WO2022121370A1 - 一种自增强淀粉基多功能材料的加工方法 - Google Patents

一种自增强淀粉基多功能材料的加工方法 Download PDF

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WO2022121370A1
WO2022121370A1 PCT/CN2021/113804 CN2021113804W WO2022121370A1 WO 2022121370 A1 WO2022121370 A1 WO 2022121370A1 CN 2021113804 W CN2021113804 W CN 2021113804W WO 2022121370 A1 WO2022121370 A1 WO 2022121370A1
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starch
self
based multifunctional
multifunctional material
material according
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English (en)
French (fr)
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缪铭
贾雪
坎帕内拉奥斯瓦尔多
金征宇
张涛
叶蕾
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江南大学
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/30—Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
    • A61K47/36—Polysaccharides; Derivatives thereof, e.g. gums, starch, alginate, dextrin, hyaluronic acid, chitosan, inulin, agar or pectin
    • 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
    • C08B31/003—Crosslinking of starch
    • C08B31/006—Crosslinking of derivatives of starch
    • 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
    • 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
    • C08B31/08—Ethers
    • C08B31/10—Alkyl or cycloalkyl ethers
    • 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
    • C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
    • C08L3/04—Starch derivatives, e.g. crosslinked derivatives
    • C08L3/06—Esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
    • C08L3/04—Starch derivatives, e.g. crosslinked derivatives
    • C08L3/08—Ethers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38—Packaging materials of special type or form
    • B65D65/46—Applications of disintegrable, dissolvable or edible materials
    • B65D65/466—Bio- or photodegradable packaging materials
    • 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
    • C08J2303/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
    • C08J2303/04—Starch derivatives
    • C08J2303/06—Esters
    • 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
    • C08J2303/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
    • C08J2303/04—Starch derivatives
    • C08J2303/08—Ethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/06—Biodegradable
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/02—Applications for biomedical use
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2312/00—Crosslinking

Definitions

  • the invention relates to a processing method of a self-enhancing starch-based multifunctional material, belonging to the field of starch deep processing.
  • plastics on the market are produced from petrochemical products. More than 75% of the plastics are petroleum-based plastics, and about 20% of the recycled plastics are basically made from petroleum-based plastics. Petroleum-based plastics, similar to PVC, PP, PE, etc., have good physical and chemical properties, but because the waste generated after use cannot be degraded, they exist in the natural environment for a long time and are the main source of white pollution. In order to reduce pollution to natural resources and reduce dependence on increasingly depleted resources, research and development of degradable polymer materials derived from renewable resources has become a focus of attention.
  • the present invention provides a processing method of a self-reinforced starch-based multifunctional material.
  • the self-reinforced starch-based multifunctional material of the present invention has excellent mechanical properties, barrier properties and antibacterial properties, and can be used as a packaging material for Food, textile, daily chemical, medicine and other fields.
  • the method has the characteristics of simple process, controllable process, green environmental protection and the like.
  • the first object of the present invention is to provide a kind of processing method of self-enhancing starch-based multifunctional material, comprising the following steps:
  • the starch nanoparticles are derived from natural plant or animal glycogen, synthetic macromolecular dendritic sugar chains or starch nanocrystals, with a molecular weight of 10 5 -10 7 g/mol and a particle size of 20-100 nm .
  • the natural plant or animal glycogen is derived from natural plant or animal tissue and is prepared by grinding, soaking, homogenizing, precipitating and drying to obtain starch nanoparticles.
  • the natural plant or animal glycogen includes corn glycogen, sorghum glycogen, rice glycogen, barley glycogen, buckwheat glycogen, thaliana glycogen, kelp glycogen, One or more of cyanobacterial glycogen, oyster glycogen, scallop glycogen, nail worm glycogen, etc., are prepared by crushing, soaking, homogenizing, precipitating and drying the raw material particles.
  • the synthetic polymer dendritic sugar chain includes a polymer dendritic sugar chain prepared by enzymatic biomimetic or chemical polymerization.
  • the enzymatic biomimetic means that the linear starch short chains undergo in vitro catalyzed synthesis of macromolecular dendritic sugar chains through the hydrolysis and transglycoside of a multifunctional carbohydrase; the chemical polychain refers to that the starch sugar chains undergo High-temperature acid-catalyzed polymerization forms polymer dendritic sugar chains.
  • the starch nanocrystals are prepared by hydrolyzing starch with concentrated acid assisted by a physical field
  • the method for hydrolyzing starch with a concentrated acid assisted by a physical field specifically includes: configuring starch into a starch milk solution, and then Add concentrated sulfuric acid or hydrochloric acid, and place it in a microwave or ultrasonic physical field to react for a period of time to obtain starch nanocrystals.
  • the organic acid anhydride reagent is a compound obtained by removing one molecule of water from one or two molecules of organic acid, including but not limited to succinic anhydride, maleic anhydride, acetic anhydride, hard One or more of fatty acid anhydride, citric anhydride, etc.
  • Antibacterial agents include but are not limited to nisin, lysozyme, chitin, ⁇ -polylysine, natamycin, thymol, eugenol, Gemini quaternary One or more of ammonium salts, etc.
  • the bulk starch includes but is not limited to grain starch, potato starch, bean starch, such as corn starch, wheat starch, potato starch, tapioca starch, rice starch, sweet potato starch, mung bean starch, etc.
  • grain starch such as corn starch, wheat starch, potato starch, tapioca starch, rice starch, sweet potato starch, mung bean starch, etc.
  • bean starch such as corn starch, wheat starch, potato starch, tapioca starch, rice starch, sweet potato starch, mung bean starch, etc.
  • amylose content in the starch is >35%.
  • the etherifying agent is a phase transfer catalyst material synthesized by charge derivatization of starch hydroxyl groups, including but not limited to ethylene oxide, propylene oxide, methyl chloride, 2-chloroethanol, One or more of oxychloropropane, monochloroacetic acid, acrylamide, dimethylsulfuric acid, monohalocarboxylic acid, cationic amine reagents, etc.; the crosslinking agent is able to form a bridge network structure between starch molecular chains
  • a class of catalyst substances including but not limited to aliphatic dihalogen compounds, tripolyphosphates, sodium trimetaphosphate, citrate esters, organic mixed acid anhydrides, urea, dimethylol urea, dimethylol ethylene urea, propylene
  • plasticizers are substances added to starch materials that can increase the plasticity of polymers, including but
  • the aliphatic dihalogen compound refers to a compound that does not contain a benzene ring or other aromatic rings, and the specific hydrogen atom on the aliphatic hydrocarbon is substituted by chlorine, fluorine or bromine atom;
  • the organic Mixed acid anhydrides refer to acid anhydrides formed by dehydration of two or more different organic acids.
  • the second object of the present invention is to provide a self-reinforcing starch-based multifunctional material processed by the above-mentioned processing method.
  • the tensile strength of the self-reinforced starch-based multifunctional material is >25MPa
  • the moisture barrier performance is ⁇ 6.0g/(m 2 ⁇ 24h)
  • the broad-spectrum bacteriostatic rate is >95%.
  • the third object of the present invention is to provide a film, a packaging product or a drug carrier and the like comprising the above-mentioned self-reinforced starch-based multifunctional material.
  • the fourth object of the present invention is to provide the above-mentioned preparation method or the application of the above-mentioned self-reinforced starch-based multifunctional material in the fields of food, textile, daily chemicals, medicine and the like.
  • the main raw materials of the present invention are common cereal starch, potato starch, bean starch and starch from other plant sources, and the raw material sources are wide and are not restricted by the place of production and season.
  • the present invention has simple steps, easy operation, controllable reaction conditions, relatively low cost, and adopts a clean and green production process, which basically does not pollute the environment.
  • the self-reinforcing starch-based multifunctional material prepared by the present invention not only has good mechanical properties, but also has high barrier properties and high antibacterial properties, and can be applied to many fields such as food, textile, daily chemicals, medicine, and has broad market prospects.
  • the present invention utilizes abundant starch resources to develop environmentally friendly and recyclable degradable materials, which conforms to the national strategic industrial development plan, and is of great significance for solving the oil crisis and plastic pollution, and building a resource-saving and environment-friendly society.
  • Example 1 is an electron microscope photograph of the self-reinforced starch-based multifunctional material obtained in Example 1.
  • Molecular weight determination Molecular weight was determined by a combined system of high performance liquid exclusion chromatography, multi-angle laser light scattering detector and refractive index detector.
  • the wavelength ⁇ of the He-Ne laser source in the multi-angle laser scattering detector is 632.8 nm
  • the Shodx OHpak SB-806 chromatographic column is selected
  • 0.1 mol/L NaNO 3 solution is used as the mobile phase
  • the flow rate is 0.2 mL/min
  • Particle size determination The sample to be tested was prepared into a 0.1% (w/v) solution, and the particle size distribution was measured with a Malvern Nano ZS analyzer at 25°C.
  • Determination of amylose content refer to GB/T 15683-2008 Determination of amylose content in rice for analysis.
  • Determination of tensile strength Refer to the national standard GB/T 1040.2-2006 Determination of Tensile Properties of Plastics Part 2: Test conditions for molded and extruded plastics for analysis.
  • Determination of moisture resistance refer to GB/T 26253-2010 Determination of water vapor transmission rate of plastic films and sheets for analysis by infrared detector method.
  • E.coli Escherichia coli
  • S.aureus Staphylococcus aureus
  • Salmonella typhimurium Salmonella typhimurium
  • Listeria monocytogenes Listeria monocytogenes
  • other food-borne The spoilage strains were streaked on the nutrient agar medium, and after culturing at 37°C for 12 hours, a single colony was picked, and then cultured in the nutrient broth medium at 37°C for 12 hours, counted on the plate, and a certain amount of bacterial liquid was drawn into 100 mL of nutrient meat.
  • Corn glycogen and synthetic polymer dendritic sugar chains can be obtained by referring to: Ming Miao, Microbial Starch-Converting Enzymes: Recent Insights and Perspectives, Comprehensive Reviews in Food Science and Food Safety 2018, 17: 1238-1260; Oyster Glycogen Purchased from sigma.
  • the obtained target product is a self-reinforced starch-based multifunctional material with a tensile strength of 34MPa, a moisture barrier property of 4.6g/(m 2 ⁇ 24h), and a broad-spectrum bacteriostatic rate of 98.2%.
  • the obtained target product is a self-reinforced starch-based multifunctional material with a tensile strength of 29MPa, a moisture barrier property of 5.1g/(m 2 ⁇ 24h), and a broad-spectrum bacteriostatic rate of 99.4%.
  • the obtained target product is a self-reinforced starch-based multifunctional material with a tensile strength of 32MPa, a moisture barrier property of 4.1g/(m 2 ⁇ 24h), and a broad-spectrum bacteriostatic rate of 99.0%.
  • the self-reinforcing starch base can also be prepared.
  • Multifunctional material its tensile strength is >25MPa, its moisture resistance is ⁇ 6.0g/(m 2 ⁇ 24h), and its broad-spectrum bacteriostatic rate is >95%.
  • Example 1 when composite nanoparticles were not prepared, according to the proportion of each substance added (weight percentage) corn starch (amylose content 51%) 100 parts, 2 parts of epichlorohydrin, 5 parts of urea, 3 parts of glycerol, After 4 parts of the bacteriostatic agent chitin was mixed evenly, it was adjusted to a moisture content of 15%; the twin-screw extruder was used as the reactor, and the temperature of the three-stage heating zone of material kneading, melt plasticization, and modified molding was set to be 60, 95, 130 °C, screw speed 150r/min, dry extrusion reaction to obtain material.
  • weight percentage corn starch (amylose content 51%) 100 parts, 2 parts of epichlorohydrin, 5 parts of urea, 3 parts of glycerol, After 4 parts of the bacteriostatic agent chitin was mixed evenly, it was adjusted to a moisture content of 15%; the twin-screw extruder was used as the reactor, and the temperature of
  • the tensile strength of the material is 21MPa
  • the moisture barrier performance is 6.7g/(m 2 ⁇ 24h)
  • the broad-spectrum bacteriostatic rate is 57%.
  • Example 1 when chitin is not added to the composite nanoparticles, according to the proportion of each substance added (weight percentage) corn starch (amylose content 51%) 100 parts, 40 parts of composite nanoparticles, 2 parts of epichlorohydrin , 5 parts of urea and 3 parts of glycerol were mixed evenly, and adjusted to a moisture content of 15%; the twin-screw extruder was used as the reactor, and the temperature of the three-stage heating zone of material kneading, melt plasticization, and modification molding was set to be 60 , 95, 130 °C, screw speed 150r/min, dry extrusion reaction to obtain materials.
  • weight percentage corn starch (amylose content 51%) 100 parts, 40 parts of composite nanoparticles, 2 parts of epichlorohydrin , 5 parts of urea and 3 parts of glycerol were mixed evenly, and adjusted to a moisture content of 15%; the twin-screw extruder was used as the reactor, and the temperature of the three-stage heating
  • the tensile strength of the material is 27MPa
  • the moisture barrier performance is 5.9g/(m 2 ⁇ 24h)
  • the broad-spectrum bacteriostatic rate is 0%.
  • Example 1 the mass fraction of acetic anhydride added in the preparation of composite nanoparticles was replaced by 0%, 0.2%, and 30%, respectively, to obtain the corresponding properties of starch-based materials.
  • the performance results of the obtained products are shown in Table 1.
  • Example 2 the mass fraction of moisture in the dry extrusion reaction was controlled to be 0%, 5%, and 40%, respectively, to obtain the corresponding properties of the starch-based material.
  • the performance results of the obtained products are shown in Table 2.
  • Example 1 the material was obtained by dry extrusion reaction without adding epichlorohydrin.
  • the tensile strength of the starch-based material was determined to be 16MPa, the moisture barrier property was 6.3g/(m 2 ⁇ 24h), and the broad-spectrum bacteriostatic rate was 96%.
  • Example 1 the dry extrusion reaction obtained the material without adding urea.
  • the tensile strength of the starch-based material was determined to be 23MPa, the moisture barrier property was 6.1g/(m 2 ⁇ 24h), and the broad-spectrum bacteriostatic rate was 97%.

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Abstract

本发明公开了一种自增强淀粉基多功能材料的加工方法，属于淀粉深加工技术领域。本发明以大宗淀粉为基体原料，首先将淀粉纳米粒子与有机酸酐试剂反应并添加抑菌剂制备得到复合纳米粒子，复合纳米粒子再与大宗淀粉、醚化剂、交联剂、增塑剂等混合，最后利用干法挤出改性结合淀粉基纳米粒组装增强技术来制备淀粉基多功能材料。本发明方法步骤简便、反应温和可控和可连续化绿色生产，所得产品不仅有良好的机械力学性能，还具有高阻隔性和高抗菌性，可应用于食品、纺织、日化、医药等诸多领域，市场前景广阔。

Description

一种自增强淀粉基多功能材料的加工方法 技术领域
本发明涉及一种自增强淀粉基多功能材料的加工方法，属于淀粉深加工领域。
背景技术
塑料制品的大量使用，在方便人类生活的同时，也带来更大的问题——“白色污染”。目前市场上的塑料大部分是由石油化工产品生产的，超过75％的塑料都是石油基塑料，约20％的再生塑料也基本是由石油基塑料再生制得的。石油基塑料类似PVC、PP、PE等拥有良好的物理化学性质，但由于其用后产生的垃圾不可被降解，长期存在于自然环境中，是产生白色污染的主要来源。为了降低对自然资源的污染和减少对日益枯竭资源的依赖，研究和开发源于可再生资源的可降解高分子材料成为人们的关注热点。
以天然可再生淀粉为原料转化制造的可降解材料作为国际战略性新兴产业，受到发达国家广泛重视，并呈现快速发展的势头。在我国，大宗淀粉资源充足，2019年淀粉产量超3200万吨，其中大部分用于制造淀粉糖、发酵制品等工业原料。与欧美发达国家相比，我国淀粉深加工水平不高，产品质量档次低且品种较少。同时，我国淀粉基材料开发利用也尚处于起步阶段，与国际先进水平相比，在产品性能、制造成本、关键技术与产业化规模等方面还存在差距。例如，日本、美国、意大利均有公司称已经成功研制出全淀粉热塑性塑料等并形成了规模化的生产销售；国内企业生产可降解淀粉塑料产品大多是填充型，而且只有添加的淀粉能够降解，而通用树脂在环境中只能发生裂解，难以回收处理并且会影响土壤的健康。基于上述原因，为了改善淀粉基材料力学性能差、耐水性差等天然缺陷，开发一种自增强淀粉基多功能材料的加工方法是有迫切需求的。
发明内容
为了解决上述问题，本发明提供了一种自增强淀粉基多功能材料的加工方法，本发明的自增强淀粉基多功能材料具有优异的机械性能、阻隔性能和抗菌性能，可以作为包装材料用于食品、纺织、日化、医药等领域。该方法具有工艺简单、过程可控、绿色环保等特点。
首先，本发明的第一个目的是提供一种自增强淀粉基多功能材料的加工方法，包括如下步骤：
(1)将淀粉纳米粒子与有机酸酐试剂在水溶液中混匀，其中有机酸酐试剂为淀粉纳米粒子的质量的0.5％-10％，调节pH条件至8-12，置于30-55℃反应2-10h，之后加入0.1-0.5wt％抗菌剂共混组装干燥制备复合纳米粒子；
(2)按照各物质添加量比例，以重量份数计，将大宗淀粉100份、复合纳米粒子20-60份、醚化剂2-5份、交联剂2-5份、增塑剂2-5份混合均匀，并调节至水分含量为10-25wt％；
(3)以双螺杆挤出机为反应器，设置物料捏合、熔融塑化、改性成型三段加热区温度分别为60-90、90-120、110-130℃，螺杆转速100-200r/min，干法挤出反应获得自增强淀粉基多功能材料。
在本发明一种实施方式中，所述淀粉纳米粒子来源于天然植物或动物糖原、合成高分子树枝状糖链或淀粉纳米晶，分子量10 5-10 7g/mol，颗粒尺寸20-100nm。
在本发明的一种实施方式中，所述天然植物或动物糖原为来源于天然植物或动物组织经粉碎、浸泡、匀浆、沉淀、干燥制备得到淀粉纳米粒子。
在本发明的一种实施方式中，所述天然植物或动物糖原包括玉米糖原、高粱糖原、稻米糖原、大麦糖原、荞麦糖原、鼠耳芥糖原、红藻糖原、蓝藻糖原、牡蛎糖原、扇贝糖原、指甲履螺糖原等一种或多种，通过将原料颗粒经粉碎、浸泡、匀浆、沉淀、干燥制备而得。
在本发明的一种实施方式中，所述合成高分子树枝状糖链包括通过酶法仿生或化学聚链反应制备获得的高分子树枝状糖链。
在本发明的一种实施方式中，所述酶法仿生是指线性淀粉短链经过多功能糖酶水解转苷体外催化合成高分子树枝状糖链；所述化学聚链是指淀粉糖链经过高温条件酸催化聚合形成高分子树枝状糖链。
在本发明的一种实施方式中，所述淀粉纳米晶通过物理场辅助浓酸水解淀粉制备获得的，所述物理场辅助浓酸水解淀粉的方法具体包括：将淀粉配置成淀粉乳溶液，然后添加浓硫酸或盐酸，并置于微波或超声物理场反应一段时间即可获得淀粉纳米晶。
在本发明一种实施方式中，所述有机酸酐试剂为一个或两个分子的有机酸去掉一分子水而成的化合物，包括但不限于丁二酸酐、顺丁烯二酸酐、乙酸酐、硬脂酸酐、柠檬酸酐等一种或多种，抗菌剂包括但不限于乳酸链球菌素、溶菌酶、甲壳素、ε-聚赖氨酸、纳他霉素、百里酚、丁香酚、Gemini季铵盐等一种或多种。
在本发明一种实施方式中，所述大宗淀粉包括但不限于谷物淀粉、薯类淀粉、豆类淀粉，如玉米淀粉、小麦淀粉、马铃薯淀粉、木薯淀粉、稻米淀粉、甘薯淀粉、绿豆淀粉等一种或多种，其中，淀粉中的直链淀粉含量>35％。
在本发明一种实施方式中，所述醚化剂为淀粉羟基电荷衍生化合成的相转移催化剂物质，包括但不限于环氧乙烷、环氧丙烷、甲基氯、2-氯乙醇、环氧氯丙烷、一氯乙酸、丙烯酰胺、二甲基硫酸、一卤代羧酸、阳离子胺类试剂等一种或多种；交联剂为能够在淀粉分子链之间 形成桥键网状结构的一类催化剂物质，包括但不限于脂肪族二卤化合物、三聚磷酸盐、三偏磷酸钠、柠檬酸酯、有机混合酸酐、尿素、二羟甲基脲、二羟甲基乙烯脲、丙烯醛、琥珀醛等一种或多种；增塑剂为添加到淀粉材料中能使聚合物塑性增加的物质，包括但不限于水、甘油、乙二醇、山梨醇、木糖醇等一种或多种。
在本发明的一种实施方式中，所述脂肪族二卤化合物是指脂肪烃上特定的氢原子由氯、氟或溴原子所取代的不含有苯环或其它芳香环的化合物；所述有机混合酸酐是指两种或多种不同有机酸脱水形成的酸酐。
本发明的第二个目的是提供上述加工方法加工得到的自增强淀粉基多功能材料。
在本发明一种实施方式中，所述自增强淀粉基多功能材料的拉伸强度>25MPa，阻湿性能<6.0g/(m 2×24h)，广谱抑菌率>95％。
本发明的第三个目的是提供包含上述自增强淀粉基多功能材料的薄膜、包装制品或药物载体等。
本发明的第四个目的是提供上述制备方法或上述自增强淀粉基多功能材料在食品、纺织、日化、医药等领域的应用。
本发明具有以下优点：
1、本发明的主要原料为普通谷类淀粉、薯类淀粉、豆类淀粉及其它植物来源的淀粉，原料来源广、不受产地和季节的限制。
2、本发明步骤简便，易于操作，反应条件可控，成本相对较低，而且采用清洁绿色生产工艺，对环境基本无污染。
3、本发明制备的自增强淀粉基多功能材料不仅有良好的机械力学性能，还具有高阻隔性和高抗菌性，可应用于食品、纺织、日化、医药等诸多领域，市场前景广阔。
4、本发明利用丰富的淀粉资源开发环境友好和可循环利用的可降解材料，符合国家战略产业发展规划，对于解决石油危机和塑料污染、建设资源节约型和环境友好型社会具有重要意义。
附图说明
图1为实施例1所得自增强淀粉基多功能材料的电镜照片。
具体实施方式
下面结合实例进一步阐明本发明的内容，但本发明所保护的内容不仅局限于下面的实例。
分子量测定：利用高效液相排阻色谱、多角度激光散射检测器和示差折光检测器联用系统测定分子量。其中多角度激光散射检测器中He-Ne激光源的波长λ为632.8nm，选用Shodx  OHpak SB-806色谱柱，0.1mol/L NaNO 3溶液作为流动相，流速为0.2mL/min，折光指数增量设定为dn/dc＝0.138。
颗粒尺寸测定：将待测样品配制成0.1％(w/v)的溶液，25℃下用马尔文Nano ZS测定仪进行粒度分布测定。
直链淀粉含量测定：参照GB/T 15683-2008大米直链淀粉含量的测定的方法进行分析。
拉伸强度测定：参照国家标准GB/T 1040.2-2006塑料拉伸性能的测定第2部分：模塑和挤塑塑料的试验条件的方法进行分析。
阻湿性能测定：参照GB/T 26253-2010塑料薄膜和薄片水蒸气透过率的测定红外检测器法的方法进行分析。
广谱抑菌率测定：大肠杆菌(E.coli)、金黄色葡萄球菌(S.aureus)、鼠伤寒沙门氏菌(S.typhimurium)、单核细胞增生李斯特菌(L.monocytogenes)等食源性腐败菌种于营养琼脂培养基上划线，37℃培养12h后，挑取单菌落，再于营养肉汤培养基中37℃培养12h，平板计数，并吸取一定量的菌液于100mL营养肉汤培养基中(最终为107CFU/mL)，再适量放入自增强淀粉基多功能材料，于恒温培养箱中37℃培养，分别在0h、4h、6h、8h、10h、12h和24h测定试样的OD600值，并对培养12h的样品进行平板计数，以测定其抑菌率大小，每组样品三次平行，计算公式如下：
Figure PCTCN2021113804-appb-000001
玉米糖原和合成高分子树枝状糖链可参考文献制得：Ming Miao，Microbial Starch-Converting Enzymes:Recent Insights and Perspectives，Comprehensive Reviews in Food Science and Food Safety 2018，17：1238-1260；牡蛎糖原购自sigma公司。
实施例1
将玉米糖原(3.1×10 7g/mol，颗粒尺寸82nm)与乙酸酐在水溶液中混匀，乙酸酐相对玉米糖原的质量份数为1％，调节pH条件至12，置于30℃反应10h，继续加入0.1％甲壳素聚集干燥制备复合纳米粒子；按照各物质添加量比例(重量百分比)玉米淀粉(直链淀粉含量51％)100份、复合纳米粒子40份、环氧氯丙烷2份、尿素5份、甘油3份混合均匀，并调节至水分含量为15％；以双螺杆挤出机为反应器，设置物料捏合、熔融塑化、改性成型三段加热区温度分别为60、95、130℃，螺杆转速150r/min，干法挤出反应获得自增强淀粉基多功能材料，其电镜照片见图1。
所得目标产物自增强淀粉基多功能材料，拉伸强度34MPa，阻湿性能4.6g/(m 2×24h)， 广谱抑菌率98.2％。
实施例2
将牡蛎糖原(7.2×10 6g/mol，颗粒尺寸67nm)与柠檬酸酐在水溶液中混匀，柠檬酸酐相对牡蛎糖原的质量份数为5％，调节pH条件至11，置于50℃反应4h，继续加入0.3％乳酸链球菌素聚集干燥制备复合纳米粒子；按照各物质添加量比例(重量百分比)木薯淀粉(直链淀粉含量36％)100份、复合纳米粒子20份、一氯乙酸5份、柠檬酸酯3份、山梨醇4份混合均匀，并调节至水分含量为20％；以双螺杆挤出机为干法反应器，设置物料捏合、熔融塑化、改性成型三段加热区温度分别为90、100、110℃，螺杆转速120r/min，挤出获得自增强淀粉基多功能材料。
所得目标产物自增强淀粉基多功能材料，拉伸强度29MPa，阻湿性能5.1g/(m 2×24h)，广谱抑菌率99.4％。
实施例3
将合成高分子树枝状糖链(8.2×10 5g/mol，颗粒尺寸44nm)与硬脂酸酐在水溶液中混匀，硬脂酸酐相对合成高分子树枝状糖链的质量份数为8％，调节pH条件至9，置于45℃反应6h，继续加入0.5％ε-聚赖氨酸聚集干燥制备复合纳米粒子；按照各物质添加量比例(重量百分比)稻米淀粉(直链淀粉含量42％)100份、复合纳米粒子60份、甲基氯4份、二甲基丙烯酸乙二醇酯2份、乙二醇4份混合均匀，并调节至水分含量为18％；以双螺杆挤出机为干法反应器，设置物料捏合、熔融塑化、改性成型三段加热区温度分别为65、90、120℃，螺杆转速160r/min，挤出获得自增强淀粉基多功能材料。
所得目标产物自增强淀粉基多功能材料，拉伸强度32MPa，阻湿性能4.1g/(m 2×24h)，广谱抑菌率99.0％。
当上述实施例中的淀粉纳米粒子、有机酸酐、抗菌剂、大宗淀粉、醚化剂、交联剂、增塑剂等替换为本发明所述的其他物质时，同样能够制备得到自增强淀粉基多功能材料，其拉伸强度>25MPa，阻湿性能<6.0g/(m 2×24h)，广谱抑菌率>95％。
对比例1
参照实施例1，当不制备复合纳米粒子，按照各物质添加量比例(重量百分比)玉米淀粉(直链淀粉含量51％)100份、环氧氯丙烷2份、尿素5份、甘油3份、抑菌剂甲壳素4份混合均匀后，并调节至水分含量为15％；以双螺杆挤出机为反应器，设置物料捏合、熔融塑化、改性成型三段加热区温度分别为60、95、130℃，螺杆转速150r/min，干法挤出反应获得材料。
经过检测，该材料的拉伸强度21MPa，阻湿性能6.7g/(m 2×24h)，广谱抑菌率57％。
对比例2
参照实施例1，当复合纳米粒子中不添加甲壳素，按照各物质添加量比例(重量百分比)玉米淀粉(直链淀粉含量51％)100份、复合纳米粒子40份、环氧氯丙烷2份、尿素5份、甘油3份混合均匀后，并调节至水分含量为15％；以双螺杆挤出机为反应器，设置物料捏合、熔融塑化、改性成型三段加热区温度分别为60、95、130℃，螺杆转速150r/min，干法挤出反应获得材料。
经过检测，该材料的拉伸强度27MPa，阻湿性能5.9g/(m 2×24h)，广谱抑菌率0％。
对比例3
参照实施例1，将复合纳米粒子制备中添加乙酸酐的质量分数分别替换为0％、0.2％、30％，制得相应的淀粉基材料性能。所得产品的性能结果如表1所示。
表1 有机酸酐试剂用量所得产品的性能结果
Figure PCTCN2021113804-appb-000002
对比例4
参照实施例1，控制干法挤出反应中水分的质量分数分别为0％、5％、40％，制得相应的淀粉基材料性能。所得产品的性能结果如表2所示。
表2 不同干法挤出反应中水分的质量分数下所制备得产品的性能结果
Figure PCTCN2021113804-appb-000003
对比例5
参照实施例1，不添加环氧氯丙烷时干法挤出反应获得材料。
经过测定淀粉基材料性能拉伸强度16MPa，阻湿性能6.3g/(m 2×24h)，广谱抑菌率96％。
对比例6
参照实施例1，不添加尿素时干法挤出反应获得材料。
经过测定淀粉基材料性能拉伸强度23MPa，阻湿性能6.1g/(m 2×24h)，广谱抑菌率97％。
虽然本发明已以较佳实施例公开如上，但其并非用以限定本发明，任何熟悉此技术的人，在不脱离本发明的精神和范围内，都可做各种的改动与修饰，因此本发明的保护范围应该以权利要求书所界定的为准。

Claims (11)

  1. 一种自增强淀粉基多功能材料的加工方法，其特征在于，所述方法包括如下步骤：
    (1)将淀粉纳米粒子与有机酸酐试剂在水溶液中混匀，其中有机酸酐试剂为淀粉纳米粒子的质量的0.5％-10％，调节pH条件至8-12，置于30-55℃反应2-10h，之后加入0.1-0.5wt％抗菌剂共混组装干燥制备复合纳米粒子，其中，所述淀粉纳米粒子来源于天然植物或动物糖原、合成高分子树枝状糖链或淀粉纳米晶，分子量10 5-10 7g/mol，颗粒尺寸20-100nm；
    (2)按照各物质添加量比例，以重量份数计，将大宗淀粉100份、复合纳米粒子20-60份、醚化剂2-5份、交联剂2-5份、增塑剂2-5份混合均匀，并调节至水分含量为10-25wt％；
    (3)以双螺杆挤出机为反应器，设置物料捏合、熔融塑化、改性成型三段加热区温度分别为60-90、90-120、110-130℃，螺杆转速100-200r/min，干法挤出反应获得自增强淀粉基多功能材料。
  2. 根据权利要求1所述的一种自增强淀粉基多功能材料的加工方法，其特征在于，有机酸酐试剂包括丁二酸酐、顺丁烯二酸酐、乙酸酐、硬脂酸酐、柠檬酸酐中的一种或多种，所述抗菌剂包括乳酸链球菌素、溶菌酶、甲壳素、ε-聚赖氨酸、纳他霉素、百里酚、丁香酚、Gemini季铵盐中的一种或多种。
  3. 根据权利要求1或2所述的一种自增强淀粉基多功能材料的加工方法，其特征在于，所述大宗淀粉包括谷物淀粉、薯类淀粉或豆类淀粉，其中，直链淀粉含量>35％。
  4. 根据权利要求3所述的一种自增强淀粉基多功能材料的加工方法，其特征在于，所述大宗淀粉包括玉米淀粉、小麦淀粉、马铃薯淀粉、木薯淀粉、稻米淀粉、甘薯淀粉、绿豆淀粉中的一种或多种。
  5. 根据权利要求1～2或4任一所述的一种自增强淀粉基多功能材料的加工方法，其特征在于，所述醚化剂包括环氧乙烷、环氧丙烷、甲基氯、2-氯乙醇、环氧氯丙烷、丙烯酰胺、二甲基硫酸、一卤代羧酸、阳离子胺类试剂中的一种或多种；所述交联剂包括脂肪族二卤化合物、三聚磷酸盐、三偏磷酸钠、柠檬酸酯、有机混合酸酐、尿素、二羟甲基脲、二羟甲基乙烯脲、丙烯醛、琥珀醛中的一种或多种；增塑剂包括水、甘油、乙二醇、山梨醇、木糖醇中的一种或多种。
  6. 根据权利要求3所述的一种自增强淀粉基多功能材料的加工方法，其特征在于，所述醚化剂包括环氧乙烷、环氧丙烷、甲基氯、2-氯乙醇、环氧氯丙烷、丙烯酰胺、二甲基硫酸、一卤代羧酸、阳离子胺类试剂中的一种或多种；所述交联剂包括脂肪族二卤化合物、三聚磷酸盐、三偏磷酸钠、柠檬酸酯、有机混合酸酐、尿素、二羟甲基脲、二羟甲基乙烯脲、丙烯醛、琥珀醛中的一种或多种；增塑剂包括水、甘油、乙二醇、山梨醇、木糖醇中的一种或多种。
  7. 根据权利要求5所述的一种自增强淀粉基多功能材料的加工方法，其特征在于，所述一卤代羧酸为一氯乙酸。
  8. 根据权利要求1～7任一所述的一种自增强淀粉基多功能材料的加工方法得到的自增强淀粉基多功能材料。
  9. 根据权利要求8所述的自增强淀粉基多功能材料，其特征在于，所述自增强淀粉基多功能材料的拉伸强度>25MPa，阻湿性能<6.0g/(m 2×24h)，广谱抑菌率>95％。
  10. 包含权利要求8或9所述的自增强淀粉基多功能材料的薄膜、包装制品或药物载体。
  11. 权利要求1～7任一所述的一种自增强淀粉基多功能材料的加工方法或权利要求8或9所述的自增强淀粉基多功能材料在食品、纺织、日化、医药领域的应用。
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