CN1465609A - Biological decomposability, water absorbent resin and preparation method thereof - Google Patents
Biological decomposability, water absorbent resin and preparation method thereof Download PDFInfo
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- CN1465609A CN1465609A CNA021245894A CN02124589A CN1465609A CN 1465609 A CN1465609 A CN 1465609A CN A021245894 A CNA021245894 A CN A021245894A CN 02124589 A CN02124589 A CN 02124589A CN 1465609 A CN1465609 A CN 1465609A
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Abstract
The present invention uses a microbial culture solution containing polyamino acid or polysaccharide and polyepoxy compound whose same molecular contains more than two functional groups capable of producing reaction with the structure of carboxyl group, hydroxyl group, aldehyde group, carbonyl group, sulfonic group, nitryl group or amino group according to the weight ratio of 100:01 to 100:10d and makes them produce reaction in the range of pH values of 3.5 to 8 to produce new type bio-degradable and water-absorbent resin. Said invention also provides its preparation method.
Description
Technical field
The present invention relates to a kind of with poly-gamma-glutamic acid with 1 or more than 2 kind polysaccharide and epoxy (epoxy) compound react and the Biodegradable, absorbent resin and the relevant manufacture method that obtain, and, from having the microbial culture medium of poly-gamma-glutamic acid throughput, directly make the method for Biodegradable, absorbent resin.
Biodegradable of the present invention, absorbent resin, because of having absorption agglutinative effect, and can be decomposed by occurring in nature Institute of Micro-biology, so but its range of application comprises: the desert afforestation material in the agriculture and garden field, soil improvement agent, the seed coating, the plant growing water-holding agent, the livestock waste solidifying agent, the composting auxiliary agent, the moisture of fecaluria and excess sludge etc. is adjusted agent, water purification mud in the civil construction field during water treatment, the moisture of excess sludge and dredging mud etc. is adjusted agent, solidifying agent, modification agent, agglutinant, deposit soil, medicine, the blood of hygiene article sector, body fluid absorbent, paper nappy, deodorizing composition, microorganism in the biological technical field, plant, the cultivation base of zooblast etc., the immobilization material of bio-reactor etc. etc.
Background technology
In recent years, absorbent resin not only can be used as materials such as paper nappy, also can be used for as fields such as medical treatment, building, building, construction such as body fluid absorbents, and as food such as freshness retention agents, as fields such as agricultural, gardening such as greening materials.
The kind of absorbent resin comprises that using starch, Mierocrystalline cellulose to carry out common frame with vinyl cyanide combines the absorbent resin that the back forms propylene system.Though this type of propylene water-absorbent resin low price can't be decomposed by the Institute of Micro-biology in the soil, existing can't be by biolytic problem.And biological solvability matter is that solution macromolecular material offal treatment problem is desired.Therefore, develop absorbent resin its necessity is arranged with Biodegradable.
In order to solve this problem, can select starch water-absorbent resin or hyaluronic acid water-absorbent resin material as tool Biodegradable absorbent resin.These have among the absorbent resin of Biodegradable, can utilize poly-gamma-glutamic acid to use as hydrogel.For example, point out in the Japanese Patent " spy opens flat 6-322358 number ", can use radioactive rays that poly-gamma-glutamic acid is shone, building bridge reaction and form poly-gamma-glutamic acid via the electronics polymerization is hydrogel.But, handle via radiation exposure that to produce poly-gamma-glutamic acid be that the related production equipment of hydrogel is complicated and restricted, cause difficulty on the production sequence and inconvenient.
In addition, Japanese Patent " spy opens flat 11-343339 " bulletin points out, can produce the tool high water absorbing capacity via the common reaction of poly-gamma-glutamic acid and poly-epoxy (polyepoxy) compound is hydrogel with stable poly-gamma-glutamic acid.
But, when producing poly-gamma-glutamic acid and be hydrogel, the shortcoming that the high density poly-gamma-glutamic acid need be provided is arranged still via the common reaction of poly-gamma-glutamic acid and polyepoxides.In addition, poly-gamma-glutamic acid in the past is the production sequence of hydrogel, need be with separation, purified poly-gamma-glutamic acid in nutrient solution essence as raw material, and after being dissolved in the solvent jointly with salt compounds, handling via radiation exposure again or react and produce and get with bridging agent such as epoxy compounds.Therefore, in the production process, need to remove thalline, separation poly-gamma-glutamic acid in the nutrient solution, purified dependent program and equipment, need also to promote that poly-gamma-glutamic acid and salt compounds thing are dissolved in the equipment of solvent, cause production cost to increase and problems such as production sequence inconvenience, need badly and solve this problem.
Summary of the invention
The object of the invention is to provide a kind of and does not need from nutrient solution to separate, refining poly-gamma-glutamic acid and can directly utilize nutrient solution to produce the manufacture method that the poly-gamma-glutamic acid with high water absorbing capacity, high stability is Biodegradable, absorbent resin easily.
The gimmick that realizes above-mentioned purpose is that exploitation is had Biodegradable to the inventor simultaneously and super absorbent resin has carried out many researchs and obtained this achievement.Manufacture method of the present invention can have high water absorbing capacity more than 3000 times, reach the absorbent resin of stability with simple program production, thereby reach aforesaid purpose directly by nutrient solution.
Biodegradable provided by the present invention, super absorbent resin and manufacture method thereof are described below.
A kind of decomposability, absorbent resin with nutrient solution (A) with react with for example poly-epoxy (polyepoxy) compound (B) that contains more than 2 functional group that can react with structures such as carboxyl, hydroxy, aldehyde radical, carbonyl, sulfuryl, nitro or amino in a part and make.
In Biodegradable as previously discussed, the absorbent resin, described nutrient solution (A) is for containing the microbial culture medium of polyamino acid or polysaccharide.
In Biodegradable as previously discussed, the absorbent resin, described polyamino acid is poly-gamma-glutamic acid, Ju Tians Door winter propylhomoserin or polylysine.
In Biodegradable as previously discussed, the absorbent resin, described polysaccharide comprises the polysaccharide that is made of glucose or fructose, or is the polysaccharide that the formed poly carboxylic acid of main component is constituted by rhamnosyl, Fucose, glucose and glucuronic acid or hyaluronic acid respectively.
In Biodegradable as previously discussed, the absorbent resin, described compound (B) is with the polyepoxides that contains 2 above functional groups in a part.
In Biodegradable as previously discussed, the absorbent resin, it is that nutrient solution (A) is 100 to react by 0.1～10 weight ratio and generated with epoxy (epoxy) compound.
The reaction of a kind of Biodegradable, absorbent resin, wherein, when nutrient solution (A) and epoxy (epoxy) when compound reacts, the pH condition enactment is 3.5～8 scopes.
The manufacture method of a kind of Biodegradable, absorbent resin, wherein, when nutrient solution (A) reacted with polyepoxides, the contained carboxyl of nutrient solution (A), hydroxy, aldehyde radical, carbonyl (carbonyl group), sulfuryl, nitro or amino etc. were 1: 1 with the actual mol ratio of epoxy group(ing) that poly-epoxy group(ing) provides.
Biodegradable as previously discussed, the manufacture method of absorbent resin, wherein, resin inside has comprised the necessary medium component of microbial growth, or in the nutrient solution by the metabolite of microorganisms producing.
Utilize polymer substance that Institute of Micro-biology produces as Biodegradable, absorbent polymer compound, include polysaccharide (Japanese Patent: the spy opens flat 5-301904 number) that poly-gamma-glutamic acid hydrogel or Alcaligenes letus B16 bacterial strain produced etc.In addition, the polyamino acid hydrogel, starch hydrogel, alginic acid hydrogel or the polysaccharide hydrogels such as hydrogel, carbonyl methyl cellulose hydrogel that also have poly aspartic acid etc.This type of Biodegradable, the manufacture method of absorbent resin is open all.For example, relevant with the manufacturing process of aforementioned polyamino acid hydrogel Japanese Patent comprises: the spy opens flat 7-224163 number, spy and opens flat 7-309943 number, spy and open flat 7-300563 number, spy and open flat 10-298282 number etc.In addition, 650716 of United States Patent (USP)s have been recorded and narrated the manufacturing process of polysaccharide hydrogel.But aforementioned patent all needs through complicated production sequence and needs purified polyamino acid or polysaccharide as raw materials for production.Thereby direct use nutrient solution proposed by the invention and polyepoxides react Biodegradable, absorbent resin and the relative manufacturing process thereof that can easyly make at other document, comprise all not put down in writing fully in these patents.
The shape of Biodegradable of the present invention, absorbent resin can also be atypic broken shape according to solid shape granulation in addition, or spherical, tabular.In addition, product of the present invention can not destroy global environment owing to have Biodegradable.Especially, resin of the present invention inside is coating the trace ingredientss such as carbon source, nitrogenous source and mineral substance of forming part as substratum, or the meta-bolites of Institute of Micro-biology's generation, therefore be suitable as very much agricultural materials such as composting auxiliary agent, seed coating, desert afforestation material.
Component for nutrient solution of the present invention (A) is also without particular limitation, for example, the microorganism of using the substratum of being made up of L-glutamic acid and peptone to cultivate Bacillus subtilus (Bacillus subtilis) and this class of Bacillus natto (Bacillus natto) just can obtain to contain the nutrient solution (Japanese Patent: the spy opens flat 1-174397) of poly-gamma-glutamic acid.Poly-gamma-glutamic acid preferably has hundreds thousand of above molecular weight, but there is no special restriction.
When building bridge reaction via polyepoxides, the non-consumption of polyepoxides is advisable with 0.1% to 10% of nutrient solution weight.Especially be the best with 0.25% to 6%.If 0.1% of the not enough nutrient solution weight of addition, the reaction of can't building bridge fully just can't obtain the high-hydroscopicity hydrogel.When addition surpasses 10% of nutrient solution weight, also can lose high-hydroscopicity.The pH scope of reacting is 3 to 8, is the best with pH4.5 to 5.5.
Specifically, the Biodegradable, absorbent resin of the present invention with high water absorbing capacity can be obtained by following method.That is, in nutrient solution, adding polyepoxides, stirring reaction obtains hydrogel.
The scope of temperature of reaction is good with 0 to 100 ℃.When waiting low temperature to react for 4 ℃, need the long reaction times, temperature of reaction is if surpass 100 ℃, then with side reactions such as concurrent decomposition reactions, and improper.
There is no particular restriction for reactive mode, and variety of way all can be carried out.Particularly, have the glass reactor of whipping appts or use incubator in oil bath, water bath, to carry out oscillatory reaction and all can reach purpose.
Indication there is no particular restriction with the classes of compounds that contains more than 2 functional group that can react with nutrient solution in a part among the present invention, but more suitable with polyepoxides.In the polyepoxides, every have the compound of 2 above epoxy group(ing) all suitable with a part, there is no special restriction, comprise ethylene glycol diglycidylether, propylene glycol diglycidylether, glycerine-1,3-diglycidylether or diglycidyl ether, polyethyleneglycol diglycidylether etc.
Embodiment
As previously discussed, of the present invention be characterized as provide do not need from nutrient solution to separate, refining polyamino acid or polysaccharide and can directly utilize nutrient solution and polyepoxides to react and the tool Biodegradable, absorbent resin and its manufacture method that obtain.The bacterial strain Bacillus subtilis gained nutrient solution after cultivating that is suitable for most producing poly-gamma-glutamic acid in following the application of the invention carries out embodiment that associated resin makes and comes that the present invention is described in more detail, but scope of the present invention is not subjected to the restriction of these embodiment.
Embodiment 1
By 0.5% yeast extract, 1.5% peptone, 0.3% urea, 0.2% Rhodiaphos DKP (K
2HPO
4), compositions such as 10% L-glutamic acid, 8% glucose, the pH value is 300 liters of 6.8 substratum of forming, and puts into 600 liters of fermenters, cultivates Bacillus subtilis in 37 ℃, after 72 hours, can obtain 40 gram poly-gamma-glutamic acids in every liter of nutrient solution.Get 10 gram nutrient solutions addings respectively and add a cover in the sample bottle for 20 milliliters, and add listed polyepoxides 400 microlitres of table one, slowly vibrate reaction 24 hours in 40 ℃.
Add a cover from 20 milliliters and to take out reaction solution the sample bottle, soak weeks in 4 ℃, to remove the poly-gamma-glutamic acid of not building bridge.Hydrogel (hydrogel) after the suction swelling just obtains hydrogel after 80 order metal mesh filters and lyophilize.Get this hydrogel again and measure its water-intake rate.
It is that hydrogel is soaked in the excessive distilled water after the fully swelling with 80 order wire netting filtering excessive moistures that water-intake rate is measured, and measures its weight in wet base.Absorb moisture weight (weight in wet base deducts dry weight) be water-intake rate divided by the ratio of dry weight again.The water-intake rate of this embodiment gained hydrogel as shown in Table 1.
Embodiment 2
According to the method for embodiment 1, get ethylene glycol diglycidylether as polyepoxides reaction 24 hours, reaction pH value then further is adjusted into shown in the table 2, and places the slow vibration of incubator to react.The result of mensuration water-intake rate as shown in Table 2.
Embodiment 3
According to the method for embodiment 2, to get ethylene glycol diglycidylether and react as polyepoxides, the addition of ethylene glycol diglycidylether and reaction times are respectively according to table three change.Its result as shown in Table 3.
Embodiment 4
According to the method for embodiment 1, to get ethylene glycol diglycidylether and react as polyepoxides, it is 24 hours that temperature of reaction is set at 40 ℃, synthesising reacting time.And cultivate Bacillussubtilis according to the method for embodiment 1, and taking out the building-up reactions that nutrient solutions carry out embodiment 2 respectively at the different incubation times shown in the table four, its result is as shown in Table 4.
Table one
N is the unit number of following constitutional formula
Table two
| Polyepoxides | Reaction times (hour) | Water-intake rate |
| Ethylene glycol diglycidylether (n=1) | ????24 | ????3,000 |
| Glycol ether diglycidylether (n=2) | ????36 | ????2,900 |
| Polyethyleneglycol diglycidylether (n=4) | ????36 | ????2,800 |
| Polyethyleneglycol diglycidylether (n=9) | ????48 | ????2,800 |
| Polyethyleneglycol diglycidylether (n=13) | ????48 | ????2,500 |
| Polyethyleneglycol diglycidylether (n=22) | ????48 | ????1,300 |
| ????pH | Water-intake rate |
| ????4.0 | ????2,900 |
| ????4.5 | ????3,000 |
| ????5.0 | ????2,900 |
| ????5.5 | ????2,400 |
| ????6.0 | ????1,800 |
| ????7.0 | ????1,700 |
Table three
| Addition (μ l) | Water-intake rate | ||||
| Reaction times (hour) | |||||
| 24 | ????48 | ????72 | ????96 | ????120 | |
| ????250 | 3,220 | ????2,700 | ????_a) | ????_a) | ????_a) |
| ????400 | 3,000 | ????2,120 | ????1,980 | ????1,426 | ????1,221 |
| ????550 | 2,370 | ????1,660 | ????1,450 | ????1,540 | ????1,070 |
| ????700 | 1,450 | ????1,530 | ????1,400 | ????1,260 | ????1,330 |
_ a): reaction solution liquefies fully
Table four
| Incubation time (hr) | Water-intake rate |
| ????36 | ????_a) |
| ????48 | ????2,550 |
| ????60 | ????3,210 |
| ????72 | ????3,000 |
| ????84 | ????2,860 |
| ????96 | ????1,580 |
_ a): do not form hydrogel in the reaction solution
The present invention synthesizes the tool water-absorbent by polyepoxides being added nutrient solution, and has the resin hydrogel of high water absorbing capacity and Biodegradable.This kind absorbent resin not only can be used for health fields such as paper nappy, more can be widely used in various fields such as medical treatment, building, construction, food, agricultural, gardening.Especially, because resin of the present invention inside is coating as trace ingredientss such as a substratum composition part non-carbon source, nitrogenous source and mineral substance, or the meta-bolites of Institute of Micro-biology's generation, therefore be suitable as very much agricultural materials such as composting auxiliary agent, seed coating, desert afforestation material.In addition, owing to have superior Biodegradable, its offal treatment also is not only safe but also easy.
Claims (9)
1. a Biodegradable, absorbent resin, it is had more than 2 and can be reacted with the compound (B) of the functional group of structural responses such as carboxyl, hydroxy, aldehyde radical, carbonyl, sulfuryl, nitro or amino and make by nutrient solution (A) and same intramolecularly.
2. Biodegradable according to claim 1, absorbent resin is characterized in that, described nutrient solution (A) is for containing the microbial culture medium of polyamino acid or polysaccharide.
3. Biodegradable according to claim 2, absorbent resin is characterized in that, described polyamino acid is poly-gamma-glutamic acid, poly aspartic acid or polylysine (polylysin).
4. Biodegradable according to claim 2, absorbent resin, it is characterized in that, described polysaccharide is by glucose or fructose constituted, or is made of by the formed poly carboxylic acid of main component rhamnosyl, Fucose, glucose and glucuronic acid or unsulphated glycolsaminoglycan respectively.
5. Biodegradable according to claim 1, absorbent resin is characterized in that, described compound (B) is with the compound that has 2 poly-epoxy-functionals in a part.
6. Biodegradable according to claim 1 and 2, absorbent resin is characterized in that, it is to be reacted with 100: 0.1～100: 10 weight ratio by nutrient solution (A) and epoxy compounds to form.
7. the reaction of a Biodegradable, absorbent resin is characterized in that, when nutrient solution (A) and epoxy compounds reacted, its pH condition was 3.5～8.
8, the preparation method of a kind of Biodegradable, absorbent resin, it is characterized in that, when nutrient solution (A) and polyepoxides reacted, the actual mol ratio between the epoxy group(ing) is provided was 1: 1 for structure such as contained carboxyl, hydroxy, aldehyde radical, carbonyl, sulfuryl, nitro or amino and poly-epoxy group(ing) in the nutrient solution (A).
9. method according to claim 8 is characterized in that, resin inside is coating the necessary medium component of microbial growth, or the metabolite of microorganisms.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102618290A (en) * | 2012-03-20 | 2012-08-01 | 珠海农神生物科技有限公司 | Method for preparing soil bio-enzyme water-retaining agent |
| CN102796686A (en) * | 2012-08-14 | 2012-11-28 | 浙江天科高新技术发展有限公司 | High water retention microbe medium and preparation method |
| CN103435746A (en) * | 2013-09-03 | 2013-12-11 | 东南大学 | Amino acid zwitter ion hydrogel material and preparation method thereof |
| CN109266360A (en) * | 2018-09-20 | 2019-01-25 | 江西理工大学 | A method of composite sand consolidation agent and building biological breadcrust containing municipal sludge |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1047389C (en) * | 1993-10-15 | 1999-12-15 | 李光德 | Method and equipment for preparation of acrylate water-absorbing resin |
| CN1053201C (en) * | 1996-07-25 | 2000-06-07 | 化学工业部北京化工研究院 | Wate-absorption resin and preparing method thereof |
| CN1122051C (en) * | 1999-12-16 | 2003-09-24 | 中国科学院长春应用化学研究所 | Synthesis of high-hydroscopicity resin polymerized at room temperature |
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2002
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102618290A (en) * | 2012-03-20 | 2012-08-01 | 珠海农神生物科技有限公司 | Method for preparing soil bio-enzyme water-retaining agent |
| CN102618290B (en) * | 2012-03-20 | 2016-04-06 | 珠海农神生物科技有限公司 | A kind of preparation method of soil organisms enzyme water-holding agent |
| CN102796686A (en) * | 2012-08-14 | 2012-11-28 | 浙江天科高新技术发展有限公司 | High water retention microbe medium and preparation method |
| CN103435746A (en) * | 2013-09-03 | 2013-12-11 | 东南大学 | Amino acid zwitter ion hydrogel material and preparation method thereof |
| CN103435746B (en) * | 2013-09-03 | 2015-07-15 | 东南大学 | Amino acid zwitter ion hydrogel material and preparation method thereof |
| CN109266360A (en) * | 2018-09-20 | 2019-01-25 | 江西理工大学 | A method of composite sand consolidation agent and building biological breadcrust containing municipal sludge |
| CN109266360B (en) * | 2018-09-20 | 2020-10-16 | 江西理工大学 | Composite sand fixing agent containing municipal sludge and method for constructing biological crust |
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