CN101353478B

CN101353478B - Preparation of biomimetic material

Info

Publication number: CN101353478B
Application number: CN2008100541793A
Authority: CN
Inventors: 孙波; 王博威; 方叶明; 安钢
Original assignee: Tianjin University of Technology
Current assignee: Tianjin University of Technology
Priority date: 2008-08-19
Filing date: 2008-08-19
Publication date: 2010-09-22
Anticipated expiration: 2028-08-19
Also published as: CN101353478A

Abstract

The invention discloses a preparation method of a biomimetic material, in particular relates to a method for preparing the composition material of poly-aspartic acid or the derivatives, chitosan, lecithin and calcium-phosphate compound. The method first compounds poly-aspartic acid or the derivatives with different side chains, and then makes the poly-aspartic acid or the derivatives with different side chains, chitosan, lecithin, calciferous solution and crosslinking agent mix, react and settle down under a certain temperature and pH value. The obtained product has the properties of biomimetic membrane materials and is an environment-friendly biomimetic material. The material has the function of absorbing heavy metals and some organics, can be used for removing heavy metals, chlorinated hydrocarbon, organic pigment and dye, and can be widely applied to pharmaceutical industry, food industry, printing and dyeing industry, waste water treatment and other fields.

Description

A kind of preparation method of biomimetic material

[technical field]

The present invention relates to the fine chemicals field of chemical engineering, is a kind of preparation method of biomimetic material, particularly relates to the method for the matrix material of preparation poly aspartic acid or derivatives thereof, chitosan, Yelkin TTS and calcium phosphorous compound.

[background technology]

In the former work, we had once developed the copolymeric material of poly aspartic acid or derivatives thereof and chitosan (referring to ZL200510015063.5 and ZL200610015364.2.But these exist the disadvantage that ratio of expansion is higher in water, physical strength is relatively poor by the copolymeric material of poly aspartic acid or derivatives thereof and chitosan merely.

[summary of the invention]

The objective of the invention is in order to satisfy the needs of application, and provide a kind of preparation method of biomimetic material, the method that promptly prepares the matrix material of poly aspartic acid or derivatives thereof, chitosan, Yelkin TTS and calcium phosphorous compound, the at first synthetic poly aspartic acid or derivatives thereof of this method with different side chains, will have then different side chains poly aspartic acid or derivatives thereof, chitosan, Yelkin TTS, contain calcium solution and mix at a certain temperature, react, precipitate.The gained material has imitative biomembranous character, is a kind of environmentally friendly biomimetic material,

The present invention discloses the method for the matrix material of this biomimetic material poly aspartic acid or derivatives thereof, chitosan, Yelkin TTS and calcium phosphorous compound for addressing the above problem.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 to be with/to have side chain on the synthetic polymer architecture, at least contain an amido on these side chains, back (descend) with), polyamines and be: 0.01-0.50: 1 wherein by the mol ratio of the polysuccinimide of succimide unit;

(2) product that step (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 (be to be with/to have side chain on the synthetic polymer architecture, contain an amido on these side chains at least, back (descending) is together) 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 solution is massfraction 1-10%, and the mass ratio of the diluted acid of chitosan and 1-10% is: 1: 1-1: 200;

(4) two solution that above-mentioned steps (2), (3) are obtained, and linking agent aliphatics or aromatic series dialdehyde mix under 20-100 ℃ of temperature and violent stirring; The poly aspartic acid or derivatives thereof of band amido side chain and the mass ratio of chitosan are 1: 99-99: 1, 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;

(5) soluble in water the making of calcium containing compound contained calcium solution, the mol ratio of the mineral acid in described calcium and the dilute acid soln is 0.1～10: 1;

(6) Yelkin TTS is dissolved in the aqueous ethanolic solution of capacity, forms milky solution, the mass ratio of Yelkin TTS and chitosan is 0.01～1: 1;

(7) three solution that above-mentioned steps (4), (5), (6) are obtained, and alkaline solution mix under the violent stirring at 20-45 ℃, control final pH 6～10;

(8) mixture that above-mentioned steps (7) is obtained descended still aging 12-72 hour at 20-45 ℃, separated then, washed, and 35～60 ℃ of further dry ageings, resulting throw out is a matrix material; Perhaps:

Step (8) is that mixture that above-mentioned steps (7) is obtained is after under 20～45 ℃ of temperature still aging 12～72 hours, be lower than 60 ℃ of following desolventizings, under 35～60 ℃ of vacuum, continue dry ageing then, the last thorough washing of resulting product is to neutral, again 60 ℃ of following vacuum-dryings to constant weight, promptly obtain matrix material; Perhaps:

Step (8) is that mixture that above-mentioned steps (7) is obtained is directly at 30～60 ℃ of following desolventizings, under 35～60 ℃ of vacuum, continue dry ageing then, the last thorough washing of resulting product is to neutral, again 60 ℃ of following vacuum-dryings to constant weight, promptly obtain matrix material.

The invention also discloses the preparation method of another kind of poly aspartic acid or derivatives thereof, chitosan, Yelkin TTS and calcium phosphorous compound matrix material.This method may further comprise the steps:

(1) polysuccinimide and polyamines, alkaline hydrolysis agent and aminolysis agent are reacted simultaneously, contained the poly aspartic acid or derivatives thereof aqueous solution of an amido side chain at least; Polyamines with mol ratio by the polysuccinimide of succimide unit is: 0.01～1.0: 1; The total mole number of polyamines, hydrolytic reagent and aminolysis agent with mol ratio by the polysuccinimide of succimide unit is: 0.1～5: 1;

(2) the preparation chitosan solution is dissolved in chitosan in the dilute acid soln, and the concentration of dilute acid soln is massfraction 1-10%, and the mass ratio of the diluted acid of chitosan and 1-10% is: 1: 1-1: 200;

(3) two solution that above-mentioned steps (1), (2) are obtained, and linking agent aliphatics or aromatic series dialdehyde mix under 20-100 ℃ of temperature and violent stirring, make mixed aqueous solution; By the poly aspartic acid or derivatives thereof of band amido side chain and the mass ratio of chitosan is 1: 99-99: 1, 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;

(4) soluble in water the making of calcium containing compound contained calcium solution, the mol ratio of the mineral acid in described calcium and the dilute acid soln is 0.1～10: 1;

(5) Yelkin TTS is dissolved in the aqueous ethanolic solution of capacity, forms milky solution, the mass ratio of Yelkin TTS and chitosan is 0.01～1: 1;

(6) three kinds of solution that above-mentioned steps (3), (4), (5) are obtained, and alkaline solution mix under the violent stirring at 20-45 ℃, control final pH 6～10;

(7) mixture that above-mentioned steps (6) is obtained 30～45 ℃ still aging 12～72 hours down, separate then, wash, 35～60 ℃ of further dry ageings, resulting throw out is a matrix material; Perhaps:

Step (7) is that mixture that above-mentioned steps (6) is obtained is after under 20～45 ℃ of temperature still aging 12～72 hours, be lower than 60 ℃ of following desolventizings, under 35～60 ℃ of vacuum, continue dry ageing then, the last thorough washing of resulting product is to neutral, again 60 ℃ of following vacuum-dryings to constant weight, promptly obtain matrix material; Perhaps:

Step (7) is that mixture that above-mentioned steps (6) is obtained is directly at 30～60 ℃ of following desolventizings, under 35～60 ℃ of vacuum, continue dry ageing then, the last thorough washing of resulting product is to neutral, again 60 ℃ of following vacuum-dryings to constant weight, promptly obtain matrix material.

Poly aspartic acid or derivatives thereof, chitosan, Yelkin TTS and the calcium phosphorous compound matrix material of the present invention's preparation can be used for removing heavy metal compound.

The present invention mixes inorganic materials wherein, and the matrix material of preparation poly aspartic acid or derivatives thereof, chitosan and inorganic materials is to improve the physical strength of material.Consider that simultaneously lipid is to constitute biomembranous important substance, thereby mix Yelkin TTS, make the more approaching biomembranous composition of composition of institute's synthetic materials.And the adding of Yelkin TTS helps to improve flexibility, the high resistance of institute's synthetic materials, and to the not permeability of polar molecule.Yelkin TTS is a kind of tensio-active agent in addition, mix tensio-active agent after, help to change the hydrophilic of material.Whole preparation process adopts cleaning chemistry technology, does not use the poisonous and harmful solvent, and the gained material is a biomimetic material, has excellent biological compatibility, can not cause secondary pollution after abandoning.Meet the requirement of ep-type material.

The matrix material of 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, and having the two function concurrently is a kind of environmentally friendly biomimetic material.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.

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 the biomimetic polymer material, biodegradable, Environmental compatibility is good.And have more functional group on this class material, and be convenient to chemical modification, also be convenient to adjust the parent/hydrophobicity of material, to adapt to different needs.In addition, by further improving the physical strength of material with the blend of inorganic materials.Can be used for removing heavy metal compound, and be widely used in medicine industry, food engineering, printing and dyeing industry, fields such as sewage disposal.

[description of drawings]

Fig. 1 is the infrared spectrogram of product;

Fig. 2 is the XRD figure spectrum of product.

[embodiment]

The method for preparing biomimetic material poly aspartic acid or derivatives thereof, chitosan, Yelkin TTS and calcium phosphorous compound matrix 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): 0.01-1.0: 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: as 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 1-10%, and the mass ratio of the diluted acid of chitosan and 1-10% is: 1: 1-1: 200; 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, and linking agent aliphatics or aromatic series dialdehyde mix under 20-100 ℃ of temperature and violent stirring.Have the poly aspartic acid or derivatives thereof of amido side chain and the mass ratio of chitosan and (promptly have the poly aspartic acid of side chain of amido and the mass ratio of chitosan, or have the poly-aspartate derivant of side chain of amido and a mass ratio of chitosan) be 1: 99-99: 1, 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.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, add linking agent then; Or the solution that (3) are obtained all or be added drop-wise in the solution that (2) obtain in batches or progressively and go, and adds linking agent then; Or after adding linking agent in the solution (2), mix with solution (3) again; Or after adding linking agent in (3) solution, mix with (2) solution again; Two solution also add, and add linking agent simultaneously.

(5) soluble in water the making of calcium containing compound contained calcium solution.

Described calcium containing compound is a calcium hydroxide, calcium chloride, nitrocalcite, calcium oxide.The mol ratio of the mineral acid in calcium and the above-mentioned dilute acid soln is 0.1～10: 1.

(6) Yelkin TTS is dissolved in the aqueous ethanolic solution of capacity, forms milky solution, the mass ratio of Yelkin TTS and chitosan is 0.01～1: 1.

Above-mentioned (4), (5) that (7) will obtain, (6) three solution, and alkaline solution mixes control final pH 6～10 under the violent stirring at certain temperature (20-45 ℃).Reasonable temperature is 30～40 ℃, pH value 7～8.Its blending means is to mix with the solution that (6) obtain after the solution that above-mentioned steps (4), (5) obtain is mixed again, and adds alkaline solution then; Or the solution that (5), (6) are obtained mixes with the solution that (4) obtain after mixing again, adds alkaline solution then; Or the solution that (4), (6) are obtained mixes with the solution that (5) obtain after mixing again, adds alkaline solution then; Or three kinds of solution that step (4), (5), (6) are obtained and adding, add alkaline solution simultaneously.

The mixture of above-mentioned (7) that (8) will obtain left standstill 12～72 hours under certain temperature (20～45 ℃), separated then, washs, promptly got matrix material at 35～60 ℃ of resulting throw outs of further dry ageing.

Step (8) can also be that the mixture of above-mentioned (7) that will obtain is in certain temperature (20～45 ℃) down after still aging 12～72 hours, be lower than 60 ℃ of following desolventizings, under 35～60 ℃ of vacuum, continue dry ageing then, the last thorough washing of resulting product is to neutral, to constant weight, promptly get required matrix material 60 ℃ of following vacuum-dryings.

Perhaps, step (8) can also be that the mixture of above-mentioned (7) that will obtain directly is being lower than 60 ℃ of following desolventizings, continues dry ageing then under 35～60 ℃ of vacuum, and the last thorough washing of resulting product is to neutral, to constant weight, promptly get required matrix material 60 ℃ of following vacuum-dryings.

The another kind of method for preparing poly aspartic acid or derivatives thereof, chitosan, Yelkin TTS and calcium phosphorous compound matrix 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.Hydrolytic reagent with mol ratio by the polysuccinimide of succimide unit is: 0.10-1.0: 1, and the total mole number of polyamines, hydrolytic reagent and aminolysis agent with mol ratio by the polysuccinimide of succimide unit is: 0.1～5: 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 1-10%, and the mass ratio of the diluted acid of chitosan and 1-10% is: 1: 1-1: 200.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, and linking agent aliphatics or aromatic series dialdehyde, (promptly have the poly aspartic acid of side chain of amido and the mass ratio of chitosan by the poly aspartic acid or derivatives thereof of band amido side chain and the mass ratio of chitosan, or have the poly-aspartate derivant of side chain of amido and a mass ratio of chitosan) be 1: 99-99: 1, the mol ratio of amido is in aldehyde radical in aliphatics or the aromatic series dialdehyde (aliphatics or aromatic series dialdehyde are oxalic dialdehyde, mda, glutaraldehyde, terephthal aldehyde etc.) and the polymkeric substance: 0.01-1.0: 1; Ratio, under 20-100 ℃ of temperature and violent stirring, mix, make mixed aqueous solution; 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, add linking agent then; Or the solution that (2) are obtained all or be added drop-wise in the solution that (1) obtain in batches or progressively and go, and adds linking agent then; Or after adding linking agent in the solution (1), mix with solution (2) again; Or after adding linking agent in (2) solution, mix with (1) solution again; Or two solution and adding, add linking agent simultaneously.

(4) soluble in water the making of calcium containing compound contained calcium solution.

(5) Yelkin TTS is dissolved in the aqueous ethanolic solution of capacity, forms milky solution, the mass ratio of Yelkin TTS and chitosan is 0.01～1: 1.

Above-mentioned (3), (4) that (6) will obtain, (5) three solution, and alkaline solution mixes control final pH 6～10 under the violent stirring at 20-45 ℃; Its blending means is to mix with the solution that (5) obtain after the solution that above-mentioned steps (3), (4) obtain is mixed again, and adds alkaline solution then; Or the solution that (4), (5) are obtained mixes with the solution that (3) obtain after mixing again, adds alkaline solution then; Or the solution that (3), (5) are obtained mixes with the solution that (4) obtain after mixing again, adds alkaline solution then.

The mixture of above-mentioned (6) that (7) will obtain descended still aging 12～72 hours in certain temperature (30～45 ℃), separated then, washs, promptly got matrix material at 35～60 ℃ of resulting throw outs of further dry ageing.

Step (7) can also be that the mixture of above-mentioned (6) that will obtain is in certain temperature (20～45 ℃) down after still aging 12～72 hours, be lower than 60 ℃ of following desolventizings, under 35～60 ℃ of vacuum, continue dry ageing then, the last thorough washing of resulting product is to neutral, to constant weight, promptly get required matrix material 60 ℃ of following vacuum-dryings.

Perhaps, step (7) can also be that the mixture of above-mentioned (6) that will obtain directly is being lower than 60 ℃ of following desolventizings, continues dry ageing then under 35～60 ℃ of vacuum, and the last thorough washing of resulting product is to neutral, to constant weight, promptly get required matrix material 60 ℃ of following vacuum-dryings.

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 aspartic acid or derivatives thereof, chitosan, Yelkin TTS and calcium phosphorous compound matrix material, and numerous embodiments can be arranged:

Embodiment 1: with an organic solvent legal system contains the poly aspartic acid and the derivative thereof of an amido side chain to the utmost less in the process of preparation poly aspartic acid or derivatives thereof, chitosan, Yelkin TTS and calcium phosphorous compound matrix 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, US 5,319,145 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, US5,288,783, US5,610,267 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 aspartic acid or derivatives thereof 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 1-10% (massfraction).The mass ratio of the diluted acid of chitosan and 1-10% is: 1: 1-1: 200.

Above-mentioned (2) that (4) will obtain, (3) two solution, and linking agent aliphatics or aromatic series dialdehyde mix under 20-100 ℃ of temperature and violent stirring.Have the poly aspartic acid or derivatives thereof of amido side chain and the mass ratio of chitosan and (promptly have the poly aspartic acid of side chain of amido and the mass ratio of chitosan, or have the poly-aspartate derivant of side chain of amido and a mass ratio of chitosan) be 1: 99-99: 1, 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.Described dialdehyde can be oxalic dialdehyde, aliphatic dialdehydes or aromatic series dialdehyde such as mda, glutaraldehyde.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, add linking agent then; Or the solution that (3) are obtained all or be added drop-wise in the solution that (2) obtain in batches or progressively and go, and adds linking agent then; Or after adding linking agent in the solution (2), mix with solution (3) again; Or after adding linking agent in (3) solution, mix with (2) solution again; Or two solution and adding, add linking agent simultaneously.

Above-mentioned (4), (5) that (7) will obtain, (6) three solution, and alkaline solution mixes control final pH 6～10 under the violent stirring at 20-45 ℃; Its blending means is to mix with the solution that (6) obtain after the solution that above-mentioned steps (4), (5) obtain is mixed again, and adds alkaline solution then; Or the solution that (5), (6) are obtained mixes with the solution that (4) obtain after mixing again, adds alkaline solution then; Or the solution that (4), (6) are obtained mixes with the solution that (5) obtain after mixing again, adds alkaline solution then.

The mixture of above-mentioned (7) that (8) will obtain descended still aging 12～72 hours in certain temperature (20～45 ℃), separated then, washs, promptly got matrix material at 35～60 ℃ of resulting throw outs of further dry ageing.

Embodiment 2: using in the process of preparation poly aspartic acid or derivatives thereof, chitosan, Yelkin TTS and calcium phosphorous compound matrix material has the water medium legal system to contain the poly aspartic acid and the derivative thereof of an amido side chain to the utmost less, 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 1-10% (massfraction).The mass ratio of the diluted acid of chitosan and 1-10% is: 1: 1-1: 200.

Above-mentioned (3) that (5) will obtain, (4) two solution, and linking agent aliphatics or aromatic series dialdehyde mix under 20-100 ℃ of temperature and violent stirring.Have the poly aspartic acid or derivatives thereof of amido side chain and the mass ratio of chitosan and (promptly have the poly aspartic acid of side chain of amido and the mass ratio of chitosan, or have the poly-aspartate derivant of side chain of amido and a mass ratio of chitosan) be 1: 99-99: 1, 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.Described dialdehyde can be oxalic dialdehyde, aliphatic dialdehydes or aromatic series dialdehyde such as mda, glutaraldehyde.Its blending means be solution that (3) are obtained all or be added drop-wise in the solution that (4) obtain in batches or progressively and go, add linking agent then; Or the solution that (4) are obtained all or be added drop-wise in the solution that (3) obtain in batches or progressively and go, and adds linking agent then; Or after adding linking agent in the solution (3), mix with solution (4) again; Or after adding linking agent in (4) solution, mix with (3) solution again; Or two solution and adding, add linking agent simultaneously.

(6) soluble in water the making of calcium containing compound contained calcium solution.

(7) Yelkin TTS is dissolved in the aqueous ethanolic solution of capacity, forms milky solution, the mass ratio of Yelkin TTS and chitosan is 0.01～1: 1.

Above-mentioned (5), (6) that (8) will obtain, (7) three solution, and alkaline solution mixes control final pH 6～10 under the violent stirring at 20-45 ℃; Its blending means is to mix with the solution that (7) obtain after the solution that above-mentioned steps (5), (6) obtain is mixed again, and adds alkaline solution then; Or the solution that (5), (7) are obtained mixes with the solution that (6) obtain after mixing again, adds alkaline solution then; Or the solution that (6), (7) are obtained mixes with the solution that (5) obtain after mixing again, adds alkaline solution then.

The mixture of above-mentioned (8) that (9) will obtain descended still aging 12～72 hours in certain temperature (20～45 ℃), separated then, washs, promptly got matrix material at 35～60 ℃ of resulting throw outs of further dry ageing.

Embodiment 3: using in the process of preparation poly aspartic acid or derivatives thereof, chitosan, Yelkin TTS and calcium phosphorous compound matrix material has the water medium legal system to contain the poly aspartic acid and the derivative thereof of an amido side chain to the utmost less, 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: 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 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 pH2-6.

(3) the preparation chitosan solution is dissolved in chitosan in the dilute acid soln, and the concentration of dilute acid soln is massfraction 1-10%, and the mass ratio of the diluted acid of chitosan and 1-10% is: 1: 1-1: 200.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, and linking agent aliphatics or aromatic series dialdehyde mix under 20-100 ℃ of temperature and violent stirring.Wherein, have the poly aspartic acid or derivatives thereof of amido side chain and the mass ratio of chitosan and (promptly have the poly aspartic acid of side chain of amido and the mass ratio of chitosan, or have the poly-aspartate derivant of side chain of amido and a mass ratio of chitosan) be 1: 99-99: 1, 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.Described dialdehyde can be oxalic dialdehyde, aliphatic dialdehydes or aromatic series dialdehyde such as mda, glutaraldehyde.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, add linking agent then; Or the solution that (3) are obtained all or be added drop-wise in the solution that (2) obtain in batches or progressively and go, and adds linking agent then; Or after adding linking agent in the solution (2), mix with solution (3) again; Or after adding linking agent in (3) solution, mix with (2) solution again; Or two solution and adding, add linking agent simultaneously.

The mixture of above-mentioned (7) that (8) will obtain directly is being lower than 60 ℃ of following desolventizings, continues the resulting product of dry ageing then under 35～60 ℃ of vacuum.The last resulting material of thorough washing to constant weight, promptly gets required matrix material 60 ℃ of following vacuum-dryings to neutral.

Embodiment 4: use the ethanol-water media legal system to contain the poly aspartic acid and the derivative thereof of an amido side chain to the utmost less in the process of preparation poly aspartic acid or derivatives thereof, chitosan, Yelkin TTS and calcium phosphorous compound matrix material, 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 ethanol-water solution of polyamines, hydrolytic reagent and/or the aminolysis agent that will contain two amidos at least mixes with polysuccinimide, the volume ratio of second alcohol and water is 0.01-1.0: 1, 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: 0.5～5: 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.

Hybrid mode can be under agitation, the aqueous solution of alcohol 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 aqueous solution of alcohol 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.

Above-mentioned (4), (5) that (7) will obtain, (6) three solution, and alkaline solution is at certain temperature (20-45 ℃), and/or certain pH (pH7～10), and mix under the violent stirring.Its blending means is to mix with the solution that (6) obtain after the solution that above-mentioned steps (4), (5) obtain is mixed again, and adds alkaline solution then; Or the solution that (5), (6) are obtained mixes with the solution that (4) obtain after mixing again, adds alkaline solution then; Or the solution that (4), (6) are obtained mixes with the solution that (5) obtain after mixing again, adds alkaline solution then.

The mixture of above-mentioned (7) that (8) will obtain after still aging 12～72 hours, is being lower than 60 ℃ of following desolventizings under certain temperature (20～45 ℃), continue the resulting product of dry ageing then under 35～60 ℃ of vacuum.The last resulting material of thorough washing to constant weight, promptly gets required matrix material 60 ℃ of following vacuum-dryings to neutral.

Embodiment 5: use the ethanol-water media legal system to contain the poly aspartic acid and the derivative thereof of an amido side chain to the utmost less in the process of preparation poly aspartic acid or derivatives thereof, chitosan, Yelkin TTS and calcium phosphorous compound matrix material, 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 ethanol-water solution, and the mol ratio of polyamines and alkali is: 1: 9-9: 1, and the volume ratio of second alcohol and water is 0.01-1.0: 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 the polyamines ethanol-water 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.

Above-mentioned (5), (6) that (8) will obtain, (7) three solution, and alkaline solution is at certain temperature (20-45 ℃), and/or certain pH (pH7～10), and mix under the violent stirring.Its blending means is to mix with the solution that (7) obtain after the solution that above-mentioned steps (5), (6) obtain is mixed again, and adds alkaline solution then; Or the solution that (5), (7) are obtained mixes with the solution that (6) obtain after mixing again, adds alkaline solution then; Or the solution that (6), (7) are obtained mixes with the solution that (5) obtain after mixing again, adds alkaline solution then.

Embodiment 6: adopt the method for control pH to prepare poly aspartic acid or derivatives thereof, chitosan, Yelkin TTS and calcium phosphorous compound matrix material, this method comprises the following steps:

Basic step with alkali and/or acid solution control pH7-10, is preferably controlled pH7-7.5 with embodiment 1 when just mixing in step (7).

Embodiment 7: adopt the method for control pH to prepare poly aspartic acid or derivatives thereof, chitosan, Yelkin TTS and calcium phosphorous compound matrix material, this method comprises the following steps:

Basic step with alkali and/or acid solution control pH7-10, is preferably controlled pH7-7.5 with embodiment 2 when just mixing in step (8).

Embodiment 8: adopt the method for control pH to prepare poly aspartic acid or derivatives thereof, chitosan, Yelkin TTS and calcium phosphorous compound matrix material, this method comprises the following steps:

Basic step with alkali and/or acid solution control pH7-10, is preferably controlled pH7-7.5 with embodiment 3 when just mixing in step (7).

Embodiment 9: adopt the method for control pH to prepare poly aspartic acid or derivatives thereof, chitosan, Yelkin TTS and calcium phosphorous compound matrix material, this method comprises the following steps:

Basic step when just mixing, with alkali or acid solution control pH7-10, is preferably controlled pH7-7.5 with embodiment 4 in step (7).

Embodiment 10: adopt the method for control pH to prepare poly aspartic acid or derivatives thereof, chitosan, Yelkin TTS and calcium phosphorous compound matrix material, this method comprises the following steps:

Basic step with alkali and/or acid solution control pH7-10, is preferably controlled pH7-7.5 with embodiment 5 when just mixing in step (8).

Embodiment 11: adopt the method for controlled temperature and/or pH to prepare poly aspartic acid or derivatives thereof, chitosan, Yelkin TTS and calcium phosphorous compound matrix material, this method comprises the following steps:

Basic step is with embodiment 1, and temperature is controlled at 20-45 ℃ when just mixing in step (7), and preferably 30-45 ℃, and/or, preferably control pH7-7.5 with alkali and/or acid solution control pH7-10.

Embodiment 12: adopt the method for controlled temperature and/or pH to prepare poly aspartic acid or derivatives thereof, chitosan, Yelkin TTS and calcium phosphorous compound matrix material, this method comprises the following steps:

Basic step is with embodiment 2, and temperature is controlled at 20-45 ℃ when just mixing in step (8), and preferably 30-45 ℃, and/or, preferably control pH7-7.5 with alkali and/or acid solution control pH7-10.

Embodiment 13: adopt the method for controlled temperature and/or pH to prepare poly aspartic acid or derivatives thereof, chitosan, Yelkin TTS and calcium phosphorous compound matrix material, this method comprises the following steps:

Basic step is with embodiment 3, and temperature is controlled at 20-45 ℃ when just mixing in step (7), and preferably 30-45 ℃, and/or, preferably control pH7-7.5 with alkali and/or acid solution control pH7-10.

Embodiment 14: adopt the method for controlled temperature and/or pH to prepare poly aspartic acid or derivatives thereof, chitosan, Yelkin TTS and calcium phosphorous compound matrix material, this method comprises the following steps:

Basic step is with embodiment 4, and when just mixing in step (7), temperature is controlled at 20-45 ℃, and preferably 30-45 ℃, and/or, preferably control pH7-7.5 with alkali and/or acid solution control pH7-10.

Embodiment 15: adopt the method for controlled temperature and/or pH to prepare poly aspartic acid or derivatives thereof, chitosan, Yelkin TTS and calcium phosphorous compound matrix material, this method comprises the following steps:

Basic step is with embodiment 5, and when just mixing in step (8), temperature is controlled at 20-45 ℃, and preferably 30-45 ℃, and/or, preferably control pH7-7.5 with alkali and/or acid solution control pH7-10.

Embodiment 16: add 10mL water and 1mL ethanol in flask, and the 1.0g weight-average molecular weight is about 15,000 polysuccinimide, formation suspension, adding 0.45g Methionin and 0.25g sodium hydroxide under violent stirring then.60 ℃ 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 2mL 3% acetic acid and 5mL 6% phosphoric acid to dissolving (solution B) fully.

Under violent stirring, the 2mL solution A is mixed with solution B.Add down the 0.5mL50% glutaraldehyde at 25 ℃ afterwards, mix solution C.

Calcium hydroxide is soluble in water, make the calcium hydroxide saturated solution, get supernatant liquor (solution D).

In addition 0.1g Yelkin TTS is dissolved in 50mL1: in the aqueous ethanolic solution of 1 (volume ratio), form emulsion (solution E).

Be added drop-wise in the reaction vessel that fills solution E in advance simultaneously with automatic titration device the above-mentioned solution C and the solution D that obtain and continuous the stirring, temperature remains on 30 ± 0.5 ℃ by water bath with thermostatic control in the reaction process, the pH value is controlled at 7-8 by automatic titration device, till solution C adds fully.Post precipitation to be generated continues ageing 72 hours, separates, washs, promptly gets matrix material 45 ℃ of vacuum-drying ageing precipitations.Product nearly weighs 1.02 grams.

(see figure 1) in the infrared spectrogram of this product is at 1418.68cm ^-1Carboxylate radical negative ion (COO in the poly aspartic acid has appearred in the place ^-) the strong absorption peak of symmetrical stretching vibration.At 1651.30cm ^-1The strong absorption peak that the place occurs can belong to the stretching vibration of acid amides C=O and the overlapping peaks of primary amine N-H formation vibration.At about 1540cm ^-1Near absorption peak can belong to carboxylate radical negative ion (COO ^-) asymmetric stretching vibration, the associating absorption peak of the C-N stretching vibration of acid amides N-H formation vibration and secondary amide.At 1744.11cm ^-1The stretching vibration peak of ester C=O in the Yelkin TTS has appearred.

In addition, in the XRD figure of product spectrum (see Fig. 2, data see Table 1), about 31.72 ° to locate be the characteristic diffraction peak of hydroxyapatite at 2 θ.

The XRD data sheet of table 1 product

The peak sequence number	2Theta(2θ)	The d-value	Intensity	I/I ₀
The peak sequence number	2Theta(2θ)	The d-value	Intensity	I/I ₀	1	19.560	4.5347	1027	46

The peak sequence number	2Theta(2θ)	The d-value	Intensity	I/I ₀
The peak sequence number	2Theta(2θ)	The d-value	Intensity	I/I ₀	2	25.860	3.4424	1587	72
3	31.720	2.8186	2212	100	2	25.860	3.4424	1587	72
3	31.720	2.8186	2212	100	4	39.340	2.2884	705	32
5	46.700	1.9435	824	37	4	39.340	2.2884	705	32
5	46.700	1.9435	824	37	6	49.580	1.8371	837	38
7	53.200	1.7203	665	30	6	49.580	1.8371	837	38
7	53.200	1.7203	665	30	8	63.340	1.4671	438	20
9	75.900	1.2525	362	16	8	63.340	1.4671	438	20

Comprehensive these data sheet open-births have become a kind of novel polyaspartic, the matrix material of chitosan, Yelkin TTS and calcium phosphorous compound.

Get 0.1 gram institute synthetic matrix material, join 50mL and contain 115.5mg/L Pb ²⁺, 70.00mg/L Cd ²⁺The aqueous solution in, absorption exchange 1 hour, consisting of of the solution after the analyzing and processing then :≤0.01mg/L Pb ²⁺, 13.70mg/L Cd ²⁺Pb ²⁺And Cd ²⁺Decreasing ratio be respectively 99.99% and 80.4%.Show that institute's synthetic matrix material has the stronger ability that removes heavy metal.

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, the mixed solvent that adds 5mL 5% hydrochloric acid and 5mL 8% phosphoric acid is to dissolving (solution B) fully.

Under violent stirring, the 1mL solution A is mixed with solution B.Then 25 ℃ add down contain the 0.2g oxalic dialdehyde the aqueous solution, mix and obtain solution C.

0.1g Yelkin TTS is dissolved in 50mL2: in the aqueous ethanolic solution of 1 (volume ratio), form emulsion (solution E).

Be added drop-wise in the reaction vessel of containing solution E in advance simultaneously with automatic titration device the above-mentioned solution C and the solution D that obtain and continuous the stirring, temperature remains on 37 ± 0.5 ℃ by water bath with thermostatic control in the reaction process, the pH value is controlled at 7-8 by automatic titration device, till solution C adds fully.Post precipitation to be generated continued ageing 24 hours, separated, washing, the drying precipitated matrix material that promptly gets again.Product nearly weighs 0.98 gram.

The product results of elemental analyses is: C: N: Ca: P (atomic ratio)=3.2: 1.37: 1.39: 1, show the matrix material that has obtained a kind of calcic phosphorus.

Embodiment 18: 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 removed by filter wherein insolubles after, add down at 20 ℃ and to contain the 0.1g oxalic dialdehyde and get the aqueous solution, obtain solution A.

Take by weighing the 0.15g chitosan in addition, add 3mL 3% acetic acid and 10mL 5% phosphoric acid to dissolving (solution B) fully.

Under violent stirring, the 5mL solution A is mixed with solution B, obtain solution C.

Take by weighing 0.38g calcium hydroxide, add water to dissolving fully, the insolubles that removes by filter wherein gets solution D.

0.05g Yelkin TTS is dissolved in 25mL1: in the aqueous ethanolic solution of 2 (volume ratios), form emulsion (solution E).

Be added drop-wise to above-mentioned solution C, solution D and the solution E that obtains in the reaction vessel of containing 10mL water in advance simultaneously and constantly stirring, temperature remains on 40 ± 0.5 ℃ by water bath with thermostatic control in the reaction process, and the pH value is controlled at 7-8 by automatic titration device.After complete soln to be added and precipitation are complete, 36-37 ℃ of following ageing 24 hours, are being lower than 60 ℃ of following decompression dehydrations then, and under 45～60 ℃ of vacuum, are continuing dry ageing 12 hours.With the washing of gained material, and under 60 ℃ of vacuum, be dried to constant weight, and pulverize.

The product results of elemental analyses is: C: N: Ca: P (atomic ratio)=2.9: 1.37: 1.39: 1, show the matrix material that has obtained a kind of calcic phosphorus.

Embodiment 19: 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 40 ℃.With dilute hydrochloric acid solution regulator solution pH 5-6, obtain solution A.

Take by weighing the 0.1g chitosan in addition, add 2mL 3% acetic acid, 10mL 2% nitric acid and 3mL 10% phosphoric acid, add 0.1mL 50% glutaraldehyde down at 20 ℃ afterwards, mix and obtain solution B to dissolving fully.

Under violent stirring, the 1mL solution A is mixed with solution B, obtain solution C.

Take by weighing the 0.2g calcium oxide, add water to dissolving fully, the insolubles that removes by filter wherein gets solution D.

0.08g Yelkin TTS is dissolved in 20mL1: in the aqueous ethanolic solution of 1 (volume ratio), form emulsion (solution E).

Under the room temperature, under vigorous stirring, solution C and solution D are splashed in the reaction vessel that fills solution E,, remain on 7-7.5 with small amounts of sodium hydroxide solution control pH simultaneously by regulating both rate of addition.After dropwising, continue to stir 24 hours, generate precipitation, ageing with sedimentation and filtration, washing, till dry ageing under 50 ℃ of vacuum is constant to material weight, and was pulverized after 48 hours under the room temperature.

The infrared spectrogram of products therefrom and the characteristic peak in the XRD figure are substantially with the characteristic peak of embodiment 16 products therefroms.In the infrared spectrogram of this product, at about 1420cm ^-1Carboxylate radical negative ion (COO in the poly aspartic acid has appearred in the place ^-) the strong absorption peak of symmetrical stretching vibration.At about 1650cm ^-1The strong absorption peak that the place occurs can belong to the stretching vibration of acid amides C=O and the overlapping peaks of primary amine N-H formation vibration.At about 1540cm ^-1Near absorption peak can belong to carboxylate radical negative ion (COO ^-) asymmetric stretching vibration, the associating absorption peak of the C-N stretching vibration of acid amides N-H formation vibration and secondary amide.At 1740cm ^-1Near the stretching vibration peak of ester C=O in the Yelkin TTS has appearred.In addition, in the XRD figure of product spectrum, about 32 ° to locate be the characteristic diffraction peak of hydroxyapatite or calcium phosphate at 2 θ.

The product results of elemental analyses is: C: N: Ca: P (atomic ratio)=3.35: 1.41: 1.41: 1, show the matrix material that has obtained a kind of calcic phosphorus.

Get 0.1 this matrix material of gram, join 50mL and contain 115.5mg/L Pb ²⁺, 70.00mg/L Cd ²⁺The aqueous solution in, absorption exchange 1 hour, Pb ²⁺And Cd ²⁺Decreasing ratio be respectively 99.99% and 77.6%.Show that institute's synthetic matrix material has the stronger ability that removes heavy metal.

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 40 ℃.With dilute hydrochloric acid solution regulator solution pH5-6.Get this solution of 5mL afterwards, at room temperature add 0.1mL 50% glutaraldehyde, mix solution A.

Take by weighing the 0.1g chitosan in addition, add 2mL 3% acetic acid, 10mL 2% hydrochloric acid and 5mL 4% phosphoric acid to dissolving (solution B) fully.

Under violent stirring, solution A is mixed with solution B, obtain solution C.

Take by weighing 0.25g calcium chloride, add water to dissolve fully solution D.

Again 0.02g Yelkin TTS is dissolved in 20mL1: in the aqueous ethanolic solution of 1 (volume ratio), form emulsion (solution E).

Under the room temperature, under vigorous stirring, solution D slowly splashed into (solution F) in the solution C, solution F and solution E are splashed into simultaneously fill 20mL1: in the reaction vessel of the aqueous ethanolic solution of 1 (volume ratio), regulate pH to 7-7.5 with 5% sodium hydroxide solution again.After treating that precipitation is fully, be lower than 60 ℃ of following decompression dehydrations, and further dry ageing 24 hours under 45～60 ℃ of vacuum.It is neutral that the gained material is washed to washing lotion, and is dried to constant weight under 60 ℃ of vacuum, pulverizes.

The product results of elemental analyses is: C: N: Ca: P (atomic ratio)=2.86: 1.2: 1.34: 1, show the matrix material that has obtained a kind of calcic phosphorus.

Embodiment 21: in flask, add the distilled water of 0.15g quadrol, 0.5g thanomin and 0.1g sodium hydroxide and 10mL, 27 ℃ 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 0.1g chitosan in addition, add 2mL 3% acetic acid, 3mL 2% sulfuric acid and 5mL 3% phosphoric acid to dissolving (solution B) fully.

Under violent stirring, the 4mL solution A is mixed with solution B.Add afterwards and contain the 0.2g mda aqueous solution, get solution C after mixing.

0.45g nitrocalcite is dissolved in the 10mL water, makes ca nitrate soln (solution D).In addition, 0.05g Yelkin TTS is dissolved in 20mL1: in the aqueous ethanolic solution of 1 (volume ratio), form emulsion (solution E).

Under the room temperature, under vigorous stirring, solution D slowly splashed into (solution F) in the solution C, solution F and solution E are splashed into simultaneously fill 20mL1: in the reaction vessel of the aqueous ethanolic solution of 1 (volume ratio), regulate pH to 7-7.5 with 8% sodium carbonate solution again.Treat precipitation fully, and after 24 hours, be lower than 60 ℃ of following decompression dehydrations 36-37 ℃ of following ageing, and further dry ageing 12 hours under 45～60 ℃ of vacuum.With the washing of gained material, and under 45 ℃ of vacuum, be dried to constant weight, and pulverize.

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 5mL 1-2% acetic acid and 10mL 5% phosphoric acid to dissolving (solution B) fully.

Under violent stirring, the 2mL solution A is mixed with solution B.Add 0.5mL 50% glutaraldehyde afterwards, mix solution C.

Calcium hydroxide is soluble in water, make the calcium hydroxide saturated solution, get supernatant liquor (solution D).Again 0.02g Yelkin TTS is dissolved in 20mL1: in the aqueous ethanolic solution of 1 (volume ratio), form emulsion (solution E).

Above-mentioned solution C, solution D and the solution E that obtains be added drop-wise to simultaneously contain 20mL1 in advance: stir in the reaction vessel of the aqueous ethanolic solution of 1 (volume ratio) and constantly, temperature remains on 30 ± 0.5 ℃ by water bath with thermostatic control in the reaction process, and the pH value is controlled at 8-9 by automatic titration device.Treat that solution C and solution E all add and generate post precipitation, continue ageing 72 hours, separate again, wash, till 60 ℃ of dryings and further ageing are precipitated to the material constant weight, promptly get matrix material.

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.35 ℃ were reacted about 6 hours down, continued to add 0.1g sodium hydroxide, restir 1 hour.With dilute hydrochloric acid solution regulator solution pH5-6, filter (solution A).

Take by weighing the 0.1g chitosan in addition, the mixed solvent that adds 10mL 1-5% acetic acid and phosphoric acid is to dissolving (solution B) fully.

Under violent stirring, the 2mL solution A is mixed with solution B.Add 0.2mL 50% glutaraldehyde afterwards, get solution C after mixing.

Take by weighing 0.6g calcium chloride, add water to dissolve fully solution D.

Under the room temperature, under vigorous stirring, solution D is slowly splashed in the solution C, obtain solution E.Again 0.05g Yelkin TTS is dissolved in 20mL1: in the aqueous ethanolic solution of 1 (volume ratio), form emulsion (solution F).

Under vigorous stirring solution E, solution F and 5% sodium hydroxide solution are splashed in the reaction vessel that fills 40 ℃ in 20mL water, by regulating three's rate of addition, control pH remains on 7-8.After dropwising, continue to stir 24 hours, generate precipitation, ageing after 48 hours under the room temperature, sedimentation and filtration, washing is dry under 50 ℃ of vacuum, and pulverize.

The infrared spectrogram of products therefrom and the characteristic peak in the XRD figure are substantially with the characteristic peak of embodiment 16 products therefroms.In the infrared spectrogram of this product, at about 1420cm ^-1Carboxylate radical negative ion (COO in the poly aspartic acid has appearred in the place ^-) the strong absorption peak of symmetrical stretching vibration.At about 1650cm ^-1The strong absorption peak that the place occurs can belong to the stretching vibration of acid amides C=O and the overlapping peaks of primary amine N-H formation vibration.At about 1540cm ^-1Near absorption peak can belong to carboxylate radical negative ion (COO ^-) asymmetric stretching vibration, the associating absorption peak of the C-N stretching vibration of acid amides N-H formation vibration and secondary amide.At 1740cm ^-1Near the stretching vibration peak of ester C=O in the Yelkin TTS has appearred.

In addition, in the XRD figure of product spectrum, about 32 ° to locate be the characteristic diffraction peak of hydroxyapatite or calcium phosphate at 2 θ.

Embodiment 24: the NaOH aqueous solution and the 80% 1 hydrazine hydrate 0.13g that add 4mL 2mol/L in the beaker of 100mL.Under violent stirring, add the 1.0g weight-average molecular weight and be about 20,000 polysuccinimide, reacted about 8 hours down at 25 ℃.Use dilute hydrochloric acid solution regulator solution pH5-6 afterwards.Filter solution A.

After making the poly aspartic acid that has the amido side chain, ensuing operation is with the operation of embodiment 16 or 17 or 18 or 20 or 21 or 23 back.

Embodiment 25: add 1g (0.01mol) weight-average molecular weight and be about 5 in the 100mL flask, pulpous state suspension in 000 the polysuccinimide 3mL water, then in batches or the mixed solution of the NaOH aqueous solution of disposable adding 3mL 2mol/L and 0.2g quadrol, reacted about 5 hours down at 25 ℃, use dilute hydrochloric acid solution regulator solution pH4-5 afterwards.Filter solution A.

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 beaker, 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 0.1g and have the poly aspartic acid of amido side chain, make it dissolving, obtain solution A with 5mL water.

Take by weighing the 0.1g chitosan in addition, add 2mL 1-2% acetic acid and 5mL 6% phosphoric acid, add the aqueous solution of 0.3mL 50% glutaraldehyde afterwards, obtain solution B to dissolving fully.

Under violent stirring, solution A is mixed with solution B.Get solution C after mixing.

Take by weighing 0.56g calcium chloride, add water to dissolve fully solution D.

Under the room temperature, under vigorous stirring, solution D is slowly splashed in the solution C, obtain solution E.In addition 0.05g Yelkin TTS is dissolved in 20mL2: in the aqueous ethanolic solution of 1 (volume ratio), form emulsion (solution F).

Under vigorous stirring solution E, solution F and 10% sodium carbonate solution are splashed in the reaction vessel that fills 40 ℃ in 20mL water, by regulating three's rate of addition, control pH remains on 7-7.4.After dropwising, continue to stir 12 hours, generate precipitation, ageing after 48 hours under the room temperature, sedimentation and filtration, washing is dry under 55 ℃ of vacuum, and pulverize.

Embodiment 27: with 0.8g polysuccinimide, 10gN, dinethylformamide (DMF) is put into the 100mL beaker, 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 beaker, 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.

After making the poly aspartic acid that has the amido side chain, ensuing operation is with the operation of embodiment 16 or 17 or 19 or 20 or 21 or 22 or 23 back.

Embodiment 28: take by weighing the poly aspartic acid that 0.3g has the amido side chain, make it dissolving with 8mL water, with dilute hydrochloric acid solution regulator solution pH3-4, add 0.2mL massfraction 50% glutaraldehyde water solution afterwards, mix and obtain solution A.Take by weighing the 0.1g chitosan in addition, with 10mL 3% phosphoric acid: the mixed acid solution of 1-2% acetic acid (volume ratio)=3: 1 (v/v) makes it to dissolve fully and obtains solution B.

The operation of back is with the operation of embodiment 20 back.

Claims

1. the preparation method of a biomimetic 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 amino side-chain at least, wherein polyamines with mol ratio by the polysuccinimide of succimide unit is: 0.01-0.50: 1;

(2) product that step (1) is obtained is hydrolyzed, and is contained the poly aspartic acid of an amino side-chain at least; Or aminolysis, or be hydrolyzed simultaneously and aminolysis, contained the poly-aspartate derivant aqueous solution of an amino 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;

(4) two solution that above-mentioned steps (2), (3) are obtained, and linking agent aliphatics or aromatic series dialdehyde mix under 20-100 ℃ of temperature and violent stirring; The poly aspartic acid or derivatives thereof of band amino side-chain and the mass ratio of chitosan are 1: 99-99: 1, and mol ratio amino in aldehyde radical in aliphatics or the aromatic series dialdehyde and the polymkeric substance is: 0.01-1.0: 1;

2. in accordance with the method for claim 1, the hybrid mode that it is characterized in that described step (7) is:

The solution that step (4), (5) are obtained mixes with the solution that step (6) obtains after mixing earlier again, adds alkaline solution then; Or:

The solution that step (5), (6) are obtained mixes with the solution that step (4) obtains after mixing earlier again, adds alkaline solution then; Or:

The solution that step (4), (6) are obtained mixes with the solution that step (5) obtains after mixing earlier again, adds alkaline solution then; Or:

Three kinds of solution that step (4), (5), (6) are obtained also add, and add alkaline solution simultaneously.

3. according to claim 1 or 2 described methods, it is characterized in that polyamines in the described step (1) is one or more the mixing in diamines or triamine, the tetramine polyamines organic bases.

4. in accordance with the method for claim 3, it is characterized in that described polyamines is L-Methionin, hydrazine hydrate, quadrol or butanediamine.

5. according to claim 1 or 2 described methods, it is characterized in that in the described step (2), described hydrolytic reagent is potassium hydroxide, sodium hydroxide or yellow soda ash, or their mixture; Described aminolysis agent is aliphatics or aromatic amine.

6. in accordance with the method for claim 5, it is characterized in that described aliphatics or aromatic amine are: methylamine, ethamine, thanomin, phenylethylamine, amphetamine or amino acid, or their mixture.

7. according to claim 1 or 2 described methods, it is characterized in that described diluted acid is the dilute aqueous soln of hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid or acetic acid, or their mixing solutions.

8. according to claim 1 or 2 described methods, it is characterized in that described aliphatics or aromatic series dialdehyde be oxalic dialdehyde, mda, glutaraldehyde or terephthal aldehyde.

9. according to claim 1 or 2 described methods, it is characterized in that described calcium containing compound is a calcium hydroxide, calcium chloride, nitrocalcite or calcium oxide.

10. according to claim 1 or 2 described methods, it is characterized in that described step (7) temperature is 30～40 ℃, control final pH value 7～8.

11. the preparation method of a biomimetic material is characterized in that may further comprise the steps:

(1) polysuccinimide and polyamines, alkaline hydrolysis agent and aminolysis agent are reacted simultaneously, contained the poly aspartic acid or derivatives thereof aqueous solution of an amino side-chain at least; Polyamines with mol ratio by the polysuccinimide of succimide unit is: 0.01～1.0: 1; The total mole number of polyamines, hydrolytic reagent and aminolysis agent with mol ratio by the polysuccinimide of succimide unit is: 0.1～5: 1;

(3) two solution that above-mentioned steps (1), (2) are obtained, and linking agent aliphatics or aromatic series dialdehyde mix under 20-100 ℃ of temperature and violent stirring, make mixed aqueous solution; By the poly aspartic acid or derivatives thereof of band amino side-chain and the mass ratio of chitosan is 1: 99-99: 1, and mol ratio amino in aldehyde radical in aliphatics or the aromatic series dialdehyde and the polymkeric substance is: 0.01-1.0: 1;