自交联型纸张—铝箔复合膜粘合剂的研究

以醋酸乙烯酯和丙烯酸丁酯为主要原料，引入自交联型单体羟甲基丙烯酸胺合成了纸张——铝箔复合膜粘合剂。探索了单体组成、自交联单体用量、缓冲剂用量和种类、核壳聚合等对粘合剂性能的影响以及该粘合剂的粘合性能。     

醋酸丙酸纤维素的合成与表征

采用非均相催化酯化法合成醋酸丙酸纤维素(CAP),研究了反应时间、温度和催化剂用量对CAP乙酰和丙酰取代度、特性粘度的影响,发现反应温度、反应时间和催化剂浓度增加虽可使产物的取代度增大,但粘度降低,得到优化的反应条件为:催化剂用量1%(wt,相对于纤维素),反应温度60℃,反应时间2 h。酯化反应使纤维素的结晶度降低。     

活性炭固载三氯化铁非均相催化合成乙酸异戊酯

以活性炭固载三氯化铁为非均相催化剂,对异戊醇与乙酸酐之间的酰化反应进行了研究,考察了催化剂用量、醇酐摩尔比、反应时间对乙酸异戊酯收率的影响。结果表明,活性炭固载三氯化铁有着较好的催化活性,当乙酸酐的加入量为0.1mol,醇酐摩尔比为1.1时,催化剂质量为0.20g,反应30min后,乙酸异戊酯收率可达到98.2%,且催化剂重复使用5次仍保持较高活性,所得产品无色透明,具有很高的纯度。产品用折光率和红外光谱进行了表征。进一步考察表明活性炭固载三氯化铁在其它酯的合成中也有着较好的催化性能。     

乙酸芳樟酯的合成研究

在无外加酯化催化剂条件下 ,采用反应 -蒸馏工艺合成了乙酸芳樟酯 ,考察了n(芳樟醇 )∶n(乙酸酐 )、反应时间、n(夹带剂 )∶n(芳樟醇 )等因素对反应的影响 ,结果表明 ,当n(芳樟醇 )∶n(乙酸酐 )≤ 1 0∶2 5 ,反应时间≥ 2 0h ,n(夹带剂 )∶n(芳樟醇 ) =2 0∶1 0时 ,产品收率可达76 9%。同时利用色谱 质谱联用 (GC MS)对产品进行表征 ,产品MS谱图与标准谱图一致。     

(Z,Z)-7,9-Dodecadienyl acetate,sex pheromone ofEpinotia tedella clerck (Lepidoptera: Tortricidae)

(Z,Z)-7,9-dodecadienyl acetate, a reported male attractant for several New World spp. ofEpinotia, was identified as the primary pheromone of femaleE. tedella (European spruce budmoth) through chemical analysis of pheromone gland washes, the electrophysiological study of male antennal receptor types, and field-trapping tests. The washes contained this compound at a level of approximately 0.4 ng per FE, along with a similar amount of the corresponding alcohol, (Z,Z)-7,9-dodecadien-1-ol. Each compound activated its own specialized type of male receptor cell. No traces of stereoisomers or monoenes were found in the washes. In field-trapping tests conducted in stands of Norway spruce in southern Germany, (Z,Z)-7,9-do-decadienyl acetate as a single chemical proved highly attractive to maleE. tedella over a range of lure doses. The corresponding alcohol or aldehyde did not show attractivity; rather, in binary combinations with the primary pheromone, these compounds, and also the (E,Z)-7,9 stereoisomeric acetate, reduced captures. A 101 blend of (E)-9- and (Z)-9-dodecenyl acetates, reported as anE. tedella male attractant, did not reveal significant captures. No otherEpinotia spp. besidesE. tedella responded to the various 7,9-do-decadienyl test baits during this study.     

对甲苯磺酸改性SBA-15的合成及催化合成乙酸正丁酯

采用浸渍法将含有磺酸基的对甲苯磺酸负载在SBA-15表面上,合成含有一定酸性的固体酸催化剂TsOH-SBA-15。催化剂的制备条件为:对甲苯磺酸的浸渍浓度为0.5 mol/L,焙烧温度为300℃,焙烧时间为4 h。用XRD,IR,DTA/TGA,氮吸附-脱附等方法对改性后的样品进行表征。结果表明,改性后的SBA-15分子筛的结构未发生变化,仍具有有序孔道结构。TsOH-SBA-15催化剂对冰乙酸和正丁醇的酯化反应具有较高的活性,正交实验结果为:反应时间80 m in,n(冰乙酸)∶n(正丁醇)=1∶1.2,催化剂用量为冰乙酸质量的5%,此时酯化率可达到95%。     

Miscibility and hydrogen bonding in blends of poly(vinyl acetate) with phenolic resin

The miscibility of phenolic resin and poly(vinyl acetate) (PVAc) blends was investigated by differential scanning calorimeter (DSC), Fourier transform infrared spectroscopy (FT-IR) and solid state ¹³C nuclear magnetic resonance (NMR). This blend displays single glass transition temperature (T_g) over entire compositions indicating that this blend system is miscible in the amorphous phase due to the formation of hydrogen bonding between hydroxyl groups of phenolic resin and carbonyl groups of PVAc. Quantitative measurements on fraction of hydrogen-bonded carbonyl group using both ¹³C solid-state NMR and FT-IR analyses result in good agreement between these two spectroscopic techniques. According to the proton spin-lattice relaxation time in the rotating frame (T_1ρ^H), the phenolic/PVAc blend is intimately mixed on a scale less than 2-3 nm. Furthermore, the inter-association equilibrium constant and its related enthalpy of phenolic/PVAc blends were determined as a function of temperatures by infrared spectra based on the Painter-Coleman association model.     

Influence of hydrogen donors on peroxide‐initiated melt grafting of vinylsilane to poly(ethylene‐co‐vinyl acetate)

A technique has been examined for reducing the extent of crosslinking resulting from 1,1‐di(t‐butylperoxy)‐3,3,5‐trimethylcyclohexane (L‐231) initiating melt grafting of vinyltriethoxysilane (VTEOS) onto poly(ethylene‐co‐vinyl acetate) (EVA). Using measurements of crosslink density and VTEOS conversion, a standard of selectivity for the EVA/VTEOS/L‐231 system at 145 °C was defined and used to assess the influence of a range of additives (0.25 mol per mole VTEOS). The data indicated that compounds such as 4‐nonene, N,N‐dimethylaniline, and cumene improve reaction selectivity, whereas dodecane and cyclohexyl acetate have no effect. A strong correlation between the minimum C? H bond dissociation energy and the influence of a given compound is evident, suggesting that a labile C? H bond is the key element of an effective additive. A mechanism of additive function on the basis of hydrogen atom donation is proposed. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2397–2402, 2002     

乙酸乙酯法竹材木质素分离技术研究

在一定的温度、压力下,利用乙酸乙酯溶解竹材中的木质素,乙酸乙酯通过蒸馏回收后,可以反复利用;而得到的高纯度木质素是重要的化工原料,整个过程形成一个封闭循环系统,基本上无三废排放。研究结果表明:乙酸乙酯浓度为80%,液固比为10∶1,反应温度155℃下保温3h,木质素的分离效果最佳。     

Sex pheromone components isolated from china corn borer,Ostrinia furnacalis guenée (lepidoptera: Pyralidae), (E)- and (Z)-12-tetradecenyl acetates

The sex pheromone components from the corn borer spreading widely in China,Ostrinia furnacalis Guenée, have been identified as (E)-and (Z)-12-tetradecenyl acetates (E andZ12–14 Ac). The ratio ofE isomer toZ isomer was 53 47. Traps containing 1 × 10^–7–1 × 10^–5 g of these compounds captured more males than did live females or their tip extract (3–6 female equivalents). Tetradecyl acetate (14 Ac) was also identified in the tip extract. Its quantity was about 1.8 times the sum of the other two isomers. However, including this compound in its natural ratio in pheromone traps resulted in a decrease in trap catches (P< 0.05).