Viscoelastic properties of cellulose derivatives: 1. Cellulose acetate

The dynamic mechanical spectrum of cellulose acetate (CA) from −130°C to 240°C has been determined at different frequencies (from 0.1 to 30 Hz). Three relaxations, designated , β and γ in order of decreasing temperature, and one shoulder (β*) above room temperature were found. Comparison with calorimetric and thermogravimetric measurements yields the conclusion that the relaxation (197°C at 3 Hz) is related to the glass-to-rubber transition and the β* shoulder (50°C–100°C) is due to loss of moisture. The β relaxation (−38°C at 3 Hz, ΔH = 100 kJ mol⁻¹) is tentatively assigned to local motions of the main chain (glucopyranose rings). The low-temperature γ relaxation (−88°C at 3 Hz, ΔH = 46 kJ mol⁻¹), is humidity-dependent: its intensity decreases when the samples are dried to moisture contents lower than that obtained by normal room conditioning (about 3%). Higher water contents shift the relaxation to lower temperatures without increasing the intensity of the mechanical loss. It is suggested that water associated with the unesterified methylol groups of cellulose acetate is responsible of the dynamic mechanical γ dispersion.     

Methyl tert-butyl ether decomposition over heteropoly acid catalyst in a cellulose acetate membrane reactor

In this study the methyl tert-butyl ether (MTBE) decomposition over H₃PW₁₂O₄₀ was carried out in a cellulose acetate membrane reactor. The permeability of methanol through the cellulose acetate membrane was about 30 and 300 times higher than that of either isobutene or MTBE, respectively. The isobutene selectivity in the fixed bed reactor was only slightly higher than the methanol selectivity due to the side reaction. In the cellulose acetate membrane reactor, however, the isobutene selectivity in the rejected stream was 68% and the methanol selectivity in the permeated stream was up to 97%. The MTBE conversion in the membrane reactor was about 7% higher than that in the membrane-free fixed bed reactor under the same reaction conditions. The enhanced performance of the membrane reactor in this reversible reaction was mainly due to the selective permeation of methanol which resulted in a methanol-deficient condition suppressing MTBE synthesis reaction.     

Microstructure determination and thermal studies of n‐acryloylcarbazole/vinyl acetate copolymers

Copolymers of N‐acryloylcarbazole (A) and vinyl acetate (V) were synthesized by bulk polymerization using benzoyl peroxide (BPO) as free‐radical initiator at 65°C in different in‐feed ratios. The composition of the copolymer was determined by ¹H‐NMR spectrum. The comonomer reactivity ratios, determined by Kelen–Tudos (KT) and nonlinear error‐in‐variables (EVM) methods, were r_A= 16.75 ± 1.38, r_V = 0.015 ± 0.002, and r_A = 16.36, r_V = 0.015, respectively. Complete spectral assignments of the ¹H and ¹³C{¹H} NMR spectra of the copolymers were done by the help of distortionless enhancement by polarization transfer (DEPT) and two‐dimensional NMR techniques such as heteronuclear single quantum coherence (HSQC) and total correlation spectroscopy (TOCSY). The methine and methylene carbon resonances were found to be compositional as well as configurational sensitive. The signals obtained were broad pertaining to the restricted rotation of bulky carbazole group. The thermal stability and glass‐transition temperatures (T_g) of the copolymers were found to be dependant on polymer composition and characteristic of rotational rigidity of the polymer chain. Variation in the values of T_g with the copolymer composition was found to be in good agreement with theoretical values obtained from Johnston and Barton equations. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2720–2733, 2007     

Male european corn borer,Ostrinia nubilalis (Hübner), antennal responses to analogs of its sex pheromone

Experiments were conducted to (1) determine whether the electroantennogram (EAG) can detect differences among the responses of antennae from males derived from the three strains ofOstrinia nubilalis (Hübner), and (2) characterize the EAG responses of each strain to isomeric forms of the natural pheromone, (E)- and (Z)-11-tetradecen-1-ol acetate (TDA), and analogs possessing differences in the terminal alkyl group, cyclopropyl (CPA), ortert-butyl (TBA).EAG responses differed among the strains in two ways: (1) Antennae fromZZ males always produced an EAG to (Z)-TDA with an extended duration of response. This signature EAG response was found to be unique to the antennal response ofZZ males to (Z)-TDA, thus providing a relatively easy method of distinguishing liveZZ males fromEE orZE males. Correlated with this longer EAG response was a longer disadaptation time, i.e., the EAG response ofZZ antennae disadapted more slowly (ca. 10 min) than the response ofEE antennae. (2) Strain differences in the relative EAG amplitudes to isomers and analogs were observed at the stimulus amounts eliciting the peak EAG amplitude as follows: TDA CPA > TBA forZZ males and both isomers; TDA > CPA TBA and CPA TDA > TBA forEE males and theE andZ isomers, respectively; CPA > TBA TDA forZE males and both isomers. Dose—response relationships were seen for all compounds if amplitude (peak height) of the EAG was used as a measure of response. However, if width of the EAG at half the peak height (peak width) was used, then only theZZ antennal response to (Z)-TDA resulted in a meaningful dose-response relationship. For all strains, the EAG amplitudes elicited by theZ isomers of any of the tested compounds were greater than those elicited by the correspondingE isomers. Therefore, correlations between the relative EAG and upwind flight responses were observed in theZZ (r = 0.86) andZE (r = 0.80) strains but were not correlated in theEE strain (r = 0.18). Temporal studies showed that adaptation, not postexcision deterioration, was responsible for the observed decreases in the EAG amplitude after repetitive stimulation or after stimulation with amounts in a descending order. Disa-daptation required at least 20 min for a moderate dose (10 g for 1 sec). Developmental studies showed that antennae from 2-day-old adults had the greatest EAG response.     

Synthesis,characterization, and antitumor activity of poly(maleic anhydride‐co‐vinyl acetate‐co‐acrylic acid)

The ternary copolymerization of maleic anhydride (MA), vinyl acetate (VA), and acrylic acid (AA) [P(MA‐co‐VA‐co‐AA)], which is considered to be an acceptor–donor–acceptor system, was carried out in 1,4‐dioxane with benzoyl peroxide as an initiator at 70°C under a nitrogen atmosphere. Constants of complex formation for the monomer systems in the study were determined by UV–visible (hydrogen‐bonding complex) and ¹H‐NMR (charge transfer complex) methods, respectively. The results show that polymerization of the P(MA‐co‐VA‐co‐AA) system proceeds by an alternating terpolymerization mechanism. It is shown that the synthesized copolymers have typical polyelectrolyte behavior, ability for reversible hydrolysis–anhydrization reactions, and semicrystalline structures. In these cases, including radical polymerization, and formation of semicrystalline structures, the hydrogen‐bonding effect plays a significant role. The in vitro cytotoxicities of the synthesized terpolymer and alternating copolymer were evaluated using Raji cells (human Burkitt lymphoma cell line). The antitumor activities of prepared anion‐active copolymers were studied using methyl–thiazol–tetrazolium colorimetric assay and 50% of the cytotoxic dose of each copolymer and terpolymer were calculated. Hydrolyzed P(MA‐co‐VA‐co‐AA) and P(MA‐alt‐AA) copolymers have sufficiently high antitumor activity, which depends on the amount of hydrogen‐bonding carboxylic groups and their regular distribution in the side chain of functional macromolecules. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3425–3432, 2006     

Effects of apitong (Dipterocarpus spp.) extractives on bond strength development and curing rate of adhesives

Emulsion polymer isocyanate ( ), polyvinyl acetate ( ) and resorcinol-formaldehyde ( ) adhesives were used to produce single lap shear specimens using resinous and non-resinous apitong (Dipterocarpus spp.) timbers. Tests showed that joints made with highly resinous apitong were about 40% weaker than similar joints made with non-resinous apitong. The resinous apitong was treated with different solvents to yield five different extractives which were characterized by infra-red analysis. Apitong extractives were then added to and adhesives and joints made with buna (Fagus crenata), a timber known to be low in extractives and easy to bond. Joints prepared using extractive-containing adhesives were generally weaker than those made with the unmodified adhesives. RF adhesives containing extractives cured more slowly than unmodified . It is thought that the acidic nature of the extractives changes the pH of the system sufficiently to affect the curing mechanism     

纳米稀土复合固体超强酸催化合成乙酸苄酯

采用共沉淀法制备了纳米稀土复合固体超强酸SO4^2-／ZrO2-2％Nd2O3催化剂，电镜分析表明，催化剂颗粒直径在25nm左右，比表面积测定：71．03m^2／g。酸强度-12．70〈Ho〈-11．99。并对合成乙酸苄酯的最佳反应条件进行了研究。研究表明：当苯甲醇与乙酸的物质的量比为1：2，反应时间为5h，反应温度为120℃，催化剂用量为6％苯甲醇的质量时，酯化率可达92．04％。研究发现，该催化剂可重复使用并可活化再生。     

用玻璃球负载纳米级SO4^2-／TiO2固体超强酸催化合成乙酸正丁酯

用玻璃球负载纳米级SO42-/TiO2固体超强酸催化合成乙酸正丁酯,对催化剂的制备条件和乙酸正丁酯的合成条件进行了研究。在最佳反应条件下,乙酸的转化率为99.3%,催化剂重复使用8次后乙酸的转化率仍高达92.3%。该催化剂选择性好,未发现有副产物生成,看来具有较好的应用前景。     

Air sampling of volatile sex pheromone components in a closed jar

A cotton wool plug, used as the source for pheromone release, was placed in closed 1-quart Mason jars, either at the mouth or at the rear of the jar. Air sampling of the two components of the sex pheromone (total 2.2 mg at the source) of the almond moth (Ephestia cautella) female showed that the saturation period near the source in still air was 20–22 hr and that far from the source was 40–50 hr, reaching a level of less than 1 ng/ml air. The ratio between the components (Z,E)-9,12-tetradecadienyl acetate, designated D, and (Z)-9-tetradecenyl acetate designated M, in the air was close to the original ratio for both sampling sites, albeit somewhat richer in the more volatile (Z)-9-tetradecenyl acetate (source 77.023.0 DM, air 73.0– 74.327.0–25.7; source 80.119.9, air 77.622.4; source 25.174.9, air 23.976. 1 DM). The total amount of pheromone per milliliter of air was two to three times larger near the source than far from it at the early stages of the evaporation and saturation process. When the amount of pheromone applied to the source was tripled (7 mg), the amount far from the source was almost tripled, or the saturation time was cut by factor of two to three.     

新型醋酸乙烯聚合引发剂的研究

采用新型引发剂过氧化二月桂酰对醋酸乙烯聚合进行研究,通过研究它在聚合过程中的分解速率常数、半衰期等性能,得出过氧化二月桂酰的分解速率常数大,半衰期与偶氮二异丁腈相似,并且产物不含有毒物质,因此它的应用范围可以更加广泛。讨论了引发剂质量、甲醇质量、反应时间对醋酸乙烯转化率和聚合度的影响。建立正交试验得到醋酸乙烯聚合的最佳工艺条件。