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1.
Betula alnoides lignin, recovered as a byproduct in autocatalyzed ethanol‐water pulping process, was converted into viscous polyether polyols through oxypropylation and liquefaction methods, with the aim of adding value to this byproduct. The oxypropylation reaction was performed by reacting autocatalyzed ethanol‐water lignin (AEL) with propylene oxide under the acidic and alkaline conditions at room temperature, respectively. In contrast, the liquefaction reaction was carried out using the mixed solvents of polyethylene glycol and glycerol at 160°C with sulfuric acid as a catalyst. The resulting polyether polyols from each method was characterized by Fourier transform‐infrared (FTIR), 1H and 31P nuclear magnetic resonance (NMR) spectroscopy, gel permeation chromatography (GPC), and thermogravimetric analysis. Quantitative 31P NMR indicated that all the aliphatic hydroxyl group values of polyols increased significantly by the above two methods. More secondary hydroxyl groups (2.016 mmol/g) were obtained in the alkaline oxypropylation reaction, whereas more primary hydroxyl groups (4.296 mmol/g) were found in the liquefied product. GPC analysis showed that the alkaline oxypropylated product (Mw 3130 g/mol, Mn 2080 g/mol) and liquefied product (Mw 4990 g/mol, Mn 4630 g/mol) have higher molecular weights than AEL (Mw 2560 g/mol, Mn 1530 g/mol). Thermal stability analysis suggested that the polyether polyols have a lower degradation temperature than AEL. These polyols used as precursors in polyurethane synthesis give promising properties, which open new avenues of exploitation of AEL. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013  相似文献   

2.
Ultrafast preparation of branched poly(methyl acrylate) (BPMA) with high‐molecular weight through single electron transfer living radical polymerization (SET‐LRP) of inimer at 25°C has been attempted, atom transfer radical polymerization (ATRP) at 60°C was also carried out for comparison. Gas chromatography, proton nuclear magnetic resonance, and triple detection size exclusion chromatography were used to analyze these polymerizations. As expected, SET‐LRP system showed much faster polymerization rate than ATRP system, the calculated apparent propagation rate constants (kpapp) are 3.69 × 10?2 min?1 and 6.23 × 10?3 min?1 for SET‐LRP and ATRP system, respectively. BPMA with high‐molecular weight (Mw.MALLS = 86,400 g mol?1) compared with that in ATRP (Mw.MALLS = 61,400 g mol?1) has been prepared. POLYM. ENG. SCI., 54:1579–1584, 2014. © 2013 Society of Plastics Engineers  相似文献   

3.
BACKGROUND: Poly(lactic acid) (PLA), coming from renewable resources, can be used to solve environmental problems. However, PLA has to have a relatively high molecular weight in order to have acceptable mechanical properties as required in many applications. Chain‐extension reaction is an effective method to raise the molecular weight of PLA. RESULTS: A high molecular weight biodegradable lactic acid polymer was successfully synthesized in two steps. First, the lactic acid monomer was oligomerized to low molecular weight hydroxyl‐terminated prepolymer; the molecular weight was then increased by chain extension using 1,6‐hexamethylene diisocyanate as the chain extender. The polymer was characterized using 1H NMR analysis, gel permeation chromatography, differential scanning calorimetry and Fourier transform infrared spectroscopy. The results showed that the obtained polymer had a Mn of 27 500 g mol?1 and a Mw of 116 900 g mol?1 after 40 min of chain extension at 180 °C. The glass transition temperature (Tg) of the low molecular weight prepolymer was 47.8 °C. After chain extension, Tg increased to 53.2 °C. The mechanical and rheological properties of the obtained polymer were also investigated. CONCLUSION: The results suggest that high molecular weight PLA can be achieved by chain extension to meet conventional uses. Copyright © 2008 Society of Chemical Industry  相似文献   

4.
The oxidative polycondensation reaction conditions of 2-[(4-chlorophenyl) imino methylene] phenol (CPIMP) were studied by air O2 and NaOCl oxidants at various temperatures and times. Optimum reaction conditions of air O2 and NaOCl were determined for CPIMP. Oligo-2-[(4-chlorophenyl) imino methylene] phenol (OCPIMP) was synthesized from the oxidative polycondensation of CPIMP with air O2 and NaOCl in alkaline medium between 50 and 90°C. The number-average molecular weight (Mn) weight-average molecular weight (Mw) and polydispersity index (PDI) values of OCPIMP were found to be 470 g mol?1, 895 g mol?1, and 1.90, using NaOCl, and 455 g mol?1, 765 g mol?1, and 1.68, using air O2, respectively. At the optimum reaction conditions, the yield of OCPIMP was found to be 62.80% (for air O2 oxidant) and 87.50% (for NaOCl oxidant). The OCPIMP was characterized by 1H-NMR, FT-IR, UV-Vis and elemental analysis. The thermogravimetric (TGA)-DTA analyses were shown to be stable of OCPIMP and its oligomer metal complexes (such as Co+2, Ni+2, and Cu+2) against thermo-oxidative decomposition. The weight loss of OCPIMP and its oligomer metal complexes (such as Co+2, Ni+2, and Cu+2) were found to be 98%, 85%, 80%, and 82%, respectively, at 1000°C.  相似文献   

5.
The amount of lignin removed from spruce wood meal at 50°C to 110°C with mono-, di-, and trichloroacetic acid, as well as its molecular weight (MW) distribution was studied. Trichloroacetic acid gives rise to the lowest Mn (2,000–4,000), the lowest Mw (4,500–8,000), the lowest upper MW limit (~40,000), and the lowest polydispersity (1.5–3.0) of lignin. The removed lignin is split by the tested acids to different extents.  相似文献   

6.
Chemical modification of polyvinyl chloride by nucleophiles is a versatile method for preparation of new functional polymers. Modification of PVC was carried out using different nucleophiles (Nu) in ethylene glycol (EG)/N,N-dimethylformamide (DMF) (1:1 by volume) solution. OH?, N3?, and SCN? were examined as nucleophiles in this study. The FTIR spectrum confirmed substitution of Cl by nucleophiles and also the elimination of HCl in the modification reaction of PVC. The glass transition temperatures (Tgs) of modified-PVC samples were in the order N3? > SCN? > OH? and were equal to 87.6, 86.8 and 78.15 °C, respectively. The T5% (the temperature at which weight loss is 5%) of PVC was 266 °C, while after 1 h modification by OH? it reduced to 197 °C. After alkaline modification, the scanning electron microscopy (SEM) images not only showed an increase in surface roughness and porosity, but also revealed a relatively large drop in average particle size from 160 to 80 µm. Molecular weight and molecular weight distribution were determined by gel permeation chromatography (GPC). The GPC results showed that the number average molecular weight (Mn) and weight average molecular weight (Mw) were decreased from 79,950 and 176,360 g mol?1 in crude PVC to 45,370 and 99,930 g mol?1, respectively, after 1 h modification by OH?. Alkaline treatment also decreased the mechanical strength of PVC.  相似文献   

7.
The coil–globule transition for poly(methyl methacrylate) (PMMA) has been studied in a theta solvent, acetonitrile (Θ = 45 °C). The viscosity of PMMA was measured as a function of temperature in the range 26–55 °C. The contraction and expansion of the molecular chains are determined using the measured viscosity values. The temperature dependence of the intrinsic viscosity can be represented by a master curve in a versus |τ|M w1/2 (g1/2 mol−1/2) plot, where τ = |T − Θ|/T is the reduced temperature and Mw‐is the weight‐average molecular weight. A universal plot of reduced viscosity versus reduced blob parameter (N/Nc) shows the attainment of the collapsed state below the theta temperature. The dimensions of PMMA in acetonitrile (Mw = 3.15 × 106 g mol−1) decrease to 63 % at 26 °C of those in the unperturbed state. The results in this work are compared with those previously published. © 2000 Society of Chemical Industry  相似文献   

8.
The aim of this study is to highlight the application and potentiality of oil palm based lignins in the synthesis of green phenolic resins. The delignification processes were conducted using Kraft and auto-catalyzed ethanol–water pulping processes. The extracted lignins were characterized using elemental analysis, Fourier transform-infrared, 1H and 13C nuclear magnetic resonance (NMR) spectroscopy, molecular weight distribution (Mn, Mw and polydispersity), thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC). The obtained FTIR results revealed that the Kraft lignin contained substantial amounts of guaiacyl units with smaller amounts of syringyl units. The molecular weight of Kraft lignin was 1564 g mol−1 which is higher than organosolv lignin at 1231 g mol−1. The activated free ring position (2.99%) of Kraft lignin was comparatively higher than that of organosolv lignin (2.06%) which was measured using Mannich reactivity analysis. Thermal analysis of Kraft lignin showed higher thermal stability compared to organosolv lignin. The structural and thermal characteristics implied that Kraft lignin had higher potential for the production of green phenolic resins when compared with organosolv lignin.  相似文献   

9.
The effects of annealing time and molecular weight on the strong melt memory effect observed in random ethylene 1‐alkene copolymers are analyzed in a series of model ethylene 1‐butene copolymers with 2.2 mol% branches. Melt memory is associated with molten clusters of ethylene sequences from the initial crystals that remain in close proximity and are unable to diffuse quickly to the randomized melt state, thus increasing the recrystallization rate. Melt memory persists even for greater than 1000 min annealing indicating a long‐lived nature of the clusters that only fully dissolve at melt temperatures above a critical value (>160 °C). Below the critical melt temperature, molecular weight and annealing temperature have a strong influence on the slow kinetics of melt memory. For the copolymers analyzed, slow dissolution of clusters is experimentally observed only for Mw < 50 000 g mol?1. More stable clusters that survive higher annealing temperatures display slower dissolution rates than clusters remaining at lower temperatures. The threshold crystallinity level to enable melt memory (Xc,threshold) decreases with increasing molecular weight and decreasing annealing temperature similarly to the variation of the chain diffusivity in the melt. The process leading to melt memory is thermally activated as the variation of Xc,threshold with temperature follows Arrhenius behavior with high activation energy (ca 108 kJ mol?1) that is independent of molecular weight. © 2018 Society of Chemical Industry  相似文献   

10.
A new monomer, exo‐3,6‐epoxy‐1,2,3,6‐tetrahydrophthalimidocaproic acid (ETCA), was prepared by reaction of maleimidocaproic acid and furan. The homopolymer of ETCA and its copolymers with acrylic acid (AA) or with vinyl acetate (VAc) were obtained by photopolymerizations using 2,2‐dimethoxy‐2‐phenylacetophenone as an initiator at 25 °C. The synthesized ETCA and its polymers were identified by FTIR, 1H NMR and 13C NMR spectroscopies. The apparent average molecular weights and polydispersity indices determined by gel permeation chromatography (GPC) were as follows: Mn = 9600 g mol?1, Mw = 9800 g mol?1, Mw/Mn = 1.1 for poly(ETCA); Mn = 14 300 g mol?1, Mw = 16 200 g mol?1, Mw/Mn = 1.2 for poly(ETCA‐co‐AA); Mn = 17 900 g mol?1, Mw = 18 300 g mol?1, Mw/Mn = 1.1 for poly(ETCA‐co‐VAc). The in vitro cytotoxicity of the synthesized compounds against mouse mammary carcinoma and human histiocytic lymphoma cancer cell lines decreased in the following order: 5‐fluorouracil (5‐FU) ≥ ETCA > polymers. The in vivo antitumour activity of the polymers against Balb/C mice bearing sarcoma 180 tumour cells was greater than that of 5‐FU at all doses tested. © 2001 Society of Chemical Industry  相似文献   

11.
This study focused on the characterization of polyhydroxybutyrate (PHB) produced from crude glycerol (CG) using mixed microbial consortia (MMC). PHB recovered from two biomass drying treatments (65°C oven drying and lyophilization) was characterized comparatively along with a commercially sourced PHB (PHB‐C). Characterization results showed that oven‐drying method caused PHB partial hydrolysis, as indicated by its lower molecular weight (Mw) (PHB‐O, 144,000 g mol?1), which further affected its physical and chemical properties. Lyophilization helped alleviate PHB hydrolysis during drying process, leading to PHB (PHB‐L) of higher Mw (309,000 g mol?1) and material properties comparable with commercial PHB. Furthermore, crystallization and morphological studies showed that PHB‐L featured faster crystallization rates and smaller spherulites as compared with PHB‐C, probably due to its lower Mw. In general, the results from this study suggested that CG‐MMC‐derived PHB‐L possessed material properties comparable with those of pure substrate/culture produced PHB. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013  相似文献   

12.
Aliphatic polycarbonates (APCs) synthesized by polycondensation of dialkyl carbonates and aliphatic diols have often been used as precursors for the preparation of novel polyurethanes. However, they could not be applied in plastics directly because of poor mechanical properties caused by low molecular weight. In the work reported in this paper, three kinds of fairly high molecular weight (Mw ≥ 166 000 g mol?1) APCs with narrow dispersity ( ) were successfully synthesized via a successive two‐step polycondensation of dimethyl carbonate and diols, using a novel TiO2/SiO2‐based catalyst. This process gave a high yield of above 85%. 1H NMR spectra indicated that there was no detectable decarboxylation happening during polycondensation at high temperature. The effects of molecular weight on the mechanical properties of the APCs are discussed. APCs with Mw greater than 70 000 g mol?1 showed useful mechanical properties. Especially, poly(butylene carbonate) and poly(hexamethylene carbonate) exhibited excellent tensile strengths of 34.1 and 40.0 MPa, respectively, when their Mw was ca 170 000 g mol?1. All the APCs showed appreciable biodegradability under enzymatic degradation. Copyright © 2011 Society of Chemical Industry  相似文献   

13.
In the present work, an analysis is carried out to provide a relationship between the Molecular Weight (Mw) of degraded LDPE films (containing Mn stearate as pro oxidant (MnSt‐LDPE) and changes in viscosity, elongation at break (EB %) and carbonyl index (CI) occurring during thermal degradation in the thermophilic phase of the compost process. The thermal treatment comprised various temperatures (50°C, 60°C, and 70°C) and exposure times, and was characterized through a so‐called Energy‐Time Factor (the product of thermal energy and exposure time). Changes in viscosity, EB %, and CI were correlated to this factor. A modified Mark‐Houwink equation was used to relate the zero shear‐rate viscosity and Mw of the degraded LDPE films. Results indicate that the EB %, Mw and viscosity decrease simultaneously with an increase in the CI as the Energy‐Time Factor augments, allowing the assessment of the variation of these properties with Mw. Calculations of the percentage abiotic degradation (%D) of LDPE films indicate that a Mw of 6 kg mol?1 corresponds to a maximum abiotic degradation degree of 91.85%, which is henceforth susceptible to biodegradation. The film treated with Energy‐Time Factor of 2.79E+09 J s mol?1 reached a 74% of biodegradation in 90 days (average time of the composting process). Results exhibit clearly the correlation between abiotic and biotic degradation. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42721.  相似文献   

14.
Coordination polymerization of styrene with a ternary catalyst system composed of catalyst neodymium tricarboxylate (Nd), co‐catalyst Al(i‐Bu)3 (Al) and chlorinating agent trichloroethane (Cl) was carried out in cyclohexane. The effects of the catalyst system preparation procedure and of the reaction conditions on catalytic activity, molecular weight and molecular weight distribution of the resultant polymers were investigated. The catalytic activity depended mainly on the molar ratios of Al/Nd and of Cl/Nd and on the ageing temperature and polymerization temperature. High polymerization conversion and high catalytic activity could be obtained at high Al/Nd ratios and/or at high ageing temperature. The catalyst system exhibited high activity of 8.32 × 104 g polystyrene (mol Nd h)?1 at 50 °C. The molecular weight of the polymers obtained reached high weight‐average (Mw) values (Mw = 4.35 × 105 g mol?1) when Al/Nd = 8, but relatively low values (6000–11 000 g mol?1) at high Al/Nd ratios. Copyright © 2005 Society of Chemical Industry  相似文献   

15.
Lignins were isolated from maize stem and sugarcane bagasse by using mild dioxane or acidic dioxane solution. The result of nitrobenzene oxidation of the isolated lignins shows that there is a high proportion of p‐hydroxyphenyl alcohol in the lignins of maize stem and sugarcane bagasse. The lignins isolated from maize stem and sugarcane bagasse have relatively same value of the weight‐average (M w = 3405–3868 g mol−1) and number‐average (M n = 1411–1612 g mol−1) molecular weights, and polydispersity (M w/M n = 2.24–2.51). Acidic dioxane treatment did attack the β‐aryl ether structures in lignins, in particular for β‐aryl syringyl ethers, and broke the ester bonds between arabinose and ferulic acid that etherified to lignins, and it also cleaved lots of bonds in hemicellulosic polymer. The proportion of β‐O‐4 (threo) guaiacyl units is higher than that of β‐O‐4 (erthreo) guaiacyl units. The phenyl glycoside and benzyl ether linkages between lignin and hemicelluloses are also demonstrated in NMR analysis. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011  相似文献   

16.
Attachment of anticancer agents to polymers has been demonstrated to improve their therapeutic profiles. A new monomer containing camptothecin, 5‐norbonene‐endo‐2,3‐dicarboxylimidoundecanoyl‐camptothecin (NDUCPT) and its homopolymer and copolymer with acrylic acid (AA) were synthesized and spectroscopically characterized. The NDUCPT content in poly(NDUCPT‐co‐AA) obtained by elemental analysis was 51%. The average molecular weights of the polymers determined by gel permeation chromatography were as follows: Mn = 12 100, Mw = 23 400 g mol?1, Mw/Mn = 1.93 for poly(NDUCPT), Mn = 15 400, Mw = 28 300 g mol?1, Mw/Mn = 1.83 for poly(NDUCPT‐co‐AA). The IC50 value of NDUCPT and its polymers against U937 cancer cells was larger than that of CPT. The in vivo antitumour activity of all polymers in Balb/C mice bearing the sarcoma 180 tumour cell line was greater than that of CPT at a dose of 100 mg kg?1. Copyright © 2003 Society of Chemical Industry  相似文献   

17.
The copolymerization of divinyl adipate (DVA) with isobutyl vinyl ether (IBVE) was conducted at 70 and 80 °C in benzene using azobisisobutyronitrile (AIBN), at a concentration as high as 0.50 mol l?1 as the initiator, where the concentrations of DVA and IBVE were 0.40 and 0.60 mol l?1, respectively. The copolymerization proceeded homogeneously, without any gelation, to yield soluble copolymers in spite of the high molar ratio of DVA as an excellent cross‐linker for IBVE. The copolymer yield increased with time, and the number‐average molecular weight (Mn = 0.9–2.4 × 104 g mol?1) from gel permeation chromatography (GPC) and molecular weight distribution (Mw/Mn = 1.5–7.6) of the resulting copolymer increased with copolymer yield. The cyanopropyl group, as a fragment of AIBN, was incorporated as a main constituent in the copolymer, the fraction of which increased from ca 10 to ca 20 % with copolymer yield, hence indicating that the copolymerization is an initiator–fragment incorporation radical polymerization. The copolymers also contained IBVE units (10–30 %) and DVA units with intact double bond (8–36 %) and without double bond (45 %). The intrinsic viscosity of the copolymer was very low (0.1 dl g?1) at 30 °C in tetrahydrofuran. The results from GPC–multi‐angle laser light scattering (MALLS), transmission electron microscopy (TEM) and MALLS revealed that individual copolymer molecules were formed as hyperbranched nanoparticles. Copyright © 2004 Society of Chemical Industry  相似文献   

18.
The electroreductive polymerization of dichloromethylphenylsilane in the presence of triphenylsilyl group‐containing disilanes such as hexaphenyldisilane followed by the electroreductive termination with chlorotriphenylsilane afforded triphenylsilyl group‐terminated polymethylphenylsilane in 15–32% yield. The isolated polymethylphenylsilane (Mn = 3350 g mol?1, Mw/Mn = 1.4) was found to react as a macroinitiator to copolymerize with dibutyldichlorosilane under electroreductive conditions producing the corresponding block copolymer (Mn = 4730 g mol?1, Mw/Mn = 1.2) in 38% yield. The ratio of monomer units (? MeSiPh? to? BuSiBu? ) of the copolymer was determined to be 75:25 using 1H NMR analysis, which was in good agreement with the calculated ratio (74:26) on the assumption that molecular weight of the macroinitiator was not changed. The block structure of the resulting copolymer, poly(methylphenylsilane)‐block‐poly(dibutylsilane), was also confirmed by comparing its 1H NMR and UV absorption spectra with those of polymethylphenylsilane, polydibutylsilane and a statistical copolymer prepared by electroreductive polymerization of dichloromethylphenylsilane with dibutyldichlorosilane. This method is applicable to the preparation of other types of macroinitiator such as triphenylsilyl group‐terminated polydibutylsilane, and polydibutylsilane‐block‐polymethylphenylsilane was also obtained using this macroinitiator. Copyright © 2011 Society of Chemical Industry  相似文献   

19.
Candida is a genus of yeast, and lipase B isolated from Candida antarctica (CALB) has been utilized as a biocatalyst for the synthesis of a variety of organic compounds including polyesters and polylactones. Among the various immobilization media reported in the literature, the porous acrylic resin utilized in Novozym-435 has been widely studied. Here, we report the enzyme recovery and reuse for the synthesis of poly(ε-caprolactone) in toluene at 70 °C for 4 h per cycle for up to 10 reaction cycles, which consistently resulted in polymers with a weight-average molecular weight, M w , of ~50,000 g mol?1 and a polydispersity index of ~1.4. In addition, the thermal properties of the resin particles used in Novozym-435, with and without the enzyme, were evaluated by TGA and DSC analysis. The effect of mechanical agitation on the enzyme stability, recovery, and reuse was also discussed. These results may have significance to enzymatic polymer synthesis as well as to the enzyme immobilization on acrylic resins and other matrices.  相似文献   

20.
Epoxy resin of 9,9′-bis-(3,5-dibromo-4-hydroxyphenyl) anthrone-10 (EANBr, EEW 490) was synthesized and was characterized by IR and 1HNMR . EANBr and EPK3251 cured resin (EANBrC) were characterized by DSC and TGA at 10°Cmin?1 under nitrogen atmosphere. Broad DSC endothermic transitions of EANBr (265.3 °C) and EANBrC (291.4 °C) are due to some physical change and further confirmed by no weight loss in their TG thermograms. EANBr and EANBrC are thermally stable up to 340 °C and 310 °C, respectively. EANBr has followed single step degradation kinetics, while EANBrC has followed two step degradation kinetics. EANBr followed apparently zero order kinetics, while EANBrC followed apparently second order (1.80) and first order (0.89) degradation kinetics, respectively. Ea and A values of EANBrC (299.7 kJmol?1 and 6.32?×?1020 s?1) were found higher than that of EANBr (201 kJmol?1 and 2.45?×?1013 s?1) due to more rigid nature of EANBrC. The ΔS* value of the first step degradation of EANBrC (146.3 JK?1 mol?1) was found much more than that of EANBr (4.6 JK?1 mol?1). Jute – EANBr composite (J-EANBr) was prepared by compression molding technique at 120 °C for 5 h and under 20 Bar pressure. The observed tensile strength, flexural strength, electric strength and volume resistivity of J-EANBr are 24.7 MPa, 19.0 MPa, 1.8 kVmm?1 and 3.5?×?1012 ohm cm, respectively. Water absorption in J-EANBr was carried out at 30 ± 2 °C against distilled water, 10% NaCl, 10% HCl, 10% HNO3, 10% H2SO4, 10% NaOH, and 10% KOH and also in boiling water. The equilibrium time and equilibrium water content for J-EANBr in different environments are 384–432 h; 12.7–15.2%, respectively. The observed equilibrium water content and diffusivity trends of J-EANBr are KOH>H2SO4>HCl>NaOH>H2O>NaCl and H2O>NaCl>NaOH>H2SO4>HCl>KOH, respectively. Good thermo-mechanical, electrical properties and excellent hydrolytic stability of J-EANBr may be useful for high temperature applications in diverse fields.  相似文献   

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