Rheology modification of PVC plastisols with poly(butylene terephthalate)-b-poly(tetramethylene glycol)

A few percent of poly(butylene)-b-poly(tetramethylene glycol) was able to turn a liquid plasticizer into a gel, and thus imparted yield stresses to the fluid. When the plasticizer contained as little as 2.5 wt % of the block copolymer, sag free plastisols were obtained. A reduction in tensile strength was found for the modified plastisols, while the elongation was not affected. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 749–753, 1997     

Application of degradation kinetics to the rheology of poly(hydroxyalkanoates)

The time‐dependent rheological behavior of a series of 3‐hydroxybuytrate‐based semicrystalline copolymers is employed to determine the expected rheological curves that would be generated in the absence of any polymer degradation. Both dynamic frequency sweep and shear rate sweep experiments were analyzed. A model for the degradation kinetics, coupled with standard rheological relationships, was employed to extrapolate the measured sweeps to predicted curves at time zero, prior to degradation. The model is broadly applicable over a wide range of frequencies or shear rates, and generates a single degradation rate constant k for each polymer studied. A similar, although ad hoc, procedure was applied to the dynamic storage and loss moduli. The model provides a method for determining the rheological behavior of degrading polymers over a time interval, typically found in processing applications. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102:1794–1802, 2006     

Miscible blends of biobased poly(lactide) with poly(methyl methacrylate): Effects of chopped glass fiber incorporation

Poly(lactide) (PLA) and poly(methyl methacrylate) (PMMA) are melt compounded with chopped glass fiber using laboratory scale twin‐screw extrusion. Physical properties are examined using differential scanning calorimetry (DSC), dynamic mechanical thermal analysis (DMTA), thermogravimetric analysis (TGA), tensile testing, impact testing, X‐ray computed tomography (CT) scanning, and field emission scanning electron microscopy (FE‐SEM). Molecular weight is determined using gel permeation chromatography (GPC). Miscibility of the blends is implied by the presence of a single glass transition temperature and homogeneous morphology. PLA/PMMA blends tend to show positive deviations from a simple linear mixing rule in their mechanical properties (e.g., tensile toughness, modulus, and stress at break). The addition of 40 wt % glass fiber to the system dramatically increases physical properties. Across all blend compositions, the tensile modulus increases from roughly 3 GPa to roughly 10 GPa. Estimated heat distortion temperatures (HDTs) are also greatly enhanced; the pure PLA sample HDT increases from 75 °C to 135 °C. Fiber filled polymer blends represent a sustainable class of earth abundant materials which should prove useful across a range of applications. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44868.     

(Nano)Fibrillar morphology development in biobased poly(butylene succinate-co-adipate)/poly(amide-11) blown films

Thin films with (nano)fibrillar morphologies were successfully obtained in fully-biobased poly(butylene succinate-co-adipate)/poly(amide-11) blends (PBSA/PA11, 85/15 wt/wt) using an extrusion-blowing process. Impacts of PA11 grade and take-up ratio on the morphology of PBSA/PA11 were particularly highlighted. Scanning electron microscopy analyses indicated that PA11 with high melt volume-flow rates are beneficial to the development of (nano)fibrillar morphologies in PBSA/PA11 blown film. On the contrary, unstable film blowing processing without fibrillar morphologies was attested for PA11 with low melt volume-flow rates. Increasing the take-up ratio during extrusion-blowing of PBSA/PA11 clearly generates finer PA11 (nano)fibrils into PBSA. Fibril diameters down to 300 nm could be reached with an optimal PA11 grade promoting enhanced mechanical properties (higher ductility and toughness). The formation of stable PA11 (nano)fibrils into PBSA is discussed via rheological assessments of viscosity/elasticity ratio. A specific attention was finally paid to the PBSA strain-hardening behavior in PBSA/PA11 using elongational rheological tests. PA11 (nano)fibrillation helps maintaining the strong PBSA strain-hardening and thus play a major role on the processability of PBSA/PA11 blends by extrusion blowing. As a conclusion, the PA11 grade represents a crucial parameter to control the production of PBSA/PA11 blown films with refined (nano)fibrillar structures and enhanced physico-chemical properties.     

聚羟基烷酸酯改性聚氯乙烯的研究

通过熔融共混的方法分别制备了聚氯乙烯/邻苯二甲酸二辛酯/聚羟基烷酸酯（PVC/DOP/PHA）和PVC/PHA共混物。研究了PHA逐步代替DOP对共混物力学性能和熔体流动性能的影响规律,利用扫描电子显微镜对所制备的试样进行微观结构分析。结果表明,随着共混体系中PHA用量的增加和DOP的等量减少,与PVC/DOP共混物相比,PVC/DOP/PHA共混物的拉伸强度由21 MPa提高至42 MPa,断裂伸长率先增加而后降低,在PHA含量为10.7 %(质量分数,下同)时出现极大值(350 %);在PVC/PHA体系中,PHA含量增加,PVC/PHA共混物的力学性能及熔体流动速率都显著提高,说明PHA可以作为PVC的一种有效的绿色增塑剂和增韧剂。     

Chemical modification of poly(N-vinylcarbazole)

Investigation of the phosphorylation reaction of poly(vinylcarbazole) was carried out using different phosphorylating reagents and in the presence of various catalysts. PCl₃, PBr₃, P₂S₅, and H₃PO₄ + P₂O₅ were examined, and it was noticed that PCl₃ and PBr₃ were the most effective phosphorylating reagents. The best results for the phosphorylation process of poly(vinylcarbazole) were obtained at 76°C when PCl₃ was used and at 140°C when PBr₃ was used. It was confirmed that the percentage of phosphorus which was introduced into the polymer can be expressed by the following formula: The optimal value of the reaction time for both these phosphorylating reagents PCl₃ and PBr₃ amounts to 6 hr. The phosphorylated poly(vinylcarbazole) obtained under these conditions shows ion exchange behavior—the value of ion-exchange capacity amounts 3.2 mval/g. The pH-metric titration curve indicates two stages of dissociation. The DTA curve shows that there is no decomposition of the phosphorylated poly(vinylcarbazole) up to a temperature of 300°C; at 550°C, there is 37.5% loss of weight. Spectrophotometric IR studies of phosphorylated poly(vinylcarbazole) indicate that the maximal quantity of phosphorus in the polymer is 11.3% P, that means one phosphone group in each monomer unit.     

Superparamagnetic biobased poly(thioether-ester) via thiol-ene polymerization in miniemulsion for hyperthermia

Thiol-ene polymerization has been pointed out as a promising technique to produce biobased polymers for biomedical applications due to its advantages, including mild conditions and rapid reaction rates without the formation of byproducts. Therefore, in this study different concentrations of magnetic nanoparticles (MNPs) were incorporated in poly(thioether-ester) (PTEE) nanoparticles by thiol-ene miniemulsion polymerization of biobased monomers to form both linear and branched cross-linked polymers. Loading efficiencies up to approximately 95% (thermogravimetric analysis) of the MNPs within the polymer matrix were obtained. In addition, the substitution of the dithiol 1,4-butanedithiol (64.2%) for the tetrathiol PTEMP (95.8%), increased the encapsulation efficiency by about 30%. Hybrid nanoparticles presented average mean diameters between 95 and260 nm with polydispersity index between 0.13 and 0.42 by DLS, negative zeta potentials around −45 mV and superparamagnetic behavior. The hyperthermia assays performed on breast cells (MDA-MB 231) have shown that the cell death was dependent on the exposure time to the AC magnetic field and the reduction in cell viability was approximately 35%. These results demonstrated the production of superparamagnetic PTEE nanoparticles via thiol-ene polymerization and highlight the promising application of these biobased materials for cancer treatment by hyperthermia.     

Surface modification of poly(vinyl chloride) with poly(methyl methacrylate)/poly(dimethyl siloxane) graft copolymers

X-ray photoelectron spectroscopy is used to study the surface segregation of siloxane in dilute blends of poly(methyl methacrylate)/poly(dimethyl siloxane) graft copolymers in poly(vinyl chloride)(PVC). The graft copolymers are found to be extremely efficient surface modifiers, which form, when added in amounts of 0.5% or more, a continuous siloxane overlayer on the surface of PVC. © 1995 John Wiley & Sons, Inc.     

Retention of a foaming agent in poly(vinyl chloride) (PVC) and chlorinated PVC

Poly(vinyl chloride) and chlorinated poly(vinyl chloride) films were saturated at 100°C with fluorotrichloromethane (Genetron-11, a foaming agent) and then allowed to desorb at RT and 65°C. The desorption data for a three month period was fitted into a mathematical relationship which could be used for long term predictions of the G-11 retention in the films. Using thermoanalytical techniques, plots of glass transition temperature vs G-11 concentration were made for the polymers under study. These plots were used to demonstrate the effect of stabilizer, polymer type and temperature on the desorption of the G-11.     

The miscibility of polyacrylates and polymethacrylates with PVC: In situ polymerization and the miscibility of poly(methyl acrylate) and poly(ethyl acrylate) with PVC

The in situ polymerization of vinyl chloride with various polyacrylates and polymethacrylates has been studied. The products were examined by dynamic mechanical analysis. Poly(methyl acrylate) and poly(ethyl acrylate) had previously produced two-phase blends with poly(vinyl chloride) (PVC) by solvent casting, but poly(ethyl acrylate) was shown to be miscible with PVC when blends were produced by in situ polymerization. Poly(methyl acrylate) and poly(octyl acrylate) were found to be immiscible with PVC whereas other polyacrylates and polymethacrylates with intermediate ester group concentrations were found to be miscible, confirming previous studies. The glass transition temperatures of the blends were measured and the deviations from the expected mean of the two base polymers were calculated as an indication of the strength of interaction between the polymers. The polymers having intermediate ester group concentrations showed the strongest interactions and the results correlated well with previously measured interaction parameters.     

远程等离子体处理对聚四氟乙烯表面的功能化改性

采用远程氩等离子体对聚四氟乙烯(PTFE)膜进行了表面改性研究,通过接触角测定仪、扫描电子显微镜(SEM)和X射线光电子能谱仪(XPS)等手段,分析研究了改性后材料表面结构、性能的变化。结果表明:PTFE表面经远程氩等离子体处理后,表面微观形态和表面化学成分均发生了变化,且处理效果优于常规氩等离子体。远程氩等离子体可以在一定程度上抑制电子、离子的刻蚀作用,强化自由基反应,使材料表面获得更好的改性效果。经远程氩等离子体短时间(100s)处理后,PTFE表面的F/C比例从1.97降至1.44,O/C比例从0.015增至0.086;表面的水接触角从108°减小到53°;表面自由能从22.4×10-5N·cm-1增加至52.3×10-5N·cm-1。     

Surface modification of poly(tetrafluoroethylene) with pulsed hydrogen plasma

Surface modification of polymers by pulsed plasma has been investigated to minimize degradation reactions occurring at the same time as the surface modification reactions. The hydrogen radical, ion, and electron concentrations in the hydrogen plasma were simulated as a function of the elapsed time after turning off the discharge. The contact angle measurement showed that hydrogen plasma treatment, regardless of pulsed or continuous plasma, led to degradation reactions as well as defluorination and oxidation on PTFE surfaces. The degradation reactions of PTFE chains initiated by the pulsed hydrogen plasma were not as vigorous as those by the continuous hydrogen plasma. A combination of the on‐time/off‐time of 30/270μs in the pulsed hydrogen plasma was efficacious in modifying PTFE surfaces. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 340–348, 2002     

Chemical modification of poly(epichlorohydrin) with unsaturated potassium carboxylates

Poly(epichlorohydrin) was modified by nucleophilic substitution with some aliphatic potassium carboxylates containing terminal double bonds (10-undecenoate, 4-pentenoate and 3-butenoate). In order to monitor the degree of substitution achieved, different reaction conditions were tested. The polyethers obtained were characterized by spectroscopic techniques, elemental analysis, thermal methods, viscosity determinations and osmometric measurements. A slight crosslinking and the reported main chain cleavage were both detected. Finally, it must be pointed out that, during the substitution reaction with the vinylacetate, isomerization to crotonic ester took place.     

Impact modification of poly(ethylene terephthalate)

The tensile and impact resistance of impact‐modified poly(ethylene terephthalate) (PET) is investigated. The impact modifiers are polyolefin‐based elastomers or elastomer blends containing glycidyl methacrylate moieties to improve the adhesion with the polyester. The tensile properties are measured on injection molded specimens at room temperature while the Izod impact strength is measured from ?40 to 20°C. The blend morphology is observed by scanning electron microscopy and the dispersed phase average diameter is determined by image analysis. The relation between the impact resistance and the phase morphology is discussed, and the critical ligament size for PET is determined. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2919–2932, 2003     

Photodegradation of some poly(vinyl chloride) (PVC) blends: PVC/ethylene-vinyl acetate (EVA) copolymers and PVC/butadiene-acrylonitrile (NBR) copolymers

Poly(vinyl chloride) (PVC) and its blends with polybutadiene-acrylonitrile (NBR) (containing 21.7 weight-percent acrylonitrile (AN), a heterogeneous two-phase system; and containing 41.6 weight-percent of AN, a homogeneous one-phase system) and with polyethylene-vinyl acetate (EVA) (containing 45 weight-percent of vinyl acetate (VA), a heterogenous two-phase system; and containing 65 weight-percent VA, a homogeneous one-phase system) were UV-irradiated (at 3500 Å UV-light (solar spectrum)). After UV irradiation the kinetics measurements were made of the formation of hydroperoxy (OOH) and carbonyl (CO) groups and the changes of mechanical properties: tensile strength, elongation to break, and impact energy. As a result of the photooxidative degradation of PVC blends, decreases of mechanical properties were observed. The effects are more severe in PVC/NBR blends, which contain unsaturated bonds (polybutadiene segments) than in the case of PVC/EVA. The phase structure plays an evident role on the UV degradation only of PVC/NBR blends. The photostability of PVC blends can be slightly improved by introducing Tinuvin P or Ni-chelates photostabilizers.     

Toughening of bismaleimide resin by modification with poly(ethylene phthalate) and poly(ethylene phthalate-co-ethylene isophthalate)

Aromatic polyesters were prepared and used to improve the brittleness of the bismaleimide resin composed of 4,4′-bismaleimidediphenyl methane and o,o′-diallyl bisphenol A. The aromatic polyesters contain poly(ethylene phthalate) (PEP) and poly(ethylene phthalate-co-ethylene isophthalate) (10 mol % isophthalate unit) (PEPI). PEP and PEPI were effective modifiers for improving the brittleness of the bismaleimide resin. The most suitable composition for the modification of the bismaleimide was inclusion of 20 wt % PEP (MW 18,200), which led to an 80% increase in the fracture toughness with retention of flexural properties and a slight decrease in the glass transition temperature, compared with the mechanical and thermal properties of the unmodified cured bismaleimide resin (Matrimid resin). Microstructures of the modified resins were examined by scanning electron microscopy and dynamic viscoelastic analysis. The thermal stability of the modified resin was slightly lower than that of the unmodified resin by thermogravimetric analysis. The toughening mechanism is discussed in terms of the morphological and dynamic viscoelastic behavior of the modified bismaleimide resin system. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65: 1349–1357, 1997     

Enhanced (thermo)mechanical properties in biobased poly(l-lactide)/poly(amide-12) blends using high shear extrusion processing without compatibilizers

Compatible and partly-biobased poly(l -lactide) (PLA)/polyamide-12 (PA12) blends (30 wt% PA12) are here processed by twin-screw extrusion at high shear without added compatibilizers and the effect of several processing parameters (screw speed, feed rate) on final properties (tensile strength, ductility, impact toughness, thermal resistance) is addressed. High tensile strengths could be maintained for these blends with a maximal ductility (225%) and impact toughness (48 kJ/m²) achieved for an optimal screw speed of 800 rpm. However, extreme screw speeds higher than 800 rpm dramatically reduce ductility and impact toughness. Concerning thermal resistance, a constant increase of the heat deflection temperature is observed with the screw speed and thermal resistance up to 123°C could be obtained. In this respect, processing conditions of PLA/PA12 blends have profound positive effects on all (thermo)mechanical properties. Blend morphologies were revealed by scanning electron microscopy and refined PA12 fibrils are detected at optimal processing conditions. Properties deterioration were correlated to a PA12 fibrillar-to-ellipsoidal shape transition at extreme screw speeds arising from PLA degradation and attesting for the importance of the PA12 fibrillation process on final properties. Consequently, PLA/PA12 blends represent interesting biobased candidates for high-performance applications and their optimization could be easily performed by playing with extrusion conditions without compatibilizers.     

PVC modification with bifunctional thiol compounds

Summary The chemical modification of PVC with bifunctional thiol compounds is reported. Aliphatic as well as aromatic compounds were tested under different reaction conditions. The modified PVC's were studied by IR and H-NMR.     

A numerical model for single screw extrusion with poly(vinyl chloride) (PVC) resins

A computer model has been developed to simulate the behavior of molten polymer in the melt conveying zone of extruders. This model, based on a hybrid finite difference/finite element resolution of the equations of change governing momentum and heat transfer, allows the prediction of the pressure profile while accounting for wall end effects as well as the solid bed velocity. Simulation results are compared with analytical and finite difference method results found in the literature. A fairly good agreement is obtained in the case of low density polyethylene. Numerical tests are also carried out with rigid poly(vinyl chloride) compound used for window profile extrusion. The good agreement found between the predictions and experimental measurements obtained on an industrial extruder confirms the performance of the proposed model.