Two-step preparation and thermal characterization of cationic 2-hydroxypropyltrimethylammonium chloride hemicellulose polymers from sugarcane bagasse

Cationic sugarcane bagasse hemicellulose derivatives with a relatively low degree of substitution (0.01-0.54) containing quaternary ammonium groups were prepared by etherification with 3-chloro-2-hydroxypropyltrimethylammonium chloride or preferably with 2,3-epoxypropyltrimethylammonium chloride using sodium hydroxide as a catalyst in aqueous solution. The extent of etherification was measured by yield percentage and degree of substitution (DS). The DS values of the products could be controlled by adjusting the molar ratio of etherifying agent to anhydroxylose units in hemicelluloses and the molar ratio of sodium hydroxide to etherifying reagent. In comparison, the etherified hemicellulose preparations were characterized by both degradative methods such as thermal analysis, and non-degradative techniques such as gel permeation chromatography (GPC), Fourier transform infrared (FT-IR), and ¹³C nuclear magnetic resonance (NMR) spectroscopy. It was found that a significant degradation of the hemicellulose polymers occurred during etherification under the alkaline conditions used. The thermal stability of the etherified hemicelluloses was lower than that of the unmodified hemicellulose polymers.     

Comprehensive analysis of the substitution pattern in dextran ethers with respect to the reaction conditions

Dextrans from Leuconostoc ssp., α-1,6-linked glucans branched at O-3, were O-methylated in DMSO with lithium dimsyl and methyl iodide under various conditions. Methyl substituent distribution was comprehensively studied in the terminal, internal, and branched glucosyl units and along and over the dextran macromolecules. The order of reactivity was O-2 > O-4 ≥ O-3. The methyl pattern in the glucosyl units significantly deviates from a random distribution with enhanced amounts of un- and trisubstituted moieties. This deviation was found to proceed on macromolecular level by means of ESI-MS of perdeuteromethylated and partially depolymerized methyl dextrans. Heterogeneity was much more pronounced than for methyl amylose prepared under comparable conditions. DS gradients in and over the material are discussed with respect to dextran structure and the mechanism of Li dimsyl alkylation. For comparison, cyanoethyl dextrans were prepared by sodium hydroxide catalyzed addition of acrylonitrile. Monomer analysis of cyanoethyl dextrans revealed that this thermodynamically controlled reaction gave a random substitution pattern with 48% of cyanoethyl groups at O-2, 33% at O-4, and 19% at O-3.      

Selective reactivities and accessibilities of the hydroxyl groups in cotton cellulose based on equilibrium data from a reversible chemical reaction

In order to determine the relative equilibrium constants for reactions of the hydroxyl groups at C₂, C₃, and C₆ of the D-glucopyranosyl units, methyl vinyl sulfone was reacted with cellulose dissolved in benzyltrimethylammonium hydroxide. The reaction was carried to constancy in distribution of substituents between the 2–0– and 6–0–positions. The distributions of substituents in the D-glucopyranosyl units were measured by gas-liquid chromatographic analysis of the products from hydrolysis of the modified cellulose. Relative equilibrium constants were then evaluated, assuming complete accessibility of all three types of hydroxyl groups of the cellulose in solution. For determination of the relative accessibilities of the individual types of hydroxyl groups in heterogeneous reactions of cotton cellulose with methyl vinyl sulfone, the reactions were carried to equilibrium distributions in media of various normalities of sodium hydroxide (i.e., media of various swelling strength). The distributions of substituents in the D-glucopyranosyl units were measured. From these values and the ratio of equilibrium constants, the relative accessibilities of the hydroxyl groups at C₂ versus those at C₆ were calculated. Apparent accessibilities of the hydroxyl groups at C₂ are approximately double those at C₆ when the reaction is carried out in 1N sodium hydroxide and about triple those at C₆ when the reaction is carried out in 0.5N sodium hydroxide.     

Carboxymethylation of hemicelluloses isolated from sugarcane bagasse

Hemicelluloses isolated from sugarcane bagasse were converted to carboxymethyl hemicelluloses (CMH) by carboxymethylation using sodium monochloroacetate and sodium hydroxide in ethanol/water medium. The reaction was performed under various temperatures, times, times of alkaline activation, the ways of the addition of alkali, and the amounts of sodium hydroxide and sodium monochloroacetate. The product had the maximum degree of substitution (DS) of 0.56. The structure of the resulting polymers was characterized with Fourier transform infrared (FT-IR) and ¹³C nuclear magnetic resonance (NMR) spectroscopies. Destructive methods such as thermal analysis and non-destructive techniques such as gel permeation chromatography (GPC) were used to characterize the carboxymethyl hemicellulose preparations. It was found that a significant degradation of the polymers occurred during carboxymethylation. The thermal stability of carboxymethyl hemicelluloses was higher than that of the native hemicelluloses.     

Novel anionic polyaddition of 2‐trifluoromethylacrylate by double Michael reaction with ethyl cyanoacetate

Novel fluorinated polymer synthesis with anionic polyaddition by double Michael addition reaction of 2‐trifluoromethylacrylate derivatives with ethyl cyanoacetate (ECA) was proposed. Diaddition product of ECA with phenyl 2‐trifluoromethylacrylate was yielded in high yield by the catalysis of sodium ethoxide in tetrahydrofuran at 60 °C. Sodium hydroxide catalyzed double Michael addition reaction also produced diaddition product in high yield. Novel anionic polyaddition of 1,4‐phenylene bis(2‐trifluoromethylacrylate) [CH₂?C(CF₃)COOC₆H₄OCOC(CF₃)?CH₂] (PBFA) with ECA afforded the polymer of 1.2 × 10⁴ as the highest molecular weight. The isolated polymer gave the polymer of 2.8 × 10⁴ as a molecular weight by the reaction of the isolated polymer with PBFA in the presence of sodium ethoxide; which proved that the polymer end groups were mainly ECA moieties. The reaction mechanism that the proton abstraction from ECA followed by the addition of 2trifluoromethylacrylate was proposed. The reaction of acetylacetone with PBFA was also examined to give the polymer of 7.6 × 10³ as the highest molecular weight catalyzed by sodium hydroxide at room temperature. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 5698–5708, 2009     

An Alternative Application to the Portuguese Agro-Industrial Residue: Wheat Straw

The effects of alkaline treatments of the wheat straw with sodium hydroxide were investigated. The optimal condition for extraction of hemicelluloses was found to be with 0.50 mol/l sodium hydroxide at 55 °C for 2 h. This resulted in the release of 17.3% of hemicellulose (% dry starting material), corresponding to the dissolution of 49.3% of the original hemicellulose. The yields were determined by gravimetric analysis and expressed as a proportion of the starting material. Chemical composition and physico-chemical properties of the samples of hemicelluloses were elucidated by a combination of sugar analyses, Fourier transform infrared (FTIR), and thermal analysis. The results showed that the treatments were very effective on the extraction of hemicelluloses from wheat straw and that the extraction intensity (expressed in terms of alkali concentration) had a great influence on the yield and chemical features of the hemicelluloses. The FTIR analysis revealed typical signal pattern for the hemicellulosic fraction in the 1,200–1,000 cm⁻¹ region. Bands between 1,166 and 1,000 cm⁻¹ are typical of xylans.     

Preparation of polymethylsilsesquioxanes by the base‐catalyzed hydrolytic polycondensation of triisopropoxy(methyl)silane

Base‐catalyzed hydrolytic polycondensation of trialkoxymethylsilane was investigated to synthesize polymethylsilsesquioxanes (PMSs). The reaction of trimethoxy(methyl)silane and triethoxy(methyl)silane with tetramethylammonium hydroxide, tetrabutylammonium hydroxide, and also coline gave insoluble gels. Polymethylsilsesquioxane (PMS‐IP) was obtained by the reaction of triisopropoxy(methyl)silane (MTIPS) with tetrabutylammonium hydroxide as a catalyst. PMS‐IP was composed primarily of T² and T³ units. The percentage of T³ units and the molecular weight of PMS‐IP increased with increases in the molar ratios of catalyst and water to MTIPS and with the reaction time. PMS‐IP was soluble in organic solvents, except for methanol, and was separated by extraction with hexane and methanol into low‐ and high‐molecular‐weight fractions of M_w 2800–4000 and 7300–88,300, respectively. PMS‐IP coating films were prepared by dip coating on the organic, inorganic, and metal substrates, using the acetone–isopropyl alcohol solution of PMS‐IP. Since PMS‐IP solutions prepared with tetrabutylammonium hydroxide were hardly used because of the low content of hydroxy groups in the polymer, they showed low adhesion when compared with those solutions prepared with hydrochloric acid. The dielectric constant of the coating film prepared from the high‐molecular‐weight PMS‐IP was 2.6. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 3623–3630, 2005     

Synthesis of new substituted 5‐methyl‐3,5‐diphenylimidazolidine‐2,4‐diones from substituted 1‐(1‐cyanoethyl‐1‐phenyl)‐3‐phenylureas

The reaction of substituted phenyl isocyanates with 2‐amino‐2‐phenylpropanenitrile and 2‐amino‐2‐(4‐nitrophenyl)propanenitrile has been used to prepare substituted 1‐(1‐cyanoethyl‐1‐phenyl)‐3‐phenylureas. In anhydrous phosphoric acid the first products to be formed from 1‐(1‐cyanoethyl‐1‐phenyl)‐3‐phenylureas are phosphates of 4‐methyl‐4‐phenyl‐2‐phenylimino‐5‐imino‐4,5‐dihydro‐1,3‐oxazoles, which on subsequent hydrolysis give the respective ureidocarboxylic acids. On prolongation of the reaction time, the phosphates of 4‐methyl‐4‐phenyl‐2‐phenylimino‐5‐imino‐4,5‐dihydro‐1,3‐oxazoles rearrange to give phosphates of 5‐methyl‐4‐imino‐3,5‐diphenylimidazolidin‐2‐ones, and these are subsequently hydrolysed to the respective substituted 5‐methyl‐3,5‐diphenylimidazolidin‐2,4‐diones. The ureidocarboxylic acids were also prepared by alkaline hydrolysis of 5‐methyl‐3,5‐diphenylimidazolidin‐2,4‐diones. The 5‐methyl‐3,5‐diphenylimidazolidin‐2,4‐diones and ureidocarboxylic acids were characterised by their ¹H and ¹³C NMR spectra. Structure of the 5‐methyl‐5‐(4‐nitrophenyl)‐3‐phenylimidazolidine‐2,4‐dione was verified by X‐ray diffraction. The alkaline hydrolysis of individual imidazolidine‐2,4‐diones was studies spectrophoto‐metrically in sodium hydroxide solutions at 25 °C. The rate‐limiting step of the base catalysed hydrolysis consists in decomposition of the tetrahedral intermediate. The reaction is faster if electron‐acceptor sub‐stituents are present in the 3‐phenyl group of imidazolidine‐2,4‐dione cycle. The pK_a values of individual 5‐methyl‐3,5‐diphenylimidazolidine‐2,4‐diones have been determined kinetically.     

(H3O)2NaAl3F12, isostructural with A2NaAl3F12 (A = K+, Rb+, Cs+) fluorides having HTB‐type sheets

The title compound, (H₃O)₂NaAl₃F₁₂ [dihydronium sodium trialuminum(III) dodecafluoride], was obtained by solvothermal synthesis from the reaction of aluminium hydroxide, sodium hydroxide, 1,2,4‐triazole and aqueous HF in ethanol at 463 K for 48 h. The structure consists of AlF₆ octahedra organized in [AlF₄⁻]_n HTB‐type sheets (HTB is hexagonal tungsten bronze) separated by H₃O⁺ and Na⁺ cations.     

Effect of sodium cation on the electrochemical reduction of CO<Subscript>2</Subscript> at a copper electrode in methanol

The electrochemical reduction of CO₂ with a Cu electrode in methanol was investigated with sodium hydroxide supporting salt. A divided H-type cell was employed; the supporting electrolytes were 80 mmol dm⁻³ sodium hydroxide in methanol (catholyte) and 300 mmol dm⁻³ potassium hydroxide in methanol (anolyte). The main products from CO₂ were methane, ethylene, carbon monoxide, and formic acid. The maximum current efficiency for hydrocarbons (methane and ethylene) was 80.6%, at −4.0 V vs Ag/AgCl, saturated KCl. The ratio of current efficiency for methane/ethylene, r _f(CH₄)/r _f(C₂H₄), was similar to those obtained in LiOH/methanol-based electrolyte and larger relative to those in methanol using KOH, RbOH, and CsOH supporting salts. In NaOH/methanol-based electrolyte, the efficiency of hydrogen formation, a competing reaction of CO₂ reduction, was suppressed to below 4%. The electrochemical CO₂ reduction to methane may be able to proceed efficiently in a hydrophilic environment near the electrode surface provided by sodium cation.     

Per-<Emphasis Type="Italic">O</Emphasis>-acylation of xylan at room temperature in dimethylsulfoxide/<Emphasis Type="Italic">N</Emphasis>-methylimidazole

The per-O-acylation of xylan-type hemicellulose was firstly carried out in dimethylsulfoxide/N-methylimidazole (DMSO/NMI) at room temperature without additional catalyst. The optimum conditions for esterification of xylan was investigated in terms of the molar ratio of reagents to anhydroxylose units (AXU) in xylan and the kinds of esterification reagents to obtain a high degree of substitution (DS, 1.98) and weight percent gain (WPG, 86.88 %) of xylan esters. In this solvent system, NMI acted as a solvent, a base and an excellent catalyst, therefore, the per-O-acylation of xylan (DS of 1.98) was readily accomplished in DMSO/NMI system at room temperature. Structure elucidation of xylan esters was characterized by FT-IR and NMR (¹H-NMR, ¹³C-NMR and HSQC). FT-IR and NMR analyses provided the direct evidence of per-O-acylation of xylan under the given conditions. Furthermore, HSQC revealed the higher reactivity of hydroxyls at C-2 position than those at C-3 position of xylan. The solubility of xylan in DMSO, DMF and CHCl₃ improved after esterification. TGA/DTG indicated that the thermal stability of xylan increased after the esterification with anhydrides, while decreased with acyl chlorides, probably due to degradation and hydrolysis of the acylated xylan at the presence of by-product hydrochloric acid.     

Efficient Regioselective Synthesis of Mono-2-O-Sulfonyl-cyclodextrins by the Combination of Sulfonyl Imidazole and Molecular Sieves

Abstract

Cyclodextrins are cyclic oligosaccharides consisting of six or more α-1,4-linked D-glucopyranose units, which possess primary hydroxyl groups at the C-6 positions and secondary hydroxyl groups at the C-2 and C-3 positions. Because cyclodextrins have a hydrophobic and optically active interior, they have been utilized as transporters of hydrophobic molecules and small molecular mimics of enzymes. The chemical modification of cyclodextrins has been investigated in order to improve these characteristics. Sulfonations of the primary or secondary hydroxyl groups of cyclodextrin have been applied for further functionalization of cyclodextrin, and several methods for regioselective sulfonations have been developed. Among these strategies, selective monotosylation of the C-6 hydroxyl group is done relatively easily by reaction of α or β-cyclodextrin and p-toluenesulfonyl chloride in pyridine^1,2 or in alkaline aqueous solution.^3,4 However, sulfonation of the secondary hydroxyl groups is more difficult and new sulfonation methods must be developed to provide precursors for cyclodextrin analogues such as amino and sulfide analogues. Several strategies for the sulfonation of one C-2 hydroxyl group have been reported. However, because reaction conditions can require specific sulfonation reagent,⁵ alkaline condition,^3-7 strict anhydrous conditions,^8,9 or use of protected C-6 hydroxyl groups,^10,11 the methodology is not convenient to employ.     

Generation and Applications of the Hydroxide Trihydrate Anion, [OH(OH2)3]−, Stabilized by a Weakly Coordinating Cation

The reaction of a strongly basic phosphazene (Schwesinger base) with water afforded the corresponding metastable hydroxide trihydrate [OH(OH₂)₃]^? salt. This is the first hydroxide solvate that is not in contact with a cation and furthermore one of rare known water‐stabilized hydroxide anions. Thermolysis in vacuum results in the decomposition of the hydroxide salt and quantitative liberation of the free phosphazene base. This approach was used to synthesize the Schwesinger base from its hydrochloride salt after anion exchange in excellent yields of over 97 %. This deprotonation method can also be used for the phosphazene‐base‐catalyzed preparation of the Ruppert–Prakash reagent Me₃SiCF₃ using fluoroform (HCF₃) as the trifluoromethyl building block and sodium hydroxide as the formal deprotonation agent.     

13C-NMR spectral studies on the distribution of substituents in some cellulose derivatives

¹³C-NMR spectra of trityl cellulose (Tr-Cell), tosyl cellulose (Ts-Cell), cellulose S-methyl xanthate (Cell-M-Xan), and cellulose formate (CF) in dimethylsulfoxide-d₆ were analyzed at 50.4 MHz. It was found that the distribution of substituents in the anhydroglucose units of these cellulose derivatives can be estimated from their ring carbon spectra. The results showed that (i) in Tr-Cell having degree of substitution (DS) lower than 1, the hydroxyl groups at C-6 carbon position are selectively tritylated, (ii) in the case of Ts-Cell, the difference in the relative DS value among three different types of hydroxyl groups is not large, although the relative reactivities of hydroxyl groups toward tosylation decrease in the order C-6 > C-2 > C-3, (iii) in Cell-M-Xan, the hydroxyl groups at C-3 carbon position are mainly substituted, and (iv) the ease of formylation is C-6 > C-2 > C-3. The 100.8 MHz ¹³C-NMR spectra of O-methyl cellulose (MC) revealed that the reactivity order in commercial MC prepared from alkali cellulose is C-6 ? C-2 > C-3. Concerning MC, its water solubility was also discussed in terms of the distribution of substituents along the cellulose chain.     

Template Effects. 2.1 Convenient Syntheses of Crown Ethers Promoted by Ba++ Ion in Aqueous Solution

The current interest in the preparation of crown ethers is due to their extensive application in many different areas.² Published synthetic procedures³ that have appeared since Pedersen's first report⁴ are based mostly on the reaction promoted by strong base between two polyoxaethylene units of varying length, one of which bears two terminal OH groups, and the other two leaving groups. We now report a different approach, based on the action of hydroxide ion on polyethylene-glycol dibromides BrCH₂(CH₂OCH₂)_x-1 CH₂Br, with X = 5, 6, and 7, in highly concentrated water solution in the presence of Ba⁺⁺ ion. The most significant feature of the present method is that it requires only one building block, bearing one less oxygen atom than the crown ether to be formed.⁵ The last oxygen     

Regioselective synthesis and antioxidant activity of a novel class of mono and C2-symmetric bis-1,2,3-triazole and acridinedione grafted macromolecules

An expedient regioselectivesynthesis of novel mono, C₂-symmetric bis-triazole and acridinedione bridged macromolecules has been achieved in good yields employing intermolecular Cu(I) catalyzed azide and alkyne click reaction. Synthesis of O-propargyl acridinedione was achieved in three good yielding steps starting from dimedone, while the symmetrical aliphatic and aryl bis-azides were derived from appropriate dibromides in the presence of sodium azide in dry DMF. The synthesized mono and C₂-symmetric bis-macromolecules have been elucidated by ¹H, ¹³C, elemental and mass spectroscopic analysis. The antioxidant activity of synthesized compounds has also been investigated.     

Kinetic study on the synthesis of some benzo[g]quinoxalin-2(1H)-one derivatives

Some novel 3-substituted benzoquinoxalinones [R = H, CH₃, C₆H₅, (CH₂)₂COOH] were synthesized by the Hinsberg reaction between 2,3-diaminonaphthalene and several α-dicarbonyl compounds. The course of the reactions was followed by the second uv/visible Derivative Spectroscopy Method at different pH values (-0.89 to 9.0) and also in organic solvents at 25°. The compound non-substituted at C-3 was the only one that could be obtained in every media in good yields (80%), having pseudo first-order anelation rate constants of relative high values (1 × 10^?1 — 1 × 10^?2 min^?1). On the other hand, only methanol could be used as the organic solvent for the synthesis of all of the other compounds; aqueous media always provided better results. In the 3-methyl derivative, as well as in the 3-phenyl derivative the change of the reaction pH medium modified the stoichiometry of the anelation, turning a non-quantitative reaction into a quantitative one. This is explained by a change in the mechanism of the reaction on going to lower hydrogen concentrations, a fact that was supported by complementary quantitative hptlc experiments. In general, pseudo first-order rate constants for the anelation were one or two logarithmic units lower than those of the non-substituted compound (R_C-3 = H), but yields were above 60% in every case. A reaction scheme is presented which includes a probable mechanism.     

On the structure and cure acceleration of phenol-urea-formaldehyde resins with different catalysts

Phenol-urea-formaldehyde (PUF) resins with different catalysts [calcium oxide (CaO), sodium carbonate (Na₂CO₃), zinc oxide (ZnO), and magnesium oxide (MgO)] were prepared to accelerate the cure of the resin at low temperature. The cure-acceleration effects of catalysts on chemical structure and cure characteristics of PUF resins were investigated by using both liquid ¹³C nuclear magnetic resonance (NMR) and differential scanning calorimetry (DSC). The liquid ¹³C NMR analysis indicated that the catalyst such as CaO seemed to present a retarded effect on the polycondensation reaction of phenolic components with urea units, while the Na₂CO₃ appeared to promote the self-condensation reaction of phenolic methylol groups at para position toward the formation of para-para methylene linkage. Both ZnO and MgO in PUF resins promoted self-condensation reaction of para methylol groups and condensation reaction of ortho methylol groups with para methylol groups. The catalysts such as Na₂CO₃, ZnO, and MgO can make PUF resins cure at a low temperature. Among these catalysts, the MgO had the most significant accelerating effect on polycondensation and cure reaction of PUF resin.     

Recent advances in molecuar and supermolecuar characterization of cellulose and cellulose derivatives

Recent advances between 1985 and early 1993 in the following topics of the characterization of molecular structure and molecular properties of cellulose and its derivates (CD) made in the authors' laboratories are briefly reviewed: (1) A theoretical basis of the assignment of carbonyl carbon peaks of ¹³C NMR spectra on cellulose acetate (CA) was given, especially when the total degree of substitution <<f>> is below 3. (2) Molar fractions of 8 kinds of unsubstituted and partially or fully substituted anhydroglucopyranose units were successfully determined for CA and sodium cellulose sulfate (NaCS). (3) The sequence distribution of substituted and unsubstituted anhydroglucopyranose units along a water–soluble CA chain was evaluated. (4) C₆-substituted (i.e., 6-O-acetyl) CA and C₂- and C₆-substituted CA were synthesized, and the full assignment of the ¹³C NMR spetrum of the former was given and a new method for evaluating the degree of substitution at C₆ position was proposed. (5) By destructing the intramolecular hydrogen bonding, cellulose becomes soluble in aq. sodium hydroxide. The specific supermolecular structure of aq. sodium hydroxide, dissolving mechanism, dissolved state and molecular parameters of cellulose in aq. sodium hydroxide were discussed. (6) The solubility behavior of CA with a wide range of total degree of substitution in solvents including water, acetone/water and acetone is controlled by the distribution of substitution and the supermolecular structure. (7) The existence of O₃-H … O'₅ intramolecular hydrogen bonds in a water-in soluble cellulose derivative with hydrophilic substituent (NaCEC) was confirmed by CP/MAS ¹³C NMR and deuteration IR method. At a relatively low degree of substitution the solubility of the derivative in water or aqueous alkali was mainly governed by considerable destruction of the intramolecular hydrogen bonds. (8) The persistence length q, evaluated directly by small-angle X-ray scattering (SAXS) on CA with different total degree of substitution <<f>> ranging from 0,8 to 2,9 confirmed definitely the conclusion drawn before by Kamide and Saito on the molecular rigidity of CD, especially the effect of <<f>> on q. (9) C₆-substituted CA shows different solubility towards dimethylacetamide and water at 20°C, as compared with C₂- and C₃-subsituted CA and C₂-, C₃- and C₆- substituted CA, whose <<f>> is ca. 0,6.     

Modification of submicron barium titanate particles via sol-gel synthesis of interface layers of SiO2 for fabrication of polymer-inorganic composites with improved dielectric properties

Modification of the surface of submicron BaTiO₃ particles by SiO₂ layer using sol-gel method has led to significant (>50%) increase in the dielectric permittivity and decrease in the dielectric losses of the composites prepared via introduction of BaTiO₃ into a matrix of poly(vinyl alcohol) cyanoethyl ester. The effect has been due to the formation of basic hydroxy groups (Brønsted centers) at the filler surface; these groups can interact with weakly acidic hydroxyl groups of poly(vinyl alcohol) cyanoethyl ester, thus improving the compatibility of the polymer matrix and the filler.