CN105482117B - Poly-aspartate/urea graft copolymer and its preparation method and application - Google Patents
Poly-aspartate/urea graft copolymer and its preparation method and application Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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Abstract
The present invention relates to a kind of poly-aspartate derivant of new amide-containing, i.e. poly-aspartate/urea graft copolymer, its structure such as following formula (I) or (II) are shown, and n therein takes 35 130；n:P=1:0.01‑1:0.99, described poly-aspartate/urea graft copolymer weight average molecular weight is 4,000 15000.Poly-aspartate derivant of the present invention is a kind of inexpensive, nontoxic, not phosphorous, biodegradable high molecular polymer, with prominent chelating and dispersive property, and dirts a variety of to calcium carbonate, calcium sulfate and calcium phosphate etc. all have excellent scale inhibition effect.The present invention also provides the preparation method of the poly-aspartate derivant, poly-aspartate is modified by the method for hydrolysis, there is many-sided advantages such as simple production process, environmental pollution are small, product scale-inhibiting properties are excellent simultaneously, and raw material is cheap, wide material sources, suitable for industrial production.
Description
Technical field
The invention belongs to high molecular polymer field, and in particular to a kind of new poly-aspartate derivant, more specifically
Ground is related to poly-aspartate/urea graft copolymer, and preparation method thereof.
Background technology
In recent years, developed rapidly with industrial, industrial water consumption increasingly increases, and wherein cooling water accounts for industry
With more than the 60% of water, therefore save cooling water and just turn into the primary goal of Industrial Water Saving.The recycling of cooling water is to save
The most effective approach of cooling water.But during the recycling of cooling water, the reason such as temperature rise, raw water quality difference causes
System contamination, fouling, reduce the heat transfer efficiency of system, add the energy resource consumption of system.Therefore, cooling water is recycled
During be necessary to take certain antiscale, scale inhibition measure.It is antiscale, the important means of scale inhibition to add antisludging agent, and it is to preventing
Very important effect is played in precipitation formation.Therefore, how to control the growth of incrustation scale, environmentally friendly, efficient water treatment scale is developed
Agent has turned into the focus that current industrial water conditioning agent is studied.The antisludging agent commonly used in current water process has natural antisludging agent, phosphorous
Antisludging agent, polycarboxylic acid scale inhibitor and new green scale inhibitor.
Poly-aspartate is as a kind of new degradable green antisludging agent, with excellent complexing power and dispersive property.
But, there was only free carboxy on poly-aspartate chain, comprehensive scale-inhibiting properties are bad.By by hydroxyl, carboxylic acid group, sulfonic group, phosphorus
The functional group that acidic group etc. has scale-inhibiting properties is incorporated into the molecular structure of poly-aspartate, can reach raising poly-aspartate
The purpose of energy.Polysuccinimide is the intermediate product for preparing poly-aspartate, and it is that a kind of activity very strong linear polyamides is sub-
Amine, with preferable reactivity, easily generates the poly-aspartate derivant with functional group side chain by amino open loop.It is logical
Cross the method modified synthesis poly-aspartate derivant of hydrolysis of polysuccinimide open loop, course of reaction is simple, reaction temperature compared with
It is low, it is not necessary to extra addition organic solvent and phosphoric acid catalyst.CN102875808A discloses a kind of containing sulfonic poly- asparagus fern
The preparation method of histidine copolymer, intermediate polysuccinimide is prepared by raw material of aspartic acid, then by 2- amino second sulphurs
Hydrochlorate and the glutamate aqueous solution are added in the suspension of polysuccinimide and water simultaneously, and solid is separated out with absolute ethyl alcohol,
Obtain containing sulfonic poly-aspartate derivant, improve scale-inhibiting properties.This method raw material aspartic acid price is somewhat expensive, no
Beneficial to industrial production, and sulfonic group has pollution to environment.
Therefore, it is necessary to develop a kind of new green scale inhibitor to overcome the limitation of prior art.
The content of the invention
The primary and foremost purpose of the present invention is to provide a kind of new poly-aspartate derivant, than existing poly-aspartate
Derivative antisludging agent has more excellent scale-inhibiting properties.
It is another object of the present invention to：A kind of method for preparing described poly-aspartate derivant is provided, had
Low cost and the advantage of environmental protection.
Another object of the present invention is：There is provided described poly-aspartate derivant water process, medicine, agricultural,
Application in the fields such as daily use chemicals.
The above-mentioned purpose of the present invention is achieved through the following technical solutions：
First there is provided a kind of poly-aspartate derivant, it is poly-aspartate/urea graft copolymer of amide-containing
(PASP/Urea), its structure such as following formula (I) or (II) are shown：
In formula (I) or (II)：Described n takes 35-130；n:P=1:0.01-1:0.99.
Currently preferred poly-aspartate derivant, its weight average molecular weight is 4000-15000.
Currently preferred poly-aspartate derivant, is prepared by following methods：It is first anti-with maleic anhydride and ethanol
Ethyl maleate should be obtained；Obtained ethyl maleate obtains ethyl maleate ammonium salt solution with ammoniacal liquor reaction again；Horse
Carry out the progress polycondensation reaction under polar solvent effect of sour mono ethyl ester ammonium salt and obtain polysuccinimide (PSI)；It is last suspended in PSI
The alkaline solution dissolved with urea is added in liquid, ammonolysis graft reaction 4-48h is carried out in a heated condition, reaction terminates regulation pH value
To neutral, poly-aspartate of the present invention/urea graft copolymer is obtained.
In addition, the present invention also provides a kind of method for preparing the poly-aspartate derivant, be first with maleic anhydride and
Ethanol synthesis obtains ethyl maleate；It is molten that obtained ethyl maleate obtains ethyl maleate ammonium salt with ammoniacal liquor reaction again
Liquid；Ethyl maleate ammonium salt carries out polycondensation reaction under polar solvent effect and obtains polysuccinimide (PSI)；Finally exist
The alkaline solution dissolved with urea is added in PSI suspensions, ammonolysis graft reaction 4-48h is carried out in a heated condition, reaction terminates
PH value is adjusted to neutrality, poly-aspartate of the present invention/urea graft copolymer is obtained,
Its substantially synthetic route is as follows：
The currently preferred method for preparing the poly-aspartate derivant, specific steps include：
(1) maleic anhydride and ethanol are with 1:1.1-1:1.5 mol ratio reacts 1.5~3h at 50~80 DEG C, obtains horse
Carry out sour mono ethyl ester；
(2) mol ratio of ammoniacal liquor, maleic anhydride monoethylester and ammoniacal liquor is added in the ethyl maleate solution obtained to (1)
For 1:1.1-1:2.0,2-5h is reacted at room temperature obtains ethyl maleate ammonium salt solution；
(3) polar solvent containing N-methyl pyrrolidones is added in the ethyl maleate ammonium salt solution obtained to (2),
Polycondensation reaction 4-10h is carried out at a temperature of 150-220 DEG C, is cooled down after the completion of reaction and solution is slowly added into absolute ethyl alcohol,
The polysuccinimide purified；
(4) polysuccinimide for obtaining step (3) is prepared into suspension, then urea is dissolved in into the formation of highly basic solvent
Mixed solution is slowly dropped in described suspension, and the mol ratio for making polysuccinimide and urea is 1:0.01-1:0.99,
Heating carries out ammonolysis graft reaction 4-48h at 50 DEG C, and reaction terminates regulation pH value to neutrality, and it is this hair to obtain brown precipitate
Bright described poly-aspartate/urea graft copolymer.
In the further preferred method for preparing the poly-aspartate derivant of the invention, the Malaysia described in step (1)
The mol ratio of acid anhydrides and ethanol is 1:1.2.
In the currently preferred method for preparing the poly-aspartate derivant, contain N-methyl described in step (3)
The polar solvent of pyrrolidones is selected from：N-methyl pyrrolidones, or N-methyl pyrrolidones and sulfolane mixed solvent；It is more excellent
In the scheme of choosing, the mass ratio of N-methyl pyrrolidones and sulfolane is 2 in described mixed solution:1-1:2；It is most preferably described
Mixed solution in N-methyl pyrrolidones and sulfolane mass ratio be 1:1.
In the currently preferred method for preparing the poly-aspartate derivant, during polycondensation reaction described in step (3)
Between be 6-8h.
In the currently preferred method for preparing the poly-aspartate derivant, the polycondensation reaction temperature described in step (3)
Spend for 180~200 DEG C.
In the currently preferred method for preparing the poly-aspartate derivant, the highly basic described in step (4) is selected from hydrogen
Mixed solvent more than one or both of sodium oxide molybdena, potassium hydroxide, caustic alcohol, cesium hydroxide or Cymag.
In the further preferred method for preparing the poly-aspartate derivant of the invention, the urea described in step (4)
The mixed solution for being dissolved in the formation of highly basic solvent is the mixed solution that urea is dissolved in caustic alcohol formation, and wherein urea and caustic alcohol rubs
You are than being 1:1.0-1:2.0.
In the currently preferred method for preparing the poly-aspartate derivant, step (4) is described to obtain brown precipitate
Afterwards, further it is dried in vacuo 10-24h.
In the currently preferred method for preparing the poly-aspartate derivant, the poly- succinyl described in step (4) is sub-
It is that polysuccinimide is dissolved in into ethanol, N,N-dimethylformamide or water equal solvent formation suspension that amine, which is prepared into suspension,；
In preferred method, polysuccinimide is dissolved in ethanol formation suspension.
In the currently preferred method for preparing the poly-aspartate derivant, the poly-aspartate that step (4) is obtained/
The grafting rate of urea is 1%-99% in urea graft copolymer.
Finally, the present invention also provides the application in antiscale or scale inhibition of the poly-aspartate derivant in water；Especially
Application in the antiscale of the industrial water including fields such as water process, medicine, agricultural, daily use chemicals or scale inhibition.
Compared with prior art, the invention provides a kind of new poly-aspartate derivant, i.e. poly-aspartate/urine
Plain graft copolymer, the compound is a kind of nontoxic, not phosphorous, degradable high molecular polymer, is introduced in its strand
Amide groups, enhances its anticorrosion-antiscaling property and dispersive property, overcome existing poly-aspartate in resistance calcium phosphate scale and
Deficiency in dispersiveness；All there is excellent scale inhibition effect for a variety of dirts such as calcium carbonate, calcium sulfate and calcium phosphate.
The present invention also provides the preparation method of the poly-aspartate/urea graft copolymer, passes through the side of hydrolysis
Method is modified to poly-aspartate, while having that simple production process, environmental pollution be small, that product scale-inhibiting properties are excellent is many
Aspect advantage, and raw material is cheap, wide material sources, suitable for industrial production.
Embodiment
Prepare embodiment 1
9.8g maleic anhydrides are weighed, 5.5g absolute ethyl alcohols are added in three-necked flask, in reacting 2.5h under 60 DEG C of temperature conditionss
Colourless solution is obtained, room temperature is cooled to, obtains ethyl maleate.
Prepare embodiment 2
9.8g maleic anhydrides are weighed, 5.5g absolute ethyl alcohols are added in three-necked flask, in reacting 2.5h under 60 DEG C of temperature conditionss
Colourless solution is obtained, room temperature is cooled to.The ammoniacal liquor of 8.9g 25% is added into three-necked flask, 3h is reacted at room temperature and obtains light yellow molten
Liquid ammonium salt solution.
Prepare embodiment 3
9.8g maleic anhydrides and 5.53g ethanol are added in three-necked flask, in being reacted under 60 DEG C of temperature conditionss, with anti-
Stop reacting to obtain colourless ethyl maleate solution after the progress answered, solid dissolving, 2.5h, be cooled to room temperature.Use constant pressure addition
Funnel adds the ammoniacal liquor of 8.9g 25% room temperature reaction 3h into three-necked flask and obtains light yellow ammonium salt solution.By 15g sulfolane and nitrogen
Methyl pyrrolidone (1:1) mixed solvent is added in flask, has white opacity appearance, in N2Protection, mechanical agitation, point water condition
Lower carry out thermal polycondensation, reacts 6h at 180 DEG C.With the rise of reaction temperature, muddiness disappears, when temperature is more than 150 DEG C, solution
Begin to change into orange, and color constantly deepens, and finally gives the sticky solution of brown.Solution is added slowly to anhydrous second while hot
In alcohol, tan precipitate is separated out, and is carried out suction filtration, is dried to obtain 9.4g polysuccinimides.
Prepare embodiment 4
9.8g maleic anhydrides and 5.6g ethanol are added in three-necked flask, in being reacted under 60 DEG C of temperature conditionss, with anti-
Stop reacting to obtain colourless ethyl maleate solution after the progress answered, solid dissolving, 2.5h, be cooled to room temperature.Use constant pressure addition
Funnel adds the ammoniacal liquor of 8.9g 25% room temperature reaction 3h into three-necked flask and obtains light yellow ammonium salt solution.By 15g sulfolane and nitrogen
Methyl pyrrolidone (1:1) mixed solvent is added in flask, has white opacity appearance, in N2Protection, mechanical agitation, point water condition
Lower carry out thermal polycondensation, reacts 6h at 180 DEG C.With the rise of reaction temperature, muddiness disappears, when temperature is more than 150 DEG C, solution
Begin to change into orange, and color constantly deepens, and finally gives the sticky solution of brown.50 DEG C are cooled to, it is sub- to poly- succinyl
The sodium hydroxide solution that 18% is added in amine system adjusts pH to 8-9, after reacting 1 hour, carries out point liquid and obtains poly- asparagus fern ammonia
Sour aqueous phase solution, then with salt acid for adjusting pH to 3, be poured into the alcohol solvent of stirring, separate out solid.Then suction filtration, ethanol
Washing 3 times, 55.0 DEG C of vacuum drying 5h obtain off-white or buff white solid, as poly-aspartate.It is aobvious according to gpc analysis result
Show, the weight average molecular weight of poly-aspartate is 7130.
Prepare embodiment 5
19.6g maleic anhydrides and 11.1g ethanol are added in three-necked flask, under 60 DEG C of temperature conditionss react, with
Stop reacting to obtain colourless ethyl maleate solution after the progress of reaction, solid dissolving, 2.5h, be cooled to room temperature.Dripped with constant pressure
Liquid funnel adds 16.2g ammoniacal liquor room temperature reaction 3h into three-necked flask and obtains light yellow ammonium salt solution.By 30g sulfolane and n-formyl sarcolysine
Base pyrrolidones (1:1) mixed solvent is added in flask, has white opacity appearance, in N2Under protection, mechanical agitation, point water condition
Carry out reacting 6h at thermal polycondensation, 180 DEG C.With the rise of reaction temperature, muddiness is disappeared, and when temperature is more than 150 DEG C, solution is opened
Beginning is changed into orange, and color is constantly deepened, and finally gives the sticky solution of brown.Solution is added slowly to absolute ethyl alcohol while hot
In, tan precipitate is separated out, and is carried out suction filtration, is dried to obtain polysuccinimide.1g polysuccinimides and ethanol is taken to be added to
Suspension is formed in flask, then the alcohol sodium solution of 0.3g urea is slowly dropped in suspension, heats and carries out at 50 DEG C
Ammonolysis reaction 10h, with salt acid for adjusting pH value to neutrality, reaction terminates brown precipitate and separated out, and suction filtration, vacuum drying obtain 1.2g
Poly-aspartate/urea graft copolymer.Shown according to gpc analysis result, the weight average molecular weight of copolymer is 9049.
Prepare embodiment 6
19.6g maleic anhydrides and 12.0g ethanol are added in three-necked flask, under 60 DEG C of temperature conditionss react, with
Stop reacting to obtain colourless ethyl maleate solution after the progress of reaction, solid dissolving, 2.5h, be cooled to room temperature.Dripped with constant pressure
Liquid funnel adds 11.7g ammoniacal liquor room temperature reaction 3h into three-necked flask and obtains light yellow ammonium salt solution.By 30g sulfolane and n-formyl sarcolysine
Base pyrrolidones (1:1.5) mixed solvent is added in flask, has white opacity appearance, in N2Protection, mechanical agitation, point water condition
Lower carry out thermal polycondensation, reacts 7h at 190 DEG C.With the rise of reaction temperature, muddiness disappears, when temperature is more than 150 DEG C, solution
Begin to change into orange, and color constantly deepens, and finally gives the sticky solution of brown.Solution is added slowly to anhydrous second while hot
In alcohol, tan precipitate is separated out, and is carried out suction filtration, is dried to obtain polysuccinimide.1.9g polysuccinimides and ethanol is taken to add
Enter and suspension is formed into flask, then the alcohol sodium solution of 0.7g urea is slowly dropped in suspension, heated at 50 DEG C
Ammonolysis reaction 10h is carried out, with salt acid for adjusting pH value to neutrality, reaction terminates brown precipitate and separated out, and suction filtration, vacuum drying are obtained
2.5g poly-aspartates/urea graft copolymer.Shown according to gpc analysis result, the weight average molecular weight of copolymer is 11300.
Prepare embodiment 7
19.6g maleic anhydrides and 12.9g ethanol are added in three-necked flask, under 60 DEG C of temperature conditionss react, with
Stop reacting to obtain colourless ethyl maleate solution after the progress of reaction, solid dissolving, 2.5h, be cooled to room temperature.Dripped with constant pressure
Liquid funnel adds 19.6g ammoniacal liquor room temperature reaction 3h into three-necked flask and obtains light yellow ammonium salt solution.By 30g sulfolane and n-formyl sarcolysine
Base pyrrolidones (1:2) mixed solvent is added in flask, has white opacity appearance, in N2Under protection, mechanical agitation, point water condition
Carry out reacting 8h at thermal polycondensation, 200 DEG C.With the rise of reaction temperature, muddiness is disappeared, and when temperature is more than 150 DEG C, solution is opened
Beginning is changed into orange, and color is constantly deepened, and finally gives the sticky solution of brown.Solution is added slowly to absolute ethyl alcohol while hot
In, tan precipitate is separated out, and is carried out suction filtration, is dried to obtain polysuccinimide.2.9g polysuccinimides and ethanol is taken to add
Suspension is formed into flask, then the alcohol sodium solution of 1.3g urea is slowly dropped in suspension, heated at 50 DEG C into
Row ammonolysis reaction 10h, with salt acid for adjusting pH value to neutrality, reaction terminates brown precipitate and separated out, and suction filtration, vacuum drying are obtained
4.1g poly-aspartates/urea graft copolymer.Shown according to gpc analysis result, the weight average molecular weight of copolymer is 10650.
Prepare embodiment 8
19.6g maleic anhydrides and 13.8g ethanol are added in three-necked flask, under 60 DEG C of temperature conditionss react, with
Stop reacting to obtain colourless ethyl maleate solution after the progress of reaction, solid dissolving, 2.5h, be cooled to room temperature.Dripped with constant pressure
Liquid funnel adds 20.4g ammoniacal liquor room temperature reaction 3h into three-necked flask and obtains light yellow ammonium salt solution.By 30g sulfolane and n-formyl sarcolysine
Base pyrrolidones (1:1) mixed solvent is added in flask, has white opacity appearance, in N2Under protection, mechanical agitation, point water condition
Carry out reacting 9h at thermal polycondensation, 170 DEG C.With the rise of reaction temperature, muddiness is disappeared, and when temperature is more than 150 DEG C, solution is opened
Beginning is changed into orange, and color is constantly deepened, and finally gives the sticky solution of brown.Solution is added slowly to absolute ethyl alcohol while hot
In, tan precipitate is separated out, and is carried out suction filtration, is dried to obtain polysuccinimide.3.9g polysuccinimides and ethanol is taken to add
Suspension is formed into flask, then the alcohol sodium solution of 1.9g urea is slowly dropped in suspension, heated at 50 DEG C into
Row ammonolysis reaction 10h, with salt acid for adjusting pH value to neutrality, reaction terminates brown precipitate and separated out, and suction filtration, vacuum drying are obtained
5.3g poly-aspartates/urea graft copolymer.Shown according to gpc analysis result, the weight average molecular weight of copolymer is 13000.
Application Example 1
Take poly-aspartate and prepare poly-aspartate/urea that embodiment 5-8 is prepared that preparation embodiment 4 is prepared
Graft copolymer carries out the contrast experiment of scale-inhibiting properties, according to the measure of GB/T16632-2008 water treatment scale performances, assesses
Poly-aspartate/influence of the urea graft copolymer to calcium carbonate scale-inhibiting properties of the present invention.Configure water sample：Calcium ion it is initial
Concentration is 240mg/L, and the concentration of bicarbonate ion is 732mg/L, and pH value is 9 and ignores the change of pH value, in 80 DEG C of constant temperature
10h is heated in water-bath.When concentration is 4mg/L, the poly-aspartate for preparing the preparation of embodiment 4 is to the scale inhibition performance of calcium carbonate
28%；And prepare poly-aspartate/scale inhibition of the urea graft copolymer under same concentration to calcium carbonate of embodiment 5-8 preparations
Rate is more than 60%, and illustrating poly-aspartate/urea graft copolymer of the present invention has resistance more more preferable than poly-aspartate
Calcium carbonate performance.
Application Example 2
Take and prepare the graft copolymer progress scale-inhibiting properties experiment that embodiment 5-8 is prepared, assess the poly- asparagus fern of the present invention
Propylhomoserin/influence of the urea graft copolymer to calcium sulfate scale-inhibiting properties.Configure water sample：Calcium ion and sulfate ion it is initial dense
Degree is 6800mg/L, and pH value is 9 and ignores the change of pH value, and 10h is heated in 80 DEG C of waters bath with thermostatic control.When concentration is 6mg/L
When, poly-aspartate/urea graft copolymer that preparation embodiment 5-8 is prepared is 100% to the scale inhibition performance of calcium sulfate, is said
Bright poly-aspartate of the invention/urea graft copolymer has prominent resistance calcium sulfate performance.
Application Example 3
Take and prepare the graft copolymer progress scale-inhibiting properties experiment that embodiment 5-8 is prepared, assess the poly- asparagus fern of the present invention
Propylhomoserin/influence of the urea graft copolymer to calcium phosphate scale-inhibiting properties.Configure water sample：The initial concentration of calcium ion is 250mg/L,
The concentration of phosphate anion is 10mg/L, and pH value is 9 and ignores the change of pH value, and 10h is heated in 80 DEG C of waters bath with thermostatic control.When dense
When spending for 8mg/L, poly-aspartate/urea graft copolymer that preparation embodiment 5-8 is prepared is equal to the scale inhibition performance of calcium phosphate
Higher than 85%, illustrate that poly-aspartate of the present invention/urea graft copolymer has prominent resistance calcium phosphate performance.
Claims (12)
1. a kind of poly-aspartate derivant, it is characterised in that it is poly-aspartate/urea graft copolymerization of amide-containing
Thing, its structure such as following formula (I) or (II) are shown：
In formula (I) or (II)：Described n takes 35-130；n:P=1:0.01-1:0.99；
It is prepared by following methods：First ethyl maleate is obtained with maleic anhydride and ethanol synthesis；Obtained maleic acid
Mono ethyl ester obtains ethyl maleate ammonium salt solution with ammoniacal liquor reaction again；Ethyl maleate ammonium salt enters under polar solvent effect
Row polycondensation reaction obtains polysuccinimide (PSI)；The last alkaline solution added in PSI suspensions dissolved with urea, is adding
Ammonolysis graft reaction 4-48h is carried out under heat condition, reaction terminates regulation pH value to neutrality, obtains described poly-aspartate/urine
Plain graft copolymer.
2. a kind of method for preparing poly-aspartate derivant described in claim 1, it is characterised in that：First use maleic anhydride and second
Alcohol reaction obtains ethyl maleate；It is molten that obtained ethyl maleate obtains ethyl maleate ammonium salt with ammoniacal liquor reaction again
Liquid；Ethyl maleate ammonium salt carries out polycondensation reaction under polar solvent effect and obtains polysuccinimide (PSI)；Finally exist
The alkaline solution dissolved with urea is added in PSI suspensions, ammonolysis reaction 4-48h is carried out in a heated condition, reaction terminates regulation
PH value obtains described poly-aspartate/urea graft copolymer to neutrality.
3. the method described in claim 2, it is characterised in that comprise the following steps：
(1) maleic anhydride and ethanol are with 1:1.1-1:1.5 mol ratio reacts 1.5~3h at 50~80 DEG C, obtains maleic acid
Mono ethyl ester；
(2) ammoniacal liquor is added in the ethyl maleate solution obtained to (1), the mol ratio of ethyl maleate and ammoniacal liquor is 1:
1.1-1:2.0,2-5h is reacted at room temperature obtains ethyl maleate ammonium salt solution；
(3) polar solvent containing N-methyl pyrrolidones, 150- are added in the ethyl maleate ammonium salt solution obtained to (2)
Polycondensation reaction 4-10h is carried out at a temperature of 220 DEG C, is cooled down after the completion of reaction and solution is slowly added into absolute ethyl alcohol, obtained
The polysuccinimide of purifying；
(4) polysuccinimide for obtaining step (3) is prepared into suspension, then urea is dissolved in into the mixing that highly basic solvent is formed
Solution is slowly dropped in described suspension, and the mol ratio for making polysuccinimide and urea is 1:0.01-1:0.99,50
Heating progress ammonolysis graft reaction 4-48h at DEG C, reaction terminates regulation pH value to neutrality, and it is described gather to obtain brown precipitate
Aspartic acid/urea graft copolymer.
4. the method described in claim 3, it is characterised in that：The polarity containing N-methyl pyrrolidones described in step (3) is molten
Agent is selected from：The mixed solution of N-methyl pyrrolidone solution or N-methyl pyrrolidones and sulfolane.
5. the method described in claim 4, it is characterised in that：N-methyl pyrrolidones and sulfolane in described mixed solution
Mass ratio is 2:1-1:2.
6. the method described in claim 4, it is characterised in that：N-methyl pyrrolidones and sulfolane in described mixed solution
Mass ratio is 1:1.
7. the method described in claim 3, it is characterised in that：Polycondensation reaction time described in step (3) is 6-8h；Described contracting
Poly- reaction temperature is 180~200 DEG C.
8. the method described in claim 3, it is characterised in that：Highly basic solvent described in step (4) is selected from sodium hydroxide, hydroxide
A kind of solution or two or more mixed solutions in potassium, caustic alcohol, cesium hydroxide or Cymag.
9. the method described in claim 3, it is characterised in that：Urea described in step (4) is dissolved in the mixing of highly basic solvent formation
Solution is the mixed solution that urea is dissolved in caustic alcohol formation, and wherein the mol ratio of urea and caustic alcohol is 1:1.0-1:2.0.
10. the method described in claim 3, it is characterised in that：Polysuccinimide described in step (4), which is prepared into suspension, is
Polysuccinimide is dissolved in ethanol, N,N-dimethylformamide or water formation suspension.
11. the method described in claim 3, it is characterised in that：Polysuccinimide described in step (4), which is prepared into suspension, is
Polysuccinimide is dissolved in ethanol formation suspension.
12. application of the poly-aspartate derivant in the antiscale of water or scale inhibition described in claim 1, it is characterised in that：Institute
The antiscale for the water stated or scale inhibition include water process, medicine, agricultural, the antiscale of the water of household chemicals field or scale inhibition.
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| CN108059713B (en) * | 2018-01-02 | 2020-10-23 | 厦门双瑞船舶涂料有限公司 | Water-based epoxy curing agent containing DOPA functional group |
| CN113527679B (en) * | 2020-04-15 | 2023-03-31 | 中国石油化工股份有限公司 | Polyaspartic acid/2-amino-4, 6-dimethoxypyrimidine graft copolymer and application thereof |
| CN112246232A (en) * | 2020-10-16 | 2021-01-22 | 李艳艳 | Polyaspartic acid modified cellulose aerogel and preparation method thereof |
| CN114956898B (en) * | 2022-06-30 | 2023-10-13 | 河北协同化学有限公司 | Nitrogen fixation fertilizer retention synergist, self-assembled nitrogen-containing fertilizer containing nitrogen fixation fertilizer retention synergist and preparation method |
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| CN103255006A (en) * | 2013-02-02 | 2013-08-21 | 广东工业大学 | Biodegradable phosphorus-free detergent additive and preparation method thereof |
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