离子液体在纳米纤维素制备中的应用进展

纳米纤维素因其优异的性能和独特的结构在很多领域都受到了关注,其制备和应用已成为相关领域的研究热点。目前纳米纤维素的制备方法众多,但依然面临着较大的挑战。离子液体因其对木质纤维素优良的溶解性能及可回收性,在纳米纤维素制备中展现了较大的潜力。基于此,综述了离子液体在纳米纤维素制备方面的应用进展,重点介绍了离子液体作为预处理手段在纳米纤维素制备方面的应用现状,以及作为溶剂和催化剂直接水解制备纳米纤维素方面的研究进展,并对制备过程中离子液体的回收情况进行了简单概述。     

A comparison of partially acetylated nanocellulose,nanocrystalline cellulose,and nanoclay as fillers for high‐performance polylactide nanocomposites

Partially acetylated cellulose nanofibers (CNF) were chemically extracted from sisal fibers and the performance of those CNF as nanofillers for polylactide (PLA) for food packaging applications was evaluated. Three PLA nanocomposites; PLA/CNF (cellulose nanofibers), PLA/CNC (nanocrystalline cellulose), and PLA/C30B (Cloisite^TM 30B, an organically modified montmorillonite clay) were prepared and their properties were evaluated. It was found that CNF reinforced composites showed a larger decrease on oxygen transmission rate (OTR) than the clay‐based composites; (PLA/CNF 1% nanocomposite showed a 63% of reduction at 23°C and 50% RH while PLA/C30B 1% showed a 26% decrease) and similar behavior on terms of water vapor barrier properties with 46 and 43%, respectively of decrease on water vapor transmission rate at 23°C and 50% RH (relative humidity). In terms of mechanical and thermomechanical properties, CNF‐based nanocomposites showed better performance than clay‐based composites without affecting significantly the optical transparency. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43257.     

Preparation and cytocompatibility of chitosan‐modified polylactide

Chitosan‐modified PLA (CMPLA) was fabricated to improve cytocompatibility of polylactide (PLA). PMAA‐grafted PLA (PMAA‐PLA) was obtained through α‐methacrylic acid (MAA) grafted polymerization on PLA surface with photooxidization and UV irradiation. Steady PMAA‐PLA microparticle suspension with an average size as 172.8 ± 3.6 nm and zeta potential as ?95.0 ± 0.6 mV was prepared through solvent volatilization. By static electricity interaction and other interactions between PMAA‐PLA microsparticles and chitosan molecules, CMPLA was obtained. FTIR, XPS, SEM, and zeta potential analyses indicated that CMPLA was modified with chitosan molecules uniformly. Compared with the PLA control, CMPLA adapted to supporting the attachment and proliferation of L929 cells better. The obtained CMPLA was expected to be used as perfect biomaterial for tissue regeneration. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Regioselective end‐functionalization of polylactide oligomers with D‐glucose and D‐galactose

D ‐glucose and D ‐galactose end‐functionalized polylactide oligomers were synthesized by controlled ring‐opening polymerization of lactide using aluminium triisopropoxide, triethylaluminium or stannous octoate as promoter. Accordingly, two selectively protected monosaccharides were studied as co‐initiators, either 1,2;5,6‐di‐O‐isopropylidene‐α‐D ‐glucofuranose (1) and 1,2;3,4‐di‐O‐isopropylidene‐α‐D ‐galactopyranose (2). In contrast to what is known in polymerization of ?‐caprolactone, both protected monosaccharides proved to be efficient co‐initiators and yielded end‐functionalized polylactide chains with controlled regioselectivity (C‐3 or C‐6 linkage), predictable molecular weights and narrow molecular weight distributions. © 2003 Society of Chemical Industry     

High‐viscosity polylactide prepared by in situ reaction of carboxyl‐ended polyester and solid epoxy

To extend the potential applications of polylactide (PLA) in film blowing, foaming, thermal molding, and so on, the high‐viscosity PLA composites with various compositions of carboxyl‐ended polyester (CP) and solid epoxy (SE) have been successfully prepared by an in situ reaction blending process. Their rheological properties, crystallization behaviors, tensile properties, and morphologies have been investigated in detail. The results show that the complex viscosity η*, G′, and G″ at low‐frequency region and the tensile strength of PLA composites are obviously improved with the addition of CP/SE, but the nonisothermal crystallization of PLA component is hindered. SEM reveals that some microphase separations existed in the as‐prepared composites. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

十二烷基二苯醚二磺酸钠及其烷基化催化剂的研究进展

介绍了十二烷基二苯醚二磺酸钠的合成及生产情况。着重阐述了二苯醚Friedel-Crafts烷基化反应催化剂的研究进展及产品应用领域的拓展情况。     

Toughening of polylactide with epoxy‐functionalized methyl methacrylate–butadiene copolymer

Glycidyl methacrylate‐functionalized methyl methacrylate–butadiene (MB‐g‐GMA) copolymers were prepared via an emulsion polymerization process. These functionalized copolymers were blended with polylactide (PLA). Dynamic mechanical analysis and differential scanning calorimetry results showed that the addition of MB‐g‐GMA did not result in a marked change in the glass transition temperature of PLA. With an increase of MB‐g‐GMA content, the tensile strength of the blends decreased; however, the elongation at break and impact strength increased significantly. From scanning electron micrographs, there was large plastic deformation (shear yielding) in blends subjected to impact tests, which was an important energy‐dissipation process and led to a toughened polymer. Rheological investigation demonstrated that there was a significant dependence of viscosity on composition. When the MB‐g‐GMA content increased, the viscosity began to increase. © 2013 Society of Chemical Industry     

Structure‐rheology responses of polylactide/calcium carbonate composites

Polylactide (PLA) and calcium carbonate (CaCO₃) were melt blended using a twin‐screw extruder. The morphology of PLA/CaCO₃ composites was observed by scanning electronic microscopy. The linear and nonlinear shear rheological behaviors of PLA/CaCO₃ melts were investigated by an advanced rheology expended system. The results show that the CaCO₃ particles are evenly dispersed in the PLA matrix. The incorporation of low CaCO₃ content (<20%) causes the reduction of the storage moduli, loss moduli, and dynamic viscosities whereas high CaCO₃ content (>30%) leads to the increase of the storage moduli, loss moduli, and dynamic viscosities. The composites with high CaCO₃ content show pseudo‐solid‐like behaviors at low frequency. High CaCO₃ content also results in a significant increase of flow activation energy and a dramatic decrease of flow index n, which is in consistent with the more serious shear‐thinning tendency of high‐filled PLA composites melts. The particular rheological responses might be attributed to the formation and destruction of the percolating network. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Study on flame‐retardancy and thermal degradation behaviors of intumescent flame‐retardant polylactide systems

Two intumescent flame‐retardant (IFR) additives, IFR‐I and IFR‐II, were synthesized and their structure was confirmed by Fourier transform infrared spectroscopy and nuclear magnetic resonance. Polylactide (PLA) was modified by the two IFRs to obtain flame‐retardant composites. The flammability of the PLA/IFR composites was characterized by the vertical burning test UL‐94 and limiting oxygen index. The limiting oxygen index values of the PLA composites increased with increase of IFR content. The PLA composite with 20 wt% IFR‐I could pass the UL‐94 V0 rating, while the composite with 30 wt% IFR‐II could not. The results of pyrolysis combustion flow calorimetry showed that the heat release capacity of PLA composites with 30 wt% IFR‐I decreased 43.1% compared with that of pure PLA. The thermal degradation and gas products of PLA/IFR‐I systems were monitored by thermogravimetric analysis and thermogravimetric analysis infrared spectrometry. Scanning electron microscopy was used to investigate the surface morphology of the char residue. Copyright © 2011 Society of Chemical Industry     

Effect of nanocellulose fibers and acetylated nanocellulose fibers on properties of poly(ethylene‐co‐vinyl acetate) foams

Cellulose nanofibers are promising materials in the development of polymeric foams, because they act as heterogeneous nucleation sites for the growth of cells during foaming. In this research, we studied the incorporation of cellulose nanoparticles in poly(ethylene‐co‐vinyl acetate)‐EVA foams. The foams were produced with different fiber contents. We observed the effect of a chemical treatment by acetylation on the cellulose fibber, that is, we evaluated the use of hydrophilic and hydrophobic cellulose nanofibers in EVA foams. The main results indicate that with the addition of only 1% of cellulose nanofibers, cell density significantly reduces when compared with the pure EVA foams. On the other hand, by increasing the cellulose content, the agglomeration of nanofibers also increases, which results in heterogeneous cell sizes. The same phenomenon was observed in the foams produced with acetylated cellulose nanofibers, regardless of the fiber content used. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44760.     

Toughening of polylactide by melt blending with linear low‐density polyethylene

Melt blending of polylactide and linear low‐density polyethylene (LLDPE) was performed in an effort to toughen polylactide. In addition, two model polylactide‐polyethylene (PLLA‐PE) block copolymers were investigated as compatibilizers. The LLDPE particle size and the impact resistance of binary and ternary blends were measured to determine the extent of compatibilization. For the amorphous polylactide (PLA), toughening was achieved only when a PLLA‐PE block copolymer was used as a compatibilizer. For the semicrystalline polylactide (PLLA), toughening was achieved in the absence of block copolymer. To decrease the variability in the impact resistance of the PLLA/LLDPE binary blend, as little as 0.5 wt % of a PLLA–;PE block copolymer was effective. The differences that were seen between the PLA and PLLA binary blends were investigated with adhesion testing. The semicrystalline PLLA did show significantly better adhesion to the LLDPE. We propose that tacticty effects on the entanglement molecular weight or miscibility of polylactide allow for the improved adhesion between the PLLA and LLDPE. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3757–3768, 2003     

High‐density green polyethylene biocomposite reinforced with cellulose fibers and using lignin as antioxidant

Aiming to manufacture biomaterials using renewable resources, we prepared, using a corotating and intermeshing twin‐screw extruder, high‐density green polyethylene composites reinforced with 20, 30, and 40 wt % of bleached cellulose fibers. Injection molded test samples are characterized for mechanical and thermal properties using thermogravimetry (TGA) and differential scanning calorimetry (DSC). These composites present improved mechanical properties relative to the pure matrix; the elastic modulus increases by 240% for the composite with 30 wt % of fiber. We characterize this composite, additionally formulated with lignin and a secondary antioxidant, by tensile and flexural mechanical properties, DSC, TGA, and oxidation induction time (OIT). Lignin has no effect on the mechanical properties; however, for the composite, the OIT increases from 24 to 77 min, clearly evidencing its effect as a stabilizer. Aging the composites for 1000 h, in a QUV chamber, confirms the stabilizing effect of lignin. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45219.     

Synergistic effect of THEIC‐Based charring agent on flame retardant properties of polylactide

A novel charring agent tris(2‐hydrooxyethyl) isocyanurate terephthalic acid ester, tetramer (TT4) was synthesized using tris(2‐hydrooxyethyl) isocyanurate and terephthalic acid as raw materials, and it was characterized by Fourier transformed infrared spectrometry and ¹H‐NMR spectrum. It was combined with ammonium polyphosphate (APP) to form intumescent flame retardants for polylactide (PLA). The combustion properties and thermal stability of PLA/APP/TT4 composites were evaluated by UL‐94 burning tests, limiting oxygen index (LOI), and thermogravimetric analyses (TGA). It was found PLA with 30 wt % of APP/TT4 (5 : 1) achieved UL‐94 V‐0 rating and a 40.6 LOI value. Results from TGA demonstrated that APP/TT4 composites could retard the degradation of PLA above 410°C. The char residue at 500°C is higher than 24%, showing a good char forming ability. Moreover, the continuous and expansionary char layer observed from the SEM images proved good charring forming ability of TT4. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41218.     

Polylactide/nano‐ and micro‐scale silica composite films. II. Melting behavior and cold crystallization

Nonisothermal crystallization of polylactide (PLA)/silica composites prepared by (i) directly blending the PLA with nanoscale colloidal silica sol and by (ii) a sol–gel process are studied by differential scanning calorimeter (DSC) at various heating rates. Samples quenched from the molten state exhibited two melting endotherms (T_ml and T_mh) due to melt‐recrystallization during the DSC scans. Lower heating rate and the presence of silica particles generate a lower peak intensity ratio of T_ml /T_mh. The nonisothermal crystallization kinetics is analyzed by modified Avrami model, Ozawa model, and Liu‐Mo models. The modified Avrami and Liu‐Mo models successfully described the nonisothermal cold crystallization processes, but Ozawa is inapplicable. The nucleation constant (K_g) is calculated by modified Lauritzen‐Hoffman equation and the activation energy by Augis‐Bennett, Kissinger, and Takhor models. These calculated parameters indicate consistently that the nanoscale silica particles seem to form more heterogeneous nucleation to increase crystallization, but microscale one form hindrance to retard crystallization. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Improvement of processability of clay/polylactide nanocomposites by a combinational method: In situ polymerization of L‐lactide and melt compounding of polylactide

A modified clay/polylactide nanocomposite was prepared. The clay was modified by grafting polylactide chains onto the surface of clay. The modified clay was melt‐compounded with a high‐molecular‐weight polylactide matrix. This novel clay/polylactide nanocomposite showed high shear‐thinning behavior when the molecular weight of the grafted poly(L ‐lactide) was rather high. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1664–1669, 2006     

Synthesis of Selectively Mono‐N‐Arylated Aliphatic Diamines via Iridium‐Catalyzed Amine Alkylation

A highly selective phosphorus/nitrogen (P,N) ligand‐based iridium catalyst system efficiently catalyzes the reaction of arylamines with unprotected amino alcohols, yielding N‐arylated aliphatic diamines in yields of up to 93%. The reaction can be performed with a wide variety of branched and linear amino alcohols in combination with various aminopyridines or substituted anilines.     

Thermal degradation behavior and gas phase flame‐retardant mechanism of polylactide/PCPP blends

The thermal degradation behavior of the blend based on polylactide (PLA) and poly(1,2‐propanediol 2‐carboxyethyl phenyl phosphinate) (PCPP) was investigated by the thermogravimetric analysis (TGA). Thermal degradation activation energies (E_a) of neat PLA and PLA/15% PCPP blend were calculated via the Flynn–Wall–Ozawa method. The E_a of the blends increased with the addition of PCPP increasing when the conversion was higher than 10%. In addition, the appropriate conversion models for the thermal degradation process of PLA and PLA/15% PCPP were studied via the Criado method. At the same time, the main gaseous decomposition products of PLA and its blend were identified by TGA/infrared spectrometry (TGA–FTIR) analysis. And it revealed that the PCPP improved the flame‐retardant property of PLA via altering the release of the flammable gas and nonflammable gas. Moreover, the PCPP improved the flame‐retardant property of PLA by inhibiting exothermic oxidation reactions in the combustion, which was further proved by pyrolysis–gas chromatography–mass spectrometry analysis. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40480.     

Synthesis and characterization of antimicrobial polylactide via ring‐opening polymerization and click chemistry methods

Novel biodegradable polylactide (PLA) copolymers bearing pendant antimicrobial agent groups were successfully fabricated with a combination of ring‐opening copolymerization and copper(I)‐catalysed azide–alkyne cycloaddition click reaction in a two‐step reaction procedure. First, biodegradable PLA copolymers bearing azido groups were synthesized by the ring‐opening copolymerization of l ‐lactide and 2,2‐ bis(azidomethyl)trimethylene carbonate in the presence of 1‐dodecanol as protic co‐initiator and tin(II) 2‐ethylhexanoate (Sn(Oct)₂) as the catalyst. Then, alkyne functionalized quaternary ammonium salts were attached onto the azido groups of the copolymers via a Huisgen 1,3‐dipolar cycloaddition reaction to give PLA imparting antimicrobial activity. The chemical structure and composition of the copolymers were clearly confirmed using ¹H NMR and Fourier transform infrared spectroscopies and gel permeation chromatography. Thermal phase transition temperatures (T_m and T_g) and the thermal stability of the polymers were investigated by DSC and TGA experiments, respectively. The antimicrobial activity tests were carried out against Gram‐negative (Escherichia coli) and Gram‐positive (Staphylococcus aureus) bacteria by the drop plate method. It was observed that antimicrobial agents are more active in the polymeric form than in the monomeric form. Also, the activity depends on the compositional ratio and the length of the alkyl group on the ammonium salts. © 2018 Society of Chemical Industry     

An Efficient and Recyclable Catalyst for N‐Alkylation of Amines and β‐Alkylation of Secondary Alcohols with Primary Alcohols: SBA‐15 Supported N‐Heterocyclic Carbene Iridium Complex

A mesoporous silica (SBA‐15)‐supported pyrimidine‐substituted N‐heterocyclic carbene iridium complex was prepared and used as a catalyst for both environmentally friendly N‐alkylation of amines and β‐alkylation of secondary alcohols with primary alcohols. The structure of the supported iridium catalyst was characterized by Fourier transform infrared (FT‐IR), ¹³C and ²⁹Si solid‐state nuclear magnetic resonance (NMR), small‐angle X‐ray scattering (SAXS), transmission electron microscopy (TEM), iridium K‐edge X‐ray absorption near‐edge structure (XANES) and extended X‐ray absorption fine structure (EXAFS) spectroscopic analyses which demonstrated that the coordination environment of the iridium centre and the 3‐dimensional‐hexagonal pore structure of SBA‐15 were retained after the immobilization. The catalyst was found to be highly efficient for both kinds of reaction on a wide range of substrates under mild conditions. Moreover, the supported iridium catalyst was obviously superior to the unsupported one in the N‐alkylation of aniline and β‐alkylation of 1‐phenylethanol with benzyl alcohol as substrate, which indicated that not only the iridium complex moiety but also the support material contributed to the catalytic activity of the supported iridium catalyst in these reactions. The supported iridium catalyst can be easily recycled by simple washing without chemical treatment, and exhibited excellent recycling performance without notable decrease in catalytic efficiency even after twelve test cycles for N‐alkylation of aniline with benzyl alcohol, nine cycles for N‐alkylation of different amines with different alcohols, and eight cycles for β‐alkylation of 1‐phenylethanol with benzyl alcohol, respectively.     

Preparation,characterization, and biodegradability of renewable resource‐based composites from recycled polylactide bioplastic and sisal fibers

The biodegradability, morphology, and mechanical thermal properties of composite materials composed of polylactide (PLA) and sisal fibers (SFs) were evaluated. Composites containing acrylic acid‐grafted PLA (PLA‐g‐AA/SF) exhibited noticeably superior mechanical properties because of greater compatibility between the two components. The dispersion of SF in the PLA‐g‐AA matrix was highly homogeneous as a result of ester formation and the consequent creation of branched and crosslinked macromolecules between the carboxyl groups of PLA‐g‐AA and hydroxyl groups in SF. Furthermore, with a lower melt temperature, the PLA‐g‐AA/SF composite is more readily processed than PLA/SF. Both composites were buried in soil to assess biodegradability. Both the PLA and the PLA‐g‐AA/SF composite films were eventually completely degraded, and severe disruption of film structure was observed after 6–10 weeks of incubation. Although the degree of weight loss after burial indicated that both materials were biodegradable even with high levels of SF, the higher water resistance of PLA‐g‐AA/SF films indicates that they were more biodegradable than those made of PLA. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011