Heterogeneous bulk polymerization of styrene in the presence of polybutadiene: Calculation of the macromolecular structure

A mathematical model is presented that simulates the polymerization of styrene in the presence of polybutadiene (PB) for producing high‐impact polystyrene (HIPS) via the heterogeneous bulk process. The model follows the polymerization in two phases; and calculates in each phase the main reaction variables and the molecular structure of the three polymeric components: free polystyrene (PS), unreacted PB, and graft copolymer. Two polymerizations (at 90 and 120°C) were carried out and simulated. The model was validated with measurements of the monomer conversion, the grafting efficiencies, and the average molecular weights. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99: 3023–3039, 2006     

Styrene–butadiene block copolymer with high cis‐1,4 microstructure

The sequential block copolymerization of styrene (St) and butadiene (Bd) was carried out with an activated rare earth catalyst composed of catalyst neodymium tricarboxylate (Nd), cocatalyst Al(i‐Bu)₃ (Al), and chlorinating agent (Cl). The microstructure, composition, and morphology of the copolymer were characterized by FTIR, ¹H NMR, ¹³C NMR, and TEM. The results show that styrene–butadiene diblock copolymer with high cis‐1,4 microstructure of butadiene units (～ 97 mol %) was synthesized. The cis‐selectivity for Bd units was almost independent on the content of styrene units in the copolymer ranging from 18.1 mol % to 29.8 mol %. The phase‐separated morphology of polystyrene (PS) domains of about 40 nm tethered by the elastomeric polybutadiene (PB) segments is observed. The PS‐b‐cis‐PB copolymer could be used as an effective compatilizer for noncompatilized binary PS/cis‐PB blends. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

The component miscibility evolution during polymerization of the polybutadiene containing styrene solutions

In situ graft copolymerization of polystyrene (PS) on polybutadiene (PB) during polymerization of PB solution in styrene monomer was investigated to determine the performance of grafting process, chain structure of generated copolymers, and their effectiveness as compatibilizing agents for incompatible PS-rich and PB-rich phases. The amount of copolymers and their chain structures at different stages of polymerization were determined by gel permeation chromatography (GPC) curves of the reactive blends (taken directly from the reaction) and physical blends (physically prepared based on total composition of reactive blends). It was demonstrated that copolymer formation started from the early stage of polymerization and continued up to the phase inversion stage. In addition, PS grafting on PB occurred initially via single-chain attachment and then converted to a double-chain scenario later on. Compatibilizing efficiency of the copolymers was evaluated by Huggins coefficient (k _H) obtained by performing dilute solution viscometry (DSV) on samples taken at different stages of conversions. The effect of molecular weight of PB on the grafting process and the effectiveness of copolymers generated were also studied. It was found that while compatibilizing role of the copolymers produced from high molecular weight PB (HPB) increases as conversion goes further, the compatibilizing efficiency of the copolymers produced from low molecular weight PB (LPB) shows a very sharp variation in a small range of conversion. Plotting k _H of physical blends against weight fraction of PB molecules in solid content of the solutions (w _PB) showed negative deviation from mixture law with a W-like pattern containing two minima with a maximum in between. While a negative deviation was assumed as indication of immiscibility of the components, upward deviation at middle values of w _PB was attributed to molecular segregations that reduce the interface between the incompatible PS-rich and PB-rich phases.     

Effect of maleic anhydride grafted polybutadiene on the compatibility of polyamide 66/acrylonitrile‐butadiene‐styrene copolymer blend

The addition of maleic anhydride grafted polybutadiene (PB‐g‐MAH) can greatly improve the compatibility of polyamide 66 (PA66)/acrylonitrile‐butadiene‐styrene copolymer (ABS) blends. Unlike the commonly used compatibilizers in polyamide/ABS blends, PB‐g‐MAH is compatible with the ABS particles' core phase polybutadiene (PB), rather than the shell styrene‐acrylonitrile (SAN). The compatibility and interaction of the components in the blends were characterized by Fourier transform‐infrared spectra (FTIR), Molau tests, melt flow index (MFI), dynamic mechanical analyses (DMA), and scanning electron microscopic (SEM) observations. The results show that PB‐g‐MAH can react with the amino end groups in PA66 while entangle with the PB phase in ABS. In this way, the compatibilizer anchors at the interface of PA66/ABS blend. The morphology study of the fracture sections before and after tensile test reveals that the ABS particles were dispersed uniformly in the PA66 matrix and the interfacial adhesion between PA66 and ABS was increased significantly. The mechanical properties of the blends thus were enhanced with the improving of the compatibility. POLYM. ENG. SCI., 2012. © 2011 Society of Plastics Engineers     

Solution and quasi‐bulk copolymerizations of styrene and methyl methacrylate in the presence of polybutadiene: Mathematical model

A mathematical model was developed for simulating the batch copolymerization of styrene (St) and methyl methacrylate (MMA) in the presence of polybutadiene (PB). It was adjusted to the measurements of three reactions carried out at 65°C, with initial comonomers ratio at the azeotropic condition, THF as solvent, and benzoyl peroxide as initiator. The measurements included: (a) conversions and grafting efficiencies by gravimetry; (b) molecular weight distributions (MWDs) by size exclusion chromatography; and (c) global mass fractions of St in the co‐ and terpolymer, by UV‐Vis spectroscopy. The model predicts the MWDs of the three polymeric components of MBS: free St‐MMA copolymer, St‐MMA‐g‐PB graft terpolymer (GT), and residual PB. In addition, it predicts the bivariate chain length distributions of the different GT topologies, with each topology characterized by the number of branches per molecule. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Bulk polymerization of styrene in the presence of polybutadiene. The use of bifunctional initiators

This work experimentally and theoretically investigates the use of bifunctional initiators in the synthesis of high-impact polystyrene (HIPS). The experimental design involved a series of nonisothermal bulk polymerizations of styrene (St) in the presence of polybutadiene (PB). The performance of three commercial initiators [2,5-dimethyl −2,5 bis(2-ethylhexanoyl peroxy] hexane or L–256; 2,5 bis(benzoyl peroxy) hexane or L–118; and ethyl 3,3 di(t-butyl peroxide) butirate or L–233] were compared to the performance of a standard monofunctional initiator (terbutylperoctoate or TPBO), and to the blank case (i.e., without initiator). From samples taken along the prepolymerization period, the phase inversion point and the 30% conversion point were estimated. For the final product, the free polystyrene (PS) molecular weights and the St grafting efficiency were measured. A mathematical model was developed that predicts the evolution of the MWDs for the free PS the residual PB, and the graft copolymer, together with the chemical composition distribution for the total graft copolymer. Compared to the monofunctional case, the L–256 initiator induces phase inversion and rubber grafting at low conversions. Also, it shortens the prepolymerization times by around 38%, without affecting the molecular characteristics of the final product. L–118 also shortens prepolymerization time with respect to TBPO; but is not as effective as L–256 or TBPO in promoting rubber grafting. At the polymerization end, the final molecular characteristics are practically independent of the initiator type because most of the polymerization in induced by monomer initiation. Due to its slow decomposition rate, the L–233 initiator is less effective that TBPO for reducing prepolymerization times and for promoting phase inversion. © 1996 John Wiley & Sons, Inc.     

Preparation and characterization of high‐impact polystyrene using different types of polybutadiene

The mechanical, morphological, and rheological properties of polymer blends based on polystyrene (PS) and three different types of polybutadiene (PB) were studied. The polymer blends containing 20% of PB were processed in a Haake mixer at 180°C and 60 rpm for 6 min. The materials exhibited impact strength superior to that of the PS. An increase was observed in the impact strength of 138, 208, and 823%, when low‐cis polybutadiene (PB_l), high‐cis polybutadiene (PB_h), and styrene–butadiene block copolymer (PB_co), were respectively used. The materials presented dispersed morphology with polybutadiene domains, with sizes inferior to 1 μm, randomly distributed in the PS matrix. The viscous and storage moduli increased as the applied frequency increased. The flow activation energy, calculated by Arrhenius equation, varied from 34 to 71 kJ/mol. In the rheological experiments all polymer blends presented pseudoplastic behavior, showing decreasing viscosities as the shear rate increased. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Polymerization of styrene in the presence of polybutadiene: determination of the molecular structure

This work experimentally and theoretically determines the molecular macrostructure of the polymer mixture that is developed (at relatively low conversions) in a solution polymerization of styrene (St) in presence of polybutadiene (PB). The reaction was carried out at 70°C in a batch‐stirred tank reactor. From samples taken along the reaction, the three polymeric components of high‐impact polystyrene (HIPS) (i.e., polystyrene  PS , residual PB, and graft copolymer) were first separated from each other by solvent extraction. Then, the graft copolymer was ozonized to isolate the St branches. The molecular weight distributions (MWDs) of the total HIPS, the three HIPS components, and the grafted St branches were determined by the size exclusion chromatography (SEC). For the graft copolymer and the total HIPS, the variation of the St mass fraction with molecular weights was also determined by SEC. All measurements were compared with theoretical estimates, and a reasonable agreement is observed. For the theoretical estimates, the mathematical model of Estenoz, D. A.; Valdez, E.; Oliva, H. M.; Meira, G. R. (J Polym Sci 1996, 59, 861) was extended to compare the MWD of the St branches with the MWD of the free PS. For the sought experimental conditions, these two distributions had very similar results but in a bulk industrial process, larger discrepancies are to be expected. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 1950–1961, 1999     

Deformation behaviour of styrene/butadiene star block copolymer/hPS blends: influence of morphology

The influence of morphology on micromechanical deformation behaviour of blends consisting of a lamellar forming styrene/butadiene star block copolymer and polystyrene homopolymer (hPS) was studied by transmission electron microscopy (TEM). The pure star block copolymer and the microphase separated blends revealing lamellar structure with polystyrene (PS) lamella thickness in the range of about 20 nm showed homogeneous plastic deformation of the PS lamellae. The macrophase separated blends with PS particles in lamellar matrix exhibited debonding at the particle–matrix interface associated with extensive plastic deformation of the surrounding matrix. The blends containing PS matrix deformed via crazing.     

Deformation mechanism of polystyrene toughened with sub‐micrometer monodisperse rubber particles

Core–shell polybutadiene‐graft‐polystyrene (PB‐g‐PS) rubber particles with different ratios of polybutadiene to polystyrene were prepared by emulsion polymerization through grafting styrene onto polybutadiene latex. The weight ratio of polybutadiene to polystyrene ranged from 50/50 to 90/10. These core‐shell rubber particles were then blended with polystyrene to prepare PS/PB‐g‐PS blends with a constant rubber content of 20 wt%. PB‐g‐PS particles with a lower PB/PS ratio (≤70/30) form a homogeneous dispersion in the polystyrene matrix, and the Izod notched impact strength of these blends is higher than that of commercial high‐impact polystyrene (HIPS). It is generally accepted that polystyrene can only be toughened effectively by 1–3 µm rubber particles through a toughening mechanism of multiple crazings. However, the experimental results show that polystyrene can actually be toughened by monodisperse sub‐micrometer rubber particles. Scanning electron micrographs of the fracture surface and stress‐whitening zone of blends with a PB/PS ratio of 70/30 in PB‐g‐PS copolymer reveal a novel toughening mechanism of modified polystyrene, which may be shear yielding of the matrix, promoted by cavitation. Subsequently, a compression‐induced activation method was explored to compare the PS/PB‐g‐PS blends with commercial HIPS, and the result show that the toughening mechanisms of the two samples are different. Copyright © 2006 Society of Chemical Industry     

Compatibilization of styrene–butadiene–styrene block copolymer in polypropylene/polystyrene blends by analysis of phase morphology

Effect of compatibilization of styrene–butadiene–styrene (SBS) block copolymer in polypropylene/polystyrene (PP/PS) blends was studied by means of small angle X‐ray scattering (SAXS) and scanning electron microscope (SEM). According to SAXS, a certain amount of SBS was located at the interface in all the analyzed samples, forming the relatively thicker interface layer penetrating into homopolymers, and the thickness of the interface layer was quantified in terms of Porod light scattering theory. The incorporation of SBS into PP/PS blends resulted in a decrease in domain size following an emulsification curve as well as an uniform size distribution, and consequently, a fine dispersion of PP domains in the PS matrix. This effect was more pronounced when the concentration of SBS was higher. A critical concentration of SBS of 15% above which the interface layer approaches to saturation and domain size attains a steady‐state was observed. Further, the morphology fluctuation of unetched fracture surface of umcompatibilized and compatibilized blends was analyzed using an integral constant Q based on Debye‐Bueche light scattering theories. Variation of Q as a function of the concentration of SBS showed that, due to the penetrating interface layer, adhesion between phases was improved, making it possible for applied stress to transfer between phases and leading to more uniform stress distribution when blends were broken; accordingly, a more complicated morphology fluctuation of fracture surface appeared. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103:365–370, 2007     

Effect of styrene–isoprene–styrene,styrene–butadiene–styrene,and styrene–butadiene–rubber on the mechanical,thermal, rheological,and morphological properties of polypropylene/polystyrene blends

The mechanical, thermal, rheological, and morphological properties of polypropylene (PP)/polystyrene (PS) blends compatibilized with styrene–isoprene–styrene (SIS), styrene–butadiene–styrene (SBS), and styrene–butadiene–rubber (SBR) were studied. The incompatible PP and PS phases were effectively dispersed by the addition of SIS, SBS, and SBR as compatibilizers. The PP/PS blends were mechanically evaluated in terms of the impact strength, ductility, and tensile yield stress to determine the influence of the compatibilizers on the performance properties of these materials. SIS‐ and SBS‐compatibilized blends showed significantly improved impact strength and ductility in comparison with SBR‐compatibilized blends over the entire range of compatibilizer concentrations. Differential scanning calorimetry indicated compatibility between the components upon the addition of SIS, SBS, and SBR by the appearance of shifts in the melt peak of PP toward the melting range of PS. The melt viscosity and storage modulus of the blends depended on the composition, type, and amount of compatibilizer. Scanning electron microscopy images confirmed the compatibility between the PP and PS components in the presence of SIS, SBS, and SBR by showing finer phase domains. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 266–277, 2003     

Compatibilization efficiency of styrene‐butadiene block copolymers as a function of their block number

Effect of block number in linear styrene‐butadiene (SB) block copolymers (BCs) on their compatibilization efficiency in blending polystyrene (PS) with polybutadiene (PB) was studied. Di‐, tri‐, or pentablocks of SB copolymers as well as their combinations were blended with the mentioned homopolymers; supramolecular structure determined by small angle X‐ray scattering method (SAXS), morphology using scanning electron microscopy (SEM) combined with image analysis (IA), and stress transfer characteristics of the blends were chosen as criteria of compatibilization efficiency of the copolymers used. It was proved that the addition of SB BCs led to remarkably finer phase structure and substantially higher toughness of PS/PB blends. Triblock copolymer showed to be the compatibilizer with higher efficiency than diblock, pentablock, and the di/triblock copolymer mixture. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Effects of the polybutadiene/poly(styrene‐co‐acrylonitrile) ratio in a polybutadiene‐g‐poly(styrene‐co‐acrylonitrile) impact modifier on the morphology and mechanical behavior of acrylonitrile–butadiene–styrene blends

Polybutadiene‐g‐poly(styrene‐co‐acrylonitrile) (PB‐g‐SAN) impact modifiers with different polybutadiene (PB)/poly(styrene‐co‐acrylonitrile) (SAN) ratios ranging from 20.5/79.5 to 82.7/17.3 were synthesized by seeded emulsion polymerization. Acrylonitrile–butadiene–styrene (ABS) blends with a constant rubber concentration of 15 wt % were prepared by the blending of these PB‐g‐SAN copolymers and SAN resin. The influence of the PB/SAN ratio in the PB‐g‐SAN impact modifier on the mechanical behavior and phase morphology of ABS blends was investigated. The mechanical tests showed that the impact strength and yield strength of the ABS blends had their maximum values as the PB/SAN ratio in the PB‐g‐SAN copolymer increased. A dynamic mechanical analysis of the ABS blends showed that the glass‐transition temperature of the rubbery phase shifted to a lower temperature, the maximum loss peak height of the rubbery phase increased and then decreased, and the storage modulus of the ABS blends increased with an increase in the PB/SAN ratio in the PB‐g‐SAN impact modifier. The morphological results of the ABS blends showed that the dispersion of rubber particle in the matrix and its internal structure were influenced by the PB/SAN ratio in the PB‐g‐SAN impact modifiers. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 2165–2171, 2005     

Bulk polymerization of styrene in presence of polybutadiene: Calculation of molecular macrostructure

In our previous publication the detailed molecular macrostructure generated in a solution polymerization of styrene (St) in the presence of polybutadiene (PB) at 60°C, was theoretically calculated. In this work, an extended kinetic mechanism that incorporates monomer thermal initiation, chain transfer to the rubber, chain transfer to the monomer, and the gel effect is proposed, with the aim of simulating a bulk high-impact polystyrene (HIPS) process. The mathematical model enables the calculation of the bivariate weight chainlength distributions (WCLDs) for the total copolymer and for each of the generated copolymer topologies and the univariate WCLDs for the free polystyrene (PS), the residual PB, and the crosslinked PB topologies. These last topologies are characterized by the number of initial PB chains per molecule; copolymer topologies are characterized by the number of PS and PB chains per molecule. The model was validated with published literature data and with new pilot plant experiments that emulate an industrial HIPS process. The literature data correspond to a dilute solution polymerization at a constant low temperature with chemical initiation and a bulk polymerization at a constant high temperature with thermal initiation. The new experiments consider different combinations of prepolymerization temperature, initiator concentration, and solvent concentration. One of the main conclusions is that most of the initial PB is transformed into copolymer. For example, for a prepolymerization temperature of 120°C with addition of initiator, the experimental measurements indicate that the final total rubber mass is approximately three times higher than the initial PB. Also, according to the model predictions, the final weight fractions are: free PS, 0.778; graft copolymer, 0.220; initial PB, 0.0015; and purely crosslinked PB, 0.0005. The final graft copolymer exhibits the following characteristics: average molecular weights, M _n,C = 492,000 and M _w,C = 976,000; average weight fraction of St, 0.722; and average number of PS and PB branches per molecule, 5.19 and 1.13, respectively. © 1996 John Wiley & Sons, Inc.     

Rapid FTIR method for quantification of styrene‐butadiene type copolymers in bitumen

The mid‐IR molar absorptivity for polystyrene (PS) and polybutadiene (PB) blocks were obtained for five styrene‐butadiene‐styrene (SBS) and SB copolymers, including linear, branched, and star copolymers, and their blends with bitumen. The average absorptivity for PS and PB blocks was 277 and 69 L mol⁻¹ cm⁻¹ and it was little affected by the S/B ratio or the copolymer architecture. In the presence of bitumen, Beer's law was obeyed but the respective PS and PB absorptivity was 242 and 68 L mol⁻¹ cm⁻¹, possibly because of weak interactions between the copolymer and bitumen. The absorptivity values were used to calculate the concentration of SB‐type copolymers in blends with bitumen with an accuracy of 10% or better. The method can be used to probe the stability of bitumen–copolymer blends in storage at 165°C, to determine the copolymer concentration in commercial polymer modified bitumen (PMB), and to assess the resistance of PMB to weathering. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1034–1041, 2001     

Nanostructured polymer blends based on polystyrene‐b‐polybutadiene‐b‐poly(methyl methacrylate) triblock copolymers modified with polystyrene and/or poly(methyl methacrylate) homopolymers

Morphologies of polymer blends based on polystyrene‐b‐ polybutadiene‐b ‐poly(methyl methacrylate) (SBM) triblock copolymer were predicted, adopting the phase diagram proposed by Stadler and co‐workers for neat SBM block copolymer, and were experimentally proved using atomic force microscopy. All investigated polymer blends based on SBM triblock copolymer modified with polystyrene (PS) and/or poly(methyl methacrylate) (PMMA) homopolymers showed the expected nanostructures. For polymer blends of symmetric SBM‐1 triblock copolymer with PS homopolymer, the cylinders in cylinders core?shell morphology and the perforated lamellae morphology were obtained. Moreover, modifying the same SBM‐1 triblock copolymer with both PS and PMMA homopolymers the cylinders at cylinders morphology was reached. The predictions for morphologies of blends based on asymmetric SBM‐2 triblock copolymer were also confirmed experimentally, visualizing a spheres over spheres structure. This work presents an easy way of using PS and/or PMMA homopolymers for preparing nanostructured polymer blends based on SBM triblock copolymers with desired morphologies, similar to those of neat SBM block copolymers. © 2017 Society of Chemical Industry     

Dynamic mechanical and morphological behavior of blends of polystyrene and poly[acrylonitrile‐g‐(ethylene‐co‐propylene‐co‐diene)‐g‐styrene] prepared by in situ polymerization of styrene

PS/AES blends were prepared by in situ polymerization of styrene in the presence of AES elastomer, a grafting copolymer of poly(styrene‐co‐acrylonitrile) – SAN and poly(ethylene‐co‐propylene‐co‐diene)–EPDM chains. These blends are immiscible and present complex phase behavior. Selective extraction of the blends' components showed that some fraction of the material is crosslinked and a grafting of PS onto AES is possible. The morphology of the noninjected blends consists of spherical PS domains covered by a thin layer of AES. After injection molding, the blends show morphology of disperse elastomeric phase morphology in a rigid matrix. Two factors could contribute to the change of morphology: (1) the stationary polymerization conditions did not allow the mixture to reach the equilibrium morphology; (2) the grafting degree between PS and AES was not high enough to ensure the morphological stability against changes during processing in the melting state. The drastic change of EPDM morphology from continuous to disperse phase has as consequence a decrease in the intensity of the loss modulus peaks corresponding to the EPDM glass transition. However, the storage modulus at temperatures between the glass transition of EPDM and PS/SAN phases does not change significantly. This effect was attributed to the presence of the SAN rigid chains in the AES. © 2009 Wiley Periodicals, Inc. Journal of Applied Polymer Science, 2009     

Effect of the molecular structure of ethene–propene and styrene–butadiene copolymers on their compatibilization efficiency in low‐density polyethylene/polystyrene blends

The effect of the molecular structure of styrene–butadiene (SB) block copolymers and ethene–propene (EPM) random copolymers on the morphology and tensile impact strength of low‐density polyethylene (LDPE)/polystyrene (PS) (75/25) blends has been studied. The molecular characteristics of SB block copolymers markedly influence their distribution in LDPE/PS blends. In all cases, an SB copolymer is present not only at the interface but also in the bulk phases; this depends on its molecular structure. In blends compatibilized with diblock copolymers, compartmentalized PS particles can also be observed. The highest toughness values have been achieved for blends compatibilized with triblock SB copolymers. A study of the compatibilization efficiency of SB copolymers with the same number of blocks has shown that copolymers with shorter PS blocks are more efficient. A comparison of the obtained results with previous results indicates that the compatibilization efficiency of a copolymer strongly depends both on the blend composition and on the properties of the components. The compatibilization efficiency of an EPM/SB mixture is markedly affected by the rheological properties of the copolymers. The addition of an EPM/SB mixture containing EPM with a higher viscosity leads to a higher improvement or at least the same improvement in the tensile impact strength of a compatibilized blend as the same amount of neat SB. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Effect of styrene‐butadiene triblock copolymer structure on its compatibilization efficiency in PS/PB and PS/PP blends

Two styrene‐butadiene triblock copolymers differing in the length of their styrene blocks (40S‐60B‐40S and 10S‐60B‐10S) were used as compatibilizers for PS/PB (4/1) and PS/PP (4/1) blends. The supramolecular structure of the copolymers determined by small‐angle X‐ray scattering (SAXS), morphology of the blends using transmission electron microscopy (TEM), and their tensile impact strength were chosen as criteria of the compatibilization efficiency of the copolymers used. Different mechanisms of compatibilization for “symmetrical” system (PS/PB/SBS) and “asymmetrical” system (PS/PP/SBS) were proved. While for the PS/PB blend, the 40S‐60B‐40S copolymer proved to be a good compatibilizer, for the PS/PP blend, surprisingly, the 10S‐60B‐10S copolymer is more efficient.