CN115466333A - Preparation method of starch octenyl succinate - Google Patents
Preparation method of starch octenyl succinate Download PDFInfo
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- CN115466333A CN115466333A CN202211264794.3A CN202211264794A CN115466333A CN 115466333 A CN115466333 A CN 115466333A CN 202211264794 A CN202211264794 A CN 202211264794A CN 115466333 A CN115466333 A CN 115466333A
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- 229920002472 Starch Polymers 0.000 title claims abstract description 173
- 239000008107 starch Substances 0.000 title claims abstract description 173
- 235000019698 starch Nutrition 0.000 title claims abstract description 173
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- GUOCOOQWZHQBJI-UHFFFAOYSA-N 4-oct-7-enoxy-4-oxobutanoic acid Chemical compound OC(=O)CCC(=O)OCCCCCCC=C GUOCOOQWZHQBJI-UHFFFAOYSA-N 0.000 title claims description 19
- 238000000034 method Methods 0.000 claims abstract description 48
- 150000002148 esters Chemical class 0.000 claims abstract description 35
- KCYQMQGPYWZZNJ-BQYQJAHWSA-N hydron;2-[(e)-oct-1-enyl]butanedioate Chemical compound CCCCCC\C=C\C(C(O)=O)CC(O)=O KCYQMQGPYWZZNJ-BQYQJAHWSA-N 0.000 claims abstract description 30
- FLISWPFVWWWNNP-BQYQJAHWSA-N dihydro-3-(1-octenyl)-2,5-furandione Chemical compound CCCCCC\C=C\C1CC(=O)OC1=O FLISWPFVWWWNNP-BQYQJAHWSA-N 0.000 claims abstract description 29
- 238000010902 jet-milling Methods 0.000 claims abstract description 19
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 41
- 238000005406 washing Methods 0.000 claims description 38
- 235000013336 milk Nutrition 0.000 claims description 36
- 239000008267 milk Substances 0.000 claims description 36
- 210000004080 milk Anatomy 0.000 claims description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- 238000001035 drying Methods 0.000 claims description 23
- 238000002156 mixing Methods 0.000 claims description 23
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- 238000007873 sieving Methods 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 13
- 239000003513 alkali Substances 0.000 claims description 11
- 239000003153 chemical reaction reagent Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000002585 base Substances 0.000 claims description 2
- 238000002525 ultrasonication Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 31
- 239000002245 particle Substances 0.000 abstract description 20
- 239000000839 emulsion Substances 0.000 abstract description 14
- 230000008569 process Effects 0.000 abstract description 14
- 238000005886 esterification reaction Methods 0.000 abstract description 9
- 239000008187 granular material Substances 0.000 abstract description 9
- 238000006467 substitution reaction Methods 0.000 abstract description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 abstract description 3
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- 239000008103 glucose Substances 0.000 abstract description 3
- 229920000642 polymer Polymers 0.000 abstract description 3
- 229920000881 Modified starch Polymers 0.000 abstract description 2
- 239000004368 Modified starch Substances 0.000 abstract description 2
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 abstract description 2
- 235000019426 modified starch Nutrition 0.000 abstract description 2
- 239000000376 reactant Substances 0.000 abstract description 2
- 229940032147 starch Drugs 0.000 description 151
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 49
- 239000000047 product Substances 0.000 description 16
- 239000000243 solution Substances 0.000 description 15
- 239000012153 distilled water Substances 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 238000003801 milling Methods 0.000 description 6
- 238000002835 absorbance Methods 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 230000001804 emulsifying effect Effects 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 125000004365 octenyl group Chemical group C(=CCCCCCC)* 0.000 description 4
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- 230000035484 reaction time Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 239000002608 ionic liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 235000019483 Peanut oil Nutrition 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 239000000312 peanut oil Substances 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 238000003746 solid phase reaction Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 101710134784 Agnoprotein Proteins 0.000 description 1
- 108010084311 Novozyme 435 Proteins 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- AKPUJVVHYUHGKY-UHFFFAOYSA-N hydron;propan-2-ol;chloride Chemical compound Cl.CC(C)O AKPUJVVHYUHGKY-UHFFFAOYSA-N 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 229940080313 sodium starch Drugs 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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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
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Biochemistry (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The invention provides a preparation method of octenyl succinic acid starch ester, belonging to the technical field of modified starch. The method comprises the steps of firstly, destroying chains of polymers and starch granules through ultrasonic treatment, so that the size of the starch granules is reduced, octenyl succinic anhydride is promoted to enter the starch granules, the accessibility of the octenyl succinic anhydride in the starch granules is improved, the substitution degree of products is improved, and the stability of octenyl succinic acid starch ester is enhanced; and then, esterification reaction is carried out simultaneously in the jet milling process, and the octenyl succinic acid starch ester is synthesized by a one-step method, so that the particle size of reactants can be reduced, the specific surface area is increased, the hydroxyl groups of carbon on 2, 3 and 6 positions of glucose in the starch are exposed, the reaction sites are increased, and the esterification reaction efficiency is improved. The octenyl succinic acid starch ester prepared by the invention has small granularity and better emulsibility and emulsion stability.
Description
Technical Field
The invention relates to the technical field of modified starch, in particular to a preparation method of octenyl succinic acid starch ester.
Background
The jet milling technology is that compressed air after drying and purification generates high-speed airflow through a nozzle, particles are driven to move at high speed in a milling cavity, the particles are milled under the action of impact collision, friction, shearing and the like, the milled particles are classified along with the airflow, the particles with qualified fineness are collected by a catcher, the coarse particles which do not meet the requirement are returned to a milling chamber to be milled continuously until the required fineness is achieved and collected, and the average particle size of jet milled products is 0.1-10 mu m. Fluidized bed type jet milling is realized mainly through mutual collision and friction among particles due to fluidization of the milling particles in the milling cavity, the particles and mill parts have small effect, so that the purity of finished powder is high, the pollution is nearly zero, the particle milling is more sufficient, the milling efficiency is better, the particle size of the product is finer and is narrow in distribution, the yield is high, the energy consumption is low, and the jet milling machine is suitable for large-scale industrialization and continuous production.
Starch Octenyl Succinate is an important esterified Starch, commercially available under the trade name pure gum, and is generally found in the form of Sodium Starch Octenyl Succinate (SSOS) and was first synthesized by Wurzburg and Caldwell et al (Caldwell C G, wurzburg O B. Polysaccharide derivatives of sulfated dicarbolic acids: US, US 2661349A.,. P.1953.). The starch octenyl succinate is obtained by esterification reaction of starch and octenyl succinic anhydride, and the main reaction process comprises the following steps: the ring of the octenyl succinic anhydride is opened, wherein one end of the ring is bonded with the hydroxyl of the starch molecule, and the other end generates a carboxylic acid, so that the pH value of the system is reduced along with the reaction, and an alkaline solution is added to neutralize the carboxylic acid during the reaction process so as to maintain the slight alkalinity of the reaction system and enable the reaction to proceed towards the esterification direction. Octenyl succinic anhydride undergoes substitution reactions primarily with the hydroxyl groups on the 2-, 3-, and 6-carbon of glucose, theoretically with 3 hydroxyl groups on the carbon chain being substituted. Starch itself is hydrophilic and when reacted with hydrophobic octenyl succinic anhydride, starch molecules bind long-chain hydrophobic octenyl groups thereby increasing hydrophobicity, and thus starch octenyl succinate esters are amphiphilic. Starch octenyl succinate is a recognized emulsifying thickener with high safety, and can also be used as food additive.
At present, the method for preparing starch octenyl succinate comprises a solid phase reaction method and a water phase method, wherein the solid phase chemical reaction method for preparing the starch octenyl succinate comprises the steps of mixing starch and alkali, properly spraying water to adjust the water content, spraying acid anhydride, uniformly mixing, heating for reaction, and no need of using an organic solvent. However, most of solid-phase chemical reactions are carried out at high temperature, and have the defects of difficult operation, slow reaction rate, poor reaction uniformity, long reaction time, high energy consumption, high cost and the like.
The water phase method for preparing octenyl succinic acid starch ester is to take water as reaction medium to form solution with the concentration of starch milk of 30-40 percent, naOH or NaHCO is used 3 And (3) keeping the reaction system weakly alkaline by using an alkaline reagent, slowly adding the OSA into the emulsion at the temperature of 30-35 ℃, continuously adding an alkaline substance, stirring until the reaction is finished, adjusting the pH value of the emulsion to about 6.5, centrifuging, washing and drying to obtain the OSA starch.
Chinese patent application CN109517079A discloses a method for preparing octenyl succinic acid starch ester, which comprises the steps of preparing starch, alkali, water, octenyl succinic anhydride and a low-boiling solvent into a pre-emulsion, carrying out jet cooking, carrying out reaction under the condition of high-temperature steam, and carrying out enzymolysis to obtain the octenyl succinic acid starch ester. The method has short preparation time, but the preparation of the pre-emulsion needs a large amount of organic solvent, the required temperature is high, and the reaction also needs enzymolysis. However, the method has high cost, large energy consumption, complex preparation method and harsh reaction conditions.
Chinese patent application CN101503476A discloses a simplified production process of octenyl succinic acid starch ester. The method improves the reaction degree of the octenyl succinic anhydride and the starch, stabilizes the final viscosity of the product, but requires a long time for the reaction and has a complicated reaction process.
Chinese patent application CN104480159A discloses a method for synthesizing starch octenyl succinate in ionic liquid. The method comprises the steps of putting starch into ionic liquid to fully dissolve the starch, and then adding 3% of octenyl succinic anhydride and 10% of lipase Novozym 435 for reaction to prepare the octenyl succinic acid starch ester. The method has high reaction efficiency, but the process for preparing the ionic liquid is complex, more organic solvents are used, more waste water is generated, the preparation time is long, and the method is not suitable for industrial large-scale production.
In conclusion, the patent adopts different methods to synthesize the octenyl succinic acid starch ester, and the prepared octenyl succinic acid starch ester has good effect, but the methods still have certain defects in the aspects of production and processing, such as complex preparation process and unstable performance of the prepared product.
Disclosure of Invention
The invention aims to provide a preparation method of octenyl succinic starch ester, and the prepared octenyl succinic starch ester has stable performance and simple preparation process.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of octenyl succinic acid starch ester, which comprises the following steps:
mixing starch with water, mixing the obtained starch milk with acid, and performing ultrasonic treatment to obtain pretreated starch;
and mixing the pretreated starch with octenyl succinic anhydride and an alkali reagent, and carrying out jet milling on the obtained mixture to obtain the octenyl succinic acid starch ester.
Preferably, the acid is hydrochloric acid, and the concentration of the hydrochloric acid is 2-10 mol/L; the mass of the acid is 1-7% of the mass of the dry base of the starch; the mass concentration of the starch milk is 20-40%.
Preferably, the power of the ultrasonic treatment is 100-500W, the time is 15-60 min, and the temperature is 25-50 ℃.
Preferably, after the ultrasonic treatment, the method further comprises: and adjusting the pH value of the obtained product to 6.5-7.5, and sequentially washing, drying, crushing and sieving to obtain the pretreated starch.
Preferably, the drying temperature is 45 ℃ and the drying time is 24h.
Preferably, the mass of the octenyl succinic anhydride is 1.5 to 7.5 percent of the dry mass of the pretreated starch.
Preferably, the mass of the alkali reagent is 0.5 to 2.5% of the dry mass of the starch.
Preferably, the pressure of the jet milling is 0.6-0.8 Mpa, and the grading rotation speed is 2400-3600 r/min.
Preferably, after the jet milling, the method further comprises: washing, drying, crushing and sieving the obtained product in sequence to obtain starch octenyl succinate;
preferably, the washing comprises ethanol washing and water washing which are sequentially carried out; the volume fraction of ethanol used for ethanol washing is 75%.
The invention provides a preparation method of octenyl succinic acid starch ester, which comprises the following steps: mixing starch with water, mixing the obtained starch milk with acid, and performing ultrasonic treatment to obtain pretreated starch; and mixing the pretreated starch with octenyl succinic anhydride and an alkali reagent, and carrying out jet milling on the obtained mixture to obtain the octenyl succinic acid starch ester. The method comprises the steps of firstly, destroying chains of polymers and starch granules through ultrasonic treatment, so that the size of the starch granules is reduced, octenyl succinic anhydride is promoted to enter the starch granules, the accessibility of the octenyl succinic anhydride in the starch granules is improved, the substitution degree of products is improved, and the stability of octenyl succinic acid starch ester is enhanced; and then, esterification reaction is carried out simultaneously in the jet milling process, and the octenyl succinic acid starch ester is synthesized by a one-step method, so that the particle size of reactants can be reduced, the specific surface area is increased, the hydroxyl groups of carbon on 2, 3 and 6 positions of glucose in the starch are exposed, the reaction sites are increased, and the esterification reaction efficiency is improved. In addition, because the starch modified octenyl succinic anhydride belongs to hydrophobic modification, effective contact sites of starch and an oil phase on an interface can be increased, stable emulsion is favorably formed, and meanwhile, a continuous film formed on the oil-water interface of the oil-in-water type emulsion liquid is firmer and less prone to rupture along with the increase of the substitution degree, so that the tension of the oil-water interface is further weakened, dispersed phase starch particles are more difficult to agglomerate and separate, and the emulsion stability effect is improved. With the increase of the hydrophobic group, the surface tension reducing ability of the esterified starch is enhanced, and thus the emulsifying property and the emulsifying stability of the obtained esterified starch are enhanced. Therefore, the octenyl succinic acid starch ester prepared by the invention has small granularity, good emulsibility and emulsion stability, high efficiency and short reaction time.
The method carries out esterification reaction through the airflow crushing process, has good reaction uniformity, does not generate high temperature and pyrolysis in the reaction process, does not denature starch, has short reaction time and high product quality, and solves the problems of poor reaction uniformity, high reaction temperature, long reaction time, complex reaction process, serious pyrolysis of raw materials and products at high temperature, poor product quality and the like of the traditional solid phase reaction.
Compared with the conventional water phase method, the method only needs to add a fixed amount of alkaline substances once to maintain the alkaline environment, reduces the generation of waste water and the consumption of the alkaline substances in the reaction process, and has good economic benefit.
Drawings
FIG. 1 is a flow diagram of the present invention for the preparation of starch octenyl succinate.
Detailed Description
The invention provides a preparation method of octenyl succinic acid starch ester, which comprises the following steps:
mixing starch with water, mixing the obtained starch milk with acid, and performing ultrasonic treatment to obtain pretreated starch;
and mixing the pretreated starch with octenyl succinic anhydride and an alkali reagent, and carrying out air flow crushing on the obtained mixture to obtain the octenyl succinic acid starch ester.
In the present invention, unless otherwise specified, all the starting materials required for the preparation are commercially available products well known to those skilled in the art.
The method comprises the steps of mixing starch with water, mixing the obtained starch milk with acid, and carrying out ultrasonic treatment to obtain the pretreated starch.
The process of mixing the starch and water is not particularly limited in the present invention, and the starch and water may be uniformly mixed according to a process well known in the art.
In the invention, the mass concentration of the starch milk is preferably 20-40%, and more preferably 30%; the acid is preferably hydrochloric acid, and the concentration of the hydrochloric acid is preferably 2-10 mol/L; the mass of the acid is preferably 1 to 7%, more preferably 5%, of the mass of the starch on a dry basis. The process of mixing the starch milk and the acid is not particularly limited, and the materials are uniformly mixed according to the process known in the field.
In the present invention, the power of the ultrasonic treatment is preferably 100 to 500W, more preferably 200 to 450W, and further preferably 300W; the time is preferably 15 to 60min, more preferably 30 to 50min, and further preferably 45min; the temperature is preferably 25 to 50 ℃, more preferably 30 to 45 ℃, and still more preferably 35 ℃. The invention utilizes cavitation bubbles generated by ultrasonic treatment to generate high-pressure change when the cavitation bubbles are broken, and a nearby water layer generates local high-speed jet flow, so that the generated shearing force can break polymer chains and break starch granules.
In the present invention, after the ultrasonic treatment, it is preferable to further include: adjusting the pH value of the obtained product to 6.5-7.5, and sequentially washing, drying, crushing and sieving to obtain the pretreated starch.
In the invention, the reagent for adjusting the pH value is sodium hydroxide aqueous solution; the concentration of the sodium hydroxide aqueous solution is not particularly limited, and the required pH value can be achieved.
In the invention, the reagent used for washing is preferably water, and the invention preferably washes until the washing liquid is neutral; the drying temperature is preferably 45 ℃ and the drying time is preferably 24h. The process of pulverizing and sieving is not particularly limited in the present invention, and may be carried out according to a process known in the art.
After the pretreated starch is obtained, the pretreated starch is mixed with octenyl succinic anhydride and an alkali reagent, and the obtained mixture is subjected to jet milling to obtain octenyl succinic acid starch ester.
In the invention, the mass of the octenyl succinic anhydride is preferably 1.5 to 7.5 percent, more preferably 3 to 6.5 percent of the dry mass of the pretreated starch; the alkaline agent is preferably sodium hydroxide or sodium bicarbonate; the amount of the alkali agent is preferably 0.5 to 2.5% by mass, more preferably 1.5 to 2% by mass, based on the dry mass of the starch. The invention utilizes the alkaline reagent to maintain the alkaline condition in the reaction process, so that the reaction is carried out towards the esterification direction.
The process for mixing the pretreated starch with the octenyl succinic anhydride and the alkali agent is not particularly limited in the present invention, and the materials are uniformly mixed according to the process well known in the art.
In the present invention, the pressure of the jet milling is preferably 0.6 to 0.8Mpa, more preferably 0.7Mpa, and the classification rotation speed is preferably 2400 to 3600r/min, more preferably 3000 to 3200r/min; the jet milling is preferably carried out in a fluid bed jet mill.
In the jet milling process, the pretreated starch undergoes an esterification reaction with octenyl succinic anhydride to form octenyl succinic starch ester.
In the present invention, after the jet milling, it is preferable to further include: and washing, drying, crushing and sieving the obtained product in sequence to obtain the octenyl succinic acid starch ester.
In the present invention, the washing preferably includes ethanol washing and water washing sequentially; the volume fraction of ethanol used for the ethanol washing is preferably 75%; the times of washing by ethanol and washing by water are preferably 2 times; the temperature of the drying is preferably 45 ℃; the pulverizing and sieving is preferably 100 mesh sieving. The drying time and the pulverization process are not particularly limited in the present invention, and may be carried out according to a process well known in the art.
FIG. 1 is a flow chart of the present invention for preparing starch octenyl succinate, wherein starch raw material is formed into starch milk, then hydrochloric acid is added, after ultrasonic treatment, drying is performed to obtain pretreated starch; stirring and mixing the pretreated starch, sodium hydroxide and octenyl succinic anhydride, carrying out jet milling treatment, and sequentially carrying out ethanol washing, water washing, drying, crushing and sieving to obtain an octenyl succinic acid starch ester sample.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Preparing 300g of starch and 700g of distilled water into a 30% starch milk solution, adding hydrochloric acid with the concentration of 2mol/L accounting for 1% of the dry mass of the starch, placing the starch milk in an ultrasonic reactor, adjusting the value of p H to 7.0 by adding a sodium hydroxide aqueous solution into the ultrasonic starch milk at the ultrasonic power of 200W and the ultrasonic temperature of 30min, washing the starch milk with distilled water until the washing liquid is neutral, drying the starch milk at the constant temperature of 45 ℃ for 24 hours, crushing and sieving the starch milk to obtain pretreated starch;
fully and uniformly stirring 500g of the pretreated starch, octenyl succinic anhydride and sodium hydroxide solid particles, wherein the mass of the octenyl succinic anhydride is 1.5% of the dry mass of the pretreated starch, the mass of the sodium hydroxide is 0.5% of the dry mass of the starch, carrying out airflow crushing treatment on the obtained starch mixture by using a fluidized bed airflow crusher, the pressure is 0.6Mpa, the classification rotating speed is 2400r/min, washing the obtained product by using ethanol and distilled water with the volume fraction of 75% in sequence, washing for 2 times, drying the washed precipitate at 45 ℃, crushing, sieving by using a 100-mesh sieve, and placing in a sealed bag to obtain the octenyl succinic acid starch ester.
Example 2
Preparing 300g of starch and 700g of distilled water into a 30% starch milk solution, adding hydrochloric acid with the concentration of 2mol/L accounting for 7% of the dry mass of the starch, placing the starch milk in an ultrasonic reactor, adjusting the value of p H to 7.0 by adding an aqueous solution of sodium hydroxide into the ultrasonic starch milk at the ultrasonic power of 300W and the ultrasonic temperature of 45min, washing the starch milk with distilled water until the washing liquid is neutral, drying the starch milk at the constant temperature of 45 ℃ for 24 hours, crushing and sieving the starch milk to obtain pretreated starch;
fully and uniformly stirring 500g of the pretreated starch, octenyl succinic anhydride and sodium hydroxide solid particles, wherein the mass of the octenyl succinic anhydride is 3% of the dry mass of the pretreated starch, the mass of the sodium hydroxide is 1.5% of the dry mass of the starch, carrying out airflow crushing treatment on the obtained starch mixture by using a fluidized bed airflow crusher, the pressure is 0.7Mpa, the classification rotating speed is 3000r/min, washing the obtained product by using ethanol and distilled water with the volume fraction of 75% in sequence, the washing times are 2 times, drying the washed precipitate at 45 ℃, crushing, sieving by using a 100-mesh sieve, and placing in a sealed bag to obtain the octenyl succinic acid starch ester.
Example 3
Preparing 30% starch milk solution from 300g of starch and 700g of distilled water, adding hydrochloric acid with the concentration of 2mol/L accounting for 5% of the dry basis weight of the starch, placing the starch milk in an ultrasonic reactor, adjusting the value of p H to 7.0 by adding sodium hydroxide aqueous solution into the ultrasonic starch milk, washing the starch milk with distilled water until the washing solution is neutral, drying the starch milk at the constant temperature of 45 ℃ for 24 hours, crushing and sieving the starch milk to obtain pretreated starch;
fully and uniformly stirring 500g of the pretreated starch, octenyl succinic anhydride and sodium hydroxide solid particles, wherein the mass of the octenyl succinic anhydride is 6.5% of the dry mass of the pretreated starch, the mass of the sodium hydroxide is 2% of the dry mass of the starch, carrying out airflow crushing treatment on the obtained starch mixture by using a fluidized bed airflow crusher, the pressure is 0.8Mpa, the classification rotating speed is 3200r/min, washing the obtained product by using ethanol and distilled water with the volume fraction of 75% in sequence, the washing times are 2 times, drying the washed precipitate at 45 ℃, crushing, sieving by using a 100-mesh sieve, and placing the crushed precipitate in a sealed bag to obtain the octenyl succinic acid starch ester.
Test example
1) Determination of degree of substitution: accurately weighing 5g starch octenylsuccinate (dry basis) prepared in different examples, adding 25mL hydrochloric acid-isopropanol solution with concentration of 2.5mol/L, continuously stirring in a magnetic stirrer for 30min, adding 90% isopropanol solution by volume, stirring for 10min, filtering with a sand core funnel, washing with 90% isopropanol by volume until the filtrate is free of Cl - Until now (with 0.1mol/L AgNO) 3 Solution test), the obtained material is added with 300mL of distilled waterDissolving, heating in boiling water bath for 20min, cooling to room temperature, titrating with 0.1mol/L standard NaOH solution to the end point (using 1% phenolphthalein as indicator), and measuring the blank with corresponding unmodified starch by the above method, the result is shown in Table 1;
the degree of substitution DS is a value calculated by formula 1:
in formula 1: v is the volume of NaOH solution consumed by titration, mL; m is the concentration of NaOH solution for titration, (mol/L); w is the dry mass/g of octenyl succinate starch ester.
2) And (3) determining the particle size by using a laser particle size analyzer: putting different starch octenylsuccinate samples into distilled water, stirring uniformly, putting into an ultrasonic instrument for ultrasonic treatment for 5min, and determining the particle size D 50 The results are shown in Table 1.
3) And (3) measuring the emulsifying property: mixing a certain amount of starch octenyl succinate samples prepared in different embodiments with deionized water to prepare 1.5% (w/w) starch milk, placing the obtained starch milk in a water bath, heating with boiling water at 100 ℃, continuously stirring for 20min, cooling the starch milk to room temperature, adding peanut oil accounting for 5% of the mass of the starch milk, homogenizing for 1.5min at 10000rpm by using a high-speed homogenizer, repeating the homogenization for 2 times, sucking 50 microliter of emulsion, injecting into 5mL of sodium dodecyl sulfate solution with the concentration of 0.1wt%, and fully and uniformly mixing. The initial absorbance of the sample was measured by an ultraviolet spectrophotometer at 500nm using a sodium lauryl sulfate solution with a concentration of 0.1wt% as a blank (A) 0 ) The absorbance value was defined as the emulsifying ability value (EA) of the sample, and the results are shown in Table 1.
4) Determination of emulsion stability: mixing starch octenylsuccinate samples prepared in different embodiments with deionized water to obtain starch milk with concentration of 1.5% (w/w), placing the obtained starch milk in a water bath, heating with boiling water at 100 deg.C, stirring for 20min, cooling to room temperature, adding peanut oil 5% of the starch milk, homogenizing at 10 deg.C with a high-speed homogenizerHomogenizing at 000rpm for 1.5min, repeating homogenizing for 2 times, standing the obtained emulsion for 10min, and measuring its absorbance at 500nm by ultraviolet spectrophotometer (A) 10 ) The emulsion stability coefficient (ESI) is calculated by equation 2:
in the formula 2, A 0 As initial absorbance value, A 10 The results are shown in Table 1 for absorbance values after standing for 10 min.
TABLE 1 Property data of the starch octenylsuccinates prepared in examples 1 to 3
As can be seen from table 1, the octenyl succinate starch ester prepared by the method of the present application has a high degree of substitution, a good degree of reaction, a small particle size, and excellent emulsifiability and emulsion stability.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A preparation method of starch octenyl succinate is characterized by comprising the following steps:
mixing starch with water, mixing the obtained starch milk with acid, and performing ultrasonic treatment to obtain pretreated starch;
and mixing the pretreated starch with octenyl succinic anhydride and an alkali reagent, and carrying out jet milling on the obtained mixture to obtain the octenyl succinic acid starch ester.
2. The method according to claim 1, wherein the acid is hydrochloric acid, and the concentration of the hydrochloric acid is 2 to 10mol/L; the mass of the acid is 1-7% of the mass of the dry base of the starch; the mass concentration of the starch milk is 20-40%.
3. The preparation method according to claim 1, wherein the power of the ultrasonic treatment is 100-500W, the time is 15-60 min, and the temperature is 25-50 ℃.
4. The method of claim 1, further comprising, after the ultrasonication, the step of: adjusting the pH value of the obtained product to 6.5-7.5, and sequentially washing, drying, crushing and sieving to obtain the pretreated starch.
5. The method according to claim 4, wherein the drying is carried out at 45 ℃ for 24 hours.
6. The method according to claim 1, wherein the mass of the octenyl succinic anhydride is 1.5 to 7.5% of the dry mass of the pretreated starch.
7. The method according to claim 1, wherein the amount of the alkali agent is 0.5 to 2.5% by mass based on the dry weight of the starch.
8. The method according to claim 1, wherein the jet milling pressure is 0.6 to 0.8Mpa and the classification rotation speed is 2400 to 3600r/min.
9. The method of claim 1, further comprising, after said jet milling: and washing, drying, crushing and sieving the obtained product in sequence to obtain the octenyl succinic acid starch ester.
10. The production method according to claim 9, wherein the washing comprises ethanol washing and water washing which are performed in this order; the volume fraction of ethanol used for ethanol washing is 75%.
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