work, a thermodynamically consistent finite-elastic constitutive model has been developed to describe the mechanical and actuation behaviours of active polymer gels. The mechanical properties were characterized by a free-energy function, and the model uses an evolving internal variable to describe the actuation state. In this work, an evolution law for the internal variable is determined from free actuation experiments on a poly(vinyl alcohol)poly(acrylic acid) (PVAPAA) gel. The complete finite-elastic/evolution law constitutive model is then used to predict the response of the PVA-PAA gel to isotonic and isometric loading and actuation. The model is shown to give relatively good agreement with experimental results.     

Melt-spun poly(tetrafluoroethylene) fibers

The recent discovery of melt-processable poly(tetrafluoroethylene) (PTFE) allows for common thermoplastic-polymer processing technologies to be applied to this unique polymer, which heretofore was considered to be highly intractable. In this paper, we report simple melt-spinning of monofilaments of a set of melt-processable (modified) PTFE grades with weight-average molar masses (M _w) ranging from 77 to 292 kg/mol. Fibers were spun at 380 °C at draw-down ratios of up to 2,750, yielding filaments of linear densities as low as 0.8 tex, corresponding to a diameter of ∼20 μm. The maximum Young’s modulus and tensile strength of as-spun fibers produced in this study were 91.7 cN/tex (1,972 MPa) and 12.0 cN/tex (258 MPa), respectively, accompanied by a strain to break of 24%.