CN114634633A - 一种溶解甲壳素的溶剂体系及其应用 - Google Patents
一种溶解甲壳素的溶剂体系及其应用 Download PDFInfo
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- C—CHEMISTRY; METALLURGY
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
- C08J3/091—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids characterised by the chemical constitution of the organic liquid
- C08J3/096—Nitrogen containing compounds
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0003—General processes for their isolation or fractionation, e.g. purification or extraction from biomass
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
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- C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
- C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
- C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
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Abstract
本发明涉天然多糖利用领域,具体是一种溶解甲壳素的溶剂及其应用。溶解甲壳素的溶剂体系由苄基三甲基氯化铵氢键受体试剂与氢键供体试剂共同组成,氢键供体试剂为乳酸、草酸、苹果酸、乙二醇和/或丙三醇的一种或两种及以上混合物。本发明溶剂体系对甲壳素的溶解度大,且溶剂成本低,安全无毒;甲壳素溶解度为0.5‑12%,溶解甲壳素的操作过程简单,便于工业化应用,可用于甲壳素的降解、预处理、纺丝等材料加工以及从虾壳、蟹壳和昆虫外壳提取甲壳素等领域。
Description
技术领域
本发明涉天然多糖利用领域,具体的说是溶解甲壳素的溶剂及其在甲壳素的降解、预处理和提取方面等应用。
背景技术
甲壳素,又称为几丁质(Chitin),是由N-乙酰氨基葡萄糖通过β-1,4糖苷键连接成的糖链,是自然界中唯一的含氮多糖。甲壳素主要存在于虾蟹壳、鱿鱼骨、乌贼等中。甲壳素可制备甲壳素基生物材料、壳聚糖及其衍生的各种寡糖、N-乙酰氨基葡萄糖(GlcNAc)及系列下游化学品,可广泛应用于食品、农业、医药、材料和工业等领域。
甲壳素中存在四级结构,一级结构是N-乙酰氨基葡萄糖由β-1,4糖苷键连接成的糖链;甲壳素的二级结构是糖链的羟基和N-乙酰氨基通过分子间和分子内的相互作用力而形成的聚合体;甲壳素的三级结构是糖链之间以氢键形成的聚集体,只与甲壳素分子主链的构象有关;甲壳素的四级结构是甲壳素的长链间以非共价键结合堆砌排列而形成的聚集体。甲壳素致密的结构和较强的分子间氢键使其不溶于水和大多数的有机试剂,限制了甲壳素的进一步的转化和利用。目前能溶解甲壳素的溶剂主要有强酸如硫酸。离子液体作为一种具有特殊溶解性能的新体系,能较好的溶解甲壳素,但是离子液体价格较贵、对环境影响不明确,限制其大规模应用。近年来,低共熔溶剂(Deep eutectic solvent,DES)作为一种新的溶解体系引起广泛的关注,其具有成本低、无毒绿色等优势。目前报道能溶解甲壳素的低共熔溶剂体系只有氢受体为氯化胆碱和甜菜碱的体系,存在甲壳素溶解度低、成本相对高的问题。
发明内容
为解决现有技术存在的问题,本发明的目的在于提供一种新的溶解甲壳素的溶剂体系及应用。
为了实现上述发明目的,本发明采用的技术方案为:
本发明提供了一种溶解甲壳素的溶剂体系,所述溶剂体系由苄基三甲基氯化铵氢键受体试剂与氢键供体试剂共同组成。
上述技术方案中,进一步地,所述氢键供体试剂为乳酸、草酸、苹果酸、乙二醇和/或丙三醇的一种或两种及以上混合物。
上述技术方案中,进一步地,所述氢键受体试剂与氢键供体试剂的摩尔比为2:1-1:5;优选比例为1:1-1:2。
本发明还提供了上述溶剂体系在溶解甲壳素中的应用。
上述技术方案中,进一步地,溶解甲壳素的温度为80-160℃;优选温度为100-140℃。
上述技术方案中,进一步地,所述溶剂体系在甲壳素降解中溶解甲壳素的应用。
上述技术方案中,进一步地,所述溶剂体系在甲壳素的预处理和材料加工中的应用。
上述技术方案中,进一步地,所述溶剂体系应用于从虾壳、蟹壳和昆虫外壳提取甲壳素。
本发明有益效果:
1.本发明以苄基三甲基氯化铵为氢键受体试剂,提供了一种新的溶解甲壳素的低共熔溶剂体系,对甲壳素的溶解度大,且溶剂成本低,安全无毒;甲壳素溶解度为0.5-12%。
2.本发明苄基三甲基氯化铵为氢键受体试剂的低共熔溶剂体系溶解甲壳素的操作过程简单,便于工业化应用,可用于甲壳素的降解、预处理、纺丝等材料加工以及从虾壳、蟹壳和昆虫外壳提取甲壳素等领域。
附图说明
图1甲壳素在不同的DES体系的溶解情况;
图2TMBAC:乳酸体系溶解后再生甲壳素的FT-IR光谱图;图中,A:无处理甲壳素,B:2%,100℃,C:10%,100℃,D:2%,140℃,E:10%,140℃;
图3不同DES体系溶解后再生甲壳素的FT-IR光谱图;图中,A:无处理甲壳素,B:10%,140℃,C:10%,100℃,D:2%,140℃,E:2%,100℃;
图4TMBAC:乳酸体系溶解后再生甲壳素的X衍射(XRD)图谱。
具体实施方式
以下结合具体实施例对本发明作进一步说明,但不以任何方式限制本发明。
实施例1苄基三甲基氯化铵氢键受体试剂的低共熔溶剂(DES)的制备
将1g苄基三甲基氯化铵(TMBAC)分别与乳酸、草酸、苹果酸、柠檬酸、乙二醇、丙三醇按一定的摩尔比(见表1)混合,放置于反应管中,在80℃和100℃的油浴锅中搅拌,直至形成无色透明的液体。
表1制备不同低共熔溶剂的比例及温度
如表1所示,苄基三甲基氯化铵(TMBAC)与乳酸、草酸、苹果酸、乙二醇、丙三醇在不同温度和不同摩尔比例下能形成均匀透明的液体,即为苄基三甲基氯化铵氢键受体的低共熔溶剂。
实施例2苄基三甲基氯化铵氢键受体试剂的低共熔溶剂溶解甲壳素
将实施例1制备的苄基三甲基氯化铵氢键受体DES溶剂(TMBAC:氢键供体的摩尔比为1:2,其中氢键供体分别为乳酸、苹果酸、草酸、甘油、乙二醇)中加入质量分数为1%、2%、3%、4%、5%、10%的甲壳素,分别在100℃下搅拌2h。甲壳素能溶解在DES中,形成透明的溶液(详见附图1,为10%重量比的甲壳素溶液),说明甲壳素已经完全溶解,溶解度超过10%,且溶解时间短,只需2h左右。
实施例3苄基三甲基氯化铵氢键受体试剂的DES预处理后甲壳素的结构表征
根据实施例2,甲壳素溶解在苄基三甲基氯化铵氢键受体DES体系中,形成粘稠的液体,加入去离子水,将甲壳素析出,离心后获得甲壳素粉末。将析出的甲壳素水洗三次,以完全去除DES溶剂,获得预处理后的甲壳素粉末,将预处理后的甲壳素粉末在冷冻干燥机中进行干燥。
采用傅里叶变换红外光谱(FT-IR)分析表征样品的官能团结构:称取100mg KBr,称取1mg样品,将两者混合研磨并压片,扫描范围为400~4000cm-1,背景与样品扫描次数均为32次。
通过FT-IR图谱发现由于NH2和OH基团的对称伸缩振动,在3472cm-1和3265cm-1处未经处理的甲壳素出现了两个特征峰。在2891cm-1处能够观察到对称的CH3和不对称的CH2的伸缩峰。由于甲壳素的分子间及分子内的氢键的存在,在1659cm-1和1624cm-1处出现了两个酰胺I谱的峰,羰基区域中出现的吸收峰均为甲壳素的特征吸收峰。红外光谱图中还有在1556cm-1处出现酰胺II谱带,在1312cm-1处出现酰胺III谱带。
FTIR图谱(附图2)可以看出甲壳素在TMBAC:乳酸=1:2(摩尔比)体系中,在不同的温度及底物浓度处理溶解后再生的甲壳素与未经处理的甲壳素的基本结构没有发生改变。
对在TMBAC:乳酸、TMBAC:草酸、TMBAC:苹果酸的摩尔比均为1:2的体系100℃下溶解2%的甲壳素进行了分析。从FT-IR的光谱图(附图3)上来看,均出现了甲壳素的特征吸收峰,在这三种DES体系下溶解的甲壳素与未处理的甲壳素的结构基本一致。
采用X射线衍射(XRD)对样品的晶体结构进行表征:室温下用X射线粉末衍射仪,在CuKα辐射对样品进行分析,电压40kV,电流40mA,扫描范围2θ=5~60°,扫描7min,结晶度(CrI:%)的计算公式如下所示:
过XRD对以TMBAC:乳酸=1:2(摩尔比)溶解后的甲壳素的晶体结构进行了表征(详见附图4),由于甲壳素的刚性结构及内部氢键,未经处理的甲壳素在2θ为9.2°、19.2°以及28°显示其特征峰。从XRD的图谱中可以看出在该DES体系下,不同的温度以及加入不同质量分数的甲壳素,在溶解后甲壳素的晶体结构与未处理之前的甲壳素均出现了典型的晶体衍射峰,但是预处理后的甲壳素峰均减弱,说明结晶度下降,有利于后续的转化利用。
通过结晶度的计算公式可以得出:未经处理的甲壳素结晶度为85.04%,100℃下溶解的质量分数为2%及10%的甲壳素的结晶度分别为57.47%和83.81%,140℃下溶解的质量分数为2%及10%的甲壳素的结晶度分别为79.92%和84.66%。甲壳素结晶度的下降使其结构更加疏松,有利于甲壳素的进一步转化利用。
表2.TMBAC:乳酸体系溶解后再生甲壳素的结晶度
通过上述的实施例可以看出,本专利所述的苄基三甲基氯化铵氢键受体试剂的低共熔溶剂(DES)可以很好的溶解甲壳素,溶解度超过10%,且不会对甲壳素的化学结构造成破坏。本专利所述苄基三甲基氯化铵氢键受体试剂的低共熔溶剂(DES)可以快速(2小时内,文献报道一般在10小时左右)溶解甲壳素,可应用于从虾壳、蟹壳和昆虫外壳提取甲壳素;可以的在溶解状态下,甲壳素可以更有效的转化利用。此外,本专利所述苄基三甲基氯化铵氢键受体试剂的低共熔溶剂(DES)预处理后的甲壳素结晶度下降,更有利于降解和转化利用,所以本项目所述的溶解甲壳素溶剂可用于甲壳素的预处理加工及生物材料制备等领域。
对于任何熟悉本领域的技术人员而言,在不脱离本发明技术方案范围情况下,都可利用上述揭示的技术内容对本发明技术方案作出许多可能的变动和修饰,或修改为等同变化的等效实施例。因此,凡是未脱离本发明技术方案的内容,依据本发明的技术实质对以上实施例所做的任何简单修改、等同变化及修饰,均应仍属于本发明技术方案保护的范围内。
Claims (10)
1.一种溶解甲壳素的溶剂体系,其特征在于:所述溶剂体系由苄基三甲基氯化铵氢键受体试剂与氢键供体试剂共同组成。
2.根据权利要求1所述溶剂体系,其特征在于:所述氢键供体试剂为乳酸、草酸、苹果酸、乙二醇和/或丙三醇的一种或两种及以上混合物。
3.根据权利要求1或2所述的溶剂体系,其特征在于:所述氢键受体试剂与氢键供体试剂的摩尔比为2:1-1:5。
4.根据权利要求3所述的溶剂体系,其特征在于:所述氢键受体试剂与氢键供体试剂的摩尔比为1:1-1:2。
5.权利要求1所述的溶剂体系在溶解甲壳素中的应用。
6.根据权利要求5所述的应用,其特征在于,溶解甲壳素的温度为80-160℃。
7.根据权利要求6所述的应用,其特征在于,溶解甲壳素的温度为100-140℃。
8.根据权利要求5所述的应用,其特征在于:所述溶剂体系在甲壳素降解中溶解甲壳素的应用。
9.根据权利要求5所述的应用,其特征在于:所述溶剂体系在甲壳素的预处理和材料加工中的应用。
10.根据权利要求5所述的应用,其特征在于:所述溶剂体系应用于从虾壳、蟹壳和昆虫外壳提取甲壳素。
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