CN107573422A - The preparation method of starch octenyl succinate anhydride - Google Patents
The preparation method of starch octenyl succinate anhydride Download PDFInfo
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- CN107573422A CN107573422A CN201710686531.4A CN201710686531A CN107573422A CN 107573422 A CN107573422 A CN 107573422A CN 201710686531 A CN201710686531 A CN 201710686531A CN 107573422 A CN107573422 A CN 107573422A
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Abstract
The present invention provides a kind of preparation method of starch octenyl succinate anhydride, and the preparation method includes：By starch and CaCl2Solution is mixed at room temperature, then centrifugation is repeatedly washed through cold distilled water, is then purified, is dried to obtain gelation pretreated starch；Using wet processing, using water as medium, esterification is carried out by gelation pretreated starch and ocentyl succinic and generates starch octenyl succinate anhydride.The preparation method of starch octenyl succinate anhydride provided by the invention, utilizes CaCl2Solution can make this principle of starch generation gelation at room temperature, first by CaCl2The chemical gel of induction is turned to pretreatment of starch means, effectively improves the combined coefficient of starch octenyl succinate anhydride, and improves the texture characteristic and emulsifying capacity of end-product.
Description
Technical field
The present invention relates to the field of chemical modification of starch, more particularly to a kind of system of new starch octenyl succinate anhydride
Preparation Method.
Background technology
Starch is a kind of wide material sources, natural polysaccharide that is cheap, biodegradable and regenerating and can largely obtain divides
Son, but native starch limits its application in the food industry in terms of functional character.Therefore, starch is changed
Property purpose be in order to eliminate the defects of native starch is present, make its preferably be applied to industrial production in.
The modified method of starch is generally divided into physics, biology, chemistry and composite modifying method.Chemic modified method is current
Using more ripe starch treatment process, it the advantage is that starch treating capacity is big, it is easy to accomplish industrialized production in enormous quantities.
Chemical modification is carried out to starch, is greatly by derivatization, such as esterification, etherificate, cross-linking reaction, in starch molecule
It is intra/inter- to introduce new functional group, thereby result in the huge change of starch functional character.
Octenyl succinic acid anhydride (octenyl succinic anhydride, OSA), molecular formula C12H18O3, have only
Special ring-type dicarboxylic acids structure, when esterification occurs with starch, make originally hydrophilic starch due to succinic acid group
Introduce and carried hydrophobic characteristic, so as to cause the amphiphilic of whole molecule.Amphiphilic polymers are in emulsification, packaging, film
It is widely used with gel production field, starch octenyl succinate anhydride has superior emulsification property, therefore in food, medicine
It is widely used with cosmetic industry and makees emulsifying agent.
Starch octenyl succinate anhydride is usually to be synthesized under the conditions of aqueous phase, and it is in the nature to be existed using OSA and starch granules
Esterification occurs under alkalescence condition.Because dissolubilities of the OSA in water is very low, so when being reacted with granular starch,
OSA is difficult to fully contact and infiltrate into inside particle with starch, and it is low to thereby result in reaction efficiency.
The content of the invention
The purpose of the present invention is to solve at least one of problem above, and the present invention provides a kind of new octenyl succinic
The preparation method of acid-starch ester.
The preparation method of starch octenyl succinate anhydride, it is characterised in that comprise the following steps：
1) by starch and CaCl2Solution is mixed at room temperature, then centrifugation is repeatedly washed through cold distilled water, then purifies, be dry
It is dry to obtain gelation pretreated starch；
2) wet processing is used, using water as medium, is esterified by gelation pretreated starch with ocentyl succinic
Reaction generation starch octenyl succinate anhydride.
Wherein, in step 1)：CaCl2The concentration of solution is 0.05-1M.
Wherein, in step 1)：CaCl2The concentration of solution is any one in 0.05M, 0.1M, 0.5M or 1M.
Wherein, in step 1)：CaCl2The concentration of solution is 1M.
Wherein, in step 1)：The temperature of cold distilled water is 2~10 DEG C, and the number for washing centrifugation is 4 times.
Wherein, in step 1)：During washing centrifugation for the first time, centrifugal force is 3000~4000g, and centrifugation time is 10~20 points
Clock.
Wherein, step 2) includes：Pretreated starch is tuned into starch milk with water；Then NaOH solution is added by starch milk
PH value is adjusted to 8；At 35 DEG C, octenyl succinic acid anhydride progress esterification is added into starch milk, keeps reaction system
PH value is 8~8.5；After reaction terminates, with the PH to 6.5 of emulsion after hydrochloric acid solution regulation reaction, then centrifuged with water and ethanol
Washing, purification are drying to obtain starch octenyl succinate anhydride.
Wherein, in step 2)：The concentration for the starch milk being adjusted to water and pretreated starch is 35%；The NaOH used is molten
The concentration of liquid is 3%；3% octenyl succinic acid anhydride of starch on dry basis quality is first weighed, it is diluted 5 times with absolute ethyl alcohol
Afterwards, then instilled within 2 hours in starch milk and carry out esterification, it is 3 hours to control the whole reaction time；The hydrochloric acid used is molten
The concentration of liquid is 3%.
Wherein, in step 1)：Purification mode filters for ethanol, is each centrifugation with water and ethanol centrifuge washing in step 2)
Washing 3 times, then purified, the mode of purification filters for ethanol.
Wherein, in step 2)：Emulsion using water and each centrifuge washing of ethanol 3 times, then purification drying will be carried out after reaction.
According to another aspect of the present invention, there is provided a kind of starch octenyl succinate anhydride prepared by the preparation method.
The invention has the advantages that：
1. the present invention utilizes CaCl2Solution can make this principle of starch generation gelation at room temperature, be made first
It is applied to for preprocessing means in the preparation method of starch octenyl succinate anhydride, is effectively improved octenyl succinic acid starch
The combined coefficient of ester, and improve the texture characteristic and emulsifying capacity of end-product.
2. the pretreatment that the present invention is carried out to starch, operation is simple, low energy.
Embodiment
The illustrative embodiments of the disclosure are described in more detail below.Although showing for the disclosure is shown in specification
Example property embodiment, it being understood, however, that may be realized in various forms the disclosure without should be by embodiments set forth herein
Limited.Conversely, there is provided these embodiments are to be able to be best understood from the disclosure, and can be by the model of the disclosure
Enclose and be completely communicated to those skilled in the art.
Embodiment 1
Using farina as examples of materials, the preparation of starch octenyl succinate anhydride is carried out, specifically includes following step
Suddenly：
1) chemical gelation pre-processes：It is respectively 0.05M CaCl by quantitative starch and concentration2Solution mixes, in room
Temperature is lower to use magnetic agitation 10 minutes, reacts in backward above-mentioned starch milk and adds 4 DEG C enough of distilled water, the starch milk that will be obtained
Centrifuged 15 minutes in 3500g, then proceed to be washed 3 times with 4 DEG C of distilled water centrifugation, obtained chemical gelation is pre-processed into sample
Product are filtered using ethanol, are positioned over air drying, are then crossed 100 eye mesh screens, are obtained gelation pretreated starch.
2) synthesis of starch octenyl succinate anhydride：Gelation pretreated starch is tuned into 35wt% starch again with water
Breast, the pH that starch milk is adjusted using 3% (w/w) NaOH solution is 8, weighs 3% octenyl succinic of starch on dry basis quality
Acid anhydrides, 5 times are diluted with absolute ethyl alcohol, is slowly added dropwise in 2 hours in starch milk, whole reaction system is tieed up under magnetic stirring
PH8-8.5,35 DEG C of temperature are held, whole reaction is carried out 3 hours, and starch milk is adjusted after then being reacted with 3% (w/w) hydrochloric acid solution
Save pH to 6.5；Obtained starch milk is first washed 3 times with water centrifugation, then washed 3 times with absolute ethyl alcohol centrifugation, obtains starch ester sample；
Obtained starch ester sample is filtered using ethanol, air drying is positioned over, then crosses 100 eye mesh screens, obtain octenyl amber
Amber acid-starch ester X1.
Embodiment 2
Equally using farina as examples of materials, carry out the preparation of starch octenyl succinate anhydride, specifically include with
Lower step：
1) chemical gelation pre-processes：It is respectively 1M CaCl by quantitative starch and concentration2Solution mixes, at room temperature
With magnetic agitation 15 minutes, react in backward above-mentioned starch milk and add 2 DEG C enough of distilled water, by obtained starch milk in
3000g is centrifuged 20 minutes, then proceedes to be washed 3 times with 2 DEG C of distilled water centrifugation, the chemical gelation pretreatment sample that will be obtained
Filtered using ethanol, be positioned over air drying, then crossed 100 eye mesh screens, obtain gelation pretreated starch.
2) synthesis of starch octenyl succinate anhydride：Gelation pretreated starch is tuned into 35wt% starch again with water
Breast, the pH that starch milk is adjusted using 3% (w/w) NaOH solution is 8, weighs 3% octenyl succinic of starch on dry basis quality
Acid anhydrides, 5 times are diluted with absolute ethyl alcohol, is slowly added dropwise in 2 hours in starch milk, whole reaction system is tieed up under magnetic stirring
PH8-8.5,35 DEG C of temperature are held, whole reaction is carried out 3 hours, and starch milk is adjusted after then being reacted with 3% (w/w) hydrochloric acid solution
Save pH to 6.5；Obtained starch milk is first washed 3 times with water centrifugation, then washed 3 times with absolute ethyl alcohol centrifugation, obtains starch ester sample；
Obtained starch ester sample is filtered using ethanol, air drying is positioned over, then crosses 100 eye mesh screens, obtain octenyl amber
Amber acid-starch ester X2.
Embodiment 3
Equally using farina as examples of materials, carry out the preparation of starch octenyl succinate anhydride, specifically include with
Lower step：
1) chemical gelation pre-processes：It is respectively 0.1M CaCl by quantitative starch and concentration2Solution mixes, in room temperature
Lower magnetic agitation 20 minutes, react in backward above-mentioned starch milk and add 6 DEG C enough of distilled water, by obtained starch milk in
4000g is centrifuged 20 minutes, then proceedes to be washed 3 times with 6 DEG C of distilled water centrifugation, the chemical gelation pretreatment sample that will be obtained
Filtered using ethanol, be positioned over air drying, then crossed 100 eye mesh screens, obtain gelation pretreated starch.
2) synthesis of starch octenyl succinate anhydride：Gelation pretreated starch is tuned into 35wt% starch again with water
Breast, the pH that starch milk is adjusted using 3% (w/w) NaOH solution is 8, weighs 3% octenyl succinic of starch on dry basis quality
Acid anhydrides, 5 times are diluted with absolute ethyl alcohol, is slowly added dropwise in 2 hours in starch milk, whole reaction system is tieed up under magnetic stirring
PH8-8.5,35 DEG C of temperature are held, whole reaction is carried out 3 hours, and starch milk is adjusted after then being reacted with 3% (w/w) hydrochloric acid solution
Save pH to 6.5；Obtained starch milk is first washed 3 times with water centrifugation, then washed 3 times with absolute ethyl alcohol centrifugation, obtains starch ester sample；
Obtained starch ester sample is filtered using ethanol, air drying is positioned over, then crosses 100 eye mesh screens, obtain octenyl amber
Amber acid-starch ester X3.
Embodiment 4
Using farina as examples of materials, the preparation of starch octenyl succinate anhydride is carried out, specifically includes following step
Suddenly：
1) chemical gelation pre-processes：It is respectively 0.5M CaCl by quantitative starch and concentration2Solution mixes, in room temperature
It is lower to use magnetic agitation 10 minutes, react in backward above-mentioned starch milk and add 10 DEG C enough of distilled water, the starch milk that will be obtained
Centrifuged 15 minutes in 4000g, then proceed to be washed 3 times with 10 DEG C of distilled water centrifugation, obtained chemical gelation is pre-processed
Sample is filtered using ethanol, is positioned over air drying, is then crossed 100 eye mesh screens, is obtained gelation pretreated starch.
2) synthesis of starch octenyl succinate anhydride：Gelation pretreated starch is tuned into 35wt% starch again with water
Breast, the pH that starch milk is adjusted using 3% (w/w) NaOH solution is 8, weighs 3% octenyl succinic of starch on dry basis quality
Acid anhydrides, 5 times are diluted with absolute ethyl alcohol, is slowly added dropwise in 2 hours in starch milk, whole reaction system is tieed up under magnetic stirring
PH8-8.5,35 DEG C of temperature are held, whole reaction is carried out 3 hours, and starch milk is adjusted after then being reacted with 3% (w/w) hydrochloric acid solution
Save pH to 6.5；Obtained starch milk is first washed 3 times with water centrifugation, then washed 3 times with absolute ethyl alcohol centrifugation, obtains starch ester sample；
Obtained starch ester sample is filtered using ethanol, air drying is positioned over, then crosses 100 eye mesh screens, ocentyl succinic
Starch ester X4.
Experimental example 1
By starch octenyl succinate anhydride X1~X4 of embodiment 1~4 and the octene for not doing the normal potato pre-processed
Base succinic acid starch ester is compared at substitution value, the aspect of emulsifying capacity two, while by the preparation method of embodiment 1~4 and not
Do the common preparation method pre-processed to be compared in terms of the combined coefficient of starch octenyl succinate anhydride, ensure except pretreatment
Outside step, the step of remaining step of common preparation method is with the preparation method of embodiment 1~4, is identical.Comparing result such as table 1 below
It is shown：
Table 1：Substitution value, emulsifying capacity and the reaction efficiency contrast of a variety of starch octenyl succinate anhydrides
As shown in Table 1, the substitution value of starch octenyl succinate anhydride X1~X4 by pretreatment is above untreated
Common starch octenyl succinate anhydride, particularly embodiment two are using 1M CaCl2The shallow lake of the chemical gelation processing induced
Powder, reaction efficiency and substitution value improve significant effect, and emulsifying capacity also increases；Illustrate to use CaCl2The chemistry of induction coagulates
Gel pre-treatment step is modified to follow-up octenyl succinic acid anhydride has facilitation.
Experimental example 2
Do not do starch octenyl succinate anhydride X1~X4 of embodiment 1~4 and the normal potato octenyl pre-processed
Succinic acid starch ester carries out texture characteristic analysis and is compared, as a result as shown in table 2 below：
Table 2：The texture characteristic of a variety of starch octenyl succinate anhydrides
As shown in Table 2, the starch octenyl succinate anhydride X1~X4 prepared in embodiment X1~X4 hardness, it is deadlocked degree and
Three aspects of chewability are superior to the octenyl succinic acid starch prepared without the commonsense method of chemical gelation pretreatment system
Ester, illustrate that chemical gelation pretreatment can improve the texture characteristic for the starch octenyl succinate anhydride being finally synthesizing.
The foregoing is only a preferred embodiment of the present invention, but protection scope of the present invention be not limited thereto,
Any one skilled in the art the invention discloses technical scope in, the change or replacement that can readily occur in,
It should all be included within the scope of the present invention.Therefore, protection scope of the present invention should be with the protection model of the claim
Enclose and be defined.
Claims (10)
1. the preparation method of starch octenyl succinate anhydride, it is characterised in that comprise the following steps：
1) by starch and CaCl2Solution mixes at room temperature, repeatedly wash-centrifuge and then purify through cold distilled water, be dried to obtain it is solidifying
Gel pretreated starch；
2) wet processing is used, esterification, which occurs, by gelation pretreated starch and ocentyl succinic generates octenyl amber
Amber acid-starch ester.
2. the preparation method of starch octenyl succinate anhydride as claimed in claim 1, it is characterised in that in the step 1)：
The CaCl2The concentration of solution is 0.05-1M.
3. the preparation method of starch octenyl succinate anhydride as claimed in claim 1, it is characterised in that in the step 1)：
The CaCl2The concentration of solution is any one in 0.05M, 0.1M, 0.5M or 1M.
4. the preparation method of starch octenyl succinate anhydride as claimed in claim 2 or claim 3, it is characterised in that the step 1)
In：
The CaCl2The concentration of solution is 1M.
5. the preparation method of starch octenyl succinate anhydride as claimed in claim 1, it is characterised in that in the step 1)：
The temperature of cold distilled water is 2~10 DEG C, and the number of washing-centrifugation is 4 times.
6. the preparation method of starch octenyl succinate anhydride as claimed in claim 1, it is characterised in that in the step 1)：
During first time washing-centrifugation, centrifugal force is 3000~4000g, and centrifugation time is 10~20 minutes.
7. the preparation method of starch octenyl succinate anhydride as claimed in claim 1, it is characterised in that the step 2) bag
Include：
Pretreated starch is tuned into starch milk with water；Then add NaOH solution and the pH value of starch milk is adjusted to 8；At 35 DEG C
Under, octenyl succinic acid anhydride progress esterification is added into starch milk, the pH value for keeping reaction system is 8~8.5；Reaction knot
Shu Hou, with the PH to 6.5 of emulsion after hydrochloric acid solution regulation reaction, then with water and ethanol centrifuge washing, then purify, be drying to obtain
Starch octenyl succinate anhydride.
8. the preparation method of starch octenyl succinate anhydride as claimed in claim 5, it is characterised in that in the step 2)：
The concentration for the starch milk being adjusted to water and pretreated starch is 35wt%；The concentration of the NaOH solution used is 3%；First
3% octenyl succinic acid anhydride of starch on dry basis quality is weighed, after it is diluted into 5 times with absolute ethyl alcohol, then is dripped within 2 hours
Enter and esterification is carried out in starch milk；It is 3 hours to control the whole reaction time；The concentration of the hydrochloric acid solution used is 3%.
9. the preparation method of starch octenyl succinate anhydride as claimed in claim 5, it is characterised in that in the step 1)：
Purification mode filters for ethanol；In the step 2)：Described with water and ethanol centrifuge washing is each centrifuge washing 3 times, then is carried out
Purification, the mode of the purification filter for ethanol.
10. a kind of starch octenyl succinate anhydride, it is characterised in that the starch octenyl succinate anhydride is by claim 1-9
Preparation method described in middle any one obtains.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111035015A (en) * | 2019-12-27 | 2020-04-21 | 浙江新和成股份有限公司 | Water-insoluble fat-soluble nutrient microcapsule and preparation method thereof |
| CN113768051A (en) * | 2020-06-09 | 2021-12-10 | 中粮营养健康研究院有限公司 | Feed additive, preparation method thereof, application of feed additive in feed and anti-feed |
| WO2023056805A1 (en) * | 2021-10-08 | 2023-04-13 | 天津科技大学 | Preparation method for modified starch-lipid binary complex |
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| CN101407552A (en) * | 2008-11-27 | 2009-04-15 | 诸城兴贸玉米开发有限公司 | Technique for producing low viscosity octenylsuccinate starch by oxidation process |
| CN101696245A (en) * | 2009-10-21 | 2010-04-21 | 甘肃农业大学 | Method for preparing octenylsuccinate potato starch ester |
| JP5637603B2 (en) * | 2011-07-27 | 2014-12-10 | 株式会社マンダム | Oily cosmetics |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101407552A (en) * | 2008-11-27 | 2009-04-15 | 诸城兴贸玉米开发有限公司 | Technique for producing low viscosity octenylsuccinate starch by oxidation process |
| CN101696245A (en) * | 2009-10-21 | 2010-04-21 | 甘肃农业大学 | Method for preparing octenylsuccinate potato starch ester |
| JP5637603B2 (en) * | 2011-07-27 | 2014-12-10 | 株式会社マンダム | Oily cosmetics |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111035015A (en) * | 2019-12-27 | 2020-04-21 | 浙江新和成股份有限公司 | Water-insoluble fat-soluble nutrient microcapsule and preparation method thereof |
| CN111035015B (en) * | 2019-12-27 | 2023-09-05 | 浙江新和成股份有限公司 | Non-water-soluble fat-soluble nutrient microcapsule and preparation method thereof |
| CN113768051A (en) * | 2020-06-09 | 2021-12-10 | 中粮营养健康研究院有限公司 | Feed additive, preparation method thereof, application of feed additive in feed and anti-feed |
| CN113768051B (en) * | 2020-06-09 | 2024-03-19 | 中粮营养健康研究院有限公司 | Feed additive, preparation method thereof, application of feed additive in feed and tianti feed |
| WO2023056805A1 (en) * | 2021-10-08 | 2023-04-13 | 天津科技大学 | Preparation method for modified starch-lipid binary complex |
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