Effect of long-chain branching molar fraction on scratch behavior of polypropylene

Polymers containing a certain amount of long-chain-branching (LCB) structure are expected to possess improved mechanical properties over those of the linear structure counterpart. However, fundamental knowledge on the structure–property relationship in LCB containing polypropylene (PP) is still illusive. In the present study, a set of model PP systems containing an increasing molar fraction of LCB (5–19 mol%) were prepared by reactive extrusion to determine how LCB content may influence the scratch behavior of PP. It is shown that with only 5 mol% of LCB content in PP can improve resistance against scratch-induced fish-scale formation by over 25%. The improvement of scratch resistance is attributed to the increases in entanglement density in LCB-containing PPs, which is evidenced by their creep-recovery behavior. The present study demonstrates that the incorporation of LCB in PP leads to higher viscoelastic recovery and increased tensile strength, which account for the observed improvement in scratch performance. The usefulness of LCB in polymers for improving scratch performance is discussed.     

Homopolymerization of styrenic monomers and their copolymerization with ethylene using group 4 non-metallocene catalysts

Homopolymerization of styrenic monomers (St, p-Me-St, p-tBu-St, p-tBuO-St) and their copolymerization with ethylene, with the use of [(^tBu2O₂NN′)ZrCl]₂(μ-O) ( 1 ) and (^tBu2O₂NN′)TiCl₂ ( 2 ), where ^tBu2O₂NN′ = Me₂N(CH₂)₂N(CH₂-2-O⁻-3,5-tBu₂-C₆H₂)₂, is explored in the presence of MMAO and (iBu)₃Al/Ph₃CB(C₆F₅)₄. The ethylene/styrenic monomers copolymerization with 1 /MMAO produces exclusively copolymers with high activity and good comonomer incorporation whereas the other catalytic systems yield mixtures of copolymers and homopolymers. The use of p-alkyl styrene derivatives instead of styrene raises the catalytic activity, comonomer incorporation and molecular weights of the copolymers. Complex 2 exhibits higher activity in homopolymerization of styrenic monomers than 1 irrespective of the kind of the activator employed. A clear dependence is observed for the molecular weight and catalyst activity against the kind of the styrenic monomer. The obtained polymers were atactic and only the complex 2 , when activated by MMAO, promoted the highly syndiospecific polymerization of p-Me-St and p-tBu-St. Poly(p-tBuO-St) exhibits fiber-forming properties.     

Detailed analysis on thermal,microstructural, mechanical,and morphological features of side chain liquid crystalline polymer/isotactic polypropylene graft copolymers: Effect of grafted and ungrafted polymer units

The main scope of this comprehensive study is to investigate the effects of poly(p-benzophenoneoxycarbonylphenyl acrylate), poly(BPOCPA), which presenting as only graft units or both graft and ungrafted units in the matrix, on the fundamental features of isotactic polypropylene (IPP). The graft copolymerization of BPOCPA onto IPP was performed with the aid of bulk melt polymerization at varying monomer content levels ranging from 5% to 40%. The thermal behavior, crystal quality, mechanical performance, and surface morphology of the samples were investigated by means of differential scanning calorimeter, X-ray diffractometer (XRD), universal mechanical test, and scanning electron microscope (SEM) techniques. Thermal analyses depicted that there existed the noteworthy enhancements in both crystalline melting temperatures and percent crystallinities of matrix polymers. Furthermore, according to XRD results, a and b parameters increased significantly at low percentages of the graft units, while the parameter c decreased in all products in consistence with the content. As for the mechanical characterization, the grafting led to remarkable improvements in modulus, tensile and impact strength of the products. SEM micrographs indicated that the samples were completely homogeneous without any phase separation and the products exhibited brittle nature with some ductility.     

Fluidizing effects of polymers with various anchoring groups in cement pastes and their sensitivity to environmental temperatures

We synthesized various polymers with different functional groups of ─COO⁻, ─SO₃⁻, and ≡N⁺─ to study the impact of the environmental temperature (25, 50, and 80 °C) on the dispersing capability by measuring the fluidity of fresh cement paste, total organic carbon, ζ potential, and isothermal calorimetry. The results show that no adsorption was observed for the cement pastes containing acrylic acid, 2-acrylamido-2-methyl propane sulfonic acid, and [3-(methacryloylamino)propyl] trimethyl ammonium chloride, probably because of the trace amount of adsorption, whereas the fluidity of the pastes was indeed improved by the addition of these chemicals. Generally, for the polymers containing various functional groups, the adsorption capability was in the order ─COO⁻ > ─SO₃⁻ > ≡N⁺─. The dispersing capability for the carboxylate superplasticizer was robust to the change in the temperature, whereas it was dramatically weakened by the increase in temperature for sulfonate superplasticizer, although the adsorption amount increased along with the temperature rise. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47494.     

Plasticization of poly(vinyl butyral) by water: Glass transition temperature and mechanical properties

The effect of plasticization by water on the mechanical properties of additive-free poly(vinyl butyral) (PVB) was investigated. PVB is hygroscopic and the amount of absorbed water was measured in various environmental conditions. Two kinds of interactions with hydrophilic sites was demonstrated. The thermal and thermomechanical studies (differential scanning calorimetry and dynamic mechanical thermal analysis) showed that water decreases the glass transition temperature thus acting as a plasticizer. This gives the material larger deformation capability and increased toughness. Surprisingly, the modulus remains high and this was explained by a structure consisting in two phases with different levels of plasticization, reflected by a double peak of relaxation associated to multiple phases with different glass transition temperature. Atomic force microscopy measurements on samples with high level of hydration shows evidence of nanometric hydrated domains acting as an elastomeric phase and thus inducing toughening of the material. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47230.     

Predicting embrittlement of polymer glasses using a hydrostatic stress criterion

In this study, the aging-induced embrittlement of three polymer glasses is investigated using a previously developed hybrid experimental–numerical method. The evolution of yield stress of unnotched tensile bars upon aging is coupled to the evolution of embrittlement of notched tensile bars using a numerical model combined with a critical hydrostatic stress criterion that determines the onset of failure. The time-to-embrittlement of notched tensile bars with a different notch geometry is predicted and in good agreement with the experimentally determined value. Next to that, the approach is extended to three polysulfone polymers, and it is shown that the value of the critical hydrostatic stress correlates well with the polymers entanglement density: : polymers with a denser entangled network display higher values, that is, a higher resistance against incipient cavitation. © 2019 The Authors. Journal of Applied Polymer Science published by Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47373.     

Effect of PEKK oligomers sizing on the dynamic mechanical behavior of poly(ether ketone ketone)/carbon fiber composites

Poly(ether ketone ketone) (PEKK)/unidirectional carbon fiber (CF) composites have a poor interface. Accordingly, PEKK oligomer (PEKKo) sizing with a chemical compatibility with PEKK is proposed for promoting interfacial interactions in order to enhance mechanical performances. The thermal stability until 500 °C has been shown by thermogravimetric analysis (TGA). In order to compare static and dynamic sizing methods, “lab sizing” and “pilot sizing” were carried out. Scanning electron microscopy images of freeze fractures of PEKK/unsized CF, PEKK/PEKKo lab-sized CF and PEKK/PEKKo pilot-sized CF show that the PEKKo sizing causes an improvement of fiber/PEKK interactions, regardless of the sizing method. Indeed, in both cases, there is a continuity of matter at the interface while we observe a poor wetting of CF by matrix in PEKK/unsized CF. Dynamic mechanical relaxations in shear were analyzed as a function of temperature. The increase of storage modulus upon sizing is observed for both methods but it is more important for PEKKo pilot sizing. In the same way, the mechanical energy loss increases, it reflects the optimization of stress transfer between matrix and fibers. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48818.     

Study on performance characteristics of fused deposition modeling 3D-printed composites by blending and lamination

Component contacting degree in a composite material is an important reference for evaluation the performance characteristics. In this article, two composite material systems involving polylactic acid (PLA) with acrylonitrile butadiene styrene (ABS) and PLA with thermoplastic polyurethane (TPU) were prepared by blending and laminating through fused deposition modeling (FDM) 3D printing technology. The mechanical and thermal properties of the as-prepared composite materials were examined. The results indicated that PLA and TPU played a dominant role in tensile strength and breaking elongation, respectively, in individual composite material. ABS and TPU changed the glass transition peek, crystallinity, and modulus of PLA. The results also suggested that although the processing design of the blending method was more suitable for the contact between two components, but the mechanical properties of laminated composites were closer to theoretical predictions. The structural design and processing technology provide a comparative method and reference basis for studying the performance characteristics of composite materials.     

Preparation and characterization of grafting styrene onto LLDPE by cyclohexane compatibilization in suspension polymerization

A novel method of grafting styrene onto linear low‐density polyethylene (LLDPE) by suspension polymerization was systematically evaluated. Cyclohexane as a compatibilizer was introduced to swell and activate the surface of LLDPE molecular chain for amplifying the contact point of styrene monomer with LLDPE. A series of copolymer of grafting polystyrene (PS) onto LLDPE, known as LLDPE‐g‐PS, were prepared with different ratios of cyclohexane/styrene monomer and various LLDPE dosages. FTIR and ¹H NMR techniques both confirmed successful PS grafting onto the LLDPE chains. In addition, SEM images of LLDPE‐g‐PS particles showed that the cross‐section morphology becomes smooth and dense with suitable cyclohexane dosages, indicating a better compatibility between LLDPE and PS. The highest grafting efficiency was 28.4% at 10 mL/g cyclohexane and styrene monomer when 8% LLDPE was added. In these conditions, the LLDPE‐g‐PS elongation at break increased by about 30 times compared with PS. Moreover, thermal gravimetric analysis (TGA) demonstrated that LLDPE‐g‐PS possesses much higher thermal stability than pure PS. Therefore, the optimal amount of cyclohexane as compatibilizer could increase the grafting efficiency and improve the toughness of PS. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41671.     

Natural rubber-graft-poly(2-hydroxyethyl acrylate) on cure characteristics and mechanical properties of silica-filled natural rubber composites

The grafting of poly(2-hydroxyethyl acrylate) onto natural rubber (NR-g-PHEA) was used to compatibilize NR composites with silica filler. The NR/silica compounds were prepared with various grafting percentages of NR-g-PHEA (0, 6.5, 10.5, and 14.5%) and fixed amounts of 3 parts per hundred of rubber (phr) NR-g-PHEA and 20 phr silica. The cure characteristics were examined using a moving die rheometer. The physicomechanical properties of NR/silica composites were determined in terms of tensile strength, bound rubber content, and dynamic mechanical analysis. Thermal properties were assessed with thermogravimetric analysis. The results showed that scorch time and cure time tend to decrease with the level of grafting in NR-g-PHEA. The NR-g-PHEA decreased tan δ, whereas bound rubber content in NR/silica compounds increased, which indicates improved silica dispersion in the NR matrix. The mechanical properties improved with level of grafting in NR-g-PHEA. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48738.     

Elastic modulus of thermoplastic elastomers investigated with the instantaneous volumetric strain method

The factors influencing the elastic modulus [K(t)] of thermoplastic elastomers (TPEs) were investigated under spherical indentation mode with the instantaneous volumetric strain method. The TPE samples were prepared by the hot-pressing method, and the variation in K(t) was investigated at different thicknesses, loading forces, and spherical indenter radii (Rs). The results demonstrate that the K(t) values of the TPEs decreased nonlinearly with the depth–radius ratio. The sample thickness [H(t)] and R showed positive and negative relationships with K(t), respectively. However, the loading force did not exhibit any significant effect on K(t). In a certain depth–radius ratio range, K(t) had strong functional relationships with H(t), R, and indentation depth. These results provide a reference for the mechanical property investigation of elastoplastic materials. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47181.     

Platinum-terpyridine complexes in polymers: A novel approach for the synthesis of self-healing metallopolymers

The synthesis of novel platinum-based metallopolymers for self-healing applications is presented. For this purpose, terpyridine-platinum complexes were studied using isothermal titration calorimetry regarding their complexation behavior with pyridine. The obtained knowledge was utilized for the preparation of metallopolymers using the reversible addition fragmentation chain-transfer -polymerization technique resulting in well-defined polymers. Crosslinking with a tetravalent pyridine-crosslinker enabled the synthesis of a metallopolymer network featuring self-healing properties. From these experiments, more information about the molecular preconditions for the design of healable metal-containing polymers could be drawn enabling a further optimization of these systems in the future. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47064.     

Modification of carbohydrate polymers via grafting of methacrylonitrile onto pregelled starch using potassium monopersulfate/Fe2+ redox pair

The graft copolymerization of reactive pregelled starch (PGS) with methacrylonitrile (MAN) was performed and the reaction conditions were optimized using potassium monopersulfate (PMPS) in the presence of ferrous ion redox pair as initiator. Emphasis was directed towards increasing the graft formation and decreasing homopolymerization. The grafting parameters were studied with respect to graft yield and graft reaction efficiency percent. In addition, the newly prepared polymethacrylonitrile (polyMAN)‐pregelled starch graft copolymers were applied to cotton textiles to see their suitability as a new sizing agent. Based on the results obtained, appropriate conditions for grafting MAN onto pregelled starch was established and the graft yield was higher under the following conditions: using 0.004 mol l^?1 potassium monopersulfate as initiator, 0.005 mol l^?1 ferrous ion concentration, 0.003 mol l^?1, sulfuric acid, 50 % MAN concentration (based on weight of substrate), material to liquor ratio 1:2.5, reaction time 60 min, and polymerization temperature 40 °C. Finally, fabric samples sized with polyMAN‐pregelled starch graft copolymers acquired higher tensile strength and abrasion resistance than that sized with original pregelled starch, while elongation at break was unaltered. Copyright © 2004 Society of Chemical Industry     

Montmorillonite as support for peroxide in the melt grafting of maleic anhydride onto polypropylene

Grafting of maleic anhydride onto polypropylene was performed in a Haake torque rheometer, in the presence of organically modified montmorillonite, MMT (used as support for the peroxide), according to a 2³ factorial design, where the maleic anhydride concentration (C_MA), peroxide concentration (C_per) and reaction time (t_r) were varied. For comparison, the reaction in the absence of MMT was also conducted. Polypropylene degradation was assessed by parallel plate rheometry and size exclusion chromatography (SEC) and percentage of reacted maleic anhydride (%MA_g) was obtained by titration and FTIR spectroscopy. The results showed differences in both systems, conventional and in the presence of MMT. The structure of polypropylene grafted with maleic anhydride, PP‐g‐MA, indicates longer branches are formed in the presence of MMT compared to in its absence, demonstrated by FTIR analysis. As in conventional reaction systems, an increase in C_per caused an increase in %MA_g and a reduction in molar mass. The variable C_MA showed to be not significant in the grafting reaction in the presence of MMT, even at high DCP levels, at a 5% significance level. On the other hand, increase in C_MA resulted in significant increase in viscosity. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44134.     

Preparation of hairy particles by grafting PEG onto the poly(styrene‐co‐maleic anhydride) surface and PEG effect on SiO2 nanoparticles adsorption

Hairy particles were prepared by immobilization of poly(ethylene glycol) (PEG) on the surface of poly(styrene‐co‐maleic anhydride) (poly(S‐co‐MA)) spheres. It was found that the carbonyl groups on the poly(S‐co‐MA) surface can be conveniently esterified with the hydroxyl groups of PEG. Chemical and morphological changes were analyzed by FT‐IR, TEM, and water contact angle. Results revealed that, with the immobilization of PEG, the morphology of poly(S‐co‐MA) turned from a smooth surface to a hairy‐like structure and the hydrophilicity of the polymer particles improved. In addition, berry‐like polymer/silica particles can be obtained by using the hairy particles as template. The PEG hairy chains show steric repulsion during the deposition of silica nanoparticles by in situ sol‐gel process. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Big effects of small nanoparticles on hydrophobically modified polyacrylamide in an aqueous solution

In this study, we investigated the self-assembly properties of small-sized (3–5 nm) oppositely charged SiO₂ nanoparticles (NPs) and hydrophobically modified polyacrylamide (hm-PAM) in aqueous solutions by rheological and structural analysis. The results show that the addition of small NPs to the hm-PAM solution remarkably enhanced its viscosity and viscoelasticity, and the viscosity remained high at elevated temperatures. Specifically, the low shear rate viscosity of the NP–hm-PAM solutions increased by up to three orders of magnitude at a very low loading of NPs (10⁻² wt %). Moreover, there appeared to be no sediment in the dispersed system after over 18 months of storage. Scanning electron microscopy and transmission electron microscopy measurements indicated that additional physical crosslinks were formed after the addition of the small silica NPs to the hm-PAM solutions. With the experiments and published results combined, we proposed a simple model of electrostatic and hydrophobic interactions for the crosslinking structure of the NP–hm-PAM composite. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47269.     

超临界二氧化碳对聚合物的增塑作用及应用

简要介绍了超临界二氧化碳的性质及其与聚合物的相互作用 ,着重论述了超临界二氧化碳对聚合物的增塑作用及应用 ,包括小分子渗透、溶胀聚合、抽提分级、聚合物脱挥及微孔材料的制备等     

Surface grafting of polymers onto glass plate: Polymerization of vinyl monomers initiated by initiating groups introduced onto the surface

The surface grafting of polymers onto a glass plate surface was achieved by the polymerization of vinyl monomers initiated by initiating groups introduced onto the surface. Azo groups were introduced onto the glass plate surface by the reaction of 4,4′-azobis(4-cyanopentanoic acid) with isocyanate groups, which were introduced by the treatment with tolylene-2,4-diisocyanate. The radical polymerization of various vinyl monomers was initiated by azo groups introduced onto the glass plate surface and the corresponding polymers were grafted from the surface: The surface grafting of polymers was confirmed by IR spectra, and the contact angle of surface, with water. The contact angle of the glass plate increased by the grafting of hydrophobic polymers, but decreased by the grafting of hydrophilic polymers. The radical postpolymerization was successfully initiated by the pendant peroxycarbonate groups of grafted polymer on the surface to give branched polymer-grafted glass plate. The cationic polymerization of vinyl monomers was also successfully initiated by benzylium perchlorate groups introduced onto the glass plate surface and the corresponding polymers were grafted onto the surface. The contact angle of the glass plate surface obtained from the cationic polymerization of styrene was larger than that obtained from the radical polymerization. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65: 2165–2172, 1997     

Factorial experimental design for grafting of vinyl monomers onto natural rubber latex

Graft copolymerization of styrene (St) and methyl methacrylate (MMA) in the presence of natural rubber latex using cumene hydroperoxide/tetraethylenepentamine redox initiator system was prepared at various process variables. The synthesized graft copolymers were purified and then characterized by Fourier transformed infrared spectroscopy analysis. A full 2⁴ factorial experimental design was applied to study the effect of various process variables on grafting efficiency. The following four independent variables considered to be mainly affecting the grafting efficiency were reaction temperature, rubber‐to‐monomer ratio, St‐to‐MMA ratio, and initiator amount used in the secondary polymerization. It was shown in this study that the reaction temperature significantly influenced the grafting efficiency, increasing as the temperature was increased. The amount of grafting increased with increasing rubber‐to‐monomer ratio and St‐to‐MMA ratio, whereas the amount of grafting decreased with increasing amount of initiator. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 455–463, 2004     

Electroactive interpenetrated biohydrogels as hybrid materials based on conducting polymers

Different levels of interpenetration of poly(hydroxymethyl-3,4-ethylenedioxythiophene) (PHMeDOT) inside a poly-γ-glutamic acid (γPGA) biohydrogel matrix, previously loaded with microparticles of poly(3,4-ethylenedioxythiophene) (PEDOT), have been obtained. The degree of interpenetration has shown influence on the morphological and electrochemical properties of the resulting biohydrogel ([PEDOT/γPGA]PHMeDOT) with a maximum after 1 h of PHMeDOT polymerization time. The high biocompatibility of all biohydrogel components, together with the combination of mechanical properties of γPGA hydrogels with the electrochemical properties of interconnected microparticles of PEDOT, makes it a promising material for next generation of biosensors.