Using Crystallisation Fractionation to Monitor Thermo‐Oxidative Degradation of Impact Poly(propylene) Copolymers

ICPPs are complex materials that contain various ethylene/propylene copolymers in addition to the majority poly(propylene) phase. To understand their molecular structure, multiple fractionation and analysis techniques are used. In this study, TREF and CRYSTAF are used to study the difference in the thermo‐oxidative degradation of two grades of ICPPs with different ethylene contents. Direct correlations are drawn between the carbonyl index, molecular weight and crystallisability at various stages of degradation. The higher ethylene content sample shows increased thermal stability. This is due to the fact that the ethylene/propylene fraction is more stable due to the higher comonomer content and lower isotacticity as well as due to the higher amount of this fraction in the material.

     

Thermo‐Mechanical Degradation of LDPE‐Based Nanocomposites

Thermo‐mechanical degradation of LDPE‐based nanocomposites was studied by mainly investigating the rheological properties. For all of the investigated processing conditions, the viscosity of the nanocomposites was higher than that of the pure‐LDPE matrix, but on increasing the severity of the mixing conditions, the difference between the viscosity of the nano‐filled polymer and that of the pure LDPE decreased. The X‐ray traces of the nanocomposites suggest that intercalation has been achieved during the melt, when less‐severe processing conditions were used. At severe processing conditions (longer mixing time, high temperature and shear stress) the thermo‐mechanical degradation was accelerated, possibly due to the loss of mass from the organoclay galleries. The variations of the viscosity in the presence of two organo‐modified montmorillonite (MMt) clays were compared to the ones observed with a MMt clay at different processing conditions.

     

Thermal Behavior of Isotactic Poly(propylene)/Maleated Poly(propylene) Blends

This paper analyzes the thermal and thermo‐oxidative degradation behavior, phase separation, melting, and crystallization of blends consisting of isotactic poly(propylene) (IPP) and poly(propylene) grafted with maleic anhydride (PP‐g‐MA). It has been established that, depending on the blend composition and crystallization/preparation procedure, the blends of IPP and PP‐g‐MA can either co‐crystallize or evidence phase separation. This conclusion has been attained by comparing the DSC results of crystallization under dynamic and isothermal conditions with X‐ray diffraction results. On the basis of the obtained results, the optimum mixing ratios have been established as 95–85 wt.‐% IPP/5–15 wt.‐% PP‐g‐MA. Thermo‐oxidative behavior has been studied by thermogravimetry and differential thermal analysis.

     

Thermal Degradation Behavior of Poly(propylene) with a Novel Silicon‐Containing Intumescent Flame Retardant

Summary: A novel intumescent flame retardant (PSiNII), containing silicon, phosphorus and nitrogen, has been synthesized and incorporated into poly(propylene) (PP). The flame retardancy of PP/PSiNII, evaluated by the limiting oxygen index (LOI) value, can be enhanced up to 29.5 vol.‐% from 17.4 vol.‐% with 20% total loading amount of PSiNII. The thermal degradation behavior of PP/PSiNII are investigated by thermogravimetric analysis (TGA) under nitrogen and air, and pressure differential scanning calorimetry (PDSC) under 1.5 MPa of oxygen. The PP/PSiNII‐3 degrades at 400 °C for different time, and the process is investigated by FTIR which indicates there is P? O in the char. The morphologies of char formed at 400 °C for 10 min and after LOI test are investigated by scanning electron microscopy (SEM). The morphological structure of the char exhibits the swollen cells in the inner and a smooth outer surface, which do good to the thermal properties and fire performance of PP. The thermal stability of PP is improved by incorporating PSiNII.

Inner surface of PP/PSiNII‐3 after LOI test.     

Controlled Degradation of Poly(propylene) in Industrial Extruders

Summary: The main objective of this work was to study the controlled degradation of PP in industrial extruders at different operating conditions. Firstly, the investigation of certain key polymer properties, such as the MI and the MWD, revealed that the changes undergone by the polymer resin during the reactive extrusion depend strongly on the operating conditions. In the absence of oxygen, the results indicated that spontaneous thermal and/or mechanical degradation were not very important. Therefore, resin properties were not expected to change during extrusion if no peroxide was fed into the extruder, in the absence of oxygen. On the other hand, in the presence of oxygen, MWD analysis showed that the MWD could be shifted towards higher or lower molecular weights, indicating that both chain growth and chain scission were possible during extrusion. Finally, simple expressions are presented here in order to allow for the monitoring and control of the important final properties of the extruded resin.

The molecular weight distribution of polymer powder and polymer pellets during extrusion.     

Temperature Sensitive Behavior of Poly(N‐isopropylacrylamide) Grafted Onto Electron Beam‐Irradiated Poly(propylene)

Summary: N‐Isopropylacrylamide (NIPAAm) was graft‐polymerized from its acetone solution onto poly(propylene) (PP) films, after electron‐beam irradiation in the presence of air oxygen. The effects of pre‐irradiation dose as well as monomer concentration, reaction temperature and reaction time on the grafting efficiency were investigated. Typical conditions for achieving maximum grafting yield were observed for 1 M monomer concentration, after PP pre‐irradiation with a 300 kGy dose and a reaction temperature of 50 °C. The location of the graft polymerization was examined by different methods including measurements of dimensional variations, calorimetry, SEM and AFM. The temperature‐responsive behavior of grafted copolymer was studied by swelling and contact angle measurements at different temperatures.

Temperature dependence of the swelling ratio in water as a function of temperature.     

Tunable Thermo‐Responsive Poly(N‐vinylcaprolactam) Cellulose Nanofibers: Synthesis,Characterization, and Fabrication

Temperature‐responsive PVCL homopolymers and functional PVCL polymers containing carboxylic acids are prepared in organic and aqueous solutions. PVCL bulk polymers are characterized using ¹H NMR, photometry, ATR‐FTIR, and thermal analysis. A finite phase transition at 37–40 °C occurs in aqueous solutions of PVCL and PVCL‐COOH. PVCL and PVCL‐COOH polymers are electrospun into fibers ranging from 100 to 2300 nm in diameter. PVCL/cellulose bi‐component films are obtained by electrospinning of CA and PVCL followed by alkaline hydrolysis. These tunable thermo‐responsive PVCL/cellulose nanofibers have potential applications in developing affinity membranes.

     

Fractionation and Analysis of an Impact Poly(propylene) Copolymer by TREF and SEC‐FTIR

TREF fractionation was combined with SEC‐FTIR analysis to measure the compositional heterogeneity within a commercial impact PP copolymer. The chemical composition of all fractions was determined as function of their molecular weight distribution. This approach proved to be highly successful at identifying different constituents within fractions exhibiting bimodal molecular weight distributions. Furthermore, the determination of ethylene and propylene crystallinity distribution across the molecular weight distribution confirmed the morphological nature of each of the components of the bimodal distribution. It is demonstrated that the combination of TREF and SEC‐FTIR provides a simple alternative to more time‐consuming conventional ways of characterising impact PP copolymers of complex heterogeneity.

     

Long‐Term Properties of Butt‐Welded Poly(propylene)

It is still not clear why the long‐term properties of plastic weld seams can only be differentiated by the very expensive medium tensile creep tests. One hypothesis for justifying this is based on the change in the structure of the weld seam surroundings, another cites the consumption of antioxidants and the following ageing in the weld seam area to be responsible for this. Butt‐welded weld seams made of poly(propylene) were systematically produced under different process parameters. Corresponding to the particular hypothesis, these weld seams were then analyzed in various ways to find correlations or to prove one of the hypotheses. Regarding their short‐term weld seam quality, the analyzed weld seams could not be differentiated through short‐term tensile or short‐term bend test. However, the medium tensile creep tests showed significant differences in both time until failure and long‐term weld seam quality. Under long‐term loading, the start of the brittle crack could be detected in most weld seams in the fine spherulite‐zone or between this zone and the area of the flow lines. This demonstrated again that only long‐term tests are suitable for examining different weld seam qualities. Depending on the welding parameters, times until failure decline with increasing heated‐tool temperature and heating time. Though these parameters lead to a higher consumption of antioxidants in the weld seam, a degradation was not detected in the breaking area. In fact, increasing heated‐tool temperatures and heating times, as well as higher joining pressures lead to a change in the internal structure of the material. This can be seen in morphological structure analyses in the larger bend of the entire weld seam area. A larger bend, however, correlates with higher residual stresses in the weld seam. In the medium tensile creep tests, these residual stresses as well as the tensile stress in the border region and the compressive stress in the middle are superimposed by the tensile stress resulting from the test stress. Thus a greater bend of the weld seam area and higher residual stresses in the weld seam itself lead to shorter times until failure in medium tensile creep tests.

Schematic representation of the formation of residual stresses in a weld seam and residual stresses in the different bended weld seam areas.     

Grafting of Hindered Amine Stabilizer in Poly(propylene) Films under γ‐Irradiation

Summary: In this paper, the grafting of a hindered amine stabilizer (HAS) is studied in isotactic poly(propylene) (PP) films under γ‐irradiation. The HAS used has a definite structure that combines a hindered amine functionality and a UV‐absorbing unit (benzylidene malonate ester group) detectable at 308 nm in the UV spectrum of PP film and 314 nm in chloroform. The stabilizer is added to the polymer at various concentration ratios: 0.1, 0.2, and 0.3 wt.‐%. The percentage of HAS grafting in the PP film at various additive concentrations is determined as a function of γ‐radiation dose in the range of 0–100 kGy by direct spectroscopic measurements through the absorption band of the stabilizer in the UV spectra of the PP film. The percentage of free HAS extracted with chloroform from the PP film versus the radiation dose is determined by UV spectroscopy for all the additive concentrations used. This study reveals that only 80% of the HAS is grafted on the 100 kGy irradiated PP matrix independent of the additive concentration used. However, the percentage of HAS grafted on PP films displays an exponential dependence on γ‐radiation dose. These results are consistent with the data obtained on the free HAS content. γ‐Irradiation grafting of HAS in the PP is accompanied by the oxidative degradation of the polymer substrate that is evaluated by increasing the carbonyl index and reducing significantly the oxidation induction time of the PP films.

The percentage of hindered amine stabilizer grafted to the PP film as a function of γ‐radiation dose.     

Dynamic Mechanical Properties of Poly(propylene) Blends with Poly[ethylene‐co‐(methyl acrylate)]

Summary: Blends of poly(propylene) (PP) were prepared with poly[ethylene‐co‐(methyl acrylate)] (EMA) having 9.0 and 21.5% methyl acrylate comonomer. A similar series of blends were compatibilized by using maleic anhydride grafted PP. The morphology and mechanical properties of the blends were investigated using differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA) in tensile mode. The DMA method and conditions were optimized for polymer film specimens and are discussed in the experimental section. The DSC results showed separate melting that is indicative of phase‐separated blends, analogous to other PP‐polyethylene blends but with the added polarity of methyl acrylate pendant side groups that may be beneficial for chemical resistance. Heterogeneous nucleation of PP was decreased in the blends because of migration of nuclei into the more polar EMA phase. The crystallinity and peak‐melting temperature did not vary significantly, although the width of the melting endotherm increased in the blends indicating a change had occurred to the crystals. DMA analysis showed the crystal‐crystal slip transition and glass transition (T_g) for PP as well as a T_g of the EMA copolymer occurring chronologically toward lower temperatures. The storage modulus of PP and the blends was generally greater with annealing at 150 °C compared with isothermal crystallization at 130 °C. The storage modulus of the blends for isothermally crystallized PP increased with 5% EMA, then decreased for higher amounts of EMA. Annealing caused a decrease with increasing copolymer content. The extent of the trend was greater for the compatibilized blends. The T_g of the blends varied over a small range, although this change was less for the compatibilized blends.

Storage modulus for PP and EMA9.0 blends annealed at 150 °C.     

In‐Situ Fiberized Poly(ethylene terephthalate) as a Reinforcement to Poly(propylene) Matrix

The reinforced poly(propylene) (PP)/poly(ethylene terephthalate) (PET) in‐situ fiberized composites were prepared by extrusion‐drawing‐injection molding. The influences of PET weight fraction (f_w) on the PET fiberization, phase morphology, and mechanical properties of the composites, together with their functional mechanisms were studied by contrast to the normal‐blended materials without drawing. The results show that as the f_w rises from 0 to 20%, the number of PET fibers increases, whereas their diameter and dispersity decrease till f_w = 15% and then increase, and the number of remained PET particles tends to rise. These changes of PET fiberization and phase morphology with f_w were attributed to the consequence of the combined actions of breakup, coalescence, and deformation of the PET dispersed phase in the PP matrix during the extrusion drawing. Correspondingly, the tensile strength (σ_t) and Young's modulus (E) of the in‐situ composites increase till f_w = 15% and then decrease, with maximum gains of σ_t and E of about 20 and 70% relative to the neat PP, respectively. This σ_t/f_w relation was ascribed to the counterbalanced result between the reinforcing effect of the dispersed phase on matrix and the interfacial flaw effect of two immiscible phases, while the E/f_w relation was considered as a representation of the rigidizing effect of the fibers on the matrix being controlled by both their number and diameter.

In‐situ PET fibres (PET/PP = 85/15) in an as‐drawn filament.     

Non‐Ionic,Poly(ethylene oxide)‐Based Surfactants as Intercalants/Dispersants/Exfoliants for Poly(propylene)‐Clay Nanocomposites

Summary: Poly(propylene) (PP)‐clay nanocomposites were prepared from unmodified montmorillonite clays (NaMMT), with poly(ethylene oxide)‐based nonionic surfactants as dispersants/intercalants/exfoliants. The primary objective of this research was to find dispersants that (a) allow PP nanocomposites to be formed by direct melt mixing; (b) are effective with unmodified clays and (c) comprise of only a minor component with respect to both the clay and the overall composition. Linear, branched, gemini and sugar‐based surfactants and structures containing poly(dimethyl siloxane) and poly(methyl methacrylate) blocks were examined. These additives were found to be effective in breaking down the clay agglomerates to tactoids, giving some expansion of the clay structure and partial exfoliation and providing substantially improved clay dispersion. The properties of the derived nanocomposites depend on the level of additive and its structure. Tensile and impact properties show significant improvement over the precursor PP. Also notable are the significantly better thermal and thermo‐oxidative stabilities, as compared to both PP and “clay alone” composites. For optimal properties, it is both necessary and desirable that the surfactant should only be a minor constituent (20–50%) of the composition, with respect to the clay. A preferred surfactant is linear PE‐block‐PEO, with a short PEO block and an alkyl chain with approximately 30 carbon atoms (C₃₀).

     

Study of novel biodegradable thermo‐sensitive hydrogels of methoxy‐poly(ethylene glycol)‐block‐polyester diblock copolymers

A series of biodegradable thermo‐sensitive hydrogels were synthesized by ring‐opening polymerization of methoxy‐poly(ethylene glycol) (mPEG) and various ester monomers, i.e. D ,L ‐lactide, glycolide, β‐propiolactone, δ‐valerolactone and ε‐caprolactone. The copolymers were characterized using ¹H NMR spectroscopy and gel permeation chromatography. The micelle properties were also measured. The results indicated that the diblock copolymers formed nano‐micelles at low concentrations in aqueous phase. The lower critical solution temperatures of the diblock copolymers were above 35 °C at 1 wt%. As the temperature increased above room temperature, the diblock copolymer solutions underwent a sol‐to‐gel phase transition, which was manifested in viscosity increases, indicative of the formation of a gel. The mPEG–polyester diblock copolymer solutions exhibited sol‐gel transition behavior as a function of temperature and polymer concentration. Copyright © 2010 Society of Chemical Industry     

Mechanisms and kinetics of thermal degradation of poly(butylene succinate‐co‐propylene succinate)s

Poly(butylene succinate) (PBSu) and two PBSu‐rich poly(butylene succinate‐co‐propylene succinate)s were studied. Copolyesters were characterized as random copolymers, based on ¹³C‐NMR spectra. TGA‐FTIR was used to monitor the degradation products at a heating rate of 5°C/min under N₂. FTIR spectra revealed that the major products were anhydrides, which were formed following two cyclic intramolecular degradation mechanisms by the breaking of the weak O‐CH₂ bonds around succinate groups. Thermal stability at heating rates of 1, 3, 5, and 10°C/min under N₂ was investigated using TGA. The model‐free methods of the Friedman and Ozawa equations are useful for studying the activation energy of degradation in each period of mass loss. The results reveal that the random incorporation of minor propylene succinate units into PBSu did not markedly affect their thermal resistance. Two model‐fitting mechanisms were used to determine the mass loss function f(α), the activation energy and the associated mechanism. The mechanism of autocatalysis nth‐order, with f(α) = α^m(1 ? α)ⁿ, fitted the experimental data much more closely than did the nth‐order mechanism given by f(α) = (1 ? α)ⁿ. The obtained activation energy was used to estimate the failure temperature (T_f). The values of T_f for a mass loss of 5% and an endurance time of 60,000 h are 160.7, 155.5, and 159.3°C for PBSu and two the copolyesters, respectively. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Formation and Distribution of Rubbery Phase in High Impact Poly(propylene) Particles

This paper reconstructs the principle of rubber incorporation in high impact poly(propylene) (hiPP) particles. The detailed information about the pores and rubber distribution inside and on the surface of hiPP particles is obtained by micro‐computed tomography and atomic force microscopy. The strong effect of homopolymer origin on hiPP particle morphology and rubber distribution is demonstrated. To obtain the most homogeneous rubber distribution, the low homopolymer porosity is required. The initial particle porosity has a negligible effect on the thickness of the rubber layer on the particle surface at the medium rubber content. The rubber forms not only along the iPP primary particles and directly or close to the pores but also on or close to the particle surface rather than it flows there. The evidence for these claims is based on the systematic investigation in dependence on EPR content, homopolymer particle porosity (prepared by different catalysts) and antistatic agent deactivating catalyst close to particle surface.

     

A Kinetic Study on the Thermal Degradation of Multi‐Walled Carbon Nanotubes‐Reinforced Poly(propylene) Composites

Summary: The influence of the multi‐walled carbon nanotubes (MWNTs) content on the thermal degradation behavior of MWNTs‐reinforced poly(propylene) (PP) composites was investigated by using non‐isothermal thermogravimetric analysis (TGA). Kinetic parameters of degradation were evaluated by using the Flynn‐Wall‐Ozawa iso‐conversional method and the pseudo first‐order method. As a result, compared with pristine PP, MWNTs‐PP nanocomposites have lower peak temperatures of degradation, narrower degradation temperature ranges and a higher amount of residual weight at the end of the degradation, which is likely to be a result of specific interactions between complimentary functional groups. The values of the reaction order of MWNTs‐PP nanocomposites determined by the Kissinger method are close to 1 in the non‐isothermal degradation process. There is a good correlation between the E_a in region II and the peak temperature of degradation for the composites.

Activation energies for degradation of different contents of MWNTs‐filled PP nanocomposites as a function of conversion.     

聚乙烯醇降解特性研究

采用凝胶色谱法（GPC）和紫外分光光度法（UV）研究了聚乙烯醇（PVA）微生物降解和化学氧化降解效果。GPC实验表明，PVA经过本实验室筛选的微生物菌株降解后，保留9min左右产生了一个小相对分子质量的峰，其峰面积约占总面积的一半；UV实验也表明了PVA在降解菌株的作用下，其浓度呈下降趋势；采用Fenton试剂（FR）对PVA进行预先氧化处理，然后再进行微生物降解。结果表明FR预处理有利于PVA的快速有效降解。     

Design and Synthesis of Mechano‐Responsive Color‐Changing Thermoplastic Elastomer Based on Poly(n‐Butyl Acrylate)–Spiropyran‐Polystyrene Comb‐Structured Graft Copolymers

Colorimetric mechanophores like spiropyran (SP) represent an emerging type of interesting signal molecule that can be incorporated into polymers or other materials as a stress transducer. In this work, a new type of spiropyran‐containing inimer molecule MA‐SP‐Br are designed and synthesized, which is incorporated into polybutylacrylate (PBA) chains through reversible addition‐fragmentation chain transfer (RAFT) copolymerization with n‐butyl acrylate (BA). PBA‐SP‐Br is then used as a macro‐initiator to graft polystyrene (PS) side chains from the PBA backbone through atom transfer radical polymerization (ATRP) of styrene. The resulting comb‐structured graft copolymer PBA‐SP‐PS contains 0.15–0.34% SP and exhibits a characteristic feature of thermoplastic elastomers. Under uniaxial stretch, the materials possess an excellent mechano‐responsivity and change color at strains as low as about 14%.     

Lignocellulosic Flour from Cladodes of Opuntia ficus‐indica Reinforced Poly(propylene) Composites

Summary: A lignocellulosic flour was obtained by grinding dried cladodes of Opuntia ficus‐indica. It was used as low cost natural filler in PP and the effect of the treatment of the filler with MAPP was also investigated. The morphology and thermal properties of these composites were evaluated by SEM and DSC, respectively. MAPP coating resulted in a better adhesion between the filler and the matrix and higher homogeneity of the material. A decrease of the degree of crystallinity of the PP matrix in presence of the untreated filler was observed. Dynamic mechanical analysis and tensile properties were also studied. High‐strain tensile properties display enhanced mechanical properties for MAPP treated‐based composites only. When conditioned in highly moist atmosphere (98% RH), both the water uptake and water diffusion coefficient decrease when the filler was treated. These effects were ascribed to the promoting interfacial adhesion induced by the coating treatment. In liquid water, this increased adhesion between the filler and the matrix results in a higher weight loss of the material. It is due to the removal of the grafted polymer from the material during the dissolution of part of the filler.

SEMs of freshly fractured surface for a PP film filled with 10 wt.‐% of MAPP treated OFI cladode (top) and calcium oxalate crystallite within the PP matrix for a 3 wt.‐% filled composite (bottom).