CN100412113C - Method for preparing interpolymer bionic membrane material of poly-asparagine and chitosan - Google Patents
Method for preparing interpolymer bionic membrane material of poly-asparagine and chitosan Download PDFInfo
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- CN100412113C CN100412113C CNB2006100153642A CN200610015364A CN100412113C CN 100412113 C CN100412113 C CN 100412113C CN B2006100153642 A CNB2006100153642 A CN B2006100153642A CN 200610015364 A CN200610015364 A CN 200610015364A CN 100412113 C CN100412113 C CN 100412113C
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Abstract
This invention discloses a method for preparing biomimic membrane material of polyasparagine and chitosan copolymer. The method comprises: preparing polyasparagine or its derivative with different side chains, copolymerizing and crosslinking with chitosan in an acidic medium to obtain environmentally friendly biomimic membrane material of polyasparagine and chitosan copolymer. The biomimic membrane material can be used for membrane separation, or as an environment-sensitive membrane material. The biomimic membrane material can be widely applied in such fields as pharmacy, food industry, printing and wastewater treatment.
Description
[technical field]
The present invention relates to the fine chemicals field of chemical engineering, particularly a kind of method for preparing poly-asparagine and chitosan copolymerization bionic membrane material.
[background technology]
Though the macromolecule member material of now having developed has better heat-resisting, chemical-resistant stability and mechanical property, cost of material is more expensive, and preparation technology is complicated, and has generally all used organic solvent in preparation process.These solvents are harmful mostly, and price is more expensive, and it is essential therefore to reclaim technology, has both increased production cost, can cause environmental pollution again.These disadvantages have seriously hindered applying of membrane technique.In addition, the biological degradability of existing macromolecule member material is relatively poor, can cause secondary pollution after abandoning.Do not meet requirement to ep-type material.Therefore be necessary the environmentally friendly mould material of further development of new, and preparation technology should adopt cleaning chemistry technology.
[summary of the invention]
The objective of the invention is in order to satisfy the needs of application, and provide a kind of method for preparing poly-asparagine and chitosan copolymerization bionic membrane material, the at first synthetic poly aspartic acid or derivatives thereof of this method with different side chains, the poly aspartic acid or derivatives thereof and the chitosan that will have different side chains then carry out the copolymerzation with cross-linking reaction in acidic medium, products therefrom-poly aspartic acid and derivative thereof and chitin copolymer have the character of class cell envelope, are a kind of environmentally friendly bionic membrane materials.
The present invention addresses the above problem a kind of method for preparing poly-asparagine and chitosan copolymerization bionic membrane material that discloses.This method may further comprise the steps:
(1) polysuccinimide and polyamines are reacted, at least the polysuccinimide that is contained the part open loop of an amido side chain (is that band (tool) has side chain on the synthetic polymer architecture, at least contain an amido on these side chains, down with), wherein polyamines with mol ratio by the polysuccinimide of succimide unit is: 0.10-1.0: 1;
Described polyamines can be one or both and the two or more mixing in diamines or triamine, the tetramine polyamines organic bases.Preferably use L-Methionin, hydrazine hydrate, quadrol, butanediamine, or except that amido, also have the polyamines of second kind of functional group, be beneficial to continue functionization.
(2) product that (1) is obtained is hydrolyzed, and is contained the poly aspartic acid of an amido side chain at least; Or aminolysis, or be hydrolyzed simultaneously and aminolysis, contained the poly-aspartate derivant aqueous solution of an amido side chain at least; Hydrolytic reagent with mol ratio by the polysuccinimide of succimide unit is: 0.10-1.0: 1, and the aminolysis agent with mol ratio by the polysuccinimide of succimide unit is: 0.10-1.0: 1;
Described hydrolytic reagent can be potassium hydroxide, sodium hydroxide, yellow soda ash, or their mixture; Described aminolysis agent can be aliphatics or aromatic amine, or has the aliphatics or the aromatic amine of second kind of functional group: methylamine, ethamine, thanomin, phenylethylamine, amphetamine, amino acid, or their mixture.
(3) preparation chitosan solution, chitosan is dissolved in the dilute acid soln, the concentration of dilute acid soln is massfraction 1-5%, the mass ratio of the diluted acid of chitosan and 1-5% is: 1: 1-1: 100, described dilute acid soln can be a hydrochloric acid, the dilute aqueous soln of nitric acid, phosphoric acid, sulfuric acid, acetic acid, or their mixture;
Above-mentioned (2) that (4) will obtain, (3) two solution by the poly aspartic acid or derivatives thereof of band amido side chain and the mass ratio of chitosan (promptly with the poly aspartic acid of the side chain of amido and the mass ratio of chitosan, or the poly-aspartate derivant of the side chain of band amido and the mass ratio of chitosan, be 1 down together): 99-99: 1 ratio mixes under 20-100 ℃ of temperature and violent stirring;
(5) mixed aqueous solution that obtains to (4) adds linking agent aliphatics or aromatic series dialdehyde, mixes under 20-100 ℃ of temperature and violent stirring; The mol ratio of amido is in aldehyde radical in aliphatics or the aromatic series dialdehyde and the polymkeric substance: 0.01-1.0: 1;
(6) solution that (5) are obtained carries out film forming by existing film, and then soaks 0.1-24 hour with alkaline aqueous solution, and wash with water to washing lotion for neutral, obtain the brown membranoid substance, be placed in the water and preserve.
The invention also discloses a kind of method for preparing poly-asparagine and chitosan copolymerization bionic membrane material.This method may further comprise the steps:
(1) polysuccinimide and polyamines, hydrolytic reagent and aminolysis agent are reacted simultaneously, at least the poly aspartic acid or derivatives thereof aqueous solution that is contained an amido side chain (is that band (tool) has side chain on the synthetic polymer architecture, at least contain an amido on these side chains, down together); The total mole number of polyamines, hydrolytic reagent and aminolysis agent and mol ratio: 1-5: 1 by the polysuccinimide of succimide unit.
Described polyamines can be one or both and the two or more mixing in diamines or triamine, the tetramine polyamines organic bases.Preferably use L-Methionin, hydrazine hydrate, quadrol, butanediamine, or except that amido, also have the polyamines of second kind of functional group, be beneficial to continue functionization; Described hydrolytic reagent can be potassium hydroxide, sodium hydroxide, yellow soda ash, or their mixture; Described aminolysis agent can be aliphatics or aromatic amine, or has the aliphatics or the aromatic amine of second kind of functional group: methylamine, ethamine, thanomin, phenylethylamine, amphetamine, amino acid, or their mixture;
(2) preparation chitosan solution, chitosan is dissolved in the dilute acid soln, the concentration of dilute acid soln is massfraction 1-5%, the mass ratio of the diluted acid of chitosan and 1-5% is: 1: 1-1: 100, used dilute acid soln can be a hydrochloric acid, the dilute aqueous soln of nitric acid, phosphoric acid, sulfuric acid, acetic acid, or their mixture;
Above-mentioned (1) that (3) will obtain, (2) two solution are 1 in the poly aspartic acid or derivatives thereof of band amido side chain and the mass ratio of chitosan: 99-99: 1 ratio, under violent stirring, mix;
(4) in the mixing solutions that (3) obtain, add linking agent aliphatics or aromatic series dialdehyde, under 20-100 ℃ of temperature and violent stirring, mix, make mixed aqueous solution; The mol ratio of amido is in aldehyde radical in aliphatics or the aromatic series dialdehyde and the polymkeric substance: 0.01-1.0: 1;
(5) solution that (4) are obtained carries out film forming by existing film, and then soaks 0.1-2.0 hour with alkaline aqueous solution, and wash with water to washing lotion for neutral, obtain the brown membranoid substance, be placed in the water and preserve.
The present invention prepares the prepared poly-asparagine of the method for poly-asparagine and chitosan copolymerization bionic membrane material and the purposes of chitosan copolymerization bionic membrane material, is to be used for membrane sepn and environment sensitive type mould material.
The invention has the beneficial effects as follows: the poly-asparagine and the bionical film of chitosan copolymerization of the present invention's design are a kind of environmentally friendly bionical films, in the structure of products therefrom, contain amido, hydroxyl, carboxyl and amide group simultaneously, have and adsorb multiple function inorganic, the organic heavy metal compound, have susceptibility some ion, pH etc.
The present invention design is environmentally friendly with poly aspartic acid and derivative thereof and this two class of chitosan, and the material with widespread use combines, exploitation has the novel material of the two function concurrently, contains amido, hydroxyl, carboxyl and amide group in the structure of products therefrom simultaneously, has multiple function.In addition because poly aspartic acid and derivative thereof are similar to peptidoglycan (containing amino acid, teichoic acid and the diamino acid) constitutional features of cell walls to chitin copolymer, therefore this multipolymer also can be considered bionical object height molecular film material, biodegradable, Environmental compatibility is good.And have more functional group on this class film, and be convenient to chemical modification, also be convenient to adjust the parent/hydrophobicity of mould material, to adapt to different needs.In addition, such mould material also can be by carrying out physically modified with inorganic materials or other macromolecular material blend, to improve the physicals of film.Can be used for membrane sepn, be used as environment sensitive type mould material etc., and be widely used in medicine industry, food engineering, printing and dyeing industry, fields such as sewage disposal.
[embodiment]
The method for preparing poly-asparagine and chitosan copolymerization bionic membrane material.May further comprise the steps:
(1) polysuccinimide and polyamines are reacted, the reaction solvent for use can be organic solvent, for example dimethyl formamide; The reaction solvent for use also can be an inorganic solvent, or the mixed solvent of the two, preferably using water medium, the polysuccinimide that is contained the part open loop of an amido side chain at least (is that band (tool) has side chain on the synthetic polymer architecture, at least contain an amido on these side chains, down together).The mol ratio of polyamines and polysuccinimide (by the succimide unit): 0.10-1.0: 1.Used polyamines can be one or both and the two or more mixing in diamines or triamine, the tetramine polyamines organic bases.Preferably use L-Methionin, hydrazine hydrate, quadrol, butanediamine etc., or have the polyamines (other amine that except that amido, also has the 3rd functional group) of second kind of functional group, be beneficial to continue functionization.Hybrid mode during the two reaction can be under agitation, the solution that will contain polyamines all or join in the solution of polysuccinimide in batches or progressively and go, perhaps all or join in the polyamines solution in batches or progressively and go, with polysuccinimide or its suspension pulpous state solution or both and add.
(2) product that (1) is obtained is hydrolyzed, and is contained the poly aspartic acid of an amido side chain at least; Or aminolysis, or be hydrolyzed simultaneously and aminolysis, contained the poly-aspartate derivant aqueous solution of an amido side chain at least; Hydrolytic reagent with mol ratio by the polysuccinimide of succimide unit is: 0.10-1.0: 1, and the aminolysis agent with mol ratio by the polysuccinimide of succimide unit is: 0.10-1.0: 1.Described hydrolytic reagent can be potassium hydroxide, sodium hydroxide, yellow soda ash, or their mixture; Described aminolysis agent can be aliphatics or aromatic amine, or has the aliphatics or the aromatic amine of second kind of functional group: methylamine, ethamine, thanomin, phenylethylamine, amphetamine, amino acid, or their mixture.
(3) the preparation chitosan solution is dissolved in chitosan in the dilute acid soln, and the concentration of dilute acid soln is massfraction 1-5%, and the mass ratio of the diluted acid of chitosan and 1-5% is: 1: 1-1: 100; Used dilute acid soln can be a hydrochloric acid, the dilute aqueous soln of nitric acid, phosphoric acid, sulfuric acid, acetic acid, or their mixture;
Above-mentioned (2) that (4) will obtain, (3) two solution (promptly have the poly aspartic acid of side chain of amido and the mass ratio of chitosan by the mass ratio of poly aspartic acid or derivatives thereof that has the amido side chain and chitosan, or have the poly-aspartate derivant of side chain of amido and a mass ratio of chitosan) be 1: 99-99: 1 ratio, under 20-100 ℃ of temperature and violent stirring, mix, its blending means is that the solution that (2) are obtained is whole, or in batches, or progressively be added drop-wise in the solution that (3) obtain and go, or the solution that (3) are obtained is whole, or in batches, or progressively be added drop-wise in the solution that (2) obtain and go, or two solution and adding;
(5) mixed aqueous solution that obtains to (4) adds linking agent aliphatics or aromatic series dialdehyde, mixes under 20-100 ℃ of temperature and violent stirring, and the mol ratio of amido is in aldehyde radical in aliphatics or the aromatic series dialdehyde and the polymkeric substance: 0.01-1.0: 1;
(6) solution that (5) are obtained carries out film forming by existing film, and then soaks 0.1-24 hour with alkaline aqueous solution, and wash with water to washing lotion for neutral, obtain the brown membranoid substance, be placed in the water and preserve.
The another kind of method for preparing poly-asparagine and chitosan copolymerization bionic membrane material of the present invention may further comprise the steps:
(1) polysuccinimide and polyamines, hydrolytic reagent and aminolysis agent are reacted simultaneously, at least the aqueous solution that is contained the poly aspartic acid or derivatives thereof of an amido side chain (is that band (tool) has side chain on the synthetic polymer architecture, at least contain an amido on these side chains, down together).The reaction solvent for use can be an organic solvent, and for example dimethyl formamide also can be an inorganic solvent, or the mixed solvent of the two, preferably uses water medium.The total mole number of polyamines, hydrolytic reagent and aminolysis agent with mol ratio by the polysuccinimide of succimide unit is: 1-5: 1.Used polyamines can be one or both and the two or more mixing in diamines or triamine, the tetramine polyamines organic bases.Preferably use L-Methionin, hydrazine hydrate, quadrol, butanediamine etc., or have the polyamines (other amine that except that amido, also has the 3rd functional group) of second kind of functional group, be beneficial to continue functionization.Described hydrolytic reagent can be potassium hydroxide, sodium hydroxide, yellow soda ash, or their mixture; Described aminolysis agent can be aliphatics or aromatic amine, or has the aliphatics or the aromatic amine of second kind of functional group: methylamine, ethamine, thanomin, phenylethylamine, amphetamine, amino acid, or their mixture.Hybrid mode during the two reaction can be under agitation, the solution that will contain polyamines, hydrolytic reagent and aminolysis agent all or join in polysuccinimide or its aaerosol solution in batches or progressively and go, perhaps all or join in the solution that contains polyamines, hydrolytic reagent and aminolysis agent in batches or progressively and go, with polysuccinimide or its aaerosol solution or both and add.
(2) the preparation chitosan solution is dissolved in chitosan in the dilute acid soln, and the concentration of dilute acid soln is massfraction 1-5%, and the mass ratio of the diluted acid of chitosan and 1-5% is: 1: 1-1: 100.Used dilute acid soln can be a hydrochloric acid, the dilute aqueous soln of nitric acid, phosphoric acid, sulfuric acid, acetic acid, or their mixture.
Above-mentioned (1) that (3) will obtain, (2) two solution (promptly have the poly aspartic acid of side chain of amido and the mass ratio of chitosan by the mass ratio of poly aspartic acid or derivatives thereof that has the amido side chain and chitosan, or have the poly-aspartate derivant of side chain of amido and a mass ratio of chitosan) be 1: 99-99: 1 ratio, under 20-100 ℃ of temperature and violent stirring, mix.Its blending means be solution that (1) is obtained all or be added drop-wise in the solution that (2) obtain in batches or progressively and go, or the solution that will (2) obtains is whole or be added drop-wise in the solution that (1) obtain in batches or progressively and go, or two solution and adding.
(4) in the mixing solutions that (3) obtain, add linking agent aliphatics or aromatic series dialdehyde, under 20-100 ℃ of temperature and violent stirring, mix, make mixed aqueous solution; The mol ratio of amido is in aldehyde radical in aliphatics or the aromatic series dialdehyde and the polymkeric substance: 0.01-1.0: 1.Aliphatics or aromatic series dialdehyde can be oxalic dialdehyde, mda, glutaraldehyde, terephthal aldehyde etc.
(5) solution that (4) are obtained carries out film forming by existing film, and then soaks 0.1-24 hour with alkaline aqueous solution, and wash with water to washing lotion for neutral, obtain the brown membranoid substance, be placed on Shui Zhongbao and deposit.Preserve.
The present invention can also be after above-mentioned two kinds of methods prepare poly aspartic acid and the derivative solution thereof that has the amido side chain and prepare chitosan solution, among one of both solution or both mixing solutionss, add film toughness toughener and/or pore-creating agent, carry out subsequent operations then; Toughener is one or both and the two or more mixing in soluble calcium salt, magnesium salts, zinc salt, nickel salt, mantoquita, molysite, the manganese salt; Toughener is 0.1-1 with mol ratio by the polysuccinimide of succimide unit: 1.Pore-creating agent can be a poly(oxyethylene glycol) 400,1000,2000 etc., and the per-cent that pore-creating agent accounts for total polymer mass is 0.01-10%.
The present invention can also be after poly aspartic acid and derivative and chitosan copolymer membrane that above-mentioned two kinds of methods prepare, and the existing reduction technique of utilization carries out restoring operation to film.
The present invention can be one or both and two or more mixing in diamines or triamine, the tetramine polyamines organic bases at polyamines described in above-mentioned two kinds of methods.Preferably use L-Methionin, hydrazine hydrate, quadrol, butanediamine, or except that amido, also have the polyamines of second kind of functional group, be beneficial to continue functionization; Described hydrolytic reagent can be potassium hydroxide, sodium hydroxide, yellow soda ash, or their mixture; Described aminolysis agent can be aliphatics or aromatic amine, or has the aliphatics or the aromatic amine of second kind of functional group: methylamine, ethamine, thanomin, phenylethylamine, amphetamine, amino acid, or their mixture.
The present invention prepares the method for poly-asparagine and chitosan copolymerization bionic membrane material, and numerous embodiments can be arranged:
Embodiment 1: with an organic solvent, the blooming intensity reinforcing agent does not prepare poly aspartic acid and derivative and chitosan copolymerization bionic membrane material, and this method comprises the following steps:
(1) preparation contains the poly aspartic acid and the derivative thereof of an amido side chain at least.Method is that polysuccinimide and polyamines or its hydrochloride are reacted in organic solvent (for example dimethyl formamide).The mol ratio of polyamines and polysuccinimide (by the succimide unit): 0.05-1.0: 1, temperature of reaction 20-100 ℃, the reaction times is 1-10 hour.After reaction finishes, add anhydrous methanol or dehydrated alcohol and separate out product, filter, filter cake is contained the polysuccinimide of the part open loop of an amido side chain at least at 40-60 ℃ of following vacuum-drying 4h.
The raw material polysuccinimide can be with traditional thermal polycondensation method, for example by aspartic acid in catalysis or do not have that high temperature polymerization obtains under the catalytic condition, can be with reference to US 5,057,597, US 5,221,733, US5,319,145 etc.; Or by Malaysia (acid) acid anhydride (being MALEIC ANHYDRIDE, cis-butenedioic anhydride), toxilic acid or fumaric acid and derivative thereof earlier with can discharge NH
3Nitrogenous compound reaction, the polymerization of dewatering then can be with reference to US 4,839,461, US 5,288,783, US 5,610,267 etc.
(2) polysuccinimide of the part open loop that contains an amido side chain at least that obtains in (1) is soluble in water, adding hydrolytic reagent or aminolysis agent is hydrolyzed or aminolysis, or be hydrolyzed simultaneously and aminolysis, contained poly-asparagine or its aqueous solution of an amido side chain at least.Hydrolytic reagent with mol ratio by the polysuccinimide of succimide unit is: 0.10-1.0: 1, the aminolysis agent with mol ratio by the polysuccinimide of succimide unit is: 0.10-1.0: 1, and the polysuccinimide of the part open loop of band amido side chain and the mass ratio of water are: 1: 99-99: 1;
(3) in addition chitosan is dissolved in the dilute acid soln.Described dilute acid soln can be a hydrochloric acid, the dilute aqueous soln of nitric acid, phosphoric acid, sulfuric acid, acetic acid, or their mixture; The concentration of dilute acid soln is 1-5% (massfraction).The mass ratio of the diluted acid of chitosan and 1-5% is: 1: 1-1: 100.
Above-mentioned (2) that (4) will obtain, (3) two solution are 1 in the poly aspartic acid of band amido side chain and the mass ratio of derivative and chitosan thereof: 99-99: 1 ratio, under 20-100 ℃ of temperature and violent stirring, mix.
(5) hybrid mode can be under violent stirring, (2) all or in batches or progressively are added drop-wise in the solution that (3) obtain go, or (3) all or in batches or progressively be added drop-wise in the solution that (2) obtain go, or two solution and adding.
(6) in above-mentioned solution, add the linking agent dialdehyde, under 20-100 ℃ of temperature and violent stirring, mix.The mol ratio of amido: 0.01-1.0 in aldehyde radical in the dialdehyde and the polymkeric substance: 1; Described dialdehyde can be oxalic dialdehyde, aliphatic dialdehydes or aromatic series dialdehyde such as mda, glutaraldehyde.
(7) solution that (6) are obtained carries out film forming by existing film, and then soaks 0.1-24 hour with alkaline aqueous solution, and wash with water to washing lotion for neutral, obtain the brown membranoid substance, be placed in the water and preserve.
Embodiment 2: with an organic solvent, the blooming intensity reinforcing agent does not prepare poly aspartic acid and derivative and chitosan copolymerization bionic membrane material, and this method comprises the following steps:
Basic step just adds reductive agent, under 25-80 ℃ with embodiment 1 in step (7) gained film, reacted 0.5-5 hour, used reductive agent can be sodium borohydride, POTASSIUM BOROHYDRIDE, or the mixture of the two, and the mol ratio of amido is in reductive agent and the polymkeric substance: 1-5: 1.
Embodiment 3: with an organic solvent, the blooming intensity reinforcing agent prepares poly aspartic acid and derivative and chitosan copolymerization bionic membrane material, and this method comprises the following steps:
Basic step just adds the film toughness toughener with embodiment 1 and example 2 in step (4) gained solution, carry out subsequent operations afterwards again.Used film toughness toughener preferentially selects CaCl
2Or Ca (NO
3)
2, CaSO
4, ZnCl
2, MgCl
2, MgSO
4In one or both and two or more mixing, or other soluble nickel salt, mantoquita, molysite, manganese salt etc.The mol ratio of film toughness toughener and polysuccinimide (by the succimide unit) is 0.1-1: 1.
Also can be at the solution (2) of the poly aspartic acid or derivatives thereof of band amido side chain, or add the film toughness toughener in the chitosan solution (3).Or several film toughness tougheners are joined in the chitosan solution (3), and other several film toughness tougheners are joined in the solution (2) of poly aspartic acid or derivatives thereof of band amido side chain.
Embodiment 4: with an organic solvent, the blooming intensity reinforcing agent does not prepare multi-hole type poly aspartic acid and derivative and chitosan copolymerization bionic membrane material, and this method comprises the following steps:
Basic step just adds pore-creating agent with embodiment 1 and example 2 in step (4) gained solution, carry out subsequent operations afterwards again.Pore-creating agent can be a poly(oxyethylene glycol) 400,1000,2000 etc., and the per-cent that pore-creating agent accounts for total polymer mass is 0.01-10%.
Embodiment 5: with an organic solvent, the blooming intensity reinforcing agent prepares multi-hole type poly aspartic acid and derivative and chitosan copolymerization bionic membrane material, and this method comprises the following steps:
Basic step just adds film toughness toughener and pore-creating agent simultaneously with embodiment 1 and example 2 in step (4) gained solution, carry out subsequent operations afterwards again.
Embodiment 6: use the water medium method, the blooming intensity reinforcing agent does not prepare poly aspartic acid and derivative and chitosan copolymerization bionic membrane material, and this method comprises the following steps:
(1) preparation contains the poly aspartic acid and the derivative aqueous solution thereof of an amido side chain at least.Method is that the polyamines that will contain two amidos at least is dissolved in the alkaliferous aqueous solution, and the mol ratio of polyamines and alkali is: 1: 9-9: 1; Then with gained solution by the mol ratio of polyamines with polysuccinimide (by the succimide unit): 0.05-1.0: 1 mixes, and temperature of reaction 20-100 ℃, the reaction times is 0.1-10 hour.
The hybrid mode of above-mentioned polyamines and polysuccinimide can be under agitation, with polyamines solution all or join in the suspension pulpous state liquid of polysuccinimide in water in batches or progressively and go, perhaps all or join in the polyamines solution in batches or progressively and go, with polysuccinimide or its suspension pulpous state aqueous solution or both and add.
(2) in the aqueous solution with the polysuccinimide of the part open loop that contains an amido side chain at least that obtains in (1), add hydrolytic reagent or aminolysis agent, proceed hydrolysis or aminolysis, or be hydrolyzed simultaneously and aminolysis, imide ring in polysuccinimide is opened all, is contained the poly aspartic acid and the derivative aqueous solution thereof of an amido side chain at least.Hydrolytic reagent with mol ratio by the polysuccinimide of succimide unit is: 0.10-1.0: 1, the aminolysis agent with mol ratio by the polysuccinimide of succimide unit is: 0.10-1.0: 1, and the polysuccinimide of the part open loop of band amido side chain and the mass ratio of water are: 1: 99-99: 1.
(3) pH of the solution that (1) is obtained with acid solution transfers to below 7, preferably pH2-6.
(4) in addition chitosan is dissolved in the dilute acid soln.Described dilute acid soln can be a hydrochloric acid, the dilute aqueous soln of nitric acid, phosphoric acid, sulfuric acid, acetic acid, or their mixture; The concentration of dilute acid soln is 1-5% (massfraction).The mass ratio of the diluted acid of chitosan and 1-5% is: 1: 1-1: 100.
(5) two solution that (3) (4) are obtained mix.The poly aspartic acid or derivatives thereof of band amido side chain and the mass ratio of chitosan are 1: 99-99: 1.
(6) hybrid mode can be under violent stirring, (3) all or in batches or progressively are added drop-wise in the solution that (4) obtain go, or (4) all or in batches or progressively be added drop-wise in the solution that (5) obtain go, or two solution and adding.
(7) in above-mentioned solution, add the linking agent dialdehyde, under 20-100 ℃ of temperature and violent stirring, mix.The mol ratio of amido: 0.01-1.0 in aldehyde radical in the dialdehyde and the polymkeric substance: 1; Make the aqueous solution of the two mixture.
(8) solution that (7) are obtained carries out film forming by existing film, and then soaks 0.1-1.0 hour with alkaline aqueous solution, and wash with water to washing lotion for neutral, obtain the brown membranoid substance, be placed in the water and preserve.
Embodiment 7: use the water medium method, the blooming intensity reinforcing agent does not prepare poly aspartic acid and derivative and chitosan copolymerization bionic membrane material, and this method comprises the following steps:
Basic step just adds reductive agent, under 25-80 ℃ with embodiment 6 in step (8) gained film, reacted 0.5-5 hour, used reductive agent can be sodium borohydride, POTASSIUM BOROHYDRIDE, or the mixture of the two, and the mol ratio of amido is in reductive agent and the polymkeric substance: 1-4: 1.
Embodiment 8: use the water medium method, the blooming intensity reinforcing agent prepares the method for poly aspartic acid and derivative and chitosan copolymerization bionic membrane material, and this method comprises the following steps:
Basic step just adds the film toughness toughener with embodiment 6 and example 7 in step (5) gained solution, carry out subsequent operations afterwards again.Used film toughness toughener preferentially selects CaCl2 or Ca (NO3) 2, CaSO4, ZnCl2, MgCl2, one or both among the MgSO4 and two or more mixing, or other soluble nickel salt, mantoquita, molysite, manganese salt etc.The mol ratio of film toughness toughener and polysuccinimide (by the succimide unit) is 0.1-1: 1.
Also can be at the solution (2) of the poly aspartic acid or derivatives thereof of being with the amido side chain, or adding film toughness toughener in the chitosan solution (4), or several film toughness tougheners are joined in the chitosan solution (4), and other several film toughness tougheners are joined in the solution (2) of the poly aspartic acid of band amido side chain and derivative thereof.
Embodiment 9: use the water medium method, the blooming intensity reinforcing agent does not prepare multi-hole type poly aspartic acid and derivative and chitosan copolymerization bionic membrane material, and this method comprises the following steps:
Basic step just adds pore-creating agent with embodiment 6 and example 7 in step (5) gained solution, carry out subsequent operations afterwards again.Pore-creating agent can be a poly(oxyethylene glycol) 400,1000,2000 etc., and the per-cent that pore-creating agent accounts for total polymer mass is 0.01-10%.
Embodiment 10: use the water medium method, the blooming intensity reinforcing agent prepares multi-hole type poly aspartic acid and derivative and chitosan copolymerization bionic membrane material, and this method comprises the following steps:
Basic step just adds film toughness toughener and pore-creating agent simultaneously with implementing embodiment 6 and example 7 in step (5) gained solution, carry out subsequent operations afterwards again.
Embodiment 11: use the water medium method, the blooming intensity reinforcing agent does not prepare poly aspartic acid and derivative and chitosan copolymerization bionic membrane material, and this method comprises the following steps:
(1) preparation contains the poly aspartic acid and the derivative aqueous solution thereof of an amido side chain at least.Method is that the aqueous solution of polyamines, hydrolytic reagent and/or the aminolysis agent that will contain two amidos at least mixes with polysuccinimide, temperature of reaction 20-100 ℃, reaction times is 0.5-10 hour, is contained poly aspartic acid and derivative or its aqueous solution of an amido side chain at least.The total mole number of polyamines, hydrolytic reagent and aminolysis agent with mol ratio by the polysuccinimide of succimide unit is: 1-5: used polyamines can be one or both and two or more the mixing in diamines or triamine, the tetramine polyamines organic bases.Preferably use L-Methionin, hydrazine hydrate, quadrol, butanediamine etc., or have the polyamines (other amine that except that amido, also has the 3rd functional group) of second kind of functional group, be beneficial to continue functionization.
Hybrid mode can be under agitation, the solution that will contain polyamines, hydrolytic reagent and/or aminolysis agent all or join in polysuccinimide or its aaerosol solution in batches or progressively and go, perhaps all or join in the solution that contains polyamines, hydrolytic reagent and/or aminolysis agent in batches or progressively and go, with polysuccinimide or its aaerosol solution or both and add.
(2) pH of the solution that (1) is obtained with acid solution transfers to below 7, preferably pH 2-6.
(3) the preparation chitosan solution is dissolved in chitosan in the dilute acid soln, and the concentration of dilute acid soln is massfraction 1-5%, and the mass ratio of the diluted acid of chitosan and 1-5% is: 1: 1-1: 100.Described dilute acid soln can be a hydrochloric acid, the dilute aqueous soln of nitric acid, phosphoric acid, sulfuric acid, acetic acid, or their mixture.
Above-mentioned (2) that (4) will obtain, (3) two solution are 1 in the poly aspartic acid or derivatives thereof of band amido side chain and the mass ratio of chitosan: 99-99: 1 ratio, under 20-100 ℃ of temperature and violent stirring, mix.Its blending means be solution that (2) are obtained all or be added drop-wise in the solution that (3) obtain in batches or progressively and go, or the solution that will (3) obtains is whole or be added drop-wise in the solution that (2) obtain in batches or progressively and go, or two solution and adding.
(5) in the mixing solutions that (4) obtain, add linking agent aliphatics or aromatic series dialdehyde, make mixed aqueous solution; The mol ratio of amido is in aldehyde radical in aliphatics or the aromatic series dialdehyde and the polymkeric substance: 0.01-1.0: 1.Aliphatics or aromatic series dialdehyde can be oxalic dialdehyde, mda, glutaraldehyde, terephthal aldehyde etc.
(6) solution that (5) are obtained carries out film forming by existing film, and then soaks 0.1-2.0 hour with alkaline aqueous solution, and wash with water to washing lotion for neutral, obtain the brown membranoid substance, be placed in the water and preserve.
Embodiment 12: use the water medium method, the blooming intensity reinforcing agent does not prepare poly aspartic acid and derivative and chitosan copolymerization bionic membrane material, and this method comprises the following steps:
Basic step just adds reductive agent with embodiment 11 in step (8) gained film, under 25-80 ℃, and reaction 0.5-5 hour, used reductive agent can be sodium borohydride, POTASSIUM BOROHYDRIDE, or the mixture of the two, and the mol ratio of amido is in reductive agent and the polymkeric substance: 1-4: 1.
Embodiment 13: use the water medium method, the blooming intensity reinforcing agent prepares the method for poly aspartic acid and derivative and chitosan copolymerization bionic membrane material, and this method comprises the following steps:
Basic step just adds the film toughness toughener with embodiment 11 and example 12 in step (4) gained solution, carry out subsequent operations afterwards again.Used film toughness toughener preferentially selects CaCl2 or Ca (NO3) 2, CaSO4, ZnCl2, MgCl2, one or both among the MgSO4 and two or more mixing, or other soluble nickel salt, mantoquita, molysite, manganese salt etc.The mol ratio of film toughness toughener and polysuccinimide (by the succimide unit) is 0.1-1: 1;
Also can be at the poly aspartic acid of band amido side chain and the solution (2) of derivative thereof, or adding film toughness toughener in the chitosan solution (3), or several film toughness tougheners are joined in the chitosan solution (3), and other several film toughness tougheners are joined in the solution (2) of the poly aspartic acid of band amido side chain and derivative thereof;
Embodiment 14: use the water medium method, the blooming intensity reinforcing agent does not prepare multi-hole type poly aspartic acid and derivative and chitosan copolymerization bionic membrane material, and this method comprises the following steps:
Basic step just adds pore-creating agent with embodiment 11 and example 12 in step (4) gained solution, carry out subsequent operations afterwards again.Pore-creating agent can be a poly(oxyethylene glycol) 400,1000,2000 etc., and the per-cent that pore-creating agent accounts for total polymer mass is 0.01-10%.
Embodiment 15: use the water medium method, the blooming intensity reinforcing agent prepares multi-hole type poly aspartic acid and derivative and chitosan copolymerization bionic membrane material, and this method comprises the following steps:
Basic step just adds film toughness toughener and pore-creating agent simultaneously with embodiment 11 or example 12 in step (4) gained solution, carry out subsequent operations afterwards again.
Embodiment 17: take by weighing the 0.16g quadrol, add the distilled water of 10mL, take by weighing the 0.66g methylamine again and add wherein, be placed on the magnetic stirrer then and stir, add the 1.0g weight-average molecular weight in the process of stirring and be about 10,000 polysuccinimide.Stop to stir behind the reaction 2.5h down at 28 ℃.Resulting product is filtered to remove insolubles wherein, obtain solution A.
Take by weighing the 0.1g chitosan in addition, add 10mL 1-5% hydrochloric acid to dissolving (solution B) fully.
Under violent stirring, the 1mL solution A is mixed with solution B.Add 0.3mL 50% glutaraldehyde down at 25 ℃ then.After mixing solution is poured on and allows its casting film-forming on the sheet glass.Leave standstill until film forming under 30 ℃.Wash with water afterwards to washing lotion and be neutral, then film is kept in the deionized water.
Embodiment 18: adding 10mL water and 1.0g weight-average molecular weight are about 15,000 polysuccinimide in flask, form suspension, add 0.45g Methionin and 0.25g sodium hydroxide then under violent stirring.80 ℃ were reacted about 3 hours down, continued to add 0.15g sodium hydroxide, restir 1 hour.With dilute nitric acid solution regulator solution pH5-6, filter, obtain solution A.
Take by weighing the 0.1g chitosan in addition, add 10mL 1-5% nitric acid to dissolving (solution B) fully.
Under violent stirring, the 2mL solution A is mixed with solution B.Add down 0.5mL 50% glutaraldehyde at 50 ℃ afterwards, after mixing solution is poured on and allows its casting film-forming on the plastic plate.40 ℃ of oven dry until film forming.Soaked 10 hours with 100mL, 2% aqueous sodium hydroxide solution afterwards, water is washed till washing lotion with film and is neutral, then film is kept in the deionized water.
Embodiment 19: add the distilled water of 0.18g quadrol, 0.45g ethamine and 8mL in flask, stir adding 1.0g polysuccinimide down.Stopped reaction behind reaction 1.5h under 60 ℃.With dilute nitric acid solution regulator solution pH 3-4, resulting solution is filtered to remove insolubles wherein, obtain solution A.
Take by weighing the 0.15g chitosan in addition, add 10mL 1-5% phosphoric acid to dissolving (solution B) fully.
Under violent stirring, the 5mL solution A is mixed with solution B.Add down 0.5mL 50% glutaraldehyde at 80 ℃ afterwards, after mixing solution is poured on and allows its casting film-forming on the plastic plate.Dry to film forming at 40 ℃.Soaked 24 hours with 100mL, 2% ammonia soln afterwards, water is washed till washing lotion with film and is neutral, then film is kept in the deionized water.
Embodiment 20: the 1.0g polysuccinimide is joined 15mL contain in the aqueous solution of 0.45g Methionin and 0.4g sodium hydroxide under violent stirring.Reacted about 3 hours down at 27 ℃.Add 0.2g CaCl afterwards
2It is fully dissolved, with dilute hydrochloric acid solution regulator solution pH 5-6 (solution A).
Take by weighing the 0.5g chitosan in addition, add 10mL 1-5% hydrochloric acid to dissolving (solution B) fully.
Under violent stirring, solution A is mixed with solution B.Add down the 0.4mL50% glutaraldehyde at 35 ℃ afterwards, after mixing solution is poured on and allows its casting film-forming on the plastic plate.Dry to film forming at 40 ℃.Soaked 12 hours with 100mL, 4% aqueous sodium carbonate afterwards, water is washed till washing lotion with film and is neutral, then film is kept in the deionized water.
Embodiment 21: in flask, add the distilled water of 0.15g quadrol, 0.5g thanomin and 0.1g sodium hydroxide and 10mL, 40 ℃ and stir under add the 1.0g polysuccinimide.Stopped reaction behind the reaction 1.5h.Resulting solution is filtered to remove insolubles wherein.Obtain solution A.
Take by weighing the 0.2g chitosan in addition, add 15mL 1-5% sulfuric acid to dissolving (solution B) fully.
Under violent stirring, the 4mL solution A is mixed with solution B.Add 0.5mL 50% glutaraldehyde afterwards, after mixing solution is poured on and allows its casting film-forming on the plastic plate.Dry to film forming at 50 ℃.Soaked 8 hours with 100mL, 2% ammonia soln afterwards, water is washed till washing lotion with film and is neutral, then film is kept in the deionized water.
Embodiment 22: add the distilled water of 0.15g quadrol, 1.2g amphetamine and 12mL in flask, stir adding 1.0g polysuccinimide down.Stopped reaction behind reaction 1.5h under 80 ℃.Resulting solution is filtered to remove insolubles wherein, obtain solution A.
Take by weighing the 0.2g chitosan in addition, add 15mL 1-5% acetic acid to dissolving (solution B) fully.
Under violent stirring, a part of solution A is mixed with solution B.Add 0.5mL 50% glutaraldehyde afterwards, after mixing solution is poured on and allows its casting film-forming on the plastic plate.Dry to film forming at 50 ℃.Water is washed till washing lotion with film and is neutral afterwards, then film is kept in the deionized water.
Embodiment 23: add 5mL water and 1.0g polysuccinimide in flask, form suspension, progressively add the aqueous solution that contains 0.4g Methionin and 0.3g sodium hydroxide then under violent stirring.27 ℃ were reacted about 6 hours down, continued to add 0.1g sodium hydroxide, restir 1 hour.Add 0.4g Ca (NO afterwards
3)
2, it is fully dissolved, with dilute hydrochloric acid solution regulator solution pH 5-6, filter (solution A).
Take by weighing the 0.1g chitosan in addition, the mixed solvent that adds 10mL 1-5% acetate and hydrochloride is to dissolving (solution B) fully.
Under violent stirring, the 2mL solution A is mixed with solution B.Add 0.2mL 50% glutaraldehyde afterwards, after mixing solution is poured on and allows its casting film-forming on the plastic plate.Dry to film forming at 50 ℃.Soaked 2 hours with 100mL, 2% aqueous sodium hydroxide solution afterwards, water is washed till washing lotion with film and is neutral.
(about 0.2g) puts into burning with prepared film, adds about 50mL water, places 45 ℃ of waters bath with thermostatic control, adds the 0.05g sodium borohydride in batches, and often vibration is burnt, and is incubated 2 hours.With deionized water film is washed till washing lotion then and is neutral, film is kept in the deionized water.
Embodiment 24: the NaOH aqueous solution and the 80% 1 hydrazine hydrate 0.13g that add 4mL 2mol/L in the burning of 100mL.Under violent stirring, add the 1.0g weight-average molecular weight and be about 20,000 polysuccinimide, reacted about 3 hours down at 25 ℃.Add 0.25g CaCl afterwards
2, it is fully dissolved, with dilute hydrochloric acid solution regulator solution pH 5-6.The filtering solution A that gets.
Take by weighing the 0.1g chitosan in addition, add 10mL 1-5% hydrochloric acid and be dipped to dissolving (solution B) fully.
The operation of back is with embodiment 23.
Embodiment 25: add 1g (0.01mol) weight-average molecular weight and be about 5 in the 100mL flask, the pulpous state suspension of 000 polysuccinimide in 3mL water, then in batches or the mixed solution of the NaOH aqueous solution of disposable adding 3mL2mol/L and 0.2g quadrol, reacted about 5 hours down at 25 ℃, add 0.25g CaCl afterwards
2, it is fully dissolved, with dilute hydrochloric acid solution regulator solution pH4-5.Filter solution A.
Take by weighing the 0.2g chitosan in addition, add 10mL 1-5% hydrochloric acid and be dipped to dissolving (solution B) fully.
The operation of back is with embodiment 18.
Embodiment 26: with 1.62g polysuccinimide, 15gN, dinethylformamide (DMF) is put into the 100mL flask, stirring makes the solid materials dissolving, with a little distilled water 0.5gL-Methionin and 0.15g NaOH are dissolved respectively in addition, mix then, mixed solution is under agitation joined in the above-mentioned polysuccinimide solution, and the solution that this is mixed is put into the microwave oven that reflux is housed then, heats 2min under power 120W.After being cooled to room temperature, adding the 50mL anhydrous methanol and separate out product.With about 50mL anhydrous methanol washing precipitate 3 times, filter, drying.
To go up the step products therefrom and put into burning, and add 10mL water and make it to become suspension, and drip the NaOH aqueous solution of 2mol/L then under room temperature and stirring, hierarchy of control pH=11～12 are until reaction system yellowly clarified liq (needing 1h approximately).After reaction finishes, add anhydrous methanol and separate out yellow product, filter, filter cake obtains having the poly aspartic acid of amido side chain at 40 ℃ of following vacuum-drying 4h.Take by weighing 0.5g and have the poly aspartic acid of amido side chain, make it dissolving, obtain solution A with 5mL water.
Take by weighing the 0.25g chitosan in addition, add 12mL 1-5% hydrochloric acid and be dipped to dissolving fully, obtain solution B.The gained solution B is progressively joined under violent stirring among the gained chitosan solution A.
Under violent stirring, a part of solution A is mixed with solution B.Add the aqueous solution contain the 0.2g mda afterwards, after mixing solution is poured on and allows its casting film-forming on the plastic plate.Dry to film forming at 50 ℃.Soaked 12 hours with 100mL, 2% aqueous sodium hydroxide solution afterwards, water is washed till washing lotion with film and is neutral, then film is kept in the deionized water.
Embodiment 27: with 0.8g polysuccinimide, 10gN, dinethylformamide (DMF) is put into 100mL and is burnt, stirring makes the solid materials dissolving, with a little distilled water 0.25gL-Methionin and 0.8g NaOH are dissolved respectively in addition, mix then, to join in the above-mentioned polysuccinimide solution under the mixed solution stirring, the solution that this is mixed at room temperature stirs 10h then, adds the 30mL anhydrous methanol afterwards and separates out product.With about 20mL anhydrous methanol washing precipitate 3 times, filter, drying.
To go up the step products therefrom and put into burning, add 10mL water and make it to become suspension, under room temperature and stirring, drip the NaOH aqueous solution of 2mol/L then, hierarchy of control pH=11～12, until reaction system yellowly clarified liq, obtain having the poly aspartic acid water solution A of amido side chain.
Take by weighing the 0.2g chitosan in addition, add 10mL 1-5% hydrochloric acid and be dipped to dissolving fully, obtain solution B.
The operation of back is with embodiment 23.
Embodiment 28: take by weighing the 0.1g chitosan, with 10mL 1-5% nitric acid: the mixed acid solution of 1-5% acetic acid (volume ratio)=3: 1 (v/v) makes it to dissolve fully (solution A).Take by weighing 0.8g in addition and have the poly aspartic acid of amido side chain, make it dissolving, with dilute hydrochloric acid solution regulator solution pH 3-4 (solution B) with 5mL water.
Under violent stirring, solution A is joined in the solution B.Afterwards, add 0.2mL massfraction 50% glutaraldehyde water solution, after mixing solution is poured on and allows its casting film-forming on the sheet glass.Dry to film forming at 50 ℃.Soaked 20 hours with 100mL, 2% aqueous sodium hydroxide solution afterwards, water is washed till washing lotion with film and is neutral, then film is kept in the deionized water.
Embodiment 29: operation steps just adds film toughness toughener 0.2g FeCl earlier substantially with embodiment 26,27,28 before adding glutaraldehyde
2, and then carry out the operation of back.
Embodiment 30: operation steps is after chitosan solution is added the 0.1g neutralized verdigris, to mix with solution B, and then carry out the operation of back substantially with embodiment 18.、
Embodiment 31: the 0.66g methylamine is changed to 0.6g and 0.2g sodium hydroxide, and all the other are operated with embodiment 17.
Embodiment 32: operation steps just adds film toughness toughener 0.2g FeCl earlier substantially with embodiment 21 before adding glutaraldehyde
3, and then carry out the operation of back.
Claims (10)
1. method for preparing poly-asparagine and chitosan copolymerization bionic membrane material is characterized in that may further comprise the steps:
(1) polysuccinimide and polyamines are reacted, contained the polysuccinimide of the part open loop of an amido side chain at least, wherein polyamines with mol ratio by the polysuccinimide of succimide unit is: 0.10-0.50: 1;
(2) product that (1) is obtained is hydrolyzed, and is contained the poly aspartic acid of an amido side chain at least; Or aminolysis, or be hydrolyzed simultaneously and aminolysis, contained the poly-aspartate derivant aqueous solution of an amido side chain at least; Hydrolytic reagent with mol ratio by the polysuccinimide of succimide unit is: 0.10-1.0: 1, and the aminolysis agent with mol ratio by the polysuccinimide of succimide unit is: 0.10-1.0: 1;
(3) the preparation chitosan solution is dissolved in chitosan in the dilute acid soln, and the concentration of dilute acid soln is massfraction 1-5%, and the mass ratio of the diluted acid of chitosan and 1-5% is: 1: 1-1: 100;
Above-mentioned (2) that (4) will obtain, (3) two solution are 1 in the poly aspartic acid or derivatives thereof of band amido side chain and the mass ratio of chitosan: 99-99: 1 ratio mixes under 20-100 ℃ of temperature and violent stirring;
(5) mixed aqueous solution that obtains to (4) adds linking agent aliphatics or aromatic series dialdehyde, mixes under 20-100 ℃ of temperature and violent stirring; The mol ratio of amido is in aldehyde radical in aliphatics or the aromatic series dialdehyde and the polymkeric substance: 0.01-1.0: 1;
(6) solution that (5) are obtained carries out film forming by existing film, and then soaks 0.1-24 hour with alkaline aqueous solution, and wash with water to washing lotion for neutral, obtain the brown membranoid substance, be placed in the water and preserve.
2. in accordance with the method for claim 1, it is characterized in that said step (4) or (5) after, add pore-creating agent, with the preparation porous-film.
3. in accordance with the method for claim 1, it is characterized in that said step (2) prepares after the aqueous solution of the poly aspartic acid or derivatives thereof that has the amido side chain and (3) prepare chitosan solution, adds the film toughness toughener among one of both solution or both mixing solutionss; Toughener is one or both and the two or more mixing in soluble calcium salt, magnesium salts, zinc salt, nickel salt, mantoquita, molysite, the manganese salt; Toughener is 0.1-1 with mol ratio by the polysuccinimide of succimide unit: 1.
4. in accordance with the method for claim 1, it is characterized in that said step (6) prepares after poly-asparagine and the chitosan copolymer membrane, add reductive agent film is carried out restoring operation.
5. according to claim 1 or 2 or 3 or 4 described methods, it is characterized in that polyamines described in the said step (1) is one or both and the two or more mixing in diamines or triamine, the tetramine polyamines organic bases.
6. according to claim 1 or 2 or 3 or 4 described methods, it is characterized in that the described hydrolytic reagent of said step (2) is potassium hydroxide, sodium hydroxide, yellow soda ash, or their mixture.
7. according to claim 1 or 2 or 3 or 4 described methods, it is characterized in that the described aminolysis agent of said step (2) is: methylamine, ethamine, thanomin, phenylethylamine, amphetamine, amino acid, or their mixture.
8. according to claim 1 or 2 or 3 or 4 described methods, it is characterized in that said diluted acid is the dilute aqueous soln of hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, acetic acid, or their mixing solutions.
9. according to claim 1 or 2 or 3 or 4 described methods, it is characterized in that said aliphatics or aromatic series dialdehyde be oxalic dialdehyde, mda, glutaraldehyde, terephthal aldehyde.
10. method for preparing poly-asparagine and chitosan copolymerization bionic membrane material is characterized in that may further comprise the steps:
(1) polysuccinimide and polyamines, hydrolytic reagent and aminolysis agent are reacted simultaneously, contained the poly aspartic acid or derivatives thereof aqueous solution of an amido side chain at least; The total mole number of polyamines, hydrolytic reagent and aminolysis agent with mol ratio by the polysuccinimide of succimide unit is: 1-5: 1.
(2) the preparation chitosan solution is dissolved in chitosan in the dilute acid soln, and the concentration of dilute acid soln is massfraction 1-5%, and the mass ratio of the diluted acid of chitosan and 1-5% is: 1: 1-1: 100;
Above-mentioned (1) that (3) will obtain, (2) two solution are 1 in the poly aspartic acid or derivatives thereof of band amido side chain and the mass ratio of chitosan: 99-99: 1 ratio, under 20-100 ℃ of temperature and violent stirring, mix;
(4) in the mixing solutions that (3) obtain, add linking agent aliphatics or aromatic series dialdehyde, under 20-100 ℃ of temperature and violent stirring, mix, make mixed aqueous solution; The mol ratio of amido is in aldehyde radical in aliphatics or the aromatic series dialdehyde and the polymkeric substance: 0.01-1.0: 1;
(5) solution that (4) are obtained carries out film forming by existing film, and then soaks 0.1-24 hour with alkaline aqueous solution, and wash with water to washing lotion for neutral, obtain the brown membranoid substance, be placed in the water and preserve.
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| CN103937040B (en) * | 2014-04-14 | 2016-03-16 | 天津理工大学 | A kind of preparation method with the biomimetic material of efficient removal heavy metal function |
| CN104231267B (en) * | 2014-09-05 | 2017-05-31 | 武汉理工大学 | A kind of preparation of modified polyaspartic acid scale inhibitor and its application process |
| CN104311850B (en) * | 2014-10-14 | 2017-07-11 | 江苏大学 | A kind of bionics method for preparation of texturing Kapton |
| CN109433016A (en) * | 2018-10-04 | 2019-03-08 | 南京航空航天大学溧水仿生产业研究院有限公司 | The preparation method of bionical water-oil separationg film |
| CN112717732A (en) * | 2020-12-29 | 2021-04-30 | 太原理工大学 | Amino-rich doped polysuccinimide semi-interpenetrating network blending membrane and preparation method and application thereof |
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