细胞壁多糖与DHP间苯甲酯键的高效形成及纸页的增强
发布时间：2018-07-15 14:28
【摘要】：纸张纤维间的氢键具有键能低和容易被水分子所破坏的特点,大大限制了纸张的应用范围。传统纸张生产过程中由于采用含甲醛胶黏剂而引起甲醛污染。植物体内木素-碳水化合物复合体(LCC)结构赋予木材细胞壁高的机械强度。本论文模拟植物体内LCC结构中苯甲酯键的生物合成过程,研究了木素脱氢聚合物(DHP)与细胞壁多糖间苯甲酯键的高效生成以及对纸张强度的增强。本论文首先研究反应体系pH值对葡萄糖醛酸与DHP生成过程中产生的亚甲基醌间加成反应的影响。以松柏醇葡萄糖苷(coniferin)为木素前驱物,在漆酶/β-葡萄糖苷酶/O2组成的木素氧化酶催化下,使松柏醇葡萄糖苷分别在不同的pH值条件下(pH=4.0,pH=5.0,pH=6.0,pH=7.0)与葡萄糖醛酸发生聚合反应,生成DHP以及DHP-葡萄糖醛酸复合体。采用红外光谱、13C-NMR、HPLC、离子色谱和元素分析相结合的方法分析产物结构和苯甲酯键数量。结果表明:松柏醇葡萄糖苷与葡萄糖醛酸作用生成DHP-葡萄糖醛酸复合体,pH值对苯甲酯键生成有重要影响,pH4.0条件有利于苯甲酯键的生成。pH6.0的条件下与葡萄糖高效加成反应;在中性条件下与蛋白质中氨基酸能够产生高效加成反应,生成DHP-蛋白质复合体。为了进一步研究植物细胞壁多糖与DHP上亚甲基醌的反应性能,本论文采用TEMPO/NaClO/NaBr氧化体系氧化法,使α-纤维素和葡甘聚糖富含适量的羧基。然后以侧链α位带13C标记的松柏醇葡萄糖苷为木素前驱物,在酸性(pH=4.0)和中性(pH=7.0)条件下与氧化后α-纤维素和葡甘聚糖发生聚合反应,生成DHP-纤维素复合体和DHP-葡甘聚糖复合体,采用红外光谱、13C-NMR进行分析。结果表明:TEMPO/NaClO/NaBr氧化体系在α-纤维素和葡甘聚糖上成功导入适量的羧基,α-纤维素和葡甘聚糖的羧基在pH4.0条件下易于与DHP生成苯甲酯键结构。在以上机理研究的基础上,以未漂白针叶木浆为研究对象,采用TEMPO/NaClO/NaBr体系对其进行氧化。然后研究DHP与富含羧基的植物纤维的聚合和抄成纸张后的干湿强度影响。结果表明:pH4.0条件下松柏醇葡萄糖苷在漆酶体系作用下生成D H P,D H P在生成过程中与纤维上的羧基生成大量的苯甲酯键;苯甲酯键对纸张的干、湿强度都有提高,尤其对湿强度的提高最为明显。松柏醇葡萄糖苷较合理用量是1 0%,纸浆纤维上的羧基合适含量是2 6 3.3 m m o l/k g,在此条件下,纸张的干抗张指数从6 2.7 6 N·m/g提高到6 5.0 1 N·m/g;湿抗张指数从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 伪 -cellulose and glucomannan rich in carboxyl groups. Then the 伪 -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 伪 -cellulose and glucomannan were polymerized with oxidized 伪 -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 伪 -cellulose and glucomannan were successfully introduced into the oxidation system of% TEMPO / NaClO / NABR, and the carboxyl groups of 伪 -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.
【学位授予单位】：湖北工业大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：TS727
本文编号：2124378
[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 伪 -cellulose and glucomannan rich in carboxyl groups. Then the 伪 -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 伪 -cellulose and glucomannan were polymerized with oxidized 伪 -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 伪 -cellulose and glucomannan were successfully introduced into the oxidation system of% TEMPO / NaClO / NABR, and the carboxyl groups of 伪 -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.
【学位授予单位】：湖北工业大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：TS727
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