【正文】
tassium borohydride is deposed by addition of dilute sulfuric acid,and the volume of hydrogen thus liberated id measured carboxyl content is consumed borohydride . 20 How to analyze the units containing double bonds? Two methods have been used with some success . One is based on the catalytic hydrogenation of the double bonds in cinnamaldehyde and cinnamyl alcohol structures and measurement of the UV difference spectrum. The other uses the difference in UV adsorption in neutral and alkaline solution to measure the amount of phenolic stilbene structures. 21 How to analyze those Carboxylic and Sulfonic Acid Groups? Both the residual lignin in kraft pulps and the soluble lignin in kraft black liquors contain carboxyl groups. Spectroscopic methods have been used for the determination of carboxylic acid groups in isolated lignin samples. 22 The residual lignin in sulfite pulps contains sulfonic acid groups that can be determined selectively in the presence of carboxyl for the soluble lignosulfonate samples isolated from sulfite spent liquors, perhaps the most reliable methods for their determination are those based on conductometric titration. 23 針、闊葉材木質素主要官能團的比較 24 二、木素的結構單元 ? 木素的基本結構單元為苯丙烷( phenyl propane unit),可用 C9表示。 25 (一)氧化分解法 ? 高錳酸鉀氧化 P87 O HO C H3C O HHH CC H2O H67HH C C HOO C HC HOH2CH3C8O H C C H C H2O HC H2O HOOCH3C910OH3C12H OC H2O HH3C13OCOC HO C HOH3CHC H3C HO HOC HH3CC HH2C O H1516C a r b o h y d r a t eC H2O HO HO C H3H C 14OC HOC HC H2OCO C H3O1. K M n O4 2.H2O2 O x i d a t i o nO x i da t i onA l k l y l a t i on3.4.M e t h y l a t i on O C H2C H3O C H3C O2C H3O C H2C H3O C H3C O2C H3C H3O2CO C H2C H3O C H3C O2C H3H3C OC H3C H2OC H3O2C26 ? 硝基苯氧化分解 ( nitrobenzene oxidation) P88 ? 分解產物中含有大量的 香草醛 ,體現(xiàn)了木素的芳香性。 ? 不同原料的木素其硝基苯氧化產物不同,每種氧化產物的含量也不一樣。 ? 針葉材 主要產物有五種,都有愈瘡木基,說明針葉材木素的單體是愈瘡木基丙烷單元。 ? 草類 木素 乙醇解產物有十五種,除上述十種外,還有五種對 羥基苯基結構的產物,說明草類木素是由愈瘡木基丙烷、紫丁香基丙烷和對 羥基苯丙烷單元構成。 30 不同原料木質素基本結構單元的比較 31 ? 不同原料木素基本結構單元的相對含量 ? 說明了為什么闊葉木中甲氧基含量高于針葉木。 ? 縮合型( condensed type)和非縮合型( uncondensed type)聯(lián)接 35 Guaiacyl propane R, H R, O, H C C C O 1 OCH3 6 5 4 3 2 α β γ 36 37 CCCCOCCCOCOβ O 4α O 4CCCOβ 1CCCOβ βCCCOCCCOβ 5O CCCOCCCOCCCO5 5CCCO4 O 5C C38 – 是最重要的木素分子結構單元( 烷基芳基醚鍵 ) – 占苯丙烷單元的 20%- 30% – 1HNMR光譜推測 ? 樺木 : 40%- 50%的木素; ? 山毛櫸 : 30- 50%的木素; CCCCOβ O 4C COO C H 3O C H 3 βO4連接 39 β5連接 ?苯基香豆?jié)M結構 典型的 β5連接結構 ?苯基香豆?jié)M結構 :甲氧基 = CCCOβ 5COCCO C H3H CCCOCOCCO C H3O C H3O C H340 – 含量為 % CCCOβ 1OO C H3O C H3 β1連接 41 – 黑液木素中: – 云杉磨木木素中: CCCO5 5CCCOO C H3H3C O 55連接 聯(lián)二苯 42 云杉: 樺木: 山毛櫸: CCCOCCCO4 O 5H3C OO C H3 4O5連接 43 – 闊葉木 針葉木 – 樺木木素 : - – 云杉木素 : CCCOβ βCCCOO C H3O C H3 ββ連接 44 β6連接和 β2連接 – 樺木木素 : - – 云杉木素 : - CCCOβ 6CCCOO C H3O C H3CCCOβ