【摘要】：紙張纖維間的氫鍵具有鍵能低和容易被水分子所破壞的特點,大大限制了紙張的應(yīng)用范圍。傳統(tǒng)紙張生產(chǎn)過程中由于采用含甲醛膠黏劑而引起甲醛污染。植物體內(nèi)木素-碳水化合物復(fù)合體(LCC)結(jié)構(gòu)賦予木材細胞壁高的機械強度。本論文模擬植物體內(nèi)LCC結(jié)構(gòu)中苯甲酯鍵的生物合成過程,研究了木素脫氫聚合物(DHP)與細胞壁多糖間苯甲酯鍵的高效生成以及對紙張強度的增強。本論文首先研究反應(yīng)體系pH值對葡萄糖醛酸與DHP生成過程中產(chǎn)生的亞甲基醌間加成反應(yīng)的影響。以松柏醇葡萄糖苷(coniferin)為木素前驅(qū)物,在漆酶/β-葡萄糖苷酶/O2組成的木素氧化酶催化下,使松柏醇葡萄糖苷分別在不同的pH值條件下(pH=4.0,pH=5.0,pH=6.0,pH=7.0)與葡萄糖醛酸發(fā)生聚合反應(yīng),生成DHP以及DHP-葡萄糖醛酸復(fù)合體。采用紅外光譜、13C-NMR、HPLC、離子色譜和元素分析相結(jié)合的方法分析產(chǎn)物結(jié)構(gòu)和苯甲酯鍵數(shù)量。結(jié)果表明:松柏醇葡萄糖苷與葡萄糖醛酸作用生成DHP-葡萄糖醛酸復(fù)合體,pH值對苯甲酯鍵生成有重要影響,pH4.0條件有利于苯甲酯鍵的生成。pH6.0的條件下與葡萄糖高效加成反應(yīng);在中性條件下與蛋白質(zhì)中氨基酸能夠產(chǎn)生高效加成反應(yīng),生成DHP-蛋白質(zhì)復(fù)合體。為了進一步研究植物細胞壁多糖與DHP上亞甲基醌的反應(yīng)性能,本論文采用TEMPO/NaClO/NaBr氧化體系氧化法,使α-纖維素和葡甘聚糖富含適量的羧基。然后以側(cè)鏈α位帶13C標(biāo)記的松柏醇葡萄糖苷為木素前驅(qū)物,在酸性(pH=4.0)和中性(pH=7.0)條件下與氧化后α-纖維素和葡甘聚糖發(fā)生聚合反應(yīng),生成DHP-纖維素復(fù)合體和DHP-葡甘聚糖復(fù)合體,采用紅外光譜、13C-NMR進行分析。結(jié)果表明:TEMPO/NaClO/NaBr氧化體系在α-纖維素和葡甘聚糖上成功導(dǎo)入適量的羧基,α-纖維素和葡甘聚糖的羧基在pH4.0條件下易于與DHP生成苯甲酯鍵結(jié)構(gòu)。在以上機理研究的基礎(chǔ)上,以未漂白針葉木漿為研究對象,采用TEMPO/NaClO/NaBr體系對其進行氧化。然后研究DHP與富含羧基的植物纖維的聚合和抄成紙張后的干濕強度影響。結(jié)果表明:pH4.0條件下松柏醇葡萄糖苷在漆酶體系作用下生成D H P,D H P在生成過程中與纖維上的羧基生成大量的苯甲酯鍵;苯甲酯鍵對紙張的干、濕強度都有提高,尤其對濕強度的提高最為明顯。松柏醇葡萄糖苷較合理用量是1 0%,紙漿纖維上的羧基合適含量是2 6 3.3 m m o l/k g,在此條件下,紙張的干抗張指數(shù)從6 2.7 6 N·m/g提高到6 5.0 1 N·m/g;濕抗張指數(shù)從2.7 5 N·m/g提高到1 7.0 6 N·m/g,提高了6.2倍。
[Abstract]:The hydrogen bond between fibers is characterized by low bond energy and easily destroyed by water molecules, which greatly limits the application of paper. Formaldehyde pollution is caused by the use of formaldehyde adhesive in traditional paper production. The structure of lignin-carbohydrate complex (LCC) in plant endows wood cell wall with high mechanical strength. In this paper, we simulated the biosynthesis of phenylmethyl ester bond in plant LCC structure, and studied the efficient formation of lignin dehydrogenation polymer (DHP) and isophenyl methyl ester bond in cell wall polysaccharide, as well as the enhancement of paper strength. In this paper, the effect of pH on the addition of methylene quinone in the formation of glucuronic acid and DHP was studied. Under the catalysis of lignin oxidase composed of laccase / 尾 -glucosidase / O _ 2, the glucuronol glucoside was polymerized with glucuronic acid at different pH values (pH ~ (4.0) ~ (+) ~ (4.0) ~ (+) ~ (5.0) ~ (+) ~ (-) ~ (6.0) ~ (-1) ~ (-1) ~ (-1) using (coniferin) as lignin precursor in the presence of laccase / 尾 -glucosidase / 尾 -glucosidase / O _ (2). DHP and DHP- glucuronic acid complex were formed. The structure of the product and the number of phenyl methyl ester bond were analyzed by IR, 13C-NMR-HPLC, ion chromatography and elemental analysis. The results show that the pH value of the DHP- glucuronic acid complex has an important effect on the formation of phenyl methyl ester bond. The pH 4.0 condition is favorable for the addition reaction of benzene methyl ester bond with glucose at pH 6.0. DHP- protein complex can be formed by addition reaction with amino acids in protein under neutral conditions. In order to further study the reaction properties of plant cell wall polysaccharides with methylene quinone on DHP, the oxidation method of TEMPO / NaClO / NABR system was used to make 偽 -cellulose and glucomannan rich in carboxyl groups. Then the 偽 -site 13C-labeled cypress glucoside was used as the lignin precursor. Under the conditions of acid (pH = 4.0) and neutral (pH = 7.0), the 偽 -cellulose and glucomannan were polymerized with oxidized 偽 -cellulose and glucomannan to form DHP- cellulose complex and DHP- glucomannan complex. The results were analyzed by 13C-NMR. The results showed that the carboxyl groups of 偽 -cellulose and glucomannan were successfully introduced into the oxidation system of% TEMPO / NaClO / NABR, and the carboxyl groups of 偽 -cellulose and glucomannan were easy to form benzyl methyl ester bond structure with DHP at pH 4.0. Based on the above studies, unbleached softwood pulp was oxidized by TEMPO / NaClO / NABR system. Then the effects of DHP and carboxyl-rich vegetable fibers on the dry and wet strength of paper were studied. The results showed that under the condition of pH 4.0, cyperidol glucoside formed a large amount of phenyl methyl ester bond with carboxyl group of fiber in the process of producing D H Pu D H P, and the dry and wet strength of paper was improved by benzene methyl ester bond. Especially, the increase of wet strength is the most obvious. The proper dosage of cypress alcohol glucoside is 10 and the proper content of carboxyl group on pulp fiber is 263.3 m m o / kg. The dry tensile index of paper increased from 62.76 N / g to 65.01 N / g, and the wet tensile index increased from 2.75 N / g to 17.06 N / g, which increased 6.2 times.
【學(xué)位授予單位】：湖北工業(yè)大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：TS727

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