CN1317969C - Chitin feed additive and its preparation method and application - Google Patents

Chitin feed additive and its preparation method and application Download PDF

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Publication number
CN1317969C
CN1317969C CNB2003101170406A CN200310117040A CN1317969C CN 1317969 C CN1317969 C CN 1317969C CN B2003101170406 A CNB2003101170406 A CN B2003101170406A CN 200310117040 A CN200310117040 A CN 200310117040A CN 1317969 C CN1317969 C CN 1317969C
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shitosan
feed
feed addictive
present
chitosan
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CN1623416A (en
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李效时
李刚
李强
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Li Xiaoshi < Del\/>
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Li Xiaoshi < Del\/>
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Abstract

The present invention relates to an additive for a chitosan feed and a preparation method and application thereof. Firstly, condensation reaction is carried out to chitosan and aldehyde containing carboxyl and hydroxy hydrophilic radicals to generate enamine; after solid-phase reaction further occurs to the enamine and inorganic reducing agent, a generated object which is washed is precipitated by ethyl alcohol; centrifuge dripping and vacuum drying are carried out to the precipitated object by the conventional method; afterwards, the additive for a chitosan feed is obtained by further oxidation of hydrolytic reagent for carrying out hydrolyzation. The additive for a chitosan feed provided by the present invention has a favorable detoxification performance and can improve the immunity of a fed object; meanwhile, the additive for a chitosan feed provided by the present invention has the characteristics of less dosage and obvious effect; in such a way, the production cost of the feed can be reduced, and the economic benefit of an enterprise for producing the feed can be improved.

Description

A kind of shitosan feed addictive and preparation method thereof and application
Technical field
The present invention relates to a kind of feed addictive and preparation method thereof and application, particularly relate to a kind of shitosan feed addictive and preparation method thereof and application.
Background technology
Freshwater fish lives in the water environment, must be subjected to the influence of many extraneous factors, and it is biological with abiotic that wherein main is.Biological pathogenic bacteria, parasite and other harmful organisms etc. of comprising; Abiotic water temperature, dissolved oxygen, carbon dioxide, ammonia, hydrogen sulfide, pH value and the surplus genus ion etc. of comprising.Though fish have certain adaptability to these factors, surpass the normal physiological activity that certain limit all can influence fish, cause the decline of fish anti-adversity ability.
In general, fish physique is good, and resistance against diseases is also strong, although pathogen is arranged, also is not easy sick.So the factor that influences fresh-water fishes health is not single, promptly be pathogen, living environment and fish body triadic relation results of interaction.Therefore, consider the fresh-water fishes health problem, promptly will strengthen the anti pathologic immunity power of fish, eliminate cause of disease and harmful organisms again, also will improve water quality, optimize living environment, be beneficial to fish body healthy growth.
Equally, other raising birds or disease resistance of animals are the key factors of the relevant raising of the influence performance of enterprises with growth cycle.If the bird or the disease resistance of animals of raising are lower, the probability that pestilence then takes place increases greatly; In addition, if the growth cycle of bird of raising or animal is oversize, also can reduce the raising economic benefit of enterprises greatly.
At present, fish, bird and disease resistance of animals in order to strengthen raising shorten its growth cycle, much raise enterprise and mostly use antibiotic and chemical synthetic drug.Feed addictive such as antibiotic and chemical synthetic drug though have good growth promotion and antibacterial effect, has also brought problems such as drug resistance and environmental pollution simultaneously.Although this method helps the productivity effect of enterprise,, these measures also do not meet the standard of relevant green feed, and also making simultaneously residually in the body of fish, bird and the animal raised has a harmful material.Therefore, solve the problem that present feed exists in actual use, make human edible food healthy more, a kind of novel feed of necessary exploitation place.
And European Union will use antibiotic in complete prohibition in 2006, and exploitation substitutes antibiotic feed addictive in the feed, and development green, safety and high-quality feed and breed had become the theme of China's animal husbandry development from now on already.China successfully joins WTO, realize the high-quality and efficient production of animal husbandry, this had both met the demand for development that China livestock products are produced, and also helped China's livestock products status of having the advantage in the competition in the international market of fierceness, constantly strengthened the ability of livestock products foreign exchange earning.At present, though the antibiotic in the animal feed has tangible resistant effect and growth promoting function, but because the long-term antibiotic that uses can produce problems such as drug resistance and environmental pollution, human beings'health is produced potential hazard, seek a kind of green, natural antibiotic substitute seems particularly important.Compare with antibiotic, shitosan is a kind of natural glycosaminoglycan, has good immunoloregulation function, shitosan can be by promoting the intestinal beneficial bacterium breeding, suppress harmful bacteria growing, safeguard the flora ecological balance in the digestive system, the maintenance letting animals feed is in health status in growth whole process, reaches to use no or little antibiotic purpose.Therefore, producing with shitosan and derivative thereof is that the feed addictive of primary raw material is just extremely urgent.
In order to solve the problems referred to above that feed exists, relevant manufacturer there's no one who doesn't or isn't seeks solution painstakingly, but do not see always that for a long time suitable invention finished by development, and common product does not have appropriate structure to address the above problem, this obviously is the problem that the anxious desire of relevant dealer solves.Because the defective of above-mentioned existing existence, the inventor actively study innovation based on abundant practical experience and professional knowledge, through constantly studying, invent, and after studying sample and improvement repeatedly, creates the present invention who has practical value finally.
Summary of the invention
Main purpose of the present invention is, overcomes the defective that above-mentioned existing feed addictive exists, and a kind of shitosan feed addictive is provided, and technical problem underlying to be solved is to improve the ability of the environment purification of feed, strengthens the immunocompetence of being raised object.
Purpose of the present invention and to solve its technical problem underlying be to adopt following technical scheme to realize.Shitosan feed addictive according to the present invention's proposition, can make by following method: at first shitosan and the aldehyde that contains carboxyl, hydroxyl hydrophilic group are carried out the derivative that substitution reaction obtains soluble chitosan, after this derivative further carries out the solid phase reduction reaction with reducing agent, with this shitosan feed addictive that obtains as shown in the formula (I).
Wherein R is the aldehyde that contains carboxyl, hydroxyl hydrophilic group, and n is between 500~5000.
The object of the invention to solve the technical problems can also be further achieved by the following technical measures.
Aforesaid a kind of shitosan feed addictive, the deacetylation of wherein said shitosan 70%~90%, viscosity is not less than 300 centistokes(cst)s, molecular weight 500,000~600, between 000.
Aforesaid a kind of shitosan feed addictive, wherein said R are the carboxyl of carbon number between 1~10, the aldehyde of hydroxyl hydrophilic group.
Aforesaid a kind of shitosan feed addictive, wherein said R are glutaraldehyde, furfural or to the carboxyl benzaldehyde.
A kind of shitosan feed addictive of the present invention, can be prepared by following technical solution, this technical scheme comprises the following step: at first shitosan carries out condensation reaction generation enamine with the aldehyde that contains carboxyl, hydroxyl hydrophilic group, this enamine further with inorganic reducing agent generation solid phase reaction after, product washing back is precipitated with ethanol, sediment is being carried out the centrifuge dripping vacuum drying with conventional method, and further being hydrolyzed by the oxydrolysis agent then promptly obtains this shitosan feed addictive.
The preparation method of the aforesaid shitosan feed addictive of stating, wherein said inorganic reducing agent is NaCNBH 3
The preparation method of the aforesaid shitosan feed addictive of stating, wherein said oxydrolysis agent is a hydrogen peroxide.
The application of the shitosan feed addictive that the present invention proposes relates to freshwater aquiculture, bird is cultured and the feed of animal-breeding.
The present invention compared with prior art has tangible advantage and beneficial effect.By above technical scheme as can be known, in order to reach aforementioned goal of the invention, major technique of the present invention thes contents are as follows:
The amino of shitosan has preferably in conjunction with the ability of halides in the water, is comparatively ideal adsorbent.But if this ability of progressive raising must be carried out chemical modification to the amino of shitosan, the experiment of experience more than 5 years shows that the derivative that carries out preparing after the chemical modification is very desirable feed addictive.This is because the derivative after the chemical modification shows organic matter (for example organic chloride, pesticide, pentachloro-acid, Polychlorinated biphenyls etc.) to be had stronger suction-operated.Its mechanism is that the cross-bond of shitosan passes through hydrophobic functional group, defends the characterization of adsorption that two acyl aliphatic chains increase many chlorine of able one thing as dehydrogenation.But these functional groups must guarantee that the spatial obstacle that cross-bond produces can not hinder absorption, by to defend two acyls crosslinked and by NaBH with dehydrogenation -First amino of chitosan derivatives of CN reduction becomes second amino, is the result that the weak ionic interaction of strong ionic interaction and hydrophobic type combines in conjunction with the organic matter that is reduced.
The present invention compares with prior art, has the following advantage:
(1) the shitosan feed addictive of the present invention's proposition has good detoxifying properties.
(2) the shitosan feed addictive of the present invention's proposition can improve the immunity of raising object.This be because the present invention can jihuokeli leukocytic generation, particularly blood in the neutral leukocyte with leaflet nuclear of phagocyte-band form nucleus increase, and graininess white blood cell, as basocyte, eosin look sexual cell and cellular cell are had a liking in vacation.And the present invention can also improve the vitality of the splenocyte of red blood cell blood forming organ, and makes its independent cell adhesion and cytophagous process obtain activating, and makes the activity of serum lysozyme higher.
(3) to have a consumption few for the shitosan feed addictive that proposes of the present invention, and the outstanding effect characteristics can reduce the production cost of feed like this, improve the economic benefit of production Feed Enterprise.
In sum, a kind of shitosan feed addictive of special construction of the present invention and preparation method thereof and application, have above-mentioned many advantages and practical value, and in like product, there is no and similarly delivered or use, it is had large improvement technically, and has produced handy and practical effect, and has the effect of enhancement really, thereby being suitable for practicality more, really is a new and innovative, progressive, practical new invention.
Above-mentioned explanation only is the general introduction of technical solution of the present invention, for can clearer understanding technological means of the present invention, and can be implemented according to the content of specification, below with preferred embodiment of the present invention and conjunction with figs. describe in detail as after.
The specific embodiment of the present invention is provided in detail by following examples and accompanying drawing thereof.
Description of drawings
Fig. 1 is the preparation method's of a kind of shitosan feed addictive of the present invention technological process.
The specific embodiment
Below in conjunction with accompanying drawing and preferred embodiment, a kind of shitosan feed addictive that foundation the present invention is proposed and preparation method thereof with use its specific embodiment, feature and effect thereof, describe in detail as after.
Seeing also shown in Figure 1ly, is the preparation method's of a kind of shitosan feed addictive of the present invention technological process.By flow chart as can be known, at first shitosan carries out condensation reaction generation enamine with the aldehyde that contains carboxyl, hydroxyl hydrophilic group, this enamine further with inorganic reducing agent generation solid phase reaction after, product washing back is precipitated with ethanol, sediment is being carried out the centrifuge dripping vacuum drying with conventional method, and further being hydrolyzed by the oxydrolysis agent then promptly obtains this shitosan feed addictive.
Embodiment 1
The detoxification ability that present embodiment explanation shitosan feed addictive of the present invention has improves the immunity of raising object.
Test by the immunity that model experiment is raised object to the detoxifying properties and the raising of shitosan feed addictive.The concrete practice is to have added the T-2-toxin of not enough lethal dose in carp feed, causes the carp slow poisoning.With the feed that has added the shitosan feed addictive carp is carried out feeding then; Every day, feeding three times, forage volume are 3% of body weight.
Result of the test shows: some index of carp (the Hematopoietic activity of phagocyte activity, activity of lysozyme, particle) has improved, and this proof shitosan feed addictive has the potentiality of very high activate immunity power.
Embodiment 2
The influence that present embodiment explanation shitosan feed addictive of the present invention is raised bird.
Test is divided into three groups, two control groups and a test group, 200 every group at random.Contrast one group of feeding basal diet; Contrast two groups of feeding basal diet+furazolidone+aureomycin; The shitosan feed addictive of test group feeding basal diet+different proportionings, result of the test is as follows:
Contrast one group: the force-fed duck body weight reaches 3100~3250g, and delivering for sale needs 38~42 days, and the death rate is 3%.The meat feed ratio of every duck is 3.2kg: 9kg;
Contrast two groups: the force-fed duck body weight reaches 3100~3250g, and delivering for sale needs 38~40 days, and survival rate is 100%.The meat feed ratio of every duck is 3.2kg: 9kg;
Test group: the force-fed duck body weight reaches 3100~3250g, and delivering for sale needs 36~39 days, and survival rate is 100%.The meat feed ratio of every duck is 3.2kg: 8kg; And lean meat percentage obviously improves, and the figure reduces relatively.Raise whole process and do not use any antibiotic and chemical synthetic drug, save 86.50 yuan of anti-disease medicines expenses altogether.Reduce food consumption, press 1.5 yuan of calculating of per kilogram, 200 ducks are saved feed cost with about 300 yuan.
The above, it only is preferred embodiment of the present invention, be not that the present invention is done any pro forma restriction, every foundation technical spirit of the present invention all still belongs in the scope of technical solution of the present invention above any simple modification, equivalent variations and modification that embodiment did.

Claims (5)

1, a kind of shitosan feed addictive, it is characterized in that this shitosan feed addictive makes by following method: at first carry out the derivative that substitution reaction obtains soluble chitosan with shitosan and glutaraldehyde or furfural or to the carboxyl benzaldehyde, this derivative further and NaCNBH 3After carrying out the solid phase reduction reaction, with the derivative as shown in the formula (I) that obtains, this derivative further by carrying out oxydrolysis with hydrogen peroxide, obtains described shitosan feed addictive;
R is glutaraldehyde, furfural or to the carboxyl benzaldehyde in its Chinese style; N is between 500~5000; The deacetylation of described shitosan 70%~90%, viscosity is not less than 300 centistokes(cst)s, molecular weight 500,000~600, between 000.
2, the preparation method of the described shitosan feed addictive of claim 1 is characterized in that this method comprises the following step:
At first shitosan and aldehyde carry out condensation reaction generation enamine, this enamine further with inorganic reducing agent generation solid phase reaction after, product washing back is precipitated with ethanol, sediment is being carried out the centrifuge dripping vacuum drying with conventional method, and further being hydrolyzed by the oxydrolysis agent then promptly obtains this shitosan feed addictive;
Wherein: inorganic reducing agent is NaCNBH 3The oxydrolysis agent is a hydrogen peroxide; Described aldehyde is glutaraldehyde, furfural or to the carboxyl benzaldehyde; The deacetylation of described shitosan 70%~90%, viscosity is not less than 300 centistokes(cst)s, molecular weight 500,000~600, between 000.
3, the application of the described shitosan feed addictive of claim 1 in the freshwater aquiculture feed.
4, the application of the described shitosan feed addictive of claim 1 in the bird breeding feed.
5, the application of the described shitosan feed addictive of claim 1 in animal-breeding feed.
CNB2003101170406A 2003-12-05 2003-12-05 Chitin feed additive and its preparation method and application Expired - Fee Related CN1317969C (en)

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Publication number Priority date Publication date Assignee Title
CN102370056B (en) * 2010-08-24 2013-09-11 北京英惠尔生物技术有限公司 Method for preparing chitooligosaccharides used for feed by enzymatic hydrolysis
CN103181416B (en) * 2011-12-30 2014-07-02 华中农业大学 Milk replacer for dairy hybrid buffalo calf
CN107880272B (en) * 2017-11-27 2020-06-05 安徽雪郎生物科技股份有限公司 β -polymalic acid chitosan oligosaccharide compound salt and preparation method and application thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0371878A1 (en) * 1988-11-30 1990-06-06 Rhone-Poulenc Sante Compositions for coating feedstuff additives for ruminants
EP0520890A1 (en) * 1991-06-28 1992-12-30 Rhone-Poulenc Nutrition Animale Pellet composition comprising active substances unprotected in the rumen of ruminants, in combination with active substances protected against degradation in the rumen of ruminants

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0371878A1 (en) * 1988-11-30 1990-06-06 Rhone-Poulenc Sante Compositions for coating feedstuff additives for ruminants
US5077052A (en) * 1988-11-30 1991-12-31 Rhone-Poulenc Sante Chitosan derivatives useful in compositions for coating feedstuff additives intended for ruminants
EP0520890A1 (en) * 1991-06-28 1992-12-30 Rhone-Poulenc Nutrition Animale Pellet composition comprising active substances unprotected in the rumen of ruminants, in combination with active substances protected against degradation in the rumen of ruminants

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
不同交联剂含量对戊二醛交联壳聚糖膜结构与性能影响的研究 陈新等,化学学报,第58卷第12期 2000 *

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Assignee: Beijing Durun Science and Technology Co., Ltd.

Assignor: Li Xiaoshi|Li Gang|Li Qiang

Contract fulfillment period: 2008.8.15 to 2013.8.15

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Denomination of invention: Chitin feed additive and its preparation method and application

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