CN103146195A - Polyaspartic acid-polyaspartic amide copolymer hydrogel and preparation method thereof - Google Patents
Polyaspartic acid-polyaspartic amide copolymer hydrogel and preparation method thereof Download PDFInfo
- Publication number
- CN103146195A CN103146195A CN2013100823536A CN201310082353A CN103146195A CN 103146195 A CN103146195 A CN 103146195A CN 2013100823536 A CN2013100823536 A CN 2013100823536A CN 201310082353 A CN201310082353 A CN 201310082353A CN 103146195 A CN103146195 A CN 103146195A
- Authority
- CN
- China
- Prior art keywords
- poly
- polyaspartic
- hydrogel
- acid
- aspartic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Polyamides (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention discloses a polyaspartic acid-polyaspartic amide copolymer hydrogel and a preparation method thereof. The hydrogel comprises the following components in a molar ratio: 1%-20% of cross-linking agent and 99%-80% of polyaspartic acid-polyaspartic amide; the hydrogel is environment-friendly and can be completely biodegradable. The preparation method of the polyaspartic acid-polyaspartic amide copolymer hydrogel comprises the following steps of: carrying out partial aminolysis of cross-linked polyaspartic amide and ammonia water and then carrying out hydrolysis in an alkali environment; or firstly partially hydrolyzing cross-linked polyaspartic amide and then carrying out aminolysis by ammonia water; and drying to obtain the polyaspartic acid-polyaspartic amide copolymer hydrogel. The hydrogel has a water absorbent rate of 250g/g-1520g/g and a normal saline water absorbent rate of 80g/g-260g/g. According to polyaspartic acid-polyaspartic amide copolymer hydrogel and the preparation method thereof disclosed by the invention, the hydrogel is improved from the polymer structure, so that the salt resistance is improved, therefore, the hydrogel has an extensive application prospect in the fields including biological medicines and the like, and in particular in the aspects of the soil improvement, soil water retention and fertilizer efficiency increase on agriculture.
Description
Technical field
The invention belongs to the biodegradable polymer technical field, be specifically related to a kind of poly-aspartic-acid and poly-asparagine copolymer aquagel and preparation thereof, especially a kind of biodegradable crosslinked poly-aspartic-acid and poly-asparagine copolymer aquagel and preparation method thereof.
Background technology
Poly-aspartic-acid is a kind of green chemical, biodegradable, nontoxic, do not destroy ecotope, be described as the new bio macromolecular material of " green " product by people, its purposes is very extensive, relates to the industries such as Treatment of Industrial Water, agricultural, medicine, household chemicals and petroleum drilling.Due to its superior performance, receive the concern of each large chemical company of the world, done a large amount of research in synthetic and application facet.
The poly-aspartic-acid hydrogel has water-absorbent, biological degradability and biocompatibility well.Have now found that, it can be digested and assimilated by the enzyme effect to be used for human body, and does not show antigenicity in human body, and its metabolite is nontoxic, is safe to the mankind; Being used for agricultural, is eco-friendly, with full environment coordination.The poly-aspartic-acid hydrogel is a kind of green functional macromolecular material of excellent property, is with a wide range of applications, and recent domestic has been done a large amount of research work.
Nineteen ninety-five Nagatomo etc., carry out chemically crosslinked to have obtained poly-aspartic-acid hydrogel (PASP) first take lysine methyl ester as linking agent at US5461085, after this, receive increasing concern, and new modification and novel gelatinous material continue to bring out.
PASP preparation of gels method is mainly radiation crosslinking method and chemical crosslink technique.Wherein the radiation crosslinking method is divided into again ultraviolet radiation crosslinking and r ray crosslinking.
Reported in the documents such as WO9937624, EP866084, US5998492, CN1814650, CN101864081 and prepared polyaspartic acids hydrogel with chemical crosslink technique, publication number is the patent of CN102690399A, discloses " poly-aspartic-acid and acrylic copolymer interpenetration network hydrogel and preparation method thereof ".
Water-absorbent, the salt tolerance aspect publication of improving hydrogel has CN101240052A, CN102153693A, CN101967208A etc., wherein have simultaneously in hydrogel-COOH and-the CONH2 group can improve the material salt tolerance.
The application document of poly-aspartic-acid (linearity) on agricultural is a lot, is mainly used in fertilizer synergist, and publication has CN102701865A, CN102674985, CN102643138, CN102617250, CN102531764, US7534280, US20070039365 etc.
In sum, prior art gained poly-aspartic-acid hydrogel although water absorbent rate is improved, its over-all properties, especially salt tolerance, keeps the material Wholly-degradable to reach environmental protection remaining to be further improved simultaneously.Agriculturally, improve the aspect such as performance as water conservation, getting fat effect, soil and be with a wide range of applications, in the urgent need to its unique topological framework and group synergy, modification poly-aspartic-acid hydrogel material; At improved performance simultaneously, need the hydrogel material of low-cost preparation polyaspartic acids excellent property.
Summary of the invention
The present invention seeks to obtain modification poly-aspartic-acid hydrogel material by designing unique topological framework and group synergy, improve its water absorbent rate and salt tolerance, maintenance material Wholly-degradable.A kind of novel poly-aspartic-acid and poly-asparagine copolymer aquagel and preparation method thereof are provided.The present invention is on the prior art basis, by aminolysis and hydrolysis, regulates and controls the topological framework of poly-aspartic-acid and poly-asparagine, obtains difference-CONH
2Hydrogel material with-COOH group ratio, excellent performance; Especially aspect salt tolerance and biodegradable, be able to further raising.
The composition of poly-aspartic-acid provided by the invention and poly-asparagine copolymer aquagel and content thereof are linking agent in molar ratio, and polyamine compounds content is 1～20%; Poly-aspartic-acid and poly-asparagine are 99～80%, and wherein poly-asparagine proportion is 1～50%.Described copolymer aquagel water absorbent rate is 250-1520g/g, and the physiological saline water absorbent rate is 80-260g/g, has higher salt tolerance.
The preparation method of poly-aspartic-acid provided by the invention and poly-asparagine copolymer aquagel is, take the poly-aspartoyl imines of the linearity of different molecular weight as raw material, produce the crosslinked poly-aspartoyl imines of different degree of crosslinking with chemical crosslink technique, through part aminolysis (ammoniacal liquor), hydrolysis again, perhaps first carry out part hydrolysis (alkaline hydrolysis), and then aminolysis, poly-aspartic-acid and poly-asparagine multipolymer obtained.By regulating the ratio (mol ratio of ammoniacal liquor and alkali is 1～50%) of ammoniacal liquor and alkali, can obtain difference-CONH
2With-the COOH mol ratio is 49～1% poly-aspartic-acid and poly-asparagine multipolymer, and wherein aminolysis and hydrolysis under the condition of-10～50 ℃, controlled difference-CONH2 and distributed with-COOH, but carry out in same reactor, and technological process is simple, and cost is low.
Described temperature of reaction preferable range is 20～50 ℃, the too low solution generation of temperature crystallization, and whole reaction is difficult to carry out; Excess Temperature, reaction is violent, and is wayward.
The poly-aspartoyl imines of the linearity of different molecular weight and linking agent mol ratio are 1～20%, most preferably are 1～10%.Linear poly-aspartoyl imines molecular weight is 5000～500000 dalton.
Linking agent is 1，2-diaminoethane, propylene diamine, Putriscine, 1,6-hexanediamine, heptamethylene diamine; Methionin, ornithine or Gelucystine or their salt, lipid; Can be also three amines or polyamine compounds.
The described ammonia of ammonolysis reaction is ammonia, ammoniacal liquor, carbonic acid ammonia or NH
4HCO
3Deng.
The described alkali of alkaline hydrolysis reaction is NaOH, KOH, Na
2CO
3, K
2CO
3Or Ca (OH)
3Deng mineral alkali or organic bases.
The solvent that aminolysis and alkaline hydrolysis reaction are used is H
2O, ethanol, methyl alcohol, DMF, DMSO etc. also can make two or more mixtures of above-mentioned solvent.Most preferably be H
2O, ethanol or methyl alcohol.
Advantage of the present invention and beneficial effect:
The present invention has prepared a novel poly-aspartic-acid of class and poly-asparagine copolymer aquagel, except having the biodegradability and biocompatibility that common aspartic acid hydrogel possesses, also has good water absorption, characteristic that saline-alkaline tolerance is strong; In addition, preparation method of the present invention is simple, and aminolysis and macromolecule alkali for hydrolysis are all carried out in water, simple to operately is easy to amplify suitability for industrialized production, and cost can be controlled at lower level, and this type of polyalcohol hydrogel agriculturally has very wide using value.
Embodiment
The water regain (water absorbent rate) that the present invention measures polyalcohol hydrogel adopts the tea bag method.
Operate as follows:
25 ℃ of temperature, under the condition of humidity 50%, with poly-aspartic-acid and the poly-asparagine copolymer analog hydrogel sample of the preparation tea bag of packing into, in the immersion deionized water, take out in a certain time interval tea bag, draining is 10 minutes in air, weighs and counts Wt, repeats above-mentioned steps with corresponding blank tea bag, be weighed as Wo, example weight is Ws, and the sample water absorbent rate is R, is calculated by following formula
Sample water absorbent rate (R)=(Wt-Wo-Ws)/Ws.
Embodiment 1:
Adding linking agent in the 250ml round-bottomed bottle is that 1% mole of crosslinked poly-imido number-average molecular weight of asparagus fern door of poly-its neutral line of asparagus fern door imide 1.000g(of lysine methyl ester is 120,000 dalton), 40ml water, the ammoniacal liquor of 5% mol ratio, stirred under 25 ℃ 12 hours, to solvent pH be till 7.8; Add again 10%(Wt%) KOH solution hydrolysis, 6 hours, solution became clear gel, continue reaction 8 hours, this hydrogel is in the convection oven of 60 ℃, after 48 hours dryings, get white (or faint yellow) solid, i.e. poly-aspartic-acid and poly-asparagine copolymer aquagel.Recording its water absorbent rate is (in deionized water) 1520g/g, and in the NaCl of the 0.9wt% aqueous solution, water absorbent rate is 80g/g.
Embodiment 2:
Step is with embodiment 1, linking agent 3% mol ratio lysine methyl ester, and number-average molecular weight is 8.2 ten thousand daltonian poly-asparagus fern door imides, 3% mol ratio ammoniacal liquor aminolysis, then with 10% KOH hydrolysis.Get faint yellow solid; Recording its water absorbent rate in deionized water is 960g/g, and in the NaCl of the 0.9wt% aqueous solution, water absorbent rate is 248g/g.
Embodiment 3:
Step is with embodiment 1, linking agent 20% mol ratio lysine methyl ester, and number-average molecular weight is 8.2 ten thousand daltonian poly-asparagus fern door imides, 1% mol ratio ammoniacal liquor aminolysis, then with 10% KOH hydrolysis.Get faint yellow solid; Recording its water absorbent rate in deionized water is 50g/g, and in the NaCl of the 0.9wt% aqueous solution, water absorbent rate is 12g/g.
Embodiment 4:
Step is with embodiment 1, linking agent 10% mol ratio lysine methyl ester, and number-average molecular weight is 0.5 ten thousand daltonian poly-asparagus fern door imides, 5% mol ratio ammoniacal liquor aminolysis, then with 10% KOH hydrolysis.Get faint yellow solid; Recording its water absorbent rate in deionized water is 900g/g, and in the NaCl of the 0.9wt% aqueous solution, water absorbent rate is 150g/g.
Embodiment 5:
Step is with embodiment 1, linking agent 3% mol ratio lysine methyl ester, and number-average molecular weight is 500,000 daltonian poly-asparagus fern door imides, 10% mol ratio ammoniacal liquor aminolysis, then with 10% KOH hydrolysis.Get faint yellow solid; Recording its water absorbent rate in deionized water is 1480g/g, and in the NaCl of the 0.9wt% aqueous solution, water absorbent rate is 280g/g.
Embodiment 6:
Step with embodiment 1, is only 3.6 ten thousand dalton with poly-asparagus fern door imide number-average molecular weight, and other and embodiment 2 are identical, get faint yellow solid, recording its water absorbent rate in deionized water is 810g/g, and in the NaCl of the 0.9wt% aqueous solution, water absorbent rate is 80g/g.
Embodiment 7:
Step is with embodiment 1, and wherein linking agent is the hexanediamine of 4% mol ratio, and poly-asparagus fern door imide number-average molecular weight is 8.2 ten thousand, and the ammoniacal liquor mol ratio is 10%, then uses 10% KOH solution, gets faint yellow solid.Recording its water absorbent rate in deionized water is 580g/g, and in the NaCl of the 0.9wt% aqueous solution, water absorbent rate is 68g/g.
Embodiment 8:
Step is with embodiment 1, and wherein linking agent is the hexanediamine of 2% mol ratio, and poly-asparagus fern door imide number-average molecular weight is 3.6 ten thousand dalton, and the ammoniacal liquor mol ratio is 8%, then uses 10% KOH solution, gets faint yellow solid.Recording its water absorbent rate in deionized water is 950g/g, and in the NaCl of the 0.9wt% aqueous solution, water absorbent rate is 160g/g.
Embodiment 9:
Step is with embodiment 1, and linking agent is the butanediamine of 5% mol ratio, and poly-asparagus fern door imide number-average molecular weight is 120,000 dalton, and the ammoniacal liquor mol ratio is 10%, gets faint yellow solid.Recording its water absorbent rate in deionized water is 960g/g, and in the NaCl of the 0.9wt% aqueous solution, water absorbent rate is 68g/g.
Embodiment 10:
Step is with embodiment 1, and linking agent is the hexanediamine of 3% mol ratio, and poly-asparagus fern door imide number-average molecular weight is 120,000 dalton, only uses ammoniacal liquor ammonia solution, does not add KOH, gets white solid.Recording its water absorbent rate in deionized water is 880g/g, and in the NaCl of the 0.9wt% aqueous solution, water absorbent rate is 72g/g.
Claims (8)
1. a poly-aspartic-acid and poly-asparagine copolymer aquagel, is characterized in that the composition of described hydrogel and content thereof are linking agent in molar ratio, and polyamine compounds content is 1～20%; Poly-aspartic-acid and poly-asparagine are 99～80%, and wherein poly-asparagine proportion is 1～50%.
2. the preparation method of a poly-aspartic-acid claimed in claim 1 and poly-asparagine copolymer aquagel, it is characterized in that described method is as follows: take the poly-aspartoyl imines of linearity as raw material, at first produce the crosslinked poly-aspartoyl imines of different degree of crosslinking with chemical crosslink technique, crosslinked poly-aspartoyl imines is dispersed in solvent, carry out the part aminolysis with ammoniacal liquor, be hydrolyzed in alkalescence again, or first carry out the part basic hydrolysis, use again the ammoniacal liquor aminolysis, drying obtains different degree of crosslinking, poly-aspartic-acid and the poly-asparagine copolymer aquagel of different poly-aspartic-acids and poly-asparagine multipolymer ratio, wherein aminolysis and hydrolysis temperature are at-10 ℃～50 ℃.
3. method according to claim 2, is characterized in that the mol ratio according to different ammoniacal liquor and alkali is 1～50%, obtains different poly-aspartic-acids and poly-asparagine mol ratio and be 49～1% copolymer aquagel.
4. method according to claim 2, is characterized in that the linear poly-imido molecular weight of Radix Asparagi is 5000～500000 dalton.
5. method according to claim 2 is characterized in that described chemical crosslink technique produces the linking agent that the poly-aspartoyl imines of different degree of crosslinking uses and be 1，2-diaminoethane, propylene diamine, Putriscine, 1,6-hexanediamine, heptamethylene diamine; Methionin, ornithine, Gelucystine or their salt, lipid; Or three amine or polyamine compounds; The poly-aspartoyl imines of the linearity of different molecular weight and linking agent mol ratio are 1～20%.
6. method according to claim 2, is characterized in that described hydrolysis alkali is NaOH, KOH, Na
2CO
3, K
2CO
3, Ca (OH)
2, organic bases.
7. method according to claim 2, is characterized in that described aminolysis ammonia is ammonia, ammoniacal liquor, carbonic acid ammonia, ammonium hydrogencarbonate.
8. method according to claim 2, is characterized in that described solvent is H
2O, ethanol, methyl alcohol, DMF, DMSO or their mixture.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013100823536A CN103146195A (en) | 2013-03-14 | 2013-03-14 | Polyaspartic acid-polyaspartic amide copolymer hydrogel and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013100823536A CN103146195A (en) | 2013-03-14 | 2013-03-14 | Polyaspartic acid-polyaspartic amide copolymer hydrogel and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103146195A true CN103146195A (en) | 2013-06-12 |
Family
ID=48544535
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2013100823536A Pending CN103146195A (en) | 2013-03-14 | 2013-03-14 | Polyaspartic acid-polyaspartic amide copolymer hydrogel and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103146195A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103694027A (en) * | 2013-08-29 | 2014-04-02 | 农业部环境保护科研监测所 | Method for saving phosphorus and improving fertilizer efficiency by copolymer of polyaspartic acid and polyasparagine |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020055613A1 (en) * | 2000-06-21 | 2002-05-09 | Mississippi Chemical Corporation | Process for production of polyasparagine and the high nitrogen content polymer formed thereby |
| CN1916052A (en) * | 2006-08-18 | 2007-02-21 | 天津理工大学 | Method for preparing interpolymer bionic membrane material of poly-asparagine and chitosan |
| CN101864081A (en) * | 2010-05-14 | 2010-10-20 | 北京化工大学 | New method for preparing polyaspartic acid hydrogels |
-
2013
- 2013-03-14 CN CN2013100823536A patent/CN103146195A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020055613A1 (en) * | 2000-06-21 | 2002-05-09 | Mississippi Chemical Corporation | Process for production of polyasparagine and the high nitrogen content polymer formed thereby |
| CN1916052A (en) * | 2006-08-18 | 2007-02-21 | 天津理工大学 | Method for preparing interpolymer bionic membrane material of poly-asparagine and chitosan |
| CN101864081A (en) * | 2010-05-14 | 2010-10-20 | 北京化工大学 | New method for preparing polyaspartic acid hydrogels |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103694027A (en) * | 2013-08-29 | 2014-04-02 | 农业部环境保护科研监测所 | Method for saving phosphorus and improving fertilizer efficiency by copolymer of polyaspartic acid and polyasparagine |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103788723B (en) | Modified soapstone, quaternary ammonium polylactide/fulvate modified soapstone composite material and preparation methods and products thereof | |
| AU2008322438B2 (en) | Hydroxypolyamide gel forming agents | |
| CN101768268B (en) | Method for preparing polyaspartic acid by crystal condensation | |
| CN101280044A (en) | Biodegradable agricultural high-absorbent resin and preparation thereof | |
| CN103145981B (en) | Polyhexamethylene guanidine phosphate and synthetic method thereof | |
| CN102504292B (en) | Organic cross linking system for polymer flooding and preparation method of cross linking agent | |
| CN103131183B (en) | A kind of polyaspartic acid water-absorbing resin and preparation method thereof | |
| CN102321195A (en) | Chitosan aminoethyl quaternary ammonium salt derivative and preparation method thereof | |
| CN103951765A (en) | O-fumarate ester-N-chitosan quaternary ammonium salt and preparation method and application thereof | |
| CN103011970A (en) | Manufacturing method of multifunctional humic acid fertilizer with water retention and fertilizer retention functions | |
| CN102787088A (en) | Enterobacter cloacae and application of enterobacter cloacae | |
| CN103113586A (en) | Method for saving nitrogen and enhancing fertilizer efficiency by using poly-aspartic acid and poly-asparagine copolymer | |
| CN102399305A (en) | Chitosan fumaroyl derivative and preparation method thereof | |
| CN103012606A (en) | Modified starch for grafting guazatine oligomer as well as preparation method and application of modified starch | |
| CN104212460A (en) | Enteromorpha liquid mulching film and preparation method thereof | |
| CN104291926A (en) | Fertilizer accelerator and its preparation method | |
| CN103146195A (en) | Polyaspartic acid-polyaspartic amide copolymer hydrogel and preparation method thereof | |
| CN103351218B (en) | Synergist for polyaspartic acid fertilizer and preparation method thereof | |
| CN107162727A (en) | The preparation of one planting fruit-trees special bacteria agent and application process | |
| CN104558244A (en) | O-pyridine acid ester chitosan as well as preparation method and application thereof | |
| CN103535369B (en) | Biological slime inhibitor and preparation method thereof | |
| CN108383945B (en) | Agricultural water-retaining agent and preparation method thereof | |
| CN104140522A (en) | Degradable polyhydroxyalkanoate | |
| CN107200853B (en) | dendrimer/carboxymethyl cellulose super-absorbent gel and preparation and application thereof | |
| CN108862642A (en) | The preparation method of modified polyaspartic acid scale inhibitor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20130612 |