CN103030701B - Preparation method of modified starch crosslinking agent - Google Patents
Preparation method of modified starch crosslinking agent Download PDFInfo
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- CN103030701B CN103030701B CN201210516811.8A CN201210516811A CN103030701B CN 103030701 B CN103030701 B CN 103030701B CN 201210516811 A CN201210516811 A CN 201210516811A CN 103030701 B CN103030701 B CN 103030701B
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Abstract
The invention relates to a preparation method of a modified starch crosslinking agent, which comprises the following steps: mixing a 1-5 wt% of starch solution and a sodium periodate solution to react for 12-24 hours, wherein the mass ratio of sodium periodate in the sodium periodate solution to starch in the starch solution is 1:8-1:1; and adding ethylene glycol into the mixed solution of the reacted starch solution and sodium periodate solution, stirring for 5-30 minutes, stopping the reaction, adding sodium chloride, evenly mixing, adding ethanol to precipitate, separating and purifying the precipitate, and drying to obtain the modified starch crosslinking agent. The preparation method of the modified starch crosslinking agent utilizes sodium periodate as the oxidizer to react at normal temperature so as to oxidize the starch, thereby obtaining the modified starch crosslinking agent. The invention has the advantages of mild reaction conditions and simple preparation technique.
Description
Technical field
The present invention relates to linking agent preparing technical field, particularly relate to a kind of preparation method of treated starch linking agent.
Background technology
The domestic research for linking agent at present, gradually by traditional chemical cross-linking agent, as glutaraldehyde, epoxy resin etc., changes to genipin that is nontoxic, that have good biocompatibility.Although conventional cross-linking agent has good cross-linking effect, its range of application is from industry until biomedical sector, have long history, but the toxicity of himself or its degraded product limits their further expansive approach in biomedical, biomaterial.Therefore, study linking agent that a class has a good biocompatibility and become one of focus that Chinese scholars explores.
Academic circles at present replaces chemical cross-linking agent with natural biological linking agent gradually at biomedical sector, to some extent solves the cytotoxicity problem that chemical cross-linking agent brings.But conventional natural biological linking agent is expensive, and extraction process is loaded down with trivial details.The genipin such as extracted from the bark of eucommia and cape jasmine, although it has good cross-linking effect and biocompatibility, because extraction process is complicated, productive rate is low, causes it expensive, and after being cross-linked, the color of material can become blue, affects attractive in appearance; After the sodium alginate extracted from marine alga carries out oxide treatment, obtain many aldehyde sodium alginates, its cross-linking effect is pretty good, but because sodium alginate extracts from marine alga, technique is loaded down with trivial details, is unfavorable for preparing linking agent fast.
Summary of the invention
Based on this, be necessary to provide a kind of preparation technology the preparation method of better simply treated starch linking agent.
A preparation method for treated starch linking agent, comprises the steps:
By mass concentration be 1 ~ 5% starch solution mix with sodium periodate solution, react 12 hours ~ 24 hours, wherein, the mass ratio of the starch in the sodium periodate in described sodium periodate solution and described starch solution is 1:8 ~ 1:1; And
Ethylene glycol is added in the mixed solution of described reacted starch solution and sodium periodate solution, stir 5 minutes ~ 30 minutes termination reactions, then add sodium-chlor, add ethanol after mixing and separate out precipitation, described precipitate and separate purifying, drying are obtained treated starch linking agent.
Wherein in an embodiment, the mass concentration of described sodium periodate solution is 5% ~ 20%.
Wherein in an embodiment, described sodium periodate solution is supersaturated solution.
Wherein in an embodiment, the mol ratio of the sodium periodate in described ethylene glycol and described sodium periodate solution is 1:1.
Wherein in an embodiment, the mass ratio of described sodium-chlor and described starch is 1:2 ~ 4:1.
Wherein in an embodiment, the volume ratio of the mixed solution of described ethanol and described reacted starch solution and sodium periodate solution is 1 ~ 10:1.
Wherein in an embodiment, the step of described separation and purification is: dissolved by described precipitation distilled water, then adds ethanol and separates out, repeat 2 ~ 5 times.
Wherein in an embodiment, in the step of described separation and purification, to separate out the volume of the ethanol of the step precipitated equal with adding ethanol after described mixing for each added ethanol.
Wherein in an embodiment, the compound method of described starch solution is that starch to be added temperature be in the distilled water of 50 DEG C ~ 80 DEG C, stirs.
Wherein in an embodiment, described by mass concentration be 1 ~ 5% starch solution mix with sodium periodate solution, react the step of 12 hours ~ 24 hours and add ethylene glycol in the mixed solution of described reacted starch solution and sodium periodate solution, the step stirring 5 minutes ~ 30 minutes termination reactions is all carried out under the condition of lucifuge.
The preparation method of above-mentioned treated starch linking agent utilizes sodium periodate to react at normal temperatures as oxygenant, and Sumstar 190 obtains treated starch linking agent.Reaction conditions is gentle, and preparation technology is simple.
Accompanying drawing explanation
Fig. 1 is preparation method's schema of the treated starch linking agent of an embodiment.
Embodiment
For enabling above-mentioned purpose of the present invention, feature and advantage become apparent more, are described in detail the specific embodiment of the present invention below in conjunction with accompanying drawing.Set forth a lot of detail in the following description so that fully understand the present invention.But the present invention can be much different from alternate manner described here to implement, those skilled in the art can when without prejudice to doing similar improvement when intension of the present invention, therefore the present invention is by the restriction of following public concrete enforcement.
Refer to Fig. 1, the preparation method of the treated starch linking agent of an embodiment, comprises the steps:
Step S110: by mass concentration be 1 ~ 5% starch solution mix with sodium periodate solution, react 12 hours ~ 24 hours.
Preparation mass concentration is the starch solution of 1 ~ 5%.In order to improve the solubleness of starch, starch is dissolved in temperature be 50 DEG C ~ 80 DEG C in distilled water, stir and obtain the starch solution that mass concentration is 1 ~ 5%.
The mass concentration of starch solution is too little, and reaction cannot be carried out; Mass concentration is excessive, and starch solution is colloidal, makes sodium periodate solution be difficult to be evenly dispersed in starch solution, and cause being difficult to make starch uniform alumina, therefore the mass concentration of starch solution is preferably 1 ~ 5%.
Starch is natural plant amylum, such as green starch, yam starch, W-Gum etc.Plant amylum is cheap, and nontoxic, is conducive to that preparation cost is low, the linking agent of good biocompatibility.
Preparation sodium periodate solution.Added by sodium periodate in distilled water, under room temperature, lucifuge stirs, compound concentration to be mass concentration be 5% ~ 20% sodium periodate solution.Sodium periodate is strong oxidizer, under lucifuge condition, avoid sodium periodate to decompose.
The concentration of sodium periodate solution is too little, may affect its oxidation effectiveness.Preferably, sodium periodate solution is supersaturated solution, to reduce water in solution as far as possible, improves oxidation effectiveness.
Starch ((C
6h
10o
5) monomer C n)
6h
10o
5in containing a vicinal diamines, in order to completely the vicinal diamines in starch is oxidized to aldehyde radical, so that starch conversion is obtained many aldehyde starch, and the amount controlling sodium periodate is exceeded, and the mass ratio of sodium periodate and starch is preferably 1:8 ~ 1:1.
If the amount of sodium periodate is excessive, containing iodide ion in the product be obtained by reacting, the time one is long, and coloured product can change.
Under lucifuge condition, stirring reaction 12 hours ~ 24 hours under normal temperature, sodium periodate and starch generation redox reaction, the vicinal diamines in starch is oxidized to aldehyde radical by sodium periodate, generates many aldehyde starch of modification.
Reaction formula is:
Answer formula from above-mentioned, the treated starch generated after reaction has multiple aldehyde radical, and aldehyde radical, as the functional group with crosslinked action, makes this treated starch have good cross-linking effect.
Step S120: add ethylene glycol in the mixed solution of reacted starch solution and sodium periodate solution, stir 5 minutes ~ 30 minutes termination reactions, then add sodium-chlor, add ethanol after mixing and separate out precipitation, precipitate and separate purifying, drying are obtained treated starch linking agent.
Under lucifuge condition, in the mixed solution of reacted starch solution and sodium periodate solution, add ethylene glycol, stir 5 minutes ~ 30 minutes termination reactions.
Ethylene glycol and sodium periodate react and stop the reaction of sodium periodate and starch.Preferably, the mol ratio of the sodium periodate in ethylene glycol and sodium periodate solution is 1: 1, and to make sodium periodate completely and glycol reaction, Quick stop reacts.
After termination reaction, in reaction solution, add sodium-chlor, the effect of sodium-chlor is formation nucleus, so that follow-up formation precipitation.The sodium-chlor amount added is too much, has sodium chloride particle after precipitation, reduces the purity of product; Very little, then the starch of modification can not precipitate the amount of sodium-chlor.Preferably, the mass ratio of sodium-chlor and starch is 1:2 ~ 4:1.
Add ethanol by Precipitation, the volume ratio of the mixed solution of ethanol and reacted starch solution and sodium periodate solution is 1 ~ 10:1.
In order to remove the sodium-chlor and sodium periodate that are mingled with in product, also separation and purification is carried out to product.The method of separation and purification is: filter after separating out precipitation, be precipitated, dissolved by precipitation distilled water, then adds ethanol and separates out precipitation, repeat 2 ~ 5 times, obtain the treated starch linking agent of pure many aldehyde radicals.
Preferably, the ethanol added each time, with equal with the volume of the ethanol added in the mixed solution of sodium periodate solution and the mixture of sodium-chlor to reacted starch solution, is separated out completely to ensure to precipitate.Because sodium-chlor and sodium periodate soluble in water, after repeating 2 ~ 5 times, substantially remove sodium-chlor and sodium periodate completely.
In order to accelerate dissolution, can precipitation be dissolved in hot distilled water, such as, in the distilled water of 40 DEG C ~ 50 DEG C.
The preparation method of above-mentioned treated starch linking agent utilizes sodium periodate as oxygenant, carries out redox reaction at normal temperatures, the vicinal diamines oxidation in starch is generated aldehyde radical, obtains treated starch linking agent.Preparation technology is simple, and reaction conditions is gentle.
Especially natural polymer starch is carried out chemical modification, make it have crosslinkable functional group, realize crosslinked object, prepare a kind of treated starch linking agent with good biocompatibility, many aldehyde radicals that cross-linking effect is good.This treated starch linking agent can be widely used in biomedical sector.
The treated starch linking agent stable in properties of the many aldehyde radicals prepared by aforesaid method, after crosslinked, the color of material can not change, and does not affect the appearance.
It is below specific embodiment.
Embodiment 1
Getting 10g yam starch, to join 1000ml temperature be in the hot distilled water of 50 DEG C, stirs and be configured to the starch solution that mass concentration is 1%; Under lucifuge condition, get 1g sodium periodate joins in 50mL distilled water, and preparation mass concentration is the sodium periodate solution of 2%.Under lucifuge condition, mix above-mentioned starch solution and above-mentioned sodium periodate solution, lucifuge oxidizing reaction 24h, add 0.26mL (0.00467mol) ethylene glycol, stir and stop oxidizing reaction in 5 minutes.Add 10g sodium-chlor, fully after mixing, add 300mL ethanol and make its Precipitation.Suction filtration, uses deionized water lysate, then with ethanol 300mL separate out, suction filtration, so repeatedly 3 final vacuum dryings.Finally obtain the treated starch linking agent of many aldehyde radicals.
Embodiment 2
Getting 20g W-Gum, to join 1000ml temperature be in the hot distilled water of 60 DEG C, stirs and be configured to the starch solution that mass concentration is 2%; Under lucifuge condition, get 1.5g sodium periodate joins in 50mL distilled water, and preparation mass concentration is the sodium periodate solution of 5%.Under lucifuge condition, mix above-mentioned starch solution and above-mentioned sodium periodate solution, lucifuge oxidizing reaction 12h, add 0.39ml (0.007005mol) ethylene glycol, stir and stop oxidizing reaction in 20 minutes.Add 80g sodium-chlor, fully after mixing, add 500mL ethanol and make its Precipitation.Suction filtration, uses deionized water lysate, then with ethanol 500mL separate out, suction filtration, so repeatedly 4 final vacuum dryings.Finally obtain the treated starch linking agent of many aldehyde radicals.
Embodiment 3
Getting 50g green starch, to join 1000ml temperature be in the hot distilled water of 80 DEG C, stirs and be configured to the starch solution that mass concentration is 5%; Under lucifuge condition, get 1.5g sodium periodate joins in 60mL distilled water, and preparation mass concentration is the sodium periodate solution of 5%.Under lucifuge condition, mix above-mentioned starch solution and above-mentioned sodium periodate solution, lucifuge oxidizing reaction 20h, add 0.39mL (0.007005mol) ethylene glycol, stir and stop oxidizing reaction in 30 minutes.Add 25g sodium-chlor, fully after mixing, add 350mL ethanol and make its Precipitation.Suction filtration, uses deionized water lysate, then with ethanol 350mL separate out, suction filtration, so repeatedly 5 final vacuum dryings.Finally obtain the treated starch linking agent of many aldehyde radicals.
The above embodiment only have expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but therefore can not be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (1)
1. a preparation method for treated starch linking agent, is characterized in that, comprises the steps:
Getting 10g yam starch, to join 1000mL temperature be in the hot distilled water of 50 DEG C, stirs and be configured to the starch solution that mass concentration is 1%; Under lucifuge condition, get 1g sodium periodate joins in 50mL distilled water, and preparation mass concentration is the sodium periodate solution of 2%; Under lucifuge condition, mix above-mentioned starch solution and above-mentioned sodium periodate solution, lucifuge oxidizing reaction 24h, add 0.00467mol ethylene glycol, stir and stop oxidizing reaction in 5 minutes; Add 10g sodium-chlor, fully after mixing, add 300mL ethanol and make its Precipitation; Suction filtration, uses deionized water lysate, then with ethanol 300mL separate out, suction filtration, so repeatedly 3 final vacuum dryings; Obtain the treated starch linking agent of many aldehyde radicals.
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| NL1004793C2 (en) * | 1996-12-16 | 1998-06-17 | Avebe Coop Verkoop Prod | Method for the oxidation of starch with periodate. |
| US20050256306A1 (en) * | 2004-05-11 | 2005-11-17 | Kyungsoo Woo | Oxidized reversibly swelling granular starch products |
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| CN101663328A (en) * | 2007-04-24 | 2010-03-03 | 纳幕尔杜邦公司 | Method for making a polysaccharide dialdehyde having high purity |
| CN101343369A (en) * | 2008-06-27 | 2009-01-14 | 贺州学院 | Dialdehyde starch crosslinked chitosan magnetic microsphere and preparation thereof |
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| "双醛淀粉的制备及其提高胶原的热稳定性研究";贺丽蓉等;《中国皮革》;20090831;第38卷(第15期);第23-27页 * |
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Inventor after: Pan Haobo Inventor after: Wang Jianyun Inventor before: Wang Jianyun Inventor before: Pan Haobo |