CN110105457A - A kind of mutual radiation method prepares the method and product of hydroxypropul starch - Google Patents
A kind of mutual radiation method prepares the method and product of hydroxypropul starch Download PDFInfo
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- CN110105457A CN110105457A CN201910454274.0A CN201910454274A CN110105457A CN 110105457 A CN110105457 A CN 110105457A CN 201910454274 A CN201910454274 A CN 201910454274A CN 110105457 A CN110105457 A CN 110105457A
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- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B31/00—Preparation of derivatives of starch
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Abstract
The invention discloses method and product that a kind of mutual radiation method prepares hydroxypropul starch, it is added after sodium hydroxide is used as catalyst, mixture that air is discharged after starch and propylene oxide mixing and is sealed and is put into60Irradiation grafting reaction is carried out in Co radiation field,, be not affected by temperature the features such as strong using gamma rays penetration power, cause starch with more low-boiling propylene oxide graft reaction to prepare hydroxypropul starch, starch molecular chain is broken using gamma rays irradiation in preparation process, degree of polymerization decline, so that starch granules is easy swelling rupture when gelatinization, gelatinization point is reduced, and by the optimization to parameters such as irradiation dose, catalyst concn, propylene oxide dosages, reaction efficiency and degree of substitution are improved.
Description
Technical field
The invention belongs to the processing preparation fields of hydroxypropul starch, and in particular to a kind of mutual radiation method prepares hydroxypropul starch
Method and product.
Background technique
Starch and propylene oxide act on obtaining hydroxypropul starch, to introduce the hydroxypropyl of nonionic in starch molecular chain
Base makes it have good hydrophily, freeze-thaw stability and flexibility (adaptability) of operation, has extensively in food medicine and other fields
Application.The preparation method of hydroxypropul starch mainly has water dispersion, organic solvent method and dry method.Water dispersion is most extensive hydroxyl
Propyl starch producing method is that continuous dispersed phase is obtained with strong alkali as a catalyst with propylene oxide at a certain temperature with water
Hydroxypropul starch increases subsequent washing and desalting difficulty since the viscosity of reaction system increases with the increase of molar substitution
Greatly, thus be suitable for preparing the hydroxypropul starch of lower molar substitution.Organic solvent method is using organic solvent as dispersing agent, in alkali
Property catalyst in the presence of starch react to obtain hydroxypropul starch with propylene oxide, this method product degree of substitution is high, but purification difficult, and
The use of organic solvent causes raw material and Environmental costs high.Dry method be starch and propylene oxide under the action of catalyst, in closed
In container, gas-solid phase reaction is carried out under certain temperature and pressure and obtains hydroxypropul starch, this method product degree of substitution height but by-product
Object is more, and equipment requirement is high, and system has risk of explosion at high temperature under high pressure, industrializes more difficult.
Summary of the invention
For disadvantages mentioned above and deficiency present in existing hydroxypropul starch technology of preparing, the present invention is intended to provide a kind of spoke altogether
The method and product that hydroxypropul starch is prepared according to method, cause and form sediment at, be not affected by temperature the features such as strong using gamma rays penetration power
Powder prepares hydroxypropul starch with more low-boiling propylene oxide graft reaction, makes to form sediment using gamma rays irradiation in preparation process
Powder molecular chain rupture, the degree of polymerization decline so that gelatinization when starch granules be easy swelling rupture, gelatinization point reduce, and by pair
The optimization of the parameters such as irradiation dose, catalyst concn, propylene oxide dosage, improves reaction efficiency and degree of substitution.
The present invention is technical solution used by realizing its technical purpose are as follows:
A kind of method that mutual radiation method prepares hydroxypropul starch, which is characterized in that the preparation method comprises the following steps:
SS1. a certain amount of starch and propylene oxide are weighed, is stirred evenly after the two is mixed；
SS2. mixture prepared by step SS1 is discharged to be sealed after air and is put into60It is anti-that irradiation grafting is carried out in Co radiation field
It answers, irradiation dose is no more than 200KGy；
SS3. the product after step SS2 irradiation distilled water and distilled water/ethyl alcohol mixed liquor is successively spent to wash, it is laggard
Row filtering；
SS4. step SS3 is washed into filtered product forced air drying at high temperature, hydroxypropul starch is made.
Preferably, in step SS1, the mass ratio of propylene oxide and starch is not more than 30:100.When propylene oxide and starch
When quality is lower than 30:100, with propylene oxide and starch quality than increasing, hydroxypropyl degree of substitution increases；When propylene oxide and starch
When mass ratio is greater than 30:100, with the increase of propylene oxide dosage, cause since homopolymerization occurs for more propylene oxide
Degree of substitution decline.
Further, in step SS1, a certain amount of sodium hydroxide is additionally added in starch and propylene oxide mixing process
As catalyst.
Further, in step SS1, the additional amount of catalyst sodium hydroxide is no more than the 3% of starch quality, preferably forms sediment
The 2% of silty amount.Sodium hydroxide has extraordinary catalytic effect in starch and the reaction of propylene oxide irradiation grafting, similarly
Under the conditions of available higher degree of substitution, using sodium hydroxide alkalization starch obtain starch cation, starch cation and ring
Nucleophilic substitution occurs for Ethylene Oxide, and activated centre is starch cation, thus addition catalyst sodium hydroxide helps to give birth to
At more stable peroxide to improve grafting rate.But sodium hydroxide and starch storage crop are especially left in certain water, easily
Agglomeration forms the state of similar colloid, is unevenly distributed sodium hydroxide, reduces with starch contact area, influences catalytic efficiency,
Thus the additional amount of catalyst sodium hydroxide is no more than the 3% of starch quality.
Preferably, in step SS2, irradiation dose is no more than 100KGy.When irradiation dose is less than 100kGy, hydroxypropul starch
Degree of substitution increases with irradiation dose and is improved, but after irradiation dose is more than 100kGy, is further added by irradiation dose hydroxypropul starch
Degree of substitution improve very little.
Further, in step SS2, irradiation dose is between 1-10kGy.At this point, degree of substitution is non-with irradiation dose increase
Often rapidly, slightly slow later, thus 10kGy or less irradiation reaction efficiency highest.When reason is that irradiation dose is smaller, irradiation is produced
Raw free radical reacts with the propylene oxide of surrounding rapidly, with the more free radicals of irradiation dose increase generation, but due to
It is difficult to migrate, except a part reacts, others can be inactivated gradually, so reaction efficiency declines.
Preferably, in step SS4, the forced air drying at 40 DEG C of filtered product is washed.
Compared with the existing technology, mutual radiation method of the invention prepares the method and product of hydroxypropul starch, is penetrated using gamma
Line penetration power is strong, the features such as not being affected by temperature, and causes starch with more low-boiling propylene oxide graft reaction to prepare hydroxypropyl
Base starch is broken starch molecular chain using gamma rays irradiation in preparation process, degree of polymerization decline, so that starch when gelatinization
Grain is easy swelling rupture, and gelatinization point reduces, and by parameters such as irradiation dose, catalyst concn, propylene oxide dosages
Optimization, improves reaction efficiency and degree of substitution.
Detailed description of the invention
Fig. 1 is influence schematic diagram of the different irradiation doses to hydroxypropul starch degree of substitution；
Fig. 2 is influence schematic diagram of the irradiation dose to hydroxypropul starch degree of substitution in the presence of catalyst；
Fig. 3 is influence schematic diagram of the different propylene oxide dosages to hydroxypropul starch degree of substitution；
Fig. 4 is influence schematic diagram of the different catalysts dosage to hydroxypropul starch degree of substitution；
Fig. 5 is the infrared spectroscopy contrast schematic diagram of ative starch and hydroxypropul starch prepared by the present invention；
Fig. 6 is ative starch and hydroxypropul starch scanning electron microscope (SEM) photograph prepared by the present invention, wherein (a) is ative starch scanning electricity
Mirror figure (b) is hydroxypropul starch scanning electron microscope (SEM) photograph prepared by the present invention；
Fig. 7 is the X ray diffracting spectrum of ative starch and hydroxypropul starch prepared by the present invention, wherein a, b, c are respectively original
Starch and degree of substitution are respectively the X ray diffracting spectrum of 0.018,0.211 hydroxypropul starch.
Specific embodiment
To make the objectives, technical solutions, and advantages of the present invention more comprehensible, right hereinafter, referring to the drawings and the embodiments,
The present invention is further described.
The method that mutual radiation method of the invention prepares hydroxypropul starch is strong using gamma rays penetration power, not by temperature shadow
The features such as ringing is caused starch with more low-boiling propylene oxide graft reaction to prepare hydroxypropul starch, is utilized in preparation process
Gamma rays irradiation is broken starch molecular chain, degree of polymerization decline, so that starch granules is easy swelling rupture, gelatinization temperature when gelatinization
Degree reduces, and by the optimization to parameters such as irradiation dose, catalyst concn, propylene oxide dosages, improve reaction efficiency and
Degree of substitution.When preparing hydroxypropul starch using mutual radiation method, mainly includes following preparation step: (1) weighing a certain amount of starch
And propylene oxide, it is stirred evenly after the two is mixed；(2) it will be sealed and be put into after the mixture discharge air of step (1) preparation60Co
Irradiation grafting reaction is carried out in radiation field, irradiation dose is no more than 200KGy；(3) product after step (2) irradiation is successively used
Distilled water and distilled water/ethyl alcohol mixed liquor washing are removed, is filtered later；(4) step (3) are washed into filtered product in height
The lower forced air drying of temperature, is made hydroxypropul starch.
In above-mentioned preparation process, different irradiation doses, propylene oxide dosage, catalyst amount replace hydroxypropul starch
Degree all has certain influence.Fig. 1 shows influence of the different irradiation doses to hydroxypropul starch degree of substitution, with mass ratio 30:100
Propylene oxide and starch are mixed, is irradiated with different dosage, it is as shown in Figure 1 to obtain product degree of substitution.Irradiation dose is less than
When 100kGy, hydroxypropul starch degree of substitution increases with irradiation dose and is improved, but after irradiation dose is more than 100kGy, is further added by
The degree of substitution of irradiation dose hydroxypropul starch improves very very little.In addition, further analysis shows that when irradiation dose is in 1-
When between 10kGy, degree of substitution is very fast with irradiation dose increase, later slightly slowly, thus 10kGy or less irradiation reaction efficiency
Highest.When irradiation dose is smaller, the free radical for irradiating generation reacts with the propylene oxide of surrounding rapidly, increases with irradiation dose
More free radicals are generated greatly, but due to being difficult to migrate, except a part reacts, others can be inactivated gradually, so reaction
Efficiency decline.
Fig. 2 is influence schematic diagram of the irradiation dose to hydroxypropul starch degree of substitution in the presence of catalyst.With mass ratio 30:
100 mix propylene oxide and starch, while the sodium hydroxide of starch quality 2% is added, with different dose deliveries, obtained hydroxyl
Propyl starch is as shown in Figure 2.To not plus catalyst it is similar, when irradiation dose be less than 100kGy when, with irradiation dose increase hydroxypropyl
Base starch degree of substitution improves, and almost no longer improves later, highest irradiation efficiency is still 10kGy or less.Comparison diagram 1 and Fig. 2
As a result, it has been found that sodium hydroxide has extraordinary catalytic effect, same item in starch and the reaction of propylene oxide irradiation grafting
Available higher degree of substitution under part.In hydroxypropul starch preparation process, the starch-grafted hydroxypropyl mechanism of base catalysis is alkalization
Starch obtains starch cation, and nucleophilic substitution occurs for starch cation and propylene oxide, activated centre be starch sun from
Son.And when no catalyst is deposited, the activated centre of starch irradiation grafting is the free radical that starch is formed under high-energy ray effect.
Under base catalysis starch irradiation grafting reaction in, alkali can alkalize starch obtain starch cation, to increase in reactivity
The presence of the heart or alkali helps to generate more stable peroxide to improve grafting rate.
Fig. 3 is influence schematic diagram of the different propylene oxide dosages to hydroxypropul starch degree of substitution.It is mixed with different mass ratioes
Cyclization Ethylene Oxide and starch, while the sodium hydroxide of starch quality 2% is added, irradiation dose 100kGy obtains hydroxypropyl shallow lake
Powder degree of substitution is as shown in Figure 3.Increase with propylene oxide and starch quality than increasing hydroxypropyl degree of substitution.Due to more epoxies third
Homopolymerization, which occurs, for alkane causes degree of substitution to decline, thus when propylene oxide and starch quality ratio are greater than 30:100, it is further added by ring
Ethylene Oxide dosage, hydroxypropyl degree of substitution increase very limited.It is that price is higher that propylene oxide and starch quality ratio, which are less than 30:100,
The higher section of propylene oxide utilization rate.
Fig. 4 is influence schematic diagram of the different catalysts dosage to hydroxypropul starch degree of substitution.With mass ratio 30:100 mixing
Propylene oxide and starch, while different proportion sodium hydroxide is added, irradiation dose 100kGy obtains product degree of substitution such as Fig. 4
It is shown.The utilization rate of sodium hydroxide is higher below 3% starch quality in gamma rays initiation reaction.But sodium hydroxide and shallow lake
Powder effect, especially leaves in certain water, and easily agglomeration forms the state similar to colloid, is unevenly distributed sodium hydroxide, with shallow lake
Powder contact area is reduced, and influences catalytic efficiency.
The infrared spectroscopy of ative starch and the hydroxypropul starch prepared using above-mentioned mutual radiation method of the invention as shown in figure 5,
3400cm-1Neighbouring broad peak is O-H key chattering absorption peak, 2931cm-1, 2890cm-1The absorption peak at place is the vibration of methylene C-H
Dynamic absorption peak, 1159cm-1For the stretching vibration absworption peak of C-O-C, 1181cm-1For the vibration absorption peak of hydroxyl C-O, form sediment with original
Powder is compared, and hydroxypropul starch is in 1159cm-1And 1181cm-1The absorption peak strength at place is opposite to be reinforced, and shows the life of hydroxypropul starch
At.
Fig. 6 is ative starch and hydroxypropul starch scanning electron microscope (SEM) photograph, and Cong Tuzhong is it can be found that starch is still after irradiation grafting
Graininess is kept, white powder is macroscopically shown as.But hydroxypropul starch particle diameter distribution is relatively wide compared with amylum body, and
And small size particle increasing proportion, surface appearance is uneven, observes the particle of some broken formation, and have many places particle poly-
Collection, this is because starch is by irradiation molecular chain rupture, while caused by reacting with propylene oxide.Ative starch and hydroxypropyl form sediment
It can be found that nanoscales cavity is presented in the performance of some particles in powder scanning electron microscope (SEM) photograph, it may be possible to due to particle internal moisture or
Other small-molecule substances are broken through in a vacuum and are formed.
In Fig. 7, a, b, c are respectively ative starch and degree of substitution is respectively the X-ray diffraction of 0.018,0.211 hydroxypropul starch
Map has apparent starch diffraction characteristic peak: 15.2 °, 17.2 °, 18.2 ° and 22.9 °, showing as the crystallization of A type.Effect of irradiation
Caused by the introducing of starch degradation and hydroxypropyl destroy the regularity of cornstarch chain to a certain extent, cause under diffracted intensity
Drop.Analysis X ray diffracting spectrum and microscopic appearance are known that starch during hydroxypropylation, and only part-structure destroys,
The main region to react is on the surface of starch granules.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Within mind and principle, any modification, equivalent substitution, improvement and etc. done be should be included within the scope of the present invention.
Claims (8)
1. a kind of method that mutual radiation method prepares hydroxypropul starch, which is characterized in that the preparation method comprises the following steps:
SS1. a certain amount of starch and propylene oxide are weighed, is stirred evenly after the two is mixed；
SS2. mixture prepared by step SS1 is discharged to be sealed after air and is put into60Irradiation grafting reaction, spoke are carried out in Co radiation field
It is no more than 200KGy according to dosage；
SS3. the product after step SS2 irradiation is successively spent into distilled water and distilled water/ethyl alcohol mixed liquor washs, carried out later
Filter；
SS4. step SS3 is washed into filtered product forced air drying at high temperature, hydroxypropul starch is made.
2. the method according to claim 1, wherein the mass ratio of propylene oxide and starch is little in step SS1
In 30:100.
3. according to the method described in claim 2, it is characterized in that, in step SS1, starch and propylene oxide mixing process
In be additionally added a certain amount of sodium hydroxide as catalyst.
4. according to the method described in claim 3, it is characterized in that, the additional amount of catalyst sodium hydroxide does not surpass in step SS1
Cross the 3% of starch quality, preferably the 2% of starch quality.
5. the method according to the claims, which is characterized in that in step SS2, irradiation dose is no more than 100KGy.
6. according to the method described in claim 5, it is characterized in that, irradiation dose is between 1-10kGy in step SS2.
7. the method according to the claims, which is characterized in that in step SS4, wash filtered product at 40 DEG C
Lower forced air drying.
8. a kind of hydroxypropul starch that the method according to any of the above-described claim is prepared.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116082529A (en) * | 2022-12-27 | 2023-05-09 | 山东福洋生物科技股份有限公司 | Preparation method of low-viscosity dry cationic starch |
| CN117209270A (en) * | 2022-12-13 | 2023-12-12 | 深圳市爱斯强科技有限公司 | Porous ceramic precursor and porous ceramic |
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| CN1887910A (en) * | 2006-07-28 | 2007-01-03 | 湖北省农业科学院辐照加工研究所 | Process of preparing non-ionic starch by initiating irradiation |
| CN101717451A (en) * | 2009-12-18 | 2010-06-02 | 张雷达 | Method for enhancing substitution degree of hydroxypropyl starch |
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2019
- 2019-05-29 CN CN201910454274.0A patent/CN110105457A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1887910A (en) * | 2006-07-28 | 2007-01-03 | 湖北省农业科学院辐照加工研究所 | Process of preparing non-ionic starch by initiating irradiation |
| CN101717451A (en) * | 2009-12-18 | 2010-06-02 | 张雷达 | Method for enhancing substitution degree of hydroxypropyl starch |
Non-Patent Citations (1)
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117209270A (en) * | 2022-12-13 | 2023-12-12 | 深圳市爱斯强科技有限公司 | Porous ceramic precursor and porous ceramic |
| CN116082529A (en) * | 2022-12-27 | 2023-05-09 | 山东福洋生物科技股份有限公司 | Preparation method of low-viscosity dry cationic starch |
| CN116082529B (en) * | 2022-12-27 | 2024-05-17 | 山东福洋生物科技股份有限公司 | Preparation method of low-viscosity dry cationic starch |
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Application publication date: 20190809 |