CN105085715A - Preparation method of O-carboxymethyl chitosan - Google Patents
Preparation method of O-carboxymethyl chitosan Download PDFInfo
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- CN105085715A CN105085715A CN201510585053.9A CN201510585053A CN105085715A CN 105085715 A CN105085715 A CN 105085715A CN 201510585053 A CN201510585053 A CN 201510585053A CN 105085715 A CN105085715 A CN 105085715A
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Abstract
The invention provides a preparation method of single-C6-site selectively-substituted O-carboxymethyl chitosan. The preparation method comprises the following steps: 1) reacting a raw material chitosan to generate benzaldehyde-modified carboxymethyl chitosan, wherein an imine structure generated by the reaction between benzaldehyde and amino Schiff base is utilized to protect the amino group on the chain; 2) carrying out carboxymethyl reaction on the reaction product and chloroacetic acid under alkaline conditions by using isopropanol as a medium to generate benzaldehyde-modified O-carboxymethyl chitosan; and 3) immersing the benzaldehyde-modified O-carboxymethyl chitosan under acidic conditions for 48 hours to remove benzaldehyde, thereby generating the single-C6-site selectively-substituted O-carboxymethyl chitosan. Compared with the N,O-carboxymethyl chitosan and N-carboxymethyl chitosan, the prepared O-carboxymethyl chitosan contains both amino and carboxy groups, and thus, has better procoagulant activity, biodegradability and bacteriostatic action. The O-carboxymethyl chitosan can accelerate injury healing and effectively prevent tissue adhesion and scar formation. The O-carboxymethyl chitosan has favorable adsorbing effects on acid ions and proteins, can be connected with multiple biological active substances, has high loading capacity for heavy metal ions, and is widely used in the fields of food, medicine, chemical industry and the like.
Description
Technical field
The present invention relates to a kind of preparation method of O-CMC, particularly relate to a kind of single C
6the preparation method of the O-CMC that position selectivity replaces.
Background technology
Cm-chitosan is a kind of water-solubility chitosan derivative, also has good water-soluble, film-forming properties, moisture retention biocompatibility, nontoxicity and biodegradable and come into one's own gradually at medical field because of it.Owing to there being 2 hydroxyl (C in chitosan molecule structure
3position and C
6position) and 1 amino (C
2position) carboxymethylation all can occur in these 3 positions.Therefore product has N, O-CMC, N-CMC and O-CMC.O-CMC is the positive polysaccharide of biodegradable not only containing active amino but also containing carboxyl, can be connected, greatly improving its load-carrying properties in medical with various bioactivators, can as the gene of a new generation and medicine targeted controlled-release solid support material.There is the preparation of O-CMC, what domestic report was more is adopt the O-position of carrying out reacting with Mono Chloro Acetic Acid at a lower temperature in alkaline medium and carboxymethyl being introduced in chitosan, but still have a small amount of N-position cm-chitosan product under the above-described reaction conditions, particularly in order to obtain have compared with the product of high substitution value or the reaction times longer time N-position product appearance can be comparatively obvious, and the impact of temperature fluctuation in reaction process, can be subject to.The present invention is raw material with chitosan, utilizes phenyl aldehyde to generate imine structure to protect the amino on its chain with amino schiff base reaction, then removes phenyl aldehyde in acid condition after accessing carboxymethyl in the basic conditions, generate O-CMC.
Summary of the invention
The present invention seeks to for the existing weak point preparing O-CMC method, providing a kind of is that protective material preparation is containing a large amount of single C of active group with phenyl aldehyde
6the preparation method of the O-CMC that position selectivity replaces.
Its principle is: free amine group and carboxyl are the important indicators weighing cm-chitosan functional property, therefore prepares cm-chitosan and should avoid consuming amino as far as possible.Be raw material with chitosan, utilize phenyl aldehyde to generate imine structure to protect the amino on its chain with amino schiff base reaction, then remove phenyl aldehyde in acid condition after accessing carboxymethyl in the basic conditions, generation O-CMC.
Realize especially by following steps:
(1) chitosan C
2the protection of bit amino: precision takes 3.0gCTS and is dissolved in 240ml1% acetum, slowly adds 180ml methyl alcohol after dissolving completely at 25 DEG C.Precision takes 3.0g phenyl aldehyde and is dissolved in 45ml methyl alcohol, dropwise adds after Homogeneous phase mixing, is warmed up to 60 DEG C of stirring reaction 4h.Slowly add 240ml5%NaOH solution and 60ml methyl alcohol, continue to stir 8h.Dewater with 95% washing with alcohol, dehydrated alcohol successively through suction filtration precipitation after having reacted, remove unreacted phenyl aldehyde, in 55 DEG C of oven dry.It is for subsequent use that reaction repeatedly accumulates product.
(2) carboxymethyl reaction: get above-mentioned reacted chitosan 5.0g (crossing 60 eye mesh screens) and be suspended in 50ml Virahol, 55 DEG C of swelling 5h.Be cooled to 25 DEG C, slowly drip 25mlM%NaOH solution under agitation, speed is 3s/d.After dropwising, continue to stir 1h, make it fully mix ,-20 DEG C of freeze overnight.After thawing next day, under condition of ice bath, drip the Ng Mono Chloro Acetic Acid that 20.0ml Virahol dissolves while stirring, speed is 5s/d.After dropwising, at 30 DEG C of stirring reaction 2h, then at 70 DEG C of reflux 2h.Outwell supernatant through suction filtration after having reacted, precipitation uses 70% successively, and 60% ethanol washs three (each 100ml respectively, soak 15min) then add the dissolving of 200ml distilled water, centrifugal going is precipitated, and is neutral with hydrochloric acid adjust pH, on reset and add ethanol to 70% of cumulative volume, separate out product.Use the washing with alcohol 1 time of 70% again, dehydrated alcohol dewaters, 55 DEG C of dry products, for subsequent use.
(3) removal of blocking group: CMC crude product 150ml0.5mol/LHCl soaking at room temperature 48h, be neutral with NaOH adjust pH, centrifugal going is precipitated.On reset and add ethanol to 70% of cumulative volume, separate out product, then use 70% washing with alcohol 3 times, dehydrated alcohol dewaters, and dries to obtain product for 55 DEG C.
The O-CMC that the present invention prepares, compared with CMC, N-cm-chitosan, not only had better short hemagglutinin, biological degradation, bacteriostatic action containing amino but also containing carboxyl; Can wound healing be accelerated, effectively prevent the formation of tissue adhesion and scar; Have good adsorption effect to acid ion, protein, can be connected with various bioactivators, the carrying capacity of heavy metal ion is strong, is widely used in the fields such as food, medicine, chemical industry.
Embodiment
The present invention will be further explained for the following examples, but the present invention is not limited only to these embodiments, the scope that these embodiments do not limit the present invention in any way.Those skilled in the art within the scope of the claims made some changes and adjustment also should be thought and belongs to the scope of the invention
Embodiment 1
(1) chitosan C
2the protection of bit amino: precision takes 3.0gCTS and is dissolved in 240ml1% acetum, slowly adds 180ml methyl alcohol after dissolving completely at 25 DEG C.Precision takes 3.0g phenyl aldehyde and is dissolved in 45ml methyl alcohol, dropwise adds after Homogeneous phase mixing, is warmed up to 60 DEG C of stirring reaction 4h.Slowly add 240ml5%NaOH solution and 60ml methyl alcohol, continue to stir 8h.Dewater with 95% washing with alcohol, dehydrated alcohol successively through suction filtration precipitation after having reacted, remove unreacted phenyl aldehyde, in 55 DEG C of oven dry.It is for subsequent use that reaction repeatedly accumulates product.
(2) carboxymethyl reaction: get above-mentioned reacted chitosan 5.0g (crossing 60 eye mesh screens) and be suspended in 50ml Virahol, 55 DEG C of swelling 5h.Be cooled to 25 DEG C, slowly drip 25ml20%NaOH solution under agitation, speed is 3s/d.After dropwising, continue to stir 1h, make it fully mix ,-20 DEG C of freeze overnight.After thawing next day, under condition of ice bath, drip the 14g Mono Chloro Acetic Acid that 20.0ml Virahol dissolves while stirring, speed is 5s/d.After dropwising, at 30 DEG C of stirring reaction 2h, then at 70 DEG C of reflux 2h.Outwell supernatant through suction filtration after having reacted, precipitation uses 70% successively, and 60% ethanol washs respectively for several times and adds the dissolving of 200ml distilled water, and centrifugal going is precipitated, and is neutral, above resets and add ethanol to 70% of cumulative volume, separate out product with hydrochloric acid adjust pH.Use the washing with alcohol 1 time of 70% again, dehydrated alcohol dewaters, 55 DEG C of dry products, for subsequent use.
(3) removal of blocking group: CMC crude product 150ml0.5mol/LHCl soaking at room temperature 48h, be neutral with NaOH adjust pH, centrifugal going is precipitated.On reset and add ethanol to 70% of cumulative volume, separate out product, then use 70% washing with alcohol 3 times, dehydrated alcohol dewaters, and dries to obtain product for 55 DEG C.
Embodiment 2
(1) chitosan C
2the protection of bit amino: precision takes 3.0gCTS and is dissolved in 240ml1% acetum, slowly adds 180ml methyl alcohol after dissolving completely at 25 DEG C.Precision takes 3.0g phenyl aldehyde and is dissolved in 45ml methyl alcohol, dropwise adds after Homogeneous phase mixing, is warmed up to 60 DEG C of stirring reaction 4h.Slowly add 240ml5%NaOH solution and 60ml methyl alcohol, continue to stir 8h.Dewater with 95% washing with alcohol, dehydrated alcohol successively through suction filtration precipitation after having reacted, remove unreacted phenyl aldehyde, in 55 DEG C of oven dry.It is for subsequent use that reaction repeatedly accumulates product.
(2) carboxymethyl reaction: get above-mentioned reacted chitosan 5.0g (crossing 60 eye mesh screens) and be suspended in 50ml Virahol, 55 DEG C of swelling 5h.Be cooled to 25 DEG C, slowly drip 25ml25%NaOH solution under agitation, speed is 3s/d.After dropwising, continue to stir 1h, make it fully mix ,-20 DEG C of freeze overnight.After thawing next day, under condition of ice bath, drip the 14g Mono Chloro Acetic Acid that 20.0ml Virahol dissolves while stirring, speed is 5s/d.After dropwising, at 30 DEG C of stirring reaction 2h, then at 70 DEG C of reflux 2h.Outwell supernatant through suction filtration after having reacted, precipitation uses 70% successively, and 60% ethanol washs respectively for several times and adds the dissolving of 200ml distilled water, and centrifugal going is precipitated, and is neutral, above resets and add ethanol to 70% of cumulative volume, separate out product with hydrochloric acid adjust pH.Use the washing with alcohol 1 time of 70% again, dehydrated alcohol dewaters, 55 DEG C of dry products, for subsequent use.
(3) removal of blocking group: CMC crude product 150ml0.5mol/LHCl soaking at room temperature 48h, be neutral with NaOH adjust pH, centrifugal going is precipitated.On reset and add ethanol to 70% of cumulative volume, separate out product, then use 70% washing with alcohol 3 times, dehydrated alcohol dewaters, and dries to obtain product for 55 DEG C.
Embodiment 3
(1) chitosan C
2the protection of bit amino: precision takes 3.0gCTS and is dissolved in 240ml1% acetum, slowly adds 180ml methyl alcohol after dissolving completely at 25 DEG C.Precision takes 3.0g phenyl aldehyde and is dissolved in 45ml methyl alcohol, dropwise adds after Homogeneous phase mixing, is warmed up to 60 DEG C of stirring reaction 4h.Slowly add 240ml5%NaOH solution and 60ml methyl alcohol, continue to stir 8h.Dewater with 95% washing with alcohol, dehydrated alcohol successively through suction filtration precipitation after having reacted, remove unreacted phenyl aldehyde, in 55 DEG C of oven dry.It is for subsequent use that reaction repeatedly accumulates product.
(2) carboxymethyl reaction: get above-mentioned reacted chitosan 5.0g (crossing 60 eye mesh screens) and be suspended in 50ml Virahol, 55 DEG C of swelling 5h.Be cooled to 25 DEG C, slowly drip 25ml25%NaOH solution under agitation, speed is 3s/d.After dropwising, continue to stir 1h, make it fully mix ,-20 DEG C of freeze overnight.After thawing next day, under condition of ice bath, drip the 10g Mono Chloro Acetic Acid that 20.0ml Virahol dissolves while stirring, speed is 5s/d.After dropwising, at 30 DEG C of stirring reaction 2h, then at 70 DEG C of reflux 2h.Outwell supernatant through suction filtration after having reacted, precipitation uses 70% successively, and 60% ethanol washs respectively and then adds the dissolving of 200ml distilled water for several times, and centrifugal going is precipitated, and is neutral, above resets and add ethanol to 70% of cumulative volume, separate out product with hydrochloric acid adjust pH.Use the washing with alcohol 1 time of 70% again, dehydrated alcohol dewaters, 55 DEG C of dry products, for subsequent use.
(3) removal of blocking group: CMC crude product 150ml0.5mol/LHCl soaking at room temperature 48h, be neutral with NaOH adjust pH, centrifugal going is precipitated.On reset and add ethanol to 70% of cumulative volume, separate out product, then use 70% washing with alcohol 3 times, dehydrated alcohol dewaters, and dries to obtain product for 55 DEG C.
Comprehensive analysis, with the yield of O-CMC and substitution value for index, it is 25%, M that the top condition of reaction is alkali concn
mono Chloro Acetic Acid/ M
benzene the chitosan of formolationbe 2.8, temperature of reaction is 70 DEG C, and now yield is 30.74%, and substitution value is 87.24%.
When the reaction medium of carboxymethyl reaction is Virahol, temperature is 70 DEG C, and NaOH is 25%, M at the final concentration of reaction solution
mono Chloro Acetic Acid/ M
the chitosan of phenyl aldehydebe respectively 2.0,2.8,3.5,4.5, in table 1.
The table substitution value of 1O-CMC and the measurement result of yield
When the reaction medium of carboxymethyl reaction is Virahol, temperature is 70 DEG C, M
mono Chloro Acetic Acid/ M
the chitosan of phenyl aldehyde=2.8, alkali concn is respectively 14.70%, 20.00%, 25.00%, 30.00%, and the yield of O-CMC, substitution value are in table 2.
The table substitution value of 2O-CMC and the measurement result of yield
Claims (8)
1. a preparation method for O-CMC, is characterized in that comprising the following steps:
(1) chitosan C
2the protection of bit amino: precision takes 3.0g chitosan and is dissolved in 240ml1% acetum, slowly adds 180ml methyl alcohol after dissolving completely at 25 DEG C.Precision takes 3.0g phenyl aldehyde and is dissolved in 45ml methyl alcohol, dropwise adds after Homogeneous phase mixing, is warmed up to 60 DEG C of stirring reaction 4h.Slowly add 240ml5%NaOH solution and 60ml methyl alcohol, continue to stir 8h.Dewater with 95% washing with alcohol, dehydrated alcohol successively through suction filtration precipitation after having reacted, remove unreacted phenyl aldehyde, in 55 DEG C of oven dry.It is for subsequent use that reaction repeatedly accumulates product.
(2) carboxymethyl reaction: get above-mentioned reacted chitosan 5.0g (crossing 60 eye mesh screens) and be suspended in 50ml Virahol, 55 DEG C of swelling 5h.Be cooled to 25 DEG C, slowly drip 25ml15 ~ 30%NaOH solution under agitation, speed is 3s/d.After dropwising, continue to stir 1h, make it fully mix ,-20 DEG C of freeze overnight.After thawing next day, under condition of ice bath, drip 5 ~ 22.5g Mono Chloro Acetic Acid that 20.0ml Virahol dissolves while stirring, speed is 5s/d.After dropwising, at 30 DEG C of stirring reaction 2h, then at 60 ~ 70 DEG C of reflux 2h.Outwell supernatant through suction filtration after having reacted, precipitation uses 70% successively, and 60% ethanol washs for several times respectively, then adds 200ml distilled water and dissolves, and centrifugal going is precipitated, and is neutral, above resets and add ethanol to 70% of cumulative volume, separate out product with hydrochloric acid adjust pH.Use the washing with alcohol 1 time of 70% again, dehydrated alcohol dewaters, 55 DEG C of dry products, for subsequent use.
(3) removal of blocking group: by the said products 150ml0.5mol/LHCl soaking at room temperature 48h, be neutral with NaOH adjust pH, centrifugal going is precipitated.On reset and add ethanol to 70% of cumulative volume, separate out product, then use 70% washing with alcohol 3 times, dehydrated alcohol dewaters, and dries to obtain product for 55 DEG C.
2. according to the preparation method of a kind of O-CMC described in claims 1, it is characterized in that: chitosan and the chloroacetic mass ratio of the middle phenyl aldehyde of step (2) control to be 1: 2,1: 2.8,1: 3.5,1: 4.5.
3. according to the preparation method of a kind of O-CMC described in claims 1, it is characterized in that: it is 60 DEG C, 65 DEG C, 70 DEG C that step (2) carboxymethyl temperature of reaction controls.
4. according to the preparation method of a kind of O-CMC described in claims 1, it is characterized in that: the concentration of step (2) carboxymethyl reaction NaOH solution controls to be 14.7%, 20%, 25%, 30%.
5. according to the preparation method of a kind of O-CMC described in claims 1, it is characterized in that: the medium of step (2) carboxymethyl reaction is ethanol, Virahol.
6. according to O-CMC preparation method a kind of described in claims 1, it is characterized in that: step (2), (3) control to be 60% ~ 70% for the low-concentration ethanol of washing precipitation.
7. according to O-CMC preparation method a kind of described in claims 1, it is characterized in that: the ratio of step (3) crude product and 0.5mol/LHCl is 1: 30.
8., according to O-CMC preparation method a kind of described in claims 1, it is characterized in that: in step (3) the soaking at room temperature time of thick product be 24,48,72h.
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| CN110917123A (en) * | 2019-11-19 | 2020-03-27 | 南京大学射阳高新技术研究院 | Preparation and application of medical biodegradable isolation adhesive |
| CN112586712A (en) * | 2020-12-07 | 2021-04-02 | 安徽省美极调味食品有限公司 | Wet diced meat seasoning capable of being stored at normal temperature and preparation method thereof |
| CN113603812A (en) * | 2021-08-31 | 2021-11-05 | 佛山泰立美生物科技有限公司 | Preparation method of selenium chromium-loaded double-element chelate and product thereof |
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