Preparation,Characterization and Properties of Cellulose Acetate-Grafted-Poly(glycidyl methacrylate) Copolymers

The cellulose acetate-grafted-poly(glycidyl methacrylate) copolymers were synthesized successfully by free radical polymerization. The resulting copolymer was characterized by proton nuclear magnetic resonance (¹H-NMR), solid-state ¹³C-NMR, Fourier transform infrared spectroscopy (FTIR) and gel permeation chromatography (GPC). The crystallization behavior, thermal properties, specific particle surface area, moisture sorption behavior of the modified cellulose acetate were investigated by wide angle X-ray diffraction (WAXD), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), Brunauer-Emmett-Teller (BET) method and Dynamic Vapor Sorption (DVS) instrument. It was found that the poly(glycidyl methacrylate) (PGMA) grafting was effective in improving the water adsorption of cellulose acetate (CA) changing the specific surface area, and reducing the T_g of copolymers.     

Synthesis of cellulose benzoates under homogeneous conditions in an ionic liquid

The ionic liquid 1-allyl-3-methylimidazolium chloride (AmimCl) as a reaction medium was studied for the synthesis of cellulose benzoates by homogeneous acylation of dissolved cellulose with benzoyl chlorides in the absence of any catalysts. Cellulose benzoates with a degree of substitution (DS) in the range from about 1 to 3.0 were accessible under mild conditions. The DS of cellulose derivatives increased with the increase of the molar ratio of benzoyl chloride/anhydroglucose unit (AGU) in cellulose, reaction time, and reaction temperature. Benzoylation of cellulose with some 4-substituted benzoyl chlorides including 4-toluoyl chloride, 4-chlorobenzoyl chloride and 4-nitrobenzoyl chloride was also readily carried out under mild conditions. Furthermore, regioselectively substituted mixed cellulose esters were synthesized in this work. All products were characterized by means of FT-IR, ¹H-NMR, and ¹³C-NMR spectroscopy. In addition, at the end of benzoylation of cellulose, the ionic liquid AmimCl was easily recycled. When the recycled AmimCl was used as the reaction media, the cellulose benzoate with a similar DS was obtained under comparable reaction conditions.     

Binding cellulose and chitosan via click chemistry: Synthesis,characterization, and formation of some hollow tubes

A novel cellulose‐click‐chitosan polymer was prepared successfully in three steps: (1) propargyl cellulose with degrees of substitution (DS) from 0.25 to 1.24 was synthesized by etherification of bamboo Phyllostachys bambusoide cellulose with propargyl chloride in DMA/LiCl in the presence of NaH. The regioselectivity of propargylation on anhydrous glucose unit determined by GC‐MS was in the order of 2 >> 6 > 3; (2) the functional azide groups were introduced onto the chitosan chains by reacting chitosan with 4‐azidobenzoic acid in [Amim]Cl/DMF and the DS ranged from 0.02 to 0.46; (3) thus, the cellulose‐click‐chitosan polymer was obtained via click reaction, that is, the Cu(I)‐catalyzed Huisgen 1,3‐dipolar cycloaddition reaction, between the terminal alkyne groups of cellulose and the azide groups on the chitosan backbone at room temperature. The successful binding of cellulose and chitosan was confirmed and characterized by FTIR and CP/MAS ¹³C NMR spectroscopy. TGA analyses indicated that the cellulose‐click‐chitosan polymer had a higher thermal stability than that of cellulose and chitosan as well as cellulose–chitosan complex. More interestingly, some hollow tubes with near millimeter length were also observed by SEM. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Novel cellulose esters derived from the levopimaric acid-maleic anhydride adduct: synthesis,characterization, and properties

Synthesis of maleated pimaric acid (MPA) cellulose esters is first reported in this work. Cellulose esterification was performed by reacting microcrystalline cellulose with monoacid chloride of MPA (MPA-Cl) in presence of pyridine as catalyst and reaction medium. The syntheses were started in a heterogeneous solid–liquid reaction medium, but as the reaction advanced, the reaction mass turned into a homogeneous solution. The effects of MPA-Cl/anhydroglucose unit molar ratio, reaction temperature, and reaction duration on the yield and degree of substitution (DS) of cellulose esters (CEs) were investigated. CEs with DS ranging from 2.6 to 2.8 were achieved at molar ratios of 5.5–6.0 after 12–16 h at 118 °C. The purified products were characterized by elemental analysis, IR and ¹³C-NMR spectroscopy, and thermogravimetric analysis. CEs are soluble or partially soluble in usual organic solvents, depending on DS. Transparent films were prepared using CE-cyclohexanone solutions.     

Synthesis and characterization of hydroxypropyl cellulose from bacterial cellulose

Bacterial cellulose produced by Acetobacter xylinum has been reacted with propyleneoxide to synthesize hydroxypropyl cellulose(HPC) under different reaction conditions while diluted by toluene. The effects of mass ratio of bacterial cellulose to propyleneoxide, dilutability of toluene, reaction temperature(T) and time(t) were investigated by series of experiments. The degree of substitution(DS), hydroxypropyl content(A) and yield(η) were compared. The optimized product exhibited cold-water solubility and hot-water gelatinization in aqueous medium. Further study was carried out with FTIR, TGA, XRD, SEM and 13C-NMR for characterization. The water/air contact angle measurement reveals that it is a good hydrophobic material with good mechanical properties.     

Homogenous synthesis of 3-allyloxy-2-hydroxypropyl-cellulose in NaOH/urea aqueous system

3-Allyloxy-2-hydroxypropylcelluloses (AHP-celluloses), reactive unsaturated cellulose derivatives, were homogeneously synthesized by the reaction of cellulose with allyl glycidyl ether (AGE) in NaOH/urea aqueous solution. Water-soluble AHP-celluloses with DS_NMR = 0.32–0.67 were prepared from microcrystalline cellulose. The degree of substitution (DS) of AHP-celluloses could be controlled by varying the molar ratio of AGE and NaOH to AGU and the reaction conditions. The structure of AHP-cellulose samples were characterized by means of FT-IR, NMR spectroscopy and size exclusion chromatography. The cellulose ether shows thermoreversible flocculation. Bromination reactions were carried out as subsequent functionalization both to illustrate the reactivity of the allyl function and to determine the DS values.     

Design,synthesis, and characterization of a combined main-chain/side-chain liquid-crystalline polymer based on ethyl cellulose

A novel combined main-chain/side-chain liquid-crystalline polymer based on an ethyl cellulose main chain containing azobenzene mesogens (AzoEC) was successfully synthesized. Molecular characterization of the resulting polymers with different degrees of substitution (DS) was performed with proton nuclear magnetic resonance (¹H NMR), Fourier-transform infrared spectroscopy (FTIR), and gel permeation chromatography (GPC). Thermal stability was investigated by thermogravimetric analysis (TGA). The phase transitions and liquid-crystalline behavior of these polymers were investigated by differential-scanning calorimetry (DSC), polarized optical microscopy (POM), and wide-angle X-ray diffraction (WAXD). The results indicate that DS has substantial effect on the liquid-crystalline behavior of these polymers. AzoEC with low DS only shows the cholesteric phase similar to ethyl cellulose (EC). However, when DS increases to a specific value, AzoEC begins to show fascinating supramolecular structures. The supramolecular structure of AzoEC with maximum DS consisted of a large-scale ordered lamellar structure formed by EC main chains and a small-scale ordered structure formed by azobenzene mesogens.     

Homogeneous methylation of wood pulp cellulose dissolved in LiOH/urea/H2O

Spruce sulphite cellulose (number average degree of polymerization 620) dissolved in an aqueous solution of 8% (w/w) LiOH*H₂O and 12% (w/w) urea was methylated with dimethyl sulphate (DMS). By varying the reaction temperature between 22 and 50 °C, the molar ratio between 9 and 15 mol DMS per mol anhydroglucose unit, and the reaction time from 4 to 24 h, methyl cellulose (MC) with degree of substitution (DS) values in the range of 1.07 and 1.59 was prepared. The chemical structure of MC was analysed by FTIR and ¹H NMR spectroscopy. The turbidity (given in nephelometric turbidity units, NTU) of the aqueous solution of MC reached an optimum of 10 NTU for a product obtained with 12 mol DMS/mol AGU at 50 °C. GPC measurements revealed polymer degradation to a certain extent. The intrinsic viscosity and the Huggins constant k of the MC samples increased with increasing DS value. The MC samples possess k values higher than 0.8, indicating association of the polymer chain. The zero-shear viscosity decreased with increase of both temperature and the amount of methylation agent due to the depolymerization. During the heating/cooling cycle (20-90 °C) of the aqueous solutions of MC, it was observed that samples synthesized at 22 °C with DS values lower than 1.3 did not undergo phase separation in aqueous solution. Phase separation hysteresis with a precipitation temperature up to 80 °C was obtained for aqueous solutions of MC with DS values between 1.07 and 1.66 synthesized at higher temperatures. The functionalization pattern determined by GLC of the corresponding partially methylated glucitol acetates is close to randomness and comparable with those of commercial MC samples.     

Preparation and properties of a new type of comb-shaped, amphiphilic cellulose derivative

Comb-shaped, amphiphilic O-(2- hydroxy-3-butoxypropyl) cellulose (HBPC) was prepared by a homogeneous reaction of cellulose with butyl glycidyl ether (BGE) in a 10% (w/w) LiCl--DMAc solution. It was found that: (a) the molar substitution (MS) of water-soluble HBPC ranges from 0.4 to 1.0, and is nearly equal to its degree of substitution (DS), indicating that the HBPC derivatives obtained are comb-shaped polymers; (b) the water-soluble HBPC shows a thermally reversible sol-gel transition in aqueous solution; and (c) the derivative having a DS of 0.6 shows surface activity with critical micelle concentration (cmc) in the order of 0.8 g/l and surface tension of 31.5 dyn/cm     

Synthesis of new polysilane-crown ether

This paper presents the synthesis of new polysilane with pendant crown ether groups. The polymer was obtained through the addition reaction of 4^′-allylbenzo-15-crown-5 to poly[methyl(H)-co-methylphenylsilane] copolymer in anhydrous toluene solution using hexachloroplatinic acid as a catalyst. The allyl functionalization of the crown ether was achieved by the coupling of the crown ether bromide with allyl magnesium chloride. The availability of the crown ether sites in complexation reactions with Cu(II) cations was tested.The chemical structures of all products and intermediates were studied using spectral methods (IR, ¹H-NMR, ¹³C-NMR, UV), gel permeation chromatography (GPC) and thermogravimetric analysis (TGA).     

13C nuclear magnetic resonance studies of cellulose acetate

¹³C-NMR spectra of ring carbons and O-acetyl carbonyl carbons of cellulose acetate (CA) in dimethyl sulfoxide-d₆ were analyzed. The CA samples with the degree of substitution (DS) ranging from 0.84 and 1.91 were prepared by homogeneous acetylation of cellulose with acetic anhydride in a 10% LiCl/dimethyl acetamide solvent. It was found that the use of these low DS samples permitted easier assignments not only of the ring carbon but also of the O-acetyl carbonyl carbon signals. The assignments were confirmed by comparing with the ¹H-NMR spectra of the samples obtained by complete acetylation of the corresponding CA samples with acetyl-d₃ chloride. Two methods for determining the distribution of O-acetyl groups of CA, i.e., the relative DS at the three different types of hydroxyl groups, were developed. One is based on the measurements of the relative intensities of the signals for the ring carbons and the other is based on the measurements of the relative intensities of the signals for the O-acetyl carbonyl carbons.     

MONOMER REACTIVITY RATIO AND THERMAL PERFORMANCE OFα-METHYL STYRENE AND GLYCIDYL METHACRYLATE COPOLYMERS

<正>Synthesis and characterization of the copolymers(PAG) ofα-methyl styrene(AMS) and glycidyl methacrylate (GMA) are presented.The copolymers of PAG were characterized by gel permeation chromatography(GPC),Fourier transform infrared spectroscopy(FTIR),nuclear magnetic resonance(~1H-NMR) and thermogravimetery(TG).Based on the copolymer compositions determined by ~1H-NMR,the reactivity ratios of AMS and GMA were found to be 0.105±0.012 and 0.883±0.046 respectively by Kelen-Tüds method.TG revealed that thermal stability of the copolymers decreased with increasing the AMS content in the copolymers,which indicated that the degradation was mainly caused by the chain scission of AMS-containing structures.Under heating,the copolymers depolymerize at their weak bonds and form chain radicals, which could further initiate other chemical reactions.     

Peracetylated cellulose: end group modification and structural analysis by means of <Superscript>1</Superscript>H-NMR spectroscopy

A homologous series of partially hydrolyzed celluloses (level-off-DP cellulose) with weight-average molecular weight (DP_w) < 150 were peracetylated and characterized by ¹H-NMR spectroscopy. The results demonstrate the utility of ¹H-NMR spectroscopy to assign the chemical shifts of all end groups of the peracetylated cellulose. On the one hand, the chemical shifts of all methine and methylene protons of the non-reducing terminal end group (TEG) as well as the - and -anomer of the reducing end group (REG) could be determined by two-dimensional NMR techniques (COSY-DQF) and by selective excitation of isolated proton signals (1D-TOCSY) of these end groups. On the other hand, the spectral resolution was high enough to determine the number-average molecular weight (DP_n) of peracetylated level-off-DP cellulose (LODP cellulose acetates) as shown in comparison with the data of gel permeation chromatography (GPC). This molecular weight determination of cellulose using end group analysis by means of ¹H-NMR spectroscopy was demonstrated for the first time. Furthermore, a specific modification of hydroxyls in end groups could be exemplified in case of 1-OH-deacetylation of the REG of peracetylated LODP cellulose.     

Modification of epoxy-novolac resins with polysiloxane containing nitrile functional groups: synthesis and characterization

Synthesis of the statistical epoxidized polycyanopropylmethylsiloxane-co-polydimethylsiloxanes (PCPMS-co-PDMS) has been demonstrated. The modified polysiloxanes were prepared via a two-step method; (1) the ring-opening polymerization of octamethylcyclotetrasiloxane (D₄) and tetramethylcyclotetrasiloxane (D₄H), (2) hydrosilylation reaction of the polysiloxane prepolymers with allyl cyanide and allyl glycidyl ether. Molar ratios of D₄H and D₄ were varied to produce the modified polysiloxanes with differences in polarity. ¹H-NMR, ²⁹Si-NMR, ¹³C-NMR and FTIR were used to monitor the formation of the modified polysiloxanes and DSC was used to study their thermal behaviors (T_g, −118 to −68 °C). The use of the modified polysiloxanes as an elastomeric component in epoxy-novolac networks was also investigated. TEM and their transition temperatures suggested that the epoxy-novolac networks with high content of PDMS modifiers exhibited microphase separation. The fracture toughness properties of the networks with the polysiloxane modifiers were improved over the controls without polysiloxanes.     

Dilute solution properties of sodium cellulose disulphate

Sodium cellulose sulphate (NaCaS), with degree of substitution (DS) of 1.90, was synthesized by reacting samples of cellulose, covering a wide range of average molecular weight, with S03/dimethyl formamide complex. A solution of NaCS in 0.5 M aq. NaCl was studied by solution viscometry, light scattering and membrane osmometry. The solution was dialysed against solvent. The following MarkHouwink-Sakurada equation and relation between the z-average radius of gyration and weightaverage molecular weight, Mw, were established for $\text{7.2 × 10}{}^4\text{?}\text{M}{}_{\mathrm{w}}\text{? 1.5 × 10}{}^6\text{at 25°}$.The NaCS with salt system was analysed according to the theory of linear non-ionic polymers. Flory's viscosity parameter φ is significantly molecular weight dependent. The partially free draining effect and the excluded volume effect were estimated and the former predominated. The unperturbed chain can be regarded as Gaussian and its dimension A was found to be 1.21 × 10^?8 cmand the conformation parameter a was 2.9.     

Characterization of methylcellulose produced from sugar cane bagasse cellulose: Crystallinity and thermal properties

In the present work, methylcellulose produced from sugar cane bagasse was characterized by FTIR, WAXD, DTA and TGA techniques. Two samples were synthesized: methylcellulose A and methylcellulose B. The only difference in the process was the addition of fresh reactants during the preparation of methylcellulose B. The ratio between the absorption intensities of the C-H stretching band at around 2900 cm⁻¹ and O-H stretching at around 3400 cm⁻¹ for methylcellulose B is higher than for methylcellulose A, indicating that methylcellulose B showed an increase in the degree of substitution (DS). Methylcellulose A presents a more heterogeneous structure, which is similar to the original cellulose as seen through FTIR and DTA. Methylcellulose B showed thermal properties similar to commercial methylcellulose. The modification of methylcellulose preparation method allows the production of a material with higher DS, crystallinity and thermal stability in relation to the original cellulose and to methylcellulose A.     

Synthesis and photopolymerization of 1-propenyl glycidyl ether

The ambifunctional monomer, 1-propenyl glycidyl ether, was prepared from allyl glycidyl ether, by a ruthenium-catalyzed isomerization reaction in high yield. 1-Propenyl glycidyl ether undergoes facile photoinduced cationic polymerization to yield a crosslinked polymer. The structure of this polymer was studied using ¹H- and, ¹³C-NMR spectroscopies and employing well-characterized related polymers as models. The model polymers were prepared by the cationic polymerization of allyl glycidyl ether with BF₃OEt₂ followed by isomerization of the pendant allyl groups by a ruthenium catalyst. Subsequently, the resulting polyether-bearing pendant 1-propenyl ether groups was subjected to a diaryliodonium salt-photoinitiated polymerization. A comparison of the spectra of the polymers indicated the presence of cyclic acetal units in the polymer backbone. © 1994 John Wiley & Sons, Inc.     

Synthesis of novel adamantoyl cellulose using differently activated carboxylic acid derivatives

New adamantane carboxylic acid esters of cellulose (adamantoylcelluloses) were synthesized homogeneously inN,N-dimethylacetamide/LiCl using differently activatedcarboxylic acid derivatives. This includes the reaction of cellulose with1-adamantoyl chloride and with adamantane-1-carboxylic acid after insitu activation with p-toluenesulfonyl chlorideand with 1,1-carbonyldiimidazole, which is a new and efficient tool. Thedegree of substitution (DS) has been determined by means of ¹H NMRspectroscopy using the perpropionylated adamantoyl cellulose samples. DS valuesas high as 2.1 were achieved. The reaction efficiency was 85% and the DS can becontrolled by the molar ratio and the reaction conditions applied. The reactionoccurs faster at the primary position compared to the secondary ones. Theproducts are soluble in various organic solvents dependent on the DS.Preliminary results of subsequent modifications and properties of theadamantoylcelluloses are discussed as well.     

Benzylation of cellulose in the solvent dimethylsulfoxide/tetrabutylammonium fluoride trihydrate

The cellulose solvent dimethylsulfoxide/tetrabutylammonium fluoride trihydrate (TBAF·3 H₂O) was studied as reaction medium for the synthesis of benzyl cellulose (BC) by treating the dissolved polymer with benzyl chloride in the presence of solid NaOH or aqueous NaOH solution. BC samples with degree of substitution (DS) between 0.40 and 2.85 were accessible applying different molar ratios. The studies show that both the TBAF·3 H₂O concentration and the molar ratio of the reagents to repeating unit influence the DS. The solubility of the BC synthesized in a different way, however, of comparable DS is different. Structural analyses were carried out by means of FTIR-, ¹H- and ¹³C NMR spectroscopy. SEC measurements revealed polymer aggregation in samples of low DS synthesized in a solvent containing 9.0% TBAF·3 H₂O. At higher concentration of TBAF·3 H₂O in the solvent, the BC samples obtained do not form aggregates. BC of high DS is crystalline and shows thermotropic liquid crystalline behavior as analyzed by means of DSC. Melting point and degradation temperature are not related to the DS.     

Structural characterization of ethyl cellulose and its use for preparing polymers with viologen moieties

The characteristics of ethyl cellulose (EC) were studied by chemical reaction and the spectra method. EC was first tosylated with tosyl chloride, and then the tosylated EC (Ts-EC) reacted with sodium iodide (NaI). By comparing the NMR spectra of EC and iodine-substituted EC (EC-I), a free hydroxyl group was proved to exist at the C-6 of the D-glucose unit of cellulose. Viologen moieties were introduced into the EC chain by the reaction of Ts-EC with 4,4′-bipyridine and n-propyl bromide. The existence of viologen was confirmed by ¹H-NMR, IR, and ESR. © 1993 John Wiley & Sons, Inc.