CN1814650A - Method for preparing poly-aspartic-acid resin - Google Patents
Method for preparing poly-aspartic-acid resin Download PDFInfo
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- CN1814650A CN1814650A CN 200610002080 CN200610002080A CN1814650A CN 1814650 A CN1814650 A CN 1814650A CN 200610002080 CN200610002080 CN 200610002080 CN 200610002080 A CN200610002080 A CN 200610002080A CN 1814650 A CN1814650 A CN 1814650A
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Abstract
This invention relates to a preparation method for poly-asparagic acid resin, which takes poly-pyrrolidine dione as the raw material to make crosslink poly-pyrrolidine dione with method of non-even phase suspended emulsion crosslink or non-even phase suspension crosslink and processes poly-asparagic acid resin by hydrolyzation characterizing that the crosslink poly-pyrrolidine dione is prepared by multi-section crosslink reaction, in which, the crosslinker is fed in for 2-4 times in equal volume and equal time interval, the crosslink poly-pyrrolidine dione and the resin are aged and crystallized and quickly dried, A ageing and crystallization process for 1-10 days under room temperature, B, quick drying process is carried out under -54-40deg.C.
Description
Technical field
The present invention relates to a kind of is raw material with the high molecular polysuccinimide, adopts heterogeneous suspension crosslinking or heterogeneous outstanding newborn crosslinking to prepare the method for poly-aspartic-acid resin.
Background technology
The super-strong moisture absorbing resin is a kind of lightly crosslinked strongly hydrophilic group that contains, and can absorb water tens times even several thousand times are to the polymkeric substance of own wt.The poly-aspartic-acid super absorbent resin is the polymkeric substance that obtains by crosslinked poly-aspartic-acid, it is except that having good biological degradability and water absorbing properties, also has good biocompatibility, even it enters human body, also can be digested and assimilated by the enzyme effect, and its apparent antigenicity in human body, its metabolite is nontoxic.The poly-aspartic-acid super absorbent resin is a kind of green functional macromolecular material of excellent property.It also is widely used at aspects such as agricultural gardening, cable, civil construction except that being used for health care product, medical treatment and food product pack.
With the polysuccinimide is raw material, and the method that adopts chemical crosslink technique to prepare poly-aspartic-acid resin is concluded and comprised following four processes: 1, produce crosslinked polysuccinimide; 2, the precipitation of crosslinked polysuccinimide, purifies and separates and drying; 3, the hydrolytic crosslinking polysuccinimide is produced poly-aspartic-acid resin; 4, the precipitation of poly-aspartic-acid resin, purifies and separates and drying.Also can be in above-mentioned four processes without second process.Now said process is described below respectively:
1, produces crosslinked polysuccinimide
Prepare the cross-linking method that crosslinked polysuccinimide adopts and mainly contain homogeneous phase solution crosslinking, heterogeneous suspension crosslinking, heterogeneous outstanding newborn crosslinking etc.Though traditional heterogeneous outstanding newborn crosslinking and heterogeneous suspension crosslinking have overcome the shortcoming that the homogeneous phase solution crosslinking is difficult to control degree of crosslinking, the poly-aspartic-acid resin of these two kinds of methods preparations is difficult to obtain having concurrently the product of gel-strength and water regain preferably.
2, the precipitation of crosslinked polysuccinimide, purifies and separates and drying
Crosslinked polysuccinimide normally precipitates, washs purifying earlier, adopts dialysis then, filters, and decant or centrifugal separation method separate.The drying mode of crosslinked polysuccinimide has forced air drying, vacuum-drying, hot-air dry, lyophilize, spraying drying, microwave drying and azeotropic dehydration drying etc.Because gel easily shrinks in drying process, is out of shape and ftractures, so drying conditions is required quite harshness, drying conditions is improper, can cause gel-strength to reduce or water regain decline, even can cause the whole process of preparation failure.Therefore, this process also is the committed step of preparation poly-aspartic-acid resin.
3, the hydrolysis of crosslinked polysuccinimide
The hydrolysis of crosslinked polysuccinimide mainly contains dual mode, and the one, directly crosslinked polysuccinimide is scattered at a certain temperature in the alkali lye of finite concentration equivalent and carries out; The 2nd, earlier crosslinked polysuccinimide is scattered in the hydrophilic solvent high-concentration alkali liquor that the drips equivalent then within a certain period of time reaction that is hydrolyzed.The hydrolysis terminal point of crosslinked polysuccinimide judges by the pH value that normally crosslinked polysuccinimide has only through sufficient hydrolysis just can present water absorbing properties preferably.
4, the precipitation of poly-aspartic-acid resin, purifies and separates and drying
The precipitation of poly-aspartic-acid resin, purifies and separates and drying process are the same with precipitation, purifies and separates and exsiccant operational condition and the influence thereof of aforesaid the 2nd the crosslinked polysuccinimide of process.
" super strength water absorbent " [Super-absorbing polymeric networks US 5998491 (1999)] adopts the water react system to carry out heterogeneous suspension crosslinking reaction.This method raw material polysuccinimide must fully be pulverized, particle diameter must be less than 100 μ m, be preferably in below the 10 μ m, the raw material polysuccinimide is suspended in aqueous phase in the reaction process, carry out crosslinking reaction in 30～80 ℃ with the diamines or the polyamine crosslinking agent aqueous solution and obtain crosslinked polysuccinimide, then with behind the dry concentrated pulping of crosslinked polysuccinimide, be hydrolyzed after being dispersed into suspension with the water/methanol solution of equal-volume ratio, the poly-aspartic-acid resin that hydrolysis is obtained is through washing, after the filtration, under 30～80 ℃, carry out normal pressure or drying under reduced pressure makes the solid poly-aspartic-acid resin.The swelling ratio of poly-aspartic-acid resin in deionized water that makes with this method is the dried glue of 10～230g/g, and the swelling ratio in salt solution is the dried glue of 1～32g/g.This method has overcome the shortcoming that reactant in the homogeneous phase solution crosslinking reaction process is easy to gelation, reactant hydrolysis last handling process ratio is easier to carry out, but because hydrophilic solvent is the poor solvent of polysuccinimide, the polysuccinimide molecular chain is difficult for stretching, reactant, linking agent and other additives are difficult to be uniformly dispersed, even easily wrap up, reaction process mass-and heat-transfer efficient is lower, speed of response is slow, and adopt one section crosslinking reaction, the water regain of product in deionized water and salt solution is all not high.
[Manufacture of crosslinked polysuccimides forprecursors of biodegradable polyaspartic acids JP 11158267 (1999)] is linking agent with the polyamines (as lysine hydrochloride) that contains at least one carboxyl in the molecule " to be used as the preparation of the crosslinked polysuccinimide resin of the crosslinked poly-aspartic-acid intermediate of biodegradability ", methyl alcohol, ethanol or water are dispersion agent, adopt the synthesizing cross-linked polysuccinimide of heterogeneous outstanding newborn crosslinking.Under 10 ℃～80 ℃ conditions, in 0.5 hour, 0.1～30mol% lysine hydrochloric acid salt brine solution is splashed into the N of polysuccinimide, in dinethylformamide (the being called for short DMF) solution, reacted 1 hour, add again after methyl alcohol is dispersed into outstanding emulsus attitude with reactant, reaction is 3 hours under 25 ℃ of conditions, adding NaOH is a catalyzer, continuation was carried out crosslinking reaction 20 hours under 25 ℃ of conditions, afterwards with methyl alcohol with reaction product precipitate, washing and filtering separation, obtain the wet cake of crosslinked polysuccinimide; Under 25～35 ℃ of conditions, after with the methanol mixing solutions the wet cake of crosslinked polysuccinimide being disperseed, to the NaOH aqueous solution that wherein drips 24.5wt%, up to the pH value is 9～11.5, continue hydrolysis 3 hours, the poly-aspartic-acid resin that obtains methanol extraction, washing, filtering separation is obtaining the solid poly-aspartic-acid resin after the drying under 20～200 ℃ of conditions again.Drying means is not particularly limited, and can adopt forced air drying, vacuum-drying, hot-air dry, steam drying, microwave drying or azeotropic dehydration drying.The poly-aspartic-acid resin that this patent system gets, the swelling ratio in deionized water are the dried glue of 100～1090g/g, and the swelling ratio in the NaCl of the 0.9wt% aqueous solution is the dried glue of 30～97g/g.This method has overcome the crosslinked shortcoming of the crosslinked and heterogeneous suspension of homogeneous phase solution, the crosslinked hydrolysis of polysuccinimide ratio of intermediate is easier to, but this method adopts one section crosslinking reaction, and reaction process is comparatively complicated, so product water regain and gel-strength still can not be taken into account.This patent adopts the azeotropic dehydration drying process complicated, and microwave drying causes the rosin products molecular rupture easily, reduces gel-strength.
" preparation of crosslinked polysuccinimide resin " [Production of cross-linkedpolysuccnimide JP 11171992 (1999)], a kind of inside and outside crosslinking is disclosed, be under 10 ℃～80 ℃ temperature, the internal crosslinker of 0.1～30mol% splashed into carry out the internal crosslinking reaction in polysuccinimide-DMF solution, after crosslinked polysuccinimide reaches 0.01～3mol%, adding dispersion agent fully disperses reactant, the NaOH aqueous solution that dripped 24.5wt% again in 3 hours in reactant carries out the partial hydrolysis reaction, under outstanding emulsus attitude, drip the surface crosslinking agent of 0.1～30mol% then, and under 25 ℃ of conditions, carry out the static surface crosslinking reaction and obtained crosslinked polysuccinimide in 20～30 hours, with alcohol or water reactant is washed, filtering separation, drying obtains the crosslinked polysuccinimide of solid under 20～200 ℃ of conditions again.With being crushed to particle diameter is that the crosslinked polysuccinimide of 1 μ m～50 μ m is scattered in 10～100 ℃ the hydrophilic solvent, again at the alkali lye that in crosslinked polysuccinimide dispersion liquid, drips equivalent 27wt% within 1～3 hour, continue hydrolysis 2 hours after dripping alkali lye, to the pH value is 9～12 to finish hydrolysis and obtain poly-aspartic-acid resin, and hydrolytic process is controlled the product water regain with the method for control swelling capacity.After hydrolysis was finished, product adopted the method for filtration, decant or centrifugation to separate through alcohol or water washing.Drying means can adopt forced air drying, vacuum-drying, hot-air dry, steam drying, microwave drying or azeotropic dehydration drying, and drying temperature is 20～200 ℃.Poly-aspartic-acid resin swelling ratio with this method preparation is the dried glue of 110～600g/g in deionized water, is the dried glue of 30～71g/g in the NaCl of the 0.9wt% aqueous solution.It is a kind of polycarboxylic acid or conventional polyamines or polythiol that is neutralized by alkali in advance and contain one to two amino that this patent requires internal crosslinking agent.This crosslinking method can produce gradient on the cross-linking density between resin inside and the outside, but the selection use and the process operation of outside cross-linking agent are all very complicated in this crosslinking method reaction process, especially internal crosslinking reaction, degree of crosslinking control is very difficult, gelation takes place in reactant easily in the reaction cross-linking process in early stage, hinders proceeding of crosslinking reaction.This patent adopts the azeotropic dehydration drying process complicated, and microwave drying causes the rosin products molecular rupture easily, reduces gel-strength.
Above-mentioned patent crosslinking reaction process is more complicated all, and the product that makes can not be taken into account high water absorption and high-gel strength, and the water absorbent rate in the NaCl of the 0.9wt% aqueous solution all is lower than the dried glue of 100g/g.
Above-mentioned patent is 20～200 ℃ to crosslinked polysuccinimide and poly-aspartic-acid resin drying temperature.Drying temperature is greater than 50 ℃, and crosslinked polysuccinimide and poly-aspartic-acid resin surface in drying process easily bends, is out of shape, ftractures, and influences water absorbing properties, gel-strength and the quality product of product.
The method that prepare at present poly-aspartic-acid resin, Shang Weijian has crosslinked polysuccinimide and poly-aspartic-acid resin is carried out the aging crystallization processing to improve the report of its water absorbing properties and gel-strength.Therefore, can't take into account this problem at poly-aspartic-acid resin product water absorbing properties and gel-strength, need traditional preparation technology be improved, the preparation technology that exploitation takes into account the poly-aspartic-acid resin of outstanding water absorbing properties and gel-strength improves the quality of products and economy.
Summary of the invention
The invention provides a kind of method that can improve poly-aspartic-acid resin water-absorbent, gel-strength and stability.This method is improved the method for traditional crosslinked polysuccinimide of preparation; Propose the multistage crosslinking reaction and prepare crosslinked polysuccinimide, aging crystallization is handled and crosslinked polysuccinimide and poly-aspartic-acid resin is carried out quick dewatering drying.
The preparation method of a kind of poly-aspartic-acid resin of the present invention, be to be 20 with molecular weight, 000～500,000 daltonian polysuccinimide is a raw material, produce crosslinked polysuccinimide with heterogeneous outstanding newborn crosslinking or heterogeneous suspension crosslinking, obtain the crosslinked polysuccinimide of solid through precipitation, separation and purification, drying; Produce poly-aspartic-acid resin through pulverizing, hydrolysis, obtain the solid poly-aspartic acid resin through precipitation, separation and purification, drying more at last, its technical characterictic is:
(1) producing crosslinked polysuccinimide is the multistage crosslinking reaction, divides 2～4 equivalent constant duration chargings to realize by linking agent;
(2) crosslinked polysuccinimide and poly-aspartic-acid resin are carried out aging crystallization processing and rapid drying processing; (A) aging crystallization is handled: at room temperature carry out 1～10 day aging crystallization; (B) rapid drying is handled: carry out under-54～40 ℃.
It is as follows that the present invention adopts heterogeneous outstanding newborn crosslinking to prepare the multistage crosslinking reaction operating process of crosslinked polysuccinimide: under normal pressure, 25～60 ℃ of conditions, polysuccinimide added in the non-proton type polar organic solvent dissolved 1～10 day, organic solvent is 10～36ml/g with the volume mass ratio of polysuccinimide; Add dispersion agent again, dispersion agent is 6～14ml/g with the volume mass ratio of polysuccinimide, and dispersed with stirring becomes uniform suspended emulsion; Divide 2～4 equivalent constant durations to add linking agent, the mass ratio of linking agent and polysuccinimide is 0.05～0.12g/g, stirs 1～6 hour, makes crosslinked polysuccinimide.
It is as follows that the present invention adopts heterogeneous suspension crosslinking to prepare the multistage crosslinking reaction operating process of crosslinked polysuccinimide: under normal pressure, 25～60 ℃ of conditions, in the polysuccinimide powder of particle diameter＜0.1mm, add dispersion agent, dispersion agent is 8～30ml/g with the volume mass ratio of polysuccinimide, stirs into uniform dispersed; Divide 2～4 equivalent constant durations to add linking agent again, the mass ratio of linking agent and polysuccinimide is 0.14～0.20g/g, stirs 1～72 hour, makes crosslinked polysuccinimide.
The present invention is when heterogeneous outstanding newborn crosslinking or heterogeneous suspension crosslinking are produced crosslinked polysuccinimide, the linking agent that adopts comprises: (A) aliphatic polyamine: 1, propylene diamine, 1,4-butanediamine, 1,5-pentamethylene diamine, 1,6-hexanediamine or heptamethylene diamine; (B) basic aminoacids: Methionin, ornithine or Gelucystine; (C) alkaline amino acid salt: lysine salt, ornithine salt or cystine salt; (D) basic aminoacids ester: Methionin ester, ornithine ester or Gelucystine ester.
When the present invention produced crosslinked polysuccinimide at heterogeneous outstanding newborn crosslinking, the non-proton type polar organic solvent of employing was N, dinethylformamide, N,N-dimethylacetamide, N-Methyl pyrrolidone, dimethyl sulfoxide (DMSO) or N, N-dimethyl-imidazolinone.
The present invention is when heterogeneous outstanding newborn crosslinking or heterogeneous suspension crosslinking are produced crosslinked polysuccinimide, and the dispersion agent of employing is: water, methyl alcohol, ethanol, propyl alcohol or Virahol.
Rapid drying of the present invention is treated to: vacuum-drying, gas blower drying or lyophilize.
The present invention is a raw material with the high molecular polysuccinimide, its molecular weight is 20,000～500,000 dalton, when molecular weight was lower than 20000 dalton, crosslinking reaction was difficult to carry out, only can obtain at present molecular weight is the following raw materials of 500000 dalton, the molecular weight height helps carrying out smoothly of crosslinking reaction, and the poly-aspartic-acid resin reticulated structure continuity that obtains is good, and water-retaining capacity and gel-strength are higher.This raw material can make or the commercially available prod with known method.
The present invention is on traditional heterogeneous outstanding newborn crosslinking and heterogeneous suspension crosslinking basis, under the precondition that does not change original linking agent and total add-on and cross-linking reaction time, adopt the linking agent feeding manner that repeatedly adds, make crosslinking reaction divide multistage to carry out.Method of the present invention can make rosin products form the multistage porous network structure with certain density gradient, connect between NEs at different levels is that the multichain network type connects, and the network structure of this product has fabulous continuity, has created favourable condition for preparing the high quality resin that has than high-gel strength and water regain.
The present invention adopts heterogeneous outstanding newborn crosslinking to prepare the employed solvent of crosslinked succinimide, must have good solubility to polysuccinimide, known non-proton type polar organic solvent mainly contains: N, dinethylformamide (being called for short DMF), N,N-dimethylacetamide, N-Methyl pyrrolidone, dimethyl sulfoxide (DMSO) or N, N-dimethyl-imidazolinone etc.
The present invention adopts heterogeneous outstanding newborn crosslinking and heterogeneous suspension crosslinking to prepare crosslinked succinimide, dispersion agent-hydrophilic solvent as succinimide, it is the polysuccinimide poor solvent, has the dispersion polysuccinimide, reduce crosslinking reaction speed, avoid the effect of reactant gelization and reunion.Known dispersion agent mainly contains: water, methyl alcohol, ethanol, propyl alcohol or Virahol etc., these dispersion agents can use separately also can mix use.
The organic solvent that the present invention adopts the known method water or dissolves each other with water, after crosslinked polysuccinimide or poly-aspartic-acid resin washed purifying, adopt methyl alcohol or ethanol as precipitation agent again, crosslinked polysuccinimide or poly-aspartic-acid resin are precipitated and the aging crystallization processing, and it is dry then to remove supernatant liquor with decantation.The present invention handles the crosslinked polysuccinimide of back preparation through aging crystallization or poly-aspartic-acid resin has good network skeleton structure and continuity is better, and pore structure is regular, the degree of crystallinity height.The aging crystallization treatment time is long more, and the network skeleton structure of product and continuity are good more, and pore structure is regular more, and degree of crystallinity is high more.The aging crystallization treatment time surpasses 10 days, then can extend manufacture cycle, and reduces the product water regain.
The present invention is to crosslinked polysuccinimide or poly-aspartic-acid resin, under-54～40 ℃ temperature condition, adopt condition of high vacuum degree or big air quantity to carry out rapid drying, the network structure that has better kept resin do not deform and the precondition that ruptures under, it is firm and have the product of better successional, larger aperture and porosity to obtain network skeleton, has further improved the performance and the quality of rosin products.
The poly-aspartic-acid resin product absorption speed that aging crystallization that the present invention adopts and drying means obtain is fast, the water regain height, and gel-strength is good.
To the crosslinked polysuccinimide preparation poly-aspartic-acid resin that is hydrolyzed, be to adopt mode that known alkali lye drips and with pH value judgement hydrolysis terminal point.Working method is as follows: use particle diameter is the crosslinked polysuccinimide powder less than 0.1mm, under 25～60 ℃ of conditions, add hydrophilic solvent as dispersion agent, dispersion agent is 10～30ml/g with the volume mass ratio of crosslinked polysuccinimide, stirred 10～20 minutes, dripping concentration again in finely dispersed crosslinked polysuccinimide is the alkali lye of 20～35wt%, added an alkali lye every 1～2 hour, each alkali lye that adds is 0.04～0.24ml/g with the volume mass ratio of crosslinked polysuccinimide, till reactant presents transparent colloid fully and do not have solid phase particles.
The water regain (swelling ratio) that the present invention measures poly-aspartic-acid resin adopts the tea bag method.Operation steps is as follows: under the condition of 23 ℃ of temperature, humidity 50%, the tea bag (diameter is the circle closing in tea bag of 400mm) that the poly-aspartic-acid resin sample is housed is immersed in the deionized water, take out tea bag at certain time intervals, draining is 15 minutes in air, weighing is designated as Wt, repeats above-mentioned steps with corresponding blank tea bag, and weighing is designated as Wo, example weight is designated as Ws, and sample water regain R is calculated by following formula:
R=(Wt-Wo-Ws)/Ws (the dried glue of unit: g/g)
The present invention adopts the gel-strength of falling ball method viscometer determining poly-aspartic-acid resin.Under 25 ℃ of conditions, the tea bag that 0.5 gram poly-aspartic-acid resin sample is housed is immersed in the deionized water, take out tea bag after 24 hours, draining is 15 minutes in air, sample is stirred, pack in the measuring tube, (diameter of stainless steel bead is measured the required time representation gel-strength of steel ball whereabouts 25cm 0.2～1.2cm), and unit is second to adopt falling ball method.
The swelling ratio of poly-aspartic-acid resin in deionized water of the present invention's preparation is the dried glue of 56～1200g/g, swelling ratio in the NaCl of the 0.9wt% aqueous solution is the dried glue of 24-146g/g, gel-strength is 9.76～26.87 seconds, compare with the high water absorption of " as the preparation of the crosslinked polysuccinimide resin of the crosslinked poly-aspartic-acid intermediate of biodegradability " [JP 11158267 (1999)], the present invention has improved 18.8% with the high water absorption of poly-aspartic-acid resin in deionized water, and the high water absorption in the NaCl of the 0.9wt% aqueous solution has improved 50.5%.The poly-aspartic-acid resin that the present invention's preparation is described has water absorbing properties, gel-strength and saline-alkaline tolerance preferably.
Waiting to inhale in the scope of solution initial pH value 4～10, adopt the poly-aspartic-acid resin of two sections crosslinking reactions preparation of the present invention, can maintain the pH value of waiting to inhale solution between 6.4～7.4 preferably, and adopt the poly-aspartic-acid resin of one section traditional crosslinking reaction preparation will wait that the pH value of inhaling solution maintains in 6.8～8.8 scopes.The poly-aspartic-acid resin that the present invention's preparation is described has pH value surge capability preferably.
The poly-aspartic-acid resin of two sections crosslinking reactions preparation of the present invention is placed on the 292nm ultraviolet lamp under irradiation, and to record the water regain variation in 1～5 day less.The poly-aspartic-acid resin that the present invention's preparation is described has better light stability.
Poly-aspartic-acid resin thermal treatment under 150 ℃ of conditions of two sections crosslinking reactions preparation of the present invention was recorded water regain in 1～5 hour to be changed less.The poly-aspartic-acid resin that the present invention's preparation is described has better thermostability.
With reference to the K6950 of Japanese Industrial Standards (JIS), the poly-aspartic-acid resin aeration is handled biodegrade test in 28 days with active sludge.With the ratio of biological oxygen demand (being called for short the BOD value) and biological oxygen demand and chemical oxygen demand (COD) (being called for short the COD value), promptly the BOD/COD value is estimated its biodegradability, it is generally acknowledged that the BOD/COD value is Biodegradable material more than or equal to 0.3 less than 0.45.The BOD/COD value is biological easily degradable material more than or equal to 0.45.Being worth the poly-aspartic-acid resin biological degradability of two sections crosslinking reactions preparation of the present invention by BOD is 13.2%, and BOD/COD value is 0.315, illustrates that poly-aspartic-acid resin that the present invention prepares was not only biodegradable but also has biologically stable preferably.The poly-aspartic-acid resin biological degradability that is worth one section traditional crosslinking reaction to prepare by BOD is 25.9%, and its BOD/COD value is 0.561, illustrates that the poly-aspartic-acid resin of one section traditional crosslinking reaction preparation can only be easy to biological degradation.
The poly-aspartic-acid resin of the present invention preparation removes to have the biodegradability and biocompatibility that common poly-aspartic-acid resin possesses, and also has all good characteristic of water regain, gel-strength, pH surge capability, saline-alkaline tolerance, light stability, thermostability and biologically stable.
The poly-aspartic-acid resin product of the present invention preparation also can be used for dustproofly fixing the sand, water conservation, anti-freezing and heat-insulating and anti-saline and alkaline occasion.
Description of drawings
Fig. 1 be embodiment 1 with the poly-aspartic-acid resin of Comparative Examples 1 preparation in the imbibition swelling process, wait to inhale the variation diagram of the pH value of solution.Among the figure: ▲-wait to inhale the solution initial pH value; The pH value of waiting to inhale solution after the poly-aspartic-acid resin imbibition swelling of ■-Comparative Examples 1 preparation; ● the pH value of waiting to inhale solution after the poly-aspartic-acid resin imbibition swelling of-embodiment 1 preparation.
Fig. 2 is embodiment 1 and the poly-aspartic-acid resin light aging test of Comparative Examples 1 preparation comparison diagram as a result.Among the figure: ▲-the poly-aspartic-acid resin illumination of embodiment 1 preparation after swelling ratio; Swelling ratio after the poly-aspartic-acid resin illumination of ■-Comparative Examples 1 preparation.
Fig. 3 is embodiment 1 and the poly-aspartic-acid resin of Comparative Examples 1 preparation heat ageing test comparison diagram as a result under 150 ℃ of conditions.Among the figure: ▲-the poly-aspartic-acid resin thermal treatment of embodiment 1 preparation after swelling ratio; Swelling ratio after the poly-aspartic-acid resin thermal treatment of ■-Comparative Examples 1 preparation.
Embodiment
Adding the 3g molecular weight in the beaker of 500ml is the N of 500000 daltonian polysuccinimides and 108ml, dinethylformamide (N, dinethylformamide is 36ml/g with the volume mass ratio of polysuccinimide), dissolving is 10 days under 25 ℃ of conditions, add 18ml water down at 40 ℃ and make dispersion agent (water is 6ml/g with the volume mass ratio of polysuccinimide), stir (1000 rev/mins of mixing speed) and made uniform suspended emulsion in 10 minutes, the hexanediamine that adds 0.24g is as linking agent (mass ratio of total consumption of hexanediamine and polysuccinimide is 0.08g/g), hexanediamine divides 2 addings: add 0.12g earlier, stirred 0.5 hour, add 0.12g again, continue to stir 0.5 hour.Add the agent of 300ml ethanol sedimentation, treat that throw out forms back aging crystallization 6 days, remove supernatant liquor, throw out 40 ℃ of forced air dryings, is made the crosslinked polysuccinimide of 3.18g solid with decantation.
It is the powder of particle diameter less than 0.1mm that the crosslinked polysuccinimide of 3.18g is pulverized, powder is added in the beaker, add 95.4ml water and ethanol equal-volume again than mixing solutions (volume mass of aqueous ethanolic solution and crosslinked polysuccinimide is than being 30ml/g), under 40 ℃, stirred 15 minutes, drip the NaOH aqueous solution of 27wt%, per hour add 3 NaOH aqueous solution (per hour add the NaOH aqueous solution and be 0.04ml/g) with crosslinked polysuccinimide volume mass ratio, when all presenting colloid, solution adds 300ml ethanol, after treating that precipitation forms, aging crystallization was handled 3 days again, remove supernatant liquor with decantation, under 40 ℃, 0.095MPa vacuum-drying obtains 3.08g solid poly-aspartic-acid resin with throw out.Recording the swelling ratio of poly-aspartic-acid resin in deionized water is 1200g/g, and the swelling ratio in the NaCl of the 0.9wt% aqueous solution is 128g/g, and gel-strength is 22.16 seconds.According to electron micrograph as can be known, the rosin products of preparation is the multistage porous network structure with certain density gradient, and in this network structure, connecting between NEs at different levels is that the multichain network type connects, and has continuity more carefully.
The poly-aspartic-acid resin of preparation is placed on initial pH value in 4～10 scope, waits to inhale in the solution after the swelling, record wait to inhale solution pH value as shown in Figure 1 between 6.4～7.4, variation is more gently near sea line; The poly-aspartic-acid resin that preparation is described has pH surge capability preferably.The poly-aspartic-acid resin of preparation is placed on the 292nm ultraviolet lamp under irradiation recorded water regain as shown in Figure 2 in 1～5 day, water regain is less with the light application time variation; The poly-aspartic-acid resin that preparation is described has light stability preferably.Poly-aspartic-acid resin thermal treatment under 150 ℃ of conditions of preparation was recorded water regain as shown in Figure 3 in 1～5 hour, and water regain changes less with heat treatment time; The poly-aspartic-acid resin that preparation is described has thermostability preferably.Being worth the poly-aspartic-acid resin biological degradability by BOD is 13.2%, and its BOD/COD value is 0.315; The poly-aspartic-acid resin that preparation is described is Biodegradable material and has biologically stable preferably.
With embodiment 1 inequality be when the crosslinked polysuccinimide of preparation, the linking agent hexanediamine divides 4 adding, after reactant formed uniform suspended emulsion, in 1 hour, every 15 minutes adding 0.06g hexanediamines, all the other conditions were identical with embodiment 1.Obtain 3.10g solid poly-aspartic-acid resin.Recording the swelling ratio of poly-aspartic-acid resin in deionized water is 1010g/g, and the swelling ratio in the NaCl of the 0.9wt% aqueous solution is 146g/g, and gel-strength is 26.87 seconds.According to electron micrograph as can be known, the poly-aspartic-acid resin of preparation is the multistage porous network structure with certain density gradient, connecting between NEs at different levels is that the multichain network type connects, finer and close and have a better continuity than the network structure of the poly-aspartic-acid resin of embodiment 1 preparation.Therefore, its gel-strength height, the water regain in salt solution is bigger, and light stability, thermostability and biologically stable are better.
Adding the 3g molecular weight in the beaker of 500ml is 300000 daltonian polysuccinimide and 72mlN, dinethylformamide (N, dinethylformamide is 24ml/g with the volume mass ratio of polysuccinimide), dissolving is 3 days under 40 ℃ of conditions, add 30ml water down at 60 ℃ and make dispersion agent (water is 10ml/g with the volume mass ratio of polysuccinimide), stir (1000 rev/mins of mixing speed) and made uniform suspended emulsion in 10 minutes, at 60 ℃ of hexanediamines that add 0.15g as linking agent (mass ratio of total consumption of hexanediamine and polysuccinimide is 0.05g/g), hexanediamine divides 2 addings: add 0.075g earlier, stirred 1 hour, add 0.075g again, continue to stir 1 hour.Add the agent of 300ml ethanol sedimentation, treat that throw out forms after, aging crystallization 10 days is removed supernatant liquor with decantation, under 40 ℃, 0.095MPa vacuum-drying makes the crosslinked polysuccinimide of solid of 3.02g with throw out.
It is the powder of particle diameter less than 0.1mm that the crosslinked polysuccinimide of 3.02g is pulverized, powder is added in the beaker, add 60ml water/ethanol equal-volume again than mixing solutions (aqueous ethanolic solution is 20ml/g with the volume mass ratio of crosslinked polysuccinimide), under 25 ℃, stirred 15 minutes, drip the NaOH aqueous solution of 27wt%, per NaOH aqueous solution (per hour add the NaOH aqueous solution and be 0.02ml/g) that added 3 in 2 hours with crosslinked polysuccinimide volume mass ratio, when all presenting colloid, solution adds 300ml ethanol, after treating that throw out forms, aging crystallization was handled 1 day, remove supernatant liquor with decantation, throw out is placed in the refrigerator-freezer-40 ℃ of freezing curing 1 day, and-54 ℃ of lyophilizes obtain 2.87g solid poly-aspartic-acid resin.Recording the swelling ratio of poly-aspartic-acid resin in deionized water is 678g/g, and the swelling ratio in the NaCl of the 0.9wt% aqueous solution is 78g/g, and gel-strength is 11.82 seconds.
Adding the 3g molecular weight in the beaker of 500ml is 20000 daltonian polysuccinimide and 24mlN, dinethylformamide (N, dinethylformamide is 10ml/g with the volume mass ratio of polysuccinimide), dissolving is 1 day under 60 ℃ of conditions, add 42ml water down at 25 ℃ and make dispersion agent (water is 14ml/g with the volume mass ratio of polysuccinimide), stir (1000 rev/mins of mixing speed) and made uniform suspended emulsion in 10 minutes, at 40 ℃ of hexanediamines that add 0.36g as linking agent (mass ratio of total consumption of hexanediamine and polysuccinimide is 0.12g/g), hexanediamine divides 2 addings: add 0.18g earlier, stirred 3 hours, add 0.18g again, continue to stir 3 hours, add the agent of 300ml ethanol sedimentation, treat that throw out forms after, aging crystallization 1 day, remove supernatant liquor with decantation, throw out is placed in the refrigerator-freezer-40 ℃ of freezing curing 1 day, and-54 ℃ of lyophilizes make the crosslinked polysuccinimide of solid of 3.12g.
It is the powder of particle diameter less than 0.1mm that the crosslinked polysuccinimide of 3.12g is pulverized, powder is added in the beaker, add 31.2ml water/ethanol equal-volume again than mixing solutions (aqueous ethanolic solution is 10ml/g with the volume mass ratio of crosslinked polysuccinimide), under 60 ℃, stirred 15 minutes, drip the NaOH aqueous solution of 27wt%, per hour add 9 NaOH aqueous solution (per hour add the NaOH aqueous solution and be 0.12ml/g) with crosslinked polysuccinimide volume mass ratio, when all presenting colloid, solution adds the agent of 300ml ethanol sedimentation, after treating that throw out forms, aging crystallization was handled 10 days, remove supernatant liquor with decantation, throw out 25 ℃ of following forced air dryings, is obtained 3.01g solid poly-aspartic-acid resin.Recording the swelling ratio of poly-aspartic-acid resin in deionized water is 56g/g, and the swelling ratio in the NaCl of the 0.9wt% aqueous solution is 24g/g, and gel-strength is 9.78 seconds.
With the 3g molecular weight is that 500000 daltonian polysuccinimides pulverizing are the powder of particle diameter less than 0.1mm, under 30 ℃, in powder, add 90ml water and make dispersion agent (water is 30ml/g with the volume mass ratio of polysuccinimide), stir (1000 rev/mins of mixing speed) and made uniform suspension in 30 minutes, the hexanediamine that adds 0.42g is as linking agent (mass ratio of total consumption of hexanediamine and polysuccinimide is 0.14g/g), hexanediamine divides 2 addings: add 0.21g earlier, stirred 4 hours, add 0.21g again, continue to stir 4 hours, add the agent of 300ml ethanol sedimentation, after treating that throw out forms, aging crystallization 3 days, remove supernatant liquor with decantation, throw out 25 ℃ of forced air dryings, is made the crosslinked polysuccinimide of solid of 3.06g.
It is the powder of particle diameter less than 0.1mm that the crosslinked polysuccinimide of 3.06g is pulverized, powder is added in the beaker, add 61.2ml water/ethanol equal-volume again than mixing solutions (aqueous ethanolic solution is 20ml/g with the volume mass ratio of crosslinked polysuccinimide), under 40 ℃, stirred 15 minutes, drip the NaOH aqueous solution of 20wt%, per hour add 3 NaOH aqueous solution (per hour add the NaOH aqueous solution and be 0.04ml/g) with crosslinked polysuccinimide volume mass ratio, when all presenting colloid, solution adds the agent of 300ml ethanol sedimentation, after treating that throw out forms, aging crystallization was handled 3 days, remove supernatant liquor with decantation, under 40 ℃, 0.095MPa vacuum-drying obtains 2.82g solid poly-aspartic-acid resin with throw out.Recording the swelling ratio of poly-aspartic-acid resin in deionized water is 589g/g, and the swelling ratio in the NaCl of the 0.9wt% aqueous solution is 78g/g, and gel-strength is 17.89 seconds.According to electron micrograph as can be known, the rosin products of preparation is the multistage porous network structure with certain density gradient, and connecting between NEs at different levels is that the multichain network type connects, and the network structure of this product has continuity preferably.
As different from Example 5 when the crosslinked polysuccinimide of preparation, the linking agent hexanediamine divides 4 addings, after reactant forms uniform suspension, in 8 hours, added 0.105g linking agent hexanediamine every 2 hours, all the other conditions are identical with embodiment 5, obtain 3.04g solid poly-aspartic-acid resin.Recording the swelling ratio of poly-aspartic-acid resin in deionized water is 350g/g, and the swelling ratio in the NaCl of the 0.9wt% aqueous solution is 89g/g, and gel-strength is 19.23 seconds.According to electron micrograph as can be known, the poly-aspartic-acid resin of preparation is the multistage porous network structure with certain density gradient, connecting between NEs at different levels is that the multichain network type connects, finer and close and have a better continuity than the network structure of the poly-aspartic-acid resin of embodiment 5 preparations.Therefore, its gel-strength and the water regain in salt solution are bigger, and light stability, thermostability and biologically stable are better.
With the 3g molecular weight is that the pulverizing of 500000 dalton's polysuccinimides is the powder of particle diameter less than 0.1mm, under 60 ℃, in powder, add 60ml water and make dispersion agent (water is 20ml/g with the volume mass ratio of polysuccinimide), stir (1000 rev/mins of mixing speed) and made uniform suspension in 20 minutes, the hexanediamine that adds 0.54g is as linking agent (mass ratio of total consumption of hexanediamine and polysuccinimide is 0.18g/g), hexanediamine divides 2 addings: add 0.27g earlier, stirred 0.5 hour, add 0.27g again, continue to stir 0.5 hour, add the agent of 300ml ethanol sedimentation, after treating that throw out forms, aging crystallization 1 day is removed supernatant liquor with decantation, and throw out is placed in the refrigerator-freezer-40 ℃ of freezing curing 1 day,-54 ℃ of lyophilizes make the crosslinked polysuccinimide of solid of 3.12g.
It is the powder of particle diameter at 0.0001～0.1mm that the crosslinked polysuccinimide of 3.12g is pulverized, powder is added in the beaker, add 31.2ml water/ethanol equal-volume again than mixing solutions (aqueous ethanolic solution is 10ml/g with the volume mass ratio of crosslinked polysuccinimide), under 25 ℃, stirred 15 minutes, the NaOH aqueous solution of Dropwise 35 wt%, added 3 NaOH aqueous solution (per hour add the NaOH aqueous solution and be 0.02ml/g) in per 2 hours with crosslinked polysuccinimide volume mass ratio, when all presenting colloid, solution adds the agent of 300ml ethanol sedimentation, after treating that throw out forms, aging crystallization was handled 6 days, remove supernatant liquor with decantation, under 40 ℃, 0.095MPa vacuum-drying obtains 3.03g solid poly-aspartic-acid resin with throw out.Recording the swelling ratio of poly-aspartic-acid resin in deionized water is 292g/g, and the swelling ratio in the NaCl of the 0.9wt% aqueous solution is 56g/g, and gel-strength is 14.26 seconds.
The 3g molecular weight is that the pulverizing of 500000 dalton's polysuccinimides is the powder of particle diameter less than 0.1mm, under 25 ℃, in powder, add 60ml water and make dispersion agent (water is 20ml/g with the volume mass ratio of polysuccinimide), stir (1000 rev/mins of mixing speed) and made uniform suspension in 20 minutes, the hexanediamine that adds 0.54g is as linking agent (mass ratio of total consumption of hexanediamine and polysuccinimide is 0.18g/g), hexanediamine divides 2 addings: add 0.27g earlier, stir after 36 hours, add 0.27g again, continue to stir 36 hours, add the agent of 300ml ethanol sedimentation, after treating that throw out forms, aging crystallization 6 days, remove supernatant liquor with decantation, throw out 25 ℃ of following forced air dryings, is made the crosslinked polysuccinimide of solid of 3.14g.
It is the powder of particle diameter less than 0.1mm that the crosslinked polysuccinimide of 3.14g is pulverized, powder is added in the beaker, add 31.4ml water/ethanol equal-volume again than mixing solutions (mixing solutions is 10ml/g with the volume mass ratio of crosslinked polysuccinimide), under 25 ℃, stirred 15 minutes, the NaOH aqueous solution of Dropwise 35 wt%, added 3 NaOH aqueous solution (per hour add the NaOH aqueous solution and be 0.02ml/g) in per 2 hours with crosslinked polysuccinimide volume mass ratio, when all presenting colloid, solution adds the agent of 300ml ethanol sedimentation, after treating that throw out forms, aging crystallization was handled 6 days, remove supernatant liquor with decantation, under 40 ℃, 0.095MPa vacuum-drying obtains 3.08g solid poly-aspartic-acid resin with throw out.Recording the swelling ratio of poly-aspartic-acid resin in deionized water is 280g/g, and the swelling ratio in the NaCl of the 0.9wt% aqueous solution is 64g/g, and gel-strength is 16.14 seconds.
The 3g molecular weight is that the pulverizing of 100000 dalton's polysuccinimides is the powder of particle diameter less than 0.1mm, under 40 ℃, in powder, add 24ml water and make dispersion agent (water is 8ml/g with the volume mass ratio of polysuccinimide), stir (1000 rev/mins of mixing speed) and made uniform suspension in 10 minutes, the hexanediamine that adds 0.60g is as linking agent (mass ratio of total consumption of hexanediamine and polysuccinimide is 0.20g/g), hexanediamine divides 2 addings: add 0.30g earlier, stir after 12 hours, add 0.30g again, continue to stir 12 hours, add the agent of 300ml ethanol sedimentation, after treating that throw out forms, aging crystallization 10 days is removed supernatant liquor with decantation, with throw out under 40 ℃, 0.095MPa vacuum-drying makes the crosslinked polysuccinimide of solid of 3.02g.
It is the powder of particle diameter less than 0.1mm that the crosslinked polysuccinimide of 3.02g is pulverized, powder is added in the beaker, add 30.2ml water/ethanol equal-volume again than mixing solutions (aqueous ethanolic solution is 10ml/g with the volume mass ratio of crosslinked polysuccinimide), under 40 ℃, stirred 15 minutes, drip the Na0H aqueous solution of 20wt%, per hour add 3 NaOH aqueous solution (per hour add the Na0H aqueous solution and be 0.04ml/g) with crosslinked polysuccinimide volume mass ratio, when all presenting colloid, solution adds the agent of 300ml ethanol sedimentation, after treating that throw out forms, aging crystallization was handled 1 day, remove supernatant liquor with decantation, throw out is placed in the refrigerator-freezer-40 ℃ of freezing curing 1 day, and-54 ℃ of lyophilizes obtain 2.88g solid poly-aspartic-acid resin.Recording the swelling ratio of poly-aspartic-acid resin in deionized water is 137g/g, and the swelling ratio in the NaCl of the 0.9wt% aqueous solution is 38g/g, and gel-strength is 9.76 seconds.
With embodiment 1 inequality be to add butanediamine as linking agent, all the other conditions are identical with embodiment 1.Obtain 3.02g solid poly-aspartic-acid resin.Recording the swelling ratio of poly-aspartic-acid resin in deionized water is 1210g/g, and the swelling ratio in the NaCl of the 0.9wt% aqueous solution is 120g/g, and gel-strength is 21.23 seconds.
Embodiment 11
With embodiment 1 inequality be to add lysine hydrochloride as linking agent, all the other conditions are identical with embodiment 1.Obtain 3.12g solid poly-aspartic-acid resin.Recording the swelling ratio of poly-aspartic-acid resin in deionized water is 1160g/g, and the swelling ratio in the NaCl of the 0.9wt% aqueous solution is 126g/g, and gel-strength is 22.30 seconds.
With embodiment 1 inequality be to add lysine methyl ester as linking agent, all the other conditions are identical with embodiment 1.Obtain 3.18g solid poly-aspartic-acid resin.Recording the swelling ratio of poly-aspartic-acid resin in deionized water is 1120g/g, and the swelling ratio in the NaCl of the 0.9wt% aqueous solution is 130g/g, and gel-strength is 22.90 seconds.
Comparative Examples 1
With embodiment 1 inequality be that the mode that adds the linking agent hexanediamine is to add (total add-on is identical) 1 time, all the other conditions are identical with embodiment 1.Make 2.91g solid poly-aspartic-acid resin.
Through measuring the swelling ratio of poly-aspartic-acid resin in deionized water is 936g/g, and the swelling ratio in the NaCl of the 0.9wt% aqueous solution is 98g/g, and gel-strength is 9.68 seconds.The poly-aspartic-acid resin of preparation is placed on initial pH value to be waited to inhale in 4～10 scope in the solution after the swelling, record and wait to inhale the pH value of solution as shown in Figure 1 between 6.8～7.8, compare with the result of embodiment 1, the pH surge capability of poly-aspartic-acid resin is poorer than the poly-aspartic-acid resin of embodiment 1 preparation.The poly-aspartic-acid resin of preparation is placed on the 292nm ultraviolet lamp under irradiation recorded water regain as shown in Figure 2 in 1～5 day, water regain with the light application time variation greatly; Poly-aspartic-acid resin thermal treatment under 150 ℃ of conditions of preparation was recorded water regain as shown in Figure 3 in 1～5 hour, and water regain changes greatly with heat treatment time; Light stability and thermostability that the poly-aspartic-acid resin for preparing is described are all poor than the poly-aspartic-acid resin of embodiment 1 preparation.Being worth the poly-aspartic-acid resin biological degradability by the BOD that records is 25.9%, and its BOD/COD value is 0.561.The poly-aspartic-acid resin that preparation is described is biological easily degradable material, illustrates that also its biologically stable is poorer than the poly-aspartic-acid resin of embodiment 1 preparation.
Comparative Examples 2
With embodiment 1 inequality be that the mode that adds the linking agent hexanediamine is that 1 time (total add-on is identical) adds, crosslinked polysuccinimide and poly-aspartic-acid resin are after throw out forms, without aging crystallization, directly remove supernatant liquor, then forced air drying under 80 ℃ of conditions with decantation.All the other conditions are identical with embodiment 1.Make 2.84g solid poly-aspartic-acid resin.
Through measuring the swelling ratio of poly-aspartic-acid resin in deionized water is 788g/g, and the swelling ratio in the NaCl of the 0.9wt% aqueous solution is 82g/g, and gel-strength is 2.96 seconds.According to electron micrograph as can be known, rosin products is a kind of single-stage porous network structure, and the voidage of this product and aperture are all less than embodiment 1, and the network continuity is poorer than embodiment 1.
Claims (7)
1, a kind of preparation method of poly-aspartic-acid resin, be to be 20 with molecular weight, 000～500,000 daltonian polysuccinimide is a raw material, produce crosslinked polysuccinimide with heterogeneous outstanding newborn crosslinking or heterogeneous suspension crosslinking, obtain the crosslinked polysuccinimide of solid through precipitation, separation and purification, drying; Produce poly-aspartic-acid resin through pulverizing, hydrolysis, obtain the solid poly-aspartic acid resin through precipitation, separation and purification, drying more at last, it is characterized in that:
(1) producing crosslinked polysuccinimide is the multistage crosslinking reaction, divides 2～4 equivalent constant duration chargings to realize by linking agent;
(2) crosslinked polysuccinimide and poly-aspartic-acid resin are carried out aging crystallization processing and rapid drying processing;
(A) aging crystallization is handled: at room temperature carry out 1～10 day aging crystallization;
(B) rapid drying is handled: carry out under-54～40 ℃.
2, method according to claim 1, it is characterized in that: it is as follows to adopt heterogeneous outstanding newborn crosslinking to prepare the multistage crosslinking reaction operating process of crosslinked polysuccinimide: under normal pressure, 25～60 ℃ of conditions, polysuccinimide added in the non-proton type polar organic solvent dissolved 1～10 day, organic solvent is 10～36ml/g with the volume mass ratio of polysuccinimide; Add dispersion agent again, dispersion agent is 6～14ml/g with the volume mass ratio of polysuccinimide, and dispersed with stirring becomes uniform suspended emulsion; Divide 2～4 equivalent constant durations to add linking agents, the mass ratio of linking agent and polysuccinimide is 0.05～0.12g/g, and stirring l～6 hour make crosslinked polysuccinimide.
3, according to the described method of claim l, it is characterized in that: it is as follows to adopt heterogeneous suspension crosslinking to prepare the multistage crosslinking reaction operating process of crosslinked polysuccinimide: under normal pressure, 25～60 ℃ of conditions, in the polysuccinimide powder of particle diameter＜0.1mm, add dispersion agent, dispersion agent is 8～30ml/g with the volume mass ratio of polysuccinimide, stirs into uniform dispersed; Divide 2～4 equivalent constant durations to add linking agent again, the mass ratio of linking agent and polysuccinimide is 0.14～0.20g/g, stirs 1～72 hour, makes crosslinked polysuccinimide.
4, according to claim 2 or 3 described methods, it is characterized in that: linking agent comprises: (A) aliphatic polyamine: 1, propylene diamine, 1,4-butanediamine, 1,5-pentamethylene diamine, 1,6-hexanediamine or heptamethylene diamine; (B) basic aminoacids: Methionin, ornithine or Gelucystine; (C) alkaline amino acid salt: lysine salt, ornithine salt or cystine salt; (D) basic aminoacids ester: Methionin ester, ornithine ester or Gelucystine ester.
5, method according to claim 2 is characterized in that: non-proton type polar organic solvent is N, dinethylformamide, N,N-dimethylacetamide, N-Methyl pyrrolidone, dimethyl sulfoxide (DMSO) or N, N-dimethyl-imidazolinone.
6, according to claim 2 or 3 described methods, it is characterized in that: dispersion agent is: water, methyl alcohol, ethanol, propyl alcohol or Virahol.
7, method according to claim 1, it is characterized in that: rapid drying is treated to: vacuum-drying, gas blower drying or lyophilize.
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| CN102040735A (en) * | 2010-11-09 | 2011-05-04 | 华东理工大学 | Aspartic acid-cyclodextrin copolymer and intermediate polymer, preparation methods of aspartic acid-cyclodextrin copolymer and intermediate polymer as well as application of aspartic acid-cyclodextrin copolymer |
| CN102250352A (en) * | 2011-05-19 | 2011-11-23 | 黑龙江大学 | Method for catalytic synthesis of polyaspartic acid by using imidazole type ionic liquid |
| CN102643441A (en) * | 2012-05-02 | 2012-08-22 | 北京化工大学 | Method for preparing polyaspartic acid type hydrogel |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5380817A (en) * | 1992-07-10 | 1995-01-10 | Rohm And Haas Company | Process for preparing polysuccinimides from aspartic acid |
| US5393868A (en) * | 1992-10-13 | 1995-02-28 | Rohm And Haas Company | Production of polysuccinimide by thermal polymerization of maleamic acid |
| US6072024A (en) * | 1997-03-21 | 2000-06-06 | Mitsui Chemicals, Inc. | Production process of cross-linked polyaspartic acid resin |
| CN1123588C (en) * | 2001-10-08 | 2003-10-08 | 北京化工大学 | Synthesis method of polyaspartic acid |
| CN1195000C (en) * | 2002-11-05 | 2005-03-30 | 中国石化上海石油化工股份有限公司 | Method for preparing poly aspartic acid |
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| CN102040735A (en) * | 2010-11-09 | 2011-05-04 | 华东理工大学 | Aspartic acid-cyclodextrin copolymer and intermediate polymer, preparation methods of aspartic acid-cyclodextrin copolymer and intermediate polymer as well as application of aspartic acid-cyclodextrin copolymer |
| CN102040735B (en) * | 2010-11-09 | 2013-06-19 | 华东理工大学 | Aspartic acid-cyclodextrin copolymer and intermediate polymer, preparation methods of same as well as application thereof |
| CN102754572A (en) * | 2011-04-26 | 2012-10-31 | 北京化工大学 | Plant cultivating substrate as well as preparation method and application of same |
| CN102754572B (en) * | 2011-04-26 | 2014-10-29 | 北京化工大学 | Plant cultivating substrate as well as preparation method and application of same |
| CN102250352A (en) * | 2011-05-19 | 2011-11-23 | 黑龙江大学 | Method for catalytic synthesis of polyaspartic acid by using imidazole type ionic liquid |
| CN102250352B (en) * | 2011-05-19 | 2012-07-25 | 黑龙江大学 | Method for catalytic synthesis of polyaspartic acid by using imidazole type ionic liquid |
| CN102643441A (en) * | 2012-05-02 | 2012-08-22 | 北京化工大学 | Method for preparing polyaspartic acid type hydrogel |
| CN102643441B (en) * | 2012-05-02 | 2014-08-13 | 北京化工大学 | Method for preparing polyaspartic acid type hydrogel |
| CN104086994A (en) * | 2014-07-03 | 2014-10-08 | 长春理工大学 | Polyaspartic acid gel and preparation method thereof |
| CN108816200A (en) * | 2018-06-19 | 2018-11-16 | 江苏东珠景观股份有限公司 | The adsorbent of metal ion in a kind of artificial swamp soil |
| CN113321808A (en) * | 2021-06-16 | 2021-08-31 | 苏州美瑞姿生物科技有限公司 | Multifunctional polyaspartic acid derivative and preparation process thereof |
| CN113321808B (en) * | 2021-06-16 | 2023-03-07 | 苏州美瑞姿生物科技有限公司 | Multifunctional polyaspartic acid derivative and preparation process thereof |
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