WO2021196270A1 - 一种新型辛烯基琥珀酸颗粒淀粉酯的高效制备方法 - Google Patents

一种新型辛烯基琥珀酸颗粒淀粉酯的高效制备方法 Download PDF

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WO2021196270A1
WO2021196270A1 PCT/CN2020/084592 CN2020084592W WO2021196270A1 WO 2021196270 A1 WO2021196270 A1 WO 2021196270A1 CN 2020084592 W CN2020084592 W CN 2020084592W WO 2021196270 A1 WO2021196270 A1 WO 2021196270A1
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starch
octenyl succinic
ionic liquid
succinic acid
octenyl
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PCT/CN2020/084592
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English (en)
French (fr)
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王书军
王晋伟
任菲
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天津科技大学
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Priority to US17/389,330 priority Critical patent/US20210355245A1/en
Publication of WO2021196270A1 publication Critical patent/WO2021196270A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B31/00—Preparation of derivatives of starch
    • C08B31/02—Esters
    • C08B31/04—Esters of organic acids, e.g. alkenyl-succinated starch
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/002—Methods
    • B29B7/005—Methods for mixing in batches
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/02—Making granules by dividing preformed material

Definitions

  • the invention relates to the field of chemical modification of starch, in particular to a method for preparing a novel octenyl succinic acid granular starch ester in an ionic liquid aqueous solution system.
  • Starch is an easy-to-obtain, renewable, non-toxic, and biodegradable natural polysaccharide molecule. As one of the most abundant polysaccharides in nature, it has been used as a multi-purpose eco-compatible biopolymer material, but the limitations of natural starch in terms of functional properties limit its application in various industries. Therefore, the purpose of modifying starch is to eliminate the defects of natural starch and make it better used in industrial production.
  • the modification methods of starch are generally divided into physical, chemical and biological modification methods.
  • the chemical modification method is a relatively mature starch processing method currently used. Its advantage is that the starch processing capacity is large and it is easy to realize industrialized mass production.
  • a large part of the chemical modification of starch is through derivatization, such as esterification, etherification or cross-linking, to introduce new functional groups in (between) starch molecules, which results in a huge change in the functional properties of starch.
  • Octenyl succinic anhydride has a molecular formula of C 12 H 18 O 3 and a molecular weight of 210.27. It has a unique cyclic dicarboxylic acid structure. When it undergoes an esterification reaction with starch, it makes the original hydrophilic Because of the introduction of succinic acid group, the starch has hydrophobic characteristics, which causes the amphiphilicity of the whole molecule. Amphiphilic polymers are widely used in the fields of emulsification, packaging, film coating and gel production. Starch octenyl succinate has superior emulsification properties and can be widely used as emulsifier or embedding in the food, medicine and cosmetic industries Materials, etc.
  • Starch octenyl succinate is generally synthesized under water phase conditions, and its essence is to use OSA and starch granules to undergo an esterification reaction under alkaline conditions. Due to the low solubility of OSA in water and the different surface structures of different types of starch granules, it is difficult for OSA to fully contact the starch granules and penetrate into the interior during the modification reaction, resulting in low reaction efficiency. Therefore, by changing the medium of the esterification reaction, it is important to affect the reactivity of starch and OSA, which will directly affect the reaction efficiency.
  • the technical problem to be solved by the present invention is to propose an efficient preparation method of a novel octenyl succinic acid granular starch ester.
  • An octenyl succinic acid granular starch ester is formed by the esterification reaction of corn starch or potato starch through octenyl succinic anhydride in a 1-ethyl-3-methylimidazole acetate ionic liquid aqueous solution.
  • the one kind of octenyl succinic acid granular starch ester is prepared by the following steps:
  • the ionic liquid is 1-ethyl-3-methylimidazole acetate, and the water is deionized water.
  • the mass ratio of the ionic liquid to water in the ionic liquid aqueous system is 2:8-8:2.
  • the mass ratio of the ionic liquid to water in the aqueous ionic liquid system is any one of 2:8, 5:5 or 8:2,
  • the mass ratio of ionic liquid to water in the aqueous ionic liquid system is 2:8.
  • the temperature of the ionic liquid aqueous solution system was 23°C, and the rotation speed was 300 rpm.
  • the corn starch or potato starch is adjusted into starch milk with a prepared ionic liquid aqueous solution; then sodium hydroxide solution is added to adjust the pH value of the starch milk to 8.5; at a certain temperature, octenyl succinic anhydride is added to the starch milk.
  • octenyl succinic anhydride is added to the starch milk.
  • the octenyl succinic acid granular starch ester is obtained.
  • Plant starches such as mung bean starch, sweet potato starch and rice starch are modified by the method and reaction system of the present invention, and similar results are obtained.
  • octenyl succinic anhydride modified starch with high degree of substitution is achieved by destroying the granular structure of the starch in an organic solvent. Through this method, although the degree of substitution is high, part of the functional properties of starch will be lost due to the destruction of its granular structure.
  • the method of the present invention adopts different technical schemes to prepare an octenyl succinic acid granular starch ester. Compared with the same conditions, the degree of substitution is improved while retaining many functional properties of the starch itself.
  • the present invention has the following advantages and effects:
  • the present invention is suitable for the esterification modification of octenyl succinic anhydride of starch from different plant sources. It is simple and easy to operate, energy-saving and low-consumption, green and sustainable, easy to industrialized production, and is the preparation of a new type of starch octenyl succinate. Provide a new idea.
  • the present invention uses the mixed solution of 1-ethyl-3-methylimidazole acetate and deionized water as the reaction medium to weakly damage the structure of starch granules, and for the first time it is applied as a modification medium
  • the modified preparation method of octenyl succinate starch ester the granular form of starch and part of its own functional properties are retained; at the same time, it is also given new properties and has good emulsification properties, including emulsification activity or emulsification stability, It effectively improves the synthesis efficiency of octenyl succinic acid granular starch ester, and greatly improves the functional properties of the final product to meet the needs of different industrial products.
  • the preparation of octenyl succinic acid granular starch ester specifically includes the following steps:
  • the corn starch or potato starch is adjusted into starch milk with a prepared ionic liquid aqueous solution; then sodium hydroxide solution is added to adjust the pH value of the starch milk to 8.5; at a certain temperature, octenyl succinic anhydride is added to the starch milk.
  • octenyl succinic anhydride is added to the starch milk.
  • the octenyl succinic acid granular starch ester is obtained.
  • the preparation of octenyl succinic acid granular starch ester specifically includes the following steps:
  • the corn starch or potato starch is adjusted into starch milk with a prepared ionic liquid aqueous solution; then sodium hydroxide solution is added to adjust the pH value of the starch milk to 8.5; at a certain temperature, octenyl succinic anhydride is added to the starch milk.
  • octenyl succinic anhydride is added to the starch milk.
  • the octenyl succinic acid granular starch ester is obtained.
  • the preparation of octenyl succinic acid granular starch ester specifically includes the following steps:
  • ionic liquid aqueous solution Add a certain quality of deionized water to a certain amount of 1-ethyl-3-methylimidazole acetate ionic liquid, and configure it to a mixture of 8:2 (w/w) The solution was magnetically stirred (300 rpm) at room temperature for 3 minutes to obtain an ionic liquid aqueous solution system.
  • the corn starch and potato starch are respectively adjusted into starch milk with the prepared ionic liquid aqueous solution; then sodium hydroxide solution is added to adjust the pH value of the starch milk to 8.5; at a certain temperature, octenyl succinic anhydride is added to the starch milk Carry out the esterification reaction, keep the pH of the reaction system at 8.4-8.5, and keep stirring; after the reaction, adjust the pH of the emulsion after the reaction to 6.5 with hydrochloric acid solution; then alternately centrifuge and wash with deionized water and 70% ethanol, and then Dry octenyl succinic acid granular starch ester.
  • the preparation of octenyl succinic acid granular starch ester specifically includes the following steps:
  • ionic liquid aqueous solution Add a certain quality of deionized water to a certain amount of 1-ethyl-3-methylimidazole acetate ionic liquid, and configure it into a mixture of 2:8 (w/w) The solution was magnetically stirred (300 rpm) at 23°C for 3 minutes to obtain an ionic liquid aqueous solution system.
  • the obtained starch milk was washed once with 70% ethanol by centrifugation, and then washed once with deionized water, repeated 3 times, with a centrifugal force of 4500 g and a centrifugal time of 10 minutes, to obtain a starch ester sample.
  • the starch ester sample was dried in an oven at 30°C for 12 hours, and then ground through a 100-mesh screen to obtain octenyl succinate corn starch ester A1 and octenyl succinate potato starch ester A2.
  • the preparation of octenyl succinic acid granular starch ester specifically includes the following steps:
  • the obtained starch milk was washed once with 70% ethanol by centrifugation, and then washed once with deionized water, repeated three times, with a centrifugal force of 4500 g and a centrifugal time of 10 minutes to obtain a starch ester sample.
  • the starch ester sample was dried in an oven at 30°C for 12 hours, and then ground through a 100-mesh screen to obtain octenyl succinate corn starch ester B1 and octenyl succinate potato starch ester B2.
  • the preparation of octenyl succinic acid granular starch ester specifically includes the following steps:
  • ionic liquid aqueous solution Add a certain quality of deionized water to a certain amount of 1-ethyl-3-methylimidazole acetate ionic liquid, and configure it to a mixture of 8:2 (w/w) The solution was magnetically stirred (300 rpm) at 23°C for 3 minutes to obtain an ionic liquid aqueous solution system.
  • the obtained starch milk was washed once with 70% ethanol by centrifugation, and then washed once with deionized water, repeated three times, with a centrifugal force of 4500 g and a centrifugal time of 10 minutes to obtain a starch ester sample.
  • the starch ester sample was dried in an oven at 30°C for 12 hours, and then ground through a 100-mesh screen to obtain octenyl succinate corn starch ester C1 and octenyl succinate potato starch ester C2.
  • the octenyl succinate corn starch esters A1 to C1 and the octenyl succinic acid potato starch esters A2 to C2 of Examples 5-7 were combined with the modified octenyl succinate corn/potato starch ester in a traditional aqueous medium.
  • the degree of substitution and emulsification ability were compared; at the same time, the octenyl succinate corn starch ester A1 ⁇ C1 and the octenyl succinate potato starch ester A2 ⁇ C2 of Examples 5-7 were compared.
  • Table 1 Comparison of degree of substitution, reaction efficiency and emulsification ability of starch octenyl succinate prepared by different reaction media
  • the preparation of octenyl succinic acid granular starch ester specifically includes the following steps:
  • ionic liquid aqueous solution Add a certain quality of deionized water to a quantitative 1-ethyl-3-methylimidazole acetate ionic liquid, and configure it into a 2:8 (w/w) mixed solution , Magnetic stirring (300 rpm) at 23° C. for 3 minutes to obtain an ionic liquid aqueous solution system.
  • the obtained starch milk was washed once with 70% ethanol by centrifugation, and then washed once with deionized water, repeated three times, with a centrifugal force of 4500 g and a centrifugal time of 10 minutes to obtain a starch ester sample.
  • the starch ester samples were dried in an oven at 30°C for 12 hours, and then ground through a 100 mesh screen to obtain octenyl succinate mung bean starch ester A3, octenyl succinate sweet potato starch ester A4 and octenyl succinate rice starch Esters A5.
  • the indicators of A3, A4 and A5 are all close to A1 and A2, but slightly worse than A1 and A2.

Abstract

提供一种新型辛烯基琥珀酸颗粒淀粉酯的高效制备方法，该制备方法包括：将1-乙基-3-甲基咪唑醋酸盐([Emim][OAc])离子液体与去离子水在室温下按照不同质量比(2:8/5:5/8:2)混合，采用湿法工艺，以离子液体水溶液为介质，通过淀粉与辛烯基琥珀酸酐进行酯化反应生成辛烯基琥珀酸颗粒淀粉酯。提供的辛烯基琥珀酸淀粉酯的制备方法，利用离子液体水溶液能够在室温下对不同植物来源淀粉颗粒结构有破坏作用，导致颗粒表面产生孔洞、空腔或褶皱等影响这一原理，首次将该体系应用于不同类型淀粉的辛烯基琥珀酸颗粒淀粉酯的制备，有效地提高辛烯基琥珀酸淀粉酯的合成效率，并保留了终产物的颗粒形态，提高了其功能性质。

Description

一种新型辛烯基琥珀酸颗粒淀粉酯的高效制备方法 技术领域
本发明涉及淀粉的化学改性领域，具体的说涉及在一种离子液体水溶液体系中新型辛烯基琥珀酸颗粒淀粉酯的制备方法。
背景技术
近年来，由于化石燃料资源的减少，各种工业产品的生物质高效利用的趋势越来越明显。淀粉是一种易于获得、可再生、无毒、可生物降解的天然多糖分子。作为自然界中最丰富的多糖之一，它已被用作多种用途的生态兼容生物高分子材料，但天然淀粉在功能性质方面的局限限制了其在各种工业中的应用。因此，对淀粉进行改性的目的是为了消除天然淀粉存在的缺陷，使其更好地应用于工业生产中。
淀粉的改性手段一般分为物理、化学和生物改性方法。化学改性法是目前应用较为成熟的淀粉处理方法，其优点在于淀粉处理量大，易于实现工业化的大批量生产。对淀粉进行化学改性，很大一部分是通过衍生化作用，如酯化、醚化或交联等反应，在淀粉分子内(间)引入新的官能团，由此造成淀粉功能性质的巨大改变。
辛烯基琥珀酸酐(octenyl succinic anhydride,OSA)，分子式为C 12H 18O 3，分子量是210.27，具有独特的环状二元羧酸结构，在与淀粉发生酯化反应时，使原本亲水的淀粉由于琥珀酸基团的引入而带有了疏水的特性，从而造成整个分子的双亲性。双亲性聚合物在乳化、包装、涂膜和凝胶生产领域中应用广泛，辛烯基琥珀酸淀粉酯具有优越的乳化特性，可在食品、医药和化妆品行业被广泛应用做乳化剂或包埋材料等。
辛烯基琥珀酸淀粉酯一般是在水相条件下合成，其本质为利用OSA与淀粉颗粒在碱性条件下发生酯化反应。由于OSA在水中的溶解度很低，且不同类型淀粉颗粒的表面结构不同，所以在发生改性反应时，OSA很难与淀粉颗粒充分接触并渗透至其内部，由此造成反应效率很低。因此，通过改变酯化反应的媒介，从而影响淀粉与OSA的反应活性很重要，会直接影响反应效率。
在过去的几十年中，室温离子液体(ionic liquids,ILs)由于具有生物可降解性、低毒性和可回收性等优点，成为人们理想的绿色溶剂和碳水化合物(纤维素和淀粉)的酯化反应介质。与传统反应介质相比，在离子液体体系中的淀粉酯化反应效率和取代度有明显的提高，但在纯离子液体体系中的改性反应条件往往是严苛的(温度高、时间长或添加催化剂)，导致淀粉颗粒结构被破坏，失去了淀粉自身的功能性质，同时产生较多副反应。
发明内容
本发明的所要解决的技术问题是提出一种新型辛烯基琥珀酸颗粒淀粉酯的高效制备方法。
为达到上述目的，本发明创造的技术方案是这样实现的：
一种辛烯基琥珀酸颗粒淀粉酯由玉米淀粉或马铃薯淀粉经辛烯基琥珀酸酐在1-乙基-3-甲基咪唑醋酸盐离子液体水溶液中酯化反应而成。
所述的一种辛烯基琥珀酸颗粒淀粉酯，由如下步骤制备而成：
1)在室温下配制不同质量比的离子液体水溶液体系用于颗粒淀粉酯的辛烯基琥珀酸酐改性；本发明指的室温是20-25℃。
2)采用湿法工艺，在离子液体水溶液体系中通过不同植物来源淀粉分别与辛烯基琥珀酸酐发生酯化反应制备颗粒状辛烯基琥珀酸淀粉酯。
优选的，所述步骤1)中：
所述离子液体选用1-乙基-3-甲基咪唑醋酸盐，水选用去离子水。
优选的，所述步骤1)中：
所述离子液体水溶液体系离子液体与水的质量比为2:8-8:2。
优选的，所述离子液体水溶液体系离子液体与水的质量比为2:8、5:5或8:2中的任意一种，
优选的，所述离子液体水溶液体系离子液体与水的质量比为2:8。
优选的，所述步骤1)中：
配制离子液体水溶液体系的温度为23℃，转速为300rpm。
优选的，所述步骤2)中：
将玉米淀粉或马铃薯淀粉用配置好的离子液体水溶液调成淀粉乳；然后加入氢氧化钠溶液将淀粉乳的pH值调节成8.5；在一定温度下，向淀粉乳中加入辛烯基琥珀酸酐进行酯化反应，保持反应体系的pH值为8.4～8.5，不断搅拌；反应结束后，用盐酸溶液调节反应后乳液的pH值至6.5；然后用去离子水和70％乙醇交替离心洗涤，再干燥即得辛烯基琥珀酸颗粒淀粉酯。
优选的，所述步骤2)中：
将玉米淀粉或马铃薯淀粉用配置好的离子液体水溶液调成浓度为15wt％淀粉乳；然后加入浓度为3％氢氧化钠溶液将淀粉乳的pH值调节成8.5；先称取淀粉干基质量3％的辛烯基琥珀酸酐，将辛烯基琥珀酸酐用异丙醇稀释3-6倍，在20～40℃温度下，在2个小时内滴入淀粉乳中进行酯化反应；酯化反应过程磁力搅拌，转速200rpm；控制整个反应时间为3-5小时；反应结束后，用浓度为3％盐酸溶液调节反应后乳液的pH值至6.5；用去离子水和70％乙醇交替各离心洗涤3遍，离心力4500g，离心时间为10分钟；干燥方式是在烘箱内30℃，放置12小时，即得辛烯基琥珀酸颗粒淀粉酯。
绿豆淀粉、红薯淀粉、大米淀粉等植物淀粉用本发明方法及反应体系来改性，得到相类似的结果。
大部分高取代度的辛烯基琥珀酸酐改性淀粉都是在有机溶剂下，破坏淀粉的颗粒结构来实现的。通过这样的方法，尽管取代度很高，但是淀粉的部分功能性质会因其颗粒结构的破坏而丧失。本发明的方法制备得到一种辛烯基琥珀酸颗粒淀粉酯采用的技术方案不同，在同等条件下对比，提高取代度的同时保留了淀粉自身的很多功能性质。
本发明与传统方法相比较具有以下优点效果：
(1)本发明适用于不同植物来源淀粉的辛烯基琥珀酸酐酯化改性，操作简单易行，节能低耗，绿色可持续，易于工业化生产，为新型辛烯基琥珀酸淀粉酯的制备提供一种新思路。
(2)本发明利用1-乙基-3-甲基咪唑醋酸盐与去离子水混合溶液作为反应介质，对淀粉颗粒结构进行弱破坏作用这一原理，首次将其作为改性介质应用于辛烯基琥珀酸淀粉酯的改性制备方法中，保留了淀粉的颗粒形态及自身部分功能性质；同时，也赋予其新的性质，有较好的乳化性能，包括乳化活性或乳化稳定性，有效地提高了辛烯基琥珀酸颗粒淀粉酯的合成效率，并极大改善了终产物的功能性质，以满足不同工业产品的需求。
具体实施方式
下面将更详细地描述本公开的示例性实施方式，对本发明作进一步的说明。虽然说明书中显示了本公开的示例性实施方式，然而应当理解，可以以各种形式实现本公开而不应被这里阐述的实施方式所限制。相反，提供这些实施方式是为了能够更透彻地理解本公开，并且能够将本公开的范围完整的传达给本领域的技术人员，以帮助本领域技术人员对本发明的发明构思、技术方案有更完整、准确和深入的理解。
实施例1
1)在室温(20-25℃)温度下配制不同质量比的离子液体水溶液体系用于颗粒淀粉酯的辛烯基琥珀酸酐改性；
2)采用湿法工艺，在离子液体水溶液体系中通过不同植物来源淀粉分别与辛烯基琥珀酸酐发生酯化反应制备颗粒状辛烯基琥珀酸淀粉酯。
实施例2
分别以玉米淀粉或马铃薯淀粉为原料实例，进行辛烯基琥珀酸颗粒淀粉酯的制备，具体包括以下步骤：
1)离子液体水溶液的配制：向一定量的1-乙基-3-甲基咪唑醋酸盐离子液体中加入一定质量的去离子水，将其配置成2:8(w/w)的混合溶液，于室温下磁力搅拌(300rpm)3分钟，得到离子液体水溶液体系。
将玉米淀粉或马铃薯淀粉用配置好的离子液体水溶液调成淀粉乳；然后加入氢氧化钠溶液将淀粉乳的pH值调节成8.5；在一定温度下，向淀粉乳中加入辛烯基琥珀酸酐进行酯化反应，保持反应体系的pH值为8.4～8.5，不断搅拌；反应结束后，用盐酸溶液调节反应后乳液的pH值至6.5；然后用去离子水和70％乙醇交替离心洗涤，再干燥即得辛烯基琥珀酸颗粒淀粉酯。
实施例3
分别以玉米淀粉或马铃薯淀粉为原料实例，进行辛烯基琥珀酸颗粒淀粉酯的制备，具体包括以下步骤：
1)离子液体水溶液的配制：向一定量的1-乙基-3-甲基咪唑醋酸盐离子液体中加入一定质量的去离子水，将其配置成5:5(w/w)的混合溶液，于室温下磁力搅拌(300rpm)3分钟，得到离子液体水溶液体系。
将玉米淀粉或马铃薯淀粉用配置好的离子液体水溶液调成淀粉乳；然后加入氢氧化钠溶液将淀粉乳的pH值调节成8.5；在一定温度下，向淀粉乳中加入辛烯基琥珀酸酐进行酯化反应，保持反应体系的pH值为8.4～8.5，不断搅拌；反应结束后，用盐酸溶液调节反应后乳液的pH值至6.5；然后用去离子水和70％乙醇交替离心洗涤，再干燥即得辛烯基琥珀酸颗粒淀粉酯。
实施例4
分别以玉米淀粉或马铃薯淀粉为原料实例，进行辛烯基琥珀酸颗粒淀粉酯的制备，具体包括以下步骤：
1)离子液体水溶液的配制：向一定量的1-乙基-3-甲基咪唑醋酸盐离子液体中加入一定质量的去离子水，将其配置成8:2(w/w)的混合溶液，于室温下磁力搅拌(300rpm)3分钟，得到离子液体水溶液体系。
将玉米淀粉和马铃薯淀粉分别用配置好的离子液体水溶液调成淀粉乳；然后加入氢氧化钠溶液将淀粉乳的pH值调节成8.5；在一定温度下，向淀粉乳中加入辛烯基琥珀酸酐进行酯化反应，保持反应体系的pH值为8.4～8.5，不断搅拌；反应结束后，用盐酸溶液调节反应后乳液的pH值至6.5；然后用去离子水和70％乙醇交替离心洗涤，再干燥即得辛烯基琥珀酸颗粒淀粉酯。
实施例5
分别以玉米淀粉或马铃薯淀粉为原料实例，进行辛烯基琥珀酸颗粒淀粉酯的制备，具体包括以下步骤：
1)离子液体水溶液的配制：向一定量的1-乙基-3-甲基咪唑醋酸盐离子液体中加入一定质量的去离子水，将其配置成2:8(w/w)的混合溶液，于23℃下磁力搅拌(300rpm)3分钟，得到离子液体水溶液体系。
2)辛烯基琥珀酸颗粒淀粉酯的合成：将玉米淀粉和马铃薯淀粉分别用配置好的离子液体水溶液调成15wt％的淀粉乳，利用3％NaOH溶液调节淀粉乳的pH值为8.5，称取淀粉干基质量的3％的辛烯基琥珀酸酐，用异丙醇稀释5倍，于2小时内缓慢滴加入淀粉乳内，整个反应体系在35℃磁力搅拌下维持pH值8.4-8.5，磁力搅拌200rpm，持续反应4小时，随后用3％HCl溶液将反应后的淀粉乳调节pH值至6.5。将得到的淀粉乳先用70％乙醇离心洗涤1遍，再用去离子水离心洗涤1遍，重复3次，离心力4500g，离心时间为10分钟，得到淀粉酯样品。将淀粉酯样品置于30℃烘箱中干燥12小时，然后研磨过100目筛网，得到辛烯基琥珀酸玉米淀粉酯A1和辛烯基琥珀酸马铃薯淀粉酯A2。
实施例6：
分别以玉米淀粉或马铃薯淀粉为原料实例，进行辛烯基琥珀酸颗粒淀粉酯的制备，具体包括以下步骤：
1)离子液体水溶液的配制：向一定量的1-乙基-3-甲基咪唑醋酸盐离子液体中加入一定质量的去离子水，将其配置成5:5(w/w)的混合溶液，于23℃下磁力搅拌(300rpm)3分钟，得到离子液体水溶液体系。
2)辛烯基琥珀酸淀粉酯的合成：将玉米淀粉或马铃薯淀粉用配置好的离子液体水溶液调成15wt％的淀粉乳，利用3％NaOH溶液调节淀粉乳的pH值为8.5，称取淀粉干基质量的3％的辛烯基琥珀酸酐，用异丙醇稀释6倍，于2小时内缓慢滴加入淀粉乳内，整个反应体系在20℃磁力搅拌下维持pH值8.4-8.5，磁力搅拌200rpm，持续反应5小时，随后用3％HCl溶液将反应后的淀粉乳调节pH值至6.5。将得到的淀粉乳先用70％乙醇离心洗涤1遍，再用去离子水离心洗涤1遍，重复3次，离心力4500g，离心时间为10分钟，得到淀粉酯样品。将淀粉酯样品置于30℃烘箱中干燥12小时，然后研磨过100目筛网，得到辛烯基琥珀酸玉米淀粉酯B1和辛烯基琥珀酸马铃薯淀粉酯B2。
实施例7：
分别以玉米淀粉或马铃薯淀粉为原料实例，进行辛烯基琥珀酸颗粒淀粉酯的制备，具体包括以下步骤：
1)离子液体水溶液的配制：向一定量的1-乙基-3-甲基咪唑醋酸盐离子液体中加入一定质量的去离子水，将其配置成8:2(w/w)的混合溶液，于23℃下磁力搅拌(300rpm)3分钟，得到离子液体水溶液体系。
2)辛烯基琥珀酸淀粉酯的合成：将玉米淀粉或马铃薯淀粉用配置好的离子液体水溶液调成15wt％的淀粉乳，利用3％NaOH溶液调节淀粉乳的pH值为8.5，称取淀粉干基质量的3％的辛烯基琥珀酸酐，用异丙醇稀释3倍，于2小时内缓慢滴加入淀粉乳内，整个反应体系在40℃磁力搅拌下维持pH值8.4-8.5，磁力搅拌200rpm，持续反应3小时，随后用3％HCl溶液将反应后的淀粉乳调节pH值至6.5。将得到的淀粉乳先用70％乙醇离心洗涤1遍，再用去离子水离心洗涤1遍，重复3次，离心力4500g，离心时间为10分钟，得到淀粉酯样品。将淀粉酯样品置于30℃烘箱中干燥12小时，然后研磨过100目筛网，得到辛烯基琥珀酸玉米淀粉酯C1和辛烯基琥珀酸马铃薯淀粉酯C2。
实验例1：
将实施例5-7的辛烯基琥珀酸玉米淀粉酯A1～C1，辛烯基琥珀酸马铃薯淀粉酯A2～C2与传统水相介质中改性处理的辛烯基琥珀酸玉米/马铃薯淀粉酯在取代度，乳化能力(乳化活性和乳化稳定性)两方面进行比较；同时将实施例5-7的辛烯基琥珀酸玉米淀粉酯A1～C1，辛烯基琥珀酸马铃薯淀粉酯A2～C2与传统水相介质中改性处理的辛烯基琥珀酸玉米/马铃薯淀粉酯的合成效率方面进行比较，保证除反应体系外，传统制备方法的其余步骤与实施例5的制备方法的步骤相同。对比结果如下表1所示：
表1：不同反应介质制备辛烯基琥珀酸淀粉酯的取代度、反应效率和乳化能力对比
Figure PCTCN2020084592-appb-000001
Figure PCTCN2020084592-appb-000002
注：数值为平均值±标准差。同一列中字母相同的值差异无统计学意义(p<0.05)。
由表1可知，在1-乙基-3-甲基咪唑醋酸盐离子液体水溶液中制备的辛烯基琥珀酸颗粒淀粉酯A1和A2的取代度均高于传统水相中制备的辛烯基琥珀酸淀粉酯，反应效率和取代度的提高效果显著，乳化活性及乳化稳定性也大幅提升，说明使用新体系—“离子液体水溶液”为反应介质，对后续的辛烯基琥珀酸酐改性具有显著的促进作用。而辛烯基琥珀酸玉米淀粉酯A1的各指标明显优于辛烯基琥珀酸马铃薯淀粉酯A2，说明玉米淀粉用于本发明的技术方案效果更好。
实施例8
分别以绿豆淀粉、红薯淀粉或大米淀粉为原料实例，进行辛烯基琥珀酸颗粒淀粉酯的制备，具体包括以下步骤：
1)离子液体水溶液的配制：向定量的1-乙基-3-甲基咪唑醋酸盐离子液体中加入一定质量的去离子水，将其配置成2:8(w/w)的混合溶液，于23℃下磁力搅拌(300rpm)3分钟，得到离子液体水溶液体系。
2)辛烯基琥珀酸颗粒淀粉酯的合成：将玉米淀粉和马铃薯淀粉分别用配置好的离子液体水溶液调成15wt％的淀粉乳，利用3％NaOH溶液调节淀粉乳的pH值为8.5，称取淀粉干基质量的3％的辛烯基琥珀酸酐，用异丙醇稀释5倍，于2小时内缓慢滴加入淀粉乳内，整个反应体系在35℃磁力搅拌下维持pH值8.4-8.5，磁力搅拌200rpm，持续反应4小时，随后用3％HCl溶液将反应后的淀粉乳调节pH值至6.5。将得到的淀粉乳先用70％乙醇离心洗涤1遍，再用去离子水离心洗涤1遍，重复3次，离心力4500g，离心时间为10分钟，得到淀粉酯样品。将淀粉酯样品置于30℃烘箱中干燥12小时，然后研磨过100目筛网，得到辛烯基琥珀酸绿豆淀粉酯A3、辛烯基琥珀酸红薯淀粉酯A4和辛烯基琥珀酸大米淀粉酯A5。
检测A3，A4，A5的各指标均与A1，A2接近，但略差于A1，A2。
以上所述，仅为本发明较佳的具体实施方式，但本发明的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明揭露的技术范围内，可轻易想到的变化或替换，都应涵盖在本发明的保护范围之内。因此，本发明的保护范围应以所述权利要求的保护范围为准。

Claims (10)

  1. 一种新型辛烯基琥珀酸颗粒淀粉酯的高效制备方法，其特征在于，包括以下步骤：
    1)在室温下配制不同质量比的离子液体水溶液体系用于颗粒淀粉酯的辛烯基琥珀酸酐改性；
    2)采用湿法工艺，在离子液体水溶液体系中通过不同植物来源淀粉与辛烯基琥珀酸酐发生酯化反应制备颗粒状辛烯基琥珀酸淀粉酯。
  2. 根据权利要求所述的一种新型辛烯基琥珀酸颗粒淀粉酯的高效制备方法，其特征在于，所述步骤1)中：所述离子液体选用1-乙基-3-甲基咪唑醋酸盐，水选用去离子水。
  3. 根据权利要求1-2任一权利要求所述的一种新型辛烯基琥珀酸颗粒淀粉酯的高效制备方法，其特征在于，所述步骤1)中：所述离子液体水溶液体系离子液体与水的质量比为2:8-8:2。
  4. 根据权利要求1-2任一权利要求所述的一种新型辛烯基琥珀酸颗粒淀粉酯的高效制备方法，其特征在于，所述步骤1)中：所述离子液体水溶液体系离子液体与水的质量比为2:8、5:5或8:2中的任意一种。
  5. 根据权利要求根据权利要求1-2任一权利要求所述的一种新型辛烯基琥珀酸颗粒淀粉酯的高效制备方法，其特征在于，所述步骤1)中：离子液体水溶液体系离子液体与水的质量比为2:8。
  6. 根据权利要求3所述的一种新型辛烯基琥珀酸颗粒淀粉酯的高效制备方法，其特征在于，所述步骤1)中：配制离子液体水溶液体系的温度为23℃，转速为300rpm。
  7. 根据权利要求3所述的一种新型辛烯基琥珀酸颗粒淀粉酯的高效制备方法，其特征在于，所述步骤2)中：将玉米淀粉或马铃薯淀粉用配置好的离子液体水溶液调成淀粉乳；然后加入氢氧化钠溶液将淀粉乳的pH值调节成8.5；在一定温度下，向淀粉乳中加入辛烯基琥珀酸酐进行酯化反应，保持反应体系的pH值为8.4～8.5，不断搅拌；反应结束后，用盐酸溶液调节反应后乳液的pH值至6.5；然后用去离子水和70％乙醇交替离心洗涤，再干燥即得辛烯基琥珀酸颗粒淀粉酯。
  8. 根据权利要求6所述的一种新型辛烯基琥珀酸颗粒淀粉酯的高效制备方法，其特征在于，所述步骤2)中：将玉米淀粉或马铃薯淀粉用配置好的离子液体水溶液调成浓度为15wt％淀粉乳；然后加入浓度为3％氢氧化钠溶液将淀粉乳的pH值调节成8.5；先称取淀粉干基质量3％的辛烯基琥珀酸酐，将辛烯基琥珀酸酐用异丙醇稀释3-6倍，在20～40℃温度下，在2个小时内滴入淀粉乳中进行酯化反应；酯化反应过程磁力搅拌，转 速200rpm；控制整个反应时间为3-5小时；反应结束后，用浓度为3％盐酸溶液调节反应后乳液的pH值至6.5；用去离子水和70％乙醇交替各离心洗涤3遍，离心力4500g，离心时间为10分钟；干燥方式是在烘箱内30℃，放置12小时，即得辛烯基琥珀酸颗粒淀粉酯。
  9. 根据权利要求7或8所述的一种新型辛烯基琥珀酸颗粒淀粉酯的高效制备方法，其特征在于，在离子液体水溶液体系中，玉米淀粉或马铃薯淀粉经过辛烯基琥珀酸酐改性后，制备成为颗粒状的辛烯基琥珀酸淀粉酯。
  10. 一种新型辛烯基琥珀酸颗粒淀粉酯，其特征在于，所述辛烯基琥珀酸颗粒淀粉酯由权利要求1-9中任意一项所述的制备方法获得。
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