CN102492055A - Method for preparing high-viscosity chitosan by using chitin - Google Patents
Method for preparing high-viscosity chitosan by using chitin Download PDFInfo
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- CN102492055A CN102492055A CN2011103565452A CN201110356545A CN102492055A CN 102492055 A CN102492055 A CN 102492055A CN 2011103565452 A CN2011103565452 A CN 2011103565452A CN 201110356545 A CN201110356545 A CN 201110356545A CN 102492055 A CN102492055 A CN 102492055A
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Abstract
The invention discloses a method for preparing high-viscosity chitosan by using chitin, belongs to the field of biological chemistry and material chemistry, and relates to an industrial production method in which the chitin is pulverized, and then is subject to microwave pretreatment and two-step deacetylation reaction, so as to obtain high-viscosity refined chitosan in a short time. First the chitin is subject to a series of pulverizing, cleaning and drying processes to obtain refined chitin; then the refined chitin is put into a 30% NaOH solution, and reacts for a short time after being preheated and stirred; a product is put into a 50% NaOH solution after being cleaned and is heated for constant-temperature reaction; and finally a product is cleaned and then dried, so as to obtain the high-viscosity chitosan. The production period of the whole process is shorted by 3 to 6 times, the energy consumption is low, the reaction temperature is easy to control, industrial large-scale production is convenient to realized, and the obtained chitosan is 80 to 90 percent in deacetylation degree, 600 to 2000 MPa.s in viscosity and more than 3*106 in viscosity-average molecular weight, and can be used as a medical absorbable hemostatic material.
Description
Affiliated technical field
The invention belongs to biological chemistry and materials chemistry field; Relate to a kind of chitin that utilizes and prepare the high viscosity methods of chitosan; Be particularly related to and a kind ofly pass through Microwave Pretreatment after utilizing chitin to pulverize; Carry out deacetylation in two steps, obtain the working method of the refining chitosan of high viscosity at short notice.
Background technology
Current chitosan is widely used in food; Many industries such as medical treatment and weaving; Have very high economic worth and growth potentialities of economy, chitosan can be divided into several types of materials with different physico-chemical properties again according to the difference of own viscosity and the difference of deacetylation; Like high viscosity chitosan, chitosan with high deacetylation degree and water-soluble chitosan etc., be applied to different fields respectively.According to Chinese marine industry standard SC/T3403-2004, the standard of deacetylating degree of chitosan is:＜75% is low deacetylation; 75～89% is middle deacetylation; 90～95% is high deacetylized;＞95% is the superelevation deacetylation.The standard of chitosan viscosity is:＜50mPas is a low-viscosity; 50～499mPas is middle viscosity; 500～1000mPas is a high viscosity;＞1000mPas is the superelevation viscosity.Wherein at medical field; Middle and high deacetylation high viscosity chitosan is because outstanding histocompatibility and absorbency; And antibiotic, hemostasis, promote characteristics such as wound healing; Be acknowledged as a kind of effective hemostatic material, its product has also dropped among the practical application in recent years, and U.S. Pat 10743052 is deacetylation 85～95% with a series of bleeding-stopping dressing product main raw materials that US10480827 describes; The high viscosity chitosan of viscosity 600～900mPas is wherein mentioned deacetylation 85% viscosity 800mPas especially and is particularly useful for hemostasia products.
The acetyl technology of taking off that present common chitin prepares the high viscosity chitosan all has certain disadvantages:
1. traditional method.Now still taken off the acetyl process in the Traditional industrial working method of extensive employing and needed chitosan heated and stirred 12～24h in high density NaOH solution usually; Efficient less energy-consumption high pollution is serious; And cross long pyroprocessing; Make most chitosan molecule splitting of chain; To obtain HMW be full-bodied chitosan molecule to difficulty, obtains high viscosity chitosan product even react for a long time through interrupter method, TRANSIENT HIGH TEMPERATURE or low temperature, and its deacetylation and viscosity are also very difficult to be controlled in the specified range simultaneously.
2. microwave reaction method.Just the someone utilized microwave heating to shorten the deacetylation time as far back as 1979; But temperature is wayward in the microwave processing process; Along with the prolongation in treatment time, temperature can be promoted to boiling point after tens minutes, and the boiling point of high density NaOH solution (generally more than 150 ℃) is far above 90 ℃ of optimal reactive temperatures; Very easily destroy the structure and the polymerization degree of chitosan molecule; The problem of temperature when not fine solution controlled microwave is reacted for a long time is difficult to obtain the chitosan product that has stable deacetylation and viscosity simultaneously, is difficult for being applied among the industrial production.
3. enzyme reaction method.Utilize the method for deacetylase to chitin deacetylase; Its production process is practiced thrift industrial chemicals; The environmental protection reduce power consumption also can obtain more high deacetylized and chitosan viscosity, but overall process is complicated; And enzyme activity in reaction is unstable and receive ambient conditions to influence very easily inactivation, and large-scale production is restricted.
4. ultrasonic response method.Supersonic method is applied to the degraded to polymer chitosan at first, has the scholar to carry out the research that ultrasonic pretreatment carries out deacetylation in recent years and has obtained certain achievement (with reference to " modern food science and technology ", the fourth phase in 2011; 418～422 pages); Its product chitosan viscosity is high, and process is simple and easy to control, and product is stable; Generally still do not want more than the 8h but the reaction times reduces than traditional method, and alkali consumption is bigger.
In recent years in the patent of announcing; A kind of chitin preparation method of the patent of publication number CN101289518A and utilize chitin to prepare methods of chitosan; Be chitin to be added in 40～45%NaOH solution by solid-liquid ratio 1: 20～25,1: 5～20 at twice heat, all processes heating 16h, efficient is low; Energy consumption is big, and needing repeatedly in the whole process, sampling detects comparatively loaded down with trivial details.The patent utilization shrimp shell of publication number CN101200505A prepares high deacetylized and the high viscosity methods of chitosan; Be by microwave treatment 15～20min among the NaOH of solid-liquid ratio 1: 20～30 adding concentration 45～50% with chitin; 78 ℃ of 2～3h that reflux of the NaOH ethanolic soln of 1: 2～4 addings 13～23% that solid-liquid ratio is pressed in the back; At last through washing, dry, pulverizing acquisition chitosan; Whole process alkali consumption is more, also need to consume in addition ethanol, and the microwave processing process temperature of long period is wayward.
Summary of the invention
The objective of the invention is to remedy the deficiency of above-mentioned technology, a kind of acquisition high viscosity methods of chitosan is provided.Present method has combined microwave treatment to take off acetyl and tradition is taken off two kinds of methods of acetyl; Under the intermittence of these two kinds of methods is handled; The energy and consumption of raw materials have been practiced thrift; Shortened the reaction times, the temperature in the reaction process has been controlled in strictness, has guaranteed the high viscosity of product chitosan molecule and more high deacetylized simultaneously.
The present invention realizes through following technology: a kind of chitin that utilizes prepares the high viscosity methods of chitosan, and this method may further comprise the steps:
(1) chitin is soaked after scouring;
(2) will be through the oven dry of the chitin after step (1) is handled;
(3) will pulverize through the chitin after step (2) is handled;
(4) will be through the washing of the chitin after step (3) is handled;
(5) will be through the oven dry of the chitin after step (4) is handled;
(6) will put in the NaOH solution of 30% massfraction through the chitin after step (5) is handled; NaOH solution and chitin mass ratio are 10～12: 1; Be preheated to 40 ℃ and stir 10min, after put into microwave reactor and react 3～5min, obtain treating products with microwaves;
Flushing with clean water was to pH value 7.2～7.5 after the treating products with microwaves that (7) will obtain through step (6) filtered;
(8) will join in the NaOH solution of 50% massfraction through the treating products with microwaves after step (7) is handled, NaOH solution and chitin mass ratio are 10～12: 1,90 ℃ of constant temperature and stir, obtain chitosan;
Flushing with clean water was to pH value 7.2～7.5 after the chitosan that (9) will obtain through step (8) filtered;
The chitosan oven dry that (10) will obtain through step (9) promptly obtains required chitosan.
Wherein: the said chitin immersion process of step (1) needs water temperature is controlled at 60 ℃ and lasting 3～6h.The said washing process of step (1) and step (4) adopts supersonic method to carry out; Step (1) and the said washing process temperature of step (4) are controlled at 40～60 ℃; In the said crushing process of step (3) chitin is crushed to 60～80 orders; Step (6) the microwave reactor magnetic flux tube frequency of using is 2450MHz, and power is 800W; The reaction times is 30～50min in the step (8).Employed NaOH solution can pass through filtered and recycled in step (7) and the step (9) before washing.
Effect of the present invention and advantage
1. the present invention adopts above-mentioned process step, and the deacetylation of chitin is controlled within the 1h, and the production cycle shortens 3～6 times, and energy consumption is low, and technology is easy, and the few and NaOH solution of alkali charge is easy to recycle, and has not only reduced cost but also environmental protection is low pollutes.
2. the present invention utilizes the short period of time microwave treatment to make reactant molecule motion aggravation in the liquid phase; Thereby quicken the reaction between chitin and NaOH; And after thermostatic process continued the characteristic that microwave quickens deacetylation, make the chitosan reach high deacetylized at short notice.
3. technical process of the present invention has prevented the hydrolysis of chitosan polymer molecule in reaction process through shortening reaction times, reduction temperature of reaction, has guaranteed that the chitosan product has high viscosity.
4. temperature condition has obtained strict control in the technical process of the present invention, and promptly under liquid-phase condition, immersion and wash temperature are controlled at 40～60 ℃; The deacetylation temperature is controlled at 90 ℃; Through repeatedly sampling proof, the deacetylating degree of chitosan of acquisition and viscosity are comparatively stable, can be used for industrial production.
5. method prepared chitosan deacetylation of the present invention is 80～90%, and viscosity is 600～2000mPas, and viscosity-average molecular weight reaches 3 * 10
6More than (index measurement is carried out by the method among the Chinese marine industry standard SC/T3403-2004), through test, the blood coagulation better performances can be used as the absorbable hemostatic material.
Embodiment
Embodiment 1:
Get the chitin of certain mass, after 60 ℃ of tap water soak 6h, under 60 ℃, use supersonic method washing 1h, the back is dried 3h down at 105 ℃, is crushed to 60～80 orders afterwards and repeats above washing and drying step.Get 10g oven dry powder and add 120g30% concentration NaOH solution, making NaOH solution and chitin mass ratio is 12: 1, puts into 800W, 2450MHz microwave reactor internal heating 5min taking-up immediately behind the stirring 10min down for 40 ℃; This moment, mixture temperature was 90 ℃, and the filtration back to pH value 7.2～7.5, adds 50% concentration NaOH solution with product with 60 ℃ of flushing with clean water; Making NaOH solution and chitin mass ratio is 12: 1; Mixing also is heated to 90 ℃, and constant temperature also stirs the 50min reaction to be finished, product with 60 ℃ of flushing with clean water to pH value 7.2～7.5; Dry 3h down at 105 ℃, obtain high viscosity chitosan powder at last.
Table 1 is deacetylation and the every variation at a distance from 10min of viscosity in the process.Can find out that by chart although very slow in reaction 30min afterreaction speed, only in 1h, the product deacetylation is near 90%, and still maintenance has the above high viscosity of 600mPas.
Deacetylation and viscosity change in time in table 1 reaction process
The external blood coagulation effect comparison experiment of different viscosity chitosans
The experiment selection:
(1) healthy new zealand rabbit.
(2) the foregoing description 50min obtains high viscosity chitosan, viscosity 665mPas, deacetylation 88%.
(3) buy two kinds of commodity chitosans, viscosity all is lower than 50mPas, and deacetylation is respectively 85% and 95%.
Method and result
(1) according to the method for patent CN01139017.4 chitosan is processed chitosan film, afterwards chopping.
(2) scratch rabbit ear artery and get blood with test tube, blood flows out and promptly to pick up counting, and adds chitosan film fragment 0.2g immediately after getting full 2mL, whenever observes the blood coagulation situation at a distance from several seconds inclination test tube, and writing time, and the result is as shown in table 2.
The external clotting time contrasted after table 2 added high viscosity chitosan and low-viscosity chitosan
Embodiment 2:
Get the chitin of certain mass, after 60 ℃ of tap water soak 6h, under 60 ℃, use supersonic method washing 1h, the back is dried 3h down at 105 ℃, is crushed to 60～80 orders afterwards and repeats above washing and drying step.Get 10g oven dry powder and add 100g30% concentration NaOH solution, making NaOH solution and chitin mass ratio is 10: 1, puts into 800W, 2450MHz microwave reactor internal heating 3min taking-up immediately behind the stirring 10min down for 40 ℃; This moment, mixture temperature was 78 ℃; The filtration back to pH value 7.2～7.5, adds 50% concentration NaOH solution with product with 60 ℃ of flushing with clean water, and making NaOH solution and chitin mass ratio is 10: 1; Mixing also is heated to 90 ℃; Constant temperature also stirs the 50min reaction to be finished, and product is dried 3h with 60 ℃ of flushing with clean water to pH value 7.2～7.5 down at 105 ℃, obtains high viscosity chitosan powder at last.
Table 3 is deacetylation and the every variation at a distance from 10min of viscosity in the process.Can find out that by chart although very slow in reaction 30min afterreaction speed, only in 1h, the product deacetylation reaches more than 85%, and still keep having 800mPas above than high viscosity.
Deacetylation and viscosity change in time in table 3 reaction process
The external blood coagulation effect comparison experiment of different viscosity chitosans
The experiment selection:
(1) healthy new zealand rabbit.
(2) the foregoing description 50min obtains high viscosity chitosan, viscosity 845mPas, deacetylation 85%.
(3) buy two kinds of commodity chitosans, viscosity all is lower than 50mPas, and deacetylation is respectively 85% and 95%.
Method and result
(1) according to the method for patent CN01139017.4 chitosan is processed chitosan film, afterwards chopping.
(2) scratch rabbit ear artery and get blood with test tube, blood flows out and promptly to pick up counting, and adds chitosan 0.2g immediately after getting full 2mL, whenever observes the blood coagulation situation at a distance from several seconds inclination test tube, and writing time, and the result is as shown in table 4.
The external clotting time contrasted after table 4 added high viscosity chitosan and low-viscosity chitosan
Claims (8)
1. one kind is utilized chitin to prepare the high viscosity methods of chitosan, and this method mainly may further comprise the steps:
(1) chitin is soaked after scouring;
(2) will be through the oven dry of the chitin after step (1) is handled;
(3) will pulverize through the chitin after step (2) is handled;
(4) will be through the washing of the chitin after step (3) is handled;
(5) will be through the oven dry of the chitin after step (4) is handled;
(6) will put in the NaOH solution of 30% massfraction through the chitin after step (5) is handled; NaOH solution and chitin mass ratio are 10～12: 1; Be preheated to 40 ℃ and stir 10min, after put into microwave reactor and react 3～5min, obtain treating products with microwaves;
Flushing with clean water was to pH value 7.2～7.5 after the treating products with microwaves that (7) will obtain through step (6) filtered;
(8) will join in the NaOH solution of 50% massfraction through the treating products with microwaves after step (7) is handled, NaOH solution and chitin mass ratio are 10～12: 1,90 ℃ of constant temperature and stir, obtain chitosan;
Flushing with clean water was to pH value 7.2～7.5 after the chitosan that (9) will obtain through step (8) filtered;
The chitosan oven dry that (10) will obtain through step (9) promptly obtains required chitosan.
2. a kind of chitin that utilizes according to claim 1 prepares the high viscosity methods of chitosan, it is characterized in that the said sheet chitin of step (1) immersion process needs water temperature is controlled at 60 ℃ and lasting 3～6 hours.
3. a kind of chitin that utilizes according to claim 1 prepares the high viscosity methods of chitosan, it is characterized in that, the said washing process of step (1) and step (4) adopts supersonic method to carry out.
4. a kind of chitin that utilizes according to claim 1 prepares the high viscosity methods of chitosan, it is characterized in that, step (1) and the said washing process temperature of step (4) are controlled at 40～60 ℃.
5. a kind of chitin that utilizes according to claim 1 prepares the high viscosity methods of chitosan, it is characterized in that, in the said crushing process of step (3) the sheet chitin is crushed to 60～80 orders.
6. a kind of chitin that utilizes according to claim 1 prepares the high viscosity methods of chitosan, it is characterized in that, step (6) the microwave reactor magnetic flux tube frequency of using is 2450MHz, and power is 800W.
7. a kind of chitin that utilizes according to claim 1 prepares the high viscosity methods of chitosan, it is characterized in that, the reaction times is 30～50min in the step (8).
8. a kind of chitin that utilizes according to claim 1 prepares the high viscosity methods of chitosan, it is characterized in that, employed NaOH solution can pass through filtered and recycled in step (7) and the step (9) before washing.
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| Application Number | Priority Date | Filing Date | Title |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103204956A (en) * | 2013-04-11 | 2013-07-17 | 天津天狮生物发展有限公司 | Preparation method of chitosan |
| CN110776111A (en) * | 2019-11-18 | 2020-02-11 | 苏州溪能环保科技有限公司 | Domestic sewage treatment agent and preparation method thereof |
-
2011
- 2011-11-11 CN CN2011103565452A patent/CN102492055A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| 李巧霞等: "微波间歇法快速制备高粘均分子量和高脱乙酰度的壳聚糖", 《过程工程学报》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103204956A (en) * | 2013-04-11 | 2013-07-17 | 天津天狮生物发展有限公司 | Preparation method of chitosan |
| CN103204956B (en) * | 2013-04-11 | 2016-09-07 | 天津天狮生物发展有限公司 | A kind of preparation method of chitosan |
| CN110776111A (en) * | 2019-11-18 | 2020-02-11 | 苏州溪能环保科技有限公司 | Domestic sewage treatment agent and preparation method thereof |
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Application publication date: 20120613 |