WO2020082294A1 - 纤维素酯及其制备方法和应用 - Google Patents

纤维素酯及其制备方法和应用 Download PDF

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WO2020082294A1
WO2020082294A1 PCT/CN2018/111861 CN2018111861W WO2020082294A1 WO 2020082294 A1 WO2020082294 A1 WO 2020082294A1 CN 2018111861 W CN2018111861 W CN 2018111861W WO 2020082294 A1 WO2020082294 A1 WO 2020082294A1
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cellulose
preparation
cellulose ester
esterification reaction
ester
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PCT/CN2018/111861
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English (en)
French (fr)
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陈少军
陈恒
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深圳大学
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B3/00—Preparation of cellulose esters of organic acids
    • C08B3/02—Catalysts used for the esterification
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B3/00—Preparation of cellulose esters of organic acids
    • C08B3/06—Cellulose acetate, e.g. mono-acetate, di-acetate or tri-acetate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B3/00—Preparation of cellulose esters of organic acids
    • C08B3/08—Preparation of cellulose esters of organic acids of monobasic organic acids with three or more carbon atoms, e.g. propionate or butyrate
    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/08—Cellulose derivatives
    • C08L1/10—Esters of organic acids, i.e. acylates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/08—Cellulose derivatives
    • C08L1/10—Esters of organic acids, i.e. acylates
    • C08L1/12—Cellulose acetate

Definitions

  • the invention belongs to the technical field of fibers, and in particular relates to a cellulose ester and a preparation method and application thereof.
  • Cellulose is a large molecular polysaccharide composed of glucose. Therefore, due to its high polarity, strong intermolecular hydrogen bonding and hydrophobic interaction, and high crystallinity, rigid main chain structure and other factors, the solubility of cellulose is poor, insoluble in water and general organic solvents. At the same time, cellulose will decompose before heating and melting, so it cannot be melt processed. This limits its corresponding chemical modification.
  • Cellulose ester is an important one among cellulose derivatives. Some cellulose esters currently synthesized have been widely used in the fields of membrane, fiber, plastic, cigarette filter and coating industry. Most cellulose esters are synthesized by esterification of cellulose with corresponding acids, acid chlorides, etc. in a homogeneous or heterogeneous system. However, factors such as longer esterification time and harsh reaction conditions limit its wide application. In addition, the high molecular weight and a large number of hydroxyl groups contained in cellulose cause strong intermolecular and intramolecular interactions due to hydrogen bonding, and cellulose is insoluble in most organic solvents.
  • the esterification of cellulose is mainly carried out in the organic phase, such as acetone, pyridine, ionic liquid, N, N-dimethylacetamide / lithium chloride and other organic solvents of.
  • organic phase such as acetone, pyridine, ionic liquid, N, N-dimethylacetamide / lithium chloride and other organic solvents of.
  • the use and handling of these solvents can cause high production costs and potentially negative impacts on the environment.
  • the use of toxic chemical reagents to modify cellulose also increases the complexity of production operations and the burden of waste disposal.
  • the purpose of the present invention is to overcome the above-mentioned shortcomings of the prior art, and to provide a cellulose ester and a preparation method thereof to solve the complexity and cost of the production process due to the use of an organic phase as a reaction solvent in the existing cellulose ester Technical problems with environmental hazards.
  • a method for preparing cellulose ester includes the following steps:
  • the acid anhydride, cellulose and esterification catalyst are added to water for mixing treatment, and the esterification reaction is carried out.
  • the esterification catalyst includes an inorganic base and / or an organic base dissolved in water.
  • the inorganic base includes at least one of alkali metal weak acid salts, ammonia water, and ammonium weak acid salts.
  • the organic base includes at least one of triethylamine, ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, pyridine, N-methylpyrrolidone, and 4-dimethylaminopyridine.
  • the alkali metal weak acid salt includes at least one of lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate, sodium acetate, potassium acetate, sodium phosphate, and potassium phosphate;
  • the weak acid salt of ammonium includes at least one of ammonium carbonate and diammonium hydrogen phosphate.
  • the content ratio of the cellulose, acid anhydride and esterification catalyst is 1: (0.1-10): (0.1-10); wherein, the cellulose is calculated as a glucose structural unit.
  • the content of the cellulose in the mixed solution is 0.1wt% -20wt%.
  • the temperature of the conditions of the esterification reaction is 0-100 ° C.
  • the acid anhydride contains Structured organic anhydride.
  • the cellulose material includes at least one of natural cellulose, regenerated cellulose, microcrystalline cellulose, cellulose nanocrystals, and related products prepared from cellulose.
  • stirring treatment is accompanied during the esterification reaction.
  • a step of separating and purifying the reaction product is further included.
  • a cellulose ester is provided.
  • the cellulose ester is prepared by the preparation method of the cellulose ester of the present invention.
  • an application of cellulose ester in fluorescence detection, cellulose biomaterial, membrane, plastic, filter material.
  • the cellulose ester preparation method of the present invention uses water as a reaction solvent. On the one hand, it can not only swell cellulose and increase the contact area of cellulose, but also effectively dissolve the esterification catalyst. Thereby, the esterification reaction between the acid anhydride and the cellulose hydroxyl group is promoted, so that the cellulose ester contains functional groups, and the original structure of the cellulose material can be effectively maintained;
  • the chemical reaction system is safe and environmentally friendly.
  • the one-time feeding greatly simplifies the process steps, improves the reaction efficiency, and reduces the economic cost.
  • the cellulose ester of the present invention is rich in functional groups, which can be further modified, and effectively retains the original mechanical properties of cellulose.
  • the cellulose ester preparation method is simple, the cost is low, and the cellulose ester obtained by the preparation is rich in functional groups and can be further modified, so its application range is effectively expanded, and the performance of the corresponding product can be improved and the corresponding reduction can be reduced.
  • the economic cost of the cost is very simple, the cost is low, and the cellulose ester obtained by the preparation is rich in functional groups and can be further modified, so its application range is effectively expanded, and the performance of the corresponding product can be improved and the corresponding reduction can be reduced. The economic cost of the cost.
  • Example 1 is an infrared spectrum of microcrystalline cellulose particles and microcrystalline cellulose ester particles in Example 5; wherein, the broken line curve is the infrared spectrum of microcrystalline cellulose, and the solid line curve is the infrared spectrum of cellulose ester
  • Example 2 is an XPS spectrum of cellulose particles and cellulose ester particles in Example 5; wherein, the dotted curve is the XPS spectrum of microcrystalline cellulose, and the solid curve is the XPS spectrum of cellulose ester;
  • FIG. 3 is a solid nuclear magnetic spectrum chart of cellulose ester particles in Example 5.
  • the quality of each component mentioned in the description of the embodiment of the present invention can not only refer to the specific content of each component, but also can express the proportional relationship of the quality between the components. It is within the range disclosed in the specification of the embodiments of the present invention to scale up or down the content of the components.
  • the mass described in the description of the embodiment of the present invention may be a mass unit known in the chemical industry such as ⁇ g, mg, g, kg, and so on.
  • the embodiments of the present invention provide a method for preparing a cellulose ester.
  • the preparation method of the cellulose ester includes the following steps:
  • the acid anhydride, cellulose and esterification catalyst are added to water for mixing treatment, and the esterification reaction is carried out.
  • the preparation method of the cellulose ester is to adopt water as a reaction solvent to construct an aqueous phase esterification reaction.
  • an esterification reaction occurs between the acid anhydride and cellulose to realize the modification treatment of cellulose to produce cellulose ester, which gives the cellulose ester corresponding properties, such as good grafting performance, And retain the good mechanical properties of cellulose.
  • the esterification catalyst includes an inorganic base and / or an organic base dissolved in water.
  • the inorganic base may include at least one of alkali metal weak acid salt, ammonia water, and ammonium weak acid salt; specifically, the alkali metal weak acid salt may include lithium carbonate, sodium carbonate, potassium carbonate, At least one of rubidium carbonate, sodium acetate, potassium acetate, sodium phosphate, and potassium phosphate; the weak acid salt of ammonium may include at least one of ammonium carbonate and diammonium hydrogen phosphate.
  • the organic base may include at least one of triethylamine, ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, pyridine, N-methylpyrrolidone, and 4-dimethylaminopyridine.
  • the basic catalysts selected above have good water solubility on the one hand, can effectively dissolve in water, improve the dispersibility of the catalyst, thereby improving the catalytic effect of the catalyst, and thereby enhancing the esterification reaction between the acid anhydride and the cellulose hydroxyl group; On the one hand, these catalysts have low cost, are harmless to the environment and human body, realize the environmental protection and safety of the preparation method, and reduce the production cost.
  • the acid anhydride contains Structured organic anhydride.
  • the organic anhydride may be, but not limited to, acetic anhydride, propionic anhydride, succinic anhydride, glutaric anhydride, adipic anhydride, maleic anhydride, itaconic anhydride, acrylic anhydride, methacrylic anhydride, chlorine At least one of acetic anhydride, bromoacetic anhydride, iodoacetic anhydride and the like.
  • These acid anhydrides can be effectively esterified and bound to cellulose, such as the introduction of double bonds, alkyl chains, chlorinated hydrocarbons and other functional groups into cellulose, thereby improving the properties of cellulose such as solubility, and its modification and surface Functionalization provides convenience.
  • the cellulose as one of the reactants can be selected from at least one of natural cellulose, regenerated cellulose, microcrystalline cellulose, cellulose nanocrystals, and related products prepared from cellulose, wherein the cellulose is prepared Related products include, for example, cellulose fiber, cellulose film, cellulose paper, cellulose microspheres, etc., which can be selected as required.
  • the temperature of the esterification reaction can be controlled at 0-100 ° C, and the esterification reaction time can be sufficient, such as 0.01-72 hours.
  • the efficiency of the esterification reaction can be effectively improved, while ensuring the stability of the original cellulose structure.
  • the esterification reaction system may be agitated, for example, the esterification reaction system may be agitated by using an additional action, and may be stirred, oscillated or ultrasonicated. Etc. Stirring the esterification reaction system can effectively enhance the dispersion of the reactants and increase the efficiency of the esterification reaction.
  • the content of the acid anhydride and the esterification reaction catalyst is preferably sufficient relative to cellulose to achieve sufficient modification treatment of cellulose.
  • the content ratio of the cellulose, acid anhydride, and esterification catalyst is 1: (0.1-10): (0.1-10); wherein, the cellulose is calculated as a glucose structural unit.
  • the content of the cellulose in the mixed solution is 0.1wt% -20wt%, further 0.1wt% -10wt%.
  • the cellulose ester is obtained by purifying the reaction mixture after the reaction.
  • the purification process includes processing steps such as filtration, centrifugation, dialysis, or vacuum drying.
  • the water phase esterification reaction system constructed by the preparation method of cellulose ester described above performs esterification reaction on cellulose, and the water solvent can not only effectively swell cellulose, but also increase cellulose and other reactants.
  • the contact area can also effectively dissolve the esterification reaction catalyst, thereby promoting the esterification reaction between the acid anhydride and the cellulose hydroxyl group, so that the cellulose ester contains functional groups, so that the cellulose ester can be further modified .
  • it can effectively maintain the original structure of the cellulose material.
  • the water phase esterification reaction system constructed by the preparation method is safe and environmentally friendly, and the one-time feeding greatly simplifies the process steps, improves the reaction efficiency, reduces the economic cost, and effectively avoids the high cost caused by the use of organic solvents. , Complex production operations and post-processing difficulties.
  • an embodiment of the present invention also provides a cellulose ester.
  • the cellulose ester is prepared by the cellulose ester preparation method described above. Therefore, the cellulose ester is rich in functional groups, can be further modified, and has good mechanical properties. Because of this, the application range of the cellulose ester has been effectively expanded.
  • the cellulose ester can be used in fluorescence detection, cellulose biomaterials, membranes, plastics, and filter materials.
  • This embodiment provides a cellulose ester and a preparation method thereof.
  • the preparation method of the cellulose ester is prepared as follows:
  • This embodiment provides a cellulose ester and a preparation method thereof.
  • the preparation method of the cellulose ester is prepared as follows:
  • This embodiment provides a cellulose ester and a preparation method thereof.
  • the cellulose ester preparation method is prepared as follows:
  • This embodiment provides a cellulose ester and a preparation method thereof.
  • the preparation method of the cellulose ester is prepared as follows:
  • This embodiment provides a cellulose ester and a preparation method thereof.
  • the preparation method of the cellulose ester is prepared as follows:
  • This embodiment provides a cellulose ester and a preparation method thereof.
  • the preparation method of the cellulose ester is prepared as follows:
  • Example 1 to Example 6 were subjected to infrared spectrum, XPS spectrum, and nuclear magnetic analysis, respectively.
  • the infrared spectrum of the microcrystalline cellulose and cellulose ester in Example 5 is shown in FIG. 1, wherein the dotted curve in FIG. 1 is the infrared spectrum of the microcrystalline cellulose, and the solid curve is the fiber Infrared spectrum of the ester.
  • the XPS spectrum of microcrystalline cellulose and cellulose ester in Example 5 is shown in FIG. 2, wherein the dotted curve in FIG. 2 is the XPS spectrum of microcrystalline cellulose, and the solid curve is cellulose ester XPS spectrum; the solid nuclear magnetic spectrum of the cellulose ester in Example 5 is shown in FIG. 3.

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Abstract

纤维素酯制备方法包括步骤有：将酸酐、纤维素材料和酯化反应催化剂加入水中进行混合处理，并进行酯化反应。所述纤维素酯制备方法采用水作为反应溶剂，溶胀纤维素，增大纤维素的接触面积的作用，还可以有效溶解酯化反应催化剂，从而促进酸酐与纤维素羟基之间的酯化反应，使得纤维素酯含有功能基团，而且还能有效保持纤维素原有结构，扩展纤维素酯的应用范围，能够提高相应产品的性能；而且所述制备方法构建的水相酯化反应体系安全，环保，而且有效简化了工序步骤，提高了反应效率，降低了经济成本。

Description

纤维素酯及其制备方法和应用 技术领域
本发明属于纤维技术领域，具体涉及一种纤维素酯及其制备方法和应用。
背景技术
目前，随着不可再生资源的逐渐枯竭和环境污染问题的日益恶化，可再生资源的开发和利用已经成为维系人类社会可持续发展的重要的议题。纤维素作为地球上最丰富的天然高分子，由于其可再生性，广泛的可获得性，低成本，生物相容性和可生物降解性等而受到关注。
纤维素是由葡萄糖组成的大分子多糖。因此，由于其本身高极性，强分子间氢键和疏水相互作用，以及高结晶度、刚性的主链结构等因素，纤维素的溶解性较差，不溶于水及一般有机溶剂。同时，纤维素在加热熔融前会分解，所以不能熔融加工。从而限制了其进行相应的化学改性。
纤维素酯是纤维素衍生物中重要的一种，目前合成的一些纤维素酯已经广泛用于膜、纤维、塑料、香烟过滤器及涂料工业等领域。大多数纤维素酯都是通过纤维素与相应酸、酰氯等在均相或非均相体系中发生酯化反应来合成的。但是酯化反应一般时间较长以及反应条件苛刻等因素限制了其广泛的应用。另外，纤维素所含的高分子量和大量的羟基由于氢键引起强烈的分子间和分子内相互作用，纤维素不溶于大多数有机溶剂。为了避免酯的水解和提高接枝率，纤维素的酯化反应主要在有机相中进行，如丙酮、吡啶、离子液体、N，N-二甲基乙酰胺/氯化锂等有机溶剂中进行的。这些溶剂的使用和处理会产生高昂的生产成本并对环境造成潜在的负面影响。同时，使用有毒化学试剂对纤维素进行改性还会增加生产操作的复杂性和废物处理的负担。
技术问题
本发明的目的在于克服现有技术的上述不足，提供一种纤维素酯及其制备 方法，以解决现有纤维素酯由于采用有机相作为反应溶剂而导致生产工艺的复杂和成本的提供以及对环境造成的危害的技术问题。
技术解决方案
为了实现上述发明目的，本发明的一方面，提供了一种纤维素酯的制备方法。所述纤维素酯的制备方法包括如下步骤：
将酸酐、纤维素和酯化反应催化剂加入水中进行混合处理，并进行酯化反应。
优选地，所述酯化反应催化剂包括无机碱和/或溶于水的有机碱。
进一步优选地，所述无机碱包括碱金属的弱酸盐、氨水、铵的弱酸盐中的至少一种。
进一步优选地，所述有机碱包括三乙胺、乙醇胺、二乙醇胺、三乙醇胺，N-甲基二乙醇胺，吡啶，N-甲基吡咯烷酮、4-二甲氨基吡啶中的至少一种。
具体地，所述碱金属的弱酸盐包括碳酸锂、碳酸钠，碳酸钾、碳酸铷、乙酸钠、乙酸钾、磷酸钠、磷酸钾中的至少一种；
具体地，所述铵的弱酸盐包括碳酸铵、磷酸氢二铵中的至少一种。
优选地，所述纤维素、酸酐和酯化反应催化剂三者的含量比为1：(0.1-10)：(0.1-10)；其中，所述纤维素是以葡萄糖结构单元计算。
优选地，所述纤维素在混合溶液中的含量为0.1wt％-20wt％。
优选地，所述酯化反应的条件的温度为0-100℃。
优选地，所述酸酐为含有
Figure PCTCN2018111861-appb-000001
结构的有机酸酐。
优选地，所述纤维素材料包括天然纤维素、再生纤维素、微晶纤维素、纤维素纳米晶、由纤维素制备的相关产品中的至少一种。
优选地，在所述酯化反应的过程中伴随有搅拌处理。
优选地，待反应结束后，还包括对反应产物进行分离纯化处理的步骤。
本发明的另一方面，提供了一种纤维素酯。所述纤维素酯由本发明纤维素酯的制备方法制备获得。
本发明的再一方面，提供了一种纤维素酯的应用。所述纤维素酯在荧光检测、纤维素生物材料、膜、塑料、过滤材料中的应用。
有益效果
与现有技术相比，本发明纤维素酯制备方法采用水作为反应溶剂，其一方面不仅可以起到溶胀纤维素，增大纤维素的接触面积的作用，还可以有效溶解酯化反应催化剂，从而促进酸酐与纤维素羟基之间的酯化反应，使得纤维素酯含有功能基团，而且还能有效保持所述纤维素材料原有结构；另一方面，所述制备方法构建的水相酯化反应体系安全，环保，一次性法投料大幅简化了工序步骤，提高了反应效率，降低了经济成本。
本发明纤维素酯富含功能基团，可以进行进一步修饰改性，还有效保留了纤维素原有的力学性能。
由于纤维素酯制备方法简便，成本低，而且制备获得的纤维素酯富含功能基团，可进行进一步的修饰改性，因此其应用范围有效被扩展，而且能够提高相应产品的性能，降低相应成本的经济成本。
附图说明
下面将结合附图及实施例对本发明作进一步说明，附图中：
图1为实施例5中微晶纤维素颗粒和微晶纤维素酯颗粒的红外谱图；其中，虚线曲线为微晶纤维素的红外谱图，实线曲线为纤维素酯的红外谱图
图2为实施例5中纤维素颗粒和纤维素酯颗粒的XPS谱图；其中，虚线曲线为微晶纤维素的XPS谱图，实线曲线为纤维素酯的XPS谱图；
图3为实施例5中纤维素酯颗粒的固体核磁谱图。
本发明的实施方式
为了使本发明要解决的技术问题、技术方案及有益效果更加清楚明白，以下结合实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。
本发明实施例说明书中所提到的各组分的质量不仅仅可以指代各组分的具 体含量，也可以表示各组分间质量的比例关系，因此，只要是按照本发明实施例说明书各组分的含量按比例放大或缩小均在本发明实施例说明书公开的范围之内。具体地，本发明实施例说明书中所述的质量可以是μg、mg、g、kg等化工领域公知的质量单位。
一方面，本发明实施例提供了一种纤维素酯的制备方法的制备方法。所述纤维素酯的制备方法包括如下步骤：
将酸酐、纤维素和酯化反应催化剂加入水中进行混合处理，并进行酯化反应。
这样，所述纤维素酯的制备方法是采用水作为反应溶剂，构建的水相酯化反应。在酯化反应催化剂的作用下，酸酐与纤维素之间发生酯化反应，实现对纤维素进行改性处理，生成纤维素酯，从赋予纤维素酯相应的性能，如良好的接枝性能，并保留纤维素良好的力学等性能。
在一实施例中，所述酯化反应催化剂包括无机碱和/或溶于水的有机碱。其中，所述无机碱可以包括碱金属的弱酸盐、氨水、铵的弱酸盐中的至少一种；具体的，所述碱金属的弱酸盐可以包括碳酸锂、碳酸钠，碳酸钾、碳酸铷、乙酸钠、乙酸钾、磷酸钠、磷酸钾中的至少一种；所述铵的弱酸盐可以包括碳酸铵、磷酸氢二铵中的至少一种。
所述有机碱可以包括三乙胺、乙醇胺、二乙醇胺、三乙醇胺，N-甲基二乙醇胺，吡啶，N-甲基吡咯烷酮、4-二甲氨基吡啶中的至少一种。
上述选用的该些碱性催化剂一方面具有良好的水溶性，能够有效溶解于水中，提高催化剂的分散性，从而提高催化剂的催化效果，从而提高酸酐与纤维素羟基之间的酯化反应；另一方面，该些催化剂成本低，对环境和人体无害，实现所述制备方法的环保安全，并降低了生产成本。
所述酸酐为含有
Figure PCTCN2018111861-appb-000002
结构的有机酸酐。如在具体实施例中，所述有机酸酐可以但不限于乙酸酐、丙酸酐、丁二酸酐、戊二酸酐、己二酸酐、马来酸酐、衣康酸酐、丙烯酸酐、甲基丙烯酸酐、氯乙酸酐，溴乙酸酐、碘乙酸酐等中的 至少一种。该些酸酐能够有效酯化结合于纤维素上，如将双键、烷基链、氯代烃等功能官能团引入纤维素，从而改善纤维素的如溶解性等性能，并为其改性和表面功能化提供便利。
所述纤维素作为反应物之一，其可以选用天然纤维素、再生纤维素、微晶纤维素、纤维素纳米晶、由纤维素制备的相关产品中的至少一种，其中，由纤维素制备的相关产品包括如纤维素纤维、纤维素薄膜、纤纤维素纸、纤维素微球等，其可以根据需要进行选用。
在上述各实施例的基础上，所述酯化反应的温度可以控制在0-100℃，酯化反应时间可以是充分的，如0.01-72小时。通过对酯化反应的温度和时间等因素进行控制和调节，能够有效提高酯化反应效率，同时保证纤维素原结构的稳定。
在进一步实施例中，在所述酯化反应的过程中，可以对酯化反应体系进行搅拌处理，如利用外加作用实现所述酯化反应体系实现搅拌处理，具体的如可以搅拌、振荡或超声等方式。对酯化反应体系进行搅拌反应能够有效增强反应物的分散度，提高酯化反应的效率。
另外，上述各实施例中的酯化反应体系中，所述酸酐、酯化反应催化剂的含量优选相对纤维素足量，以实现对纤维素充分的改性处理。一实施例中，所述纤维素、酸酐和酯化反应催化剂三者的含量比为1：(0.1-10)：(0.1-10)；其中，所述纤维素是以葡萄糖结构单元计算。另一实施例中，所述纤维素在混合溶液中的含量为0.1wt％-20wt％，进一步为0.1wt％-10wt％。通过对优化反应的含量比例和浓度，从而提高酯化反应效率，提高纤维素酯的得率。
待所述酯化反应结束后，通过对反应后的反应混合物进行纯化处理，从而得到所述纤维素酯。具体实施例中，所述纯化处理包括过滤、离心、透析或真空干燥等处理步骤。
因此，上文所述的纤维素酯的制备方法构建的水相酯化反应体系对纤维素进行酯化反应，水溶剂不仅能够有效起到溶胀纤维素的作用，增大纤维素与其 他反应物接触的面积，还可以有效溶解酯化反应催化剂，从而促进酸酐与纤维素羟基之间的酯化反应，使得纤维素酯含有功能基团，从而使得所述纤维素酯可进行进一步的修饰改性。而且有效能够保持所述纤维素材料的原有结构。而且所述制备方法构建的水相酯化反应体系安全，环保，而且一次性法投料大幅简化了工序步骤，提高了反应效率，降低了经济成本，有效避免可以避免有机溶剂使用带来的高成本、复杂生产操作以及后处理困难等问题。
在上文所述纤维素酯制备方法的基础上，本发明实施例还提供了一种纤维素酯。所述纤维素酯是由上文所述纤维素酯制备方法制备形成。因此，所述纤维素酯富含有功能基团，可被进一步修饰改性，而且具有良好的机械性能。正因此如此，所述纤维素酯的应用范围得到了有效的扩展，如所述纤维素酯可以在荧光检测、纤维素生物材料、膜、塑料、过滤材料中的应用。
现结合具体实例，对本发明实施例进行进一步详细说明。
实施例1
本实施例提供一种纤维素酯及其制备方法。所述纤维素酯制备方法按照如下方法制备：
将30毫摩尔的碳酸钠，30毫摩尔的乙酸酐和1.62克的微晶纤维素依次加入到50mL水中，室温搅拌12小时；然后离心分离，再用甲醇漂洗，离心分离，最后，经真空干燥得到颗粒状的纤维素酯。
实施例2
本实施例提供一种纤维素酯及其制备方法。所述纤维素酯制备方法按照如下方法制备：
将30毫摩尔的碳酸钾，30毫摩尔甲基丙烯酸酐和1.62克的纤维素薄膜依次加入到50mL水中，40℃振荡12小时；然后取出，再用甲醇漂洗，最后，经真空干燥得到纤维素酯薄膜。
实施例3
本实施例提供一种纤维素酯及其制备方法。所述纤维素酯制备方法按照如 下方法制备：
将30毫摩尔的碳酸钾，30毫摩尔甲基丙烯酸酐和0.81克的纤维素纳米晶依次加入到50mL水中，50℃搅拌12小时；然后离心分离，再用甲醇透析，最后，经真空干燥得到纤维素酯纳米颗粒。
实施例4
本实施例提供一种纤维素酯及其制备方法。所述纤维素酯制备方法按照如下方法制备：
将10毫摩尔的碳酸钾，10毫摩尔甲基丙烯酸酐和1.62克的微晶纤维素依次加入到50mL水中，20℃振荡12小时；然后取出，再用甲醇漂洗，最后，经真空干燥得到颗粒状的纤维素酯。
实施例5
本实施例提供一种纤维素酯及其制备方法。所述纤维素酯制备方法按照如下方法制备：
将60毫摩尔的碳酸钾，60毫摩尔甲基丙烯酸酐和1.62克的微晶纤维素依次加入到50mL水中，40℃振荡12小时；然后取出，再用甲醇漂洗，最后，经真空干燥得到颗粒状的纤维素酯。
实施例6
本实施例提供一种纤维素酯及其制备方法。所述纤维素酯制备方法按照如下方法制备：
将90毫摩尔的碳酸钾，90毫摩尔甲基丙烯酸酐和1.62克的微晶纤维素依次加入到50mL水中，60℃振荡12小时；然后取出，再用甲醇漂洗，最后，经真空干燥得到颗粒状的纤维素酯。
对比例1
将30毫摩尔的氢氧化钠，30毫摩尔甲基丙烯酸酐和1.62克的微晶纤维素依次加入到50mL水中，60℃振荡12小时；然后取出，再用甲醇漂洗，最后，经真空干燥得到颗粒状的纤维素，产物中未检测到纤维素酯的生成。
纤维素酯相关特性测试
将实施例1-实施例6提供的纤维素和纤维素酯分别进行红外谱图、XPS谱图和核磁分析。其中，所述实施例5中的微晶纤维素和纤维素酯的红外谱图为图1所示，其中，图1中的虚线曲线为微晶纤维素的红外谱图，实线曲线为纤维素酯的红外谱图。所述实施例5中的微晶纤维素和纤维素酯的XPS谱图为图2所示，其中，图2中的虚线曲线为微晶纤维素的XPS谱图，实线曲线为纤维素酯的XPS谱图；所述实施例5中的纤维素酯的固体核磁谱图为图3所示。
由图1可知，相对微晶纤维素的红外谱图可知，实施例提供的纤维素酯含有
Figure PCTCN2018111861-appb-000003
基团特征峰，因此，通过实施例5的酯化反应，在纤维素上成功接枝改性。
由图2可知，微晶纤维素的晶体结构未发生明显变化。
由图3可知，核磁谱图上出现甲基丙烯酸酯的特征峰，说明甲基丙烯酸酯已经接枝到纤维素基体上。
另外，实施例1-4、6中纤维素和纤维素酯分别测得的红外、XPS和核磁分析的图谱分别与图1-3相似。
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。

Claims (10)

  1. 一种纤维素酯的制备方法，其特征在于，包括如下步骤：
    将酸酐、纤维素材料和酯化反应催化剂加入水中进行混合处理，并进行酯化反应。
  2. 根据权利要求1所述的制备方法，其特征在于：所述酯化反应催化剂包括无机碱和/或溶于水的有机碱。
  3. 根据权利要求2所述的制备方法，其特征在于：所述无机碱包括碱金属的弱酸盐、氨水、铵的弱酸盐中的至少一种；
    所述有机碱包括三乙胺、乙醇胺、二乙醇胺、三乙醇胺，N-甲基二乙醇胺，吡啶，N-甲基吡咯烷酮、4-二甲氨基吡啶中的至少一种。
  4. 根据权利要求3所述的制备方法，其特征在于：所述碱金属的弱酸盐包括碳酸锂、碳酸钠，碳酸钾、碳酸铷、乙酸钠、乙酸钾、磷酸钠、磷酸钾中的至少一种；
    所述铵的弱酸盐包括碳酸铵、磷酸氢二铵中的至少一种。
  5. 根据权利要求1-2、4-5任一项所述的制备方法，其特征在于：所述纤维素、酸酐和酯化反应催化剂三者的含量比为1：(0.1-10)：(0.1-10)；其中，所述纤维素是以葡萄糖结构单元计算；和/或
    所述纤维素在混合溶液中的含量为0.1wt％-20wt％。
  6. 根据权利要求1-2、4-5任一项所述的制备方法，其特征在于：所述酯化反应的条件的温度为0-100℃。
  7. 根据权利要求1-2、4-5任一项所述的制备方法，其特征在于：所述酸酐为含有
    Figure PCTCN2018111861-appb-100001
    结构的有机酸酐；和/或
    所述纤维素材料包括天然纤维素、再生纤维素、微晶纤维素、纤维素纳米晶、由纤维素制备的相关产品中的至少一种。
  8. 根据权利要求1-2、4-5任一项所述的制备方法，其特征在于：在所述酯 化反应的过程中伴随有搅拌处理；和/或
    待反应结束后，还包括对反应产物进行分离纯化处理的步骤。
  9. 一种纤维素酯，其特征在于：所述纤维素酯是由权利要求1-8任一项所述制备方法制备获得。
  10. 根据权利要求9所述的纤维素酯在荧光检测、纤维素生物材料、膜、塑料、过滤材料中的应用。
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