Enhancement of β-nucleated crystallization in polypropylene random copolymer via adding isotactic polypropylene

Polypropylene random copolymer (PPR) is one of important polypropylene types for the application fields needing for excellent toughness. Because of the random copolymer chain configuration, the polymorphic behavior of PPR is difficult to be altered even by adding β-nucleating agent (β-NA). In this study, a promising method was developed by adding isotactic polypropylene (iPP) into PPR/β-NA blend, which has leaded to a surprising enhancement in the β-crystallization capability of PPR. At the optimal component condition, the β-crystal content of PPR can reach the highest level of 92 % and the β-crystallization capability is improved by 56%. As a result of high β-crystal contents, a superior mechanical toughness has been attained. On the other hand, the fractional crystallization experiment suggests that the stereoregular chains of iPP could assist the formation of primary β-nuclei at the very early stage of crystallization. This special crystallization event dominates the final polymorphic composition in PPR. Furthermore, it is demonstrated that impact polypropylene copolymer (IPC) can be used to substitute iPP for the improvement of β-crystal content of PPR. This provides a huge possibility to improve the low temperature properties of PPR to enlarge its applications.     

Improvement of interfacial adhesion between wood and polypropylene in wood–polypropylene composites

N-vinylformamide-grafted polypropylene (VFPP) was successfully synthesized through a free radical grafting reaction. Both polymeric methylene diphenyl diisocyanate (PMDI) and VFPP were effective compatibilizers for increasing both the strength and stiffness of the resulting wood–PP (polypropylene) composites. Both the modulus of rupture (MOR) and the modulus of elasticity (MOE) of the resulting wood–PP composites were further increased when PMDI and VFPP were used together as an integrated compatibilizer system. This new PMDI-VFPP compatibilizer system was comparable to maleic-anhydride-grafted polypropylene in terms of enhancing the strength and stiffness of the wood–PP composites. Study of the fractured surfaces of the wood–PP composites with scanning electron microscopy revealed that this new PMDI-VFPP compatibilizer system greatly improved the interfacial adhesion between wood and PP. This PMDI-VFPP compatibilizer system also greatly reduced the water absorption of the resulting wood–PP composites. In this PMDI-VFPP compatibilizer system, PMDI is proposed to function as a wood-binding domain and VFPP to function as a PP-binding domain. PMDI reacted with the amide group in VFPP, thus forming covalent linkages between PMDI and VFPP.     

Rheological study of recycled polypropylene–starch blends

Blends of recycled polypropylene (PP) and starch (S) with the compositions polypropylene 83 wt%–starch 17 wt% (PP83/S17) (blend 1a), polypropylene 68.8 wt%–starch 31.2 wt% (PP 68.8/S 31.2) (blend 2a) and polypropylene 89.5 wt%–starch 10.5 wt% (PP 89.5/S 10.5) (blend 3a) were synthesized. Maleated polypropylene (MAPP) was used as a compatibilizer. The compositions of the compatibilized blends were PP73/S15/MAPP12 (blend 1b), PP55/S25/MAPP20 (blend 2b) and PP85/S10/MAPP5 (blend 3b). The occurrence of a reaction between MAPP and starch was studied using Fourier transform infrared analysis. Thermal and rheological properties such as the complex viscosity, storage and loss modulus of the blends with a compatibilizer were found to be higher than those of the blends without a compatibilizer. The compatibilized and uncompatibilized blends, as well as recycled PP, were characterized using differential scanning calorimetry, thermogravimetric analysis and cone-and-plate rheometry. The storage and loss modulus values of blend 3b were observed to be the best. The best compatibilizing effect was exhibited by blend 3b at a loading of 5 wt% MAPP because this compatibilizer content yielded the highest complex viscosity and visco-elastic behavior. The presence of a functional compatibilizer enhanced the interactions between starch and recycled PP, which was confirmed by a rise in the melt viscosity, storage modulus and thermal stability. These blends were also characterized in terms of their water uptake by performing water absorption tests. Blend 2b containing 20 % MAPP was observed to absorb the maximum amount of water at 25 °C.     

Effect of spatial confinement on the development of β phase of polypropylene

The focus of this study was the effect of spatial confinement on the development of nucleating agent-induced β phase polypropylene (PP) in the dynamically vulcanized thermoplastic elastomers (TPVs) based on dynamically vulcanized PP/ethylene-propylene-diene rubber (EPDM) blend. The melting behaviors, crystalline structures and the morphologies of the blends were studied by differential scanning calorimetry (DSC), wide-angle X-ray diffraction (WAXD) and scanning electron microscopy (SEM). The results indicate that the EPDM phase undergoes a series of changes from the dispersed phase to a continuous one, and again to the dispersed phase with increased content of curing agent, and the PP component always shows itself in a continuous phase. In this process, with the content of the nucleating agent unchanged, the content of β phase PP in the blends initially increases a little and then decreases with increasing PF (Phenolic resin) content. We believe spatial confinement provides a good explanation for the development of β phase PP.     

Laminated polypropylene material — A new form of floor covering

Conclusions -- An efficient technological process has been developed for preparing an ecologically clean floor covering, which is a nonwoven polypropylene needle-punched material laminated with polypropylene film. In the preparation process, an extrusion method is used for applying a face layer of thermoplastic polypropylene using a slot-like spinneret. The nonwoven needle-punched material is produced from a melt of granulated polypropylene with aerodynamic stretching of the fibers on an LPP-2400GT line. The floor covering can be made with a design applied on the base (nonwoven material) or with coloring the face layer in bulk.-- Figures have been given for the properties of floor coverings prepared on experimental stands; advantages and defects of the new type of floor coverings have been noted.Translated from Khimicheskie Volokna, No. 2, pp. 33–34, March–April, 1993.     

Quantitative study of photocatalyzed oxidation of ethylene–propylene rubber and atactic polypropylene

The effect of photoactive pigments such as ZnO, CdS, and TiO₂ on the photooxidation (with and without water vapor) of ethylene–propylene rubber and atactic polypropylene were examined. The effects of surface treatment (passivation) and low granulometry (nanopigments) were also studied for TiO₂. A drastic increase of ketone and an inhibition of carboxylic acid formation for ZnO filled polymers were revealed and quantitatively measured by using derivatization reactions. Such a phenomenon, as well as a small decrease of average molecular weight, were explained by a modification of the ZnO decomposition mechanism of tertiary hydroperoxides. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 1681–1689, 1998     

Non-isothermal crystallization kinetics of polypropylene and hyperbranched polyester blends☆

Polypropylene (PP) with different contents of the second generation hyperbranched polyester (HBP) is prepared by melt blending method. The non-isothermal crystallization kinetics of PP and PP/HBP blend...     

Exploring temperature dependence of the toughening behavior of β-nucleated impact polypropylene copolymer

In this study, the effects of α- and β-nucleating agents (α-NA and β-NA) on the toughening behavior of impact polypropylene copolymer were ascertained with respect to three test temperatures (23, 0 and ?15 °C). The addition of α-NA impacted the toughness slightly for all test temperatures. However, the tendency of impact strength vs. β-NA content at 0 °C significantly differs from that of the other two temperatures. Importantly, a close correlation between toughness at 0 °C and chain mobility of the amorphous portion has been well revealed for the first time by achieving a linearly fitting between impact strength at 0 °C and β-relaxation peak intensity in DMA spectrum. A comparative investigation between the situations containing α-NA or β-NA offers new insights into the physical origin of the toughening behavior for a multiphase multicomponent polyolefin system. The chain mobility of matrix amorphous portion plays a dominant role on toughening.     

Exploring the roles of molecular structure on the β-crystallization of polypropylene random copolymer

To investigate effects of molecular structures on β-crystallization of polypropylene random copolymer (PPR), PPR-A and PPR-B with similar molecular weight and distribution but significantly different polymorphic behavior were used. Wide-angle X-ray diffraction (WAXD), Fourier transform infrared spectroscopy (FT-IR), solvent fractionation combined with successive self-nucleation and annealing (SSA) and Gel Permeation Chromatography (GPC) were applied. Results revealed that after addition of same amount of β-nucleating agent (β-NA), large amount of β-phase is obtained in PPR-A (K _β  = 0.603), while no β-phase can be seen from PPR-B; Structure characterizations revealed that they have similar molecular weight but different total amount and distribution of ethylene comonomer: the total content of ethylene comonomer of PPR-A is higher compared with PPR-B, but its ethylene comonomer distribution is less uniform. In this way, PPR-A possesses high molecular weight high isotactic fraction, which cannot be seen from PPR-B due to its more uniform comonomer distribution. Therefore, the presence of highly isotactic PP (HPP) is the key factor in β-crystallization of PPR. For verification, HPP with low or high molecular weights are respectively added into β-nucleated PPR-B. Results revealed that HPP was effective in enhancing β-crystallization of PPR-B; higher molecular weight of HPP was more favorable and more effective.     

Preparation and characterization of wood-fiber-reinforced polyamide 6–polypropylene blend composites

In this study, we used lithium chloride (LiCl) as a modifier to decrease the melting temperature (T _m) of polyamide 6 (PA6), and then, we fabricated wood-fiber-reinforced PA6–polypropylene (PP) blend composites via hot pressing. From crystallization analysis, the composites exhibited a lower T _m and a lower processing temperature compared to PA6. Color and Fourier transform infrared analyses showed that severe thermal degradation and discoloration of the composites could be prevented by the incorporation of LiCl. LiCl had positive effects on the mechanical properties of the final product and the interfacial compatibility among PA6, PP, and wood fiber. The flexural strength increased by 8.5%. In addition, both maleic anhydride grafted PP and wood fiber improved the mechanical properties. The flexural strengths increased by 7.9 and 40%, respectively. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47413.     

Formation of β-cylindrites under supercooled extrusion of isotactic polypropylene at low shear stress

Formation of β-cylindrites of isotactic polypropylene under various wall shear stress (σ_w), supercooled temperature of melt (T_e) and crystallization temperature (T_c) has been investigated by polarized light microscopy (PLM), wide angle X-ray diffraction (WAXD), and differential scanning calorimeter (DSC). To have better control over the thermomechanical history, instead of a reciprocating screw, the samples were prepared by extruding supercooled melt through capillary die. β-cylindrites can be observed by PLM in the extruded specimen even at a lower σ_w (0.020 MPa), and the number of β-cylindrites nuclei increases rapidly with the lowering of T_e. The nucleation density of β-cylindrites increases with the raising of wall shear stress under a given T_e of 160 °C. Furthermore, at lower supercooled temperature of melt (145 °C), the radius of β-cylindrites decreases with the increasing of σ_w, and the number of β-cylindrites nuclei almost remain invariant. At relatively higher σ_w (0.090 MPa), a saturation of β-cylindrites nuclei is observed with decreasing T_c. A modified model based on above results has been proposed to explain the effect of the original structure of quiescent supercooled melt on the formation of β-cylindrites under low shear stress.     

Changes in optical texture of α-spherulites of isotactic polypropylene upon partial melting and recrystallization

Textural changes in -phase spherulites of isotactic polypropylene (iPP) in a sequence of thermal events were examined by means of polarized light microscopy (PLM). This sequence of thermal events involves isothermal crystallization (atT_c = 117 to 140 °C), followed by heating (at 5 °C/min) to nearly complete melting, and then recrystallization upon cooling (at -40°C/min) to T_c During isothermal crystallization, the a-spherulites were of mixed birefringenceat T_c = 117 to 127 °C or of negative birefringence at T_c = 140 °C; upon heating towards melting, the spherulitec birefringence consistently truned negative. More interestingly, after recrystallization during cooling back to Tc from nearcomplate melting, all spherulites exhibited positive birefringence. The recrystallization could also result in speckles of positive birefringence when T_c was high or upon slower cooling. The changes in optical texture are explained in terms of contributions from tangential (or, cross-hatched) subsidiary lamellae which (as compared to the radial dominant lamellae) are relatively low-melting but thicken and recrystallize more readily in the present temperature range.     

Preparation and properties of dynamically vulcanised blends of isobutylene–isoprene rubber and isotactic polypropylene

Abstract

Dynamic vulcanisation was employed to prepare blends of isobutylene–isoprene rubber (IIR) and isotactic polypropylene (iPP) with superior properties. The preparation technology, the effects of the presence of IIR on the crystallisation properties of iPP and the mechanical properties of the IIR/iPP thermoplastic vulcanisates (TPVs) were investigated. It was revealed that, under regular shearing at 180°C, dynamic vulcanisation for 10 min produced IIR/iPP TPVs of excellent properties; while degradation occurred when the duration of vulcanisation was extended to 15 min. Incorporation of IIR into iPP dramatically reduced the size of the iPP spherulites, and thus decreased the melting temperature and the degree of crystallinity of the iPP. When the IIR content was 50 wt-%, maximally balanced mechanical properties of IIR/iPP TPVs were obtained with a Charpy impact strength of 53·6 kJ m^?2 and a tensile strength of 31·3 MPa.     

Crosslinking of β-cyclodextrin and combining with ammonium polyphosphate for flame-retardant polypropylene

This work presents the synthesis of crosslinked hexamethylene diisocyanate β-cyclodextrins (HDI-CDs) by reacting β-cyclodextrin (β-CD) with HDI as a crosslinking agent at different feed ratios. As a novel char-forming agent, the HDI-CDs are combined with ammonium polyphosphate (APP) and applied in polypropylene (PP) to form intumescent flame-retardant composites. The structure of HDI-CDs is characterized by Fourier transform infrared spectra (FTIR), ¹³C nuclear magnetic resonance spectroscopy, and nitrogen adsorption–desorption test. The thermogravimetric analysis (TGA) results indicate that HDI-CDs have better char-forming performance than β-CD. FTIR spectra, X-ray diffraction, and Raman spectra characterization demonstrate that the reaction between HDI-CDs and APP contributes to the formation of a more stable char layer than β-CD and APP. According to the results of TGA, scanning electron microscopy, limiting oxygen index (LOI), UL-94, and X-ray photoelectron spectroscopy test, when the crosslinking degree of HDI-CDs is high enough (not less than β-CD:HDI = 1:3.6), the PP/APP/HDI-CDs composites can form a compact and dense char layer during combustion. Among all composites, PP/APP/HDI-CD(4) shows the best flame-retardant performance, which can pass the UL 94 V-0 rating with an LOI value of 32.8% when the loading of flame retardants is 28 wt %. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48320.     

The effect of soluble β-nucleator's content on crystalline structure and performance of polypropylene pipe

Strength-toughness clash of polypropylene (PP) pipe is an insurmountable bottleneck for the potential application. Here, we successfully prepared PP pipe with simultaneously enhanced toughness and hoop strength via addition of soluble β-nucleators (β-NAs) and application of helical flow in the extrusion. The outstanding combination of strength and toughness in the PP pipe depended on the loading content of β-NAs and the helical pattern, which determined the morphology and alignment of β-crystals. At the low content, β-NAs dissolved completely into the PP melts and distributed homogeneously to promote the formation of β-spherulites in the PP pipe. When the loading content exceeded the solubility limit, the β-NAs partially dissolved and upon cooling, the dissolved β-NAs grew preferentially on the undissolved ones along one direction, assembling into the fibrous aggregates. With the guidance of helical flow, the fibrous β-NAs aligned off the axis and functioned as an oriented template to trigger the PP crystallization on the surface into hybrid β-shish-kebab with fibrous β-NAs as shish. Increasing rotation speed of mandrel and die elevated hoop contribution to obtain the β-shish-kebab with a deviated angle of 55°, endowing the prepared pipe with high hoop strength and toughness.     

Design of new polypropylene–woodflour composites: Processing and physical characterization

Woodflour/polypropylene composites were prepared with 10 and 20% in weight of woodflour (WF). The influence of the WF, the compatibilizer, and processing aid (WP) in the crystalline structure of the polypropylene was studied by thermal analysis. The results showed that the WF acts as a nucleating agent, increasing the crystallization rate of the PP at the cooling rates studied. The morphological study by SEM proved that the WP increased the dispersion of the filler into the PP matrix, and the ionomer, used like compatibilized improved the adhesion between the PP and the filler obtaining a more uniform morphology. The mechanical properties indicated that the incorporation of the ionomer and the WP enhanced the ductility of the composites at the same time that the materials reached a more uniform morphology. The amount of additives (compatibilizer and WP) included in the woodflour-plastic composite (WPC) formulations was small, for this, the formulations are suitable to use in a possible industrial application. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

Synergistic toughening effects of nucleating agent and ethylene–octene copolymer on polypropylene

The synergistic toughening effect of nucleating agent (NA) and ethylene–octene copolymer (POE) on polypropylene was studied in the present work. Two different nucleating agents, such as α-form nucleating agent 1,3 : 2,4-bis (3,4-dimethylbenzylidene) sorbitol (DMDBS, Millad 3988) and β-form nucleating agent aryl amides compounds (TMB-5), were selected to blend with PP or PP/POE blends, respectively. The results show that PP containing 0.5–0.25 wt % DMDBS or 0.5–0.25 wt % TMB-5 has relatively low impact strength. For PP/POE blends, although the impact strength increases gradually with the increasing of POE content, high content of POE is needed to obtain the available PP toughness. However, once nucleating agent and POE are simultaneously added into PP, PP/POE/NA blends show great improvement of toughness even at low POE content. Furthermore, the synergistic toughening effect of POE/TMB-5 is more apparent than that of POE/DMDBS. SEM results show that whether DMDBS or TMB-5 has no apparent effect on the morphologies of POE in the PP/POE/NA blends. Further investigations using DSC and POM indicate that both DMDBS and TMB-5 induce the apparent enhancement of the crystallization temperature of PP and the sharp decrease of spherulites size of PP in the PP/POE/NA blends. The possible synergistic toughening mechanism is discussed in the work. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008