CN100588456C - Method for preparing polyaspartic acid heavy metal absorbing resin by aqueous medium method - Google Patents
Method for preparing polyaspartic acid heavy metal absorbing resin by aqueous medium method Download PDFInfo
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- CN100588456C CN100588456C CN200410072743A CN200410072743A CN100588456C CN 100588456 C CN100588456 C CN 100588456C CN 200410072743 A CN200410072743 A CN 200410072743A CN 200410072743 A CN200410072743 A CN 200410072743A CN 100588456 C CN100588456 C CN 100588456C
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Abstract
This is the way to make heavy metal attaching resin. Take mixing reactivation in the alkaline water solution, and then take further water solution, open the rest yaan ring not reacted, last take off water in vacuum. The resin after heated has the attaching water and heavy metal ability. The craft of the invention is simple, has few steps, and costs little. It has few waster water, so it's the cleaner craft. The resin by this craft can be used as heavy metal attaching dose, taking off heavy metal by Chinese herbal medicine, solve waster water and other fields. The metal attaching quantity can achieve 200mg Pb/g. the resin can be used as attaching dose, the hygiene healthy care thing of day life, keeping water in agriculture, chemical controlling material and other fields.
Description
[technical field]
The present invention relates to the method in the fine chemicals field, particularly preparing polyaspartic acid heavy metal absorbing resin by aqueous medium method of Chemical Engineering.
[technical background]
Crosslinked poly-aspartic-acid resin is a kind of broad-spectrum material.Wherein water-soluble cross-linked poly-aspartate (salt) can be used as thickener, suspension stabilizer, flocculant, medicine and carries agent etc.And water-insoluble cross-linked poly-aspartic acid (salt) is widely used in the key areas such as control release of health care product, agriculture water-loss reducer, wastewater treatment, chemicals because of having stronger water imbibition and heavy metal absorption property.
The method of crosslinked poly-day of preparation at present (door) winter propylhomoserin (salt) generally all adopts organic solvent method, the N that mentions in patent CN 1198444A for example, dinethylformamide (DMF), dimethyl sulfoxide (DMSO) (DMSO) etc.These organic solvents are harmful mostly, and price is more expensive, and it is essential therefore to reclaim technology, produces waste water thus, causes secondary pollution.Operating process is also comparatively loaded down with trivial details in addition.Therefore suddenly wait to develop production technology more cheap and that more clean.
[summary of the invention]
Purpose of the present invention is exactly in order to solve the problems of the prior art, to prepare the crosslinked poly-aspartic-acid resin of water-insoluble synthesis technique more cheap and that more clean and develop.As reaction medium, operating procedure is few with water for this technology, produces waste water hardly.
The present invention addresses the above problem the technical scheme that is adopted to be:
A kind of method of preparing polyaspartic acid heavy metal absorbing resin by aqueous medium method is characterized in that the method for preparing the water-insoluble cross-linked poly-aspartic acid comprises the following steps:
(1) organic crosslinking agent that will contain two amidos at least is dissolved in the aqueous solution that contains alkali, and the mol ratio of crosslinking agent and alkali is: 10: 90～90: 10;
(2) with above-mentioned solution by crosslinking agent and mol ratio by the polysuccinimide of succimide unit: 0.01～1.0 mixes, and under 20～60 ℃ of temperature, in 1～10 hour reaction time, generates the poly-aspartate of crosslinked partial hydrolysis;
(3) continue to add aqueous slkali to the whole hydrolysis of the imide ring in the polysuccinimide;
(4) weight ratio of adding and cross-linked poly-aspartic acid is 0.05～0.5: 1 glutaraldehyde, carries out secondary cross-linking under 15～35 ℃ of reaction temperatures;
(5) will go up step products 25～60 ℃ of following vacuum drying, or vacuum drying again after separating out with methyl alcohol, until generating gel.
The method of second kind of preparing polyaspartic acid heavy metal absorbing resin by aqueous medium method is characterized in that the method for preparing the water-insoluble cross-linked poly-aspartic acid comprises the following steps:
(1) preparation contains the neutral salt acid salt aqueous solution of the crosslinking agent of at least two amidos;
(2) above-mentioned solution is mixed with polysuccinimide, crosslinking agent is 0.10～0.40 with mol ratio by the polysuccinimide of succimide unit, and reaction temperature is 20～60 ℃, and the reaction time is 1～10 hour;
(3) drip aqueous alkali in the reactant mixture that in step (2), obtains in batches or progressively, finish until cross-linking reaction, the mol ratio of crosslinking agent and alkali is 10: 90～90: 10, and used alkali is NaOH or potassium hydroxide, and alkali concn is 1mol/L to 10mol/L;
(4) add glutaraldehyde and carry out the secondary cross-linking step;
(5) separate out in vacuum drying under 25～60 ℃ of temperature or with methyl alcohol after vacuum drying again, until forming gel.
The method of the third preparing polyaspartic acid heavy metal absorbing resin by aqueous medium method is characterized in that the method for preparing the water-insoluble cross-linked poly-aspartic acid comprises the following steps:
(1) stirring is added to the water polysuccinimide down, makes the suspension pulpous state aqueous solution of polysuccinimide;
(2) aqueous alkali of the crosslinking agent of at least two amidos of preparation, the mol ratio of crosslinking agent and alkali is 10: 90～90: 10;
(3) solution that obtains in the step (2) is added drop-wise in the solution that obtains in the step (1) in batches or progressively, finish until reaction, crosslinking agent with mol ratio by the polysuccinimide of succimide unit is: 0.10～0.40, reaction temperature is controlled at 20～60 ℃, and the reaction time is 1～10 hour;
(4) add glutaraldehyde and carry out the secondary cross-linking step;
(5) vacuum drying under 25～60 ℃ of temperature, or vacuum drying again after separating out with methyl alcohol are until forming gel.
The method of the 4th kind of preparing polyaspartic acid heavy metal absorbing resin by aqueous medium method is characterized in that the method for preparing the water-insoluble cross-linked poly-aspartic acid comprises the following steps:
(1) organic crosslinking agent that will contain two amidos at least is dissolved in the aqueous solution that contains alkali, and the mol ratio of crosslinking agent and alkali is: 10: 90～90: 10;
(2) with above-mentioned solution by crosslinking agent and mol ratio by the polysuccinimide of succimide unit: 0.01～1.0 mixes, and under 20～60 ℃ of temperature, through reaction in 1～10 hour, generates the poly-aspartate of crosslinked partial hydrolysis;
(3) continue to add aqueous slkali to the whole hydrolysis of the imide ring in the polysuccinimide;
(4) add template agent: CaCl in the solution that in step (3), obtains
2Or Ca (NO
3)
2, CaSO
4, ZnCl
2, MgCl
2In one or both and two or more mixing, the template agent is 0.1～1: 1 with mol ratio by the polysuccinimide of succimide unit;
(5) will go up step products 25～60 ℃ of following vacuum drying, or vacuum drying again after separating out with methyl alcohol, until generating gel;
(6) or between step (4) (5), add glutaraldehyde and carry out the secondary cross-linking step.
The method of the 5th kind of preparing polyaspartic acid heavy metal absorbing resin by aqueous medium method is characterized in that the method for preparing the water-insoluble cross-linked poly-aspartic acid comprises the following steps:
(1) preparation contains the neutral salt acid salt aqueous solution of the crosslinking agent of at least two amidos;
(2) above-mentioned solution is mixed with polysuccinimide, crosslinking agent is 0.10～0.40 with mol ratio by the polysuccinimide of succimide unit, and reaction temperature is 20～60 ℃, and the reaction time is 1～10 hour;
(3) drip aqueous alkali in the reactant mixture that in step (2), obtains in batches or progressively, finish until cross-linking reaction, the mol ratio of crosslinking agent and alkali is 10: 90～90: 10, and used alkali is NaOH or potassium hydroxide, and alkali concn is 1mol/L to 10mol/L;
(4) add template agent: CaCl in the solution that in step (3), obtains
2Or Ca (NO
3)
2, CaSO
4, ZnCl
2, MgCl
2In one or both and two or more mixing, the template agent is 0.1～1: 1 with mol ratio by the polysuccinimide of succimide unit;
(5) separate out in vacuum drying under 25～60 ℃ of temperature or with methyl alcohol after vacuum drying again, until forming gel;
(6) or between step (4) (5), add glutaraldehyde and carry out the secondary cross-linking step.
The method of the 6th kind of preparing polyaspartic acid heavy metal absorbing resin by aqueous medium method is characterized in that the method for preparing the water-insoluble cross-linked poly-aspartic acid comprises the following steps:
(1) stirring is added to the water polysuccinimide down, makes the suspension pulpous state aqueous solution of polysuccinimide;
(2) aqueous alkali of the crosslinking agent of at least two amidos of preparation;
(3) solution that obtains in the step (2) being added drop-wise in batches or progressively the middle solution of step (1) finishes until reaction;
(4) add template agent: CaCl in the solution that in step (3), obtains
2Or Ca (NO
3)
2, CaSO
4, ZnCl
2, MgCl
2In one or both and two or more mixing, the template agent is 0.1～1: 1 with mol ratio by the polysuccinimide of succinyl industry amine unit;
(5) adding weight ratio with cross-linked poly-aspartic acid in the solution that obtains in (4) is 0.05～0.5: 1 glutaraldehyde, carries out secondary cross-linking under 15～35 ℃ of reaction temperatures;
(6) separate out in vacuum drying under 25～60 ℃ of temperature or with methyl alcohol after vacuum drying again, until forming gel;
(7) the gained resin is carried out the stripper plate agent, the complexing agent that the stripper plate agent is used is a disodium edta, citric acid or natrium citricum.
As reaction medium, the technical process step is few with water for process of the present invention, and synthetic cost is low.The waste water growing amount is few, is cleaning procedure more.This technology gained resin can be used as heavy metal absorbent, and be used for Chinese medicine and remove heavy metal, fields such as wastewater treatment, its heavy metal adsorption capacity can reach 200mg Pb
2+/ g dried resin.The gained resin also can be used as water absorbing agent and is applicable to the fields such as control release function material of daily-use sanitary health treatment, agricultural water-loss reducer, chemicals.
[specific embodiment]
The method of first kind of preparing polyaspartic acid heavy metal absorbing resin by aqueous medium method comprises the following steps:
(1) organic crosslinking agent that will contain two amidos at least is dissolved in the aqueous solution that contains alkali, and the mol ratio of crosslinking agent and alkali is: 10: 90～90: 10, used alkali was NaOH or potassium hydroxide, and alkali concn is 1mol/L to 10mol/L.
Above-mentioned crosslinking agent can be one or both in the polyamines organic bases such as diamines or triamine, tetramine and two or more mixing.Said diamines organic base can be L-lysine, hydrazine hydrate, ethylenediamine, butanediamine etc.
(2) with above-mentioned solution by the mol ratio of crosslinking agent with polysuccinimide (by the succimide unit): 0.15～0.3 mixes, under 25～35 ℃ of temperature, (can adopt common heating or heating using microwave), reacted 3～6 hours, and generated the poly-aspartate of crosslinked partial hydrolysis.The weight average molecular weight of the poly-succinyl industry of raw material amine is 10,000～30,000, and the weight ratio of water and polysuccinimide is 1～20: 1, best 2～10: 1.
(3) continue to add aqueous slkali to the whole hydrolysis of the imide ring in the polysuccinimide;
(4) will go up step products at 30～45 ℃ of following vacuum drying 6-24 hours, or vacuum drying again after separating out with methyl alcohol, finish until generating gel.
In order to accelerate to form the speed of gel, can be 0.05～0.5: 1 glutaraldehyde in the weight ratio of back adding of the step (3) of said method and cross-linked poly-aspartic acid, under 15～35 ℃ of reaction temperatures, carry out secondary cross-linking, and then carry out step (4).
The method of second kind of preparing polyaspartic acid heavy metal absorbing resin by aqueous medium method comprises the following steps:
(1) preparation contains the neutral salt acid salt aqueous solution of the crosslinking agent of at least two amidos, and the mol ratio of crosslinking agent and alkali is 10: 90～90: 10;
Above-mentioned crosslinking agent can be one or both in the polyamines organic bases such as diamines or triamine, tetramine and two or more mixing.Said diamines organic base can be L-lysine, hydrazine hydrate, ethylenediamine, butanediamine etc.
(2) above-mentioned solution is mixed with polysuccinimide, the weight average molecular weight of raw material polysuccinimide is 10,000～30,000, the mol ratio of crosslinking agent and polysuccinimide (by the succimide unit) is 0.01～1.0, be preferably 0.10～0.40, reaction temperature is 25～40 ℃ (can adopt common heating or heating using microwave), and the reaction time is 3～6 hours; The weight ratio of water and polysuccinimide is 2～20: 1, best 1～10: 1.
(3) drip aqueous alkali in the reactant mixture that obtains in (2) in batches or progressively, finish until cross-linking reaction, used alkali is NaOH or potassium hydroxide, and alkali concn is 1mol/L to 10mol/L;
(4) at 25～60 ℃, preferably be controlled under 35～45 ℃ of temperature vacuum drying or separate out with methyl alcohol after the about 6-24 of vacuum drying hour again, until generating gel.
The weight ratio of adding and cross-linked poly-aspartic acid is 0.05～0.5: 1 glutaraldehyde after the step (3) of said method, carries out secondary cross-linking under 15～35 ℃ of reaction temperatures, and then carries out step (4).
The method of the third preparing polyaspartic acid heavy metal absorbing resin by aqueous medium method comprises the following steps:
(1) under strong agitation, polysuccinimide is added to the water, the suspension pulpous state aqueous solution of preparation polysuccinimide, the weight average molecular weight of raw material polysuccinimide is 10,000～30,000.
Above-mentioned crosslinking agent can for: a kind of in the polyamines organic bases such as diamines or triamine, tetramine or two dashes and two or more mixing.Said diamines organic base can be L-lysine, hydrazine hydrate, ethylenediamine, butanediamine etc.
(2) aqueous alkali of the crosslinking agent of at least two amidos of preparation, the mol ratio of crosslinking agent and alkali is 10: 90～90: 10; Used alkali is NaOH or potassium hydroxide, and alkali concn is 1mol/L to 10mol/L.
(3) solution that obtains in (2) is added drop-wise in the solution that obtains in (1) in batches or progressively, finish until reaction, the mol ratio of crosslinking agent and polysuccinimide (by the succimide unit) is: 0.01～1.0, be preferably 0.10～0.40, reaction temperature is controlled at 25～40 ℃ (can adopt common heating or heating using microwave), and the reaction time is preferably 3～6 hours; The weight ratio of water and polysuccinimide is 2～20: 1, best 1～10: 1.
(4) at 25～60 ℃, be preferably in vacuum drying under 35～45 ℃ of temperature, or after separating out with methyl alcohol the about 6-24 of vacuum drying hour again, until generating gel.
The weight ratio of adding and cross-linked poly-aspartic acid is 0.05～0.5: 1 glutaraldehyde after the step (3) of said method, carries out secondary cross-linking under 15～35 ℃ of reaction temperatures, and then carries out step (4).
The method of the 4th kind of preparing polyaspartic acid heavy metal absorbing resin by aqueous medium method comprises the following steps:
(1) organic crosslinking agent that will contain two amidos at least is dissolved in the aqueous solution that contains alkali, and the mol ratio of crosslinking agent and alkali is: 10: 90～90: 10, used alkali was NaOH or potassium hydroxide, and alkali concn is 1mol/L to 10mol/L.
Above-mentioned crosslinking agent can be one or both in the polyamines organic bases such as diamines or triamine, tetramine and two or more mixing.Said diamines organic base can be L-lysine, hydrazine hydrate, ethylenediamine, butanediamine etc.
(2) with above-mentioned solution by the mol ratio of crosslinking agent with polysuccinimide (by the succimide unit): 0.15～0.3 mixes, under 25～35 ℃ of temperature, (can adopt common heating or heating using microwave), reacted 3～6 hours, and generated the poly-aspartate of crosslinked partial hydrolysis.The weight average molecular weight of raw material polysuccinimide is 10,000～30,000, and the weight ratio of water and polysuccinimide is 1～20: 1, best 2～10: 1.
(3) continue to add aqueous slkali to the whole hydrolysis of the imide ring in the polysuccinimide;
(4) add template agent: CaCl in the solution that in (3), obtains
2Or Ca (NO
3)
2, CaSO
4, ZnCl
2, MgCl
2In one or both and two or more mixing, the mol ratio of template agent and polysuccinimide (by the succimide unit) is 0.1～0.5: 1;
(5) will go up step products 25～60 ℃ of following vacuum drying, or vacuum drying again after separating out with methyl alcohol, finish until generating gel.
The weight ratio of adding and cross-linked poly-aspartic acid is 0.05～0.5: 1 glutaraldehyde after the step (4) of said method, carries out secondary cross-linking under 15～35 ℃ of reaction temperatures, and then carries out step (5).
Need, also can carry out the stripper plate agent to above-mentioned gained resin, the complexing agent that the stripper plate agent is used is disodium edta (EDTA), citric acid or natrium citricum.
The method of the 5th kind of preparing polyaspartic acid heavy metal absorbing resin by aqueous medium method comprises the following steps:
(1) preparation contains the neutral salt acid salt aqueous solution of the crosslinking agent of at least two amidos, and the mol ratio of crosslinking agent and alkali is 10: 90～90: 10;
Above-mentioned crosslinking agent can be one or both in the polyamines organic bases such as diamines or triamine, tetramine and two or more mixing.Said diamines organic base can be L-lysine, hydrazine hydrate, ethylenediamine, butanediamine etc.
(2) above-mentioned solution is mixed with polysuccinimide, the weight average molecular weight of raw material polysuccinimide is 10,000～30,000, the mol ratio of crosslinking agent and polysuccinimide (by the succimide unit) is 0.01～1.0, be preferably 0.10～0.40, reaction temperature is 25～40 ℃ (can adopt common heating or heating using microwave), and the reaction time is preferably 3～6 hours; The weight ratio of water and polysuccinimide is 2～20: 1, best 1～10: 1.
(3) drip aqueous alkali in the reactant mixture that obtains in (2) in batches or progressively, finish until cross-linking reaction, used alkali is NaOH or potassium hydroxide, and alkali concn is 1mol/L to 10mol/L;
(4) add template agent: CaCl in the solution that in (3), obtains
2Or Ca (NO
3)
2, CaSO
4, ZnCl
2, MgCl
2In one or both and two or more mixing, the mol ratio of template agent and polysuccinimide (by the succimide unit) is 0.1～1: 1, is preferably 0.1～0.5: 1;
(5) separate out in vacuum drying under 25～60 ℃ of temperature or with methyl alcohol after vacuum drying 6-24 hour again, until generating gel.
The weight ratio of adding and cross-linked poly-aspartic acid is 0.05～0.5: 1 glutaraldehyde after the step (4) of said method, carries out secondary cross-linking under 15～35 ℃ of reaction temperatures, and then carries out step (5).
Need, also can carry out the stripper plate agent to above-mentioned gained resin, the complexing agent that the stripper plate agent is used is disodium edta (EDTA), citric acid or natrium citricum.
The method of the 6th kind of preparing polyaspartic acid heavy metal absorbing resin by aqueous medium method comprises the following steps:
(1) stirring is added to the water polysuccinimide down, makes the suspension pulpous state aqueous solution of polysuccinimide; The weight average molecular weight of raw material polysuccinimide is 10,000～30,000.
Above-mentioned crosslinking agent can be one or both in the polyamines organic bases such as diamines or triamine, tetramine and two or more mixing.Said diamines organic base can be L-lysine, hydrazine hydrate, ethylenediamine, butanediamine etc.
(2) aqueous alkali of the crosslinking agent of at least two amidos of preparation, the mol ratio of crosslinking agent and alkali is 10: 90～90: 10; Used alkali is NaOH or potassium hydroxide, and alkali concn is 1mol/L to 10mol/L.
(3) solution that obtains in (2) is added drop-wise in the solution that obtains in (1) in batches or progressively, finish until reaction, the mol ratio of crosslinking agent and polysuccinimide (by the succimide unit) is: 0.01～1.0, be preferably 0.10～0.40, reaction temperature is controlled at 20～60 ℃, be preferably in 25～40 ℃ (can adopt common heating or heating using microwave), the reaction time is 1～10 hour, is preferably 3～6 hours; The weight ratio of water and polysuccinimide is 2～20: 1, best 1～10: 1.
(4) add template agent: CaCl in the solution that in (3), obtains
2Or Ca (NO
3)
2, CaSO
4, ZnCl
2, MgCl
2In one or both and two or more mixing, the mol ratio of template agent and polysuccinimide (by the succimide unit) is 0.1～1: 1, is preferably 0.1～0.5: 1;
(5) adding weight ratio with cross-linked poly-aspartic acid in the solution that obtains in (4) is 0.05～0.5: 1 glutaraldehyde, carries out secondary cross-linking under 15～35 ℃ of reaction temperatures;
(6) vacuum drying under 35～45 ℃ of temperature, or after separating out with methyl alcohol vacuum drying 6-24 hour again, until generating gel.
(7) the gained resin is carried out the stripper plate agent, the complexing agent that the stripper plate agent is used is disodium edta (EDTA), citric acid or natrium citricum.
Design of the present invention is to be that 10,000 to 30,000 polysuccinimide carries out cross-linking reaction with organic crosslinking agent in alkaline aqueous solution with weight average molecular weight.Remaining unreacted imide ring is opened in further basic hydrolysis then, and vacuum dehydration at a certain temperature at last or adding glutaraldehyde carry out secondary cross-linking and obtain hydrogel.The gained resin has water imbibition and heavy metal adsorption capacity after drying.Be that the present invention is a basic skills with first, second and third kind aqueous medium method preparation method, can before vacuum drying, increase or not add glutaraldehyde simultaneously and carry out the secondary cross-linking step.Based on the above method, the template of adding agent step can also be arranged, also can carry out stripper plate agent step again.Thereby realize purpose of the present invention.
According to the present invention, outside dewatering, do not need other any organic solvents.So just avoid the use of poisonous and expensive organic solvents, also avoided the removal process of solvent, simplified technology, and can significantly reduce the growing amount of waste water.The raw material polysuccinimide can obtain with the hot polymerization compression method of spreading, for example can be by aspartic acid in catalysis or do not have that high temperature polymerization obtains under the catalytic condition, and the method for preparing polysuccinimide can be with reference to US5, and 057,597, US5,35,010, US319,145 etc.In order to obtain the resin of water-insoluble cross-linked poly-aspartic acid at last, the weight average molecular weight of raw material polysuccinimide should be at least greater than 10,000 is best more than 20,000, and this can or add catalyst by suitable raising reaction temperature, prolongation reaction time and realize.The thermal polycondensation reaction also can be operated under vacuum, sees US5,142,062.
As long as say that in principle effectively the crosslinking agent of crosslinked butanediimide ring all can use.Suitable crosslinking agent has polyamines, sees CN 1198444A and US5, and 525,682, US5,525,703.Preferably use L-lysine, hydrazine hydrate, ethylenediamine, butanediamine, or except that amido, also have other amine of the 3rd functional group, be beneficial to continue functionization.
Cross-linking process carries out under strong agitation, and the alkaline aqueous solution that will contain crosslinking agent joins in the water slurry of polysuccinimide, and crosslinking temperature is 20～60 ℃, 2～20 hours reaction time, best 3～10 hours.The degree of cross linking is controlled by the consumption of crosslinking agent, should make resulting cross-linked poly-aspartic acid have enough water-insolubles.
The crosslinked poly-succinamide that obtains above can continue hydrolysis, to open remaining imide ring.Carboxyl number on the polymer is many more, and its water imbibition and heavy metal adsorption capacity are also strong more.Used alkali is NaOH or potassium hydroxide.Hydrolysising reacting temperature is less than 80 ℃.Be preferably in 25～40 ℃, in 0.5～3 hour reaction time, the consumption of alkali is 0.40～0.45g NaOH/g polysuccinimide.
The method of testing of the absorption property of heavy metal is as follows: take by weighing a certain amount of cross-linked poly-aspartic acid hydrogel, add finite concentration Pb (NO
3)
2Aqueous solution V ml, adsorbed one hour, filter, use Pb
2+Ion selective electrode method is measured Pb in the solution of absorption front and back
2+Concentration.Adsorption capacity is calculated as follows:
Q＝(C
2-C
1)×V/W (mg/g)
C in the formula
1, C
2Be Pb in the solution before and after the absorption
2+Concentration, mg/L, W are the weight of dried hydrogel, V is the volume of solution.
Embodiment 1 adds the NaOH aqueous solution (8mmol) and the 80% 1 hydrazine hydrate 0.13g (2.1mmol) of 4ml 2mol/L in the flask of 100ml.Under strong agitation, adding 1.0g (0.01mol) weight average molecular weight is 20,000 polysuccinimide, reacted about 3 hours down at 25 ℃, dry under vacuum then, baking temperature remains on 35-40 ℃, dry 8 hours, obtain the water-insoluble poly-aspartic acid resin.
Embodiment 2 adds the pulpous state suspension of 1g (0.01mol) polysuccinimide in 3ml water in the 100ml flask, then in batches or the mixed liquor of the NaOH aqueous solution of disposable adding 2ml 2mol/L and 0.24g 80% 1 hydrazine hydrate solution, reacted about 5 hours down at 25 ℃, under vacuum dry 6 hours then, 50 ℃ of baking temperatures.Obtain the water-insoluble poly-aspartic acid resin.
Embodiment 3 adds 6ml water and 1.0g polysuccinimide in the 100ml flask, form suspension, adds 0.45g lysine and 0.25g NaOH then under strong agitation.27 ℃ were reacted about 5 hours down, continued to add 0.15g NaOH, stirred 1 hour again.Add 0.4ml 50% glutaraldehyde afterwards, generate the cross-linked poly-aspartic acid hydrogel.
Embodiment 4 operating procedures just before vacuum drying, are separated out cross-linked poly-aspartic acid with methyl alcohol, and then are carried out vacuum drying substantially with example 1 and example 2.
Embodiment 5 operating procedures are substantially with example 1, and example 2 just changes vacuum drying into adding 50% glutaraldehyde 0.3ml, generates gel.
Embodiment 6 operating procedures just will add glutaraldehyde and change under vacuum dry substantially with example 3.
Embodiment 7 operating procedures are substantially with example 1, and example 2 just adds 0.5ml and contains CaCl before vacuum drying
20.5g the aqueous solution, and then vacuum drying.
Embodiment 8 operating procedures are substantially with example 1, and example 2 just added 0.5ml and contains CaCl before adding glutaraldehyde
20.5g the aqueous solution, and then add glutaraldehyde.
Claims (9)
1 one kinds of aqueous medium legal systems are equipped with the method for poly-aspartate heavy metal polymeric adsorbent, it is characterized in that the method for preparing the water-insoluble cross-linked poly-aspartic acid comprises the following steps:
(1) organic crosslinking agent that will contain two amidos at least is dissolved in the aqueous solution that contains alkali, and the mol ratio of crosslinking agent and alkali is: 10: 90～90: 10;
(2) with above-mentioned solution by crosslinking agent and mol ratio by the polysuccinimide of succimide unit: 0.01～1.0 mixes, and under 20～60 ℃ of temperature, in 1～10 hour reaction time, generates the poly-aspartate of crosslinked partial hydrolysis;
(3) continue to add aqueous slkali to the whole hydrolysis of the imide ring in the polysuccinimide;
(4) weight ratio of adding and cross-linked poly-aspartic acid is 0.05～0.5: 1 glutaraldehyde, carries out secondary cross-linking under 15～35 ℃ of reaction temperatures;
(5) will go up step products 25～60 ℃ of following vacuum drying, or vacuum drying again after separating out with methyl alcohol, until generating gel.
2 in accordance with the method for claim 1, it is characterized in that the said crosslinking agent of step (2) is: one or both in diamines or triamine, the tetramine polyamines organic base and two or more mixing.
3 in accordance with the method for claim 2, it is characterized in that said diamines organic base is: L-lysine, hydrazine hydrate, ethylenediamine, butanediamine.
4 in accordance with the method for claim 1, it is characterized in that the said vacuum drying temperature of step (5) is controlled at 30～45 ℃.
5 one kinds of aqueous medium legal systems are equipped with the method for poly-aspartate heavy metal polymeric adsorbent, it is characterized in that the method for preparing the water-insoluble cross-linked poly-aspartic acid comprises the following steps:
(1) preparation contains the neutral salt acid salt aqueous solution of the crosslinking agent of at least two amidos;
(2) above-mentioned solution is mixed with polysuccinimide, crosslinking agent is 0.10～0.40 with mol ratio by the polysuccinimide of succimide unit, and reaction temperature is 20～60 ℃, and the reaction time is 1～10 hour;
(3) drip aqueous alkali in the reactant mixture that in step (2), obtains in batches or progressively, finish until cross-linking reaction, the mol ratio of crosslinking agent and alkali is 10: 90～90: 10, and used alkali is NaOH or potassium hydroxide, and alkali concn is 1mol/L to 10mol/L;
(4) add glutaraldehyde and carry out the secondary cross-linking step;
(5) separate out in vacuum drying under 25～60 ℃ of temperature or with methyl alcohol after vacuum drying again, until forming gel.
6 one kinds of aqueous medium legal systems are equipped with the method for poly-aspartate heavy metal polymeric adsorbent, it is characterized in that the method for preparing the water-insoluble cross-linked poly-aspartic acid comprises the following steps:
(1) stirring is added to the water polysuccinimide down, makes the suspension pulpous state aqueous solution of polysuccinimide;
(2) aqueous alkali of the crosslinking agent of at least two amidos of preparation, the mol ratio of crosslinking agent and alkali is 10: 90～90: 10;
(3) solution that obtains in the step (2) is added drop-wise in the solution that obtains in the step (1) in batches or progressively, finish until reaction, crosslinking agent with mol ratio by the polysuccinimide of succimide unit is: 0.10～0.40, reaction temperature is controlled at 20～60 ℃, and the reaction time is 1～10 hour;
(4) add glutaraldehyde and carry out the secondary cross-linking step;
(5) vacuum drying under 25～60 ℃ of temperature, or vacuum drying again after separating out with methyl alcohol are until forming gel.
7 one kinds of aqueous medium legal systems are equipped with the method for poly-aspartate heavy metal polymeric adsorbent, it is characterized in that the method for preparing the water-insoluble cross-linked poly-aspartic acid comprises the following steps:
(1) organic crosslinking agent that will contain two amidos at least is dissolved in the aqueous solution that contains alkali, and the mol ratio of crosslinking agent and alkali is: 10: 90～90: 10;
(2) with above-mentioned solution by crosslinking agent and mol ratio by the polysuccinimide of succimide unit: 0.01～1.0 mixes, and under 20～60 ℃ of temperature, through reaction in 1～10 hour, generates the poly-aspartate of crosslinked partial hydrolysis;
(3) continue to add aqueous slkali to the whole hydrolysis of the imide ring in the polysuccinimide;
(4) add template agent: CaCl in the solution that in step (3), obtains
2Or Ca (NO
3)
2, CaSO
4, ZnCl
2, MgCl
2In one or both and two or more mixing, the template agent is 0.1～1: 1 with mol ratio by the polysuccinimide of succimide unit;
(5) will go up step products 25～60 ℃ of following vacuum drying, or vacuum drying again after separating out with methyl alcohol, until generating gel;
(6) or between step (4) (5), add glutaraldehyde and carry out the secondary cross-linking step.
8 one kinds of aqueous medium legal systems are equipped with the method for poly-aspartate heavy metal polymeric adsorbent, it is characterized in that the method for preparing the water-insoluble cross-linked poly-aspartic acid comprises the following steps:
(1) preparation contains the neutral salt acid salt aqueous solution of the crosslinking agent of at least two amidos;
(2) above-mentioned solution is mixed with polysuccinimide, crosslinking agent is 0.10～0.40 with mol ratio by the polysuccinimide of succimide unit, and reaction temperature is 20～60 ℃, and the reaction time is 1～10 hour;
(3) drip aqueous alkali in the reactant mixture that in step (2), obtains in batches or progressively, finish until cross-linking reaction, the mol ratio of crosslinking agent and alkali is 10: 90～90: 10, and used alkali is NaOH or potassium hydroxide, and alkali concn is 1mol/L to 10mol/L;
(4) add template agent: CaCl in the solution that in step (3), obtains
2Or Ca (NO
3)
2, CaSO
4, ZnCl
2, MgCl
2In one or both and two or more mixing, the template agent is 0.1～1: 1 with mol ratio by the polysuccinimide of succimide unit;
(5) separate out in vacuum drying under 25～60 ℃ of temperature or with methyl alcohol after vacuum drying again, until forming gel;
(6) or between step (4) (5), add glutaraldehyde and carry out the secondary cross-linking step.
9 one kinds of aqueous medium legal systems are equipped with the method for poly-aspartate heavy metal polymeric adsorbent, it is characterized in that the method for preparing the water-insoluble cross-linked poly-aspartic acid comprises the following steps:
(1) stirring is added to the water polysuccinimide down, makes the suspension pulpous state aqueous solution of polysuccinimide;
(2) aqueous alkali of the crosslinking agent of at least two amidos of preparation;
(3) solution that obtains in the step (2) being added drop-wise in batches or progressively the middle solution of step (1) finishes until reaction;
(4) add template agent: CaCl in the solution that in step (3), obtains
2Or Ca (NO
3)
2, CaSO
4, ZnCl
2, MgCl
2In one or both and two or more mixing, the template agent is 0.1～1: 1 with mol ratio by the polysuccinimide of succimide unit;
(5) adding weight ratio with cross-linked poly-aspartic acid in the solution that obtains in (4) is 0.05～0.5: 1 glutaraldehyde, carries out secondary cross-linking under 15～35 ℃ of reaction temperatures;
(6) separate out in vacuum drying under 25～60 ℃ of temperature or with methyl alcohol after vacuum drying again, until forming gel;
(7) the gained resin is carried out the stripper plate agent, the complexing agent that the stripper plate agent is used is a disodium edta, citric acid or natrium citricum.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200410072743A CN100588456C (en) | 2004-11-17 | 2004-11-17 | Method for preparing polyaspartic acid heavy metal absorbing resin by aqueous medium method |
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| CN1314729C (en) * | 2005-09-09 | 2007-05-09 | 天津理工大学 | Prepn process of copolymer of polyaspartic acid and chitosan |
| CN102643441B (en) * | 2012-05-02 | 2014-08-13 | 北京化工大学 | Method for preparing polyaspartic acid type hydrogel |
| CN103131183B (en) * | 2013-03-14 | 2015-10-14 | 北京化工大学 | A kind of polyaspartic acid water-absorbing resin and preparation method thereof |
| CN109280396A (en) * | 2018-08-22 | 2019-01-29 | 泉州三欣新材料科技有限公司 | A kind of preparation method and application of high-biocompatibility hydrogel microsphere |
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