Electrospinning of cyclodextrin functionalized poly(methyl methacrylate) (PMMA) nanofibers

Cyclodextrin functionalized PMMA nanofibers (PMMA/CD) were successfully produced by electrospinning technique with the goal to develop functional nanowebs. Bead-free uniform electrospun PMMA/CD nanofibers were obtained from a homogeneous solution of CDs and PMMA in dimethylformamide (DMF) using three different types of CDs, α-CD, β-CD and γ-CD. The electrospinning conditions were optimized in order to form bead-free PMMA/CD nanofibers by varying the concentrations of PMMA and CDs in the solutions. The concentration of CDs was varied from 5% up to 50% w/w, with respect to the PMMA matrix. We find that the presence of the CDs in the PMMA solutions facilitates the electrospinning of bead-free nanofibers from the lower polymer concentrations and this behavior is attributed to the high conductivity and viscosity of the PMMA/CD solutions. The X-ray diffraction (XRD) spectra of PMMA/CD nanowebs did not show any significant diffraction peaks indicating that the CD molecules are homogeneously distributed within the PMMA matrix and does not form any phase separated crystalline aggregates. Furthermore, attenuated total reflection Fourier transform infrared (ATR-FTIR) studies elucidate that some CD molecules are located on the surface of the nanowebs. This suggests that these CD functionalized nanowebs may have the potential to be used as molecular filters and/or nanofilters for waste treatment purposes.     

Electrospinning of linear and highly branched segmented poly(urethane urea)s

Electrospun fibrous mats were formed from linear and highly branched poly(urethane urea)s. The highly branched poly(urethane urea)s were synthesized using an A₂+B₃ methodology, where the A₂ species is an oligomeric soft segment. Since the molecular weight of the A₂ oligomer is above the entanglement molecular weight, the highly branched polymers formed electrospun fibers unlike typical hyperbranched polymers that do not entangle. Stress-strain experiments revealed superior elongation for the electrospun fibrous mats. In particular, the highly branched fiber mats did not fail at 1300% elongation, making the electrospun mats promising for potential applications where enhanced tear strength resistance is required.     

The limits of linear viscoelasticity in poly(methyl methacrylate) and poly(ethyl methacrylate)

The limit of linear viscoelasticity is determined for poly(methyl methacrylate) (PMMA) and poly(ethyl methacrylate) (PEMA) in uniaxial tension creep over the temperature range of 20° to T_g ?10°C. The time span covered is from 10 to 1000 sec. The linear limit is defined as the point at which the creep compliance deviates by more than 1% from its mean value in the linear viscoelastic range. For both materials, the stress limit of linear viscoelasticity falls to a minimum or plateau level at a temperature below T_g. It is suggested that the β-mechanism plays an important role in the existence of this minimum.     

Cracking and healing in poly(methyl methacrylate): effect of solvent

In this work, the solvent-induced structural changes of PMMA (poly(methyl methacrylate)) are studied via desorpon of methanol in 2-ethylhexyl alcohol. The desorption of methanol from PMMA specimens causes the shrinking (mass loss) and cracking of the PMMA specimens. The crack density of the cracks induced by the methanol desorption increases with the increase of the immersion time and temperature and approaches plateau. The absorption-induced crack healing of the cracked PMMA specimens is observed via absorption of methanol, resulting in the increase in tensile strength. The cracked PMMA specimens immersed in methanol at higher temperatures have higher tensile strength than at lower temperatures due to the healing of more cracks. The possibility of introducing functional particles, such as quantum dots, into PMMA through absorption-induced migration of particles has been demonstrated via the absorption-induced embedment of carbon particles in the cracked PMMA.     

Water sorption of poly(methyl methacrylate): 1. Effects of molecular weight

A sample of poly(methyl methacrylate), PMMA, of low molecular weight (10⁴ D) took up less water (1.2%) than samples of high molecular weight (10⁶ D: 2.0%). In contrast, the uptake of water was only slightly dependent on molecular weight for samples made by radiolysis in the glassy state. It is concluded that uptake of water depends on the closer molecular packing possible in polymers of lower molecular weight. However during radiolysis in the glassy state, this potential is not fully realized because of limited mobility. In more detail, the small changes in the diffusion coefficient and uptake of water in irradiated samples were consistent with closer packing in samples with M_n ⩽ 10 000. It is concluded that molecular packing proceeds more readily below the critical molecular weight for formation of an entangled network.     

Swelling of poly(methyl methacrylate) thin films in low molecular weight alcohols

The effects of solvent size, temperature, and polymer molecular weight on the swelling of poly(methyl methacrylate) (PMMA) thin films in low molecular weight alcohols were investigated using an in situ ellipsometer. Apparent activation energies were indicative of non-Fickian diffusion, although optical data showed substantial Fickian character for swelling in methanol and moderate Fickian character in ethanol. Penetration rates were strongly dependent on the solvent molar volume for methanol, ethanol, and isopropanol, but 1-butanol and 2-pentanol had rates similar to isopropanol. The effective cross sections of these longer molecules are similar to isopropanol, and this apparently explains the similar penetration rates. The effect of polymer molecular weight (MW) on methanol penetration rates (21–27°C) was investigated with monodisperse PMMA (M_n = 6.4–40.0 × 10⁴ g/mol). A minimum at intermediate MW was observed. Isopropanol swelling rates (45–52°C) were insensitive to MW. The swelling data were also used to determine parameters for transport models that describe the swelling of thin polymer films.     

Fatigue crack propagation in poly(methyl methacrylate): Effect of molecular weight and internal plasticization

In spite of the importance of fatigue behavior in engineering plastics, relatively few fundamental studies have been made of the effects of polymer structure, molecular weight, composition, and morphology on fatigue crack propagation (FCP). As, part of a broad program for the study of such effects, the role of molecular weight and internal plasticization has been studied in poly(methyl methacrylate) (PMMA) which had been specially prepared and characterized with respect to molecular weight, dynamic mechanical behavior, and, in some cases, stress-strain response. As expected, values of fracture toughness, K_c, varied considerably as the molecular weight was rai ed, from 0.7 MPa, √m at M _v = 1.0 × 10⁵ to 1.1 at M_v, = 4.8 × 10⁶. However, a specific effect of fatigue was noted: over the same range of K_c, values of FCP rate decreased by two orders of magnitude as molecular weight was; increased. It is proposed that this high sensitivity is due to differences in the degree of chain disentanglement effected by the cyclic loading, with consequent differences in the strength of the craze preceding the crack. With PMMA plasticized internally with a low level (10 percent) of n-butyl acrylate (nBA), the FCP rate and K_c, were similar to those of controls, with very high rates shown. At higher nBA levels (up to 30 percent), the sensitivity of FCP rate to stress intensity factor range decreased considerably, K_c, increased by 30 percent and the pre-exponential constant in the growth rate law increased. Plasticization weakens the polymer but at high degrees leads to enough hysteretic heating to induce local creep and crack blunting.     

悬浮聚合法制取不同分子量级别的聚甲基丙烯酸甲酯

采用粉状MgCO3 作为分散剂 ,悬浮聚合制取了分子量从 2 4× 10 4 ～ 2 5 4× 10 4 的聚甲基丙烯酸甲酯。考察了温度、引发剂种类和浓度、分子量调节剂、转化率对聚合物分子量的影响规律 ,用粘度法测量了聚合物聚甲基丙烯酸甲酯 (PMMA)的分子量。结果表明 :温度的升高、引发剂浓度的增大、分子量调节剂的加入都会导致分子量的减小 ,随着转化率的提高 ,聚合物的分子量增大。在同等条件下 ,引发剂过氧化苯甲酰 (BPO)聚合所得的分子量较偶氮二异丁腈 (AIBN)高。通过实验 ,得到了满足作者需求的分子量 (96× 10 4 ～ 10 0× 10 4 )的聚合物的聚合条件为 :分散剂MgCO3 用量 1% ,单体∶水相 =1∶2 5 (质量比 ) ,引发剂BPO浓度 0 5 % ,反应温度 70℃ ,反应时间 3h。     

Influence of molecular weight on the fracture of poly(methyl methacrylate) (PMMA)

A model is proposed to explain the dependence of fracture parameters on the molecular weight of glassy polymers. The model assumes that the fracture event occurs in two stages; the first involves the orientation of polymer chain segments between entanglement points and the second, the fracture itself. A value has been calculated, (～0.6J m^?2), for the fracture surface energy corresponding to the lower critical molecular weight between entanglements, M=M_e. Allowing for the simplifying assumptions made in its derivation, this value is in good agreement with that found experimentally. It is proposed that, after the chain segments between entanglements crossing a plane have been fully extended, two possible mechanisms are involved; chain ‘pull-out’ up to a maximum governed by the time scale of the local fracture event, or chain scission. Using the concept of a reptating chain it is proposed that above M ～2 M_e there is a relationship between the fracture energy (γ) and the molecular weight of the form γ∝ ∝M² up to a critical value of M, above which γ is constant. It has been shown that there is some agreement with experimental relationships determined independently.     

Effect of molecular weight distribution on fatigue crack propagation in poly(methyl methacrylate)

It is well established that both molecular weight (M) and its distribution (MD) affect many polymer properties such as mechanical behavior. Thus studies have shown that fatigue life is enhanced by increases in M. Research here has shown that with notched specimens fatigue crack propagation (FCP) rates are dramatically decreased by increasing M, even when the M is high enough that the static fraeture energy has essentially reached its asymptotic limit. In this study, specimens of poly(methyl methacrylate) containing either high- or low-M tails were prepared and characterized. The earlier finding that FCP rates are inversely related to average M was confirmed, but specific effects of M distribution were observed. At constant Mⁿ, a low-M tail had little effect on FCP resistance, while a high-M tail improved FCP resistance of polymers whose average M was too low for effective entanglements. Thus with high-M tails, it was possible to test specimens whose average M's were too low to permit machining. It is proposed that the effects noted are due to relative stabilization or destabilization of crazes ahead of the crack.     

Role of chain entanglements on fiber formation during electrospinning of polymer solutions: good solvent, non-specific polymer-polymer interaction limit

Chain entanglements are one of many parameters that can significantly influence fiber formation during polymer electrospinning. While the importance of chain entanglements has been acknowledged, there is no clear understanding of how many entanglements are required to affect/stabilize fiber formation. In this paper, polymer solution rheology arguments have been extrapolated to formulate a semi-empirical analysis to explain the transition from electrospraying to electrospinning in the good solvent, non-specific polymer-polymer interaction limit. Utilizing entanglement and weight average molecular weights (M_e, M_w), the requisite polymer concentration for fiber formation may be determined a priori, eliminating the laborious trial-and-error methodology typically employed to produce electrospun fibers. Incipient, incomplete fiber formation is correctly predicted for a variety of polymer/solvent systems at one entanglement per chain. Complete, stable fiber formation occurs at ≥2.5 entanglements per chain.     

Synthesis, characterization, and electrospinning of zwitterionic poly(sulfobetaine methacrylate)

Poly(sulfobetaine methacrylate) (PSBMA) can be potentially utilized in filtration and wound dressing applications for which nanofibers structures are highly desirable. In this work, a series of PSBMAs with different molecular weights were synthesized, characterized, and electrospun into nanofibers. The polymer molecular weight was controlled by varying the amount of redox initiators in the free radical polymerization of SBMA, with the highest molecular weight achieved at an intermediate initiator concentration. From the intrinsic viscosity measurements, the Mark-Houwink parameters for PSBMA (at 21 °C in 0.2 M NaCl solution) was determined as a = 0.4071 and k = 2.06 × 10⁻³. Thermogravimetric (TGA) analysis shows that the PSBMAs were thermally stable up to at least 250 °C. Fourier transform infrared (FTIR) spectra indicate major structural changes of both polymer backbone and pendant groups by thermal degradation. Results from differential scanning calorimetry (DSC), TGA, and FTIR characterizations all demonstrate the existence of water strongly bound in PSBMA. DSC analysis also indicates different degrees of crystallinity for the PSBMAs of different sizes. Viscosity of the PSBMA solutions, a critical parameter for electrospinning, increased with the solution concentration and the polymer molecular weight. For the electrospinning of PSBMA, it was found that high solution concentration and high molecular weight favored the formation of smooth fibers while low solution concentration or low molecular weight led to the formation of beaded fibers or beads. Fiber diameters ranging from 200 to 570 nm were achieved by controlling solution concentration and polymer molecular weight. The characterization data and electrospinning results were finally correlated to explore the relationships between fiber formation, viscosity, molecular weight, and concentration.     

Studies of cyclic and linear poly(dimethyl siloxanes): 1. Limiting viscosity number-molecular weight relationships

The limiting viscosity numbers of ten cyclic and ten linear poly(dimethyl siloxane) fractions have been measured in a π-solvent (butanone at 293K) and in two ‘good’ solvents (toluene and cyclohexane at 298K). The dimethyl siloxane fractions studied were in the molecular weight range $\text{800 <}\text{M}\text{?}{}_{\mathrm{w}}\text{< 17 000}$. The data obtained are compared with related studies published in the literature. The ratio of the limiting viscosity numbers [η]_r and [η]_l of the cyclic and linear poly(dimethyl siloxanes) with $\text{M}\text{?}{}_{\mathrm{w}}\text{> 2500}$ was found to be 0.67 in butanone at 293K. This value is identical (within experimental error) to the theoretical ratio $\text{[η]}{}_{\mathrm{r}}\text{[η]}{}_{\mathrm{l}}\text{= 0.66}$ predicted by Bloomfield and Zimm and others for ring and chain polymers in π-solvents. The ratio $\text{[η]}{}_{\mathrm{r}}\text{[η]}{}_{\mathrm{l}}$ was found to be somewhat smaller for the higher molecular weight polymers in the ‘good’ solvents.     

Hydrolysis induced formation of macrovoids in poly(methyl methacrylate)

In the PMMA with saturated methanol and ethanol desorbed in the distilled water, because of the phase inversion, the macrovoids are produced. The size and the quantity of macrovoids near the surface layer are larger than those inside of the specimens. If the hydrolysis temperature is lower, the macrovoids formed tend to be of close‐type. On the contrary, if the temperature is higher, there will be open‐type macrovoids. Because of the occurrence of macrovoids, the size of which is smaller than the visible wavelength, the light will scatter, thereby reducing the transmittance of the specimens. The transmittance decreased as the hydrolysis temperature and hydrolysis time was increased. This phenomenon is much obvious when using ethanol, instead of methanol, as the solvent. The scattering intensity of the specimens after hydrolysis is inversely proportional to the visible wavelength with an exponent, n, in the range from 0.03 to 2.40 for methanol and 0.02 to 0.15 for ethanol. The exponent is equal to 4 corresponding to the Rayleigh scattering. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99: 3451–3465, 2006     

Influence of molecular weight of poly (methyl methacrylate) on its miscibility with poly (vinyl chloride) in the solution

In this work, the molecular weight effect on miscibility between poly(vinyl chloride) (PVC) and poly(methyl methacrylate) (PMMA) in cyclohexanone(CH) solutions at 30 °C was examined by the viscometric method. Three samples of PMMA were prepared by emulsion polymerization, which molecular weights were changed by tert-dodecyl-mercaptan (TDDM) content. The parameter Δb is used to predict polymer-polymer miscibility of PVC/PMMA/cyclohexanone blend. Δb values indicated that the highest molecular weight of PMMA is immiscible with PVC resin. The molecular weight of PMMA decrease with the increase of the contention of TDDM, and the contribution of miscibility PVC/PMMA blend in CH is better.     

Synthesis of polymer gel electrolyte with high molecular weight poly(methyl methacrylate)-clay nanocomposite

Polymer nanocomposite gel electrolytes consisting of high molecular weight poly(methyl methacrylate) PMMA-clay nanocomposite, ethylene carbonate (EC)/propylene carbonate (PC) as plasticizer, and LiClO₄ electrolyte are reported. Montmorillonite clay was ion exchanged with a zwitterionic surfactant (octadecyl dimethyl betaine) and dispersed in methyl methacrylate, which was then polymerized to synthesize PMMA-clay nanocomposites. The nanocomposite was dissolved in a mixture of EC/PC with LiClO₄, heated and pressed to obtain polymer gel electrolyte. X-ray diffraction (XRD) of the gels indicated intercalated clay structure with d-spacings of 2.85 and 1.40 nm. In the gel containing plasticizer, the clay galleries shrink suggesting intercalation rather than partial exfoliation observed in the PMMA-clay nanocomposite. Ionic conductivity varied slightly and exhibited a maximum value of 8 × 10⁻⁴ S/cm at clay content of 1.5 wt.%. The activation energy was determined by modeling the conductivity with a Vogel-Tamman-Fulcher expression. The clay layers are primarily trapped inside the polymer matrix. Consequently, the polymer does not interact significantly with LiClO₄ electrolyte as shown by FTIR. The presence of the clay increased the glass transition temperature (Tg) of the gel as determined by differential scanning calorimetry. The PMMA nanocomposite gel electrolyte shows a stable lithium interfacial resistance over time, which is a key factor for use in electrochemical applications.     

Influence of the molecular weight of poly(methyl methacrylate) on fracture morphology in notched tension

Specimens of poly(methyl methacrylate) (PMMA) were prepared by radiolysis of a polymer from an initial viscosity-average molecular weight ($\text{M}\text{?}{}_{\mathrm{v}}$) of 1.2 × 10⁶ down to 2.6 × 10³. At a molecular weight of 1 × 10⁵, abrupt changes in fracture morphology were observed correlating with a similarly abrupt decrease in fracture surface energy (γ). As the molecular weight was decreased further, the fracture morphology resembled more that of very brittle materials such as silicate glasses. Evidence was obtained that Wallner lines can influence the disposition of ribs but not their spacing. An empirical relationship was established between functions of rib spacing (r) and fracture surface energy.     

Residual stress craze and crack formation in poly(methyl methacrylate)

Samples of poly(methyl methacrylate) with a central circular hole are compressed, and crazes form on or after unloading, provided that the strain attains or exceeds a threshold value ?_t. Crazes induced in air are transformed rapidly to cracks, but environmental crazes are more stable. These residual stress crazes form at the diameter of the hole on a plane perpendicular to the applied stress direction. In contrast, during loading, crazes form on the vertical plane containing the hole axis. Unloading crazes are relatively insensitive to changes in strain rate, whereas loading erazes have a pronounced rate dependence. Environmental residual stress crazing exhibits an apparent rate sensitivity at constant time, but the critical applied strain ?_t is essentially constant, irrespective of rate, if the sample is in contact with the environment for a sufficiently long time to ensure that the minimum ?_t is obtained. Residual stress crazes appear to initiate at the equator of the hole, and the maximum tensile residual strain, indicated by a strain gauge, occurs in this position.