Composites prepared from silica gel and furfuryl alcohol with p-toluenesulfphonic acid as the catalyst

Summary Composites of furfuryl alcohol and silica gel or Aerosil were prepared using p-toluenesulphonic acid as catalyst at room temperature. The molar ratio furfuryl alcohol/p-toluensulphonic acid was varied between 64.7 and 10. The surface of silica gel was partially coated when composite was prepared with the lower quantity of acid while the use of the higher proportion of acid produces the start of particle agglutination. The thickness of the polymer layer completely coating the surface of the composites ranged between around 10 to 39 ?. Preliminary results suggest that composites could be used as adsorbent of organic pollutants from water.     

Crosslinked poly(vinyl alcohol) and starch composite films: Study of their physicomechanical,thermal, and swelling properties

Crosslinked poly(vinyl alcohol) was blended with 10, 20, 40, and 50 wt % starch by a solution‐casting process. The solution‐cast films were dried, and then their physicomechanical properties including tensile strength, tensile elongation, tensile modulus, tear strength and density, and burst strength and density were tested. Thermal analysis was performed by differential scanning calorimetry. A moisture analysis of the PVA/starch films was performed and their moisture content determined. Also investigated were the films'resistance to solubility in water, 5% acetic acid, 50% ethanol, and sunflower oil and their swelling characteristics in 50% ethanol and sunflower oil. The prepared PVA/starch blends showed significant improvement in tensile modulus and in resistance to solubility in water, 5% acetic acid, and 50% ethanol. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1127–1132, 2007     

糠醇生产中废弃物的循环回用新工艺

将糠醛液相加氢生产糠醇产生的废渣置于真空干燥箱中 ,在较低的负压状态下保持 1 30℃的温度 ,蒸馏回收废渣中的有机物 ,返回糠醇精制车间获得合格的糠醇与糠醛产品 ;剩余的固体废弃物与纯碱混合 ,在反射炉中焙烧 ,浸取获得铬酸钠水溶液 ;最后剩下的粗氧化铜溶于硝酸得到硝酸铜溶液 ;将铬酸钠溶液、硝酸铜溶液按一定比例混合 ,加入氨水搅拌 ,分离出的沉淀经传统方法焙烧活化、造粒制得新催化剂 ,回用于糠醛液相加氢生产糠醇。铬组分和铜组分的回收率均在 90 %以上     

The free-radically prepared copolymers of acrylonitrile with furfuryl alcohol and similar furan derivatives

The preparation of copolymers of acrylonitrile with furfuryl alcohol, furfuryl acetate, bis-2,5-hydroxymethyl furan and bis-2,5-acetoxymethyl furan by a free radical reaction is described. Proton and ¹³C-n.m.r. spectroscopy has been used to characterise the residues that form from the furan monomers by the addition reaction. The residues produced by a 5,4-addition to the furfuryl alcohol ring or by 2,3-addition to the 2,5-dihydroxyfuran ring are susceptible to acid and undergo a rearrangement which removes the olefinic structure. The copolymers are decomposed to a hard, glassy carbonaceous material by heating in nitrogen in a process that has been examined by thermogravimetric analysis and elemental analysis. The copolymers prepared from furan monomers that contain a methylol group decompose more readily at a lower temperature than those which lack the group or than those in which the alcohol has been acetylated.     

Promoting the dispersibility of silica and interfacial strength of rubber/silica composites prepared by latex compounding

The dispersibility of precipitated silica and its interfacial interaction with rubber matrix can affect the performances of tires which is a difficult problem to be solved. A well-dispersed silica dispersion was obtained through ball milling and modification process followed by heat treatment to enhance the properties of NR composites prepared by latex compounding. Benefiting from the modifier Si-747, the well-dispersed silica/NR composite (Silica-MSH-C) shows excellent tensile strength of 30.8 ± 0.5 MPa, which is 17.6 ± 3.8% higher than latex compounding pure silica/NR composite (Silica-C) and 21.7 ± 4.3% higher than traditional mechanical blending pure silica/NR composite (T-Silica-C). The tan delta values indicate that Silica-MSH-C has better dynamic properties and also has stronger interface strength according to swelling tests, heat capacity curves and Mooney-Rivlin equation. The molecular dynamics (MD) simulation further shows the binding energy between NR and Si-747 modified SiO₂ is 58.88 Kcal/mol larger than the value of NR and pure silica.     

糠醇加氢制1,2-戊二醇催化剂的制备及性能研究

采用化学共沉淀方法制备了铜氧化物催化剂FAH-1。在30 mL绝热微型固定床反应器上,研究了催化剂催化糠醇加氢制备1,2-戊二醇的性能,并对相关工艺条件进行了考察。实验结果表明：FAH-1催化剂表现出良好的糠醇加氢活性和选择性,在反应温度为160 ℃、反应压力为6 MPa、液时体积空速为0.3 h ^-1、氢油体积比为10 000∶1条件下,糠醇加氢反应的转化率和选择性分别为91.80%和41.52%,1,2-戊二醇单程收率达到38.12%,1 000 h长周期评价催化剂性能稳定。制得的1,2-戊二醇样品纯度高、质量好,满足后续加工对1,2-戊二醇的质量要求。反应过程采用固定床反应器,具有较好的工业化前景。     

Composites from furfuryl alcohol and inorganic solids by cationic initiation, 3. Scanning electron microscopic investigations of solid poly(furfuryl alcohol)-silica composites

Composites of poly(furfuryl alcohol) grafted onto silica, with different percentage of grafting, have been investigated by scanning electron microscopy, elemental analysis and UV/Vis-reflectance spectroscopy. The size of the silica particles used for the coating procedure is not changed till a percentage of grafting to around 30%. A content of polymer higher than 35 wt.-% enhances the bonding between the particles due to the crosslinking of poly(furfuryl alcohol) on the surface with those in solution leading to the agglomeration of the particles. A general model of cross-linked poly(furfuryl alcohol)-silica composites is suggested.     

Organic/inorganic hybrid composites prepared by polymerization compounding and controlled free radical polymerization

A new method to produce highly filled and well dispersed polymer solid composites using controlled free radical polymerization has been developed. Grafting of polymers onto ultrafine silica was done in bulk polymerization at 120 °C in presence of N-tert-butyl-1-diethylphosphono2,2-dimethyl propyl nitroxide (DEPN) as a nitroxide stable free radical. Optimum conditions for tert-butyl hydroperoxide grafting onto fumed silica were first determined. The percentage of grafting, the architecture of grafted polymers, the length of chains, and the polydispersity index can be controlled at will using this approach. The effect of the number of grafted polymer chains combined with its molecular weight on the processing of these materials was investigated. The syntheses performed in this work gave grafting percentages of polymers and copolymers ranging from 12 to 88 wt%. All ‘synthesized’ composites gave stable suspensions in toluene and tetrahydrofuran.     

Study of polyaniline polyacrylamide composites by positron annihilation technique

Polyaniline doped with nonoxidizing Bronsted acids is recognized as a conducting material, as its electrical conductivity changes with percentage of doping. In the present work, different percentages of doped polyaniline were blended with polyacrylamide and their electrical conductivities as well as the positron annihilation lifetimes were measured. Analysis of data yielded three lifetime components. It was observed that the value of the short lifetime component remained constant for doping concentration, whereas that of the intermediate component τ₂ decreased. The relative intensity pertaining to τ₂, however, increased with the increase in doped PANI concentration. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 930–933, 2003     

Dynamic-mechanical thermal analysis of aramid-silica hybrid composites prepared in a sol-gel process

Several types of nonbonded and chemically bonded composites of silica with linear and linear-nonlinear aramid polymers were prepared using the sol-gel process. The linear polyamide chains were synthesized by the reaction of a mixture of m- and p-phenylene diamines and terephthaloyl chloride in dimethyl acetamide. The nonlinear chains were prepared using 1,3,5-benzenetricarbonylchloride along with tereph-thaloyl chloride, thereby significantly increasing the average functionality of the monomers. These increased functionality chains were then endcapped with aminophenyl-trimethoxysilane. Silica networks chemically bonded to the polyamide chains were produced by the addition of tetramethoxysilane to the aramid solution and its subsequent hydrolysis and condensation. The films cast from these solutions were yellow, and those containing up to 25 wt % silica were also transparent. Dynamic-mechanical thermal analysis was carried out to characterize interfacial bonding and interactions, in particular through the use of values of the glass transition temperatures T_g of the polymers. The presence of the silica caused increases in T_g, with the increases being largest for the composites in which there was strong interfacial bonding between the polymer chains and the ceramic silica phase. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 63: 1345–1352, 1997     

Mechanical,morphological, and thermal properties of chemically treated pine needles reinforced thermosetting composites

Natural fibers are widely used as reinforcement in composites. Pine needles are one of the major biowaste generated by Pinus roxburgii plant. This species is found abundantly in the forests of Himachal Pradesh. In this work, composites of urea–resorcinol–formaldehyde resin‐reinforced with Pine needles fibers were prepared. Fibers were chemically modified to improve their compatibility with matrix. These fibers were mercerized with NaOH solution and acetylated to increase their hydrophobic character. The chemically modified fibers were characterized with Fourier transform infrared spectra, ¹³C‐nuclear magnetic resonance (NMR) spectroscopy, and scanning electron microscopy. The composites were prepared with treated and untreated fibers containing 30% fibers by weight using compression molding technique. The morphology of the materials thus obtained was evaluated by scanning electron microscopy. The chemical modifications of fibers improve fiber–matrix adhesion and also have markedly effect on mechanical properties of composites. Moreover, the thermal resistance of these composites was improved on chemical modification. These results indicate that chemically modified fibers exhibit better compatibility with the polymer matrix than that of untreated fiber. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci, 2013     

Dielectric and thermal studies of the segmental dynamics of poly(methyl methacrylate)/silica nanocomposites prepared by the sol–gel method

Poly(methyl methacrylate)/silica (PMMA/SiO_x) nanocomposites were synthesized via sol–gel method and studied by various techniques. The dispersion of the silica particles (10–100 nm) in the matrix was probed by transmission electron microscopy (TEM), while solid‐state NMR and Raman spectroscopy detected the formation of an inorganic network with high degree of crosslinking. To elucidate the impact of the filler on the molecular dynamics of the PMMA, different methods were used; namely differential scanning calorimetry, thermally stimulated depolarization current and broadband dielectric relaxation spectroscopy. All three methods observed a significant impact of the nanoparticles on the segmental dynamics of the matrix, which was expressed as an increase of the glass transition temperature (T_g) in terms of calorimetry and as a shift of the α (segmental) relaxation to lower frequencies in terms of dielectric spectroscopy. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Preparation, characterization and pyrolysis of poly(furfuryl alcohol)/porous silica glass nanocomposites: novel route to carbon template

In this paper we report the preparation of glassy carbon through the pyrolysis of poly(furfuryl alcohol) inside the pores of Vycor glass, which was used as a template. Different routes to the in situ polymerization of furfuryl alcohol inside the pores of Vycor glass were developed. The nanocomposites glass/polymer obtained were characterized by several techniques. Carbonization of these nanocomposites produces new silica glass/carbon nanocomposites, which were characterized and treated with HF to remove the silica fraction. It was found that the resulting carbon presents low crystallinity when compared to graphite. However, it presents more order than the glassy carbon resulting from the pyrolysis of the free poly(furfuryl alcohol) resin.     

Properties and structure of poly(vinyl alcohol)/silica composites

The relationships between the properties and structure are discussed for poly(vinyl alcohol)(PVA)/silica composites prepared through the sol‐gel process. The composites became stiff and brittle with increasing the silica content. The properties of the composites were changed drastically at around the composition of PVA/silica = 70/30 wt %. For example, there was no large change in the Young's modulus above 30 wt % of silica content (Pure PVA: 31.8 MPa, silica 30%: 52.6 MPa, silica 50%: 55.2 MPa). Consequently, it was considered that the three‐dimensional network structure of silica could be formed in the composite with more than 30 wt % of silica in PVA. From this behavior, it could be considered that the crystal growth of PVA was remarkably inhibited by silica network. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 133–138, 1999     

Mechanical and thermal flow properties of wood flour–biodegradable polymer composites

Wood flour (WF)–polycaprolactone (PCL) and polybutylenesuccinate–butylenecarbonate (PBSC) composites were prepared by knead processing. The effects of a compatibilizer on the tensile and thermal flow properties of the composites were investigated. PCL‐graft‐maleic anhydride (PCL‐g‐MA) was used as a compatibilizer. Tensile properties were improved by adding PCL‐g‐MA to both composites. The tensile strength and Young's modulus were increased from 13 to 27 MPa and 581 to 1011 MPa in WF–PCL (50/50, w/w) composites, respectively, and from 17 to 28 MPa and 814 to 1007 Mpa in WF–PBSC (50/50, w/w) composites, respectively, with the addition of 5% PCL‐g‐MA. Elongation at break increased from 4 to 7% and from 3 to 6% in the WF–PCL and the WF–PBSC composites, respectively. Tensile strength was further increased with increasing WF content in the presence of PCL‐g‐MA. Thermal flow temperature and melt viscosity of the composites were increased, and water absorption and thickness swelling were improved with the addition of PCL‐g‐MA. It was found from the burial test that all composites were more than 40% degraded within 6 weeks, and there was no considerable difference in degradation between composites with PCL‐g‐MA and those without. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1900–1905, 2003     

Enhanced mechanical and thermal properties of polyurethane/functionalised graphene oxide composites by in situ polymerisation

ABSTRACT

Isocyanate-functionalised graphene (iGO) was prepared and incorporated into a thermoplastic polyurethane via an in situ polymerisation. Firstly, graphene oxide was successfully modified using a mixture of isocyanate- and diisocyanate-containing compounds, leading to the formation of good dispersions of resulting functional graphene oxide in organic solvents, such as N,N-dimethylacetamide and N,N-dimethylformamide. The addition of iGO into polyurethane matrix improved both mechanical and thermal properties in the polyurethane/iGO composites relative to neat polyurethane. An addition of only 0.03?wt-% of functionalised graphene into the polyurethane increased Young’s modulus by 1.4 times and tensile strength by two times. Meanwhile, the elongation at break was similar to that of the neat polymer. In addition, dynamic mechanical analysis also confirmed the improvement in storage modulus of the polymer composites especially at high-temperature range. We believe that the developed modification approach for graphene oxide and polyurethane/graphene composites presented herein could be useful in polymer/graphene composite development.     

Synthesis and characterization of epoxidized phenolic novolacs modified by furfuryl alcohol

The possibility of reacting furfuryl alcohol with the p-position of phenolic rings, under acid conditions, was proved using different experimental techniques: size exclusion chromatography, Fourier transform infrared spectroscopy and ¹³C NMR. This reaction was then used in the modification of phenolic novolacs with furfuryl alcohol. After reaction with epichlorohydrin, epoxidized phenolic novolacs (EPN) modified with furan rings were obtained. They could be cured with aromatic diamines in a similar way to conventional EPNs. The presence of furan rings should improve burning resistance and smoke emission characteristics of the resulting networks.     

ZrO2/SiO2催化乙醇乙醛制备1,3-丁二烯

采用干混法、浸渍法、溶胶凝胶法3种制备方法制备ZrO₂/SiO₂,在固定床微型反应器中进行催化剂的活性评价。通过溶胶凝胶法制备的ZrO₂/SiO₂对丁二烯选择性最高,达到64.77%。采用氨气程序升温脱附(NH₃-TPD)、X射线衍射(XRD)、透射电镜(TEM)等手段对催化剂表面酸性以及表面结构进行了表征,结果表明锆在二氧化硅表面均匀分布有利于乙醇乙醛转化率以及对1,3-丁二烯选择性的提高,同时1,3-丁二烯的生成需要合适的酸性位。以溶胶凝胶法制备的ZrO₂/SiO₂为催化剂,对其制备条件进行了优化,得出最佳制备条件为焙烧温度650℃、硝酸浓度2mol/L、混合温度30℃。     

Mechanical,thermal and morphological properties of heat-treated wood-polypropylene composites and comparison of the composites with PROMETHEE method

ABSTRACT

The aim of the paper was to determine the mechanical, thermal, and morphological properties of heat-treated wood-polypropylene polymer composites (WPCs) and to select the composites having the optimum properties with the PROMETHEE method. In this study, polypropylene (PP) as a matrix, wood thermally treated at 180°C and 220°C as reinforcement filler were examined for preparing composites. The PP composites were compounded using a twin-screw extruder and test specimens were prepared by compression moulding. According to the test results, the thermal and mechanical properties of the WPCs generally increased with the addition of heat-treated wood fillers. The SEM images showed that the wood fillers dispersed better in the PP matrix as the particle size decreased from 40 mesh to 100 mesh. The WPCs having the optimum mechanical and thermal properties were determined for 40 mesh heat-treated wood at 220°C and 20?wt-% loadings with PROMETHEE method.     

Synthesis and characterization of acrylic rubber/silica hybrid composites prepared by sol‐gel technique

The organic–inorganic hybrid composites comprising acrylic rubber and silica were synthesized through sol–gel technique at ambient temperature. The composites were generated through the acid‐catalyzed hydrolysis and subsequent condensations of inorganic tetraethoxysilane (TEOS) in the organic acrylic rubber (ACM), solvated in tetrahydrofuran. The morphology of the hybrid materials was investigated by using the transmission electron microscope (TEM) and scanning electron microscope (SEM). Transmission electron micrographs revealed that the silica particles, uniformly distributed over the rubber matrix, are of nanometer scale (20–90 nm). The scanning electron micrographs demonstrated the existence of silica frameworks dispersed in the rubber matrix of the hybrid composites. The X‐ray silicon mapping also supported that observation. There was no evidence of chemical interaction between the rubber phase and the dispersed inorganic phase, as confirmed from the infrared spectroscopic analysis and solubility measurements. Dynamic mechanical analysis indicated mechanical reinforcements within the hybrid composites. The composites containing in situ silica, formed by sol–gel technique, demonstrated superior tensile strengths and tensile modulus values at 300% elongations with increasing proportions of tetraethoxysilane. However, the improvements in physical properties with similar proportions of precipitated silica were not significant. Maximum tensile strength and tensile modulus were obtained when the rubber phase in the hybrid composites was cured with ammonium benzoate and hexamethylenediamine carbamate system, as compared with benzoyl peroxide cured system. Thermal stability of the hybrid composites was not improved appreciably with respect to the virgin rubber specimen. Residue analysis from thermogravimetric study together with infrared spectroscopic analysis indicated the presence of unhydrolyzed tetraethoxysilane in the hybrid composites. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2579–2589, 2004