CN1314459C - Method for preparing superabsorbent with polyglutamic acid synthesized by microbial fermentation - Google Patents
Method for preparing superabsorbent with polyglutamic acid synthesized by microbial fermentation Download PDFInfo
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- CN1314459C CN1314459C CNB2005100147346A CN200510014734A CN1314459C CN 1314459 C CN1314459 C CN 1314459C CN B2005100147346 A CNB2005100147346 A CN B2005100147346A CN 200510014734 A CN200510014734 A CN 200510014734A CN 1314459 C CN1314459 C CN 1314459C
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Abstract
The present invention provides a method for preparing water absorbent by using polyglutamic acid synthesized by microorganism fermentation, which relates to a method for processing macromolecular substances by particle radiation. The present invention has the operation steps: preparing 1 to 10 wt% of water solution of polyglutamic acid synthesized by microorganism fermentation; radiating the water solution of polyglutamic acid synthesized by microorganism fermentation, which is prepared in the first step by using cobalt bomb [60]<Co> as gamma radiation sources in the condition of nitrogen filled protection, wherein the radiation dose rate is from 0.5kGy/ hour to 5.0kGy/ hour, and the radiation integral dose is from 2 to 150kGy; thoroughly swelling the radiated gelatin at the temperature of 2 to 8DEGC, wherein the swelling time is from 4 to 8 days, and water used as the swelling medium is changed once a day in order to remove impurities in the gelatin and monomers which are not crosslinked; freezing and drying the gelatin in an ordinary vacuum drier to constant weight to obtain the water absorbent. The method has the advantages of simple production process, no environmental pollution, high stability of products and high water absorption rate.
Description
Technical field
Technical scheme of the present invention relates to particle radiation handles polymer substance, specifically uses the method for the synthetic preparing super strength water absorbent from polyglutamic acid prepared of gamma-rays radiation treatment microbial fermentation.
Background technology
Gamma-polyglutamic acid-(γ-PGA) is by the outer stickum of the synthetic born of the same parents of microbial fermentation, by the glutamic acid monomer by the γ peptide bond in conjunction with shape or.It is biodegradable, water-soluble, edible, nontoxic, has excellent biological compatibility, is widely used in fields such as medicine, weaving, food, cosmetics, environment, agricultural.
Hydrogel is to absorb water in a large number, but can not be dissolved in a class material of water.Hydrophilic micromolecule can spread in hydrogel.Hydrogel has excellent biological compatibility, compare with hydrophobic polymer, has only much weak interaction with the enzyme that is immobilized or cell, the enzyme or the cell that are fixed in the hydrogel can keep biomolecule activity for a long time, and it can also absorb a certain amount of blood, urine, normal saline and tissue fluid simultaneously.Therefore hydrogel has many purposes at biochemistry, medical domain.
The method of traditional preparation process water absorption hydrogel is to use through third rare crosslinked starch and cellulose to form the water absorption hydrogel of acrylic acid series of compounds.Though the price of these acrylic acid series hydrogels is cheap, can't partly be decomposed by the microorganism in the soil, and face the difficulty of offal treatment and human body is toxic problem.Since hydrogel in biological field application and people to the care of environmental issue, promoted research to the biodegradable hydrogel.Traditional technology is to select for use biodegradable starch system, hyaluronic acid system or polyamino acid based material as the used raw material of the biodegradable water absorption hydrogel of preparation, and the applied chemistry cross-linking method synthesizes biodegradable hydrogel.Traditional technology is the production process complexity not only, and the hydrogel water absorption rate that makes thus is very low, also causes environmental pollution.
From the nineties in last century, it is that raw material prepares biodegradable water absorption hydrogel that the scientific worker begins one's study with gamma-polyglutamic acid-, and synthetic method has chemical crosslink technique and two kinds of methods of physical crosslinking method.Open (polymer material science and engineerings such as new people, 2003,19 (2): 203-205) utilize chemical crosslink technique, with polyglutamic acid 12%, dosage of crosslinking agent is 18.75% of a polyglutamic acid amount, about pH 5,40 ℃ of constant temperature water bath oscillating reactionss 48 hours, the high water absorbing capacity of gained resin reaches 1600g/g.CN 200410004665.6 discloses stable and biodegradable high-hydroscopicity gamma-polyglutamic acid-hydrogel by three-dimensional cross-linked effect gained and preparation method thereof, and the mixture that uses chemical compound that has three or more functional groups' chemical compound or have three or more functional groups and the chemical compound with two functional groups is as cross-linking agent.Chemical crosslink technique operational approach complexity, reactions steps are many, long action time, operative temperature is higher, the product productive rate is low and biocompatibility is poor, the gel water absorption rate is generally not high, and the use of a large amount of chemical cross-linking agents causes environmental pollution.Choi and Kunioka (Radia.Phys.Chem.1995,46 (2): 175-179) introduced and adopt a kind of physical crosslinking method for preparing the super-strong moisture absorbing polyglutamic acid hydrogel, but the water absorption rate of products obtained therefrom is only up to 1400, and quality is more crisp.
Summary of the invention
Technical problem to be solved by this invention is: provide a kind of production process simple, do not cause the method with the synthetic preparing super strength water absorbent from polyglutamic acid prepared of microbial fermentation of environmental pollution.
The present invention solves this technical problem the technical scheme that is adopted: with the method for the synthetic preparing super strength water absorbent from polyglutamic acid prepared of microbial fermentation, its operating procedure is as follows:
The first step, preparation weight percent concentration are 1～10% the synthetic polyglutamic aqueous acid of usefulness microbial fermentation;
Second step is with the cobalt source
60Co is a gamma-ray radiation source, and for preparing in to the first step under the nitrogen filled protection condition carries out radiation with the synthetic polyglutamic aqueous acid of microbial fermentation, and radiation dose rate is 0.5kGy/ hour～5.0kGy/ hour, and total radiation dose is 2～150kGy;
The 3rd step, gel abundant swelling under 2～8 ℃ after the radiation, swelling time is 4～8 days, changes every day once as the water of swelling medium, does not have crosslinked monomer and the impurity in the gel to remove;
In the 4th step, lyophilization promptly makes super strength water absorbent to constant weight in common vacuum drier.
Above-mentioned Gy is international radiation dose unit, and Chinese translation is a gray(Gy), and kGy is a kilogray.
In the said method, the way that is more preferably is: in the first step of said method, and selected weight average molecular weight Mw＞1,000,000 with the synthetic polyglutamic acid of microbial fermentation; Or in second step of said method, earlier by first step preparation with the synthetic polyglutamic aqueous acid of microbial fermentation in add 0.01～1.00% chemical cross-linking agent diglycidyl ether of ethylene glycol, epoxy resin, diamine or the saturated dihalide that consumption is this aqueous solution weight, and then it is carried out radiation with same condition; The purity of used nitrogen 〉=99.99%.
The invention has the beneficial effects as follows: the inventive method is simple to operate, the main technique step is exactly a step, promptly utilize gamma-rays crosslinking with radiation polyglutamic acid to make it form the polyglutamic acid hydrogel of high-hydroscopicity, the multistep reaction and the complex process that do not need chemical crosslink technique fully, exposure time is shorter action time than chemical crosslinking, at room temperature can carry out, irradiation method is unaffected to the biocompatibility of product, so production process is simple, production efficiency is high, energy consumption is low and good product quality; Need not add any chemical cross-linking agent in the method for the present invention, perhaps just when gamma-rays crosslinking with radiation polyglutamic acid, add extremely a small amount of, 0.01～1.00% the chemical cross-linking agent that promptly has only raw material polyglutamic acid aqueous solution weight, therefore product does not need extra sterilization, do not have secondary pollution, do not cause environmental pollution yet; In actual production, the amount of the raw material polyglutamic acid that the inventive method is used is less, has saved production cost greatly; The polyglutamic acid gel of the inventive method preparation has stability preferably, places down at 4 ℃ and disintegrate does not still take place in 15 days, has stronger withstand voltage and heatproof water-retaining property simultaneously; Be higher than 1,000 with weight average molecular weight in the inventive method, 000 polyglutamic acid directly can form the super strength water absorbent of water absorption rate up to 5,000 times through the gamma-rays crosslinking with radiation; Evidence, the chemical cross-linking agent that adds minute quantity when carrying out the gamma-rays crosslinking with radiation not only can not cause environmental pollution and secondary pollution, but has further shortened the crosslinked used time, has increased the degree of cross linking, has further improved the water absorption rate of gel.
Success is developed with the difficulty of the synthetic preparing super strength water absorbent from polyglutamic acid prepared of gamma-rays radiation treatment microbial fermentation very big, comprises exploring in practice and research forms polyglutamic acid hydrogel in theory radiation condition: the selection of suitable accumulated dose and the selection of (3) gamma-rays dose,optimum rate of the selection of (1) polyglutamic acid aqueous solution optimum concentration, (2) gamma-rays.The inventor just finally succeeds through long-term and arduous work.
Description of drawings
The present invention is further described below in conjunction with drawings and Examples.
Fig. 1 is with the photo in kind before and after the super strength water absorbent suction of the inventive method preparation.
Among the figure, the photo in kind after 1. the super strength water absorbent of the photo in kind before the super strength water absorbent suction of the inventive method preparation, 2. the inventive method preparation absorbs water.
The specific embodiment
Embodiment 1
Add the 2ml deionized water in the irradiation tube of the special nut of 10ml, dissolving is with the synthetic polyglutamic acid 20mg of microbial fermentation, prepares to such an extent that weight percent concentration is 1% polyglutamic acid aqueous solution; With the cobalt source
60Co is a gamma-ray radiation source, under the nitrogen filled protection condition polyglutamic aqueous acid in the above-mentioned irradiation tube is carried out radiation, and radiation dose rate is 0.5kGy/ hour, and total radiation dose is 2kGy; Gel after the radiation descended abundant swellings 4 days at 2 ℃, changed the swelling WATER AS FLOW MEDIUM every day one time, did not have crosslinked monomer and the impurity in the gel to remove; Lyophilization in common vacuum drier, vacuum be the operating time be 12 hours to constant weight, promptly make super strength water absorbent.After testing, the water absorption rate of this super strength water absorbent is 90 times.
Embodiment 2
Add the 2ml deionized water in the irradiation tube of 10ml band nut, dissolving is with the synthetic polyglutamic acid 80mg of microbial fermentation, prepares to such an extent that weight percent concentration is 4% polyglutamic acid aqueous solution; With the cobalt source
60Co is a gamma-ray radiation source, under the nitrogen filled protection condition polyglutamic aqueous acid in the above-mentioned irradiation tube is carried out radiation, and radiation dose rate is 1.2kGy/ hour, and total radiation dose is 40kGy; Gel after the radiation descended abundant swellings 5 days at 3 ℃, and changing a swelling WATER AS FLOW MEDIUM every day does not have crosslinked monomer and the impurity in the gel to remove; Lyophilization in common vacuum drier, vacuum be the operating time be 18 hours to constant weight, promptly make super strength water absorbent.After testing, the water absorption rate of this super strength water absorbent is 480 times.
Embodiment 3
Add the 2ml deionized water in the irradiation tube of 10ml band nut, dissolving is with the synthetic polyglutamic acid 120mg of microbial fermentation, prepares to such an extent that weight percent concentration is 6% polyglutamic acid aqueous solution; With the cobalt source
60Co is a gamma-ray radiation source, under the nitrogen filled protection condition polyglutamic aqueous acid in the above-mentioned irradiation tube is carried out radiation, and radiation dose rate is 1.0kGy/ hour, and total radiation dose is 10kGy; Gel after the radiation descended abundant swellings 6 days at 4 ℃, changed the swelling WATER AS FLOW MEDIUM every day one time, did not have crosslinked monomer and the impurity in the gel to remove; Lyophilization in common vacuum drier, vacuum be the operating time be 22 hours to constant weight, promptly make super strength water absorbent.After testing, the water absorption rate of this super strength water absorbent is 2100 times.Fig. 1 is the photo in kind of the super strength water absorbent suction front and back of present embodiment just, and the weight of the gel (2) in the photo after the suction is 2100 times of the preceding gel (1) of suction.
Embodiment 4
Add the 2ml deionized water in the irradiation tube of 10ml band nut, dissolving is with the synthetic polyglutamic acid 160mg of microbial fermentation, prepares to such an extent that weight percent concentration is 8% polyglutamic acid aqueous solution; With the cobalt source
60Co is a gamma-ray radiation source, under the nitrogen filled protection condition polyglutamic aqueous acid in the above-mentioned irradiation tube is carried out radiation, and radiation dose rate is 2.5kGy/ hour, and total radiation dose is 100kGy; Gel after the radiation descended abundant swellings 7 days at 6 ℃, changed the swelling WATER AS FLOW MEDIUM every day one time, did not have crosslinked monomer and the impurity in the gel to remove; Lyophilization in common vacuum drier, vacuum be the operating time be 28 hours to constant weight, promptly make super strength water absorbent.After testing, the water absorption rate of this super strength water absorbent is 125 times.
Embodiment 5
Add the 2ml deionized water in the irradiation tube of 10ml band nut, dissolving is with the synthetic polyglutamic acid 100mg of microbial fermentation, prepares to such an extent that weight percent concentration is 5% polyglutamic acid aqueous solution; With the cobalt source
60Co is a gamma-ray radiation source, under the nitrogen filled protection condition polyglutamic aqueous acid in the above-mentioned irradiation tube is carried out radiation, and radiation dose rate is 4.0kGy/ hour, and total radiation dose is 20kGy; Gel after the radiation descended abundant swellings 8 days at 8 ℃, changed the swelling WATER AS FLOW MEDIUM every day one time, did not have crosslinked monomer and the impurity in the gel to remove; Lyophilization in common vacuum drier, vacuum be the operating time be 36 hours to constant weight, promptly make super strength water absorbent.After testing, the water absorption rate of this super strength water absorbent is 2000 times.
Embodiment 6
Add the 2ml deionized water in the irradiation tube of 10ml band nut, dissolving is with the polyglutamic acid 110mg of the synthetic weight average molecular weight Mw of microbial fermentation＞1,000,000, prepares to such an extent that weight percent concentration is 5.5% polyglutamic acid aqueous solution; With the cobalt source
60Co is a gamma-ray radiation source, under the nitrogen filled protection condition of purity 〉=99.99% of used nitrogen the polyglutamic aqueous acid in the above-mentioned irradiation tube is carried out radiation, and radiation dose rate is 2.0kGy/ hour, and total radiation dose is 8kGy; Gel after the radiation descended abundant swellings 6 days at 4 ℃, changed the swelling WATER AS FLOW MEDIUM every day one time, did not have crosslinked monomer and the impurity in the gel to remove; Lyophilization in common vacuum drier, vacuum be the operating time be 22 hours to constant weight, promptly make super strength water absorbent.After testing, the water absorption rate of this super strength water absorbent is 5000 times.
Embodiment 7
Add the 2ml deionized water in the irradiation tube of 10ml band nut, dissolving is with the synthetic polyglutamic acid 80mg of microbial fermentation, prepares to such an extent that weight percent concentration is 4% polyglutamic acid aqueous solution; In this polyglutamic aqueous acid, add consumption and be 0.01% chemical cross-linking agent diglycidyl ether of ethylene glycol of this aqueous solution weight, again with the cobalt source
60Co is a gamma-ray radiation source, under the nitrogen filled protection condition of purity 〉=99.99% of used nitrogen the polyglutamic aqueous acid in the above-mentioned irradiation tube is carried out radiation, and radiation dose rate is 5kGy/ hour, and total radiation dose is 40kGy; Gel after the radiation descended abundant swellings 5 days at 3 ℃, changed the swelling WATER AS FLOW MEDIUM every day one time, did not have crosslinked monomer and the impurity in the gel to remove; Lyophilization in common vacuum drier, vacuum be the operating time be 18 hours to constant weight, promptly make super strength water absorbent.After testing: the water absorption rate of this super strength water absorbent is 3500 times.
Embodiment 8
Add the 2ml deionized water in the irradiation tube of 10ml band nut, dissolving is with the synthetic polyglutamic acid 80mg of microbial fermentation, prepares to such an extent that weight percent concentration is 4% polyglutamic acid aqueous solution; In this polyglutamic aqueous acid, add consumption and be 0.25% chemical cross-linking agent epoxy resin of this aqueous solution weight, again with the cobalt source
60Co is a gamma-ray radiation source, under the nitrogen filled protection condition polyglutamic aqueous acid in the above-mentioned irradiation tube is carried out radiation, and radiation dose rate is 5kGy/ hour, and total radiation dose is 80kGy; Gel after the radiation descended abundant swellings 4 days at 6 ℃, changed the swelling WATER AS FLOW MEDIUM every day one time, did not have crosslinked monomer and the impurity in the gel to remove; Lyophilization in common vacuum drier, vacuum be the operating time be 30 hours to constant weight, promptly make super strength water absorbent.After testing, the water absorption rate of this super strength water absorbent is 3100 times.
Embodiment 9
Add the 2ml deionized water in the irradiation tube of 10ml band nut, dissolving is with the synthetic polyglutamic acid 80mg of microbial fermentation, prepares to such an extent that weight percent concentration is 4% polyglutamic acid aqueous solution; In this polyglutamic aqueous acid, add consumption and be 0.5% chemical cross-linking agent diglycidyl ether of ethylene glycol of this aqueous solution weight, again with the cobalt source
60Co is a gamma-ray radiation source, under the nitrogen filled protection condition polyglutamic aqueous acid in the above-mentioned irradiation tube is carried out radiation, and radiation dose rate is 1kGy/ hour, and total radiation dose is 4kGy; Gel after the radiation descended abundant swellings 4 days at 6 ℃, changed the swelling WATER AS FLOW MEDIUM every day one time, did not have crosslinked monomer and the impurity in the gel to remove; Lyophilization in common vacuum drier, vacuum be the operating time be 12 hours to constant weight, promptly make super strength water absorbent.After testing, the water absorption rate of this super strength water absorbent is 4500 times.
Embodiment 10
Add the 2ml deionized water in the irradiation tube of 10ml band nut, dissolving is with the synthetic polyglutamic acid 80mg of microbial fermentation, prepares to such an extent that weight percent concentration is 4% polyglutamic acid aqueous solution; In this polyglutamic aqueous acid, add consumption and be 1.00% chemical cross-linking agent dichloroethanes of this aqueous solution weight, again with the cobalt source
60Co is a gamma-ray radiation source, under the nitrogen filled protection condition polyglutamic aqueous acid in the above-mentioned irradiation tube is carried out radiation, and radiation dose rate is 5kGy/ hour, and total radiation dose is 40kGy; Gel after the radiation descended abundant swellings 5 days at 3 ℃, changed the swelling WATER AS FLOW MEDIUM every day one time, did not have crosslinked monomer and the impurity in the gel to remove; Lyophilization in common vacuum drier, vacuum be the operating time be 18 hours to constant weight, promptly make super strength water absorbent.After testing, the water absorption rate of this super strength water absorbent is 2500 times.
Embodiment 11
Add the 2ml deionized water in the irradiation tube of 10ml band nut, dissolving is with the polyglutamic acid 80mg of the synthetic weight average molecular weight Mw of microbial fermentation＞1,000,000, prepares to such an extent that weight percent concentration is 4% polyglutamic acid aqueous solution; In this polyglutamic aqueous acid, add consumption and be 0.05% chemical cross-linking agent hexamethylene diamine of this aqueous solution weight, again with the cobalt source
60Co is a gamma-ray radiation source, under the nitrogen filled protection condition of purity 〉=99.99% of used nitrogen the polyglutamic aqueous acid in the above-mentioned irradiation tube is carried out radiation, and radiation dose rate is 0.5kGy/ hour, and total radiation dose is 2kGy; Gel after the radiation descended abundant swellings 4 days at 2 ℃, changed the swelling WATER AS FLOW MEDIUM every day one time, did not have crosslinked monomer and the impurity in the gel to remove; Lyophilization in common vacuum drier, vacuum be the operating time be 12 hours to constant weight, promptly make super strength water absorbent.After testing, the water absorption rate of this super strength water absorbent is 1700 times.
In the foregoing description, gel content is at room temperature to adopt gravimetric method to detect, and promptly wipes gel surface moisture with filter paper and weighs and obtain.Formula below gel content and specific water content adopt calculates: gel content (%)=Wd/Ws * 100; Specific water content=(Wo-Wd)/Wd.Wherein Wd and Ws represent the PGA content that exists in gel dry weight and the preceding solution of radiation respectively; Wo represents with the gel weight after the deionized water swelling.Detect the water absorption rate that obtains water absorbing agent thus.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102093582A (en) * | 2011-01-04 | 2011-06-15 | 上海大学 | Preparation method of radiation crosslinking hydrogel |
| CN103804697B (en) * | 2012-11-09 | 2016-02-03 | 山东福瑞达生物科技有限公司 | A kind of preparation method of polyglutamic acid hydrogel and the application in composite fertilizer thereof |
| JP6168892B2 (en) * | 2013-07-23 | 2017-07-26 | ユニ・チャーム株式会社 | Water absorbent |
| CN107802894A (en) * | 2017-10-11 | 2018-03-16 | 广州新诚生物科技有限公司 | A kind of bio-medical gel and preparation method thereof |
| CN108208522A (en) * | 2017-12-28 | 2018-06-29 | 安徽佛子岭面业有限公司 | A kind of vermicelli are into the processing method of case packing moisture barrier bag |
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| CN1629220A (en) * | 2003-12-19 | 2005-06-22 | 东海生物科技股份有限公司 | Stable and biodegradable superabsorbent γ-polyglutamic acid hydrogel obtained by three-dimensional crosslinking and its preparation method |
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| CN1629220A (en) * | 2003-12-19 | 2005-06-22 | 东海生物科技股份有限公司 | Stable and biodegradable superabsorbent γ-polyglutamic acid hydrogel obtained by three-dimensional crosslinking and its preparation method |
Non-Patent Citations (1)
| Title |
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| γ-聚谷氨酸及高吸水树脂的制备研究 张新民，南京工业大学博士学位论文 2003 * |
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