萜烯邻苯二酚树脂-生漆共聚涂料研究(Ⅱ)--萜烯邻苯二酚树脂-生漆共聚涂料的合成及性能研究

以萜烯树脂、邻苯二酚为基本原料,在催化荆作用下合成萜烯邻苯二酚树脂;再将此树脂与生漆通过聚合反应生成萜烯邻苯二酚树脂-生漆共聚涂料,探讨了制备萜烯邻苯二酚树脂-生漆共聚涂料的工艺条件及各种性能,并测定了催化剂对共聚涂料膜性能的影响。实验结果表明,加入催化荆后缩短了萜烯邻苯二酚树脂-生漆共聚涂料的干燥时间,最佳条件下,反应时间可缩短3h．干燥时间可缩短24h,并改进了该涂料的膜附着力、硬度、厚度和耐汽油性等性能。讨论了萜烯邻苯二酚树脂与生漆的不同质量比和不同反应时间对此共聚涂料性能的影响,并进行了紫外光谱分析测试,结果表明生漆中的邻苯二酚和萜烯邻苯二酚树脂中的邻苯二酚都参与了聚合反应。得到最佳漆膜的条件为,用汽油作溶剂,按萜烯邻苯二酚树脂与生漆的质量比1：4,加入总溶质l％(质量分数)的催化荆,室温反应5．5h,涂膜后干燥3d。     

萜烯邻苯二酚树脂一生漆共聚涂料研究（Ⅰ）——萜烯-邻苯二酚功能基树脂的分离提纯

以萜烯树脂和邻苯二酚为原料,合成了萜烯-邻苯二酚树脂.采用柱层析法分离萜烯树脂和萜烯-邻苯二酚树脂,分别采用中性氧化铝和强碱性阴离子交换树脂作固定相,汽油、乙醇、NaOH-乙醇溶液作洗脱剂对萜烯树脂和萜烯-邻苯二酚树脂进行分离提纯.通过对洗脱液进行紫外光谱分析,表明用中性氧化铝作固定相,分别用汽油、乙醇和NaOH-乙醇溶液洗脱,能较好地分离萜烯树脂和萜烯-邻苯二酚树脂.     

萜烯邻苯二酚树脂-生漆共聚涂料研究(Ⅰ)--萜烯-邻苯二酚功能基树脂的分离提纯

以萜烯树脂和邻苯二酚为原料,合成了萜烯-邻苯二酚树脂.采用柱层析法分离萜烯树脂和萜烯-邻苯二酚树脂,分别采用中性氧化铝和强碱性阴离子交换树脂作固定相,汽油、乙醇、NaOH-乙醇溶液作洗脱剂对萜烯树脂和萜烯-邻苯二酚树脂进行分离提纯.通过对洗脱液进行紫外光谱分析,表明用中性氧化铝作固定相,分别用汽油、乙醇和NaOH-乙醇溶液洗脱,能较好地分离萜烯树脂和萜烯-邻苯二酚树脂.     

硫酸-离子液体复合催化剂催化松香聚合反应工艺的研究

首次将3种硫酸-离子液体复合催化剂[H2SO4-（C2mim）BF4、H2SO4-（C4mim）BF4和H2SO4-（C8mim）BF4]用于催化松香聚合反应中，H2SO4-（C4mim）BF4和H2SO4-（C8mim）BF4均显示出很好的催化活性。以H2SO4-（C8mim）BF4为代表，详细考察了不同溶剂、H2SO4用量、反应温度和反应时间等因素对反应结果的影响，得到较佳的工艺条件：松香和甲苯质量比1：1，催化剂用量为松香质量的30％．反应温度70℃，反应时间4h。在该条件下，得到的聚合产物软化点为135℃，酸值为142mg/g并对H2SO4-（C8mim）BF4复合催化剂的重复使用性能进行了考察，该复合催化剂克服了传统催化剂的一些缺点，既简化了产物的分离。又可以重复使用。     

大茴香油聚合树脂的合成及应用研究

以乙酸乙酯为溶剂 ,无水AlCl3作催化剂 ,由大茴香油在室温下反应 4h ,合成了聚合物大茴香油聚合树脂 (简称PAOR) ,凝固点降低法测定了树脂的分子质量 ,对树脂进行IR、UV测试分析 ,并考察了树脂对桔皮色素的柱层析吸附分离性能。结果表明 ,合成树脂的分子质量约 1.0 2× 10 3,PAOR在 965cm- 1吸收峰减弱 ,在 70 0～ 80 0cm- 1之间出现 3个新峰 ;PAOR紫外最大吸收峰蓝移 11nm ,表明大茴香油中的双键参与了聚合反应 ,产物中存在芳环三取代物。讨论了反应机理 ,PAOR对桔皮色素有良好的吸附作用 ,树脂的重复使用性较好。     

萜烯酚树脂性能研究

由中国脂松节油和苯酚共缩聚得到的萜烯酚树脂的性能、结构。实验结果指出，萜烯酚树脂的密度Ｄ＾２５４＝１．０４，碘值（Ⅰ％）１８％～２０％，酚羟基值（ＯＨ％）为１．３％。软化点１００．０～１３５．０℃的萜烯酚树脂，ＶＰＯ测定的分子量为６００～６３０。不同软化点树脂在稀浓度下表现等同的溶液粘度，较高浓度时，软化点高溶液粘度较大。根据对萜烯酚树脂性能和ＩＲ的研究结果，讨论了树脂的可能形成机理。     

水溶性钯-膦配合物催化松香加氢反应的研究

制备并表征了具有温控功能的膦配体脂肪醇聚氧乙烯醚亚磷酸邻苯二酚酯(FAPEPP),将其与钯的配合物用于催化松香加氢反应的研究,考察了反应时间、反应温度、氢气压力、催化剂用量等因素对反应的影响.在松香5g、m(松香): m(甲苯): m(水)1: 2: 2、氯化钯0.090%、n(氯化钯): n(膦配体)1: 10、氢气压力5MPa,反应温度160℃,反应时间3h的较佳工艺条件下,产物氢化松香中枞酸的质量分数小于1%,去氢枞酸的质量分数5.6%,符合GB/T 14020-2006国家标准;并对催化剂的重复使用性能进行了考察,催化剂相不经过处理直接重复使用5次后,产品氢化松香仍然符合国家标准中关于枞酸和去氢枞酸的指标要求.     

松香醇聚氧乙烯醚的合成及其结构与性能关系研究

首次系统研究松香醇与环氧乙烷的加成反应。在低温条件下，此反应属于离子对机理，高温下为离子机理，得出较适宜的反应条件：催化剂KOH，用量为松香醇用量的0.5%-0.6%，温度150℃，压力0.2-0.3MPa，脱水条件100-140℃/1.33kPa,30min。测定了合成产品的表面物理化学性能：表面张力（δ）达到33.0-39.8dyn/cm；临界胶束浓度（CMC）在10^-4数量级；钙皂分散指数（LSDP）5.1%-13.5%；对松节油乳化力（EP）为64-185S；浊点（CP）26-77℃；HLB值8.9-16.2。研究了环氧乙烷聚合度（n）对产品表面物理化学性能的影响：随着n的增加，δ先下降，然后逐渐上升，CMC、LSDP、CP、HLB值逐渐升高，EP先升高，到n=10时，变化趋于平缓。     

利用不同工艺催化大豆油裂解制备可再生燃料油

以大豆油为原料,考察了间歇式反应工艺,旋转锥式反应工艺和精馏反应工艺3种裂解工艺对裂解产物性能的影响,并探讨了多种催化剂的催化裂解效果。结果表明,优选反应条件为:催化剂质量分数5%精馏温度320～350℃,裂解温度460～480℃,滴加速度35 g/h。在碱性催化剂Na2CO3的参与下,利用精馏反应工艺裂解大豆油产物的分子组成得到优化。通过红外光谱、气质联用和凝胶色谱对裂解产物的分析表明,产物具有较低的平均相对分子质量,主要成分为C24以下的烷烃、烯烃、醛、羧酸等。从化学组成及燃料性能来看,裂解产物的性质与石化柴油相近。     

6-(4-甲基-3-戊烯基)-5,8-二氢-1,4-萘二酚的合成研究

以月桂烯与对苯醌为原料,合成了萘二酚衍生物,采用GC-MS、熔点测定、红外光谱和1H NMR等手段对实验产物进行了鉴定,确证产物为6-(4-甲基-3-戊烯基)-5,8-二氢-1,4-萘二酚。利用单因素试验研究了催化剂种类、催化剂用量、溶剂种类、反应温度、反应物物质的量之比和反应时间对产物得率的影响,得到适宜的工艺条件为:n(月桂烯)∶n(对苯醌)1∶1,催化剂为氯化锌,其用量为对苯醌质量的15%,溶剂为乙酸乙酯,反应温度80℃,反应时间10 h。在上述条件下,反应选择性较高,产物得率为81.0%。     

Decomposition and nutrient loss from prunings of different contour hedgerow species in tea plantations in the sloping highlands of Sri Lanka

Contour hedgerows of multipurpose tree species in the sloping tea lands of Sri Lanka are expected to reduce soil erosion and also add significant amounts of plant nutrients to the soil via periodic prunings. The objective of this experiment was to characterize the biomass decomposition pattern and quantify the amount of nutrients added through prunings of six tree species (Calliandra calothyrsus, Senna spectabilis, Euphatorium innulifolium, Flemingia congesta, Gliricidia sepium and Tithonia diversifolia) currently being used in hedgerows associated with tea. Withered leaf and stem prunings (50 g) were enclosed in 2-mm litter bags, placed at 5-cm depth and retrieved after one, three, six, nine and 12 weeks. Loss of initial dry weight, N, P and K was measured. Single exponential decay function adequately described both dry weight and nutrient loss. Tree species differed significantly in their rate of breakdown with decomposition constants (k) varying from 0.0299 to 0.2006 week⁻¹ for leaves and from 0.0225 to 0.0633 week⁻¹ for stems. Gliricidia showed the highest k for leaves with the rest in the following descending order: Senna > Tithonia ≥ Euphatorium > Calliandra > Flemingia. A similar pattern was observed for loss of all nutrients with Calliandra and Flemingia always having lower k values than the rest. Although N immobilization was not observed, immobilization of P and K was observed during the first week of incubation in some species, particularly in stem prunings. Annual biomass of prunings differed significantly between tree species in the following descending order: Calliandra > Senna > Flemingia > Tithonia > Gliricidia > Euphatorium. Calliandra added the greatest amount of nutrients annually to the soil with Euphatorium adding the least. Calliandra prunings provided the annual total K requirement and 49% of the N requirement of mature tea. However, none of the species provided more than 5% of the P requirement. It is concluded that among the tree species tested, Calliandra and Flemingia are the most suitable for contour hedgerows in tea plantations of this agroclimatic region because of their higher soil nutrient enrichment capacity and slower decomposition rates which would minimize leaching losses. This revised version was published online in June 2006 with corrections to the Cover Date.     

Effects of Seed Weight and Seed Type on Early Seedling Growth of Pinus sylvestris under Harsh and Optimal Conditions

The effects of seed weight and seed type on seedling growth of Pinus sylvestris (L.) were studied by seeding individually weighed orchard and stand seed in different mixtures under harsh (direct seeding in field) and optimal (seeding in nursery) conditions. In the nursery experiment an increase in the seed weight from 3 to 7 mg increased the seedling height by 10-27% and total weight by 27-113%, and decreased the height/diameter ratio by 5-6% after 2 yrs. With elimination of seed weight effects, orchard seedlings were 2% taller than stand seedlings in year 2. Without elimination of seed weight effects, orchard seedlings were 7-13% taller. In the field experiment an increase in the seed weight from 3 to 7 mg increased seedling height by 18-65%, stem volume by 81-274% and the number of top-buds by 23-34% in year 5. After elimination of seed weight effects, orchard seedlings were 7-13% taller than stand seedlings and without elimination of seed weight effects 20-21% taller after 5 yrs. Even after elimination of both seed weight and genetic effects orchard seedlings were 3-9% larger than stand seedlings in the field experiment. In conclusion, the influence of seed weight and seed type on growth traits and slenderness is highly significant and the influence seems to be greater in harsh conditions.     

Modelling of adequate pretwist for obtaining straight timber

Abstract

Wood in general and wooden studs in particular are often distorted owing to uneven shrinkage during the drying process in the sawmill. Twist is often the most detrimental of all types of distortion, and it is caused by spiral grain in combination with variations in moisture content. For sawmills, the objective is to produce dried, straight boards, and one method of dealing with boards with excessive spiral grain is to sort them out and then dry them in a pretwisted position to obtain straight boards after drying. A model using the finite element (FE) method for the simulation of drying twist distortions was first calibrated against laboratory experiments in which boards were dried with and without restraints and pretwists. After the calibration, the FE results were compared with industrial test results for boards that were dried without restraints or with restraints with zero pretwist, i.e. straight restraints. The FE model used an elastic–ideally plastic material model to obtain permanent deformations. The calibration was to set the yield stresses so that there was a good match between FE results and results from the laboratory experiments. The comparison between the industrial test results and the FE results showed that the FE model is capable of realistic simulations of drying boards with and without restraints and presumably also pretwists.     

Potential to harness superior nutritional qualities of exotic baobabs if local adaptation can be conferred through grafting

Baobab leaves form an important part of the local diet in Sahel countries and elsewhere in Africa. Existing leaf nutritional data and agroforestry performance information are based solely on Adansonia digitata L., the baobab of continental Africa. The introduction potential of Adansonia species from the center of diversity in Madagascar and from Australia remains untapped. To assess this potential, the mineral contents and B₁ and B₂ vitamin levels of dried baobab leaves were determined for five-year old trees of A. digitata, A. gibbosa (A. Cunn.) Guymer ex D. Baum, A. rubrostipa Jum. & H. Perrier (syn. A. fony Baill.), A. perrieri Capuron and A. za Baill. grown in an introduction trial in Mali. Nutritional data were evaluated against survival and vigor to identify promising germplasm. Leaf vitamin and crude protein contents were highest in the Madagascar species, especially A. rubrostipa (B₁ 88 mg 100 g⁻¹, B₂ 187 mg 100 g⁻¹, protein 20.7% dry weight). However, the local species far outperformed the introductions in survival, tree height, basal diameter and resistance to termites. We suggest grafting as a way of harnessing the vigor of well-adapted local baobab varieties to the superior nutritional profiles of A. rubrostipa and others. Cross-species grafting tests in Adansonia were successful, thus creating new agroforestry possibilities with different scion/rootstock combinations.     

Biogeochemical impacts of clearfelling and reforestation on blanket-peatland streams: II. major ions and dissolved organic carbon

Streams and drains in blanket-peatland forest in western Ireland were sampled weekly over 5 years, 1996–2000, using continuous, depth-proportional passive sampling. Analysis was for pH, alkalinity by Gran titration, anions by IC, metals by ICP, aluminium speciation by loaded-resin exchange, and dissolved organic carbon (DOC) by absorbance at 320 nm.

Effects of felling are identified graphically from two forest drains whose catchments (both about 1 ha) were clearfelled, and partial clearfelling of one larger catchment (somewhat over 1 km²), in summer 1999. Calcium concentrations and alkalinity were increased in the drain- and streamwater from the felled areas. The pH was increased in drains, while in the larger stream, pH range decreased while the mean increased. Phosphorus increased markedly with clearfell, in the absence of recent fertilising, and also increased with fertilising; these results are reported in an accompanying paper. Ammonium-nitrogen concentrations were increased in the two drains with felling, and temporarily decreased in the larger stream. Nitrate increased in some cases. Potassium and manganese concentrations also increased. Concentrations of DOC and organic monomeric aluminium increased gradually, subject to a continuing strong annual cycle. There were no clearfelling effects on concentrations of solphate, suspended solids or inorganic monomeric aluminium. In the two drains (fully clearfelled), concentrations of sodium, chloride and magnesium, and conductivity, were all reduced after felling. Fertilising effects other than for phosphorus were indistinct.

Effects of the combined clearfell–reforestation treatment were testable statistically, using randomised intervention analysis, between two larger streams (1 km²) as a treatment–control comparison. There were statistically significant positive responses in streamwater concentrations of nitrate, potassium, calcium, DOC and aluminium fractions. The implications for management practice depend on whether the loss of nutrients is sustainable for future crop productivity, and whether critical limits and loads of receiving ecosystems are exceeded.     

Effect of Drought on Growth and Mortality of Actively Growing Norway Spruce Container Seedlings Planted in Summer

Survival, root egress and height growth of 13-month-old actively growing Norway spruce ( Picea abies (L.) Karst.) container seedlings exposed to preplanting drying treatments (0, 4, and 8 days) and postplanting drought periods (1, 2, 3, and 4 weeks) were studied in the field between 5 July and 18 August 1999. The mortality of seedlings increased and the height growth and root egress decreased throughout the postplanting drought period. Postplanting performance was also affected by preplanting drying treatments. The results indicate that no risk of excessive mortality and growth restrictions occurs when actively growing seedlings are planted in summer, provided that seedlings are well watered before planting and the drought period does not exceed 3 weeks.     

Rehabilitation of diseased cacao fields in Peru through shade regulation and timing of biocontrol measures

The objective of this case study was to test the effectiveness of biocontrol for the rehabilitation of abandoned, diseased (moniliasis, witches' broom and black pod) cocoa and to develop testable hypotheses regarding the effect of shade and biocontrol timing. Three trial fields differed in their shade regimes. Biocontrol was administered starting either at flowering or pod filling. Disease incidence and yield were compared with cultural control alone. Biocontrol reduced moniliasis from 49% to 25%, independent of the shading regime and application time. Witches' broom was most severe without shade and unaffected by biocontrol. No significant effects on black pod were observed. Although biocontrol increased percentage healthy fruit independent of shading and timing, only the shaded plot with biocontrol from flowering onwards responded with increased yield. Our hypothesis is: 'In the rehabilitation of abandoned cacao, only fields under sustainable shade management and early onset of biocontrol can realise their production potential.' This revised version was published online in June 2006 with corrections to the Cover Date.     

Growth of Phlebiopsis gigantea in wood of seven conifer species

Heterobasidion parviporum and Heterobasidion annosum are widely distributed root‐rot fungi that infect conifers throughout Europe. Infection of conifer stumps by spores of these pathogens can be controlled by treating fresh stumps with a competing non‐pathogenic fungus, Phlebiopsis gigantea. In this study, growth of three Latvian strains of P. gigantea and the biological control agent ‘Rotstop’ strain was evaluated in stem pieces of Norway spruce, Scots pine, lodgepole pine, Douglas‐fir, Weymouth pine, Siberian larch and Sitka spruce. The growth rates of one H. parviporum and one H. annosum isolate were also measured in the same stem pieces. The growth rate of P. gigantea varied greatly in wood of different conifer species. It was higher in the three pine species, lower in Norway spruce and lowest in Sitka spruce and Siberian larch, and in Douglas‐fir, this fungus did not grow. The largest area of wood occupied by P. gigantea was in lodgepole pine. Growth of Latvian isolates of P. gigantea in the wood of Pinus and Picea species was comparable to that of the Rotstop isolate. Consequently, stump treatment with local P. gigantea isolates should be recommended. However, our results suggest that Douglas‐fir stump treatment against Heterobasidion by P. gigantea may be ineffective and other stump treatment methods should be considered.     

Growth of Mixed Birch-Coniferous Stands in Relation to Pure Coniferous Stands at Similar Sites in South-eastern Norway

Mean age, mean and top heights and yield were studied in 20 mixed stands of birch ( Betula pubescens Ehrh. and B. pendula Roth) and Picea abies (L.) Karst. and nine mixed stands of birch and Pinus sylvestris L. in south-eastern Norway. Each mixed stand and the adjacent pure coniferous stand (control) were growing under the same site conditions and had not been commercially thinned. There were no significant differences in mean age at breast height or in top heights between birch and conifers in the mixed stands, while mean height was significantly higher for birch than for spruce. A growth index was calculated based on total volume and age at breast height. For the spruce sites the growth in young mixed stands (birch < 17 m) was superior to that of pure spruce, while the difference was insignificant in older stands. The growth index correlated positively with the ratio between generatively and vegetatively regenerated birch trees, and negatively with the age of the oldest species in the mixture and with site quality. For the pine sites there was no significant difference in the growth index between mixed birch-pine and pure pine stands. A mixture effect of birch on the volume yield of spruce or pine could not be demonstrated.     

Defoliation by the Needle-shortening Pine Gall Midge,Thecodiplosis brachyntera,on Pines in Central Sweden

An outbreak of the needle-shortening pine gall midge, Thecodiplosis brachyntera , occurred on Scots pine, Pinus sylvestris (L.) and lodgepole pine, P. contorta (Dougl.) in central Sweden during 1995-1998. The larval feeding of T. brachyntera kills current-year needles and heavy infestation causes severe defoliation. A pattern of fluctuating defoliation among years and sites was found on both pine species. Defoliation was evenly distributed in the crown of P. sylvestris during years of high as well as low infestation; apical whorls had as much defoliation as basal whorls. In P. contorta , however, there was a tendency for defoliation to be concentrated on branches in the most apical whorls. Growth ring increments on P. sylvestris with high levels of defoliation (71%) did not differ from trees with moderate levels (26%) of defoliation. Shoot lengths were significantly shorter, however, on heavily infested trees the year after defoliation.