CN1341125A - 纤维素的选择性氧化方法 - Google Patents
纤维素的选择性氧化方法 Download PDFInfo
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- CN1341125A CN1341125A CN00804200.4A CN00804200A CN1341125A CN 1341125 A CN1341125 A CN 1341125A CN 00804200 A CN00804200 A CN 00804200A CN 1341125 A CN1341125 A CN 1341125A
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- oxidation
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- cellulose
- aldehyde
- compound
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Classifications
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
- D21H11/16—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only modified by a particular after-treatment
- D21H11/20—Chemically or biochemically modified fibres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
- C08B15/02—Oxycellulose; Hydrocellulose; Cellulosehydrate, e.g. microcrystalline cellulose
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
- D21C9/001—Modification of pulp properties
- D21C9/002—Modification of pulp properties by chemical means; preparation of dewatered pulp, e.g. in sheet or bulk form, containing special additives
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Biochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
- Materials For Medical Uses (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Multicomponent Fibers (AREA)
Abstract
一种纤维素的氧化方法,其中在有例如Mn、Fe、Cu的过渡金属与例如聚胺的络合物或氧化酶的情况下使用氧化剂将例如TEMPO的硝酰基化合物氧化,并且所得亚硝鎓离子用于选择性地将纤维素的6-羟基-亚甲基基团氧化成醛甲基和羧酸基团。
Description
本发明涉及使用亚硝鎓离子(氧代铵离子)氧化纤维素和纤维素衍生物的方法,该亚硝鎓离子是通过氧化硝酰基,特别是2,2,6,6-四甲基哌啶-1-氧基(TEMPO)而获得的。
从De Nooy在Synthesis 1996,1153-1174中的评论以及WO95/07303中已知一种通过化学方式再氧化TEMPO的方法。
Horton等人在Carbohydrate Research,26(1973)1-19中报道了通过光解6-叠氮基-6-脱氧-纤维素将纤维素氧化为6-醛基-纤维素的方法。
根据本发明发现,使用亚硝鎓离子可以氧化纤维素,特别是纤维素纤维,不需使用氯基氧化剂,而使用过氧化氢或氧作为最终氧化剂。使用能够氧化的酶或过渡金属与络合剂的过渡络合物作为中间氧化剂进行本发明的氧化。该氧化导致形成纤维素6-醛。这些醛可以其(半)缩醛形式和相关结构存在。
在以下的描述中,为了简便起见仅针对TEMPO,但应理解为,其它适宜的硝酰基,即缺少α-氢原子的有机硝酰基化合物,例如2,2,5,5-四甲基哌啶-N-氧基(PROXYL)、4-羟基-TEMPO、4-乙酰氨基-TEMPO及其衍生物和WO95/07303中所述的那些都可以替代TEMPO。这些二叔烷基硝酰基特别适宜选择性地将伯醇氧化成醛官能基,特别是在有不应被氧化的仲醇官能基的情况下。低位阻硝酰基,例如4,4-二甲基噁唑烷-N-氧基(DOXYL),适宜优先将仲醇氧化成酮官能基,例如在生产酮基纤维素或酮基淀粉时。这些活性氧化种为亚硝鎓离子(氧代铵离子>N+=O),它是就地通过氧化相应的羟胺和硝酰基生产的。如果需要的话,该反应可以分两步进行,首先生产亚硝鎓离子,其次氧化该醇官能基。
硝酰基的催化量,以纤维素的伯醇官能基计优选为0.1-25%wt,或者相对该伯醇优选为0.1-25mol%。还可以将该硝酰基固定,例如通过将4-羟基-TEMPO的羟基偶联到适宜载体上,或者以聚合硝酰基的形式如:-[(CH3)2C-NO-C(CH3)2-A-]n-,其中A可以为亚烷基和/或杂原子,n为例如10至高达几百的数。
本发明的方法使得纤维素葡糖酐单元氧化为相应醛。如果需要的话,还可以使用已知的氧化剂如次氯酸盐、亚氯酸盐、过氧化氢或者使用TEMPO-介导的氧化在更剧烈的条件下如40-80℃的高温或者长期与反应条件接触将该伯产物进一步氧化为相应羧酸。或者,使用相对低的pH(例如pH 3-7)、控制地加入氧化剂、降低氧浓度或者首先制备亚硝鎓离子溶液(两步法)可以增加醛/羧酸比。
适宜用本方法氧化的不同化合物由羟烷基纤维素如羟丙基纤维素、羟乙基纤维素组成。
伯醇官能基(6-CH2OH)氧化获得具有完整环系统的相应醛,并且如果需要的话,氧化成羧酸。这些产物可用作官能纤维素衍生物的中间体,其中醛基进一步与例如胺化物等反应。它们还可用作交联纤维素衍生物的中间体,其中醛基进一步与例如二胺试剂反应。
本发明所用的催化剂为过渡金属的络合物,即过渡金属与作为络合剂且具有一个或多个自由电子对的有机分子,特别是氮化物的配位化合物。适宜的氮化物包括氨基酸、菲咯啉和其它聚胺。与过渡金属形成络合物的聚胺应理解为包括至少两个胺氮原子并且这些氮原子被至少两个碳原子隔开的化合物。优选这些聚胺包括至少3个氮原子,这些氮原子被两个或多个,特别是2个或3个,尤其是2个,碳原子隔开。这些氮原子的剩余化合价优选与小烷基,特别是甲基相连。这些聚胺还可以有醚或醇官能基。这些聚胺可以为直链或环状。这些聚胺应为碱性,即不应含有酸官能基。可以使用的聚胺的例子为2,2’-联吡啶、2,2’-联吡咯、2-(二甲氨基甲基)吡啶、四甲基乙二胺、五甲基二乙三胺、1,4-二甲基哌嗪、1,4,7-三甲基-1,4,7-三嗪烷(triazonane)(=三氮杂环壬烷)、1,4,7-三甲基-1,4,7-三氮烯环壬烷、1,4,7,10-四甲基-1,4,7,10-四氮杂环十二烷、1,2-双(4-甲基-1-哌嗪基)乙烷、1,2-双(4,7-二甲基-1,4,7-三氮杂壬-1-基)乙烷、及其相应化合物,其中一个或多个所述甲基被例如乙基取代。还可以使用卟吩和其它卟啉和相应大环聚胺化合物。组氨酸和具有一附加氮原子的可比较的氨基酸、及其寡肽如组氨酸基组氨酸,为适宜的络合剂的其它例子。优选双哌啶基类、三嗪烷类的化合物和剩余化合价与甲基相连的胺。使这些络合物为中性所需的抗衡离子可以为普通抗衡离子,优选无毒的抗衡离子如氧离子、卤离子、高氯酸根离子、乙酰丙酮酸根离子、硝酸根离子、硫酸根离子等。
金属络合物中所用的过渡金属尤其包括周期表第四周期中从钒到锌的元素,优选锰、铁、钴、镍和铜,尤其是锰、铁、钴和铜。尽管不是优选,但是也可以使用更高周期的相应金属。这些金属络合物需要过氧化氢、烷基和芳(烷)基氢过氧化物(如叔丁基氢过氧化物)、氧或亚氯酸盐作为最终电子受体相对络合基中2-4个氮原子适宜地可以使用约1个金属原子。
可以催化量,例如相应于硝酰基化合物的约等摩尔量使用该金属络合物。相对于待氧化的醇,金属络合物的适宜量例如为1-25mol%。
本发明所用的催化剂也可以为氧化还原酶或者在有适宜氧化还原体系的情况下能够氧化的其它酶。在本发明方法中所用的氧化还原酶,即在没有其它氧化还原体系的情况下能够氧化的酶,包括过氧化物酶和氧化酶,特别是多元酚氧化酶和漆酶。
可用于本发明的过氧化物酶(EC 1.11.1.1-1.11.1.11)包括为辅因子非依赖型的过氧化物酶,特别是典型的过氧化物酶(EC 1.11.1.7)。过氧化物酶可以来自任意源,包括植物、细菌、丝状和其它真菌和酵母。例子有辣根过氧化物酶、豆壳过氧化物酶、髓过氧化物酶、乳过氧化物酶、Arthromyces和鬼伞过氧化物酶。几种过氧化物酶可商购获得。这些过氧化物酶需要过氧化氢作为电子受体。
多元酚氧化酶(EC 1.10.3.1)包括酪氨酸酶和儿茶酚氧化酶,例如木质素过氧化物酶。适宜的多元酚氧化酶可以从真菌、植物或动物获得。这些多元酚氧化酶需要氧作为电子受体。漆酶(EC 1.10.3.2)有时分为多元酚氧化酶,但是它们也可以分为不同类,有时称之为为对二元酚氧化酶。漆酶可从植物源或微生物,特别是真菌源,例如杂色栓菌种获得。这些漆酶也需要氧作为电子受体。
可以在相对温和条件下,例如在pH5-10和温度15-60℃(取决于特定金属络合物或酶)实施本发明的方法。反应培养基可以为含水培养基、或均匀混合培养基如水与仲或叔醇的混合物或者醚/水混合物、或不均匀培养基如水与水不能混合的有机溶剂如疏水醚、烃或卤代烃的混合物。在后一情况下,该金属络合物或酶和/或硝酰基和氧化剂可以存在于水相和醇底物中,并且其醛或酮产物可以有机相存在。如果需要的话,可以使用相转移催化剂。反应培养基也可以是固体/液体混合物,特别是当硝酰基固定在固体载体上时。当底物或产物相对较敏感或者当产物与其它试剂分离可能存在困难时不均匀反应培养基困难是有利的。
本发明还涉及新型纤维素氧化产物及其衍生物,它们可以用本发明的方法获得。这些包括如下纤维素:除了每100个单糖单元中至少1个羟甲基氧化为羧基之外,每100个,特别是每50个或者甚至每25个单糖单元中至少1个羟甲基转化成醛甲基(carbaldehydegroup),无论其是否为半缩醛或类似形式,只要每个分子平均含有至少1个醛甲基(不包括寡糖或多糖的还原端的可能(半缩醛化)醛基)。除醛基之外,按照本发明获得的产物可以含有其它官能基,特别是通过进一步氧化或羧烷基化获得的羧基。
本发明的新型衍生物非常适合作为湿强度添加剂、吸水性聚合物等,特别是作为与醇、胺和能够与醛官能基偶联的其它试剂进一步官能化用的原料。这些试剂包括交联剂(二胺、二醇等),它们可用于交联该纤维素衍生物或将它们偶联到氨基酸、蛋白质、活性基团等上。
本发明还涉及通过将上述醛纤维素衍生物与例如胺偶联获得的衍生物,尤其是通过还原胺化作用产生附加权利要求书中定义的纤维素的亚氨基或氨基衍生物。同样,为了进一步衍生,这些醛纤维素衍生物可以与羟官能基化合物如乙醇酸反应缩醛化。
本发明的纤维素及其衍生物的氧化使得在产物中既有醛基又有羧基。由于所得氧化纤维提高了纸张的湿强度和组织应用,因此该方法对氧化纤维素纤维特别有用。该方法还可用于氧化纤维素,产生吸水性纤维素物料,如果需要的话之后将产物进一步氧化或羧甲基化或其它衍生。
实施例:常规
使用Blumenkrantz等人的方法(Anal.Biochem.54,(1973)484)测定糖醛酸(6-COOH的己吡喃糖单元)含量。该方法的使用如下:将5ml样品悬浮于水中,加入20ml硼酸(0.0125M)于浓(95-97%)硫酸中的溶液。使最终体积(V)为25ml。将0.2ml的该溶液加入0.2ml纯水中,然后加入1.0ml的该硫酸硼酸试剂。将该溶液在100℃下加热5分钟。在冰中冷却之后加入20μl的3-羟基联苯(0.2%w/w)水溶液,这样变成粉红色。培养15分钟之后在520nm下测定消光校准曲线是以D-葡糖醛酸作为参照物质为基础的。
通过以下方法测定醛含量:减去法(测定用亚氯酸盐和过氧化氢氧化醛之前和之后的糖醛酸含量)、加入盐酸羟胺产生一肟并反滴定释放的盐酸、13CNMR光谱法(相应于葡糖酐单元C1的C6醛信号的强度,或者肟中C6(C=N)的强度)。实施例1:生产6-醛纤维素
将1g完全无氯漂白和薄片干燥的牛皮纸浆(Grapho Celeste),烘箱干燥的干重)悬浮于100ml水中。向该悬液中加入18mg的TEMPO(0.1mmol)和9mg的过氧化物酶(HRPO),VI型(290U/mg)。用醋酸水溶液(0.1M)将其pH调整至5.1。在8小时内逐步(每2分钟30-50μl)加入过氧化氢溶液(1.5ml 30%于50ml)。过氧化物加入之后pH降低,但是几分钟之后它回到其最初值;因此在反应期间没有必要调整pH。21小时之后通过加入氯化羟铵并用氢氧化钠水溶液(0.1M)滴定分析样品。按照该分析,样品含有160μmol C6-醛/g纤维素。实施例2:用漆酶氧化纤维素
向2g用氢氧化钠溶液和水处理活化的纤维素纤维中加入17mg重组杂色栓菌漆酶(Wacker Chemie)。在密封系统中将该溶液(pH 6.0-5.1)与氧接触,以便可以通过量气管测定氧随时间的消耗量。反应1天之后氧的消耗量为20ml(0.8mmol)。第二步,向反应混合物中加入0.2ml过氧化氢(30%w/w)和250mg亚氯酸钠(Aldrich,80%)。在pH4-4.5下静置1天之后,获得几乎均匀的混合物,从其中取出样品。测定整个反应混合物的糖醛酸含量。按照采用的Blumenkrantz法其含量为0.7mmol,它具有350mmol/g。实施例3:氧化纤维素纤维
向2g悬浮于25ml水中的纤维素纤维(与实施例1中相同)中加入28mg辣根过氧化物酶(HRP,Sigma)、20mg TEMPO。使该混合物的pH为5.3,然后在3小时内以100μl份加入lmmol的过氧化氢溶液(5ml 0.6%,w/w)。尽管添加相对较快,但是几乎不能看见气体(氧)放出。按照Blumenkrantz法糖醛酸的产率为9%。该实施例说明了过氧化氢加入速度的影响,与实施例1相比该速度较快,导致羧酸水平相对较高。实施例4:用通过铜/联吡啶催化的氧氧化纤维素纤维
将1g纤维素纤维(CTMP)悬浮于50ml水中。然后加入l0ml的5%(w/w)TEMPO溶液、0.4ml的硝酸铜溶液(0.4M)和10ml的联吡啶溶液(0.05M)。通过搅拌的溶液冒出氧气。1天之后将这些纤维通过过滤收集,用水重复洗涤并在真空下干燥。干纤维的糖醛酸含量(采用的Blumenkrantz)为9%。实施例5:生产6-醛-6-羧基纤维素
生产6-醛-6-羧基纤维素。将1g完全无氯漂白和薄片干燥的牛皮纸浆(Grapho Celeste),烘箱干燥的干重)悬浮于20ml水中。向该悬液中加入20mg的TEMPO(0.1mmol)和19mg的过氧化物酶(HRPO),VI型(290U/mg)。用醋酸水溶液(0.1M)将其pH调整至5.5。在6小时内逐步(每10分钟50ml)加入过氧化氢溶液(1.2ml 3%)。2l小时之后通过加入氯化羟铵并用氢氧化钠水溶液(0.05M)滴定分析样品。按照该分析,样品含有300μmol C6-醛/g纤维素。此外发现样品含有糖醛酸(100μmol/g)。
Claims (10)
1.一种使用亚硝鎓离子氧化纤维素的方法,所述亚硝鎓离子是通过氧化硝酰基化合物获得的,特征在于所述硝酰基化合物是在有氧化酶或过渡金属与络合剂的络合物存在下被氧化的。
2.如权利要求1的方法,其中所述硝酰基化合物为二叔硝酰基化合物,特别是2,2,6,6-四甲基哌啶-1-氧基(TEMPO)。
3.如权利要求1或2的方法,其中所述过渡金属为锰、铁、钴、镍、铜或钒。
4.如权利要求1-3任一的方法,其中所述络合剂为含氮化合物。
5.如权利要求4的方法,其中所述络合剂为联吡啶或三嗪烷或(聚)组氨酸。
6.如权利要求1的方法,其中所述氧化酶为过氧化物酶、多元酚氧化酶或漆酶。
7.如权利要求1-6任一的方法,其中生产每25个单糖单元和平均每个分子含有至少1个载有1个醛甲基的环单糖链基团的纤维素衍生物。
8.一种被氧化的纤维素或其化学衍生物,其每100个单糖单元和平均每个分子含有至少1个载有1个6-醛甲基的环单糖链基团和至少1个载有1个6-羧基的环单糖链基团。
9.一种纤维素衍生物,在该衍生物中,至少一部分通过氧化引入的6-醛甲基已转化成具有式-CH=N-R或-CH2-NHR的基团,其中R为H、羟基、氨基或基团R1、OR1或NHR1,其中R1为C1-C20烷基、C1-C20酰基、糖基、或者与糖基偶联或能够与糖基偶联的基团。
10.一种纤维素衍生物,在该衍生物中,至少一部分通过氧化引入的6-醛甲基已转化成具有式-CH(OR3)-O-CH2-COOR2或-CH(-O-CH2-COOR2)2的基团,其中R2为H、金属阳离子或任选经过取代的铵基,并且R3为H或与纤维素的脱氢羟基的氧原子相连的直接键。
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- 2000-02-24 CN CN00804200.4A patent/CN1341125A/zh active Pending
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Also Published As
Publication number | Publication date |
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HUP0105300A3 (en) | 2004-04-28 |
US6716976B1 (en) | 2004-04-06 |
ZA200106740B (en) | 2002-08-15 |
JP2002537448A (ja) | 2002-11-05 |
RU2001125920A (ru) | 2004-02-20 |
ATE271068T1 (de) | 2004-07-15 |
DE60012148T2 (de) | 2005-07-21 |
WO2000050463A1 (en) | 2000-08-31 |
AU776991B2 (en) | 2004-09-30 |
EP1155039B1 (en) | 2004-07-14 |
HUP0105300A2 (hu) | 2002-04-29 |
CZ20012873A3 (cs) | 2002-01-16 |
PL350423A1 (en) | 2002-12-16 |
BR0008475A (pt) | 2002-02-05 |
DE60012148D1 (de) | 2004-08-19 |
EP1155039A1 (en) | 2001-11-21 |
ZA200106416B (en) | 2002-11-04 |
ES2223462T3 (es) | 2005-03-01 |
DK1155039T3 (da) | 2004-11-08 |
AU2833000A (en) | 2000-09-14 |
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